Tag Archives: buckyballs

What is a buckybomb?

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I gather buckybombs have something to do with cancer treatments. From a March 18, 2015 news item on ScienceDaily,

In 1996, a trio of scientists won the Nobel Prize for Chemistry for their discovery of Buckminsterfullerene — soccer-ball-shaped spheres of 60 joined carbon atoms that exhibit special physical properties.

Now, 20 years later, scientists have figured out how to turn them into Buckybombs.

These nanoscale explosives show potential for use in fighting cancer, with the hope that they could one day target and eliminate cancer at the cellular level — triggering tiny explosions that kill cancer cells with minimal impact on surrounding tissue.

“Future applications would probably use other types of carbon structures — such as carbon nanotubes, but we started with Bucky-balls because they’re very stable, and a lot is known about them,” said Oleg V. Prezhdo, professor of chemistry at the USC [University of Southern California] Dornsife College of Letters, Arts and Sciences and corresponding author of a paper on the new explosives that was published in The Journal of Physical Chemistry on February 24 [2015].

A March 19, 2015 USC news release by Robert Perkins, which despite its publication date originated the news item, describes current cancer treatments with carbon nanotubes and this new technique with fullerenes,

Carbon nanotubes, close relatives of Bucky-balls, are used already to treat cancer. They can be accumulated in cancer cells and heated up by a laser, which penetrates through surrounding tissues without affecting them and directly targets carbon nanotubes. Modifying carbon nanotubes the same way as the Buckybombs will make the cancer treatment more efficient — reducing the amount of treatment needed, Prezhdo said.

To build the miniature explosives, Prezhdo and his colleagues attached 12 nitrous oxide molecules to a single Bucky-ball and then heated it. Within picoseconds, the Bucky-ball disintegrated — increasing temperature by thousands of degrees in a controlled explosion.

The source of the explosion’s power is the breaking of powerful carbon bonds, which snap apart to bond with oxygen from the nitrous oxide, resulting in the creation of carbon dioxide, Prezhdo said.

I’m glad this technique would make treatment more effective but I do pause at the thought of having exploding buckyballs in my body or, for that matter, anyone else’s.

The research was highlighted earlier this month in a March 5, 2015 article by Lisa Zynga for phys.org,

The buckybomb combines the unique properties of two classes of materials: carbon structures and energetic nanomaterials. Carbon materials such as C60 can be chemically modified fairly easily to change their properties. Meanwhile, NO2 groups are known to contribute to detonation and combustion processes because they are a major source of oxygen. So, the scientists wondered what would happen if NO2 groups were attached to C60 molecules: would the whole thing explode? And how?

The simulations answered these questions by revealing the explosion in step-by-step detail. Starting with an intact buckybomb (technically called dodecanitrofullerene, or C60(NO2)12), the researchers raised the simulated temperature to 1000 K (700 °C). Within a picosecond (10-12 second), the NO2 groups begin to isomerize, rearranging their atoms and forming new groups with some of the carbon atoms from the C60. As a few more picoseconds pass, the C60 structure loses some of its electrons, which interferes with the bonds that hold it together, and, in a flash, the large molecule disintegrates into many tiny pieces of diatomic carbon (C2). What’s left is a mixture of gases including CO2, NO2, and N2, as well as C2.

I encourage you to read Zynga’s article in whole as she provides more scientific detail and she notes that this discovery could have applications for the military and for industry.

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

Buckybomb: Reactive Molecular Dynamics Simulation by Vitaly V. Chaban, Eudes Eterno Fileti, and Oleg V. Prezhdo. J. Phys. Chem. Lett., 2015, 6 (5), pp 913–917 DOI: 10.1021/acs.jpclett.5b00120 Publication Date (Web): February 24, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Cute, adorable roundworms help measure nanoparticle toxicity

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Caption: Low-cost experiments to test the toxicity of nanomaterials focused on populations of roundworms. Rice University scientists were able to test 20 nanomaterials in a short time, and see their method as a way to determine which nanomaterials should undergo more extensive testing. Credit: Zhong Lab/Rice University

Caption: Low-cost experiments to test the toxicity of nanomaterials focused on populations of roundworms. Rice University scientists were able to test 20 nanomaterials in a short time, and see their method as a way to determine which nanomaterials should undergo more extensive testing.
Credit: Zhong Lab/Rice University

Until now, ‘cute’ and ‘adorable’ are not words I would have associated with worms of any kind or with Rice University, for that matter. It’s amazing what a single image can do, eh?

A Feb. 3, 2015 news item on Azonano describes how roundworms have been used in research investigating the toxicity of various kinds of nanoparticles,

The lowly roundworm is the star of an ambitious Rice University project to measure the toxicity of nanoparticles.

The low-cost, high-throughput study by Rice scientists Weiwei Zhong and Qilin Li measures the effects of many types of nanoparticles not only on individual organisms but also on entire populations.

