Sometime in the last few years I was asked about carbon sequestration (or carbon capture) and nanotechnology and had no answer for the question until now (drat!). A July 13, 2015 Rice University (Texas, US) news release (also on EurekAlert) describes some research into buckyballs and the possibility they could be used to confine greenhouse gases,
Rice University scientists are forging toward tunable carbon-capture materials with a new study that shows how chemical changes affect the abilities of enhanced buckyballs to confine greenhouse gases.
The lab of Rice chemist Andrew Barron found last year that carbon-60 molecules (aka buckyballs, discovered at Rice in the 1980s) gain the ability to sequester carbon dioxide when combined with a polymer known as polyethyleneimine (PEI).
Two critical questions – how and how well – are addressed in a new paper in the American Chemical Society journal Energy and Fuels.
The news release expands on the theme,
The amine-rich combination of C60 and PEI showed its potential in the previous study to capture emissions of carbon dioxide, a greenhouse gas, from such sources as industrial flue gases and natural-gas wells.
In the new study, the researchers found pyrolyzing the material – heating it in an oxygen-free environment – changes its chemical composition in ways that may someday be used to tune what the scientists call PEI-C60 for specific carbon-capture applications.
“One of the things we wanted to see is at what point, chemically, it converts from being something that absorbed best at high temperature to something that absorbed best at low temperature,” Barron said. “In other words, at what point does the chemistry change from one to the other?”
Lead author Enrico Andreoli pyrolyzed PEI-C60 in argon at various temperatures from 100 to 1,000 degrees Celsius (212 to 1,832 degrees Fahrenheit) and then evaluated each batch for carbon uptake.
He discovered the existence of a transition point at 200 C, a boundary between the material’s ability to soak in carbon dioxide through chemical means as opposed to physical absorption.
The material that was pyrolyzed at low temperatures became gooey and failed at pulling in carbon from high-temperature sources by chemical means. The opposite was true for PEI-C60 pyrolyzed at high heat. The now-porous, brittle material became better in low-temperature environments, physically soaking up carbon dioxide molecules.
At 200 C, they found the heat treatment breaks the polymer’s carbon-nitrogen bonds, leading to a drastic decrease in carbon capture by any means.
“One of the goals was to see if can we make this a little less gooey and still have chemical uptake, and the answer is, not really,” Barron said. “It flips from one process to the other. But this does give us a nice continuum of how to get from one to the other.”
Andreoli found that at its peak, untreated PEI-C60 absorbed more than a 10th of its weight in carbon dioxide at high temperatures (0.13 grams per gram of material at 90 C). Pyrolyzed PEI-C60 did nearly as well at low temperatures (0.12 grams at 25 C).
The researchers, with an eye on potential environmental benefits, continue to refine their process. “This has definitely pointed us in the right direction,” Barron said.
Rice University, renowned for nanoscale science, has installed microscopes that will allow researchers to peer deeper than ever into the fabric of the universe.
The Titan Themis scanning/transmission electron microscope, one of the most powerful in the United States, will enable scientists from Rice as well as academic and industrial partners to view and analyze materials smaller than a nanometer — a billionth of a meter — with startling clarity.
The microscope has the ability to take images of materials at angstrom-scale (one-tenth of a nanometer) resolution, about the size of a single hydrogen atom.
Images will be captured with a variety of detectors, including X-ray, optical and multiple electron detectors and a 4K-resolution camera, equivalent to the number of pixels in the most modern high-resolution televisions. The microscope gives researchers the ability to create three-dimensional structural reconstructions and carry out electric field mapping of subnanoscale materials.
“Seeing single atoms is exciting, of course, and it’s beautiful,” said Emilie Ringe, a Rice assistant professor of materials science and nanoengineering and of chemistry. “But scientists saw single atoms in the ’90s, and even before. Now, the real breakthrough is that we can identify the composition of those atoms, and do it easily and reliably.” Ringe’s research group will operate the Titan Themis and a companion microscope that will image larger samples.
A June 29, 2015 Rice University news release, which originated the news item, provides more information about electron microscopes, incident electron beams, and the specifics of the second new piece of equipment being installed,
Electron microscopes use beams of electrons rather than rays of light to illuminate objects of interest. Because the wavelength of electrons is so much smaller than that of photons, the microscopes are able to capture images of much smaller things with greater detail than even the highest-resolution optical microscope.
“The beauty of these newer instruments is their analytical capabilities,” Ringe said. “Before, in order to see single atoms, we had to work a machine for an entire day and get it just right and then take a picture and hold our breath. These days, seeing atoms is routine.
“And now we can probe a particular atom’s chemical composition. Through various techniques, either via scattering intensity, X-rays emission or electron-beam absorption, we can figure out, say, that we’re looking at a palladium atom or a carbon atom. We couldn’t do that before.”
Ringe said when an electron beam ejects a bound electron from a target atom, it creates an empty site. “That can be filled by another electron within the atom, and the energy difference between this electron and the missing electron is emitted as an X-ray,” she said. “That X-ray is like a fingerprint, which we can read. Different types of atoms have different energies.”
