Tag Archives: carbon nanotubes

R.I.P. Mildred Dresselhaus, Queen of Carbon

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I’ve been hearing about Mildred Dresselhaus, professor emerita (retired professor) at the Massachusetts Institute of Technology (MIT), just about as long as I’ve been researching and writing about nanotechnology (about 10 years total* including the work for my master’s project with the almost eight years on this blog).

She died on Monday, Feb. 20, 2017 at the age of 86 having broken through barriers for those of her gender, barriers for her subject area, and barriers for her age.

Mark Anderson in his Feb. 22, 2017 obituary for the IEEE (Institute of Electrical and Electronics Engineers) Spectrum website provides a brief overview of her extraordinary life and accomplishments,

Called the “Queen of Carbon Science,” Dresselhaus pioneered the study of carbon nanostructures at a time when studying physical and material properties of commonplace atoms like carbon was out of favor. Her visionary perspectives on the sixth atom in the periodic table—including exploring individual layers of carbon atoms (precursors to graphene), developing carbon fibers stronger than steel, and revealing new carbon structures that were ultimately developed into buckyballs and nanotubes—invigorated the field.

“Millie Dresselhaus began life as the child of poor Polish immigrants in the Bronx; by the end, she was Institute Professor Emerita, the highest distinction awarded by the MIT faculty. A physicist, materials scientist, and electrical engineer, she was known as the ‘Queen of Carbon’ because her work paved the way for much of today’s carbon-based nanotechnology,” MIT president Rafael Reif said in a prepared statement.

Friends and colleagues describe Dresselhaus as a gifted instructor as well as a tireless and inspired researcher. And her boundless generosity toward colleagues, students, and girls and women pursuing careers in science is legendary.

…

In 1963, Dresselhaus began her own career studying carbon by publishing a paper on graphite in the IBM Journal for Research and Development, a foundational work in the history of nanotechnology. To this day, her studies of the electronic structure of this material serve as a reference point for explorations of the electronic structure of fullerenes and carbon nanotubes. Coauthor, with her husband Gene Dresselhaus, of a leading book on carbon fibers, she began studying the laser vaporation of carbon and the “carbon clusters” that resulted. Researchers who followed her lead discovered a 60-carbon structure that was soon identified as the icosahedral “soccer ball” molecular configuration known as buckminsterfullerene, or buckyball. In 1991, Dresselhaus further suggested that fullerene could be elongated as a tube, and she outlined these imagined objects’ symmetries. Not long after, researchers announced the discovery of carbon nanotubes.

When she began her nearly half-century career at MIT, as a visiting professor, women consisted of just 4 percent of the undergraduate student population.  So Dresselhaus began working toward the improvement of living conditions for women students at the university. Through her leadership, MIT adopted an equal and joint admission process for women and men. (Previously, MIT had propounded the self-fulfilling prophecy of harboring more stringent requirements for women based on less dormitory space and perceived poorer performance.) And so promoting women in STEM—before it was ever called STEM—became one of her passions. Serving as president of the American Physical Society, she spearheaded and launched initiatives like the Committee on the Status of Women in Physics and the society’s more informal committees of visiting women physicists on campuses around the United States, which have increased the female faculty and student populations on the campuses they visit.

If you have the time, please read Anderson’s piece in its entirety.

One fact that has impressed me greatly is that Dresselhaus kept working into her eighties. I featured a paper she published in an April 27, 2012 posting at the age of 82 and she was described in the MIT write up at the time as a professor, not a professor emerita. I later featured Dresselhaus in a May 31, 2012 posting when she was awarded the Kavli Prize for Nanoscience.

It seems she worked almost to the end. Recently, GE (General Electric) posted a video “What If Scientists Were Celebrities?” starring Mildred Dresselhaus,

H/t Mark Anderson’s obituary Feb. 22, 2017 piece. The video was posted on Feb. 8, 2017.

Goodbye to the Queen of Carbon!

*The word ‘total’ added on March 14, 2022.

Drive to operationalize transistors that outperform silicon gets a boost

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Dexter Johnson has written a Jan. 19, 2017 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers]) about work which could lead to supplanting silicon-based transistors with carbon nanotube-based transistors in the future (Note: Links have been removed),

The end appears nigh for scaling down silicon-based complimentary metal-oxide semiconductor (CMOS) transistors, with some experts seeing the cutoff date as early as 2020.

While carbon nanotubes (CNTs) have long been among the nanomaterials investigated to serve as replacement for silicon in CMOS field-effect transistors (FETs) in a post-silicon future, they have always been bogged down by some frustrating technical problems. But, with some of the main technical showstoppers having been largely addressed—like sorting between metallic and semiconducting carbon nanotubes—the stage has been set for CNTs to start making their presence felt a bit more urgently in the chip industry.

Peking University scientists in China have now developed carbon nanotube field-effect transistors (CNT FETs) having a critical dimension—the gate length—of just five nanometers that would outperform silicon-based CMOS FETs at the same scale. The researchers claim in the journal Science that this marks the first time that sub-10 nanometer CNT CMOS FETs have been reported.

More importantly than just being the first, the Peking group showed that their CNT-based FETs can operate faster and at a lower supply voltage than their silicon-based counterparts.

A Jan. 20, 2017 article by Bob Yirka for phys.org provides more insight into the work at Peking University,

One of the most promising candidates is carbon nanotubes—due to their unique properties, transistors based on them could be smaller, faster and more efficient. Unfortunately, the difficulty in growing carbon nanotubes and their sometimes persnickety nature means that a way to make them and mass produce them has not been found. In this new effort, the researchers report on a method of creating carbon nanotube transistors that are suitable for testing, but not mass production.

