Tag Archives: Japan

Mechanically strong organic nanotubes made with light

This research comes from Nagoya University in Japan according to an Aug. 30, 2016 news item on Nanowerk,

Organic nanotubes (ONTs) are tubular nanostructures composed of organic molecules that have unique properties and have found various applications, such as electro-conductive materials and organic photovoltaics. A group of scientists at Nagoya University have developed a simple and effective method for the formation of robust covalent ONTs from simple molecules. This method is expected to be useful in generating a range of nanotube-based materials with desirable properties.

An Aug. 30, 2016 Nagoya University press release (also on EurekAlert), which originated the news item, provides more information,

Kaho Maeda, Dr. Hideto Ito, Professor Kenichiro Itami of the JST-ERATO Itami Molecular Nanocarbon Project and the Institute of Transformative Bio-Molecules (ITbM) of Nagoya University, and their colleagues have reported in the Journal of the American Chemical Society, on the development of a new and simple strategy, “helix-to-tube” to synthesize covalent organic nanotubes.

Organic nanotubes (ONTs) are organic molecules with tubular nanostructures. Nanostructures are structures that range between 1 nm and 100 nm, and ONTs have a nanometer-sized cavity. Various 
applications of ONTs have been reported, including molecular recognition materials, transmembrane ion channel/sensors, electro-conductive materials, and organic photovoltaics. Most ONTs are constructed by a self-assembly process based on weak non-covalent interactions such as hydrogen bonding, hydrophobic interactions and π-π interactions between aromatic rings. Due to these relatively weak interactions, most non-covalent ONTs possess a relatively fragile structure (Figure 1).

Figure 1. Conventional synthetic method for non-covalent ONTs, their applications and disadvantages.

Covalent ONTs, whose tubular skeletons are cross-linked by covalent bonding (a bond made by sharing of electrons between atoms) could be synthesized from non-covalent ONTs. While covalent ONTs show higher stability and mechanical strength than non-covalent ONTs, the general synthetic strategy for covalent ONTs was yet to be established (Figure 2).

Figure 2. Covalent ONTs derived from non-covalent ONTs by cross-linking, their properties and disadvantages.

A team led by Hideto Ito and Kenichiro Itami has succeeded in developing a simple and effective method for the synthesis of robust covalent ONTs (tube) by an operationally simple light irradiation of a readily accessible helical polymer (helix). This so-called “helix-to-tube” strategy is based on the following steps: 1) polymerization of a small molecule (monomer) to make a helical polymer followed by, 2) light-induced cross-linking at longitudinally repeating pitches across the whole helix to form covalent nanotubes (Figure 3).

Figure 3. New synthetic approach towards covalent ONTs through longitudinal cross-linking between helical pitches in helical polymers.

With their strategy, the team designed and synthesized diacetylene-based helical polymers (acetylenes are molecules that contain carbon-carbon triple bonds), poly(m-phenylene diethynylene)s (poly-PDEs), which has chiral amide side chains that are able to induce a helical folding through hydrogen-bonding interactions (Figure 4).

Figure 4. Molecular design for helical poly-PDE bearing chiral amide side chains.

The researchers revealed that light-induced cross-linking at longitudinally aligned 1,3-butadiyne moieties (a group of molecules that contain four carbons with triple bonds at the first and third carbons) could generate the desired covalent ONT (Figure 5). “This is the first time in the world to show that the photochemical polymerization reaction of diynes is applicable to the cross-linking reaction of a helical polymer,” says Maeda, a graduate student who mainly conducted the experiments.

The “helix-to-tube” method is expected to be able to generate a range of ONT-based materials by simply changing the arene (aromatic ring) unit in the monomer.

Figure 5. Synthesis of a covalent ONT by photochemical cross-linking between longitudinal aligned 1,3-butadiyne moieties (red lines).

“One of the most difficult parts of this research was how to obtain scientific evidence on the structures of poly-PDEs and covalent ONTs,” says Ito, one of the leaders of this study. “We had little experience with the analysis of polymers and macromolecules such as ONTs. Fortunately, thanks to the support of our collaborators in Nagoya University, who are specialists in these particular research fields, we finally succeeded in characterizing these macromolecules by various techniques including spectroscopy, X-ray diffraction, and microscopy.”

