Tag Archives: graphene oxide

Fake graphene

Michael Berger’s October 9, 2018 Nanowerk Spotlight article about graphene brings to light a problem, which in hindsight seems obvious, fake graphene (Note: Links have been removed),

Peter Bøggild over at DTU [Technical University of Denmark] just published an interesting opinion piece in Nature titled “The war on fake graphene”.

The piece refers to a paper published in Advanced Materials (“The Worldwide Graphene Flake Production”) that studied graphene purchased from 60 producers around the world.

The study’s [“The Worldwide Graphene Flake Production”] findings show unequivocally “that the quality of the graphene produced in the world today is rather poor, not optimal for most applications, and most companies are producing graphite microplatelets. This is possibly the main reason for the slow development of graphene applications, which usually require a customized solution in terms of graphene properties.”

A conclusion that sounds even more damming is that “our extensive studies of graphene production worldwide indicate that there is almost no high quality graphene, as defined by ISO [International Organization for Standardization], in the market yet.”

The team also points out that a large number of the samples on the market labelled as graphene are actually graphene oxide and reduced graphene oxide. Furthermore, carbon content analysis shows that in many cases there is substantial contamination of the samples and a large number of companies produce material a with low carbon content. Contamination has many possible sources but most likely, it arises from the chemicals used in the processes.

Peter Bøggild’s October 8, 2018 opinion piece in Nature

Graphite is composed of layers of carbon atoms just a single atom in thickness, known as graphene sheets, to which it owes many of its remarkable properties. When the thickness of graphite flakes is reduced to just a few graphene layers, some of the material’s technologically most important characteristics are greatly enhanced — such as the total surface area per gram, and the mechanical flexibility of the individual flakes. In other words, graphene is more than just thin graphite. Unfortunately, it seems that many graphene producers either do not know or do not care about this. …

Imagine a world in which antibiotics could be sold by anybody, and were not subject to quality standards and regulations. Many people would be afraid to use them because of the potential side effects, or because they had no faith that they would work, with potentially fatal consequences. For emerging nanomaterials such as graphene, a lack of standards is creating a situation that, although not deadly, is similarly unacceptable.

It seems that the high-profile scientific discoveries, technical breakthroughs and heavy investment in graphene have created a Wild West for business opportunists: the study shows that some producers are labelling black powders that mostly contain cheap graphite as graphene, and selling them for top dollar. The problem is exacerbated because the entry barrier to becoming a graphene provider is exceptionally low — anyone can buy bulk graphite, grind it to powder and make a website to sell it on.

Nevertheless, the work [“The Worldwide Graphene Flake Production”] is a timely and ambitious example of the rigorous mindset needed to make rapid progress, not just in graphene research, but in work on any nanomaterial entering the market. To put it bluntly, there can be no quality without quality control.

Here are links to and citations for the study providing the basis for both Berger’s Spotlight article and Bøggild’s opinion piece,

The Worldwide Graphene Flake Production by Alan P. Kauling, Andressa T. Seefeldt, Diego P. Pisoni, Roshini C. Pradeep, Ricardo Bentini, Ricardo V. B. Oliveira, Konstantin S. Novoselov [emphasis mine], Antonio H. Castro Neto. Advanced Materials Volume 30, Issue 44 November 2, 2018 1803784 https://doi.org/10.1002/adma.201803784

The study which includes Konstantin Novoselov, a Nobel prize winner for his and Andre Geim’s work at the University of Manchester where they first isolated graphene, is behind a paywall.

Human lung enzyme can degrade graphene

Caption: A human lung enzyme can biodegrade graphene. Credit: Fotolia Courtesy: Graphene Flagship

The big European Commission research programme, Grahene Flagship, has announced some new work with widespread implications if graphene is to be used in biomedical implants. From a August 23, 2018 news item on ScienceDaily,

Myeloperoxidase — an enzyme naturally found in our lungs — can biodegrade pristine graphene, according to the latest discovery of Graphene Flagship partners in CNRS, University of Strasbourg (France), Karolinska Institute (Sweden) and University of Castilla-La Mancha (Spain). Among other projects, the Graphene Flagship designs based like flexible biomedical electronic devices that will interfaced with the human body. Such applications require graphene to be biodegradable, so our body can be expelled from the body.

An August 23, 2018 Grapehene Flagship press release (mildly edited version on EurekAlert), which originated the news item, provides more detail,

To test how graphene behaves within the body, researchers analysed how it was broken down with the addition of a common human enzyme – myeloperoxidase or MPO. If a foreign body or bacteria is detected, neutrophils surround it and secrete MPO, thereby destroying the threat. Previous work by Graphene Flagship partners found that MPO could successfully biodegrade graphene oxide.

