Tag Archives: Sweden

A new, stable open-shell carbon molecule from Oregon

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

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

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

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

 

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

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

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

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

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

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

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

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

This paper is behind a paywall.

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

Implications of nanoplastic in the aquatic food chain

As plastic breaks down in the oceans into plastic nanoparticles, they enter the food chain when they are ingested by plankton. Researchers in Sweden have published a study about the process. From a May 23, 2016 news item on ScienceDaily,

Plastic accounts for nearly eighty per cent of all waste found in our oceans, gradually breaking down into smaller and smaller particles. New research from Lund University in Sweden investigates how nanosized plastic particles affect aquatic animals in different parts of the food chain.

“Not very many studies have been done on this topic before. Plastic particles of such a small size are difficult to study,” says Karin Mattsson.

A May 23, 2016 Lund University press release, which originated the news item, provides more detail,

“We tested how polystyrene plastic particles of different sizes, charge and surface affect the zooplankton Daphnia. It turned out that the size of the nanoparticles that were most toxic to the Daphnia in our study was 50 nanometers”, says Karin Mattsson.

Because zooplankton like Daphnia are also food for many other aquatic animals, the researchers wanted to study the effect of plastic particles higher up in the food chain. They found that fish that ate Daphnia containing nanoplastics experienced a change in their predatory behaviour and poor appetite. In several studies, researchers also discovered that the nanoparticles had the ability to cross biological barriers, such as the intestinal wall and brain.

“Although in our study we used much larger amounts of nanoplastic than those present in oceans today, we suspect that plastic particles may be accumulated inside the fish. This means that even low doses could ultimately have a negative effect”, says Karin Mattsson.

Plastic breaks down very slowly in nature, and once the microscopically small plastic particles reach lakes and oceans they are difficult to remove. Plastic particles also bind environmental toxins that can become part of the food chain when consumed accidentally.

“Our research indicates the need for more studies and increased caution in the use of nanoplastics”, she says.

Karin Mattsson is a physicist and her research project was produced in collaboration between the Centre for Environmental and Climate Research, the Division Biochemistry and Structural Biology and the Division of Aquatic Biology at Lund University. Karin Mattsson is also affiliated with NanoLund, where several studies are currently conducted to evaluate the safety of nanoparticles.

Here’s a link to and a citation for a paper published online in 2014 and in print in 2015,

Altered Behavior, Physiology, and Metabolism in Fish Exposed to Polystyrene Nanoparticles by Karin Mattsson, Mikael T. Ekvall, Lars-Anders Hansson, Sara Linse, Anders Malmendal, and Tommy Cedervall. Environ. Sci. Technol., 2015, 49 (1), pp 553–561 DOI: 10.1021/es5053655
Publication Date (Web): November 07, 2014

Copyright © 2014 American Chemical Society

More recently, Karin Mattson has published her PhD thesis on the topic (I believe it is written in Swedish).

Removing viruses from water with a ‘mille-feuille’ filter

Mille-feuille is a pastry and it’s name translates to ‘a thousand leaves’, which hints at how a ‘mille-feuille’ nanofilter is constructed. From a May 18, 2016 news item on Nanowerk,

A simple paper sheet made by scientists at Uppsala University can improve the quality of life for millions of people by removing resistant viruses from water. The sheet, made of cellulose nanofibers, is called the mille-feuille filter as it has a unique layered internal architecture resembling that of the French puff pastry mille-feuille (Eng. thousand leaves).

Caption: The sheet made of cellulose nanofibers in the mille-feuille filter which can remove resistant viruses from water. Research led by Albert Mihranyan, Professor of Nanotechnology at Uppsala University, Image by Simon Gustafsson. Credit: Simon Gustafsson

Caption: The sheet made of cellulose nanofibers in the mille-feuille filter which can remove resistant viruses from water. Research led by Albert Mihranyan, Professor of Nanotechnology at Uppsala University, Image by Simon Gustafsson. Credit: Simon Gustafsson

A May 18, 2016 Uppsala University (Sweden) press release on EurekAlert, which originated the news item, expands on the theme,

With a filter material directly from nature, and by using simple production methods, we believe that our filter paper can become the affordable global water filtration solution and help save lives. Our goal is to develop a filter paper that can remove even the toughest viruses from water as easily as brewing coffee’, says Albert Mihranyan, Professor of Nanotechnology at Uppsala University, who heads the study.

Access to safe drinking water is among the UN’s Sustainable Development Goals. More than 748 million people lack access to safe drinking water and basic sanitation. Water-borne infections are among the global causes for mortality, especially in children under age of five, and viruses are among the most notorious water-borne infectious microorganisms. They can be both extremely resistant to disinfection and difficult to remove by filtration due to their small size.

Today we heavily rely on chemical disinfectants, such as chlorine, which may produce toxic by-products depending on water quality. Filtration is a very effective, robust, energy-efficient, and inert method of producing drinking water as it physically removes the microorganisms from water rather than inactivates them. But the high price of efficient filters is limiting their use today.

‘Safe drinking water is a problem not only in the low-income countries. Massive viral outbreaks have also occurred in Europe in the past, including Sweden, continues Mihranyan referring to the massive viral outbreak in Lilla Edet municipality in Sweden in 2008, when more than 2400 people or almost 20% of the local population got infected with Norovirus due to poor water. ‘ Cellulose is one of the most common filtering media used in daily life from tea-bags to vacuum cleaners. However, the general-purpose filter paper has too large pores to remove viruses. In 2014, the group has described for the first time a paper filter that can remove large size viruses, such as influenza virus.

Small size viruses have been much harder to get rid of, as they are extremely resistant to physical and chemical inactivation. A successful filter should not only remove viruses but also feature high flow, low fouling, and long life-time, which makes advanced filters very expensive to develop. Now, with the breakthrough achieved using the mille-feuille filter the long awaited shift to affordable advanced filtration solutions may at last become a reality. Another application of the filter includes production of therapeutic proteins and vaccines.

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

Mille-feuille paper: a novel type of filter architecture for advanced virus separation applications by Simon Gustafsson, Pascal Lordat, Tobias Hanrieder, Marcel Asper,  Oliver Schaeferb, and Albert Mihranyan, Mater. Horiz., 2016, Advance Article DOI: 10.1039/C6MH00090H First published online 18 May 2016

This paper is behind a paywall.

Measuring the van der Waals forces between individual atoms for the first time

A May 13, 2016 news item on Nanowerk heralds the first time measuring the van der Waals forces between individual atoms,

Physicists at the Swiss Nanoscience Institute and the University of Basel have succeeded in measuring the very weak van der Waals forces between individual atoms for the first time. To do this, they fixed individual noble gas atoms within a molecular network and determined the interactions with a single xenon atom that they had positioned at the tip of an atomic force microscope. As expected, the forces varied according to the distance between the two atoms; but, in some cases, the forces were several times larger than theoretically calculated.

A May 13, 2016 University of Basel press release (also on EurekAlert), which originated the news item, provides an explanation of van der Waals forces (the most comprehensive I’ve seen) and technical details about how the research was conducted,

Van der Waals forces act between non-polar atoms and molecules. Although they are very weak in comparison to chemical bonds, they are hugely significant in nature. They play an important role in all processes relating to cohesion, adhesion, friction or condensation and are, for example, essential for a gecko’s climbing skills.

Van der Waals interactions arise due to a temporary redistribution of electrons in the atoms and molecules. This results in the occasional formation of dipoles, which in turn induce a redistribution of electrons in closely neighboring molecules. Due to the formation of dipoles, the two molecules experience a mutual attraction, which is referred to as a van der Waals interaction. This only exists temporarily but is repeatedly re-formed. The individual forces are the weakest binding forces that exist in nature, but they add up to reach magnitudes that we can perceive very clearly on the macroscopic scale – as in the example of the gecko.