A Feb. 2, 2015 Rice University news release (also on EurekAlert), which originated the news item, provides more details about the research,

The Rice researchers tested 20 types of nanoparticles and determined that five, including the carbon-60 molecules (“buckyballs”) discovered at Rice in 1985, showed little to no toxicity.

Others were moderately or highly toxic to Caenorhabditis elegans, several generations of which the researchers observed to see the particles’ effects on their health.

The results were published by the American Chemical Society journal Environmental Sciences and Technology. They are also available on the researchers’ open-source website.

“Nanoparticles are basically new materials, and we don’t know much about what they will do to human health and the health of the ecosystem,” said Li, an associate professor of civil and environmental engineering and of materials science and nanoengineering. “There have been a lot of publications showing certain nanomaterials are more toxic than others. So before we make more products that incorporate these nanomaterials, it’s important that we understand we’re not putting anything toxic into the environment or into consumer products.

“The question is, How much cost can we bear?” she said. “It’s a long and expensive process to do a thorough toxicological study of any chemical, not just nanomaterials.” She said that due to the large variety of nanomaterials being produced at high speed and at such a large scale, there is “an urgent need for high-throughput screening techniques to prioritize which to study more extensively.”

Rice’s pilot study proves it is possible to gather a lot of toxicity data at low cost, said Zhong, an assistant professor of biosciences, who has performed extensive studies on C. elegans, particularly on their gene networks. Materials alone for each assay, including the worms and the bacteria they consumed and the culture media, cost about 50 cents, she said.

The researchers used four assays to see how worms react to nanoparticles: fitness, movement, growth and lifespan. The most sensitive assay of toxicity was fitness. In this test, the researchers mixed the nanoparticles in solutions with the bacteria that worms consume. Measuring how much bacteria they ate over time served as a measure of the worms’ “fitness.”

“If the worms’ health is affected by the nanoparticles, they reproduce less and eat less,” Zhong said. “In the fitness assay, we monitor the worms for a week. That is long enough for us to monitor toxicity effects accumulated through three generations of worms.” C. elegans has a life cycle of about three days, and since each can produce many offspring, a population that started at 50 would number more than 10,000 after a week. Such a large number of tested animals also enabled the fitness assay to be highly sensitive.

The researchers’ “QuantWorm” system allowed fast monitoring of worm fitness, movement, growth and lifespan. In fact, monitoring the worms was probably the least time-intensive part of the project. Each nanomaterial required specific preparation to make sure it was soluble and could be delivered to the worms along with the bacteria. The chemical properties of each nanomaterial also needed to be characterized in detail.

The researchers studied a representative sampling of three classes of nanoparticles: metal, metal oxides and carbon-based. “We did not do polymeric nanoparticles because the type of polymers you can possibly have is endless,” Li explained.

They examined the toxicity of each nanoparticle at four concentrations. Their results showed C-60 fullerenes, fullerol (a fullerene derivative), titanium dioxide, titanium dioxide-decorated nanotubes and cerium dioxide were the least damaging to worm populations.

Their “fitness” assay confirmed dose-dependent toxicity for carbon black, single- and multiwalled carbon nanotubes, graphene, graphene oxide, gold nanoparticles and fumed silicon dioxide.

They also determined the degree to which surface chemistry affected the toxicity of some particles. While amine-functionalized multiwalled nanotubes proved highly toxic, hydroxylated nanotubes had the least toxicity, with significant differences in fitness, body length and lifespan.

A complete and interactive toxicity chart for all of the tested materials is available online.

Zhong said the method could prove its worth as a rapid way for drug or other companies to narrow the range of nanoparticles they wish to put through more expensive, dedicated toxicology testing.

“Next, we hope to add environmental variables to the assays, for example, to mimic ultraviolet exposure or river water conditions in the solution to see how they affect toxicity,” she said. “We also want to study the biological mechanism by which some particles are toxic to worms.”

Here’s a citation for the paper and links to the paper and to the researchers’ website,

A multi-endpoint, high-throughput study of nanomaterial toxicity in Caenorhabditis elegans by Sang-Kyu Jung, Xiaolei Qu, Boanerges Aleman-Meza, Tianxiao Wang, Celeste Riepe, Zheng Liu, Qilin Li, and Weiwei Zhong. Environ. Sci. Technol., Just Accepted Manuscript DOI: 10.1021/es5056462 Publication Date (Web): January 22, 2015
Copyright © 2015 American Chemical Society

Nanomaterial effects on C. elegans

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This heat map indicates whether a measurement for the nanomaterial-exposed worms is higher (yellow), or lower (blue) than the control worms. Black indicates no effects from nanomaterial exposure.

Clicking on colored blocks to see detailed experimental data.

The published paper is open access but you need an American Chemical Society site registration to access it. The researchers’ site is open access.