However, the structure of non-functionalized graphene was thought to be more resistant to degradation. To test this, the team looked at the effects of MPO ex vivo on two graphene forms; single- and few-layer.

Alberto Bianco, researcher at Graphene Flagship Partner CNRS, explains: “We used two forms of graphene, single- and few-layer, prepared by two different methods in water. They were then taken and put in contact with myeloperoxidase in the presence of hydrogen peroxide. This peroxidase was able to degrade and oxidise them. This was really unexpected, because we thought that non-functionalized graphene was more resistant than graphene oxide.”

Rajendra Kurapati, first author on the study and researcher at Graphene Flagship Partner CNRS, remarks how “the results emphasize that highly dispersible graphene could be degraded in the body by the action of neutrophils. This would open the new avenue for developing graphene-based materials.”

With successful ex-vivo testing, in-vivo testing is the next stage. Bengt Fadeel, professor at Graphene Flagship Partner Karolinska Institute believes that “understanding whether graphene is biodegradable or not is important for biomedical and other applications of this material. The fact that cells of the immune system are capable of handling graphene is very promising.”

Prof. Maurizio Prato, the Graphene Flagship leader for its Health and Environment Work Package said that “the enzymatic degradation of graphene is a very important topic, because in principle, graphene dispersed in the atmosphere could produce some harm. Instead, if there are microorganisms able to degrade graphene and related materials, the persistence of these materials in our environment will be strongly decreased. These types of studies are needed.” “What is also needed is to investigate the nature of degradation products,” adds Prato. “Once graphene is digested by enzymes, it could produce harmful derivatives. We need to know the structure of these derivatives and study their impact on health and environment,” he concludes.

Prof. Andrea C. Ferrari, Science and Technology Officer of the Graphene Flagship, and chair of its management panel added: “The report of a successful avenue for graphene biodegradation is a very important step forward to ensure the safe use of this material in applications. The Graphene Flagship has put the investigation of the health and environment effects of graphene at the centre of its programme since the start. These results strengthen our innovation and technology roadmap.”

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

Degradation of Single‐Layer and Few‐Layer Graphene by Neutrophil Myeloperoxidase by Dr. Rajendra Kurapati, Dr. Sourav P. Mukherjee, Dr. Cristina Martín, Dr. George Bepete, Prof. Ester Vázquez, Dr. Alain Pénicaud, Prof. Dr. Bengt Fadeel, Dr. Alberto Bianco. Angewandte Chemie https://doi.org/10.1002/anie.201806906 First published: 13 July 2018

This paper is behind a paywall.

Better hair dyes with graphene and a cautionary note

Beauty products aren’t usually the first applications that come to mind when discussing graphene or any other research and development (R&D) as I learned when teaching a course a few years ago. But research and development  in that field are imperative as every company is scrambling for a short-lived competitive advantage for a truly new products or a perceived competitive advantage in a field where a lot of products are pretty much the same.

This March 15, 2018 news item on ScienceDaily describes graphene as a potential hair dye,

Graphene, a naturally black material, could provide a new strategy for dyeing hair in difficult-to-create dark shades. And because it’s a conductive material, hair dyed with graphene might also be less prone to staticky flyaways. Now, researchers have put it to the test. In an article published March 15 [2018] in the journal Chem, they used sheets of graphene to make a dye that adheres to the surface of hair, forming a coating that is resistant to at least 30 washes without the need for chemicals that open up and damage the hair cuticle.

Courtesy: Northwestern University

A March 15, 2018 Cell Press news release on EurekAlert, which originated the news item, fills in more the of the story,

Most permanent hair dyes used today are harmful to hair. “Your hair is covered in these cuticle scales like the scales of a fish, and people have to use ammonia or organic amines to lift the scales and allow dye molecules to get inside a lot quicker,” says senior author Jiaxing Huang, a materials scientist at Northwestern University. But lifting the cuticle makes the strands of the hair more brittle, and the damage is only exacerbated by the hydrogen peroxide that is used to trigger the reaction that synthesizes the dye once the pigment molecules are inside the hair.

These problems could theoretically be solved by a dye that coats rather than penetrates the hair. “However, the obvious problem of coating-based dyes is that they tend to wash out very easily,” says Huang. But when he and his team coated samples of human hair with a solution of graphene sheets, they were able to turn platinum blond hair black and keep it that way for at least 30 washes–the number necessary for a hair dye to be considered “permanent.”

This effectiveness has to do with the structure of graphene: it’s made of up thin, flexible sheets that can adapt to uneven surfaces. “Imagine a piece of paper. A business card is very rigid and doesn’t flex by itself. But if you take a much bigger sheet of newspaper–if you still can find one nowadays–it can bend easily. This makes graphene sheets a good coating material,” he says. And once the coating is formed, the graphene sheets are particularly good at keeping out water during washes, which keeps the water from eroding both the graphene and the polymer binder that the team also added to the dye solution to help with adhesion.

