Tag Archives: single-walled carbon nanotubes

Colo(u)ring your carbon nanotubes

Finnish research is highlighted in an August 28, 2018 news item on phys.org,

A method developed at Aalto University, Finland, can produce large quantities of pristine single-walled carbon nanotubes in select shades of the rainbow. The secret is a fine-tuned fabrication process—and a small dose of carbon dioxide. The films could find applications in touch screen technologies or as coating agents for new types of solar cells.

An August 28, 2018 Aalto University press release (also on EurekAlert), which originated the news item, provides more detail,

Samples of the colourful carbon nanotube thin films, as produced in the fabrication reactor. Image: Aalto University.

Single-walled carbon nanotubes, or sheets of one atom-thick layers of graphene rolled up into different sizes and shapes, have found many uses in electronics and new touch screen devices. By nature, carbon nanotubes are typically black or a dark grey.

In their new study published in the Journal of the American Chemical Society (JACS), Aalto University researchers present a way to control the fabrication of carbon nanotube thin films so that they display a variety of different colours—for instance, green, brown, or a silvery grey.

The researchers believe this is the first time that coloured carbon nanotubes have been produced by direct synthesis. Using their invention, the colour is induced straight away in the fabrication process, not by employing a range of purifying techniques on finished, synthesized tubes.

With direct synthesis, large quantities of clean sample materials can be produced while also avoiding damage to the product in the purifying process—which makes it the most attractive approach for applications.

‘In theory, these coloured thin films could be used to make touch screens with many different colours, or solar cells that display completely new types of optical properties,’ says Esko Kauppinen, Professor at Aalto University.

To get carbon structures to display colours is a feat in itself. The underlying techniques needed to enable the colouration also imply finely detailed control of the structure of the nanotube structures. Kauppinen and his team’s unique method, which uses aerosols of metal and carbon, allows them to carefully manipulate and control the nanotube structure directly from the fabrication process.

‘Growing carbon nanotubes is, in a way, like planting trees: we need seeds, feeds, and solar heat. For us, aerosol nanoparticles of iron work as a catalyst or seed, carbon monoxide as the source for carbon, so feed, and a reactor gives heat at a temperature more than 850 degrees Celsius,’ says Dr. Hua Jiang, Senior Scientist at Aalto University.

Professor Kauppinen’s group has a long history of using these very resources in their singular production method. To add to their repertoire, they have recently experimented with administering small doses of carbon dioxide into the fabrication process.

‘Carbon dioxide acts as a kind of graft material that we can use to tune the growth of carbon nanotubes of various colors,’ explains Jiang.

With an advanced electron diffraction technique, the researchers were able to find out the precise atomic scale structure of their thin films. They found that they have very narrow chirality distributions, meaning that the orientation of the honeycomb-lattice of the tubes’ walls is almost uniform throughout the sample. The chirality more or less dictates the electrical properties carbon nanotubes can have, as well as their colour.

The method developed at Aalto University promises a simple and highly scalable way to fabricate carbon nanotube thin films in high yields.

‘Usually you have to choose between mass production or having good control over the structure of carbon nanotubes. With our breakthrough, we can do both,’ trusts Dr. Qiang Zhang, a postdoctoral researcher in the group.

Follow-up work is already underway.

‘We want to understand the science of how the addition of carbon dioxide tunes the structure of the nanotubes and creates colours. Our aim is to achieve full control of the growing process so that single-walled carbon nanotubes could be used as building blocks for the next generation of nanoelectronics devices,’ says professor Kauppinen.

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

Direct Synthesis of Colorful Single-Walled Carbon Nanotube Thin Films by Yongping Liao, Hua Jiang, Nan Wei, Patrik Laiho, Qiang Zhang, Sabbir A. Khan, and Esko I. Kauppinen. J. Am. Chem. Soc., 2018, 140 (31), pp 9797–9800 DOI: 10.1021/jacs.8b05151 Publication Date (Web): July 26, 2018

Copyright © 2018 American Chemical Society

This paper appears to be open access.

For the curious, here’s a peek at the coloured carbon nanotube films,


Caption: Samples of the colorful carbon nanotube thin films, as produced in the fabrication reactor. Credit: Authors / Aalto University

Carbon nanotubes for enhanced wheat growth?

It’s been a long time (Oct. 22, 2009 posting; scroll down about 20% of the way) since I’ve written about carbon nanotubes and their possible use in agriculture but now a December 6, 2017 news item on ScienceDaily raises the topic again,

The introduction of purified carbon nanotubes appears to have a beneficial effect on the early growth of wheatgrass, according to Rice University scientists. But in the presence of contaminants, those same nanotubes could do great harm.

The Rice lab of chemist Andrew Barron grew wheatgrass in a hydroponic garden to test the potential toxicity of nanoparticles on the plant. To their surprise, they found one type of particle dispersed in water helped the plant grow bigger and faster.

They suspect the results spring from nanotubes’ natural hydrophobic (water-avoiding) nature that in one experiment apparently facilitated the plants’ enhanced uptake of water.

The research appears in the Royal Society of Chemistry journal Environmental Science: Nano.

A December 6, 2017 Rice University news release (also on EurekAlert), which originated the news item, expands on the theme,

The lab mounted the small-scale study with the knowledge that the industrial production of nanotubes will inevitably lead to their wider dispersal in the environment. The study cited rapid growth in the market for nanoparticles in drugs, cosmetic, fabrics, water filters and military weapons, with thousands of tons produced annually.