She said the incident electron beam loses a bit of energy when it knocks an atom’s electron loose, and that energy loss can also be measured with a spectroscope to identify the atom. The X-ray and electron techniques are independent but complementary. “Typically, you use either/or, and it depends on what element you’re looking at,” Ringe said.
The second instrument, a Helios NanoLab 600 DualBeam microscope, will be used for three-dimensional imaging, analysis of larger samples and preparation of thin slices of samples for the more powerful Titan next door.
Both tools reside in the university’s Brockman Hall for Physics, which opened in 2011 and features sophisticated vibration-dampening capabilities. The microscopes require the best possible isolation from vibration, electric fields and acoustic noise to produce the best images, Ringe said.
“We have wanted a high-end microscopy facility at Rice because so many of us are working on nanomaterials,” said Pulickel Ajayan, a professor and founding chair of Rice’s Department of Materials Science and NanoEngineering. “This has been an issue because in order to be competitive you have to have the best atomic-scale characterization techniques. This will put us in business in terms of imaging and understanding new materials.”
He said the facility will position Rice as one of the most competitive institutions to recruit students and faculty, attract grants and publish groundbreaking results.
“A visual image of something on an atomic level can give you so much more information than a few numbers can,” said Peter Rossky, a theoretical chemist and dean of Rice’s Wiess School of Natural Sciences. Comparing images of the same material taken by an older electron microscope and the Titan Themis was like “the difference between a black-and-white TV and high-definition color,” he said.
Ringe said Rice’s Titan is a fourth-generation model manufactured in the Netherlands. It’s the latest and most powerful model and the first to be installed in the United States.
“Taking a complex image — not just a picture but a spectrum image that has lots of energy information — in the older model would take about 35 minutes,” she said. “By that time, the electron beam has destroyed whatever you were trying to look at.
“With this generation, you have the data you need in about two minutes. You can generate a lot more data more quickly. It’s not just better; it’s enabling.”
Edwin Thomas, the William and Stephanie Sick Dean of Rice’s George R. Brown School of Engineering, expects the new instruments to ignite the already strong research culture at the university. “This is going to influence the kind of people who will be attracted to apply to and then come to Rice,” said Thomas, a materials scientist. “I’m sure there will be people on campus who, once they find out the capabilities, are going to shift their compasses and take advantage of these machines. The whole point is to have an impact on science and society.”
Rice plans to host a two-day workshop in September to introduce the microscopes and their capabilities to the research community at the university and beyond. [emphasis mine] Beginning this summer, Ringe said, the electron microscopy center will be open to Rice students and faculty as well as researchers from other universities and industry.
Ringe looks forward to bringing researchers into the new microscopy lab — and to the research that will emerge.
“I hope everyone’s going to come out with a blockbuster paper with images from these instruments,” she said. “I would like every paper from Rice to have fantastic, crystal-clear, atomic-resolution images and the best possible characterization.”
To sum this up, there are two new pieces of equipment (Titan Themis scanning/transmission electron microscope and Helios NanoLab 600 DualBeam microscope) in Rice University’s 2011 facility, Brockman Hall for Physics. They are very excited about having the most powerful microscope in the US (the Titan) and hope to be holding a two-day workshop on these new microscopes for the research community at Rice and at other institutions.
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 , 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:
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.
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 email@example.com.
Regular readers know I have a long-standing interest in memristor and artificial brains. I have three memristor-related pieces of research, published in the last month or so, for this post.
First, there’s some research into nano memory at RMIT University, Australia, and the University of California at Santa Barbara (UC Santa Barbara). From a May 12, 2015 news item on ScienceDaily,
RMIT University researchers have mimicked the way the human brain processes information with the development of an electronic long-term memory cell.
Researchers at the MicroNano Research Facility (MNRF) have built the one of the world’s first electronic multi-state memory cell which mirrors the brain’s ability to simultaneously process and store multiple strands of information.
The development brings them closer to imitating key electronic aspects of the human brain — a vital step towards creating a bionic brain — which could help unlock successful treatments for common neurological conditions such as Alzheimer’s and Parkinson’s diseases.
“This is the closest we have come to creating a brain-like system with memory that learns and stores analog information and is quick at retrieving this stored information,” Dr Sharath said.
“The human brain is an extremely complex analog computer… its evolution is based on its previous experiences, and up until now this functionality has not been able to be adequately reproduced with digital technology.”
The ability to create highly dense and ultra-fast analog memory cells paves the way for imitating highly sophisticated biological neural networks, he said.
The research builds on RMIT’s previous discovery where ultra-fast nano-scale memories were developed using a functional oxide material in the form of an ultra-thin film – 10,000 times thinner than a human hair.
Dr Hussein Nili, lead author of the study, said: “This new discovery is significant as it allows the multi-state cell to store and process information in the very same way that the brain does.