A use for fullerenes—inside insulation plastic for high-voltage cables

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A Jan. 27, 2015 news item on Nanowerk, describes research which suggests that there may a new use for buckminsterfullerenes (or what they’re calling ‘carbon nanoballs’),

Researchers at Chalmers University of Technology [Sweden] have discovered that the insulation plastic used in high-voltage cables can withstand a 26 per cent higher voltage if nanometer-sized carbon balls are added. This could result in enormous efficiency gains in the power grids of the future, which are needed to achieve a sustainable energy system.

The renewable energy sources of tomorrow will often be found far away from the end user. Wind turbines, for example, are most effective when placed out at sea. Solar energy will have the greatest impact on the European energy system if focus is on transport of solar power from North Africa and Southern Europe to Northern Europe.

“Reducing energy losses during electric power transmission is one of the most important factors for the energy systems of the future,” says Chalmers researcher Christian Müller. “The other two are development of renewable energy sources and technologies for energy storage.”

The Jan. 27, 2015 Chalmers University of Technology press release (also on EurekAlert) by Johanna Wilde, which originated the news item, provides more information about the research,

Together with colleagues from Chalmers and the company Borealis in Stenungsund, he [Müller] has found a powerful method for reducing energy losses in alternating current cables.  The results were recently published in Advanced Materials, a highly ranked scientific journal.

The researchers have shown that different variants of the C60 carbon ball, a nanomaterial in the fullerene molecular group, provide strong protection against breakdown of the insulation plastic used in high-voltage cables. Today the voltage in the cables has to be limited to prevent the insulation layer from getting damaged. The higher the voltage the more electrons can leak out into the insulation material, a process which leads to breakdown.

It is sufficient to add very small amounts of fullerene to the insulation plastic for it to withstand a voltage that is 26 per cent higher, without the material breaking down, than the voltage that plastic without the additive can withstand.

“Being able to increase the voltage to this extent would result in enormous efficiency gains in power transmission all over the world,” says Christian Müller. “A major issue in the industry is how transmission efficiency can be improved without making the power cables thicker, since they are already very heavy and difficult to handle.”

Using additives to protect the insulation plastic has been a known concept since the 1970s, but until now it has been unknown exactly what and how much to add. Consequently, additives are currently not used at all for the purpose, and the insulation material is manufactured with the highest possible degree of chemical purity.

In recent years, other researchers have experimented with fullerenes in the electrically conductive parts of high-voltage cables. Until now, though, it has been unknown that the substance can be beneficial for the insulation material.

The Chalmers researchers have now demonstrated that fullerenes are the best voltage stabilizers identified for insulation plastic thus far. This means they have a hitherto unsurpassed ability to capture electrons and thus protect other molecules from being destroyed by the electrons.

To arrive at these findings, the researchers tested a number of molecules that are also used within organic solar cell research at Chalmers. The molecules were tested using several different methods, and were added to pieces of insulation plastic used for high-voltage cables. The pieces of plastic were then subjected to an increasing electric field until they crackled. Fullerenes turned out to be the type of additive that most effectively protects the insulation plastic.

The press release includes some facts about buckyballs or buckminsterfullerenes or fullerenes or C60 or carbon nanoballs, depending on what you want to call them,

 Facts: Carbon ball C60

  • The C60 carbon ball is also called buckminsterfullerene. It consists of 60 carbon atoms that are placed so that the molecule resembles a nanometer-sized football. C60 is included in the fullerene molecular class.
  • Fullerenes were discovered in 1985, which resulted in the Nobel Prize in Chemistry in 1996. They have unique electronic qualities and have been regarded as very promising material for several applications. Thus far, however, there have been few industrial usage areas.
  • Fullerenes are one of the five forms of pure carbon that exist. The other four are graphite, graphene/carbon nanotubes, diamond and amorphous carbon, for example soot.

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

A New Application Area for Fullerenes: Voltage Stabilizers for Power Cable Insulation by Markus Jarvid, Anette Johansson, Renee Kroon, Jonas M. Bjuggren, Harald Wutzel, Villgot Englund, Stanislaw Gubanski, Mats R. Andersson, and Christian Müller. Advanced Materials DOI: 10.1002/adma.201404306 Article first published online: 12 DEC 2014

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Here’s an image of wind turbines, an example of equipment which could benefit greatly from better insulation.,

Images: Lina Bertling, Jan-Olof Yxell, Carolina Eek Jaworski, Anette Johansson, Markus Jarvid, Christian Müller

Images: Lina Bertling, Jan-Olof Yxell, Carolina Eek Jaworski, Anette Johansson, Markus Jarvid, Christian Müller

You can find this image and others by clicking on the Chalmers University press release link (assuming the page hasn’t been moved). You can find more information about Borealis (the company Müller is working with) here.

