Tag Archives: pigments

Using melanin in bioelectronic devices

Brazilian researchers are working with melanin to make biosensors and other bioelectronic devices according to a Dec. 20, 2016 news item on phys.org,

Bioelectronics, sometimes called the next medical frontier, is a research field that combines electronics and biology to develop miniaturized implantable devices capable of altering and controlling electrical signals in the human body. Large corporations are increasingly interested: a joint venture in the field has recently been announced by Alphabet, Google’s parent company, and pharmaceutical giant GlaxoSmithKline (GSK).

One of the challenges that scientists face in developing bioelectronic devices is identifying and finding ways to use materials that conduct not only electrons but also ions, as most communication and other processes in the human organism use ionic biosignals (e.g., neurotransmitters). In addition, the materials must be biocompatible.

Resolving this challenge is one of the motivations for researchers at São Paulo State University’s School of Sciences (FC-UNESP) at Bauru in Brazil. They have succeeded in developing a novel route to more rapidly synthesize and to enable the use of melanin, a polymeric compound that pigments the skin, eyes and hair of mammals and is considered one of the most promising materials for use in miniaturized implantable devices such as biosensors.

A Dec. 14, 2016 FAPESP (São Paulo Research Foundation) press release, which originated the news item, further describes both the research and a recent meeting where the research was shared (Note: A link has been removed),

Some of the group’s research findings were presented at FAPESP Week Montevideo during a round-table session on materials science and engineering.

The symposium was organized by the Montevideo Group Association of Universities (AUGM), Uruguay’s University of the Republic (UdelaR) and FAPESP and took place on November 17-18 at UdelaR’s campus in Montevideo. Its purpose was to strengthen existing collaborations and establish new partnerships among South American scientists in a range of knowledge areas. Researchers and leaders of institutions in Uruguay, Brazil, Argentina, Chile and Paraguay attended the meeting.

“All the materials that have been tested to date for applications in bioelectronics are entirely synthetic,” said Carlos Frederico de Oliveira Graeff, a professor at UNESP Bauru and principal investigator for the project, in an interview given to Agência FAPESP.

“One of the great advantages of melanin is that it’s a totally natural compound and biocompatible with the human body: hence its potential use in electronic devices that interface with brain neurons, for example.”

Application challenges

According to Graeff, the challenges of using melanin as a material for the development of bioelectronic devices include the fact that like other carbon-based materials, such as graphene, melanin is not easily dispersible in an aqueous medium, a characteristic that hinders its application in thin-film production.

Furthermore, the conventional process for synthesizing melanin is complex: several steps are hard to control, it can last up to 56 days, and it can result in disorderly structures.

In a series of studies performed in recent years at the Center for Research and Development of Functional Materials (CDFM), where Graeff is a leading researcher and which is one of the Research, Innovation and Dissemination Centers (RIDCs) funded by FAPESP, he and his collaborators managed to obtain biosynthetic melanin with good dispersion in water and a strong resemblance to natural melanin using a novel synthesis route.

The process developed by the group at CDMF takes only a few hours and is based on changes in parameters such as temperature and the application of oxygen pressure to promote oxidation of the material.

By applying oxygen pressure, the researchers were able to increase the density of carboxyl groups, which are organic functional groups consisting of a carbon atom double bonded to an oxygen atom and single bonded to a hydroxyl group (oxygen + hydrogen). This enhances solubility and facilitates the suspension of biosynthetic melanin in water.

“The production of thin films of melanin with high homogeneity and quality is made far easier by these characteristics,” Graeff said.

By increasing the density of carboxyl groups, the researchers were also able to make biosynthetic melanin more similar to the biological compound.

In living organisms, an enzyme that participates in the synthesis of melanin facilitates the production of carboxylic acids. The new melanin synthesis route enabled the researchers to mimic the role of this enzyme chemically while increasing carboxyl group density.

“We’ve succeeded in obtaining a material that’s very close to biological melanin by chemical synthesis and in producing high-quality film for use in bioelectronic devices,” Graeff said.

Through collaboration with colleagues at research institutions in Canada [emphasis mine], the Brazilian researchers have begun using the material in a series of applications, including electrical contacts, pH sensors and photovoltaic cells.

More recently, they have embarked on an attempt to develop a transistor, a semiconductor device used to amplify or switch electronic signals and electrical power.

“Above all, we aim to produce transistors precisely in order to enhance this coupling of electronics with biological systems,” Graeff said.

I’m glad to have gotten some information about the work in South America. It’s one of FrogHeart’s shortcomings that I have so little about the research in that area of the world. I believe this is largely due to my lack of Spanish language skills. Perhaps one day there’ll be a universal translator that works well. In the meantime, it was a surprise to see Canada mentioned in this piece. I wonder which Canadian research institutions are involved with this research in South America.