“Think of an old camera which could only take pictures in black and white. The same analogy applies here, rather than just black and white memories we now have memories in full color with shade, light and texture, it is a major step.”
While these new devices are able to store much more information than conventional digital memories (which store just 0s and 1s), it is their brain-like ability to remember and retain previous information that is exciting.
“We have now introduced controlled faults or defects in the oxide material along with the addition of metallic atoms, which unleashes the full potential of the ‘memristive’ effect – where the memory element’s behaviour is dependent on its past experiences,” Dr Nili said.
Nano-scale memories are precursors to the storage components of the complex artificial intelligence network needed to develop a bionic brain.
Dr Nili said the research had myriad practical applications including the potential for scientists to replicate the human brain outside of the body.
“If you could replicate a brain outside the body, it would minimise ethical issues involved in treating and experimenting on the brain which can lead to better understanding of neurological conditions,” Dr Nili said.
The research, supported by the Australian Research Council, was conducted in collaboration with the University of California Santa Barbara.
Here’s a link to and a citation for this memristive nano device,
The second published piece of memristor-related research comes from a UC Santa Barbara and Stony Brook University (New York state) team but is being publicized by UC Santa Barbara. From a May 11, 2015 news item on Nanowerk (Note: A link has been removed),
In what marks a significant step forward for artificial intelligence, researchers at UC Santa Barbara have demonstrated the functionality of a simple artificial neural circuit (Nature, “Training and operation of an integrated neuromorphic network based on metal-oxide memristors”). For the first time, a circuit of about 100 artificial synapses was proved to perform a simple version of a typical human task: image classification.
“It’s a small, but important step,” said Dmitri Strukov, a professor of electrical and computer engineering. With time and further progress, the circuitry may eventually be expanded and scaled to approach something like the human brain’s, which has 1015 (one quadrillion) synaptic connections.
For all its errors and potential for faultiness, the human brain remains a model of computational power and efficiency for engineers like Strukov and his colleagues, Mirko Prezioso, Farnood Merrikh-Bayat, Brian Hoskins and Gina Adam. That’s because the brain can accomplish certain functions in a fraction of a second what computers would require far more time and energy to perform.
… As you read this, your brain is making countless split-second decisions about the letters and symbols you see, classifying their shapes and relative positions to each other and deriving different levels of meaning through many channels of context, in as little time as it takes you to scan over this print. Change the font, or even the orientation of the letters, and it’s likely you would still be able to read this and derive the same meaning.
In the researchers’ demonstration, the circuit implementing the rudimentary artificial neural network was able to successfully classify three letters (“z”, “v” and “n”) by their images, each letter stylized in different ways or saturated with “noise”. In a process similar to how we humans pick our friends out from a crowd, or find the right key from a ring of similar keys, the simple neural circuitry was able to correctly classify the simple images.
“While the circuit was very small compared to practical networks, it is big enough to prove the concept of practicality,” said Merrikh-Bayat. According to Gina Adam, as interest grows in the technology, so will research momentum.
“And, as more solutions to the technological challenges are proposed the technology will be able to make it to the market sooner,” she said.
Key to this technology is the memristor (a combination of “memory” and “resistor”), an electronic component whose resistance changes depending on the direction of the flow of the electrical charge. Unlike conventional transistors, which rely on the drift and diffusion of electrons and their holes through semiconducting material, memristor operation is based on ionic movement, similar to the way human neural cells generate neural electrical signals.
“The memory state is stored as a specific concentration profile of defects that can be moved back and forth within the memristor,” said Strukov. The ionic memory mechanism brings several advantages over purely electron-based memories, which makes it very attractive for artificial neural network implementation, he added.
“For example, many different configurations of ionic profiles result in a continuum of memory states and hence analog memory functionality,” he said. “Ions are also much heavier than electrons and do not tunnel easily, which permits aggressive scaling of memristors without sacrificing analog properties.”
This is where analog memory trumps digital memory: In order to create the same human brain-type functionality with conventional technology, the resulting device would have to be enormous — loaded with multitudes of transistors that would require far more energy.
“Classical computers will always find an ineluctable limit to efficient brain-like computation in their very architecture,” said lead researcher Prezioso. “This memristor-based technology relies on a completely different way inspired by biological brain to carry on computation.”
To be able to approach functionality of the human brain, however, many more memristors would be required to build more complex neural networks to do the same kinds of things we can do with barely any effort and energy, such as identify different versions of the same thing or infer the presence or identity of an object not based on the object itself but on other things in a scene.
Potential applications already exist for this emerging technology, such as medical imaging, the improvement of navigation systems or even for searches based on images rather than on text. The energy-efficient compact circuitry the researchers are striving to create would also go a long way toward creating the kind of high-performance computers and memory storage devices users will continue to seek long after the proliferation of digital transistors predicted by Moore’s Law becomes too unwieldy for conventional electronics.
This paper is behind a paywall but a free preview is available through ReadCube Access.