The graphene dye has additional advantages. Each coated hair is like a little wire in that it is able to conduct heat and electricity. This means that it’s easy for graphene-dyed hair to dissipate static electricity, eliminating the problem of flyaways on dry winter days. The graphene flakes are large enough that they won’t absorb through the skin like other dye molecules. And although graphene is typically black, its precursor, graphene oxide, is light brown. But the color of graphene oxide can be gradually darkened with heat or chemical reactions, meaning that this dye could be used for a variety of shades or even for an ombre effect.

What Huang thinks is particularly striking about this application of graphene is that it takes advantage of graphene’s most obvious property. “In many potential graphene applications, the black color of graphene is somewhat undesirable and something of a sore point,” he says. Here, though, it’s applied to a field where creating dark colors has historically been a problem.

The graphene used for hair dye also doesn’t need to be of the same high quality as it does for other applications. “For hair dye, the most important property is graphene being black. You can have graphene that is too lousy for higher-end electronic applications, but it’s perfectly okay for this. So I think this application can leverage the current graphene product as is, and that’s why I think that this could happen a lot sooner than many of the other proposed applications,” he says.

Making it happen is his next goal. He hopes to get funding to continue the research and make these dyes a reality for the people whose lives they would improve. “This is an idea that was inspired by curiosity. It was very fun to do, but it didn’t sound very big and noble when we started working on it,” he says. “But after we deep-dived into studying hair dyes, we realized that, wow, this is actually not at all a small problem. And it’s one that graphene could really help to solve.”

Northwestern University’s Amanda Morris also wrote a March 15, 2018 news release (it’s repetitive but there are some interesting new details; Note: Links have been removed),

It’s an issue that has plagued the beauty industry for more than a century: Dying hair too often can irreparably damage your silky strands.

Now a Northwestern University team has used materials science to solve this age-old problem. The team has leveraged super material graphene to develop a new hair dye that is less harmful [emphasis mine], non-damaging and lasts through many washes without fading. Graphene’s conductive nature also opens up new opportunities for hair, such as turning it into in situ electrodes or integrating it with wearable electronic devices.

Dying hair might seem simple and ordinary, but it’s actually a sophisticated chemical process. Called the cuticle, the outermost layer of a hair is made of cells that overlap in a scale-like pattern. Commercial dyes work by using harsh chemicals, such as ammonia and bleach, to first pry open the cuticle scales to allow colorant molecules inside and then trigger a reaction inside the hair to produce more color. Not only does this process cause hair to become more fragile, some of the small molecules are also quite toxic.

Huang and his team bypassed harmful chemicals altogether by leveraging the natural geometry of graphene sheets. While current hair dyes use a cocktail of small molecules that work by chemically altering the hair, graphene sheets are soft and flexible, so they wrap around each hair for an even coat. Huang’s ink formula also incorporates edible, non-toxic polymer binders to ensure that the graphene sticks — and lasts through at least 30 washes, which is the commercial requirement for permanent hair dye. An added bonus: graphene is anti-static, so it keeps winter-weather flyaways to a minimum.

“It’s similar to the difference between a wet paper towel and a tennis ball,” Huang explained, comparing the geometry of graphene to that of other black pigment particles, such as carbon black or iron oxide, which can only be used in temporary hair dyes. “The paper towel is going to wrap and stick much better. The ball-like particles are much more easily removed with shampoo.”

This geometry also contributes to why graphene is a safer alternative. Whereas small molecules can easily be inhaled or pass through the skin barrier, graphene is too big to enter the body. “Compared to those small molecules used in current hair dyes, graphene flakes are humongous,” said Huang, who is a member of Northwestern’s International Institute of Nanotechnology.

Ever since graphene — the two-dimensional network of carbon atoms — burst onto the science scene in 2004, the possibilities for the promising material have seemed nearly endless. With its ultra-strong and lightweight structure, graphene has potential for many applications in high-performance electronics, high-strength materials and energy devices. But development of those applications often require graphene materials to be as structurally perfect as possible in order to achieve extraordinary electrical, mechanical or thermal properties.

The most important graphene property for Huang’s hair dye, however, is simply its color: black. So Huang’s team used graphene oxide, an imperfect version of graphene that is a cheaper, more available oxidized derivative.

“Our hair dye solves a real-world problem without relying on very high-quality graphene, which is not easy to make,” Huang said. “Obviously more work needs to be done, but I feel optimistic about this application.”

Still, future versions of the dye could someday potentially leverage graphene’s notable properties, including its highly conductive nature.

