Tag Archives: biodegradable

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.

Nontoxic, biodegradable orthopedic implant for damaged bones

Unlike most of the science items on phys.org this April 14, 2017 news item is not a publication announcement,

Purdue University researchers are developing a nontoxic, biodegradable orthopedic implant that could be safely absorbed by the body after providing adequate support to damaged bones.

The development of the technology originated in the lab of Lia Stanciu, a professor of materials engineering at Purdue in 2009. The technology could eliminate the need for a second surgery to remove conventional hardware.

“Currently, most implants use stainless steel and titanium alloys for strength. This can cause long-term change in the mechanics of the specific region and eventual long-term deterioration,” Stanciu said. “Additionally medical operations that require an orthopedic implant must be followed-up with a second surgery to remove the implant or the accompanying hardware of the implant resulting in higher medical costs and an increased risk of complications.”

An April 13, 2017 Purdue University news release, which originated the news item, provides a bit more detail and a hint as to what may have occasioned the news release,

Co-inventors of the technology are Stanciu; Eric Nauman, a professor in Purdue’s College of Engineering and director of the College of Engineering Honors Programs; Michael J Heiden, a PhD candidate; and Mahdi Dehestani, a graduate research assistant, both in Purdue’s School of Materials Engineering.

Nauman said the resorbable metal technology provides superior properties compared to conventional metals.

“The implant has high porosity, which is empty space in the material, in which optimal vascular invasion can occur. This provides a way for cells to optimally absorb the material,” he said. “Our technology is able to provide short-term fixation but eliminate the need for long-term hardware such as titanium or stainless steel that may require second surgeries to be retrieved,”

The orthopedic implant also uses manganese, which provides a better degradation rate, Stanciu added.

“Current resorbable metals are made with magnesium; however, this provides many adverse side effects to the body and degrades very quickly,” she said. “We decided to use manganese instead of magnesium. Through studies we found that we can control the degradation rates from 22 millimeters per year to 1.2 millimeters per year pretty consistently. We also saw that manganese has a very good corrosion rate over time.”

Nauman said the technology still exhibits the usual benefits associated with using biomaterials.

“With this technology we are able to tailor the surfaces such as de-alloying the surface to provide a better material for cells to grab on to and grow,” he said. “We were also able to show that we could control cell attachment proliferation, an increase of the number of cells. Our technology still has all these usual benefits in addition to controlling the degradation rates of the metals.”

The Purdue Research Foundation’s Office of Technology Commercialization has patented the technology and it is available for license. For information call 765-588-3470 or email innovation@prf.org.

I believe they’re looking for a commercial partner of some kind.

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.

Antibiotic synthetic spider silk

I have a couple of questions, what is ‘click’ chemistry and how does a chance meeting lead to a five-year, interdisciplinary research project on synthetic spider silk? From a Jan. 4, 2017 news item on ScienceDaily,

A chance meeting between a spider expert and a chemist has led to the development of antibiotic synthetic spider silk.

After five years’ work an interdisciplinary team of scientists at The University of Nottingham has developed a technique to produce chemically functionalised spider silk that can be tailored to applications used in drug delivery, regenerative medicine and wound healing.

The Nottingham research team has shown for the first time how ‘click-chemistry’ can be used to attach molecules, such as antibiotics or fluorescent dyes, to artificially produced spider silk synthesised by E.coli bacteria. The research, funded by the Biotechnology and Biological Sciences Research Council (BBSRC) is published today in the online journal Advanced Materials.

A Jan. 3, 2016 University of Nottingham press release (also on EurekAlert), which originated the news item, provides a few more details about ‘click’ chemistry (not enough for me) and more information about the research,

The chosen molecules can be ‘clicked’ into place in soluble silk protein before it has been turned into fibres, or after the fibres have been formed. This means that the process can be easily controlled and more than one type of molecule can be used to ‘decorate’ individual silk strands.

Nottingham breakthrough

In a laboratory in the Centre of Biomolecular Sciences, Professor Neil Thomas from the School of Chemistry in collaboration with Dr Sara Goodacre from the School of Life Sciences, has led a team of BBSRC DTP-funded PhD students starting with David Harvey who was then joined by Victor Tudorica, Leah Ashley and Tom Coekin. They have developed and diversified this new approach to functionalising ‘recombinant’ — artificial — spider silk with a wide range of small molecules.