The third and last piece of research, which is from Rice University, hasn’t received any publicity yet, unusual given Rice’s very active communications/media department. Here’s a link to and a citation for their memristor paper,
This paper is behind a paywall but a free preview is available through ReadCube Access.
Dexter Johnson has written up the RMIT research (his May 14, 2015 post on the Nanoclast blog on the IEEE [Institute of Electrical and Electronics Engineers] website). He linked it to research from Mark Hersam’s team at Northwestern University (my April 10, 2015 posting) on creating a three-terminal memristor enabling its use in complex electronics systems. Dexter strongly hints in his headline that these developments could lead to bionic brains.
For those who’d like more memristor information, this June 26, 2014 posting which brings together some developments at the University of Michigan and information about developments in the industrial sector is my suggestion for a starting point. Also, you may want to check out my material on HP Labs, especially prominent in the story due to the company’s 2008 ‘discovery’ of the memristor, described on a page in my Nanotech Mysteries wiki, and the controversy triggered by the company’s terminology (there’s more about the controversy in my April 7, 2010 interview with Forrest H Bennett III).
A May 7, 2015 news item on phys.org describes research that could have a major impact on photonics applications,
In a study that could open doors for new applications of photonics from molecular sensing to wireless communications, Rice University [Texas, US] scientists have discovered a new method to tune the light-induced vibrations of nanoparticles through slight alterations to the surface to which the particles are attached.
n a study published online this week in Nature Communications, researchers at Rice’s Laboratory for Nanophotonics (LANP) used ultrafast laser pulses to induce the atoms in gold nanodisks to vibrate. These vibrational patterns, known as acoustic phonons, have a characteristic frequency that relates directly to the size of the nanoparticle. The researchers found they could fine-tune the acoustic response of the particle by varying the thickness of the material to which the nanodisks were attached.
Our results point toward a straightforward method for tuning the acoustic phonon frequency of a nanostructure in the gigahertz range by controlling the thickness of its adhesion layer,” said lead researcher Stephan Link, associate professor of chemistry and in electrical and computer engineering.
Light has no mass, but each photon that strikes an object imparts a miniscule amount of mechanical motion, thanks to a phenomenon known as radiation pressure. A branch of physics known as optomechanics has developed over the past decade to study and exploit radiation pressure for applications like gravity wave detection and low-temperature generation.
Link and colleagues at LANP specialize in another branch of science called plasmonics that is devoted to the study of light-activated nanostructures. Plasmons are waves of electrons that flow like a fluid across a metallic surface.
When a light pulse of a specific wavelength strikes a metal particle like the puck-shaped gold nanodisks in the LANP experiments, the light energy is converted into plasmons. These plasmons slosh across the surface of the particle with a characteristic frequency, in much the same way that each phonon has a characteristic vibrational frequency.
The study’s first author, Wei-Shun Chang, a postdoctoral researcher in Link’s lab, and graduate students Fangfang Wen and Man-Nung Su conducted a series of experiments that revealed a direct connection between the resonant frequencies of the plasmons and phonons in nanodisks that had been exposed to laser pulses.
“Heating nanostructures with a short light pulse launches acoustic phonons that depend sensitively on the structure’s dimensions,” Link said. “Thanks to advanced lithographic techniques, experimentalists can engineer plasmonic nanostructures with great precision. Based on our results, it appears that plasmonic nanostructures may present an interesting alternative to conventional optomechanical oscillators.”
Chang said plasmonics experts often rely on substrates when using electron-beam lithography to pattern plasmonic structures. For example, gold nanodisks like those used in the experiments will not stick to glass slides. But if a thin substrate of titanium or chromium is added to the glass, the disks will adhere and stay where they are placed.
“The substrate layer affects the mechanical properties of the nanostructure, but many questions remain as to how it does this,” Chang said. “Our experiments explored how the thickness of the substrate impacted properties like adhesion and phononic frequency.”
Link said the research was a collaborative effort involving research groups at Rice and the University of Melbourne in Victoria, Australia.
“Wei-Shun and Man-Nung from my lab did the ultrafast spectroscopy,” Link said. “Fangfang, who is in Naomi Halas’ group here at Rice, made the nanodisks. John Sader at the University of Melbourne, and his postdoc Debadi Chakraborty calculated the acoustic modes, and Yue Zhang, a Rice graduate student from Peter Nordlander’s group at Rice simulated the optical/plasmonic properties. Bo Shuang of the Landes’ research group at Rice contributed to the analysis of the experimental data.”
Water is the key component in a Rice University process to reliably create patterns of metallic and semiconducting wires less than 10 nanometers wide.
The technique by the Rice lab of chemist James Tour builds upon its discovery that the meniscus – the curvy surface of water at its edge – can be an effective mask to make nanowires.
The Rice team of Tour and graduate students Vera Abramova and Alexander Slesarev have now made nanowires between 6 and 16 nanometers wide from silicon, silicon dioxide, gold, chromium, tungsten, titanium, titanium dioxide and aluminum. They have also made crossbar structures of conducting nanowires from one or more of the materials.