To create the transistors, the researchers took a novel approach—instead of growing carbon nanotubes that had certain desired properties, they grew some and put them randomly on a silicon surface and then added electronics that would work with the properties they had—clearly not a strategy that would work for mass production, but one that allowed for building a carbon nanotube transistor that could be tested to see if it would verify theories about its performance. Realizing there would still be scaling problems using traditional electrodes, the researchers built a new kind by etching very tiny sheets of graphene. The result was a very tiny transistor, the team reports, capable of moving more current than a standard CMOS transistor using just half of the normal amount of voltage. It was also faster due to a much shorter switch delay, courtesy of a gate capacitance of just 70 femtoseconds.

Peking University has published an edited and more comprehensive version of the phys.org article first reported by Lisa Zyga and edited by Arthars,

…

Now in a new paper published in Nano Letters, researchers Tian Pei, et al., at Peking University in Beijing, China, have developed a modular method for constructing complicated integrated circuits (ICs) made from many FETs on individual CNTs. To demonstrate, they constructed an 8-bits BUS system–a circuit that is widely used for transferring data in computers–that contains 46 FETs on six CNTs. This is the most complicated CNT IC fabricated to date, and the fabrication process is expected to lead to even more complex circuits.

SEM image of an eight-transistor (8-T) unit that was fabricated on two CNTs (marked with two white dotted lines). The scale bar is 100 μm. (Copyright: 2014 American Chemical Society)

Ever since the first CNT FET was fabricated in 1998, researchers have been working to improve CNT-based electronics. As the scientists explain in their paper, semiconducting CNTs are promising candidates for replacing silicon wires because they are thinner, which offers better scaling-down potential, and also because they have a higher carrier mobility, resulting in higher operating speeds.

Yet CNT-based electronics still face challenges. One of the most significant challenges is obtaining arrays of semiconducting CNTs while removing the less-suitable metallic CNTs. Although scientists have devised a variety of ways to separate semiconducting and metallic CNTs, these methods almost always result in damaged semiconducting CNTs with degraded performance.

To get around this problem, researchers usually build ICs on single CNTs, which can be individually selected based on their condition. It’s difficult to use more than one CNT because no two are alike: they each have slightly different diameters and properties that affect performance. However, using just one CNT limits the complexity of these devices to simple logic and arithmetical gates.

…

The 8-T unit can be used as the basic building block of a variety of ICs other than BUS systems, making this modular method a universal and efficient way to construct large-scale CNT ICs. Building on their previous research, the scientists hope to explore these possibilities in the future.

“In our earlier work, we showed that a carbon nanotube based field-effect transistor is about five (n-type FET) to ten (p-type FET) times faster than its silicon counterparts, but uses much less energy, about a few percent of that of similar sized silicon transistors,” Peng said.

“In the future, we plan to construct large-scale integrated circuits that outperform silicon-based systems. These circuits are faster, smaller, and consume much less power. They can also work at extremely low temperatures (e.g., in space) and moderately high temperatures (potentially no cooling system required), on flexible and transparent substrates, and potentially be bio-compatible.”

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

Scaling carbon nanotube complementary transistors to 5-nm gate lengths by Chenguang Qiu, Zhiyong Zhang, Mengmeng Xiao, Yingjun Yang, Donglai Zhong, Lian-Mao Peng. Science  20 Jan 2017: Vol. 355, Issue 6322, pp. 271-276 DOI: 10.1126/science.aaj1628

This paper is behind a paywall.

Nanotechnology cracks Wall Street (Daily)

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David Dittman’s Jan. 11, 2017 article for wallstreetdaily.com portrays a great deal of excitement about nanotechnology and the possibilities (I’m highlighting the article because it showcases Dexter Johnson’s Nanoclast blog),

When we talk about next-generation aircraft, next-generation wearable biomedical devices, and next-generation fiber-optic communication, the consistent theme is nano: nanotechnology, nanomaterials, nanophotonics.

For decades, manufacturers have used carbon fiber to make lighter sports equipment, stronger aircraft, and better textiles.

Now, as Dexter Johnson of IEEE [Institute of Electrical and Electronics Engineers] Spectrum reports [on his Nanoclast blog], carbon nanotubes will help make aerospace composites more efficient:

Now researchers at the University of Surrey’s Advanced Technology Institute (ATI), the University of Bristol’s Advanced Composite Centre for Innovation and Science (ACCIS), and aerospace company Bombardier [headquartered in Montréal, Canada] have collaborated on the development of a carbon nanotube-enabled material set to replace the polymer sizing. The reinforced polymers produced with this new material have enhanced electrical and thermal conductivity, opening up new functional possibilities. It will be possible, say the British researchers, to embed gadgets such as sensors and energy harvesters directly into the material.

When it comes to flight, lighter is better, so building sensors and energy harvesters into the body of aircraft marks a significant leap forward.

Johnson also reports for IEEE Spectrum on a “novel hybrid nanomaterial” based on oscillations of electrons — a major advance in nanophotonics:

Researchers at the University of Texas at Austin have developed a hybrid nanomaterial that enables the writing, erasing and rewriting of optical components. The researchers believe that this nanomaterial and the techniques used in exploiting it could create a new generation of optical chips and circuits.

…

Of course, the concept of rewritable optics is not altogether new; it forms the basis of optical storage mediums like CDs and DVDs. However, CDs and DVDs require bulky light sources, optical media and light detectors. The advantage of the rewritable integrated photonic circuits developed here is that it all happens on a 2-D material.

“To develop rewritable integrated nanophotonic circuits, one has to be able to confine light within a 2-D plane, where the light can travel in the plane over a long distance and be arbitrarily controlled in terms of its propagation direction, amplitude, frequency and phase,” explained Yuebing Zheng, a professor at the University of Texas who led the research… “Our material, which is a hybrid, makes it possible to develop rewritable integrated nanophotonic circuits.”