Watching buckyballs (buckminsterfullerenes) self-assemble in real-time

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For the 5% or less of the world who need this explanation, the reference to a football later in this post is, in fact, a reference to a soccer ball. Moving on to a Nov. 5, 2014 news item on Nanowerk (Note: A link has been removed),

Using DESY’s ultrabright X-ray source PETRA III, researchers have observed in real-time how football-shaped carbon molecules arrange themselves into ultra-smooth layers. Together with theoretical simulations, the investigation reveals the fundamentals of this growth process for the first time in detail, as the team around Sebastian Bommel (DESY and Humboldt Universität zu Berlin) and Nicola Kleppmann (Technische Universität Berlin) reports in the scientific journal Nature Communications (“Unravelling the multilayer growth of the fullerene C60 in real-time”).

This knowledge will eventually enable scientists to tailor nanostructures from these carbon molecules for certain applications, which play an increasing role in the promising field of plastic electronics. The team consisted of scientists from Humboldt-Universität zu Berlin, Technische Universität Berlin, Universität Tübingen and DESY.

Here’s an image of the self-assembling materials,

Caption: This is an artist's impression of the multilayer growth of buckyballs. Credit: Nicola Kleppmann/TU Berlin

Caption: This is an artist’s impression of the multilayer growth of buckyballs.
Credit: Nicola Kleppmann/TU Berlin

A Nov. 5, 2014 DESY (Deutsches Elektronen-Synchrotron) press release (also on EurekAlert), describes the work further,

The scientists studied so called buckyballs. Buckyballs are spherical molecules, which consist of 60 carbon atoms (C60). Because they are reminiscent of American architect Richard Buckminster Fuller’s geodesic domes, they were christened buckminsterfullerenes or “buckyballs” for short. With their structure of alternating pentagons and hexagons, they also resemble tiny molecular footballs. [emphasis mine]

Using DESY’s X-ray source PETRA III, the researchers observed how buckyballs settle on a substrate from a molecular vapour. In fact, one layer after another, the carbon molecules grow predominantly in islands only one molecule high and barely form tower-like structures..“The first layer is 99% complete before 1% of the second layer is formed,” explains DESY researcher Bommel, who is completing his doctorate in Prof. Stefan Kowarik’s group at the Humboldt Universität zu Berlin. This is how extremely smooth layers form.

“To really observe the growth process in real-time, we needed to measure the surfaces on a molecular level faster than a single layer grows, which takes place in about a minute,” says co-author Dr. Stephan Roth, head of the P03 measuring station, where the experiments were carried out. “X-ray investigations are well suited, as they can trace the growth process in detail.”

“In order to understand the evolution of the surface morphology at the molecular level, we carried out extensive simulations in a non-equilibrium system. These describe the entire growth process of C60 molecules into a lattice structure,” explains Kleppmann, PhD student in Prof. Sabine Klapp’s group at the Institute of Theoretical Physics, Technische Universität Berlin. “Our results provide fundamental insights into the molecular growth processes of a system that forms an important link between the world of atoms and that of colloids.”

Through the combination of experimental observations and theoretical simulations, the scientists determined for the first time three major energy parameters simultaneously for such a system: the binding energy between the football molecules, the so-called “diffusion barrier,” which a molecule must overcome if it wants to move on the surface, and the Ehrlich-Schwoebel barrier, which a molecule must overcome if it lands on an island and wants to hop down from that island.

“With these values, we now really understand for the first time how such nanostructures come into existence,” stresses Bommel. “Using this knowledge, it is conceivable that these structures can selectively be grown in the future: How must I change my temperature and deposition rate parameters so that an island of a particular size will grow. This could, for example, be interesting for organic solar cells, which contain C60.” The researchers intend to explore the growth of other molecular systems in the future using the same methods.

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

Unravelling the multilayer growth of the ​fullerene C60 in real time by S. Bommel, N. Kleppmann, C. Weber, H. Spranger, P. Schäfer, J. Novak, S.V. Roth, F. Schreiber, S.H.L. Klapp, & S. Kowarik. Nature Communications 5, Article number: 5388 doi:10.1038/ncomms6388 Published 05 November 2014

This article is open access.

I was not able to find any videos of these buckyballs assembling in real-time. Presumably, there are technical issues with recording the process, financial issues, or some combination thereof. Still, I can’t help but feel teased (tongue in cheek) by these scientists who give me an artist’s concept instead. Hopefully, budgets and/or technology will allow the rest of us to view this process at some time in the future.

Buckydiamondoids steer electron flow

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One doesn’t usually think about buckyballs (Buckminsterfullerenes) and diamondoids as being together in one molecule but that has not stopped scientists from trying to join them and, in this case, successfully. From a Sept. 9, 2014 news item on ScienceDaily,

Scientists have married two unconventional forms of carbon — one shaped like a soccer ball, the other a tiny diamond — to make a molecule that conducts electricity in only one direction. This tiny electronic component, known as a rectifier, could play a key role in shrinking chip components down to the size of molecules to enable faster, more powerful devices.