“Although it took us about a year to synthesize the covalent ONT, it took another one and a half year to determine the structure of the nanotube,” says Maeda. “I was extremely excited when I first saw the transmission electron microscopy (TEM) images, which indicated that we had actually made the covalent ONT that we were expecting,” she continues (Figure 6).

Figure 6. TEM images of the bundle structures of covalent ONT

“The best part of the research for me was finding that the photochemical cross-linking had taken place on the helix for the first time,” says Maeda. “In addition, photochemical cross-linking is known to usually occur in the solid phase, but we were able to show that the reaction takes place in the solution phase as well. As the reactions have never been carried out before, I was dubious at first, but it was a wonderful feeling to succeed in making the reaction work for the first time in the world. I can say for sure that this was a moment where I really found research interesting.”

“We were really excited to develop this simple yet powerful method to achieve the synthesis of covalent ONTs,” says Itami, the director of the JST-ERATO project and the center director of ITbM. “The “helix-to-tube” method enables molecular level design and will lead to the synthesis of various covalent ONTs with fixed diameters and tube lengths with desirable functionalities.”

“We envisage that ongoing advances in the “helix-to-tube” method may lead to the development of various ONT-based materials including electro-conductive materials and luminescent materials,” says Ito. “We are currently carrying out work on the “helix-to-tube” methodology and we hope to synthesize covalent ONTs with interesting properties for various applications.”

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

Construction of Covalent Organic Nanotubes by Light-Induced Cross-Linking of Diacetylene-Based Helical Polymers by Kaho Maeda, Liu Hong, Taishi Nishihara, Yusuke Nakanishi, Yuhei Miyauchi, Ryo Kitaura, Naoki Ousaka, Eiji Yashima, Hideto Ito, and Kenichiro Itami. J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.6b05582 Publication Date (Web): August 3, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

A carbon nanomaterial ‘pot’ for drug delivery

Japanese scientists have developed a new material, which could be used as a carrier for drugs. From an Aug. 5, 2016 news item on phys.org,

A novel, pot-shaped, carbon nanomaterial developed by researchers from Kumamoto University, Japan is several times deeper than any hollow carbon nanostructure previously produced. This unique characteristic enables the material to gradually release substances contained within and is expected to be beneficial in applications such as drug delivery systems.

An Aug. 5, 2016 Kumamoto University press release on EurekAlert, which despite the discrepancy in the dates originated the news item, discusses carbon and the discovery in more detail,

Carbon is an element that is light, abundant, has a strong binding force, and eco-friendly. The range of carbon-based materials is expected to become more widespread in the eco-friendly society of the future. Recently, nanosized (one-billionth of a meter) carbon materials have been developed with lengths, widths, or heights below 100 nm [nanometre]. These materials take extreme forms such as tiny grained substances, thin sheet-like substances, and slim fibrous substances. Example of these new materials are fullerenes, which are hollow cage-like carbon molecules; carbon nanotubes, cylindrical nanostructures of carbon molecules; and graphene, one-atom thick sheets of carbon molecules.

Why are these tiny substances needed? One reason is that reactions with other materials can be much larger if a substance has an increased surface area. When using nanomaterials in place of existing materials, it is possible to significantly change surface area without changing weight and volume, thereby improving both size and performance. The development of carbon nanomaterials has provided novel nanostructured materials with shapes and characteristics that surpass existing materials.

Now, research from the laboratory of Kumamoto University’s Associate Prof. Yokoi has resulted in the successful development of a container-type carbon nanomaterial with a much deeper orifice than that found in similar materials. To create the new material, researchers used their own, newly developed method of material synthesis. The container-shaped nanomaterial has a complex form consisting of varied layers of stacked graphene at the bottom, the body, and the neck areas of the container, and the graphene edges along the outer surface of the body were found to be very dense. Due to these innovate features, Associate Prof. Yokoi and colleagues named the material the “carbon nanopot.”