“People could apply this dye to make hair conductive on the surface,” Huang said. “It could then be integrated with wearable electronics or become a conductive probe. We are only limited by our imagination.”

So far, Huang has developed graphene-based hair dyes in multiple shades of brown and black. Next, he plans to experiment with more colors.

Interestingly, the tiny note of caution”less harmful” doesn’t appear in the Cell Press news release. Never fear, Dr. Andrew Maynard (Director Risk Innovation Lab at Arizona State University) has written a March 20, 2018 essay on The Conversation suggesting a little further investigation (Note: Links have been removed),

Northwestern University’s press release proudly announced, “Graphene finds new application as nontoxic, anti-static hair dye.” The announcement spawned headlines like “Enough with the toxic hair dyes. We could use graphene instead,” and “’Miracle material’ graphene used to create the ultimate hair dye.”

From these headlines, you might be forgiven for getting the idea that the safety of graphene-based hair dyes is a done deal. Yet having studied the potential health and environmental impacts of engineered nanomaterials for more years than I care to remember, I find such overly optimistic pronouncements worrying – especially when they’re not backed up by clear evidence.

Tiny materials, potentially bigger problems

Engineered nanomaterials like graphene and graphene oxide (the particular form used in the dye experiments) aren’t necessarily harmful. But nanomaterials can behave in unusual ways that depend on particle size, shape, chemistry and application. Because of this, researchers have long been cautious about giving them a clean bill of health without first testing them extensively. And while a large body of research to date doesn’t indicate graphene is particularly dangerous, neither does it suggest it’s completely safe.

A quick search of scientific papers over the past few years shows that, since 2004, over 2,000 studies have been published that mention graphene toxicity; nearly 500 were published in 2017 alone.

This growing body of research suggests that if graphene gets into your body or the environment in sufficient quantities, it could cause harm. A 2016 review, for instance, indicated that graphene oxide particles could result in lung damage at high doses (equivalent to around 0.7 grams of inhaled material). Another review published in 2017 suggested that these materials could affect the biology of some plants and algae, as well as invertebrates and vertebrates toward the lower end of the ecological pyramid. The authors of the 2017 study concluded that research “unequivocally confirms that graphene in any of its numerous forms and derivatives must be approached as a potentially hazardous material.”

These studies need to be approached with care, as the precise risks of graphene exposure will depend on how the material is used, how exposure occurs and how much of it is encountered. Yet there’s sufficient evidence to suggest that this substance should be used with caution – especially where there’s a high chance of exposure or that it could be released into the environment.

Unfortunately, graphene-based hair dyes tick both of these boxes. Used in this way, the substance is potentially inhalable (especially with spray-on products) and ingestible through careless use. It’s also almost guaranteed that excess graphene-containing dye will wash down the drain and into the environment.

Undermining other efforts?

I was alerted to just how counterproductive such headlines can be by my colleague Tim Harper, founder of G2O Water Technologies – a company that uses graphene oxide-coated membranes to treat wastewater. Like many companies in this area, G2O has been working to use graphene responsibly by minimizing the amount of graphene that ends up released to the environment.

Yet as Tim pointed out to me, if people are led to believe “that bunging a few grams of graphene down the drain every time you dye your hair is OK, this invalidates all the work we are doing making sure the few nanograms of graphene on our membranes stay put.” Many companies that use nanomaterials are trying to do the right thing, but it’s hard to justify the time and expense of being responsible when someone else’s more cavalier actions undercut your efforts.

Overpromising results and overlooking risk

This is where researchers and their institutions need to move beyond an “economy of promises” that spurs on hyperbole and discourages caution, and think more critically about how their statements may ultimately undermine responsible and beneficial development of a technology. They may even want to consider using guidelines, such as the Principles for Responsible Innovation developed by the organization Society Inside, for instance, to guide what they do and say.

If you have time, I encourage you to read Andrew’s piece in its entirety.

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

Multifunctional Graphene Hair Dye by Chong Luo, Lingye Zhou, Kevin Chiou, and Jiaxing Huang. Chem DOI: https://doi.org/10.1016/j.chempr.2018.02.02 Publication stage: In Press Corrected Proof

This paper appears to be open access.

*Two paragraphs (repetitions) were deleted from the excerpt of Dr. Andrew Maynard’s essay on August 14, 2018

Gamechanging electronics with new ultrafast, flexible, and transparent electronics

There are two news bits about game-changing electronics, one from the UK and the other from the US.

United Kingdom (UK)

An April 3, 2017 news item on Azonano announces the possibility of a future golden age of electronics courtesy of the University of Exeter,

Engineering experts from the University of Exeter have come up with a breakthrough way to create the smallest, quickest, highest-capacity memories for transparent and flexible applications that could lead to a future golden age of electronics.