Despite their widespread use, Barron said few researchers have looked at the impact of environmental nanoparticles — whether natural or man-made — on plant growth.

The researchers planted wheatgrass seeds in multiple replicates in cotton wool and fed them with dispersions that contained raw single-walled or multi-walled nanotubes, purified single-walled nanotubes or iron oxide nanoparticles that mimicked leftover catalyst often attached to nanotubes. The solutions were either water or tetrahydrofuran (THF), an industrial solvent. Some of the seeds were fed pure water or THF as a control.

Rice University researchers tested the effects of carbon nanotubes on the growth of wheatgrass. While some showed no effect, purified single-walled nanotubes in water (5) enhanced the plants' growth, while the same nanotubes in a solvent (6) retarded their development. The photos at left show the plants after four days and at right after eight days, with odd-numbered plants growing in water and evens in a solvent. Numbers 1 and 2 are controls without nanotubes; 3-4 contain raw single-walled tubes; 5-6 purified single-walled tubes; 7-8 raw multi-walled tubes; 9-10 low-concentration iron-oxide nanoparticles and 11-12 high-concentration iron-oxide nanoparticles.

Rice University researchers tested the effects of carbon nanotubes on the growth of wheatgrass. While some showed no effect, purified single-walled nanotubes in water (5) enhanced the plants’ growth, while the same nanotubes in a solvent (6) retarded their development. The photos at left show the plants after four days and at right after eight days, with odd-numbered plants growing in water and evens in a solvent. Numbers 1 and 2 are controls without nanotubes; 3-4 contain raw single-walled tubes; 5-6 purified single-walled tubes; 7-8 raw multi-walled tubes; 9-10 low-concentration iron-oxide nanoparticles and 11-12 high-concentration iron-oxide nanoparticles. Click on the image for a larger version. Photos by Seung Mook Lee

After eight days, the plantings showed that purified single-walled nanotubes in water enhanced the germination rate and shoot growth of wheatgrass, which grew an average of 13 percent larger than plants in plain water. Raw single- and multi-walled nanotubes and particles in either solution had little effect on the plants’ growth, they found.

However, purified single-walled nanotubes in THF retarded plant development by 45 percent compared to single-walled nanotubes in water, suggesting the nanotubes act as a carrier for the toxic substance.

The concern, Barron said, is that if single-walled nanotubes combine with organic pollutants like pesticides, industrial chemicals or solvents in the environment, they may concentrate and immobilize the toxins and enhance their uptake by plants.

Nothing seen in the limited study indicated whether carbon nanotubes in the environment, and potentially in plants, will rise up the food chain and be harmful to humans, he said.

On the other hand, the researchers said it may be worth looking at whether hydrophobic substrates that mimic the positive effects observed in single-walled nanotubes could be used for high-efficiency channeling of water to seeds.

“Our work confirms the importance of thinking of nanomaterials as part of a system rather in isolation,” Barron said. “It is the combination with other compounds that is important to understand.”

Seung Mook Lee, a former visiting student research assistant from Memorial High School in Houston and now an undergraduate student at the University of California, Berkeley, is lead author of the paper. Co-authors are Rice research scientist Pavan Raja and graduate student Gibran Esquenazi. Barron is the Charles W. Duncan Jr.–Welch Professor of Chemistry and a professor of materials science and nanoengineering at Rice and the Sêr Cymru Chair of Low Carbon Energy and Environment at Swansea University, Wales (UK).

The Welsh Government Sêr Cymru Program and the Robert A. Welch Foundation supported the research.

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

Effect of raw and purified carbon nanotubes and iron oxide nanoparticles on the growth of wheatgrass prepared from the cotyledons of common wheat (triticum aestivum) by Seung Mook Lee, Pavan M. V. Raja, Gibran L. Esquenazi, and Andrew R. Barron. Environ. Sci.: Nano, 2018, Advance Article DOI: 10.1039/C7EN00680B First published on 09 Nov 2017

This paper appears to be behind a paywall.

OECD (Organization for Economic Cooperation and Development) Dossiers on Nanomaterials Are of “Little to No Value for assessing risk?”

The announcement that a significant portion of the OECD’s (Organization for Economic Cooperation and Development) dossiers on 11 nanomaterials have next to no value for assessing risk seems a harsh judgment from the Center for International Environmental Law (CIEL). From a March 1, 2017 posting by Lynn L. Bergeson on the Nanotechnology Now,

On February 23, 2017, the Center for International Environmental Law (CIEL) issued a press release announcing a new report, commissioned by CIEL, the European Environmental Citizens’ Organization for Standardization (ECOS), and the Oeko-Institute, that “shows that most of the information made available by the Sponsorship Testing Programme of the Organisation for Economic Co-operation and Development (OECD) is of little to no value for the regulatory risk assessment of nanomaterials.”

Here’s more from the Feb. 23, 3017 CIEL press release, which originated the posting,

The study published today [Feb. 23, 2017] was delivered by the Institute of Occupational Medicine (IOM) based in Singapore. IOM screened the 11,500 pages of raw data of the OECD dossiers on 11 nanomaterials, and analysed all characterisation and toxicity data on three specific nanomaterials – fullerenes, single-walled carbon nanotubes, and zinc oxide.

“EU policy makers and industry are using the existence of the data to dispel concerns about the potential health and environmental risks of manufactured nanomaterials,” said David Azoulay, Senior Attorney for CIEL. “When you analyse the data, in most cases, it is impossible to assess what material was actually tested. The fact that data exists about a nanomaterial does not mean that the information is reliable to assess the hazards or risks of the material.”