The process is promising for the semiconductor industry as it seeks to make circuits ever smaller. State-of-the-art integrated circuit fabrication allows for signal wires that approach 10 nanometers, visible only with powerful microscopes. These are the paths that connect the billions of transistors in modern electronic devices.
“This could have huge ramifications for chip production since the wires are easily made to sub-10-nanometer sizes,” Tour said of the Rice process. “There’s no other way in the world to do this en masse on a surface.”
Current approaches to making such tiny wires take several paths. Lithography, the standard method for etching integrated circuits, is approaching the physical limits of its ability to shrink them further. Bulk synthesis of semiconducting and metallic nanowires is also possible, but the wires are difficult to position in integrated circuits.
Water’s tendency to adhere to surfaces went from an annoyance to an advantage when the Rice researchers found they could use it as a mask to make patterns. The water molecules gather wherever a raised pattern joins the target material and forms a curved meniscus created by the surface tension of water.
The meniscus-mask process involves adding and then removing materials in a sequence that ultimately leaves a meniscus covering the wire and climbing the sidewall of a sacrificial metal mask that, when etched away, leaves the nanowire standing alone.
Tour said the process should work with modern fabrication technology with no modifications to existing equipment and minimal changes in fabrication protocols. No new tools or materials are needed.
The researchers have provided an image,
These nanowires were created at Rice University through a process called meniscus-mask lithography. From left, they’re made of silicon, silicon dioxide, gold, chromium, tungsten, titanium, titanium dioxide and aluminum. The scale bar is 1 micron for all images. (Credit: Tour Group/Rice University)
I have two items about implants and brains and an item about being able to exert remote control of the brain, all of which hint at a cyborg future for at least a few of us.
e-Dura, the spinal column, and the brain
The first item concerns some research, at the École Polytechnique de Lausanne (EPFL) which features flexible electronics. From a March 24, 2015 article by Ben Schiller for Fast Company (Note: Links have been removed),
Researchers at the Swiss Federal Institute of Technology, in Lausanne, have developed the e-Dura—a tiny skinlike device that attaches directly to damaged spinal cords. By sending out small electrical pulses, it stimulates the cord as if it were receiving signals from the brain, thus allowing movement.
“The purpose of the neuro-prosthesis is to excite the neurons that are on the spinal cord below the site of the injury and activate them, just like if they were receiving information from the brain,” says Stéphanie Lacour, a professor at the institute.
EPFL scientists have managed to get rats walking on their own again using a combination of electrical and chemical stimulation. But applying this method to humans would require multifunctional implants that could be installed for long periods of time on the spinal cord without causing any tissue damage. This is precisely what the teams of professors Stéphanie Lacour and Grégoire Courtine have developed. Their e-Dura implant is designed specifically for implantation on the surface of the brain or spinal cord. The small device closely imitates the mechanical properties of living tissue, and can simultaneously deliver electric impulses and pharmacological substances. The risks of rejection and/or damage to the spinal cord have been drastically reduced. An article about the implant will appear in early January  in Science Magazine.
So-called “surface implants” have reached a roadblock; they cannot be applied long term to the spinal cord or brain, beneath the nervous system’s protective envelope, otherwise known as the “dura mater,” because when nerve tissues move or stretch, they rub against these rigid devices. After a while, this repeated friction causes inflammation, scar tissue buildup, and rejection.
Here’s what the implant looks like,
The press release describes how the implant is placed (Note: A link has been removed),
Flexible and stretchy, the implant developed at EPFL is placed beneath the dura mater, directly onto the spinal cord. Its elasticity and its potential for deformation are almost identical to the living tissue surrounding it. This reduces friction and inflammation to a minimum. When implanted into rats, the e-Dura prototype caused neither damage nor rejection, even after two months. More rigid traditional implants would have caused significant nerve tissue damage during this period of time.
The researchers tested the device prototype by applying their rehabilitation protocol — which combines electrical and chemical stimulation – to paralyzed rats. Not only did the implant prove its biocompatibility, but it also did its job perfectly, allowing the rats to regain the ability to walk on their own again after a few weeks of training.
“Our e-Dura implant can remain for a long period of time on the spinal cord or the cortex, precisely because it has the same mechanical properties as the dura mater itself. This opens up new therapeutic possibilities for patients suffering from neurological trauma or disorders, particularly individuals who have become paralyzed following spinal cord injury,” explains Lacour, co-author of the paper, and holder of EPFL’s Bertarelli Chair in Neuroprosthetic Technology.
The press release goes on to describe the engineering achievements,
Developing the e-Dura implant was quite a feat of engineering. As flexible and stretchable as living tissue, it nonetheless includes electronic elements that stimulate the spinal cord at the point of injury. The silicon substrate is covered with cracked gold electric conducting tracks that can be pulled and stretched. The electrodes are made of an innovative composite of silicon and platinum microbeads. They can be deformed in any direction, while still ensuring optimal electrical conductivity. Finally, a fluidic microchannel enables the delivery of pharmacological substances – neurotransmitters in this case – that will reanimate the nerve cells beneath the injured tissue.