The carbon nanopot has an outer diameter of 20 ~ 40 nm, an inner diameter of 5 ~ 30 nm, and a length of 100 ~ 200 nm. During its creation, the carbon nanopot is linked to a carbon nanofiber with a length of 20 ~ 100 μm [micrometre] meaning that the carbon nanopot is also available as a carbon nanofiber. At the junction between nanopots, the bottom of one pot simply sits on the opening of the next without sharing a graphene sheet connection. Consequently, separating nanopots is very easy.

“From a detailed surface analysis, hydrophilic hydroxyl groups were found clustered along the outer surface of the carbon nanopot body,” said Associate Prof. Yokoi. “Graphene is usually hydrophobic however, if hydroxyl groups are densely packed on the outer surface of the body, that area will be hydrophilic. In other words, carbon nanopots could be a unique nanomaterial with both hydrophobic and hydrophilic characteristics. We are currently in the process of performing a more sophisticated surface analysis in order to get that assurance.”

Since this new carbon nanopot has a relatively deep orifice, one of its expected uses is to improve drug delivery systems by acting as a new foundation for medicine to be carried into and be absorbed by the body.

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

Novel pot-shaped carbon nanomaterial synthesized in a submarine-style substrate heating CVD method by Hiroyuki Yokoi, Kazuto Hatakeyama, Takaaki Taniguchi, Michio Koinuma, Masahiro Hara, and Yasumichi Matsumoto. Journal of Materials Research / Volume 31 / Issue 01 / 2016, pp 117-126 DOI: http://dx.doi.org/10.1557/jmr.2015.389 (About DOI) Published online: 13 January 2016

Copyright © Materials Research Society 2016

I’m not sure why there’s this push for publicity so long after the publication date. In any event, this paper is behind a paywall.

Inspiration from the sea for titanium implants (mussels) and adhesive panels for flexible sensors (octopuses/octopi/octopodes)

I have two sea-inspired news bits both of which concern adhesion.

Mussels and titanium implants

A July 8, 2016 news item on ScienceDaily features some mussel-inspired research from Japan into how to make better titanium implants,

Titanium is used medically in applications such as artificial joints and dental implants. While it is strong and is not harmful to tissues, the metal lacks some of the beneficial biological properties of natural tissues such as bones and natural teeth. Now, based on insights from mussels–which are able to attach themselves very tightly to even metallic surfaces due to special proteins found in their byssal threads–scientists from RIKEN have successfully attached a biologically active molecule to a titanium surface, paving the way for implants that can be more biologically beneficial.

A July 11, 2016 RIKEN press release (also on EurekAlert but dated July 8, 2016), which originated the news item, provides more information,

The work began from earlier discoveries that mussels can attach to smooth surfaces so effectively thanks to a protein, L-DOPA, which is known to be able to bind very strongly to smooth surfaces such as rocks, ceramics, or metals (…). Interestingly, the same protein functions in humans as a precursor to dopamine, and is used as a treatment for Parkinson’s disease.

According to Chen Zhang of the RIKEN Nano Medical Engineering Laboratory, the first author of the paper published in Angewandte Chemie, “We thought it would be interesting to try to use various techniques to attach a biologically active protein—in our case we chose insulin-like growth factor-1, a promoter of cell proliferation—to a titanium surface like those used in implants” (…).

Using a combination of recombinant DNA technology and treatment with tyrosinase, they were able to create a hybrid protein that contained active parts of both the growth factor and L-DOPA. Tests showed that the proteins were able to fold normally, and further experiments in cell cultures demonstrated that the IGF-1 was still functioning normally. Thanks to the incorporation of the L-DOPA, the team was able to confirm that the proteins bound strongly to the titanium surface, and remained attached even when the metal was washed with phosphate-buffered saline, a water-based solution. Zhang says, “This is similar to the powerful properties of mussel adhesive, which can remain fixed to metallic materials even underwater.”

According to Yoshihiro Ito, Team Leader of the Emergent Bioengineering Research Team of the RIKEN Center for Emergent Matter Science, “We are very excited by this finding, because the modification process is a universal one that could be used with other proteins. It could allow us to prepare new cell-growth enhancing materials, with potential applications in cell culture systems and regenerative medicine. And it is particularly interesting that this is an example of biomimetics, where nature can teach us new ways to do things. The mussel has given us insights that could be used to allow us to live healthier lives.”