Here’s an illustration the scientists have provided,

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

A Sept. 9, 2014 Stanford University news release by Glenda Chui (also on EurekAlert), which originated the news item, provides some information about this piece of international research along with background information on buckyballs and diamondoids (Note: Links have been removed),

“We wanted to see what new, emergent properties might come out when you put these two ingredients together to create a ‘buckydiamondoid,'” said Hari Manoharan of the Stanford Institute for Materials and Energy Sciences (SIMES) at the U.S. Department of Energy’s SLAC National Accelerator Laboratory. “What we got was basically a one-way valve for conducting electricity – clearly more than the sum of its parts.”

The research team, which included scientists from Stanford University, Belgium, Germany and Ukraine, reported its results Sept. 9 in Nature Communications.

Many electronic circuits have three basic components: a material that conducts electrons; rectifiers, which commonly take the form of diodes, to steer that flow in a single direction; and transistors to switch the flow on and off. Scientists combined two offbeat ingredients – buckyballs and diamondoids – to create the new diode-like component.

Buckyballs – short for buckminsterfullerenes – are hollow carbon spheres whose 1985 discovery earned three scientists a Nobel Prize in chemistry. Diamondoids are tiny linked cages of carbon joined, or bonded, as they are in diamonds, with hydrogen atoms linked to the surface, but weighing less than a billionth of a billionth of a carat. Both are subjects of a lot of research aimed at understanding their properties and finding ways to use them.

In 2007, a team led by researchers from SLAC and Stanford discovered that a single layer of diamondoids on a metal surface can emit and focus electrons into a tiny beam. Manoharan and his colleagues wondered: What would happen if they paired an electron-emitting diamondoid with another molecule that likes to grab electrons? Buckyballs are just that sort of electron-grabbing molecule.

Details are then provided about this specific piece of research (from the Stanford news release),

For this study, diamondoids were produced in the SLAC laboratory of SIMES researchers Jeremy Dahl and Robert Carlson, who are world experts in extracting the tiny diamonds from petroleum. The diamondoids were then shipped to Germany, where chemists at Justus-Liebig University figured out how to attach them to buckyballs.

The resulting buckydiamondoids, which are just a few nanometers long, were tested in SIMES laboratories at Stanford. A team led by graduate student Jason Randel and postdoctoral researcher Francis Niestemski used a scanning tunneling microscope to make images of the hybrid molecules and measure their electronic behavior. They discovered that the hybrid is an excellent rectifier: The electrical current flowing through the molecule was up to 50 times stronger in one direction, from electron-spitting diamondoid to electron-catching buckyball, than in the opposite direction. This is something neither component can do on its own.

While this is not the first molecular rectifier ever invented, it’s the first one made from just carbon and hydrogen, a simplicity researchers find appealing, said Manoharan, who is an associate professor of physics at Stanford. The next step, he said, is to see if transistors can be constructed from the same basic ingredients.

“Buckyballs are easy to make – they can be isolated from soot – and the type of diamondoid we used here, which consists of two tiny cages, can be purchased commercially,” he said. “And now that our colleagues in Germany have figured out how to bind them together, others can follow the recipe. So while our research was aimed at gaining fundamental insights about a novel hybrid molecule, it could lead to advances that help make molecular electronics a reality.”

Other research collaborators came from the Catholic University of Louvain in Belgium and Kiev Polytechnic Institute in Ukraine. The primary funding for the work came from U.S. the Department of Energy Office of Science (Basic Energy Sciences, Materials Sciences and Engineering Divisions).

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

Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids by Jason C. Randel, Francis C. Niestemski,    Andrés R. Botello-Mendez, Warren Mar, Georges Ndabashimiye, Sorin Melinte, Jeremy E. P. Dahl, Robert M. K. Carlson, Ekaterina D. Butova, Andrey A. Fokin, Peter R. Schreiner, Jean-Christophe Charlier & Hari C. Manoharan. Nature Communications 5, Article number: 4877 doi:10.1038/ncomms5877 Published 09 September 2014

This paper is open access. The scientists provided not only a standard illustration but a pretty picture of the buckydiamondoid,

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules -- diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right -- to create "buckydiamondoids," center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices. Credit: Manoharan Lab/Stanford University

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules — diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right — to create “buckydiamondoids,” center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices.
Credit: Manoharan Lab/Stanford University

Water cages made of buckyballs could affect nuclear magnetic resonance and magnetic resonance imaging (MRI)

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I wasn’t expecting to find this May 20, 2014 news item on Nanowerk to be* quite so fascinating, especially as It gets off to a slow start (a link has been removed),

In a new paper in The Journal of Chemical Physics (“Nuclear spin conversion of water inside fullerene cages detected by low-temperature nuclear magnetic resonance”), produced by AIP Publishing, a research team in the United Kingdom and the United States describes how water molecules “caged” in fullerene spheres (“buckyballs”) are providing a deeper insight into spin isomers — varieties of a molecule that differ in their nuclear spin. The results of this work may one day help enhance the analytical and diagnostic power of nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI).