The dossiers were published in 2015 by the OECD’s Working Party on Manufactured Nanomaterials (WPMN), which has yet to draw conclusions on the data quality. Despite this missing analysis, some stakeholders participating in EU policy-making – notably the European Chemicals Agency (ECHA) and the European Commission’s Joint Research Centre – have presented the dossiers as containing information on nano-specific human health and environmental impacts. Industry federations and individual companies have taken this a step further emphasizing that there is enough information available to discard most concerns about potential health or environmental risks of manufactured nanomaterials.

“Our study shows these claims that there is sufficient data available on nanomaterials are not only false, but dangerously so,” said Doreen Fedrigo, Senior Policy Officer of ECOS. ”The lack of nano-specific information in the dossiers means that the results of the tests cannot be used as evidence of no ‘nano-effect’ of the tested material. This information is crucial for regulators and producers who need to know the hazard profile of these materials. Analysing the dossiers has shown that legislation detailing nano-specific information requirements is crucial for the regulatory risk assessment of nanomaterials.”

The report provides important recommendations on future steps in the governance of nanomaterials. “Based on our analysis, serious gaps in current dossiers must be filled in with characterisation information, preparation protocols, and exposure data,” said Andreas Hermann of the Oeko-Institute. “Using these dossiers as they are and ignoring these recommendations would mean making decisions on the safety of nanomaterials based on faulty and incomplete data. Our health and environment requires more from producers and regulators.”

CIEL has an Analysis of OECD WPMN Dossiers Regarding the Availability of Data to Evaluate and Regulate Risk (Dec 2016) webpage which provides more information about the dossiers and about the research into the dossiers and includes links to the report, the executive summer, and the dataset,

The Sponsorship Testing Programme of the Working Party on Manufactured Nanomaterials (WPMN) of the Organisation for Economic Co-operation and Development (OECD) started in 2007 with the aim to test a selection of 13 representative nanomaterials for many endpoints. The main objectives of the programme were to better understand what information on intrinsic properties of the nanomaterials might be relevant for exposure and hazards assessment and assess the validity of OECD chemicals Test Guidelines for nanomaterials. The testing programme concluded in 2015 with the publication of dossiers on 11 nanomaterials: 11,500 pages of raw data to be analysed and interpreted.

The WPMN has not drawn conclusions on the data quality, but some stakeholders participating in EU policy-making – notably the European Chemicals Agency and the European Commission’s Joint Research Centre – presented the dossiers as containing much scientific information that provided a better understanding of their nano-specific human health and environmental impacts. Industry federations and individual companies echoed the views, highlighting that there was enough information available to discard most concerns about potential health or environmental risks of manufactured nanomaterials.

As for the OECD, it concluded, even before the publication of the dossiers, that “many of the existing guidelines are also suitable for the safety assessment of nanomaterials” and “the outcomes (of the sponsorship programme) will provide useful information on the ‘intrinsic properties’ of nanomaterials.”

The Center for International Environmental Law (CIEL), the European Citizens’ Organisation for Standardisation (ECOS) and the Öko-Institut commissioned scientific analysis of these dossiers to assess the relevance of the data for regulatory risk assessment.

The resulting report: Analysis of OECD WPMN dossiers regarding the availability of data to evaluate and regulate risk, provides insights illustratating how most of the information made available by the sponsorship programme is of little to no value in identifying hazards or in assessing risks due to nanomaterials.

The analysis shows that:

  • Most studies and documents in the dossiers contain insufficient characterisation data about the specific nanomaterial addressed (size, particle distribution, surface shape, etc.), making it impossible to assess what material was actually tested.
  • This makes it impossible to make any firm statements regarding the nano-specificity of the hazard data published, or the relationship between observed effects and specific nano-scale properties.
  • Less than 2% of the study records provide detail on the size of the nanomaterial tested. Most studies use mass rather than number or size distribution (so not following scientifically recommended reporting practice).
  • The absence of details on the method used to prepare the nanomaterial makes it virtually impossible to correlate an identified hazard with specific nanomaterial characteristic. Since the studies do not indicate dispersion protocols used, it is impossible to assess whether the final dispersion contained the intended mass concentration (or even the actual presence of nanomaterials in the test system), how much agglomeration may have occurred, and how the preparation protocols may have influenced the size distribution.
  • There is not enough nano-specific information in the dossiers to inform about nano-characteristics of the raw material that influence their toxicology. This information is important for regulators and its absence makes information in the dossier irrelevant to develop read-across guidelines.
  • Only about half of the endpoint study records using OECD Test Guideliness (TGs) were delivered using unaltered OECD TGs, thereby respecting the Guidelines’ requirements. The reasons for modifications of the TGs used in the tests are not clear from the documentation. This includes whether the study record was modified to account for challenges related to specific nanomaterial properties or for other, non-nano-specific reasons.
  • The studies do not contain systematic testing of the influence of nano-specific characteristics on the study outcome, and they do not provide the data needed to assess the effect of nano-scale features on the Test Guidelines. Given the absence of fundamental information on nanomaterial characteristics, the dossiers do not provide evidence of the applicability of existing OECD Test Guidelines to nanomaterials.