Fixed within the nano-beaker

To measure the van der Waals forces, scientists in Basel used a low-temperature atomic force microscope with a single xenon atom on the tip. They then fixed the individual argon, krypton and xenon atoms in a molecular network. This network, which is self-organizing under certain experimental conditions, contains so-called nano-beakers of copper atoms in which the noble gas atoms are held in place like a bird egg. Only with this experimental set-up is it possible to measure the tiny forces between microscope tip and noble gas atom, as a pure metal surface would allow the noble gas atoms to slide around.

Compared with theory

The researchers compared the measured forces with calculated values and displayed them graphically. As expected from the theoretical calculations, the measured forces fell dramatically as the distance between the atoms increased. While there was good agreement between measured and calculated curve shapes for all of the noble gases analyzed, the absolute measured forces were larger than had been expected from calculations according to the standard model. Above all for xenon, the measured forces were larger than the calculated values by a factor of up to two.

The scientists are working on the assumption that, even in the noble gases, charge transfer occurs and therefore weak covalent bonds are occasionally formed, which would explain the higher values.

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

Van der Waals interactions and the limits of isolated atom models at interfaces by Shigeki Kawai, Adam S. Foster, Torbjörn Björkman, Sylwia Nowakowska, Jonas Björk, Filippo Federici Canova, Lutz H. Gade, Thomas A. Jung, & Ernst Meyer. Nature Communications 7, Article number: 11559  doi:10.1038/ncomms11559 Published 13 May 2016

This is an open access paper.

Nanosafety Cluster newsletter—excerpts from the Spring 2016 issue

The European Commission’s NanoSafety Cluster Newsletter (no.7) Spring 2016 edition is some 50 pp. long and it provides a roundup of activities and forthcoming events. Here are a few excerpts,

“Closer to the Market” Roadmap (CTTM) now finalised

Hot off the press! the Cluster’s “Closer to the Market” Roadmap (CTTM)  is  a  multi-dimensional,  stepwise  plan  targeting  a framework to deliver safe nano-enabled products to the market. After some years of discussions, several consultations of a huge number of experts in the nanosafety-field, conferences at which the issue of market implementation of nanotechnologies was talked  about,  writing  hours/days,  and  finally  two public consultation rounds, the CTTM is now finalized.

As stated in the Executive Summary: “Nano-products and nano-enabled applications need a clear and easy-to-follow human and environmental safety framework for the development along the innovation chain from initial idea to market and beyond that facilitates  navigation  through  the  complex  regulatory and approval processes under which different product categories fall.

Download it here, and get involved in its implementation through the Cluster!
Authors: Andreas Falk* 1, Christa Schimpel1, Andrea Haase3, Benoît Hazebrouck4, Carlos Fito López5, Adriele Prina-Mello6, Kai Savolainen7, Adriënne Sips8, Jesús M. Lopez de Ipiña10, Iseult Lynch11, Costas Charitidis12, Visser Germ13

NanoDefine hosts Synergy Workshop with NSC projects

NanoDefine  organised  the  2nd Nanosafety  Cluster  (NSC)  Synergy Workshop  at  the  Netherlands  House  for Education  and  Research  in Brussels  on  2nd  February  2016. The  aim  was  to  identify  overlaps and synergies existing between different projects that could develop into
outstanding cooperation opportunities.

One central issue was the building of a common ontology and a European framework for data management and analysis, as planned within eNanoMapper, to facilitate a closer interdisciplinary collaboration between  NSC projects and to better address the need for proper data storage, analysis and sharing (Open Access).

Unexpectedly, there’s a Canadian connection,

Discovering protocols for nanoparticles: the soils case
NanoFASE WP7 & NanoSafety Cluster WG3 Exposure

In NanoFASE, of course, we focus on the exposure to nanomaterials. Having consistent and meaningful protocols to characterize the fate of nanomaterials in different environments is therefore of great interest to us. Soils and sediments are in this respect very cumbersome. Also in the case of conventional chemicals has the development of  protocols for fate description in terrestrial systems been a long route.

The special considerations of nanomaterials make this job even harder. For instance, how does one handle the fact that the interaction between soils and nanoparticles is always out of equilibrium? How does one distinguish between the nanoparticles that are still mobile and those that are attached to soil?

In the case of conventional chemicals, a single measurement of a filtered soil suspension often suffices to find the mobile fraction, as long one is sure that equilibrium has been attained. Equilibrium never occurs in the case of  nanoparticles, and the distinction between attached/suspended particles is analytically less clear to do.

Current activity in NanoFASE is focusing at finding protocols to characterize this interaction. Not only does the protocol have to provide meaningful parameters that can be used, e.g. in modelling, but also the method itself should be fast and cheap enough so that a lot of data can be collected in a reasonable amount of time. NanoFASE is  in a good position to do this, because of its focus on fate and because of the many international collaborators.

For  instance,  the Swedish  Agricultural  University (Uppsala)  is  collaborating  with  McGill  University (Montreal, Canada [emphasis mine]), an advisory partner to NanoFASE, in developing the OECD [Organization for Economic Cooperation and Development] protocol for column tests (OECD test nr 312:  “Leaching in soil columns”). The effort is led by Yasir Sultan from Environment Canada and by Karlheinz Weinfurtner from the Frauenhofer institute in Germany. Initial results show the transport of nanomaterials in soil columns to be very limited.

The OECD protocol therefore does not often lead to measurable breakthrough curves that can be modelled to provide information about  nanomaterial  mobility  in  soils  and  most  likely  requires adaptations  to  account  for  the  relatively  low mobility  of  typical pristine nanomaterials.

OECD 312 prescribes to use 40 cm columns, which is most likely too long to show a breakthrough in the case of nanoparticles. Testing in NanoFASE will therefore focus on working with shorter columns and also investigating the effect of the flow speed.

The progress and the results of this action will be reported on our website (www.nanofase.eu).

ENM [engineered nanomaterial] Transformation in and Release from Managed Waste Streams (WP5): The NanoFASE pilot Wastewater Treatment Plant is up and running and producing sludge – soon we’ll be dosing with nanoparticles to test “real world” aging.

Now, wastewater,

ENM [engineered nanomaterial] Transformation in and Release from Managed Waste Streams (WP5): The NanoFASE pilot Wastewater Treatment Plant is up and running and producing sludge – soon we’ll be dosing with nanoparticles to test “real world” aging.

WP5 led by Ralf Kaegi of EAWAG [Swiss Federal Institute of Aquatic Science and Technology] (Switzerland) will establish transformation and release rates of ENM during their passage through different reactors. We are focusing on wastewater treatment plants (WWTPs), solid waste and dedicated sewage sludge incinerators as well as landfills (see figure below). Additionally, lab-scale experiments using pristine and well characterized materials, representing the realistic fate relevant forms at each stage, will allow us to obtain a mechanistic understanding of the transformation processes in waste treatment reactors. Our experimental results will feed directly into the development of a mathematical model describing the transformation and transfer of ENMs through the investigated reactors.

I’m including this since I’ve been following the ‘silver nanoparticle story’ for some time,

NanoMILE publication update: NanoMILE on the air and on the cover

Dramatic  differences  in  behavior  of  nano-silver during  the  initial  wash  cycle  and  for  its  further dissolution/transformation potential over time depending on detergent composition and form.