The work was done by RIKEN researchers in collaboration with Professor Peibiao Zhang of the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, and Professor Yi Wang of the School of Pharmaceutical Sciences, Jilin University. The work was partially supported by the Japan Society for the Promotion of Science KAKENHI (Grant Number 15H01810 and 22220009), CAS-JSPS joint fund (GJHZ1519), and RIKEN MOST joint project.

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

A Bioorthogonal Approach for the Preparation of a Titanium-Binding Insulin-like Growth-Factor-1 Derivative by using Tyrosinase by Chen Zhang, Hideyuki Miyatake, Yu Wang, Takehiko Inaba, Yi Wang, Peibiao Zhang, and Prof. Yoshihiro Ito. Angewandte Chemie International Edition DOI: 10.1002/anie.201603155 Version of Record online: 6 JUL 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Octopuses/octopi/octopodes and adhesive panels

Before launching into the science part of this news bit, here’s some grammar (from the Octopus Wikipedia entry; Note: Links have been removed),

The standard pluralized form of “octopus” in the English language is “octopuses” /ˈɒktəpʊsɪz/,[10] although the Ancient Greek plural “octopodes” /ɒkˈtɒpədiːz/, has also been used historically.[9] The alternative plural “octopi” — which misguidedly assumes it is a Latin “-us”-word — is considered grammatically incorrect.[11][12][13][14] It is nevertheless used enough to make it notable, and was formally acknowledged by the descriptivist Merriam-Webster 11th Collegiate Dictionary and Webster’s New World College Dictionary. The Oxford English Dictionary (2008 Draft Revision)[15] lists “octopuses”, “octopi”, and “octopodes”, in that order, labelling “octopodes” as rare and noting that “octopi” derives from the apprehension that octōpus comes from Latin.[16] In contrast, New Oxford American Dictionary (3rd Edition 2010) lists “octopuses” as the only acceptable pluralization, with a usage note indicating “octopodes” as being still occasionally used but “octopi” as being incorrect.[17]

Now the news. A July 12, 2016 news item on Nanowerk highlights some research into adhesives and octopuses,

With increased study of bio-adhesives, a significant effort has been made in search for novel adhesives that will combine reversibility, repeated usage, stronger bonds and faster bonding time, non-toxic, and more importantly be effective in wet and other extreme conditions.

A team of Korean scientists-made up of scientists from Korea Institute of Science and Technology (KIST) and UNIST has recently found a way to make building flexible pressure sensors easier–by mimicking the suction cups on octopus’s tentacles.

A July 5, 2016 UNIST (Ulsan National Institute of Science and Technology) press release, which originated the news item, provides more information,

According to the research team, “Although flexible pressure sensors might give future prosthetics and robots a better sense of touch, building them requires a lot of laborious transferring of nano- and microribbons of inorganic semiconductor materials onto polymer sheets.”

In search of an easier way to process this transfer printing, Prof. Hyunhyub Ko (School of Energy and Chemical Engineering, UNIST) and his colleagues turned to the octopus suction cups for inspiration.

An octopus uses its tentacles to move to a new location and uses suction cups underneath each tentacle to grab onto something. Each suction cup contains a cavity whose pressure is controlled by surrounding muscles. These can be made thinner or thicker on demand, increasing or decreasing air pressure inside the cup, allowing for sucking and releasing as desired.

By mimicking muscle actuation to control cavity-pressure-induced adhesion of octopus suckers, Prof. Ko and his team engineered octopus-inspired smart adhesive pads. They used the rubbery material polydimethylsiloxane (PDMS) to create an array of microscale suckers, which included pores that are coated with a thermally responsive polymer to create sucker-like walls.

The team discovered that the best way to replicate organic nature of muscle contractions would be through applied heat. Indeed, at room temperature, the walls of each pit sit in an ‘open’ state, but when the mat is heated to 32°C, the walls contract, creating suction, therby allowing the entire mate to adhere to a material (mimicking the suction function of an octopus). The adhesive strength also spiked from .32 kilopascals to 94 kilopascals at high temperature.