The analysis therefore dispels several myths created by some stakeholders following publication of the dossiers and provides important perspective for the governance of nanomaterials. In particular, the analysis makes recommendations to:

  • Systematically assess the validity of existing Test Guidelines for relevance to nanomaterials
  • Develop Test Guidelines for dispersion and other test preparations
  • Define the minimum characteristics of nanomaterials that need to be reported
  • Support the build-up of exposure database
  • Fill the gaps in current dossiers with characterisation information, preparation protocols and exposure data

Read full report.
Read executive summary.
Download full dataset.

This is not my area of expertise and while I find the language a bit inflammatory, it’s my understanding that there are great gaps in our understanding of nanomaterials and testing for risk assessment has been criticized for many of the reasons pointed out by CIEL, ECOS, and the Oeko-Institute.

You can find out more about CIEL here; ECOS here; and the Oeko-Institute (also known as Öko-Institute) here.

Carbon nanotubes: faster, cheaper, easier, and more consistent

One of the big problems with nanomaterials has to do with production issues such as: consistent size and shape. It seems that scientists at the US National Institute of Standards and Technology (NIST) have developed a technique for producing carbon nanotubes (CNTs) which addresses these issues. From a July 19, 2016 news item on Nanotechnology Now,

Just as many of us might be resigned to clogged salt shakers or rush-hour traffic, those working to exploit the special properties of carbon nanotubes have typically shrugged their shoulders when these tiniest of cylinders fill with water during processing. But for nanotube practitioners who have reached their Popeye threshold and “can’t stands no more,” the National Institute of Standards and Technology (NIST) has devised a cheap, quick and effective strategy that reliably enhances the quality and consistency of the materials–important for using them effectively in applications such as new computing technologies.

To prevent filling of the cores of single-wall carbon nanotubes with water or other detrimental substances, the NIST researchers advise intentionally prefilling them with a desired chemical of known properties. Taking this step before separating and dispersing the materials, usually done in water, yields a consistently uniform collection of nanotubes. In quantity and quality, the results are superior to water-filled nanotubes, especially for optical applications such as sensors and photodetectors.

A July 15, 2016 NIST news release, which originated the news item, expands on the theme,

The approach opens a straightforward route for engineering the properties of single-wall carbon nanotubes—rolled up sheets of carbon atoms arranged like chicken wire or honey combs—with improved or new properties.

“This approach is so easy, inexpensive and broadly useful that I can’t think of a reason not to use it,” said NIST chemical engineer Jeffrey Fagan.

In their proof-of-concept experiments, the NIST team inserted more than 20 different compounds into an assortment of single-wall carbon nanotubes with an interior diameter that ranged from more than 2 down to about 0.5 nanometers. Led by visiting researcher Jochen Campo, the scientists tested their strategy by using hydrocarbons called alkanes as fillers.

The alkanes, which include such familiar compounds as propane and butane, served to render the nanotube interiors unreactive. In other words, the alkane-filled nanotubes behaved almost as if they were empty—precisely the goal of Campo, Fagan and colleagues.

Compared with nanotubes filled with water and possibly ions, acids and other unwanted chemicals encountered during processing, empty nanotubes possess far superior properties. For example, when stimulated by light, empty carbon nanotubes fluoresce far brighter and with sharper signals.

Yet, “spontaneous ingestion” of water or other solvents by the nanotubes during processing is an “endemic but often neglected phenomenon with strong implications for the development of nanotube applications,” the NIST team wrote in a recent article in Nanoscale Horizons.

Perhaps because of the additional cost and effort required to filter out and gather nanotubes, researchers tend to tolerate mixed batches of unfilled (empty) and mostly filled single-wall carbon nanotubes. Separating unfilled nanotubes from these mixtures requires expensive ultracentrifuge equipment and, even then, the yield is only about 10 percent, Campo estimates.

“If your goal is to use nanotubes for electronic circuits, for example, or for fluorescent anti-cancer image contrast agents, then you require much greater quantities of materials of consistent composition and quality,” Campo explained, who was exploring these applications while doing postdoctoral research at the University of Antwerp. “This particular need inspired development of the new prefilling method by asking the question, can we put some passive chemical into the nanotube instead to keep the water out.”

From the very first simple experiments, the answer was yes. And the benefits can be significant. In fluorescence experiments, alkane-filled nanotubes emitted signals two to three times stronger than those emitted by water-filled nanotubes. Performance approached that of empty nanotubes—the gold standard for these comparisons.

As important, the NIST-developed prefilling strategy is controllable, versatile and easily incorporated into existing methods for processing single-wall carbon nanotubes, according to the researchers.

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

Enhancing single-wall carbon nanotube properties through controlled endohedral filling by J. Campo, Y. Piao, S. Lam, C. M. Stafford, J. K. Streit, J. R. Simpson, A. R. Hight Walker, and J. A. Fagan. Nanoscale Horiz., 2016,1, 317-324 DOI: 10.1039/C6NH00062B First published online 10 May 2016

This paper is open access but you do need to register on the site (it is a free registration).

Wireless, wearable carbon nanotube-based gas sensors for soldiers

Researchers at MIT (Massachusetts Institute of Technology) are hoping to make wireless, toxic gas detectors the size of badges. From a June 30, 2016 news item on Nanowerk,

MIT researchers have developed low-cost chemical sensors, made from chemically altered carbon nanotubes, that enable smartphones or other wireless devices to detect trace amounts of toxic gases.

Using the sensors, the researchers hope to design lightweight, inexpensive radio-frequency identification (RFID) badges to be used for personal safety and security. Such badges could be worn by soldiers on the battlefield to rapidly detect the presence of chemical weapons — such as nerve gas or choking agents — and by people who work around hazardous chemicals prone to leakage.