Who knew that mixing graphene with homemade Silly Putty would create a potentially groundbreaking new material that could make “wearables” actually useful?

Next-generation biomedical devices will undoubtedly include some of this stuff:

A dash of graphene can transform the stretchy goo known as Silly Putty into a pressure sensor able to monitor a human pulse or even track the dainty steps of a small spider.

The material, dubbed G-putty, could be developed into a device that continuously monitors blood pressure, its inventors hope.

The guys who made G-putty often rely on “household stuff” in their research.

It’s nice to see a blogger’s work be highlighted. Congratulations Dexter.

G-putty was mentioned here in a Dec. 30, 2016 posting which also includes a link to Dexter’s piece on the topic.

Sniffing out disease (Na-Nose)

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The ‘artificial nose’ is not a newcomer to this blog. The most recent post prior to this is a March 15, 2016 piece about Disney using an artificial nose for art conservation. Today’s (Jan. 9, 2016) piece concerns itself with work from Israel and ‘sniffing out’ disease, according to a Dec. 30, 2016 news item in Sputnik News,

A team from the Israel Institute of Technology has developed a device that from a single breath can identify diseases such as multiple forms of cancer, Parkinson’s disease, and multiple sclerosis. While the machine is still in the experimental stages, it has a high degree of promise for use in non-invasive diagnoses of serious illnesses.

The international team demonstrated that a medical theory first proposed by the Greek physician Hippocrates some 2400 years ago is true, certain diseases leave a “breathprint” on the exhalations of those afflicted. The researchers created a prototype for a machine that can pick up on those diseases using the outgoing breath of a patient. The machine, called the Na-Nose, tests breath samples for the presence of trace amounts of chemicals that are indicative of 17 different illnesses.

A Dec. 22, 2016 Technion Israel Institute of Technology press release offers more detail about the work,

An international team of 56 researchers in five countries has confirmed a hypothesis first proposed by the ancient Greeks – that different diseases are characterized by different “chemical signatures” identifiable in breath samples. …

Diagnostic techniques based on breath samples have been demonstrated in the past, but until now, there has not been scientific proof of the hypothesis that different and unrelated diseases are characterized by distinct chemical breath signatures. And technologies developed to date for this type of diagnosis have been limited to detecting a small number of clinical disorders, without differentiation between unrelated diseases.

The study of more than 1,400 patients included 17 different and unrelated diseases: lung cancer, colorectal cancer, head and neck cancer, ovarian cancer, bladder cancer, prostate cancer, kidney cancer, stomach cancer, Crohn’s disease, ulcerative colitis, irritable bowel syndrome, Parkinson’s disease (two types), multiple sclerosis, pulmonary hypertension, preeclampsia and chronic kidney disease. Samples were collected between January 2011 and June 2014 from in 14 departments at 9 medical centers in 5 countries: Israel, France, the USA, Latvia and China.

The researchers tested the chemical composition of the breath samples using an accepted analytical method (mass spectrometry), which enabled accurate quantitative detection of the chemical compounds they contained. 13 chemical components were identified, in different compositions, in all 17 of the diseases.

According to Prof. Haick, “each of these diseases is characterized by a unique fingerprint, meaning a different composition of these 13 chemical components.  Just as each of us has a unique fingerprint that distinguishes us from others, each disease has a chemical signature that distinguishes it from other diseases and from a normal state of health. These odor signatures are what enables us to identify the diseases using the technology that we developed.”

With a new technology called “artificially intelligent nanoarray,” developed by Prof. Haick, the researchers were able to corroborate the clinical efficacy of the diagnostic technology. The array enables fast and inexpensive diagnosis and classification of diseases, based on “smelling” the patient’s breath, and using artificial intelligence to analyze the data obtained from the sensors. Some of the sensors are based on layers of gold nanoscale particles and others contain a random network of carbon nanotubes coated with an organic layer for sensing and identification purposes.

The study also assessed the efficiency of the artificially intelligent nanoarray in detecting and classifying various diseases using breath signatures. To verify the reliability of the system, the team also examined the effect of various factors (such as gender, age, smoking habits and geographic location) on the sample composition, and found their effect to be negligible, and without impairment on the array’s sensitivity.

“Each of the sensors responds to a wide range of exhalation components,” explain Prof. Haick and his previous Ph.D student, Dr. Morad Nakhleh, “and integration of the information provides detailed data about the unique breath signatures characteristic of the various diseases. Our system has detected and classified various diseases with an average accuracy of 86%.

This is a new and promising direction for diagnosis and classification of diseases, which is characterized not only by considerable accuracy but also by low cost, low electricity consumption, miniaturization, comfort and the possibility of repeating the test easily.”

“Breath is an excellent raw material for diagnosis,” said Prof. Haick. “It is available without the need for invasive and unpleasant procedures, it’s not dangerous, and you can sample it again and again if necessary.”