A May 20, 2014 American Institute of Physics (AIP) news release on EurekAlert, which originated the news item, provides some information about water molecules prior to describing the research in more detail,

Water molecules can exist as one of two isomers depending on how the spins of their two hydrogen atoms are oriented: ortho, where the spins are parallel and have a spin number of 1, and para, where the spins are antiparallel and have a spin number of 0. Scientists believe that any given molecule can transform from ortho- into para- spin states and vice versa, a process known as nuclear spin conversion.

“Currently, mechanisms for this conversion are not completely understood, nor how long it takes the molecules to transform from one spin isomer to the other,” said Salvatore Mamone, a post-doctoral physicist at the University of Southampton and lead author on the JCP paper. “To study this, we had to figure out how to reduce the strong intermolecular interactions that are responsible for aggregation and lower the rotational mobility of the water molecules.”

Next, there’s a brief summarized version of the research (from the news release),

The answer was to use chemical reactions to open a hole in fullerene (C60, also known as a buckyball) spheres, inject water molecules and then close the “cages” to form a complex referred to as H2O@C60. “At the end of this synthetic preparation nicknamed ‘molecular surgery,’ we find that 70 to 90 percent of the cages are filled, giving us a significant quantity of water molecules to examine,” Mamone said. “Because the [water] molecules are kept separated by the cages, there is a large rotational freedom that makes observation of the ortho and para isomers possible.”

This is followed by more technical details,

In their experiment, the researchers quickly cooled the individual H2O@C60 samples from 50 Kelvin (minus 223 degrees Celsius) to 5 K (minus 268 degrees Celsius) and then monitored their NMR signal every few minutes over several days.

“As the observed NMR signal is proportional to the amount of ortho-water in the sample [para-water with its spin number of 0 is “NMR silent”], we can track the percentages of ortho and para isomers at any time and any temperature,” Mamone explained. “At 50 K, we find that 75 percent of the water molecules are ortho, while at 5 K, they become almost 100 percent para. Therefore, we know that after the quick temperature jump, equilibrium is restored by conversion from ortho to para—and we see that conversion in real time.”

A surprising outcome of the experiment was that the researchers observed a second-order rate law in the kinetics of the spin conversion which proves that pairs of molecules have to interact for conversion to occur. “Previous studies have speculated that other nuclear spins can cause conversion but we found this not to be the case for H2O@C60,” Mamone said.

Next up, the research team plans to study the roles of isomer concentrations and temperature in the conversion process, the conversion of para-water to ortho (“back conversion”), how to detect single ortho- and para-water molecules on surfaces, and spin isomers in other fullerene-caged molecules.

Bravo to the news release writer for a very nice explanation of the science!

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

Nuclear spin conversion of water inside fullerene cages detected by low-temperature nuclear magnetic resonance by Salvatore Mamone, Maria Concistré, Elisa Carignani, Benno Meier, Andrea Krachmalnicoff, Ole G. Johannessen, Xuegong Lei, Yongjun Li, Mark Denning, Marina Carravetta, Kelvin Goh, Anthony J. Horsewill, Richard J. Whitby and Malcolm H. Levitt.  J. Chem. Phys. 140, 194306 (2014) DOI: 10.1063/1.4873343

This is an open access paper.

* ‘to be’ added on July 16, 2014.

Isis Innovation (University of Oxford, UK) spins out buckyball company, Designer Carbon Materials

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Buckyballs are also known as Buckminsterfullerenes. The name is derived from Buckminster Fuller who designed something he called geodesic domes, from the Wikipedia entry (Note: Links have been removed),

Buckminsterfullerene (or bucky-ball) is a spherical fullerene molecule with the formula C60 [C = carbon; 60 is the number of carbon atoms in the molecule]. It has a cage-like fused-ring structure (truncated icosahedron) which resembles a soccer ball, made of twenty hexagons and twelve pentagons, with a carbon atom at each vertex of each polygon and a bond along each polygon edge.

It was first generated in 1985 by Harold Kroto, James R. Heath, Sean O’Brien, Robert Curl, and Richard Smalley at Rice University.[2] Kroto, Curl and Smalley were awarded the 1996 Nobel Prize in Chemistry for their roles in the discovery of buckminsterfullerene and the related class of molecules, the fullerenes. The name is a reference to Buckminster Fuller, as C60 resembles his trademark geodesic domes. Buckminsterfullerene is the most commonly naturally occurring fullerene molecule, as it can be found in small quantities in soot.[3][4] Solid and gaseous forms of the molecule have been detected in deep space.[5]

Here’s a model of a buckyball,

Courtesy: Isis Innovation (Oxford University)

Courtesy: Isis Innovation (Oxford University)

An April 15, 2014 University of Oxford (Isis Innovation) news release (h/t phys.org) describes the news research and some technical details while avoiding any mention of how they’ve tackled the production problems (a major issue, which has seriously constrained their commercial use),

The firm, Designer Carbon Materials, has been established by Isis Innovation, the University of Oxford’s technology commercialisation company, and will cost-effectively manufacture commercially useful quantities of the spherical carbon cage structures. Designer Carbon Materials is based on research from Dr Kyriakos Porfyrakis of Oxford University’s Department of Materials.