In an effort to better relate nanomaterial aging procedures to those which they are most likely to undergo during the life cycle of nano-enhanced products, in this paper we describe the various transformations which are possible when exposing Ag engineered nanoparticles (ENPs) to a suite of commercially available washing detergents (Figure 1). While Ag ENP transformation and washing of textiles has received considerable attention in recent years, our study is novel in that we (1) used several commercially available detergents allowing us to estimate the various changes possible in individual homes and commercial washing settings; (2) we have continued  method  development  of  state  of  the  art nanometrology techniques, including single particle ICP-MS, for the detection and characterization of ENPs in complex media; and (3) we were able to provide novel additions to the knowledge base of the environmental nanotechnology research community both in terms of the analytical methods (e.g. the first time ENP aggregates have been definitively analyzed via single particle ICP-MS) and broadening the scope of “real world” conditions that should be considered when understanding AgENP through their life cycle.

Our findings, which were recently published in Environmental Science and Toxicology (2015, 49: 9665), indicate that the washing detergent chemistry causes dramatic differences in ENP behavior during the initial wash cycle and has ramifications for the dissolution/transformation potential of the Ag ENPs over time (see Figure 2). The use of silver as an  antimicrobial  treatment  in  textiles  continues  to garner  considerable  attention.  Last  year  we  published  a manuscript in ACS Nano that considered how various silver treatments to textiles (conventional and nano) both release  nano-sized  material  after  the  wash  cycle  with  similar chemical  characteristics.  That  study  essentially conveyed that multiple silver treatments would become more similar through the product life cycle. Our newest  work expands this by investigating one silver ENP under various washing conditions thereby creating more varied silver products as an end result.

Fascinating stuff if you’ve been following the issues around nanotechnology and safety.

Towards the end of the newsletter on pp. 46-48, they list opportunities for partnerships, collaboration, and research posts and they list websites where you can check out job opportunities. Good Luck!

Dissipating heat with graphene-based film

As the summer approaches here in the Northern Hemisphere I think longingly of frost and snow and so readers may find more than the usual number of stories about ‘cooling’. On that note, Chalmers Technical University (Sweden) is announcing some new research into cooling graphene-based films, from an April 29, 2016 news item on ScienceDaily,

Heat dissipation in electronics and optoelectronics is a severe bottleneck in the further development of systems in these fields. To come to grips with this serious issue, researchers at Chalmers University of Technology have developed an efficient way of cooling electronics by using functionalized graphene nanoflakes. …

“Essentially, we have found a golden key with which to achieve efficient heat transport in electronics and other power devices by using graphene nanoflake-based film. This can open up potential uses of this kind of film in broad areas, and we are getting closer to pilot-scale production based on this discovery,” says Johan Liu, Professor of Electronics Production at Chalmers University of Technology in Sweden.

An April 29, 2016 Chalmers Technical University press release (also on EurekAlert), which originated the news item, describes the work in more detail,

The researchers studied the heat transfer enhancement of the film with different functionalized amino-based and azide-based silane molecules, and found that the heat transfer efficiency of the film can be improved by over 76 percent by introducing functionalization molecules, compared to a reference system without the functional layer. This is mainly because the contact resistance was drastically reduced by introducing the functionalization molecules.

Meanwhile, molecular dynamic simulations and ab initio calculations reveal that the functional layer constrains the cross-plane scattering of low-frequency phonons, which in turn enhances in-plane heat-conduction of the bonded film by recovering the long flexural phonon lifetime. The results suggested potential thermal management solutions for electronic devices.

In the research, scientists studied a number of molecules that were immobilized at the interfaces and at the edge of graphene nanoflake-based sheets forming covalent bonds. They also probed interface thermal resistance by using a photo-thermal reflectance measurement technique to demonstrate an improved thermal coupling due to functionalization.

“This is the first time that such systematic research has been done. The present work is much more extensive than previously published results from several involved partners, and it covers more functionalization molecules and also more extensive direct evidence of the thermal contact resistance measurement,” says Johan Liu.

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

Functionalization mediates heat transport in graphene nanoflakes by Haoxue Han, Yong Zhang, Nan Wang, Majid Kabiri Samani, Yuxiang Ni, Zainelabideen Y. Mijbil, Michael Edwards, Shiyun Xiong, Kimmo Sääskilahti, Murali Murugesan, Yifeng Fu, Lilei Ye, Hatef Sadeghi, Steven Bailey, Yuriy A. Kosevich, Colin J. Lambert, Johan Liu, & Sebastian Volz. Nature Communications 7, Article number: 11281  doi:10.1038/ncomms11281 Published 29 April 2016

This is an open access paper.

Macchiarini controversy and synthetic trachea transplants (part 2 of 2)

For some bizarre frosting on this disturbing cake (see part 1 of the Macchiarini controversy and synthetic trachea transplants for the medical science aspects), a January 5, 2016 Vanity Fair article by Adam Ciralsky documents Macchiarini’s courtship of an NBC ([US] National Broadcasting Corporation) news producer who was preparing a documentary about him and his work,

Macchiarini, 57, is a magnet for superlatives. He is commonly referred to as “world-renowned” and a “super-surgeon.” He is credited with medical miracles, including the world’s first synthetic organ transplant, which involved fashioning a trachea, or windpipe, out of plastic and then coating it with a patient’s own stem cells. That feat, in 2011, appeared to solve two of medicine’s more intractable problems—organ rejection and the lack of donor organs—and brought with it major media exposure for Macchiarini and his employer, Stockholm’s Karolinska Institute, home of the Nobel Prize in Physiology or Medicine. Macchiarini was now planning another first: a synthetic-trachea transplant on a child, a two-year-old Korean-Canadian girl named Hannah Warren, who had spent her entire life in a Seoul hospital. …

Macchiarini had come to Vieira’s [Meredith Vieira, American journalist] attention in September 2012, when she read a front-page New York Times story about the doctor. She turned to [Benita] Alexander, one of her most seasoned and levelheaded producers, to look into a regenerative-medicine story for television.

When Alexander and Macchiarini found themselves together in Illinois for a period of weeks in the spring of 2013—brought there by the NBC special—they met frequently for quiet dinners. The trachea transplant on Hannah Warren, the Korean-Canadian girl, was being performed at Children’s Hospital of Illinois, in Peoria, and the procedure was fraught with risks, not least because Macchiarini’s technique was still a work in progress even for adults. (Christopher Lyles, an American who became the second person to receive an artificial trachea, died less than four months after his surgery at Karolinska.) “He’s a brilliant scientist and a great technical surgeon,” said Dr. Richard Pearl, who operated alongside Macchiarini in Illinois. Like others, Pearl described his Italian colleague as a Renaissance man, fluent in half a dozen languages. Another person, who would get to know him through Alexander, compared Macchiarini to “the Most Interesting Man in the World,” the character made famous in Dos Equis beer commercials.

In Peoria, Macchiarini’s medical magic appeared to have its limitations. Hannah Warren died from post-surgical complications less than three months after the transplant. Her anatomy “was much more challenging than we realized,” Pearl recounted. “Scientifically, the operation itself worked. It was just a shame what happened. When you’re doing something for the first time, you don’t have a textbook. It was the hardest operation I’ve ever scrubbed on.”

Then, there was the romance (from the Ciralsky article),

The personal relationship between Alexander and Macchiarini continued to blossom. In June 2013, they flew to Venice for what Alexander called “an incredibly romantic weekend.” Macchiarini bought her red roses and Venetian-glass earrings and took her on a gondola ride under the Bridge of Sighs. Like a pair of teenagers, they attached love locks to the Ponte dell’Accademia bridge, one of them bearing the inscription “B—P 23/6/13, 4 Ever.” Alexander told me that, “when he took me to Venice, we were still shooting the story … He always paid for everything … gifts, expensive dinners, flowers—the works. When it came to money, he was incredibly generous.”

It is a bedrock principle at NBC and every other news organization that journalists must avoid conflicts of interest, real or apparent. Alexander was not oblivious to this. “I knew that I was crossing the line in the sense that it’s a basic and well-understood rule of journalism that you don’t become involved with one of the subjects of your story, because your objectivity could clearly become compromised,” she told me. “I never once thought about him paying for the trip as him ‘buying’ me in some fashion, or potentially using money to influence me, because, from my perspective anyway … that just wasn’t the case. We were just crazy about each other, and I was falling in love.”