Here’s a schematic of the study, which the researchers have made available,

Diagram: A schematic view of the study. Two breath samples were taken from each subject, one was sent for chemical mapping using mass spectrometry, and the other was analyzed in the new system, which produced a clinical diagnosis based on the chemical fingerprint of the breath sample. Courtesy: Tech;nion

There is also a video, which covers much of the same ground as the press release but also includes information about the possible use of the Na-Nose technology in the European Union’s SniffPhone project,

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

Diagnosis and Classification of 17 Diseases from 1404 Subjects via Pattern Analysis of Exhaled Molecules by Morad K. Nakhleh, Haitham Amal, Raneen Jeries, Yoav Y. Broza, Manal Aboud, Alaa Gharra, Hodaya Ivgi, Salam Khatib, Shifaa Badarneh, Lior Har-Shai, Lea Glass-Marmor, Izabella Lejbkowicz, Ariel Miller, Samih Badarny, Raz Winer, John Finberg, Sylvia Cohen-Kaminsky, Frédéric Perros, David Montani, Barbara Girerd, Gilles Garcia, Gérald Simonneau, Farid Nakhoul, Shira Baram, Raed Salim, Marwan Hakim, Maayan Gruber, Ohad Ronen, Tal Marshak, Ilana Doweck, Ofer Nativ, Zaher Bahouth, Da-you Shi, Wei Zhang, Qing-ling Hua, Yue-yin Pan, Li Tao, Hu Liu, Amir Karban, Eduard Koifman, Tova Rainis, Roberts Skapars, Armands Sivins, Guntis Ancans, Inta Liepniece-Karele, Ilze Kikuste, Ieva Lasina, Ivars Tolmanis, Douglas Johnson, Stuart Z. Millstone, Jennifer Fulton, John W. Wells, Larry H. Wilf, Marc Humbert, Marcis Leja, Nir Peled, and Hossam Haick. ACS Nano, Article ASAP DOI: 10.1021/acsnano.6b04930 Publication Date (Web): December 21, 2016

Copyright © 2017 American Chemical Society

This paper appears to be open access.

As for SniffPhone, they’re hoping that Na-Nose or something like it will allow them to modify smartphones in a way that will allow diseases to be detected.

I can’t help wondering who will own the data if your smartphone detects a disease. If you think that’s an idle question, here’s an excerpt from Sue Halpern’s Dec. 22, 2016 review of two books (“Weapons of Math Destruction: How Big Data Increases Inequality and Threatens Democracy” by Cathy O’Neil and “Virtual Competition: The Promise and Perils of the Algorithm-Driven Economy” by Ariel Ezrachi and Maurice E. Stucke) for the New York Times Review of Books,

We give our data away. We give it away in drips and drops, not thinking that data brokers will collect it and sell it, let alone that it will be used against us. There are now private, unregulated DNA databases culled, in part, from DNA samples people supply to genealogical websites in pursuit of their ancestry. These samples are available online to be compared with crime scene DNA without a warrant or court order. (Police are also amassing their own DNA databases by swabbing cheeks during routine stops.) In the estimation of the Electronic Frontier Foundation, this will make it more likely that people will be implicated in crimes they did not commit.

Or consider the data from fitness trackers, like Fitbit. As reported in The Intercept:

During a 2013 FTC panel on “Connected Health and Fitness,” University of Colorado law professor Scott Peppet said, “I can paint an incredibly detailed and rich picture of who you are based on your Fitbit data,” adding, “That data is so high quality that I can do things like price insurance premiums or I could probably evaluate your credit score incredibly accurately.”

Halpern’s piece is well worth reading in its entirety.

Liquid biopsy chip that uses carbon nanotubes in place of microfluidics

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They’re calling this a breakthrough technology in a Dec. 15, 2016 news item on ScienceDaily,

A chip developed by mechanical engineers at Worcester Polytechnic Institute (WPI) [UK] can trap and identify metastatic cancer cells in a small amount of blood drawn from a cancer patient. The breakthrough technology uses a simple mechanical method that has been shown to be more effective in trapping cancer cells than the microfluidic approach employed in many existing devices.

The WPI device uses antibodies attached to an array of carbon nanotubes at the bottom of a tiny well. Cancer cells settle to the bottom of the well, where they selectively bind to the antibodies based on their surface markers (unlike other devices, the chip can also trap tiny structures called exosomes produced by cancers cells). This “liquid biopsy,” described in a recent issue of the journal Nanotechnology, could become the basis of a simple lab test that could quickly detect early signs of metastasis and help physicians select treatments targeted at the specific cancer cells identified.

A Dec. 15, 2016 WPI press release (also on EurekAlert), which originated the news item, explains the breakthrough in more detail (Note: Links have been removed),

Metastasis is the process by which a cancer can spread from one organ to other parts of the body, typically by entering the bloodstream. Different types of tumors show a preference for specific organs and tissues; circulating breast cancer cells, for example, are likely to take root in bones, lungs, and the brain. The prognosis for metastatic cancer (also called stage IV cancer) is generally poor, so a technique that could detect these circulating tumor cells before they have a chance to form new colonies of tumors at distant sites could greatly increase a patient’s survival odds.

“The focus on capturing circulating tumor cells is quite new,” said Balaji Panchapakesan, associate professor of mechanical engineering at WPI and director of the Small Systems Laboratory. “It is a very difficult challenge, not unlike looking for a needle in a haystack. There are billions of red blood cells, tens of thousands of white blood cells, and, perhaps, only a small number of tumor cells floating among them. We’ve shown how those cells can be captured with high precision.”

The device developed by Panchapakesan’s team includes an array of tiny elements, each about a tenth of an inch (3 millimeters) across. Each element has a well, at the bottom of which are antibodies attached to carbon nanotubes. Each well holds a specific antibody that will bind selectively to one type of cancer cell type, based on genetic markers on its surface. By seeding elements with an assortment of antibodies, the device could be set up to capture several different cancer cells types using a single blood sample. In the lab, the researchers were able to fill a total of 170 wells using just under 0.3 fluid ounces (0.85 milliliter) of blood. Even with that small sample, they captured between one and a thousand cells per device, with a capture efficiency of between 62 and 100 percent.

In a paper published in the journal Nanotechnology [“Static micro-array isolation, dynamic time series classification, capture and enumeration of spiked breast cancer cells in blood: the nanotube–CTC chip”], Panchapakesan’s team, which includes postdoctoral researcher Farhad Khosravi, the paper’s lead author, and researchers at the University of Louisville and Thomas Jefferson University, describe a study in which antibodies specific for two markers of metastatic breast cancer, EpCam and Her2, were attached to the carbon nanotubes in the chip. When a blood sample that had been “spiked” with cells expressing those markers was placed on the chip, the device was shown to reliably capture only the marked cells.