The team reports that the mat worked as envisioned—they made some indium gallium arsenide transistors that sat on a flexible substrate and also used it to move some nanomaterials to a different type of flexible material.

Prof. Ko and his team expect that their smart adhesive pads can be used as the substrate for wearable health sensors, such as Band-Aids or sensors that stick to the skin at normal body temperatures but fall off when rinsed under cold water.

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

Octopus-Inspired Smart Adhesive Pads for Transfer Printing of Semiconducting Nanomembranes by Hochan Lee, Doo-Seung Um, Youngsu Lee, Seongdong Lim, Hyung-jun Kim,  and Hyunhyub Ko. Advanced Materials DOI: 10.1002/adma.201601407 Version of Record online: 20 JUN 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Getting one step closer to molecular robots

A July 5, 2016 news item on ScienceDaily announced research from Hokkaido University (Japan),

Scientists at Japan’s Hokkaido University have developed light-powered molecular motors that repetitively bend and unbend, bringing us closer to molecular robots.

A July 6, 2016 Hokkaido University press release (also on EurekAlert), which originated the news item, expands on the theme,

Researchers are working on mimicking cellular systems to develop molecular motors that can move or even deliver drugs to target tissues. Engineering such motors may ultimately lead to molecular robots that can execute more complex tasks. To this end, researchers must find ways to convert motion at the molecular level to motion at the macroscopic level. They also must find ways to cause chemical reactions to repeat autonomously and continuously.
Yoshiyuki Kageyama, Sadamu Takeda and colleagues at Hokkaido University’s Department of Chemistry have successfully created a chemical compound, or a crystalline assembly, which autonomously repeated flipping under blue light.

The team made crystals composed of an organic compound, called azobenzene, commonly used in dye manufacturing, and oleic acid, commonly found in cooking oil. Azobenzene molecules take two structurally different forms: cis and trans. They repetitively convert from one form to the other under blue right. The scientists tested if this would influence the structure of the azobenzene-oleic acid crystal, which contained unequal amounts of cis– and trans-azobenzene.

By applying blue light to the crystals in solution, the team observed, under a microscope, an oscillatory bending-unbending motion of the thin crystals, suggesting the existence of two stable structures, bent or unbent, depending on the cis/trans ratio. The frequency of the motion increased when the light intensity was increased. Some crystal complexes even exhibited ‘swimming-like’ motions in the water. Previously reported light-responsive materials have been limited in their ability to deform. The properties of the compounds in the Hokkaido University-developed crystals, however, allowed for a two-step switching mechanism, resulting in regular repetitive oscillations.

Schematic illustration of each step of the self-oscillatory motion. (Ikegami T. et. al., Angewandte Chemie International Edition, May 19, 2016)

Schematic illustration of each step of the self-oscillatory motion. (Ikegami T. et. al., Angewandte Chemie International Edition, May 19, 2016)

“The ability to self-organize rhythmic motions, such as the repetitive flipping motion we observed, is one of the fundamental characteristics of living organisms”, says Kageyama. “This mechanism can be used in the future to develop bio-inspired molecular motors and robots that will find applications in wide areas, including medicine”.

You can observe the flipping here in this video provided by Hokkaido University,

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

Dissipative and Autonomous Square-Wave Self-Oscillation of a Macroscopic Hybrid Self-Assembly under Continuous Light Irradiation by Tomonori Ikegami, Dr. Yoshiyuki Kageyama, Kazuma Obara, and Prof. Sadamu Takeda. Angewandte Chemie International Edition Volume 55, Issue 29, pages 8239–8243, July 11, 2016 DOI: 10.1002/anie.201600218 Version of Record online: 19 MAY 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Peruvian scientist Marino Morikawa nanoremediates wetlands

Peru’s El Cascajo Lake has undergone a successful nanotechology-enabled remediation technique developed by scientist Marino Morikawa and which he hopes can be used to clean up Lake Titicaca according to a July 6, 2016 news item on news.co.cr,

Peruvian scientist Marino Morikawa, who “revived” polluted wetlands in 15 days using nanotechnology, now plans to try to clean up Lake Titicaca and the Huacachina lagoon, an oasis in the middle of the desert.