A June 30, 2016 MIT news release (also on EurekAlert), which originated the news item, describes the technology further,

“Soldiers have all this extra equipment that ends up weighing way too much and they can’t sustain it,” says Timothy Swager, the John D. MacArthur Professor of Chemistry and lead author on a paper describing the sensors that was published in the Journal of the American Chemical Society. “We have something that would weigh less than a credit card. And [soldiers] already have wireless technologies with them, so it’s something that can be readily integrated into a soldier’s uniform that can give them a protective capacity.”

The sensor is a circuit loaded with carbon nanotubes, which are normally highly conductive but have been wrapped in an insulating material that keeps them in a highly resistive state. When exposed to certain toxic gases, the insulating material breaks apart, and the nanotubes become significantly more conductive. This sends a signal that’s readable by a smartphone with near-field communication (NFC) technology, which allows devices to transmit data over short distances.

The sensors are sensitive enough to detect less than 10 parts per million of target toxic gases in about five seconds. “We are matching what you could do with benchtop laboratory equipment, such as gas chromatographs and spectrometers, that is far more expensive and requires skilled operators to use,” Swager says.

Moreover, the sensors each cost about a nickel to make; roughly 4 million can be made from about 1 gram of the carbon nanotube materials. “You really can’t make anything cheaper,” Swager says. “That’s a way of getting distributed sensing into many people’s hands.”

The paper’s other co-authors are from Swager’s lab: Shinsuke Ishihara, a postdoc who is also a member of the International Center for Materials Nanoarchitectonics at the National Institute for Materials Science, in Japan; and PhD students Joseph Azzarelli and Markrete Krikorian.

Wrapping nanotubes

In recent years, Swager’s lab has developed other inexpensive, wireless sensors, called chemiresistors, that have detected spoiled meat and the ripeness of fruit, among other things [go to the end of this post for links to previous posts about Swager’s work]. All are designed similarly, with carbon nanotubes that are chemically modified, so their ability to carry an electric current changes when exposed to a target chemical.

This time, the researchers designed sensors highly sensitive to “electrophilic,” or electron-loving, chemical substances, which are often toxic and used for chemical weapons.

To do so, they created a new type of metallo-supramolecular polymer, a material made of metals binding to polymer chains. The polymer acts as an insulation, wrapping around each of the sensor’s tens of thousands of single-walled carbon nanotubes, separating them and keeping them highly resistant to electricity. But electrophilic substances trigger the polymer to disassemble, allowing the carbon nanotubes to once again come together, which leads to an increase in conductivity.

In their study, the researchers drop-cast the nanotube/polymer material onto gold electrodes, and exposed the electrodes to diethyl chlorophosphate, a skin irritant and reactive simulant of nerve gas. Using a device that measures electric current, they observed a 2,000 percent increase in electrical conductivity after five seconds of exposure. Similar conductivity increases were observed for trace amounts of numerous other electrophilic substances, such as thionyl chloride (SOCl2), a reactive simulant in choking agents. Conductivity was significantly lower in response to common volatile organic compounds, and exposure to most nontarget chemicals actually increased resistivity.

Creating the polymer was a delicate balancing act but critical to the design, Swager says. As a polymer, the material needs to hold the carbon nanotubes apart. But as it disassembles, its individual monomers need to interact more weakly, letting the nanotubes regroup. “We hit this sweet spot where it only works when it’s all hooked together,” Swager says.

Resistance is readable

To build their wireless system, the researchers created an NFC tag that turns on when its electrical resistance dips below a certain threshold.

Smartphones send out short pulses of electromagnetic fields that resonate with an NFC tag at radio frequency, inducing an electric current, which relays information to the phone. But smartphones can’t resonate with tags that have a resistance higher than 1 ohm.

The researchers applied their nanotube/polymer material to the NFC tag’s antenna. When exposed to 10 parts per million of SOCl2 for five seconds, the material’s resistance dropped to the point that the smartphone could ping the tag. Basically, it’s an “on/off indicator” to determine if toxic gas is present, Swager says.

According to the researchers, such a wireless system could be used to detect leaks in Li-SOCl2 (lithium thionyl chloride) batteries, which are used in medical instruments, fire alarms, and military systems.

The next step, Swager says, is to test the sensors on live chemical agents, outside of the lab, which are more dispersed and harder to detect, especially at trace levels. In the future, there’s also hope for developing a mobile app that could make more sophisticated measurements of the signal strength of an NFC tag: Differences in the signal will mean higher or lower concentrations of a toxic gas. “But creating new cell phone apps is a little beyond us right now,” Swager says. “We’re chemists.”

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

Ultratrace Detection of Toxic Chemicals: Triggered Disassembly of Supramolecular Nanotube Wrappers by Shinsuke Ishihara, Joseph M. Azzarelli, Markrete Krikorian, and Timothy M. Swager. J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.6b03869 Publication Date (Web): June 23, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Here are links to other posts about Swager’s work featured here previously:

Carbon nanotubes sense spoiled food (April 23, 2015 post)

Smart suits for US soldiers—an update of sorts from the Lawrence Livermore National Laboratory (Feb. 25, 2014 post)

Come, see my etchings … they detect poison gases (Oct. 9, 2012 post)

Soldiers sniff overripe fruit (May 1, 2012 post)

Siberian carbon nanotube industry

I like to focus on the Russians from time to time as I find their nanotechnology strategy quite interesting. The government created an agency, RUSNANO Corporation whose mandate has changed at least once since its beginning. Two things that have remained consistent is Anatoly Chubais who leads the organization and the nanotechnology focus. Here’s the latest news in an Oct. 16, 2015 news item in the Siberian Times,

Some 28% of total greenhouse gas emissions ste the result of  production of traditional materials, such as steel, cement, paper, aluminium and plastics, said Anatoly Chubais.