In addition to capturing tumor cells, Panchapakesan says the chip will also latch on to tiny structures called exosomes, which are produced by cancers [sic] cells and carry the same markers. “These highly elusive 3-nanometer structures are too small to be captured with other types of liquid biopsy devices, such as microfluidics, due to shear forces that can potentially destroy them,” he noted. “Our chip is currently the only device that can potentially capture circulating tumor cells and exosomes directly on the chip, which should increase its ability to detect metastasis. This can be important because emerging evidence suggests that tiny proteins excreted with exosomes can drive reactions that may become major barriers to effective cancer drug delivery and treatment.”

Panchapakesan said the chip developed by his team has additional advantages over other liquid biopsy devices, most of which use microfluidics to capture cancer cells. In addition to being able to capture circulating tumor cells far more efficiently than microfluidic chips (in which cells must latch onto anchored antibodies as they pass by in a stream of moving liquid), the WPI device is also highly effective in separating cancer cells from the other cells and material in the blood through differential settling.

While the initial tests with the chip have focused on breast cancer, Panchapakesan says the device could be set up to detect a wide range of tumor types, and plans are already in the works for development of an advanced device as well as testing for other cancer types, including lung and pancreas cancer. He says he envisions a day when a device like his could be employed not only for regular follow ups for patients who have had cancer, but in routine cancer screening.

“Imagine going to the doctor for your yearly physical,” he said. “You have blood drawn and that one blood sample can be tested for a comprehensive array of cancer cell markers. Cancers would be caught at their earliest stage and other stages of development, and doctors would have the necessary protein or genetic information from these captured cells to customize your treatment based on the specific markers for your cancer. This would really be a way to put your health in your own hands.”

“White blood cells, in particular, are a problem, because they are quite numerous in blood and they can be mistaken for cancer cells,” he said. “Our device uses what is called a passive leukocyte depletion strategy. Because of density differences, the cancer cells tend to settle to the bottom of the wells (and this only happens in a narrow window), where they encounter the antibodies. The remainder of the blood contents stays at the top of the wells and can simply be washed away.”

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

Static micro-array isolation, dynamic time series classification, capture and enumeration of spiked breast cancer cells in blood: the nanotube–CTC chip by Farhad Khosravi, Patrick J Trainor, Christopher Lambert, Goetz Kloecker, Eric Wickstrom, Shesh N Rai, and Balaji Panchapakesan. Nanotechnology, Volume 27, Number 44 DOI http://dx.doi.org/10.1088/0957-4484/27/44/44LT03 Published 29 September 2016

© 2016 IOP Publishing Ltd

This paper is open access.

Water that freezes solid at over 100 degrees Celsius

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The ‘magical property’ of water that freezes at temperatures higher than 100 degrees Celsius occurs at the nanoscale according to this Nov. 28, 2016 news item on Nanowerk,

It’s a well-known fact that water, at sea level, starts to boil at a temperature of 212 degrees Fahrenheit, or 100 degrees Celsius. And scientists have long observed that when water is confined in very small spaces, its boiling and freezing points can change a bit, usually dropping by around 10 C or so.

But now, a team at MIT [Massachusetts Institute of Technology] has found a completely unexpected set of changes: Inside the tiniest of spaces — in carbon nanotubes whose inner dimensions are not much bigger than a few water molecules — water can freeze solid even at high temperatures that would normally set it boiling.

A Nov. 28, 2016 MIT news release (also on EurekAlert), which originated the news item, expands on the theme,

The discovery illustrates how even very familiar materials can drastically change their behavior when trapped inside structures measured in nanometers, or billionths of a meter. And the finding might lead to new applications — such as, essentially, ice-filled wires — that take advantage of the unique electrical and thermal properties of ice while remaining stable at room temperature.

…

“If you confine a fluid to a nanocavity, you can actually distort its phase behavior,” Strano says, referring to how and when the substance changes between solid, liquid, and gas phases. Such effects were expected, but the enormous magnitude of the change, and its direction (raising rather than lowering the freezing point), were a complete surprise: In one of the team’s tests, the water solidified at a temperature of 105 C or more. (The exact temperature is hard to determine, but 105 C was considered the minimum value in this test; the actual temperature could have been as high as 151 C.)

“The effect is much greater than anyone had anticipated,” Strano says.

It turns out that the way water’s behavior changes inside the tiny carbon nanotubes — structures the shape of a soda straw, made entirely of carbon atoms but only a few nanometers in diameter — depends crucially on the exact diameter of the tubes. “These are really the smallest pipes you could think of,” Strano says. In the experiments, the nanotubes were left open at both ends, with reservoirs of water at each opening.

Even the difference between nanotubes 1.05 nanometers and 1.06 nanometers across made a difference of tens of degrees in the apparent freezing point, the researchers found. Such extreme differences were completely unexpected. “All bets are off when you get really small,” Strano says. “It’s really an unexplored space.”

In earlier efforts to understand how water and other fluids would behave when confined to such small spaces, “there were some simulations that showed really contradictory results,” he says. Part of the reason for that is many teams weren’t able to measure the exact sizes of their carbon nanotubes so precisely, not realizing that such small differences could produce such different outcomes.

In fact, it’s surprising that water even enters into these tiny tubes in the first place, Strano says: Carbon nanotubes are thought to be hydrophobic, or water-repelling, so water molecules should have a hard time getting inside. The fact that they do gain entry remains a bit of a mystery, he says.