El Cascajo, an ecosystem of roughly 50 hectares (123 acres) in Chancay district, located north of Lima, began its recovery in 2010 with two inventions that Morikawa came up with using his own resources and money.

The idea of restoring the wetlands came from a call from Morikawa’s father, who told the scientist that El Cascajo, where they used to go fishing when Marino was a child, “was in very bad condition,” Morikawa told EFE.

Marino Morikawa, who earned a degree in environmental science from Japan’s Tsukuba University, visited the wetlands and found a dump for sewage ringed by an illegal landfill where migratory birds fed.

The stinky swamp was covered by aquatic plants, Morikawa said.

The fifteen day timeline for the cleanup seems to be contradicted in this June 22, 2014 article by Rosana Pinheiro for Agencia Plano (a Latin American news portal) describes the situation at Lake El Cascajo and the nanotechnology in more detail,

Peruvian scientist Marino Morikawa created a cleanse system using nanobubbles to decontaminate lake El Cascajo, located at Chancay district, north of Lima, Peru’s capital. After nearly four years of the start of the project, 90% of the lake waters are recovered, and the place is now visited once again by at least 70 species of migratory birds.

The lake was once home to more than a thousand species of migratory birds in the 1990s. …

The [nanotechnology-enabled] treatment is done with tiny bubbles, the nanobubbles, a thousand times smaller than the ones we can see in a glass of soda. These bubbles attract bacteria and metals using static charge and then decompose, releasing free radicals which destroy viruses present in water. The process has been recognized by the Commission of Science, Technology and Innovation of the Peruvian Congress.

Biofilters were also deployed to ease the cleaning process of the water. Morikawa divided the wetland area with pieces of bamboo, creating sectors to order the withdrawal of the aquatic weeds.

… At the beginning, in December 2010, he worked alone, making daily visits to the region to develop the project. After some time, he started receiving help from friends, local population and local government.

A few months after the beginning of the treatment, it was possible to see that El Cascajo waters were more crystalline. However, it was only in January 2013 that “a miracle happened” as Morikawa says: Thousands of migratory birds returned to the lake and occupied about 70% of the area, forming a white cover around the water.

Whether this took fifteen days or several months seems less important than the remediation of the wetlands, Lake El Cascajo, the return of the birds, and a better functioning ecosystem. Let’s hope the same success can be enjoyed at Lake Titicaca.

There are more details in both pieces which I encourage you to read in their entirety.

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)

International nano news bits: Belarus and Vietnam

I have two nano news bits, one concerning Belarus and the other concerning Vietnam.


From a June 21, 2016 news item on Belarus News,

In the current five-year term Belarus will put efforts into developing robot technology, nano and biotechnologies, medical industry and a number of other branches of the national economy that can make innovative products, BelTA learned from Belarusian Economy Minister Vladimir Zinovsky on 21 June [2016].

The Minister underlined that the creation of new kinds of products, the development of conventional industries will produce their own results in economy and will allow securing a GDP growth rate as high as 112-115% in the current five-year term.

The last time Belarus was mentioned here was in a June 24, 2014 posting (scroll down about 25% of the way to see Belarus mentioned) about the European Union’s Graphene Flagship programme and new partners in the project. There was also a March 6, 2013 posting about Belarus and a nanotechnology partnership with Indonesia. (There are other mentions but those are the most recent.)


Vietnam has put into operation its first bio-nano production plant. From a June 21, 2016 news item on vietnamnet,

The Vietlife biological nano-plant was officially put into operation on June 20 [2016] at the North Thang Long Industrial Park in Hanoi.

It is the first plant producing biological nano-products developed entirely by Vietnamese scientists with a successful combination of traditional medicine, nanotechnology and modern drugs.

At the inauguration, Professor, Academician Nguyen Van Hieu, former president of Vietnam Academy of Science and Technology, who is the first to bring nanotechnology to Vietnam, reviewed the milestones of nanotechnology around the world and in the country.

In 2000, former US President Bill Clinton proposed American scientists research and develop nanotechnology for the first time.

Japan and the Republic of Korea then began developing the new technology.