Yet the use of single-walled carbon nanotubes lower the consumption of materials in production and thus reduces emissions. Now OCSiAl, a portfolio company of Rosnano, has created the world’s first industrial production technology of single-walled carbon nanotubes, he said.

The unique technology of synthesis of single-walled carbon nanotubes, which can be used as an additive for most materials, was developed in Russia at production plant Graphetron 1.0, created and launched in Novosibirsk’s university and research satellite Akademgorodok.

… In the past year were made 200 kg of nanotubes.  This year will be about one ton, and in the next two – three years it is planned to reach an annual level of 30 – 40 tons. For reference – the global market last year, offered only two tons.’

Chubais said that ‘our calculations show that if the rate of use of materials with nano-additive grows as we expect – and we have a fairly conservative assumptions – by 2030, the volume of emission reductions from this factor will be equal to, or greater than, reducing the volume of emissions from the use of all renewable energy in the world.’

OCSiAl have published a ‘Manifesto of the Carbon Century’ where they argue  for the production of more effective materials. …

Given the scantiness of the information I get about RUSNANO and Russian nanotechnology efforts it’s difficult to infer much from this or my Sept. 12, 2014 posting (the most recent posting till now) where Chubais proposed creating a joint China-Russian nanotechnology investment fund. As for OCSiAL (I was unaware of just how close the Russian connection is), a Nov. 18, 2014 posting was the most recent one to feature the company, which proposed opening a production plant in Israel.

US White House establishes new initiatives to commercialize nanotechnology

As I’ve noted several times, there’s a strong push in the US to commercialize nanotechnology and May 20, 2015 was a banner day for the efforts. The US White House announced a series of new initiatives to speed commercialization efforts in a May 20, 2015 posting by Lloyd Whitman, Tom Kalil, and JJ Raynor,

Today, May 20 [2015], the National Economic Council and the Office of Science and Technology Policy held a forum at the White House to discuss opportunities to accelerate the commercialization of nanotechnology.

In recognition of the importance of nanotechnology R&D, representatives from companies, government agencies, colleges and universities, and non-profits are announcing a series of new and expanded public and private initiatives that complement the Administration’s efforts to accelerate the commercialization of nanotechnology and expand the nanotechnology workforce:

  • The Colleges of Nanoscale Science and Engineering at SUNY Polytechnic Institute in Albany, NY and the National Institute for Occupational Safety and Health are launching the Nano Health & Safety Consortium to advance research and guidance for occupational safety and health in the nanoelectronics and other nanomanufacturing industry settings.
  • Raytheon has brought together a group of representatives from the defense industry and the Department of Defense to identify collaborative opportunities to advance nanotechnology product development, manufacturing, and supply-chain support with a goal of helping the U.S. optimize development, foster innovation, and take more rapid advantage of new commercial nanotechnologies.
  • BASF Corporation is taking a new approach to finding solutions to nanomanufacturing challenges. In March, BASF launched a prize-based “NanoChallenge” designed to drive new levels of collaborative innovation in nanotechnology while connecting with potential partners to co-create solutions that address industry challenges.
  • OCSiAl is expanding the eligibility of its “iNanoComm” matching grant program that provides low-cost, single-walled carbon nanotubes to include more exploratory research proposals, especially proposals for projects that could result in the creation of startups and technology transfers.
  • The NanoBusiness Commercialization Association (NanoBCA) is partnering with Venture for America and working with the National Science Foundation (NSF) to promote entrepreneurship in nanotechnology.  Three companies (PEN, NanoMech, and SouthWest NanoTechnologies), are offering to support NSF’s Innovation Corps (I-Corps) program with mentorship for entrepreneurs-in-training and, along with three other companies (NanoViricides, mPhase Technologies, and Eikos), will partner with Venture for America to hire recent graduates into nanotechnology jobs, thereby strengthening new nanotech businesses while providing needed experience for future entrepreneurs.
  • TechConnect is establishing a Nano and Emerging Technologies Student Leaders Conference to bring together the leaders of nanotechnology student groups from across the country. The conference will highlight undergraduate research and connect students with venture capitalists, entrepreneurs, and industry leaders.  Five universities have already committed to participating, led by the University of Virginia Nano and Emerging Technologies Club.
  • Brewer Science, through its Global Intern Program, is providing more than 30 students from high schools, colleges, and graduate schools across the country with hands-on experience in a wide range of functions within the company.  Brewer Science plans to increase the number of its science and engineering interns by 50% next year and has committed to sharing best practices with other nanotechnology businesses interested in how internship programs can contribute to a small company’s success.
  • The National Institute of Standards and Technology’s Center for Nanoscale Science and Technology is expanding its partnership with the National Science Foundation to provide hands-on experience for students in NSF’s Advanced Technology Education program. The partnership will now run year-round and will include opportunities for students at Hudson Valley Community College and the University of the District of Columbia Community College.
  • Federal agencies participating in the NNI [US National Nanotechnology Initiative], supported by the National Nanotechnology Coordination Office [NNCO], are launching multiple new activities aimed at educating students and the public about nanotechnology, including image and video contests highlighting student research, a new webinar series focused on providing nanotechnology information for K-12 teachers, and a searchable web portal on nano.gov of nanoscale science and engineering resources for teachers and professors.