Alexander made her way to Stockholm at a later date (from the Ciralsky article),

Macchiarini was in Stockholm to attend to Yesim Cetir, a 25-year-old Turkish woman whose artificial trachea had failed. As Swedish television later reported, “It has taken nearly 100 surgeries to support the cell tissue around the airpipes. Her breathing is bad, and to avoid suffocation, her respiratory tract must be cleansed from mucus every fourth hour. She has now been lying in the hospital for nearly 1,000 days.” NBC’s special would come to include skeptical commentary from Dr. Joseph Vacanti, who questioned the sufficiency of Macchiarini’s research, but Cetir’s post-operative complications were not mentioned.

Prior to the NBC documentary’s (A Leap of Faith) airing, the romance became an engagement (from the Ciralsky article),

Macchiarini proposed to Benita Alexander on Christmas Day 2013, Alexander said. In the months leading up to the airing of A Leap of Faith, in June 2014, Macchiarini and Alexander went on trips to the Bahamas, Turkey, Mexico, Greece, and Italy. They went on shopping sprees and ate their way through Michelin-starred restaurants. Macchiarini even took Alexander and her daughter to meet his mother at her home, in Lucca. “She cooked homemade gnocchi,” Alexander recalled. Macchiarini’s mother shared pictures from the family photo album while her son translated. Emanuela Pecchia, the woman whom Macchiarini had married years earlier, lived only a short distance away. When Macchiarini informed Alexander, during a dinner cruise later that summer, that his divorce had finally come through, she recounted, he gave her an engagement ring.

In the months that followed, the doctor and his fiancée began planning their wedding in earnest. They set a date for July 11, 2015, in Rome. But their desire to marry in the Catholic Church was complicated by the fact that she is Episcopalian and divorced. Divorce would have been an issue for Macchiarini as well. However, Alexander said, Macchiarini insisted that he would fix things by visiting his friend and patient in the Vatican.

In October 2014, Alexander recalled, Macchiarini told her that he had met with Pope Francis for four hours and that the Pontiff consented to the couple’s marriage and, in yet another sign of his progressive tenure, vowed to officiate. Alexander said Macchiarini referred to himself as Pope Francis’s “personal doctor” and maintained that in subsequent meetings his patient offered to host the wedding at his summer residence, the Apostolic Palace of Castel Gandolfo.

Shortly after quitting her job in anticipation of her July 2015 wedding to Macchiarini, Alexander learned that Pope Francis who was supposed to officiate was in fact scheduled to be in South America during that time.  From the Ciralsky article,

As Alexander would discover with the help of a private investigator named Frank Murphy, virtually every detail Macchiarini provided about the wedding was false. A review of public records in Italy would also seem to indicate that Macchiarini remains married to Emanuela Pecchia, his wife of nearly 30 years. Murphy, who spent 15 years as a Pennsylvania State Police detective, told me, “I’ve never in my experience witnessed a fraud like this, with this level of international flair…. The fact that he could keep all the details straight and compartmentalize these different lives and lies is really amazing.

Ciralsky broaches the question of why someone with Macchiarini’s accomplishments would jeopardize his position in such a way,

To understand why someone of considerable stature could construct such elaborate tales and how he could seemingly make others believe them, I turned to Dr. Ronald Schouten, a Harvard professor who directs the Law and Psychiatry Service at Massachusetts General Hospital. “We’re taught from an early age that when something is too good to be true, it’s not true,” he said. “And yet we ignore the signals. People’s critical judgment gets suspended. In this case, that happened at both the personal and institutional level.” Though he will not diagnose from a distance, Schouten, who is one of the nation’s foremost authorities on psychopathy, observed, “Macchiarini is the extreme form of a con man. He’s clearly bright and has accomplishments, but he can’t contain himself. There’s a void in his personality that he seems to want to fill by conning more and more people.” When I asked how Macchiarini stacks up to, say, Bernie Madoff, he laughed and said, “Madoff was an ordinary con man with a Ponzi scheme. He never claimed to be the chairman of the Federal Reserve. He didn’t suggest he was part of a secret international society of bankers. This guy is really good.”

In addition to the romance, Ciralsky and Vanity Fair checked out Macchiarini’s résumé,

Vanity Fair contacted many of the schools at which Macchiarini claimed to have either earned a degree or held an academic post. While the University of Pisa confirmed that he indeed received an M.D. and had specialized in surgery, the University of Alabama at Birmingham denied that Macchiarini earned a master’s in biostatistics or that he participated in a two-year fellowship in thoracic surgery. In fact, according to U.A.B. spokesman Bob Shepard, the only record the school has for Macchiarini indicates that he did a six-month non-surgical fellowship in hematology/oncology—which according to the current Accreditation Council for Graduate Medical Education guidelines is 30 months shy of what is required for a clinical fellowship in that field. The University of Paris—Sud never responded to repeated requests for comment, but Hannover Medical School wrote to say that Macchiarini had been neither a full nor an associate professor there, merely an adjunct.

Comments

As I noted in part 1, there are medical science and ethical issues to be considered. As well, Macchiarini’s romantic behaviour certainly seems fraudulent as do parts of his curriculum vitae (CV) and there’s more about Macchiarini’s professional accomplishments (read Ciralsky’s entire January 5, 2016 Vanity Fair article for details).

The romantic and CV chicanery may or may not suggest serious problems with Macchiarini’s revolutionary procedure and ethics. History is littered with stories of people who achieved extraordinary advances and were not the most exemplary human beings. Paracelsus, founder of the field of toxicology and an important contributor in the fields of medicine and science, was reputedly a sketchy character. Caravaggio now remembered for his art, killed someone (accidentally or not) and was known for his violent behaviour even in a time when there was higher tolerance for it.

What I’m saying is that Macchiarini may be pioneering something important regardless of how you view his romantic chicanery and falsified CV. Medical research can be high risk and there is no way to avoid that sad fact. However, criticisms of the work from Macchiarini’s colleagues need to be addressed and the charge that a Russian patient who was not in imminent danger and not properly advised of the extremely high risk must also be addressed.

It should also be remembered that Macchiarini did not pull this off by himself. Institutions such as the Karolinska Institute failed to respond appropriately in the initial stages. As well, the venerable medical journal, The Lancet seems reluctant to address the situation even now.

Before dissecting the Alexander situation, it should be said that she showed courage in admitting her professional transgression and discussing a painful and humiliating romantic failure. All of us are capable of misjudgments and wishful thinking, unfortunately for her, this became an international affair.

More critically, Alexander, a journalist, set aside her ethics for a romance and what seems to be surprisingly poor research by Alexander’s team.  (Even I had a little something about this in 2013.) How did a crack NBC research team miss the problems? (For the curious, this Bryan Burrough April 30, 2015 article for Vanity Fair highlighting scandals plaguing NBC News may help to answer the question about NBC research.)

Finally, there’s an enormous amount of pressure on stem cell scientists due to the amounts of money and the degree of prestige involved. Ciralsky’s story notes the pressure when he describes how Macchiarini got one of this positions at an Italian facility in Florence through political machinations. (The situation is a little more complicated than I’ve described here but an accommodation in Macchiarini’s favour was made.) Laura Margottini’s Oct. 7, 2014 article for Science magazine provides a synopsis of another stem cell controversy in Italy.

Stem cell controversies have not been confined to Italy or Europe for that matter. There was the South Korean scandal in 2006 (see a Sept. 19, 2011 BBC [British Broadcasting Corporation] news online post for an update and synopsis) when a respected scientist was found to have falsified research results. Up to that  point, South Korea was considered the world leader in the field.