Just two years later, in 2002, Vietnamese scientists also recommended research on nanotechnology and got the approval from the Party and State.

Academician Hieu said that Vietnam does not currently use nanotechnology to manufacture flat-screen TVs or smartphones. However, in Southeast Asia Vietnam has pioneered the research and successful applications of nanotechnology in production of probiotics combined with traditional medicine in health care, opening up a new potential science research in Vietnam.

Cam Ha JSC and scientists at the Vietnam Academy of Science and Technology have co-operated with a number of laboratories in the US, Australia and Japan to study and successfully develop a bio-nano production line in sync with diverse technologies.

Vietlife is the first plant to combine traditional medicine with nanotechnology and modern medicine. It consists of three technological lines: NANO MICELLE No. 1, 2 and 3; a NANO SOL-GEL chain; a packaging line, and a bio-nano research centre.

Nghia [Prof. Dr. Nguyen Duc Nghia, former deputy director of the Chemistry Institute under the Vietnam Academy of Science and Technology] said the factory has successfully produced some typical bio products, including Nanocurcumin NDN22+ from Vietnamese turmeric by nano micelle and Nano Sol-Gel methods. Preclinical experiment results indicate that at a concentration of about 40ppm, NDN22+ solution can kill 100% of rectum cancer tumors and prostate tumor cells within 72 hours. [emphasis mine]

In addition, it also manufactures other bio-nano products like Nanorutin from luscious trees and Nanolycopen from gac (Momordica cochinchinensis) oil.

Unfortunately, this news item does not include links to the research supporting the claims regarding nanocurcumin NDN22+. Hopefully, I will stumble across it soon.

“Brute force” technique for biomolecular information processing

The research is being announced by the University of Tokyo but there is definitely a French flavour to this project. From a June 20, 2016 news item on ScienceDaily,

A Franco-Japanese research group at the University of Tokyo has developed a new “brute force” technique to test thousands of biochemical reactions at once and quickly home in on the range of conditions where they work best. Until now, optimizing such biomolecular systems, which can be applied for example to diagnostics, would have required months or years of trial and error experiments, but with this new technique that could be shortened to days.

A June 20, 2016 University of Tokyo news release on EurekAlert, which originated the news item, describes the project in more detail,

“We are interested in programming complex biochemical systems so that they can process information in a way that is analogous to electronic devices. If you could obtain a high-resolution map of all possible combinations of reaction conditions and their corresponding outcomes, the development of such reactions for specific purposes like diagnostic tests would be quicker than it is today,” explains Centre National de la Recherche Scientifique (CNRS) researcher Yannick Rondelez at the Institute of Industrial Science (IIS) [located at the University of Tokyo].

“Currently researchers use a combination of computer simulations and painstaking experiments. However, while simulations can test millions of conditions, they are based on assumptions about how molecules behave and may not reflect the full detail of reality. On the other hand, testing all possible conditions, even for a relatively simple design, is a daunting job.”

Rondelez and his colleagues at the Laboratory for Integrated Micro-Mechanical Systems (LIMMS), a 20-year collaboration between the IIS and the French CNRS, demonstrated a system that can test ten thousand different biochemical reaction conditions at once. Working with the IIS Applied Microfluidic Laboratory of Professor Teruo Fujii, they developed a platform to generate a myriad of micrometer-sized droplets containing random concentrations of reagents and then sandwich a single layer of them between glass slides. Fluorescent markers combined with the reagents are automatically read by a microscope to determine the precise concentrations in each droplet and also observe how the reaction proceeds.

“It was difficult to fine-tune the device at first,” explains Dr Anthony Genot, a CNRS researcher at LIMMS. “We needed to create generate thousands of droplets containing reagents within a precise range of concentrations to produce high resolution maps of the reactions we were studying. We expected that this would be challenging. But one unanticipated difficulty was immobilizing the droplets for the several days it took for some reactions to unfold. It took a lot of testing to create a glass chamber design that was airtight and firmly held the droplets in place.” Overall, it took nearly two years to fine-tune the device until the researchers could get their droplet experiment to run smoothly.