A March 31, 2017 University of Exeter press release (also on EurekAlert), which originated the news item, expands on the theme (Note: Links have been removed),

Engineering experts from the University of Exeter have developed innovative new memory using a hybrid of graphene oxide and titanium oxide. Their devices are low cost and eco-friendly to produce, are also perfectly suited for use in flexible electronic devices such as ‘bendable’ mobile phone, computer and television screens, and even ‘intelligent’ clothing.

Crucially, these devices may also have the potential to offer a cheaper and more adaptable alternative to ‘flash memory’, which is currently used in many common devices such as memory cards, graphics cards and USB computer drives.

The research team insist that these innovative new devices have the potential to revolutionise not only how data is stored, but also take flexible electronics to a new age in terms of speed, efficiency and power.

Professor David Wright, an Electronic Engineering expert from the University of Exeter and lead author of the paper said: “Using graphene oxide to produce memory devices has been reported before, but they were typically very large, slow, and aimed at the ‘cheap and cheerful’ end of the electronics goods market.

“Our hybrid graphene oxide-titanium oxide memory is, in contrast, just 50 nanometres long and 8 nanometres thick and can be written to and read from in less than five nanoseconds – with one nanometre being one billionth of a metre and one nanosecond a billionth of a second.”

Professor Craciun, a co-author of the work, added: “Being able to improve data storage is the backbone of tomorrow’s knowledge economy, as well as industry on a global scale. Our work offers the opportunity to completely transform graphene-oxide memory technology, and the potential and possibilities it offers.”

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

Multilevel Ultrafast Flexible Nanoscale Nonvolatile Hybrid Graphene Oxide–Titanium Oxide Memories by V. Karthik Nagareddy, Matthew D. Barnes, Federico Zipoli, Khue T. Lai, Arseny M. Alexeev, Monica Felicia Craciun, and C. David Wright. ACS Nano, 2017, 11 (3), pp 3010–3021 DOI: 10.1021/acsnano.6b08668 Publication Date (Web): February 21, 2017

Copyright © 2017 American Chemical Society

This paper appears to be open access.

United States (US)

Researchers from Stanford University have developed flexible, biodegradable electronics.

A newly developed flexible, biodegradable semiconductor developed by Stanford engineers shown on a human hair. (Image credit: Bao lab)

A human hair? That’s amazing and this May 3, 2017 news item on Nanowerk reveals more,

As electronics become increasingly pervasive in our lives – from smart phones to wearable sensors – so too does the ever rising amount of electronic waste they create. A United Nations Environment Program report found that almost 50 million tons of electronic waste were thrown out in 2017–more than 20 percent higher than waste in 2015.

Troubled by this mounting waste, Stanford engineer Zhenan Bao and her team are rethinking electronics. “In my group, we have been trying to mimic the function of human skin to think about how to develop future electronic devices,” Bao said. She described how skin is stretchable, self-healable and also biodegradable – an attractive list of characteristics for electronics. “We have achieved the first two [flexible and self-healing], so the biodegradability was something we wanted to tackle.”

The team created a flexible electronic device that can easily degrade just by adding a weak acid like vinegar. The results were published in the Proceedings of the National Academy of Sciences (“Biocompatible and totally disintegrable semiconducting polymer for ultrathin and ultralightweight transient electronics”).

“This is the first example of a semiconductive polymer that can decompose,” said lead author Ting Lei, a postdoctoral fellow working with Bao.

A May 1, 2017 Stanford University news release by Sarah Derouin, which originated the news item, provides more detail,

In addition to the polymer – essentially a flexible, conductive plastic – the team developed a degradable electronic circuit and a new biodegradable substrate material for mounting the electrical components. This substrate supports the electrical components, flexing and molding to rough and smooth surfaces alike. When the electronic device is no longer needed, the whole thing can biodegrade into nontoxic components.

Biodegradable bits

Bao, a professor of chemical engineering and materials science and engineering, had previously created a stretchable electrode modeled on human skin. That material could bend and twist in a way that could allow it to interface with the skin or brain, but it couldn’t degrade. That limited its application for implantable devices and – important to Bao – contributed to waste.

Flexible, biodegradable semiconductor on an avacado

The flexible semiconductor can adhere to smooth or rough surfaces and biodegrade to nontoxic products. (Image credit: Bao lab)

Bao said that creating a robust material that is both a good electrical conductor and biodegradable was a challenge, considering traditional polymer chemistry. “We have been trying to think how we can achieve both great electronic property but also have the biodegradability,” Bao said.

Eventually, the team found that by tweaking the chemical structure of the flexible material it would break apart under mild stressors. “We came up with an idea of making these molecules using a special type of chemical linkage that can retain the ability for the electron to smoothly transport along the molecule,” Bao said. “But also this chemical bond is sensitive to weak acid – even weaker than pure vinegar.” The result was a material that could carry an electronic signal but break down without requiring extreme measures.