‘It is possible to insert a variety of useful atoms or atomic clusters into the hollow interior of these ball-like molecules, giving them new and intriguing abilities. Designer Carbon Materials will focus on the production of these value-added materials for a range of applications,’ said Dr Porfyrakis.

‘For instance, fullerenes are currently used as electron acceptors in polymer-based solar cells achieving some of the highest power conversion efficiencies known for these kinds of solar cells. Our endohedral fullerenes are even better electron-acceptors and therefore have the potential to lead to efficiencies exceeding 10 per cent.

‘The materials could also be developed as superior MRI contrast agents for medical imaging and as diagnostics for Alzheimer’s and Parkinson’s, as they are able to detect the presence of superoxide free radical molecules which may cause these conditions. We are receiving fantastic interest from organisations developing these applications, who until now have been unable to access useful quantities of these materials.’

The manufacturing process, patented by Isis Innovation, will continue to be developed by Designer Carbon Materials as it also makes its first sales of these extremely high-value materials.

Tom Hockaday, managing director of Isis Innovation, said: ‘This is a great example of an Isis spin-out which is both looking at exciting future applications for its technology and also answering a real market need. There is already significant demand for these nanomaterials and we expect the first customer orders will be fulfilled over the next few months.’

Investment in the company has been led by Oxford Technology Management and the Oxford Invention Fund. Lucius Carey from Oxford Technology Management said: ‘We are delighted to be investing in Designer Carbon Materials. The purposes of the investment will be to move into commercial premises and to scale up.’

Isis Innovation is a University of Oxford initiative and you can find out more about Isis Innovation here. As for the new spin-out company, Designer Carbon Materials, they have no website that I’ve been able to find but there is this webpage on the Isis Innovation website.

Université de Montréal (Canada) collaborates with University of Houston (US) for a new theory and better solar cells

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Solar cell efficiency is not good as researchers from  l’Université de Montréal (UdeM, located in Quebec, Canada) and the University of Houston (UH, located Texas, US) note in a Jan. 29, 2014 joint UH/UdeM news release written by Lisa Merkl (UH) on EurekAlert,

“Scientists don’t fully understand what is going on inside the materials that make up solar cells. We were trying to get at the fundamental photochemistry or photophysics that describes how these cells work,” Bittner said [Eric Bittner, a John and Rebecca Moores Professor of Chemistry and Physics in UH’s College of Natural Sciences and Mathematics,].

Solar cells are made out of organic semiconductors – typically blends of materials. However, solar cells made of these materials have about 3 percent efficiency. Bittner added that the newer materials, the fullerene/polymer blends, only reach about 10 percent efficiency.

“There is a theoretical limit for the efficiency of the ideal solar cell – the Shockley-Queisser limit. The theory we published describes how we might be able to get above this theoretical limit by taking advantage of quantum mechanical effects,” Bittner said. “By understanding these effects and making use of them in the design of a solar cell, we believe you can improve efficiency.”

Silva [Carlos Silva, an associate professor at the Université de Montréal and Canada Research Chair in Organic Semiconductor Materials] added, “In polymeric semiconductors, where plastics form the active layer of solar cells, the electronic structure of the material is intimately correlated with the vibrational motion within the polymer chain. Quantum-mechanical effects due to such vibrational-electron coupling give rise to a plethora of interesting physical processes that can be controlled to optimize solar cell efficiencies by designing materials that best exploit them.”

Unfortunately, there’s no more information about this model other than this (from the news release),

“Our theoretical model accomplishes things that you can’t get from a molecular model,” he [Bittner] said. “It is mostly a mathematical model that allows us to look at a much larger system with thousands of molecules. You can’t do ordinary quantum chemistry calculations on a system of that size.”

The calculations have prompted a series of new experiments by Silva’s group to probe the outcomes predicted by their model.

Bittner and Silva’s next steps involve collaborations with researchers who are experts in making the polymers and fabricating solar cells.

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

Noise-induced quantum coherence drives photo-carrier generation dynamics at polymeric semiconductor heterojunctions by Eric R. Bittner & Carlos Silva. Nature Communications 5, Article number: 3119 doi:10.1038/ncomms4119 Published 29 January 2014

This article is behind a paywall although you can get a free preview via ReadCube Access.

Rice University (Texas) researchers ‘soften’ a buckyball (buckminster fullerene)

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A Jan. 16, 2014 Rice University news release landed in my mailbox this morning and revealed that researchers have ‘detuned’ or softened the atomic bonks in a molecule known as a buckminster fullenere (aka, buckyball),

Rice University scientists have found they can control the bonds between atoms in a molecule.