Interestingly, May 20, 2015 is also the day the NNCO held its second webinar for small- and medium-size businesses in the nanotechnology community. You can find out more about that webinar and future ones by following the links in my May 13, 2015 posting.

Since the US White House announcement, OCSiAl has issued a May 26, 2015 news release which provides a brief history and more details about its newly expanded NanoComm program,

OCSiAl launched the iNanoComm, which stands for the Integrated Nanotube Commercialization Award, program in February 2015 to help researchers lower the cost of their most promising R&D projects dedicated to SWCNT [single-walled carbon nanotube] applications. The first round received 33 applications from 28 university groups, including The Smalley-Curl Center for Nanoscale Science and Technology at Rice University and the Concordia Center for Composites at Concordia University [Canada] among others. [emphasis mine] The aim of iNanoComm is to stimulate universities and research organizations to develop innovative market products based on nano-augmented materials, also known as clean materials.

Now the program’s criteria are being broadened to enable greater private sector engagement in potential projects and the creation of partnerships in commercializing nanotechnology. The program will now support early stage commercialization efforts connected to university research in the form of start-ups, technology transfers, new businesses and university spinoffs to support the mass commercialization of SWCNT products and technologies.

The announcement of the program’s expansion took place at the 2015 Roundtable of the US NanoBusiness Commercialization Association (NanoBCA), the world’s first non-profit association focused on the commercialization of nanotechnologies. NanoBCA is dedicated to creating an environment that nurtures research and innovation in nanotechnology, promotes tech-transfer of nanotechnology from academia to industry, encourages private capital investments in nanotechnology companies, and helps its corporate members bring innovative nanotechnology products to market.

“Enhancing iNanoComm as a ‘start-up incubator’ is a concrete step in promoting single-wall carbon nanotube applications in the commercial world,” said Max Atanassov, CEO of OCSiAl USA. “It was the logical thing for us to do, now that high quality carbon nanotubes have become broadly available and are affordably priced to be used on a mass industrial scale.”

Vince Caprio, Executive Director of NanoBCA, added that “iNanoComm will make an important contribution to translating fundamental nanotechnology research into commercial products. By facilitating the formation of more start-ups, it will encourage more scientists to pursue their dreams and develop their ideas into commercially successful businesses.”

For more information on the program expansion and how it can reduce the cost of early stage research connected to university projects, visit the iNanoComm website at www.inanocomm.org or contact info@inanocomm.org.

h/t Azonano May 27, 2015 news item

Carbon nanotubes sense spoiled food


Courtesy: MIT (Massachusetts Institute of Technology)

I love this .gif; it says a lot without a word. However for details, you need words and here’s what an April 15, 2015 news item on Nanowerk has to say about the research illustrated by the .gif,

MIT [Massachusetts Institute of Technology] chemists have devised an inexpensive, portable sensor that can detect gases emitted by rotting meat, allowing consumers to determine whether the meat in their grocery store or refrigerator is safe to eat.

The sensor, which consists of chemically modified carbon nanotubes, could be deployed in “smart packaging” that would offer much more accurate safety information than the expiration date on the package, says Timothy Swager, the John D. MacArthur Professor of Chemistry at MIT.

An April 14, 2015 MIT news release (also on EurekAlert), which originated the news item, offers more from Dr. Swager,

It could also cut down on food waste, he adds. “People are constantly throwing things out that probably aren’t bad,” says Swager, who is the senior author of a paper describing the new sensor this week in the journal Angewandte Chemie.

This latest study is builds on previous work at Swager’s lab (Note: Links have been removed),

The sensor is similar to other carbon nanotube devices that Swager’s lab has developed in recent years, including one that detects the ripeness of fruit. All of these devices work on the same principle: Carbon nanotubes can be chemically modified so that their ability to carry an electric current changes in the presence of a particular gas.

In this case, the researchers modified the carbon nanotubes with metal-containing compounds called metalloporphyrins, which contain a central metal atom bound to several nitrogen-containing rings. Hemoglobin, which carries oxygen in the blood, is a metalloporphyrin with iron as the central atom.

For this sensor, the researchers used a metalloporphyrin with cobalt at its center. Metalloporphyrins are very good at binding to nitrogen-containing compounds called amines. Of particular interest to the researchers were the so-called biogenic amines, such as putrescine and cadaverine, which are produced by decaying meat.

When the cobalt-containing porphyrin binds to any of these amines, it increases the electrical resistance of the carbon nanotube, which can be easily measured.

“We use these porphyrins to fabricate a very simple device where we apply a potential across the device and then monitor the current. When the device encounters amines, which are markers of decaying meat, the current of the device will become lower,” Liu says.

In this study, the researchers tested the sensor on four types of meat: pork, chicken, cod, and salmon. They found that when refrigerated, all four types stayed fresh over four days. Left unrefrigerated, the samples all decayed, but at varying rates.

There are other sensors that can detect the signs of decaying meat, but they are usually large and expensive instruments that require expertise to operate. “The advantage we have is these are the cheapest, smallest, easiest-to-manufacture sensors,” Swager says.

“There are several potential advantages in having an inexpensive sensor for measuring, in real time, the freshness of meat and fish products, including preventing foodborne illness, increasing overall customer satisfaction, and reducing food waste at grocery stores and in consumers’ homes,” says Roberto Forloni, a senior science fellow at Sealed Air, a major supplier of food packaging, who was not part of the research team.