The implant can also be used to monitor electrical impulses from the brain in real time. When they did this, the scientists were able to extract with precision the animal’s motor intention before it was translated into movement.
“It’s the first neuronal surface implant designed from the start for long-term application. In order to build it, we had to combine expertise from a considerable number of areas,” explains Courtine, co-author and holder of EPFL’s IRP Chair in Spinal Cord Repair. “These include materials science, electronics, neuroscience, medicine, and algorithm programming. I don’t think there are many places in the world where one finds the level of interdisciplinary cooperation that exists in our Center for Neuroprosthetics.”
For the time being, the e-Dura implant has been primarily tested in cases of spinal cord injury in paralyzed rats. But the potential for applying these surface implants is huge – for example in epilepsy, Parkinson’s disease and pain management. The scientists are planning to move towards clinical trials in humans, and to develop their prototype in preparation for commercialization.
EPFL has provided a video of researcher Stéphanie Lacour describing e-Dura and expressing hopes for its commercialization,
Here’s a link to and a citation for the paper,
Electronic dura mater for long-term multimodal neural interfaces by Ivan R. Minev, Pavel Musienko, Arthur Hirsch, Quentin Barraud, Nikolaus Wenger, Eduardo Martin Moraud, Jérôme Gandar, Marco Capogrosso, Tomislav Milekovic, Léonie Asboth, Rafael Fajardo Torres, Nicolas Vachicouras, Qihan Liu, Natalia Pavlova, Simone Duis, Alexandre Larmagnac, Janos Vörös, Silvestro Micera, Zhigang Suo, Grégoire Courtine, Stéphanie P. Lacour. Science 9 January 2015: Vol. 347 no. 6218 pp. 159-163 DOI: 10.1126/science.1260318
This paper is behind a paywall.
Carbon nanotube fibres could connect to the brain
Researchers at Rice University (Texas, US) are excited about the possibilities that carbon nanotube fibres offer in the field of implantable electronics for the brain. From a March 25, 2015 news item on Nanowerk,
Carbon nanotube fibers invented at Rice University may provide the best way to communicate directly with the brain.
The fibers have proven superior to metal electrodes for deep brain stimulation and to read signals from a neuronal network. Because they provide a two-way connection, they show promise for treating patients with neurological disorders while monitoring the real-time response of neural circuits in areas that control movement, mood and bodily functions.
New experiments at Rice demonstrated the biocompatible fibers are ideal candidates for small, safe electrodes that interact with the brain’s neuronal system, according to the researchers. They could replace much larger electrodes currently used in devices for deep brain stimulation therapies in Parkinson’s disease patients.
They may also advance technologies to restore sensory or motor functions and brain-machine interfaces as well as deep brain stimulation therapies for other neurological disorders, including dystonia and depression, the researchers wrote.
The fibers created by the Rice lab of chemist and chemical engineer Matteo Pasquali consist of bundles of long nanotubes originally intended for aerospace applications where strength, weight and conductivity are paramount.
The individual nanotubes measure only a few nanometers across, but when millions are bundled in a process called wet spinning, they become thread-like fibers about a quarter the width of a human hair.
“We developed these fibers as high-strength, high-conductivity materials,” Pasquali said. “Yet, once we had them in our hand, we realized that they had an unexpected property: They are really soft, much like a thread of silk. Their unique combination of strength, conductivity and softness makes them ideal for interfacing with the electrical function of the human body.”
The simultaneous arrival in 2012 of Caleb Kemere, a Rice assistant professor who brought expertise in animal models of Parkinson’s disease, and lead author Flavia Vitale, a research scientist in Pasquali’s lab with degrees in chemical and biomedical engineering, prompted the investigation.
“The brain is basically the consistency of pudding and doesn’t interact well with stiff metal electrodes,” Kemere said. “The dream is to have electrodes with the same consistency, and that’s why we’re really excited about these flexible carbon nanotube fibers and their long-term biocompatibility.”
Weeks-long tests on cells and then in rats with Parkinson’s symptoms proved the fibers are stable and as efficient as commercial platinum electrodes at only a fraction of the size. The soft fibers caused little inflammation, which helped maintain strong electrical connections to neurons by preventing the body’s defenses from scarring and encapsulating the site of the injury.
The highly conductive carbon nanotube fibers also show much more favorable impedance – the quality of the electrical connection — than state-of-the-art metal electrodes, making for better contact at lower voltages over long periods, Kemere said.
The working end of the fiber is the exposed tip, which is about the width of a neuron. The rest is encased with a three-micron layer of a flexible, biocompatible polymer with excellent insulating properties.