Seeing the new system producing results was revelatory. “You start with a screen full of randomly-colored dots, and then suddenly the computer rearranges them into a beautiful high-resolution map, revealing hidden information about the reaction dynamics. Seeing them all slide into place to produce something that had only ever been seen before through simulation was almost magical,” enthuses Rondelez.

“The map can tell us not only about the best conditions of biochemical reactions, it can also tell us about how the molecules behave in certain conditions. Using this map we’ve already found a molecular behavior that had been predicted theoretically, but had not been shown experimentally. With our technique we can explore how molecules talk to each other in test tube conditions. Ultimately, we hope to illuminate the intimate machinery of living molecular systems like ourselves,” says Rondelez.

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

High-resolution mapping of bifurcations in nonlinear biochemical circuits by A. J. Genot, A. Baccouche, R. Sieskind, N. Aubert-Kato, N. Bredeche, J. F. Bartolo, V. Taly, T. Fujii, & Y. Rondelez. Nature Chemistry (2016)
doi:10.1038/nchem.2544 Published online 20 June 2016

This paper is behind a paywall.

A new, stable open-shell carbon molecule from Oregon

This discovery could one day make organic solar cells more efficient than silicon ones. Researchers at the University of Oregon announced their discovery in a June 9, 2016 news item on ScienceDaily,

University of Oregon chemists have synthesized a stable and long-lasting carbon-based molecule that, they say, potentially could be applicable in solar cells and electronic devices.

The molecule changes its bonding patterns to a magnetic biradical state when heated; it then returns to a fully bonded non-magnetic closed state at room temperature. That transition, they report, can be done repeatedly without decomposition. It remains stable in the presence of both heat and oxygen.

A June 9, 2016 University of Oregon news release on EurekAlert, which originated the news item, provides more detail,


Biradical refers to organic compounds, known as open-shell molecules, that have two free-flowing, non-bonding electrons. Producing them using techniques to control their electron spin, and thus provide semiconducting properties, in a heated state has been hampered by instability since the first synthetic biradical hydrocarbon was made in 1907.

“Potentially our approach could help to make organic solar cells more efficient than silicon solar cells, but that’s probably far in the future,” said UO doctoral student Gabriel E. Rudebusch, the paper’s lead author. “Our synthesis is rapid and efficient. We easily can make a gram of this compound, which is very stable when exposed to oxygen and heat. This stability has been almost unheard of in the literature about biradical compounds.”

The four-step synthesis of the compound — diindenoanthracene, or DIAn — and how it held up when tested in superconducting materials were detailed in a proof-of-principle paper published online May 23 by the journal Nature Chemistry. The UO team collaborated with experts in Japan, Spain and Sweden.

The molecular framework for the new molecule involves the hydrocarbon anthracene, which has three linearly fused hexagonal benzene rings, in combination with two five-membered pentagonal rings.

“The big difference between our new molecule and a lot of other biradical molecules that have been produced is those five-membered rings,” said co-author Michael M. Haley, who holds the UO’s Richard M. and Patricia H. Noyes Professorship in Chemistry. “They have the inherent ability to accept electrons or give up electrons. This means DIAn can move both negative and positive charges, which is an essential property for useful devices such as transistors and solar cells. Also, we can heat up our molecule to 150 degrees Celsius, bring it back to room temperature and heat it up again, repeatedly, and we see no decomposition in its reaction to oxygen. The unique features of DIAn are essential if these molecules are to have a use in the real world.”

Haley’s lab is now seeking to develop derivatives of the new molecule to help move the technology forward into potential applications.

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

Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals by Gabriel E. Rudebusch, José L. Zafra, Kjell Jorner, Kotaro Fukuda, Jonathan L. Marshall, Iratxe Arrechea-Marcos, Guzmán L. Espejo, Rocío Ponce Ortiz, Carlos J. Gómez-García, Lev N. Zakharov, Masayoshi Nakano, Henrik Ottosson, Juan Casado & Michael M. Haley. Nature Chemistry (2016)  doi:10.1038/nchem.2518 Published online 23 May 2016

This paper is behind a paywall.

There is another June 9, 2016 University of Oregon news release by Jim Barlow about this discovery. It covers much of the same material but focuses more closely on Rudebusch’s perspective.