In addition to the biodegradable polymer, the team developed a new type of electrical component and a substrate material that attaches to the entire electronic component. Electronic components are usually made of gold. But for this device, the researchers crafted components from iron. Bao noted that iron is a very environmentally friendly product and is nontoxic to humans.

The researchers created the substrate, which carries the electronic circuit and the polymer, from cellulose. Cellulose is the same substance that makes up paper. But unlike paper, the team altered cellulose fibers so the “paper” is transparent and flexible, while still breaking down easily. The thin film substrate allows the electronics to be worn on the skin or even implanted inside the body.

From implants to plants

The combination of a biodegradable conductive polymer and substrate makes the electronic device useful in a plethora of settings – from wearable electronics to large-scale environmental surveys with sensor dusts.

“We envision these soft patches that are very thin and conformable to the skin that can measure blood pressure, glucose value, sweat content,” Bao said. A person could wear a specifically designed patch for a day or week, then download the data. According to Bao, this short-term use of disposable electronics seems a perfect fit for a degradable, flexible design.

And it’s not just for skin surveys: the biodegradable substrate, polymers and iron electrodes make the entire component compatible with insertion into the human body. The polymer breaks down to product concentrations much lower than the published acceptable levels found in drinking water. Although the polymer was found to be biocompatible, Bao said that more studies would need to be done before implants are a regular occurrence.

Biodegradable electronics have the potential to go far beyond collecting heart disease and glucose data. These components could be used in places where surveys cover large areas in remote locations. Lei described a research scenario where biodegradable electronics are dropped by airplane over a forest to survey the landscape. “It’s a very large area and very hard for people to spread the sensors,” he said. “Also, if you spread the sensors, it’s very hard to gather them back. You don’t want to contaminate the environment so we need something that can be decomposed.” Instead of plastic littering the forest floor, the sensors would biodegrade away.

As the number of electronics increase, biodegradability will become more important. Lei is excited by their advancements and wants to keep improving performance of biodegradable electronics. “We currently have computers and cell phones and we generate millions and billions of cell phones, and it’s hard to decompose,” he said. “We hope we can develop some materials that can be decomposed so there is less waste.”

Other authors on the study include Ming Guan, Jia Liu, Hung-Cheng Lin, Raphael Pfattner, Leo Shaw, Allister McGuire, and Jeffrey Tok of Stanford University; Tsung-Ching Huang of Hewlett Packard Enterprise; and Lei-Lai Shao and Kwang-Ting Cheng of University of California, Santa Barbara.

The research was funded by the Air Force Office for Scientific Research; BASF; Marie Curie Cofund; Beatriu de Pinós fellowship; and the Kodak Graduate Fellowship.

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

Biocompatible and totally disintegrable semiconducting polymer for ultrathin and ultralightweight transient electronics by Ting Lei, Ming Guan, Jia Liu, Hung-Cheng Lin, Raphael Pfattner, Leo Shaw, Allister F. McGuire, Tsung-Ching Huang, Leilai Shao, Kwang-Ting Cheng, Jeffrey B.-H. Tok, and Zhenan Bao. PNAS 2017 doi: 10.1073/pnas.1701478114 published ahead of print May 1, 2017

This paper is behind a paywall.

The mention of cellulose in the second item piqued my interest so I checked to see if they’d used nanocellulose. No, they did not. Microcrystalline cellulose powder was used to constitute a cellulose film but they found a way to render this film at the nanoscale. From the Stanford paper (Note: Links have been removed),

… Moreover, cellulose films have been previously used as biodegradable substrates in electronics (28⇓–30). However, these cellulose films are typically made with thicknesses well over 10 μm and thus cannot be used to fabricate ultrathin electronics with substrate thicknesses below 1–2 μm (7, 18, 19). To the best of our knowledge, there have been no reports on ultrathin (1–2 μm) biodegradable substrates for electronics. Thus, to realize them, we subsequently developed a method described herein to obtain ultrathin (800 nm) cellulose films (Fig. 1B and SI Appendix, Fig. S8). First, microcrystalline cellulose powders were dissolved in LiCl/N,N-dimethylacetamide (DMAc) and reacted with hexamethyldisilazane (HMDS) (31, 32), providing trimethylsilyl-functionalized cellulose (TMSC) (Fig. 1B). To fabricate films or devices, TMSC in chlorobenzene (CB) (70 mg/mL) was spin-coated on a thin dextran sacrificial layer. The TMSC film was measured to be 1.2 μm. After hydrolyzing the film in 95% acetic acid vapor for 2 h, the trimethylsilyl groups were removed, giving a 400-nm-thick cellulose film. The film thickness significantly decreased to one-third of the original film thickness, largely due to the removal of the bulky trimethylsilyl groups. The hydrolyzed cellulose film is insoluble in most organic solvents, for example, toluene, THF, chloroform, CB, and water. Thus, we can sequentially repeat the above steps to obtain an 800-nm-thick film, which is robust enough for further device fabrication and peel-off. By soaking the device in water, the dextran layer is dissolved, starting from the edges of the device to the center. This process ultimately releases the ultrathin substrate and leaves it floating on water surface (Fig. 3A, Inset).