Strano and his team used highly sensitive imaging systems, using a technique called vibrational spectroscopy, that could track the movement of water inside the nanotubes, thus making its behavior subject to detailed measurement for the first time.

The team can detect not only the presence of water in the tube, but also its phase, he says: “We can tell if it’s vapor or liquid, and we can tell if it’s in a stiff phase.” While the water definitely goes into a solid phase, the team avoids calling it “ice” because that term implies a certain kind of crystalline structure, which they haven’t yet been able to show conclusively exists in these confined spaces. “It’s not necessarily ice, but it’s an ice-like phase,” Strano says.

Because this solid water doesn’t melt until well above the normal boiling point of water, it should remain perfectly stable indefinitely under room-temperature conditions. That makes it potentially a useful material for a variety of possible applications, he says. For example, it should be possible to make “ice wires” that would be among the best carriers known for protons, because water conducts protons at least 10 times more readily than typical conductive materials. “This gives us very stable water wires, at room temperature,” he says.

…

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

Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes by Kumar Varoon Agrawal, Steven Shimizu, Lee W. Drahushuk, Daniel Kilcoyne, & Michael S. Strano. Nature Nanotechnology (2016)  doi:10.1038/nnano.2016.254 Published online 28 November 2016

This paper is behind a paywall.

Spinach and plant nanobionics

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Who knew that spinach leaves could be turned into electronic devices? The answer is: engineers at the Massachusetts Institute of Technology, according to an Oct. 31, 2016 news item on phys.org,

Spinach is no longer just a superfood: By embedding leaves with carbon nanotubes, MIT engineers have transformed spinach plants into sensors that can detect explosives and wirelessly relay that information to a handheld device similar to a smartphone.

This is one of the first demonstrations of engineering electronic systems into plants, an approach that the researchers call “plant nanobionics.”

An Oct. 31, 2016 MIT news release (also on EurekAlert), which originated the news item, describes the research further (Note: Links have been removed),

“The goal of plant nanobionics is to introduce nanoparticles into the plant to give it non-native functions,” says Michael Strano, the Carbon P. Dubbs Professor of Chemical Engineering at MIT and the leader of the research team.

In this case, the plants were designed to detect chemical compounds known as nitroaromatics, which are often used in landmines and other explosives. When one of these chemicals is present in the groundwater sampled naturally by the plant, carbon nanotubes embedded in the plant leaves emit a fluorescent signal that can be read with an infrared camera. The camera can be attached to a small computer similar to a smartphone, which then sends an email to the user.

“This is a novel demonstration of how we have overcome the plant/human communication barrier,” says Strano, who believes plant power could also be harnessed to warn of pollutants and environmental conditions such as drought.

Strano is the senior author of a paper describing the nanobionic plants in the Oct. 31 [2016] issue of Nature Materials. The paper’s lead authors are Min Hao Wong, an MIT graduate student who has started a company called Plantea to further develop this technology, and Juan Pablo Giraldo, a former MIT postdoc who is now an assistant professor at the University of California at Riverside.

Environmental monitoring

Two years ago, in the first demonstration of plant nanobionics, Strano and former MIT postdoc Juan Pablo Giraldo used nanoparticles to enhance plants’ photosynthesis ability and to turn them into sensors for nitric oxide, a pollutant produced by combustion.

Plants are ideally suited for monitoring the environment because they already take in a lot of information from their surroundings, Strano says.

“Plants are very good analytical chemists,” he says. “They have an extensive root network in the soil, are constantly sampling groundwater, and have a way to self-power the transport of that water up into the leaves.”

Strano’s lab has previously developed carbon nanotubes that can be used as sensors to detect a wide range of molecules, including hydrogen peroxide, the explosive TNT, and the nerve gas sarin. When the target molecule binds to a polymer wrapped around the nanotube, it alters the tube’s fluorescence.

In the new study, the researchers embedded sensors for nitroaromatic compounds into the leaves of spinach plants. Using a technique called vascular infusion, which involves applying a solution of nanoparticles to the underside of the leaf, they placed the sensors into a leaf layer known as the mesophyll, which is where most photosynthesis takes place.

They also embedded carbon nanotubes that emit a constant fluorescent signal that serves as a reference. This allows the researchers to compare the two fluorescent signals, making it easier to determine if the explosive sensor has detected anything. If there are any explosive molecules in the groundwater, it takes about 10 minutes for the plant to draw them up into the leaves, where they encounter the detector.

To read the signal, the researchers shine a laser onto the leaf, prompting the nanotubes in the leaf to emit near-infrared fluorescent light. This can be detected with a small infrared camera connected to a Raspberry Pi, a $35 credit-card-sized computer similar to the computer inside a smartphone. The signal could also be detected with a smartphone by removing the infrared filter that most camera phones have, the researchers say.

“This setup could be replaced by a cell phone and the right kind of camera,” Strano says. “It’s just the infrared filter that would stop you from using your cell phone.”

Using this setup, the researchers can pick up a signal from about 1 meter away from the plant, and they are now working on increasing that distance.

Michael McAlpine, an associate professor of mechanical engineering at the University of Minnesota, says this approach holds great potential for engineering not only sensors but many other kinds of bionic plants that might receive radio signals or change color.

“When you have manmade materials infiltrated into a living organism, you can have plants do things that plants don’t ordinarily do,” says McAlpine, who was not involved in the research. “Once you start to think of living organisms like plants as biomaterials that can be combined with electronic materials, this is all possible.”

“A wealth of information”

In the 2014 plant nanobionics study, Strano’s lab worked with a common laboratory plant known as Arabidopsis thaliana. However, the researchers wanted to use common spinach plants for the latest study, to demonstrate the versatility of this technique. “You can apply these techniques with any living plant,” Strano says.