They have shown that when these ‘silk’ fibres are ‘decorated’ with the antibiotic levofloxacin it is slowly released from the silk, retaining its anti-bacterial activity for at least five days.

Neil Thomas, a Professor of Medicinal and Biological Chemistry, said: “Our technique allows the rapid generation of biocompatible, mono or multi-functionalised silk structures for use in a wide range of applications. These will be particularly useful in the fields of tissue engineering and biomedicine.”

Remarkable qualities of spider silk

Spider silk is strong, biocompatible and biodegradable. It is a protein-based material that does not appear to cause a strong immune, allergic or inflammatory reaction. With the recent development of recombinant spider silk, the race has been on to find ways of harnessing its remarkable qualities.

The Nottingham research team has shown that their technique can be used to create a biodegradable mesh which can do two jobs at once. It can replace the extra cellular matrix that our own cells generate, to accelerate growth of the new tissue. It can also be used for the slow release of antibiotics.

Professor Thomas said: “There is the possibility of using the silk in advanced dressings for the treatment of slow-healing wounds such as diabetic ulcers. Using our technique infection could be prevented over weeks or months by the controlled release of antibiotics. At the same time tissue regeneration is accelerated by silk fibres functioning as a temporary scaffold before being biodegraded.”

The medicinal properties of spider silk recognised for centuries.

The medicinal properties of spider silk have been recognised for centuries but not clearly understood. The Greeks and Romans treated wounded soldiers with spider webs to stop bleeding. It is said that soldiers would use a combination of honey and vinegar to clean deep wounds and then cover the whole thing with balled-up spider webs.

There is even a mention in Shakespeare’s Midsummer Night’s Dream: “I shall desire you of more acquaintance, good master cobweb,” the character ‘Bottom’ said. “If I cut my finger, I shall make bold of you.”

The press release goes on to describe the genesis of the project and how this multidisciplinary team was formed in more detail,

The idea came together at a discipline bridging university ‘sandpit’ meeting five years ago. Dr Goodacre says her chance meeting at that event with Professor Thomas proved to be one of the most productive afternoons of her career.

Dr Goodacre, who heads up the SpiderLab in the School of Life Sciences, said: “I got up at that meeting and showed the audience a picture of some spider silk. I said ‘I want to understand how this silk works, and then make some.’

“At the end of the session Neil came up to me and said ‘I think my group could make that.’ He also suggested that there might be more interesting ‘tweaks’ one could make so that the silk could be ‘decorated’ with different, useful, compounds either permanently or which could be released over time due to a change in the acidity of the environment.”

The approach required the production of the silk proteins in a bacterium where an amino acid not normally found in proteins was included. This amino acid contained an azide group which is widely used in ‘click’ reactions that only occur at that position in the protein. It was an approach that no-one had used before with spider silk — but the big question was — would it work?

Dr Goodacre said: “It was the start of a fascinating adventure that saw a postdoc undertake a very preliminary study to construct the synthetic silks. He was a former SpiderLab PhD student who had previously worked with our tarantulas. Thanks to his ground work we showed we could produce the silk proteins in bacteria. We were then joined by David Harvey, a new PhD student, who not only made the silk fibres, incorporating the unusual amino acid, but also decorated it and demonstrated its antibiotic activity. He has since extended those first ideas far beyond what we had thought might be possible.”

David Harvey’s work is described in this paper but Professor Thomas and Dr Goodacre say this is just the start. There are other joint SpiderLab/Thomas lab students working on uses for this technology in the hope of developing it further.

David Harvey, the lead author on this their first paper, has just been awarded his PhD and is now a postdoctoral researcher on a BBSRC follow-on grant so is still at the heart of the research. His current work is focused on driving the functionalised spider silk technology towards commercial application in wound healing and tissue regeneration.

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

Antibiotic Spider Silk: Site-Specific Functionalization of Recombinant Spider Silk Using “Click” Chemistry by David Harvey, Philip Bardelang, Sara L. Goodacre, Alan Cockayne, and Neil R. Thomas. Advanced Materials DOI: 10.1002/adma.201604245 Version of Record online: 28 DEC 2016

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

This paper is behind a paywall.

I imagine Mr. Cockayne’s name has led to much teasing over the years. People who have names with that kind of potential tend to either change them or double down and refuse to compromise.