Finally, I don’t have any grand thoughts; it’s just interesting to see different approaches to flexible electronics.

Graphene in the bone

An international team of US, Brazilian, and Indian scientists has developed a graphene-based material they believe could be used in bone implants. From a Sept. 2, 2016 news item on ScienceDaily,

Flakes of graphene welded together into solid materials may be suitable for bone implants, according to a study led by Rice University scientists.

The Rice lab of materials scientist Pulickel Ajayan and colleagues in Texas, Brazil and India used spark plasma sintering to weld flakes of graphene oxide into porous solids that compare favorably with the mechanical properties and biocompatibility of titanium, a standard bone-replacement material.

A Sept. 2, 2016 Rice University news release (also on EurekAlert), which originated the news item, explains the work in more detail,

The researchers believe their technique will give them the ability to create highly complex shapes out of graphene in minutes using graphite molds, which they believe would be easier to process than specialty metals.

“We started thinking about this for bone implants because graphene is one of the most intriguing materials with many possibilities and it’s generally biocompatible,” said Rice postdoctoral research associate Chandra Sekhar Tiwary, co-lead author of the paper with Dibyendu Chakravarty of the International Advanced Research Center for Powder Metallurgy and New Materials in Hyderabad, India. “Four things are important: its mechanical properties, density, porosity and biocompatibility.”

Tiwary said spark plasma sintering is being used in industry to make complex parts, generally with ceramics. “The technique uses a high pulse current that welds the flakes together instantly. You only need high voltage, not high pressure or temperatures,” he said. The material they made is nearly 50 percent porous, with a density half that of graphite and a quarter of titanium metal. But it has enough compressive strength — 40 megapascals — to qualify it for bone implants, he said. The strength of the bonds between sheets keeps it from disintegrating in water.

The researchers controlled the density of the material by altering the voltage that delivers the highly localized blast of heat that makes the nanoscale welds. Though the experiments were carried out at room temperature, the researchers made graphene solids of various density by raising these sintering temperatures from 200 to 400 degrees Celsius. Samples made at local temperatures of 300 C proved best, Tiwary said. “The nice thing about two-dimensional materials is that they give you a lot of surface area to connect. With graphene, you just need to overcome a small activation barrier to make very strong welds,” he said.

With the help of colleagues at Hysitron in Minnesota, the researchers measured the load-bearing capacity of thin sheets of two- to five-layer bonded graphene by repeatedly stressing them with a picoindenter attached to a scanning electron microscope and found they were stable up to 70 micronewtons. Colleagues at the University of Texas MD Anderson Cancer Center successfully cultured cells on the material to show its biocompatibility. As a bonus, the researchers also discovered the sintering process has the ability to reduce graphene oxide flakes to pure bilayer graphene, which makes them stronger and more stable than graphene monolayers or graphene oxide.

“This example demonstrates the possible use of unconventional materials in conventional technologies,” Ajayan said. “But these transitions can only be made if materials such as 2-D graphene layers can be scalably made into 3-D solids with appropriate density and strength.

“Engineering junctions and strong interfaces between nanoscale building blocks is the biggest challenge in achieving such goals, but in this case, spark plasma sintering seems to be effective in joining graphene sheets to produce strong 3-D solids,” he said.

The researchers have produced an animation depicting of graphene oxide layers being stacked,

A molecular dynamics simulation shows how graphene oxide layers stack when welded by spark plasma sintering. The presence of oxygen molecules at left prevents the graphene layers from bonding, as they do without oxygen at right. Courtesy of the Ajayan and Galvão groups

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

3D Porous Graphene by Low-Temperature Plasma Welding for Bone Implants by Dibyendu Chakravarty, Chandra Sekhar Tiwary, Cristano F. Woellner, Sruthi Radhakrishnan4, Soumya Vinod, Sehmus Ozden, Pedro Alves da Silva Autreto, Sanjit Bhowmick, Syed Asif, Sendurai A Mani, Douglas S. Galvao, and Pulickel M. Ajayan. Advanced Materials DOI: 10.1002/adma.201603146 Version of Record online: 26 AUG 2016

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

This paper is behind a paywall.