The challenge is in placing the tips. “That’s really just a matter of having a brain atlas, and during the experiment adjusting the electrodes very delicately and putting them into the right place,” said Kemere, whose lab studies ways to connect signal-processing systems and the brain’s memory and cognitive centers.
Doctors who implant deep brain stimulation devices start with a recording probe able to “listen” to neurons that emit characteristic signals depending on their functions, Kemere said. Once a surgeon finds the right spot, the probe is removed and the stimulating electrode gently inserted. Rice carbon nanotube fibers that send and receive signals would simplify implantation, Vitale said.
The fibers could lead to self-regulating therapeutic devices for Parkinson’s and other patients. Current devices include an implant that sends electrical signals to the brain to calm the tremors that afflict Parkinson’s patients.
“But our technology enables the ability to record while stimulating,” Vitale said. “Current electrodes can only stimulate tissue. They’re too big to detect any spiking activity, so basically the clinical devices send continuous pulses regardless of the response of the brain.”
Kemere foresees a closed-loop system that can read neuronal signals and adapt stimulation therapy in real time. He anticipates building a device with many electrodes that can be addressed individually to gain fine control over stimulation and monitoring from a small, implantable device.
“Interestingly, conductivity is not the most important electrical property of the nanotube fibers,” Pasquali said. “These fibers are intrinsically porous and extremely stable, which are both great advantages over metal electrodes for sensing electrochemical signals and maintaining performance over long periods of time.”
The paper is open access provided you register on the website.
Remote control for stimulation of the brain
Mo Costandi, neuroscientist and freelance science writer, has written a March 24, 2015 post for the Guardian science blog network focusing on neuronal remote control,
Two teams of scientists have developed new ways of stimulating neurons with nanoparticles, allowing them to activate brain cells remotely using light or magnetic fields. The new methods are quicker and far less invasive than other hi-tech methods available, so could be more suitable for potential new treatments for human diseases.
Researchers have various methods for manipulating brain cell activity, arguably the most powerful being optogenetics, which enables them to switch specific brain cells on or off with unprecedented precision, and simultaneously record their behaviour, using pulses of light.
This is very useful for probing neural circuits and behaviour, but involves first creating genetically engineered mice with light-sensitive neurons, and then inserting the optical fibres that deliver light into the brain, so there are major technical and ethical barriers to its use in humans.
Nanomedicine could get around this. Francisco Bezanilla of the University of Chicago and his colleagues knew that gold nanoparticles can absorb light and convert it into heat, and several years ago they discovered that infrared light can make neurons fire nervous impulses by heating up their cell membranes.
Polina Anikeeva’s team at the Massachusetts Institute of Technology adopted a slightly different approach, using spherical iron oxide particles that give off heat when exposed to an alternating magnetic field.
Although still in the experimental stages, research like this may eventually allow for wireless and minimally invasive deep brain stimulation of the human brain. Bezanilla’s group aim to apply their method to develop treatments for macular degeneration and other conditions that kill off light-sensitive cells in the retina. This would involve injecting nanoparticles into the eye so that they bind to other retinal cells, allowing natural light to excite them into firing impulses to the optic nerve.
Costandi’s article is intended for an audience that either understands the science or can deal with the uncertainty of not understanding absolutely everything. Provided you fall into either of those categories, the article is well written and it provides links and citations to the papers for both research teams being featured.
Taken together, the research at EPFL, Rice University, University of Chicago, and Massachusetts Institute of Technology provides a clue as to how much money and intellectual power is being directed at the brain.
A Feb. 10, 2015 news item on Azonano features injectable nanoparticles that act as antioxidants useful in case of injury, in particular, brain injury,
Injectable nanoparticles that could protect an injured person from further damage due to oxidative stress have proven to be astoundingly effective in tests to study their mechanism.
Scientists at Rice University, Baylor College of Medicine and the University of Texas Health Science Center at Houston (UTHealth) Medical School designed methods to validate their 2012 discovery that combined polyethylene glycol-hydrophilic carbon clusters — known as PEG-HCCs — could quickly stem the process of overoxidation that can cause damage in the minutes and hours after an injury.
The tests revealed a single nanoparticle can quickly catalyze the neutralization of thousands of damaging reactive oxygen species molecules that are overexpressed by the body’s cells in response to an injury and turn the molecules into oxygen. These reactive species can damage cells and cause mutations, but PEG-HCCs appear to have an enormous capacity to turn them into less-reactive substances.
The researchers hope an injection of PEG-HCCs as soon as possible after an injury, such as traumatic brain injury or stroke, can mitigate further brain damage by restoring normal oxygen levels to the brain’s sensitive circulatory system.
“Effectively, they bring the level of reactive oxygen species back to normal almost instantly,” said Rice chemist James Tour. “This could be a useful tool for emergency responders who need to quickly stabilize an accident or heart attack victim or to treat soldiers in the field of battle.” Tour led the new study with neurologist Thomas Kent of Baylor College of Medicine and biochemist Ah-Lim Tsai of UTHealth.