So far, the researchers have also engineered spinach plants that can detect dopamine, which influences plant root growth, and they are now working on additional sensors, including some that track the chemicals plants use to convey information within their own tissues.

“Plants are very environmentally responsive,” Strano says. “They know that there is going to be a drought long before we do. They can detect small changes in the properties of soil and water potential. If we tap into those chemical signaling pathways, there is a wealth of information to access.”

These sensors could also help botanists learn more about the inner workings of plants, monitor plant health, and maximize the yield of rare compounds synthesized by plants such as the Madagascar periwinkle, which produces drugs used to treat cancer.

“These sensors give real-time information from the plant. It is almost like having the plant talk to us about the environment they are in,” Wong says. “In the case of precision agriculture, having such information can directly affect yield and margins.”

Once getting over the excitement, questions spring to mind. How could this be implemented? Is somebody  going to plant a field of spinach and then embed the leaves so they can detect landmines? How will anyone know where to plant the spinach? And on a different track, is this spinach edible? I suspect that if spinach can be successfully used as a sensor, it might not be for explosives but for pollution as the researchers suggest.

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

Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics by Min Hao Wong, Juan P. Giraldo, Seon-Yeong Kwak, Volodymyr B. Koman, Rosalie Sinclair, Tedrick Thomas Salim Lew, Gili Bisker, Pingwei Liu, & Michael S. Strano. Nature Materials (2016) doi:10.1038/nmat4771 Published online 31 October 2016

This paper is behind a paywall.

The last posting here which featured Strano’s research is in an Aug. 25, 2015 piece about carbon nanotubes and medical sensors.

Solar and wind energy storage via food waste and carbon nanotubes

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Scientists are researching devices other than batteries for wind and solar energy storage according to an Oct. 27, 2016 news item on Nanowerk,

Saving up excess solar and wind energy for times when the sun is down or the air is still requires a storage device. Batteries get the most attention as a promising solution although pumped hydroelectric storage is currently used most often. Now researchers reporting in ACS’ Journal of Physical Chemistry C are advancing another potential approach using sugar alcohols — an abundant waste product of the food industry — mixed with carbon nanotubes.

An Oct. 26, 2016 American Chemical Society (ACS) news release, which originated the news item, expands on the theme,

Electricity generation from renewables has grown steadily over recent years, and the U.S. Energy Information Administration (EIA) expects this rise to continue. To keep up with this expansion, use of battery and flywheel energy storage has increased in the past five years, according to the EIA. These technologies take advantage of chemical and mechanical energy. But storing energy as heat is another feasible option. Some scientists have been exploring sugar alcohols as a possible material for making thermal storage work, but this direction has some limitations. Huaichen Zhang, Silvia V. Nedea and colleagues wanted to investigate how mixing carbon nanotubes with sugar alcohols might affect their energy storage properties.

The researchers analyzed what happened when carbon nanotubes of varying sizes were mixed with two types of sugar alcohols — erythritol and xylitol, both naturally occurring compounds in foods. Their findings showed that with one exception, heat transfer within a mixture decreased as the nanotube diameter decreased. They also found that in general, higher density combinations led to better heat transfer. The researchers say these new insights could assist in the future design of sugar alcohol-based energy storage systems.

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

Nanoscale Heat Transfer in Carbon Nanotubes – Sugar Alcohol Composite as Heat Storage Materials
by Huaichen Zhang, Camilo C. M. Rindt, David M. J. Smeulders, and Silvia V. Nedea. J. Phys. Chem. C, 2016, 120 (38), pp 21915–21924 DOI: 10.1021/acs.jpcc.6b05466 Publication Date (Web): August 30, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Boron nitride-graphene hybrid nanostructures could lead to next generation ‘green’ cars

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An Oct. 24, 2016 phys.org news item describes research which may lead to improved fuel storage in ‘green’ cars,

Layers of graphene separated by nanotube pillars of boron nitride may be a suitable material to store hydrogen fuel in cars, according to Rice University scientists.

The Department of Energy has set benchmarks for storage materials that would make hydrogen a practical fuel for light-duty vehicles. The Rice lab of materials scientist Rouzbeh Shahsavari determined in a new computational study that pillared boron nitride and graphene could be a candidate.

An Oct. 24, 2016 Rice University news release (also on EurekAlert), which originated the news item, provides more detail (Note: Links have been removed),

Shahsavari’s lab had already determined through computer models how tough and resilient pillared graphene structures would be, and later worked boron nitride nanotubes into the mix to model a unique three-dimensional architecture. (Samples of boron nitride nanotubes seamlessly bonded to graphene have been made.)

Just as pillars in a building make space between floors for people, pillars in boron nitride graphene make space for hydrogen atoms. The challenge is to make them enter and stay in sufficient numbers and exit upon demand.

In their latest molecular dynamics simulations, the researchers found that either pillared graphene or pillared boron nitride graphene would offer abundant surface area (about 2,547 square meters per gram) with good recyclable properties under ambient conditions. Their models showed adding oxygen or lithium to the materials would make them even better at binding hydrogen.

They focused the simulations on four variants: pillared structures of boron nitride or pillared boron nitride graphene doped with either oxygen or lithium. At room temperature and in ambient pressure, oxygen-doped boron nitride graphene proved the best, holding 11.6 percent of its weight in hydrogen (its gravimetric capacity) and about 60 grams per liter (its volumetric capacity); it easily beat competing technologies like porous boron nitride, metal oxide frameworks and carbon nanotubes.

At a chilly -321 degrees Fahrenheit, the material held 14.77 percent of its weight in hydrogen.

The Department of Energy’s current target for economic storage media is the ability to store more than 5.5 percent of its weight and 40 grams per liter in hydrogen under moderate conditions. The ultimate targets are 7.5 weight percent and 70 grams per liter.