Finally,  if there are two survivors, is there a possibility that this procedure could be made successful for more patients or that some patients are better candidates than others?

Additional notes

Macchiarini is mounting a defence for himself according to a March 30, 2016 news item on phys.org and a Swedish survey indicates that the average Swede’s trust in researchers still remains high despite the Macchiarini imbroglio according to an April 15, 2016 news item on phys.org.

For anyone interested in the timeline and updates for this scandal, Retraction Watch offers this: http://retractionwatch.com/2016/02/12/reading-about-embattled-trachea-surgeon-paolo-macchiarini-heres-what-you-need-to-know/

Macchiarini controversy and synthetic trachea transplants (part 1 of 2)

Having featured Paolo Macchiarini and his work on transplanting synthetic tracheas into humans when it was lauded (in an Aug. 2, 2011 post titled: Body parts nanostyle), it seems obligatory to provide an update now that he and his work are under a very large cloud. Some of this is not new, there were indications as early as this Dec. 27, 2013 post titled: Trachea transplants: an update which featured an article by Gretchen Vogel in Science magazine hinting at problems.

Now, a Feb. 4, 2016 article by Gretchen Vogel for Science magazine provides a more current update and opens with this (Note: Links have been removed),

The Karolinska Institute (KI) in Stockholm “has lost its confidence” in surgeon Paolo Macchiarini, a senior researcher at the institute, and will end its ties with him. In a statement issued today, KI said that it won’t renew Macchiarini’s contract after it expires on 30 November 2016.

The move comes in the wake of a chilling three-part TV documentary about Macchiarini, a former media darling who was cleared of scientific misconduct charges by KI vice-chancellor Anders Hamsten last summer. Among other things, The Experiments, broadcast in January by Swedish public television channel SVT, suggests that Macchiarini didn’t fully inform his patients about the risks of his pioneering trachea implants. Most of the patients died, including at least one—a woman treated in Krasnodar, Russia—who was not seriously ill before the surgery.

For a profession that has “do no harm” as one of its universal tenets, the hint that a patient not in dire need agreed to a very risky procedure without being properly apprised of the risks is chilling.

Macchiarini’s behavriour is not the only concern, the Karolinska Institute is also being held to account (from the Vogel article),

The film has also raised questions about the way Hamsten and other administrators at KI, Sweden’s most prestigious university and home of the selection committee for the Nobel Prize in Physiology or Medicine, have handled the scandal. Today [Feb. 4, 2016], the Institute’s Board decided to launch an independent review, to be led by an experienced lawyer, into KI’s 5-year relationship with Macchiarini. Among the things the inquiry should address is whether any errors were made or laws were broken when Macchiarini was hired; whether misconduct charges against him were handled properly; and why, given the controversy, he was given a new 1-year contract  as a senior researcher after his appointment as a visiting professor at KI ended in October 2015.

Getting back to Macchiarini (from the Vogel article),

In 2014, colleagues at KI alleged that Macchiarini’s papers made his transplants seem more successful than they were, omitting serious complications. Two patients treated at Karolinska died, and a third has been in intensive care since receiving a trachea in 2012. The Illinois patient also died, as did three patients in Russia. Bengt Gerdin, a professor emeritus of surgery at Uppsala University in Sweden who investigated the charges at KI’s request, concluded in May 2015 that differences between published papers and lab records constituted scientific misconduct. But Hamsten rejected that conclusion in August, based on additional material Macchiarini submitted later.

The documentary shows footage of a patient who says Macchiarini reassured him before the surgery that experiments had been done on pigs, when in fact none had taken place. It also follows the wrenching story of the first patient in Krasnodar. A 33-year-old woman, she was living with a tracheostomy that she said caused her pain, but her condition was not life-threatening. The film suggests that she wasn’t fully aware of the risks of the operation, and that Macchiarini and his colleagues knew about problems with the implant before the surgery. The patient’s first implant failed, and she received a second one in 2013. She died in 2014.

So in May 2015, an investigator concluded there had been scientific misconduct and, yet, Macchiarini’s contract is renewed in the fall of 2015.

Kerry Grens in a March 7, 2016 article for The Scientist provides information about the consequences of the latest investigation into Macchiarini’s work (Note: Links have been removed),

Karl-Henrik Grinnemo, a surgeon at the Karolinska Institute and one of a number of colleagues who voiced concerns about the conduct of fellow surgeon Paolo Macchiarini, is no longer a coauthor on a 2011 The Lancet study led by Macchiarini that described an artificial windpipe. Grinnemo asked to be removed from the paper, and the journal complied last week (March 3).

Grinnemo’s removal from the study is the latest in a string of repercussions related to an investigation of Macchiarini’s work. Last month, the head of the Karolinska Institute, Anders Hamsten, resigned because the institution’s initial investigation concluded no wrongdoing. Hamsten said he and his colleagues were probably wrong about Macchiarini; the institute has launched another investigation into the surgeon’s work.

A March 23, 2016 news item on phys.org announces Macchiarini’s firing from the Karolinska Institute and provides a brief description of his work with synthetic tracheas (Note: A link has been removed),

Sweden’s Karolinska Institute (KI), which awards the Nobel Prize for Medicine, on Wednesday [March 23, 2016] dismissed a Italian transplant surgeon suspected of research fraud and ethical breaches, in an affair that has plunged the renowned institution into crisis.

“It is impossible for KI to continue to have any cooperation with Paolo Macchiarini. He has acted in a way that has had very tragic consequences for the people affected and their families. His conduct has seriously damaged confidence in KI,” human resource director Mats Engelbrektson said in a statement.

Macchiarini, a 57-year-old visiting professor at Karolinska since 2010, rose to fame for carrying out the first synthetic trachea, or windpipe, transplant in 2011.

It was a plastic structure seeded with the patient’s own stem cells—immature cells that grow into specialised cells of the body’s organs.

The surgeon performed three such operations in Stockholm and five others around the world, and the exploit was initially hailed as a game-changer for transplant medicine.

But six of the eight patients reportedly died, and allegations ensued that the risky procedure had been carried out on at least one individual who had not been life-threateningly ill.

Macchiarini is also suspected of lying about his scientific research and his past experience with prestigious medical research centres.

“Paolo Macchiarini supplied false or misleading information in the CV he submitted to KI” and “demonstrated scientific negligence” in his research, said the institute.

H/t to Don Bright, a reader who informed me about this April 2, 2016 posting by Pierre Delaere (a long time Macchiarini critic), published in Leonid Schneider’s blog, For Better Science,

I have written this overview as a trachea surgeon working at KU Leuven and privileged witness of the “Tracheal regeneration scandal” from the very start.

Because of its immense scale, the scandal is difficult to grasp and explain. Fortunately, we have recently been provided with an excellent overview in the 3 x 1-hour documentary by Bosse Lindquist on Swedish national TV. Due to Paolo Macchiarini’s appetite for the spotlights and thanks to the professional standards of the Swedish top producer this is probably the very first case of a medical crime played out in the media. Anyone who has seen this brilliant investigative documentary cannot help but wonder why there are still people who doubt that this is a case of gross medical misconduct.

The story began in Barcelona in 2008 with the publication in The Lancet of a report on a regenerated windpipe, featuring Paolo Macchiarini (PM) as its first author (Macchiarini et al. Lancet 2008). This ground-breaking achievement consisted of bringing to life a dead windpipe from a donor, by putting it in a plastic box, a so-called ‘bioreactor’ together with bone marrow fluid (stem cells). A few weeks later, I wrote a letter to The Lancet, pointing out:

    “The main drawback of the proposed reconstruction is the lack of an intrinsic blood supply to the trachea. We know that a good blood supply is the first requirement in all other tissue and organ transplantations. Therefore, the reported success of this technique is questionable” (correspondence by Delaere and Hermans, Lancet 2009).