The news release goes on to describe the antioxidant particles and previous research,
PEG-HCCs are about 3 nanometers wide and 30 to 40 nanometers long and contain from 2,000 to 5,000 carbon atoms. In tests, an individual PEG-HCC nanoparticle can catalyze the conversion of 20,000 to a million reactive oxygen species molecules per second into molecular oxygen, which damaged tissues need, and hydrogen peroxide while quenching reactive intermediates.
Tour and Kent led the earlier research that determined an infusion of nontoxic PEG-HCCs may quickly stabilize blood flow in the brain and protect against reactive oxygen species molecules overexpressed by cells during a medical trauma, especially when accompanied by massive blood loss.
Their research targeted traumatic brain injuries, after which cells release an excessive amount of the reactive oxygen species known as a superoxide into the blood. These toxic free radicals are molecules with one unpaired electron that the immune system uses to kill invading microorganisms. In small concentrations, they contribute to a cell’s normal energy regulation. Generally, they are kept in check by superoxide dismutase, an enzyme that neutralizes superoxides.
But even mild traumas can release enough superoxides to overwhelm the brain’s natural defenses. In turn, superoxides can form such other reactive oxygen species as peroxynitrite that cause further damage.
“The current research shows PEG-HCCs work catalytically, extremely rapidly and with an enormous capacity to neutralize thousands upon thousands of the deleterious molecules, particularly superoxide and hydroxyl radicals that destroy normal tissue when left unregulated,” Tour said.
“This will be important not only in traumatic brain injury and stroke treatment, but for many acute injuries of any organ or tissue and in medical procedures such as organ transplantation,” he said. “Anytime tissue is stressed and thereby oxygen-starved, superoxide can form to further attack the surrounding good tissue.”
These details about the research are also noted in the news release,
The researchers used an electron paramagnetic resonance spectroscopy technique that gets direct structure and rate information for superoxide radicals by counting unpaired electrons in the presence or absence of PEG-HCC antioxidants. Another test with an oxygen-sensing electrode, peroxidase and a red dye confirmed the particles’ ability to catalyze superoxide conversion.
“In sharp contrast to the well-known superoxide dismutase, PEG-HCC is not a protein and does not have metal to serve the catalytic role,” Tsai said. “The efficient catalytic turnover could be due to its more ‘planar,’ highly conjugated carbon core.”
The tests showed the number of superoxides consumed far surpassed the number of possible PEG-HCC bonding sites. The researchers found the particles have no effect on important nitric oxides that keep blood vessels dilated and aid neurotransmission and cell protection, nor was the efficiency sensitive to pH changes.
“PEG-HCCs have enormous capacity to convert superoxide to oxygen and the ability to quench reactive intermediates while not affecting nitric oxide molecules that are beneficial in normal amounts,” Kent said. “So they hold a unique place in our potential armamentarium against a range of diseases that involve loss of oxygen and damaging levels of free radicals.”
The study also determined PEG-HCCs remain stable, as batches up to 3 months old performed as good as new.
They’re not billing this as a joint US-China project but with Rice University being in Texas, US and Shandong University being in Shandong (province) in China, I think it’s reasonable to describe it that way. Here’s more about the project from a Feb. 4, 2015 news item on Azonano,
Scientists from Rice University and Shandong University, China, celebrated the opening of the Joint Center for Carbon Nanomaterials, a collaborative facility to study nanotechnology, on Feb. 1 .
Rice faculty members Pulickel Ajayan and Jun Lou, the chair and associate chair, respectively, of the university’s Department of Materials Science and NanoEngineering, took part in the ceremony along with Rice alumnus Lijie Ci, director of the new center and a professor of materials science and engineering at Shandong. The center’s dedication was part of the first International Workshop on Engineering and Applications of Nanocarbon, held Jan. 31-Feb. 2 .
“We at Rice University are excited and honored to collaborate with Shandong University on this important endeavor,” Rice President David Leebron said in a message recorded for the ceremony. [emphasis mine] “The center represents and combines two very important initiatives for Rice: research excellence and applications in nanosciences and long-term partnerships with the best institutions worldwide.”
“A lot of people are working on carbon nanoscience on both campuses, and we expect they will be interested in taking part,” Ajayan said. “Nanotubes and graphene are essentially the building blocks for the center, but Lijie wants to build ecologically relevant, applied research that can be commercialized. That’s the long-term goal. All of the experience we have had in the area will be beneficial.”
Ajayan expects students from both universities will travel. “People from Rice will be engaged in some of the activities of this joint center, including advising students there. And we hope Shandong students will have the opportunity to come to Rice for a short time,” he said. “The center also contributes to Rice’s goal to build closer connections with China.” [emphases mine]
Ajayan and Ci came to Rice together in 2007 from Rensselaer Polytechnic Institute; Ajayan was a faculty member and Ci was a postdoctoral researcher. At Rice, they introduced the darkest material ever measured at the time of its invention in 2008, an accomplishment that landed them in the Guinness Book of World Records.
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.
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,