Shahsavari said hydrogen atoms adsorbed to the undoped pillared boron nitride graphene, thanks to  weak van der Waals forces. When the material was doped with oxygen, the atoms bonded strongly with the hybrid and created a better surface for incoming hydrogen, which Shahsavari said would likely be delivered under pressure and would exit when pressure is released.

“Adding oxygen to the substrate gives us good bonding because of the nature of the charges and their interactions,” he said. “Oxygen and hydrogen are known to have good chemical affinity.”

He said the polarized nature of the boron nitride where it bonds with the graphene and the electron mobility of the graphene itself make the material highly tunable for applications.

“What we’re looking for is the sweet spot,” Shahsavari said, describing the ideal conditions as a balance between the material’s surface area and weight, as well as the operating temperatures and pressures. “This is only practical through computational modeling, because we can test a lot of variations very quickly. It would take experimentalists months to do what takes us only days.”

He said the structures should be robust enough to easily surpass the Department of Energy requirement that a hydrogen fuel tank be able to withstand 1,500 charge-discharge cycles.

Shayeganfar [Farzaneh Shayeganfar], a former visiting scholar at Rice, is an instructor at Shahid Rajaee Teacher Training University in Tehran, Iran.

 

Caption: Simulations by Rice University scientists show that pillared graphene boron nitride may be a suitable storage medium for hydrogen-powered vehicles. Above, the pink (boron) and blue (nitrogen) pillars serve as spacers for carbon graphene sheets (gray). The researchers showed the material worked best when doped with oxygen atoms (red), which enhanced its ability to adsorb and desorb hydrogen (white). Credit: Lei Tao/Rice University

Caption: Simulations by Rice University scientists show that pillared graphene boron nitride may be a suitable storage medium for hydrogen-powered vehicles. Above, the pink (boron) and blue (nitrogen) pillars serve as spacers for carbon graphene sheets (gray). The researchers showed the material worked best when doped with oxygen atoms (red), which enhanced its ability to adsorb and desorb hydrogen (white). Credit: Lei Tao/Rice University

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

Oxygen and Lithium Doped Hybrid Boron-Nitride/Carbon Networks for Hydrogen Storage by Farzaneh Shayeganfar and Rouzbeh Shahsavari. Langmuir,  DOI: 10.1021/acs.langmuir.6b02997 Publication Date (Web): October 23, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

I last featured research by Shayeganfar and  Shahsavari on graphene and boron nitride in a Jan. 14, 2016 posting.

Self-healing lithium-ion batteries for textiles

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It’s easy to forget how hard we are on our textiles. We rip them, step on them, agitate them in water, splatter them with mud, and more. So, what happens when we integrate batteries and electronics into them? An Oct. 20, 2016 news item on phys.org describes one of the latest ‘textile batter technologies’,

Electronics that can be embedded in clothing are a growing trend. However, power sources remain a problem. In the journal Angewandte Chemie, scientists have now introduced thin, flexible, lithium ion batteries with self-healing properties that can be safely worn on the body. Even after completely breaking apart, the battery can grow back together without significant impact on its electrochemical properties.

wiley_selfhealinglithiumionbattery

© Wiley-VCH

An Oct. 20, 2016 Wiley Angewandte Chemie International Edition press release (also on EurekAlert), which originated the news item, describes some of the problems associated with lithium-ion batteries and this new technology designed to address them,

Existing lithium ion batteries for wearable electronics can be bent and rolled up without any problems, but can break when they are twisted too far or accidentally stepped on—which can happen often when being worn. This damage not only causes the battery to fail, it can also cause a safety problem: Flammable, toxic, or corrosive gases or liquids may leak out.

A team led by Yonggang Wang and Huisheng Peng has now developed a new family of lithium ion batteries that can overcome such accidents thanks to their amazing self-healing powers. In order for a complicated object like a battery to be made self-healing, all of its individual components must also be self-healing. The scientists from Fudan University (Shanghai, China), the Samsung Advanced Institute of Technology (South Korea), and the Samsung R&D Institute China, have now been able to accomplish this.

The electrodes in these batteries consist of layers of parallel carbon nanotubes. Between the layers, the scientists embedded the necessary lithium compounds in nanoparticle form (LiMn2O4 for one electrode, LiTi2(PO4)3 for the other). In contrast to conventional lithium ion batteries, the lithium compounds cannot leak out of the electrodes, either while in use or after a break. The thin layer electrodes are each fixed on a substrate of self-healing polymer. Between the electrodes is a novel, solvent-free electrolyte made from a cellulose-based gel with an aqueous lithium sulfate solution embedded in it. This gel electrolyte also serves as a separation layer between the electrodes.

After a break, it is only necessary to press the broken ends together for a few seconds for them to grow back together. Both the self-healing polymer and the carbon nanotubes “stick” back together perfectly. The parallel arrangement of the nanotubes allows them to come together much better than layers of disordered carbon nanotubes. The electrolyte also poses no problems. Whereas conventional electrolytes decompose immediately upon exposure to air, the new gel is stable. Free of organic solvents, it is neither flammable nor toxic, making it safe for this application.

The capacity and charging/discharging properties of a battery “armband” placed around a doll’s elbow were maintained, even after repeated break/self-healing cycles.

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

A Self-Healing Aqueous Lithium-Ion Battery by Yang Zhao, Ye Zhang, Hao Sun, Xiaoli Dong, Jingyu Cao, Lie Wang, Yifan Xu, Jing Ren, Yunil Hwang, Dr. In Hyuk Son, Dr. Xianliang Huang, Prof. Yonggang Wang, and Prof. Huisheng Peng. Angewandte Chemie International Edition DOI: 10.1002/anie.201607951 Version of Record online: 12 OCT 2016

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

This paper is behind a paywall.