Delaere goes on to recount and critique the story of the first synthetic trachea,

…  PM had mounted bone marrow extract (‘stem cells’) on a plastic tube (‘bioartificial trachea’) in a plastic box (‘bioreactor’). After a day or two this creation was ‘successfully’ transplanted in a patient with a trachea defect. This occurred in the Karolinska hospital in July 2011 and was reported on in The Lancet shortly afterwards . Biologically speaking, the procedure is absolutely implausible.

In reality an important part of the windpipe had been replaced by a synthetic tube, and the presence of stem cells made no difference to this whatsoever.

For those not in the field, this procedure may still seem acceptable. A blood vessel can also be replaced by synthetic material because the material can grow into the sterile environment of the blood stream. However, this is completely impossible if the synthetic material is exposed to an environment of inhaled air full of bacteria. The laws of biology allow us to predict accurately what will happen after part of the windpipe has been replaced by a synthetic tube. After some time, the suturing between the synthetic tube and the surrounding tissue will come loose, leading to a number of serious complications. These complications inevitably lead to death in the short (months) or in the mid-long term (a few years). How long the patient will survive also depends on the options still left to treat complications. In most cases so far, a metal stent had to be implanted to keep the airway open in the sutured area.It is entirely predictable that additional complications after placement of the metal stent will ultimately lead to the patient’s death, usually by asphyxiation or by bleeding out after complete rupture of the sutures. This gruesome fate awaiting patients was clearly shown in the documentary. Replacing a part of the trachea by a synthetic tube can therefore be compared to death by medical torture. The amount of suffering it induces is directly proportional to the duration between implantation and the patient’s death.

Delaere describes his own and others’ efforts to bring these issues to light,

Since 2011, I have contacted both the President of KI and the Editors of The Lancet with well-documented information to clarify that what had happened was completely unacceptable. These alerts were repeated in 2013 and 2014. Since 2014, four doctors from KI, who had seen it all happen, have been collecting evidence to show the extent of misconduct [Matthias Corbascio, Thomas Fux, Karl-Henrik Grinnemo and Oscar Simonsson, their letter to Vice-Chancellor Hamsten from June 22, 2015, and its attachments available here; -LS]. Not only did KI not react to the doctors’ complaint, these doctors were in fact intimidated and threatened with dismissal. KI’s Ethical Commission came to a verdict of ‘no misconduct’ in April 2015 following an inquiry based on a series of complaints filed by myself [verdict available from SVT here, -LS]. The Lancet Editor did not even bother to reply to my complaints.

In the reports, eight patients were given synthetic tracheas with six now dead and, allegedly, two still living. Delaere comments,

… To prove that this transplantation technique is effective, reports about the long-term success of this technique in the first 2 patients in Barcelona and London is still being spread. What the real situation of the two patients is at the moment is very difficult to establish. For some time now, reports about these two cases seem to have disappeared from the face of the earth. After the air has been cleared in Sweden, the same will probably happen in London and Barcelona.

Comments

Sometimes medical research can be very dangerous. While, a 25% chance of success (two of Macchiarini’s eight patients undergoing the synthetic trachea transplant have allegedly survived) is not encouraging, it’s understandable that people in dire circumstances and with no other options might want to take a chance.

It’s troubling that the woman in Russia was not in dire straights and that she may not have known how dangerous the procedure is. It would have been unethical of Macchiarini to knowingly perform the procedure under those circumstances.

I am wrestling with some questions about the composite used to create the synthetic trachea and the surviving patients. My understanding is that the composite was designed for eventual deterioration as the patient’s own harvested stem cells fully formed the trachea. Whether the trachea is the one I imagined or he plastic one described by Delaere, how did two patients survive and what is their condition now? The first patient Andemariam Teklesenbet Beyene in 2011 had apparently completed his PhD studies by 2013 (my Dec. 27, 2013 posting). Assuming Beyene is one of the two survivors, what has happened to him and the other one?

As for Delaere’s comments, he certainly raises some red flags not only regarding the procedure but the behaviour of the Lancet editorial team and the Karolinska Institute (they seem to be addressing the issues by firing Macchiarini and with the  resignations of the staff and board).

There are two more twists to this story, which carries on in part 2.

With over 150 partners from over 20 countries, the European Union’s Graphene Flagship research initiative unveils its work package devoted to biomedical technologies

An April 11, 2016 news item on Nanowerk announces the Graphene Flagship’s latest work package,

With a budget of €1 billion, the Graphene Flagship represents a new form of joint, coordinated research on an unprecedented scale, forming Europe’s biggest ever research initiative. It was launched in 2013 to bring together academic and industrial researchers to take graphene from the realm of academic laboratories into European society in the timeframe of 10 years. The initiative currently involves over 150 partners from more than 20 European countries. The Graphene Flagship, coordinated by Chalmers University of Technology (Sweden), is implemented around 15 scientific Work Packages on specific science and technology topics, such as fundamental science, materials, health and environment, energy, sensors, flexible electronics and spintronics.

Today [April 11, 2016], the Graphene Flagship announced in Barcelona the creation of a new Work Package devoted to Biomedical Technologies, one emerging application area for graphene and other 2D materials. This initiative is led by Professor Kostas Kostarelos, from the University of Manchester (United Kingdom), and ICREA Professor Jose Antonio Garrido, from the Catalan Institute of Nanoscience and Nanotechnology (ICN2, Spain). The Kick-off event, held in the Casa Convalescència of the Universitat Autònoma de Barcelona (UAB), is co-organised by ICN2 (ICREA Prof Jose Antonio Garrido), Centro Nacional de Microelectrónica (CNM-IMB-CSIC, CIBER-BBN; CSIC Tenured Scientist Dr Rosa Villa), and Institut d’Investigacions Biomèdiques August Pi i Sunyer (IDIBAPS; ICREA Prof Mavi Sánchez-Vives).

An April 11, 2016 ICN2 press release, which originated the news item, provides more detail about the Biomedical Technologies work package and other work packages,

The new Work Package will focus on the development of implants based on graphene and 2D-materials that have therapeutic functionalities for specific clinical outcomes, in disciplines such as neurology, ophthalmology and surgery. It will include research in three main areas: Materials Engineering; Implant Technology & Engineering; and Functionality and Therapeutic Efficacy. The objective is to explore novel implants with therapeutic capacity that will be further developed in the next phases of the Graphene Flagship.

The Materials Engineering area will be devoted to the production, characterisation, chemical modification and optimisation of graphene materials that will be adopted for the design of implants and therapeutic element technologies. Its results will be applied by the Implant Technology and Engineering area on the design of implant technologies. Several teams will work in parallel on retinal, cortical, and deep brain implants, as well as devices to be applied in the periphery nerve system. Finally, The Functionality and Therapeutic Efficacy area activities will centre on development of devices that, in addition to interfacing the nerve system for recording and stimulation of electrical activity, also have therapeutic functionality.

Stimulation therapies will focus on the adoption of graphene materials in implants with stimulation capabilities in Parkinson’s, blindness and epilepsy disease models. On the other hand, biological therapies will focus on the development of graphene materials as transport devices of biological molecules (nucleic acids, protein fragments, peptides) for modulation of neurophysiological processes. Both approaches involve a transversal innovation environment that brings together the efforts of different Work Packages within the Graphene Flagship.

A leading role for Barcelona in Graphene and 2D-Materials

The kick-off meeting of the new Graphene Flagship Work Package takes place in Barcelona because of the strong involvement of local institutions and the high international profile of Catalonia in 2D-materials and biomedical research. Institutions such as the Catalan Institute of Nanoscience and Nanotechnology (ICN2) develop frontier research in a supportive environment which attracts talented researchers from abroad, such as ICREA Research Prof Jose Antonio Garrido, Group Leader of the ICN2 Advanced Electronic Materials and Devices Group and now also Deputy Leader of the Biomedical Technologies Work Package. Until summer 2015 he was leading a research group at the Technische Universität München (Germany).