The new device also requires very little power and could be incorporated into a wireless platform Swager’s lab recently developed that allows a regular smartphone to read output from carbon nanotube sensors such as this one.

The funding sources are interesting, as I am appreciating with increasing frequency these days (from the news release),

The researchers have filed for a patent on the technology and hope to license it for commercial development. The research was funded by the National Science Foundation and the Army Research Office through MIT’s Institute for Soldier Nanotechnologies.

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

Single-Walled Carbon Nanotube/Metalloporphyrin Composites for the Chemiresistive Detection of Amines and Meat Spoilage by Sophie F. Liu, Alexander R. Petty, Dr. Graham T. Sazama, and Timothy M. Swager. Angewandte Chemie International Edition DOI: 10.1002/anie.201501434 Article first published online: 13 APR 2015

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

There are other posts here about the quest to create food sensors including this Sept. 26, 2013 piece which features a critique (by another blogger) about trying to create food sensors that may be more expensive than the item they are protecting, a problem Swager claims to have overcome in an April 17, 2015 article by Ben Schiller for Fast Company (Note: Links have been removed),

Swager has set up a company to commercialize the technology and he expects to do the first demonstrations to interested clients this summer. The first applications are likely to be for food workers working with meat and fish, but there’s no reason why consumers shouldn’t get their own devices in due time.

There are efforts to create visual clues for food status. But Swager says his method is better because it doesn’t rely on perception: it produces hard data that can be logged and tracked. And it also has potential to be very cheap.

“The resistance method is a game-changer because it’s two to three orders of magnitude cheaper than other technology. It’s hard to imagine doing this cheaper,” he says.

Cute, adorable roundworms help measure nanoparticle toxicity

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.

Oh so cute! Baby nanotubes!

Scientists from the US National Institute of Standards and Technology and from two US universities have successfully filmed the formation of single-walled carbon nanotubes (SWCNTs) according to a Dec. 2, 2014 news item on Nanowerk,

Single-walled carbon nanotubes are loaded with desirable properties. In particular, the ability to conduct electricity at high rates of speed makes them attractive for use as nanoscale transistors. But this and other properties are largely dependent on their structure, and their structure is determined when the nanotube is just beginning to form.

In a step toward understanding the factors that influence how nanotubes form, researchers at the National Institute of Standards and Technology (NIST), the University of Maryland, and Texas A&M have succeeded in filming them when they are only a few atoms old. These nanotube “baby pictures” give crucial insight into how they germinate and grow, potentially opening the way for scientists to create them en masse with just the properties that they want.

A Dec. 1, 2014 NIST news release, which originated the news item, explains how scientists managed to make movies of SWCNTs as they formed,

To better understand how carbon nanotubes grow and how to grow the ones you want, you need to understand the very beginning of the growth process, called nucleation. To do that, you need to be able to image the nucleation process as it happens. However, this is not easy because it involves a small number of fast-moving atoms, meaning you have to take very high resolution pictures very quickly.

Because fast, high-resolution cameras are expensive, NIST scientists instead slowed the growth rate by lowering the pressure inside their instrument, an environmental scanning transmission electron microscope. Inside the microscope’s chamber, under high heat and low pressure, the team watched as carbon atoms generated from acetylene rained down onto 1.2-nanometer bits of cobalt carbide, where they attached, formed into graphene, encircled the nanoparticle, and began to grow into nanotubes.

“Our observations showed that the carbon atoms attached only to the pure metal facets of the cobalt carbide nanoparticle, and not those facets interlaced with carbon atoms,” says NIST chemist Renu Sharma, who led the research effort. “The burgeoning tube then grew above the cobalt-carbon facets until it found another pure metal surface to attach to, forming a closed cap. Carbon atoms continued to attach at the cobalt facets, pushing the previously formed graphene along toward the cap in a kind of carbon assembly line and lengthening the tube. This whole process took only a few seconds.”

According to Sharma, the carbon atoms seek out the most energetically favorable configurations as they form graphene on the cobalt carbide nanoparticle’s surface. While graphene has a mostly hexagonal, honeycomb-type structure, the geometry of the nanoparticle forces the carbon atoms to arrange themselves into pentagonal shapes within the otherwise honeycomb lattice. Crucially, these pentagonal irregularities in the graphene’s structure are what allows the graphene to curve and become a nanotube.

Because the nanoparticles’ facets also appear to play a deciding role in the nanotube’s diameter and chirality, or direction of twist, the group’s next step will be to measure the chirality of the nanotubes as they grow. The group also plans to use metal nanoparticles with different facets to study their adhesive properties to see how they affect the tubes’ chirality and diameter.

The researchers have made one of their movies available for viewing, but, despite my efforts, I cannot find a way to embed the silent movie. Happily, you can find the ‘baby carbon nanotube’ movie alongside NIST’s Dec. 1, 2014 NIST news release,

As for the research paper, here’s a link and a citation for it,

Nucleation of Graphene and Its Conversion to Single-Walled Carbon Nanotubes by Matthieu Picher, Pin Ann Lin, Jose L. Gomez-Ballesteros, Perla B. Balbuena, and Renu Sharma. Nano Lett., 2014, 14 (11), pp 6104–6108 DOI: 10.1021/nl501977b Publication Date (Web): October 20, 2014

Copyright © 2014 American Chemical Society

This paper is behind a paywall.