The molecule in question is carbon-60, also known as the buckminsterfullerene and the buckyball, discovered at Rice in 1985. The scientists led by Rice physicists Yajing Li and Douglas Natelson found that it’s possible to soften the bonds between atoms by applying a voltage and running an electric current through a single buckyball.

…

“This doesn’t mean we’re going to be able to arbitrarily dial around the strength of materials or anything like that,” Natelson said. “This is a very specific case, and even here it was something of a surprise to see this going on.

“But in general, if we can manipulate the charge distribution on molecules, we can affect their vibrations. We can start thinking, in the future, about controlling things in a better way.”

The effect appears when a buckyball attaches to a gold surface in the optical nano antenna used to measure the effects of an electric current on intermolecular bonds through a technique called Raman spectroscopy.

Natelson’s group built the nano antenna a few years ago to trap small numbers of molecules in a nanoscale gap between gold electrodes. Once the molecules are in place, the researchers can chill them, heat them, blast them with energy from a laser or electric current and measure the effect through spectroscopy, which gathers information from the frequencies of light emitted by the object of interest.

With continuing refinement, the researchers found they could analyze molecular vibrations and the bonds between the atoms in the molecule. That ability led to this experiment, Natelson said.

Natelson compared the characteristic vibrational frequencies exhibited by the bonds to the way a guitar string vibrates at a specific frequency based on how tightly it’s wound. Loosen the string and the vibration diminishes and the tone drops.

The nano antenna is able to detect the “tone” of detuned vibrations between atoms through surface-enhanced Raman spectroscopy (SERS), a technique that improves the readings from molecules when they’re attached to a metal surface. Isolating a buckyball in the gap between the gold electrodes lets the researchers track vibrations through the optical response seen via SERS.

When a buckyball attaches to a gold surface, its internal bonds undergo a subtle shift as electrons at the junction rearrange themselves to find their lowest energetic states. The Rice experiment found the vibrations in all the bonds dropped ever so slightly in frequency to compensate.

“Think of these molecules as balls and springs,” Natelson said. “The atoms are the balls and the bonds that hold them together are the springs. If I have a collection of balls and springs and I smack it, it would show certain vibrational modes.

“When we push current through the molecule, we see these vibrations turn on and start to shake,” Natelson said. “But we found, surprisingly, that the vibrations in buckyballs get softer, and by a significant amount. It’s as if the springs get floppier at high voltages in this particular system.” The effect is reversible; turn off the juice and the buckyball goes back to normal, he said.

The researchers used a combination of experimentation and sophisticated theoretical calculations to disprove an early suspicion that the well-known vibrational Stark effect was responsible for the shift. The Stark effect is seen when molecules’ spectral responses shift under the influence of an electric field. The Molecular Foundry, a Department of Energy User Facility at Lawrence Berkeley National Laboratory, collaborated on the calculations component.

Natelson’s group had spied similar effects on oligophenylene vinylene molecules used in previous experiments, also prompting the buckyball experiments. “A few years ago we saw hints of vibrational energies moving around, but nothing this clean or this systematic. It does seem like C-60 is kind of special in terms of where it sits energetically,” he said.

The discovery of buckyballs, which earned a Nobel Prize for two Rice professors, kick-started the nanotechnology revolution. “They’ve been studied very well and they’re very chemically stable,” Natelson said of the soccer-ball-shaped molecules. “We know how to put them on surfaces, what you can do to them and have them still be intact. This is all well understood.” He noted other researchers are looking at similar effects through the molecular manipulation of graphene, the single-atomic-layer form of carbon.

“I don’t want to make some grand claim that we’ve got a general method for tuning the molecular bonding in everything,” Natelson said. “But if you want chemistry to happen in one spot, maybe you want to make that bond really weak, or at least make it weaker than it was.

“There’s a long-sought goal by some in the chemistry community to gain precise control over where and when bonds break. They would like to specifically drive certain bonds, make sure certain bonds get excited, make sure certain ones break. We’re offering ways to think about doing that.”

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

Voltage tuning of vibrational mode energies in single-molecule junctions by Yajing Li, Peter Doak, Leeor Kronik, Jeffrey B. Neatonc, and Douglas Natelsona. PNAS.  doi: 10.1073/pnas.1320210111

This paper is behind a paywall so you need either a subscription to the journal or access to a research library with a subscription or, alternatively, there are two short-term rental options (which for reasons that escape me were difficult to access) here.

As business models go, I don’t believe that aspect of the PNAS model is going to prove successful. Why not make all the options available from the page containing the abstract as do other academic publishers?

Getting back to the buckyball, the researchers have provided an image to illustrate their work,

Rice University scientists discovered the bonds in a carbon-60 molecule – a buckyball – can be "detuned" when exposed to an electric current in an optical antenna. (Credit: Natelson Group/Rice University)

Rice University scientists discovered the bonds in a carbon-60 molecule – a buckyball – can be “detuned” when exposed to an electric current in an optical antenna. (Credit: Natelson Group/Rice University)