Further Graphene Flagship events in Barcelona are planned; in May 2016 ICN2 will also host a meeting of the Spintronics Work Package. ICREA Prof Stephan Roche, Group Leader of the ICN2 Theoretical and Computational Nanoscience Group, is the deputy leader of this Work Package led by Prof Bart van Wees, from the University of Groningen (The Netherlands). Another Work Package, on optoelectronics, is led by Prof Frank Koppens from the Institute of Photonic Sciences (ICFO, Spain), with Prof Andrea Ferrari from the University of Cambridge (United Kingdom) as deputy. Thus a number of prominent research institutes in Barcelona are deeply involved in the coordination of this European research initiative.

Kostas Kostarelos, the leader of the Biomedical Technologies Graphene Flagship work package, has been mentioned here before in the context of his blog posts for The Guardian science blog network (see my Aug. 7, 2014 post for a link to his post on metaphors used in medicine).

When based on plastic materials, contemporary art can degrade quickly

There’s an intriguing April 1, 2016 article by Josh Fischman for Scientific American about a problem with artworks from the 20th century and later—plastic-based materials (Note: A link has been removed),

Conservators at museums and art galleries have a big worry. They believe there is a good chance the art they showcase now will not be fit to be seen in one hundred years, according to researchers in a project  called Nanorestart. Why? After 1940, artists began using plastic-based material that was a far cry from the oil-based paints used by classical painters. Plastic is also far more fragile, it turns out. Its chemical bonds readily break. And they cannot be restored using techniques historically relied upon by conservators.

So art conservation scientists have turned to nanotechnology for help.

Sadly, there isn’t any detail in Fischman’s article (*ETA June 17, 2016 article [for Fast Company] by Charlie Sorrel, which features some good pictures, a succinct summary of Fischman’s article and a literary reference [Kurt Vonnegut’s Bluebeard]I*) about how nanotechnology is playing or might play a role in this conservation effort. Further investigation into the two projects (NanoRestART and POPART) mentioned by Fischman didn’t provide much more detail about NanoRestART’s science aspect but POPART does provide some details.

NanoRestART

It’s probably too soon (this project isn’t even a year-old) to be getting much in the way of the nanoscience details but NanoRestART has big plans according to its website homepage,

The conservation of this diverse cultural heritage requires advanced solutions at the cutting edge of modern chemistry and material science in an entirely new scientific framework that will be developed within NANORESTART project.

The NANORESTART project will focus on the synthesis of novel poly-functional nanomaterials and on the development of highly innovative restoration techniques to address the conservation of a wide variety of materials mainly used by modern and contemporary artists.

In NANORESTART, enterprises and academic centers of excellence in the field of synthesis and characterization of nano- and advanced materials have joined forces with complementary conservation institutions and freelance restorers. This multidisciplinary approach will cover the development of different materials in response to real conservation needs, the testing of such materials, the assessment of their environmental impact, and their industrial scalability.

NanoRestART’s (NANOmaterials for the REStoration of works of ART) project page spells out their goals in the order in which they are being approached,

The ground-breaking nature of our research can be more easily outlined by focussing on specific issues. The main conservation challenges that will be addressed in the project are:

 

Conservation challenge 1Cleaning of contemporary painted and plastic surfaces (CC1)

Conservation challenge 2Stabilization of canvases and painted layers in contemporary art (CC2)

Conservation challenge 3Removal of unwanted modern materials (CC3)

Conservation challenge 4Enhanced protection of artworks in museums and outdoors (CC4)

The European Commission provides more information about the project on its CORDIS website’s NanoRestART webpage including the start and end dates for the project and the consortium members,

From 2015-06-01 to 2018-12-01, ongoing project

CHALMERS TEKNISKA HOEGSKOLA AB
Sweden
MIRABILE ANTONIO
France
NATIONALMUSEET
Denmark
CONSIGLIO NAZIONALE DELLE RICERCHE
Italy
UNIVERSITY COLLEGE CORK, NATIONAL UNIVERSITY OF IRELAND, CORK
Ireland
MBN NANOMATERIALIA SPA
Italy
KEMIJSKI INSTITUT
Slovenia
CHEVALIER AURELIA
France
UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL
Brazil
UNIVERSITA CA’ FOSCARI VENEZIA
Italy
AKZO NOBEL PULP AND PERFORMANCE CHEMICALS AB
Sweden
COMMISSARIAT A L ENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
France
ARKEMA FRANCE SA
France
UNIVERSIDAD DE SANTIAGO DE COMPOSTELA
Spain
UNIVERSITY COLLEGE LONDON
United Kingdom
ZFB ZENTRUM FUR BUCHERHALTUNG GMBH
Germany
UNIVERSITAT DE BARCELONA
Spain
THE BOARD OF TRUSTEES OF THE TATE GALLERY
United Kingdom
ASSOCIAZIONE ITALIANA PER LA RICERCA INDUSTRIALE – AIRI
Italy
THE ART INSTITUTE OF CHICAGO
United States
MINISTERIO DE EDUCACION, CULTURA Y DEPORTE
Spain
STICHTING HET RIJKSMUSEUM
Netherlands
UNIVERSITEIT VAN AMSTERDAM
Netherlands
UNIVERSIDADE FEDERAL DO RIO DE JANEIRO
Brazil
ACCADEMIA DI BELLE ARTI DI BRERA
Italy

It was a bit surprising to see Brazil and the US as participants but The Art Institute of Chicago has done nanotechnology-enabled conservation in the past as per my March 24, 2014 posting about a Renoir painting. I’m not familiar with the Brazilian organization.

POPART

POPART (Preservation of Plastic Artefacts in museum collections) mentioned by Fischman was a European Commission project which ran from 2008 – 2012. Reports can be found on the CORDIS Popart webpage. The final report has some interesting bits (Note: I have added subheads in the [] square brackets),

To achieve a valid comparison of the various invasive and non-invasive techniques proposed for the identification and characterisation of plastics, a sample collection (SamCo) of plastics artefacts of about 100 standard and reference plastic objects was gathered. SamCo was made up of two kinds of reference materials: standards and objects. Each standard represents the reference material of a ‘pure’ plastic; while each object represents the reference of the same plastic as in the standards, but compounded with pigments, dyestuffs, fillers, anti oxidants, plasticizers etc.  Three partners ICN [Instituut Collectie Nederland], V&A [Victoria and Albert Museum] and Natmus [National Museet] collected different natural and synthetic plastics from the ICN reference collections of plastic objects, from flea markets, antique shops and from private collections and from their own collection to contribute to SamCo, the sample collection for identification by POPART partners. …

As a successive step, the collections of the following museums were surveyed:

-Victoria & Albert Museum (V&A), London, U.K.
-Stedelijk Museum, Amsterdam, The Netherlands
-Musée d’Art Moderne et d’Art Contemporaine (MAMAC) Nice, France
-Musée d’Art moderne, St. Etienne, France
-Musée Galliera, Paris, France

At the V&A approximately 200 objects were surveyed. Good or fair conservation conditions were found for about 85% of the objects, whereas the remaining 15% was in poor or even in unacceptable (3%) conditions. In particular, crazing and delamination of polyurethane faux leather and surface stickiness and darkening of plasticized PVC were observed. The situation at the Stedelijk Museum in Amsterdam was particularly favourable because a previous survey had been done in 1995 so that it was possible to make a comparison with the Popart survey in 2010. A total number of 40 objects, which comprised plastics early dating from the 1930’s until the newer plastics from the 1980’s, were considered and their actual conservation state compared with the 1995 records. Of the objects surveyed in 2010, it can be concluded that 21 remained in the same condition. 13 objects containing PA, PUR, PVC, PP or natural rubber changed due to chemical and physical degradation while works of art containing either PMMA or PS changed due to mechanical damages and incorrect artist’s technique (inappropriate adhesive) into a lesser condition. 6 works of art (containing either PA or PMMA or both) changed into a better condition due to restoration or replacements.  More than 230 objects have been examined in the 3 museums in France. A particular effort was devoted to the identification of the constituting plastics materials. Surveys have been undertaken without any sophisticated equipment, in order to work in museums everyday conditions. Plastics hidden by other materials or by paint layers were not or hardly accessible, it is why the final count of some plastics may be under estimated in the final results. Another outcome is that plastic identification has been made at a general level only, by trying to identify the polymer family each plastic belongs to. Lastly, evidence of chemical degradation processes that do not cause visible or perceptible damage have not been detected and could not be taken in account in the final results.