Cute, adorable roundworms help measure nanoparticle toxicity

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Nanomaterial effects on C. elegans

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

Clicking on colored blocks to see detailed experimental data.

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

Graphene and radioactive waste

In fact, the material in question is graphene oxide and researchers at Rice University (Texas) and Lomonosov Moscow State University have found that it can rapidly remove radioactive material from water  From the Jan. 8, 2013 news item on ScienceDaily,

A collaborative effort by the Rice lab of chemist James Tour and the Moscow lab of chemist Stepan Kalmykov determined that microscopic, atom-thick flakes of graphene oxide bind quickly to natural and human-made radionuclides and condense them into solids. The flakes are soluble in liquids and easily produced in bulk.

The Rice University Jan. 8, 2013 news release, which originated the news item, was written by Mike Williams and provides additional insight and quotes from the researchers (Note: Links have been removed),

The discovery, Tour said, could be a boon in the cleanup of contaminated sites like the Fukushima nuclear plants damaged by the 2011 earthquake and tsunami. It could also cut the cost of hydraulic fracturing (“fracking”) for oil and gas recovery and help reboot American mining of rare earth metals, he said.

Graphene oxide’s large surface area defines its capacity to adsorb toxins, Kalmykov said. “So the high retention properties are not surprising to us,” he said. “What is astonishing is the very fast kinetics of sorption, which is key.”

“In the probabilistic world of chemical reactions where scarce stuff (low concentrations) infrequently bumps into something with which it can react, there is a greater likelihood that the ‘magic’ will happen with graphene oxide than with a big old hunk of bentonite,” said Steven Winston, a former vice president of Lockheed Martin and Parsons Engineering and an expert in nuclear power and remediation who is working with the researchers. “In short, fast is good.”

Here’s how it works (from the news release; Note: Links have been removed),

The researchers focused on removing radioactive isotopes of the actinides  and lanthanides  – the 30 rare earth elements in the periodic table – from liquids, rather than solids or gases. “Though they don’t really like water all that much, they can and do hide out there,” Winston said. “From a human health and environment point of view, that’s where they’re least welcome.”

Naturally occurring radionuclides are also unwelcome in fracking fluids that bring them to the surface in drilling operations, Tour said. “When groundwater comes out of a well and it’s radioactive above a certain level, they can’t put it back into the ground,” he said. “It’s too hot. Companies have to ship contaminated water to repository sites around the country at very large expense.” The ability to quickly filter out contaminants on-site would save a great deal of money, he said.

He sees even greater potential benefits for the mining industry. Environmental requirements have “essentially shut down U.S. mining of rare earth metals, which are needed for cell phones,” Tour said. “China owns the market because they’re not subject to the same environmental standards. So if this technology offers the chance to revive mining here, it could be huge.”

Tour said that capturing radionuclides does not make them less radioactive, just easier to handle. “Where you have huge pools of radioactive material, like at Fukushima, you add graphene oxide and get back a solid material from what were just ions in a solution,” he said. “Then you can skim it off and burn it. Graphene oxide burns very rapidly and leaves a cake of radioactive material you can then reuse.”

The low cost and biodegradable qualities of graphene oxide should make it appropriate for use in permeable reactive barriers, a fairly new technology for in situ groundwater remediation, he said.

Romanchuk, Slesarev, Kalmykov and Tour are co-authors of the paper with Dmitry Kosynkin, a former postdoctoral researcher at Rice, now with Saudi Aramco. Kalmykov is radiochemistry division head and a professor at Lomonosov Moscow State University. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science at Rice.

Here’s a ‘before’ shot of solution with graphene oxide and an ‘after’ shot where radionuclides have been added and begun to clump,

A new method for removing radioactive material from solutions is the result of collaboration between Rice University and Lomonosov Moscow State University. The vial at left holds microscopic particles of graphene oxide in a solution. At right, graphene oxide is added to simulated nuclear waste, which quickly clumps for easy removal. Image by Anna Yu. Romanchuk/Lomonosov Moscow State University

A new method for removing radioactive material from solutions is the result of collaboration between Rice University and Lomonosov Moscow State University. The vial at left holds microscopic particles of graphene oxide in a solution. At right, graphene oxide is added to simulated nuclear waste, which quickly clumps for easy removal. Image by Anna Yu. Romanchuk/Lomonosov Moscow State University

As noted in the ScienceDaily news item, the research has been published in the Royal Society’s Physical Chemistry Chemical Physics journal,

Anna Yu. Romanchuk, Alexander Slesarev, Stepan N. Kalmykov, Dmitry Kosynkin, James M Tour. Graphene Oxide for Effective Radionuclide Removal. Physical Chemistry Chemical Physics, 2012; DOI: 10.1039/C2CP44593J

This article is behind a paywall.