… The most damaged artefacts resulted constituted by cellulose acetate, cellulose nitrate and PVC.

[Polly (the doll)]

One of the main issues that is of interest for conservators and curators is to assess which kinds of plastics are most vulnerable to deterioration and to what extent they can deteriorate under the environmental conditions normally encountered in museums. Although one might expect that real time deterioration could be ascertained by a careful investigation of museum objects on display or in storage, real objects or artworks may not sampled due to ethical considerations. Therefore, reference objects were prepared by Natmus in the form of a doll (Polly) for simultaneous exposures in different environmental conditions. The doll comprised of 11 different plastics representative of types typically found in modern museum collections. The 16 identical dolls realized were exposed in different places, not only in normal exhibit conditions, but also in some selected extreme conditions to ascertain possible acceleration of the deterioration process. In most cases the environmental parameters were also measured. The dolls were periodically evaluated by visual inspection and in selected cases by instrumental analyses. 

In conclusion the experimental campaign carried out with Polly dolls can be viewed as a pilot study aimed at tackling the practical issues related to the monitoring of real three dimensional plastic artworks and the surrounding environment.

The overall exposure period (one year and half) was sufficient to observe initial changes in the more susceptible polymers, such as polyurethane ethers and esters, and polyamide, with detectable chromatic changes and surface effects. Conversely the other polymers were shown to be stable in the same conditions over this time period.

[Polly as an awareness raising tool]

Last but not least, the educational and communication benefits of an object like Polly facilitated the dissemination of the Popart Project to the public, and increased the awareness of issues associated with plastics in museum collections.

[Cleaning issues]

Mechanical cleaning has long been perceived as the least damaging technique to remove soiling from plastics. The results obtained from POPART suggest that the risks of introducing scratches or residues by mechanical cleaning are measurable. Some plastics were clearly more sensitive to mechanical damage than others. From the model plastics evaluated, HIPS was the most sensitive followed by HDPE, PVC, PMMA and CA. Scratches could not be measured on XPS due to its inhomogeneous surfaces. Plasticised PVC scratched easily, but appeared to repair itself because plasticiser migrated to surfaces and filled scratches.

Photo micrographs revealed that although all 22 cleaning materials evaluated in POPART scratched test plastics, some scratches were sufficiently shallow to be invisible to the naked eye. Duzzit and Scotch Brite sponges as well as all paper based products caused more scratching of surfaces than brushes and cloths. Some cleaning materials, notably Akapad yellow and white sponges, compressed air, latex and synthetic rubber sponges and goat hair brushes left residues on surfaces. These residues were only visible on glass-clear, transparent test plastics such as PMMA. HDPE and HIPS surfaces both had matte and roughened appearances after cleaning with dry-ice. XPS was completely destroyed by the treatment. No visible changes were present on PMMA and PVC.

Of the cleaning methods evaluated, only canned air, natural and synthetic feather duster left surfaces unchanged. Natural and synthetic feather duster, microfiber-, spectacle – and cotton cloths, cotton bud, sable hair brush and leather chamois showed good results when applied to clean model plastics.

Most mechanical cleaning materials induced static electricity after cleaning, causing immediate attraction of dust. It was also noticed that generally when adding an aqueous cleaning agent to a cleaning material, the area scratched was reduced. This implied that cleaning agents also functioned as lubricants. A similar effect was exhibited by white spirit and isopropanol.
Based on cleaning vectors, Judith Hofenk de Graaff detergent, distilled water and Dehypon LS45 were the least damaging cleaning agents for all model plastics evaluated. None of the aqueous cleaning agents caused visible changes when used in combination with the least damaging cleaning materials. Sable hair brush, synthetic feather duster and yellow Akapad sponge were unsuitable for applying aqueous cleaning agents. Polyvinyl acetate sponge swelled in contact with solvents and was only suitable for aqueous cleaning processes.

Based on cleaning vectors, white spirit was the least damaging solvent. Acetone and Surfynol 61 were the most damaging for all model plastics and cannot be recommended for cleaning plastics. Surfynol 61 dissolved polyvinyl acetate sponge and left a milky residue on surfaces, which was particularly apparent on clear PMMA surfaces. Surfynol 61 left residues on surfaces on evaporating and acetone evaporated too rapidly to lubricate cleaning materials thereby increasing scratching of surfaces.

Supercritical carbon dioxide induced discolouration and mechanical damage to the model plastics, particularly to XPS, CA and PMMA and should not be used for conservation cleaning of plastics.

Potential Impact:
Cultural heritage is recognised as an economical factor, the cost of decay of cultural heritage and the risk associated to some material in collection may be high. It is generally estimated that plastics, developed at great numbers since the 20th century’s interbellum, will not survive that long. This means that fewer generations will have access to lasting plastic art for study, contemplation and enjoyment. On the other hand will it normally be easier to reveal a contemporary object’s technological secrets because of better documentation and easier access to artists’ working methods, ideas and intentions. A first more or less world encompassing recognition of the problems involved with museum objects made wholly or in part of plastics was through the conference ‘Saving the twentieth century” held in Ottawa, Canada in 1991. This was followed later by ‘Modern Art, who cares’ in Amsterdam, The Netherlands in 1997, ‘Mortality Immortality? The Legacy of Modern Art’ in Los Angeles, USA in 1998 and, for example much more recent, ‘Plastics –Looking at the future and learning from the Past’ in London, UK in 2007. A growing professional interest in the care of plastics was clearly reflected in the creation of an ICOM-CC working group dedicated to modern materials in 1996, its name change to Modern Materials and Contemporary Art in 2002, and its growing membership from 60 at inception to over 200 at the 16th triennial conference in Lisbon, Portugal in 2011 and tentatively to over 300 as one of the aims put forward in the 2011-2014 programme of that ICOM-CC working group. …

[Intellectual property]

Another element pertaining to conservation of modern art is the copyright of artists that extends at least 50 years beyond their death. Both, damage, value and copyright may influence the way by which damage is measured through scientific analysis, more specifically through the application of invasive or non invasive techniques. Any selection of those will not only have an influence on the extent of observable damage, but also on the detail of information gathered and necessary to explain damage and to suggest conservation measures.

[How much is deteriorating?]

… it is obvious from surveys carried out in several museums in France, the UK and The Netherlands that from 15 to 35 % of what I would then call an average plastic material based collection is in a poor to unacceptable condition. However, some 75 % would require cleaning,

I hope to find out more about how nanotechnology is expected to be implemented in the conservation and preservation of plastic-based art. The NanoRestART project started in June 2015 and hopefully more information will be disseminated in the next year or so.

While it’s not directly related, there was some work with conservation of daguerreotypes (19th century photographic technique) and nanotechnology mentioned in my Nov. 17, 2015 posting which was a followup to my Jan. 10, 2015 posting about the project and the crisis precipitating it.