More on the blue tarantula noniridescent photonics

Covered in an Oct. 19, 2016 posting here, some new details have been released about noniridescent photonics and blue tarantulas, this time from the Karlsruhe Institute of Technology (KIT) in a Nov. 17, 2016 (?) press release (also on EurekAlert; h/t Nanowerk Nov. 17, 2016 news item) ,

Colors are produced in a variety of ways. The best known colors are pigments. However, the very bright colors of the blue tarantula or peacock feathers do not result from pigments, but from nanostructures that cause the reflected light waves to overlap. This produces extraordinarily dynamic color effects. Scientists from Karlsruhe Institute of Technology (KIT), in cooperation with international colleagues, have now succeeded in replicating nanostructures that generate the same color irrespective of the viewing angle. DOI: 10.1002/adom.201600599

In contrast to pigments, structural colors are non-toxic, more vibrant and durable. In industrial production, however, they have the drawback of being strongly iridescent, which means that the color perceived depends on the viewing angle. An example is the rear side of a CD. Hence, such colors cannot be used for all applications. Bright colors of animals, by contrast, are often independent of the angle of view. Feathers of the kingfisher always appear blue, no matter from which angle we look. The reason lies in the nanostructures: While regular structures are iridescent, amorphous or irregular structures always produce the same color. Yet, industry can only produce regular nanostructures in an economically efficient way.

Radwanul Hasan Siddique, researcher at KIT in collaboration with scientists from USA and Belgium has now discovered that the blue tarantula does not exhibit iridescence in spite of periodic structures on its hairs. First, their study revealed that the hairs are multi-layered, flower-like structure. Then, the researchers analyzed its reflection behavior with the help of computer simulations. In parallel, they built models of these structures using nano-3D printers and optimized the models with the help of the simulations. In the end, they produced a flower-like structure that generates the same color over a viewing angle of 160 degrees. This is the largest viewing angle of any synthetic structural color reached so far.


Flower-shaped nanostructures generate the color of the blue tarantula. (Graphics: Bill Hsiung, University of Akron)

 


The 3D print of the optimized flower structure is only 15 µm in dimension. A human hair is about three times as thick. (Photo: Bill Hsiung, Universtiy of Akron)

Apart from the multi-layered structure and rotational symmetry, it is the hierarchical structure from micro to nano that ensures homogeneous reflection intensity and prevents color changes.

Via the size of the “flower,” the resulting color can be adjusted, which makes this coloring method interesting for industry. “This could be a key first step towards a future where structural colorants replace the toxic pigments currently used in textile, packaging, and cosmetic industries,” says Radwanul Hasan Siddique of KIT’s Institute of Microstructure Technology, who now works at the California Institute of Technology. He considers short-term application in textile industry feasible.


The synthetically generated flower structure inspired by the blue tarantula reflects light in the same color over a viewing angle of 160 degrees. (Graphics: Derek Miller)  

Dr. Hendrik Hölscher thinks that the scalability of nano-3D printing is the biggest challenge on the way towards industrial use. Only few companies in the world are able to produce such prints. In his opinion, however, rapid development in this field will certainly solve this problem in the near future.

Once again, here’s a link to and a citation for the paper,

Tarantula-Inspired Noniridescent Photonics with Long-Range Order by Bor-Kai Hsiung, Radwanul Hasan Siddique, Lijia Jiang, Ying Liu, Yongfeng Lu, Matthew D. Shawkey, and Todd A. Blackledge. Advanced Materials DOI: 10.1002/adom.201600599 Version of Record online: 11 OCT 2016

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

The paper is behind a paywall. You can see the original Oct. 19, 2016 posting for my comments and some excerpts from the paper.

Noniridescent photonics inspired by tarantulas

Last year, I was quite taken with a structural colour story centering on tarantulas which was featured in my Dec. 7, 2015 posting.

Cobalt Blue Tarantula [downloaded from http://www.tarantulaguide.com/tarantula-pictures/cobalt-blue-tarantula-4/]

Cobalt Blue Tarantula [downloaded from http://www.tarantulaguide.com/tarantula-pictures/cobalt-blue-tarantula-4/]

On Oct. 17, 2016 I was delighted to receive an email with the latest work from the same team who this time around crowdfunded resources to complete their research. Before moving on to the paper, here’s more from the team’s crowdfunder on Experiment was titled “The Development of Non-iridescent Structurally Colored Material Inspired by Tarantula Hairs,”

Many vibrant colors in nature are produced by nanostructures rather than pigments. But their application is limited by iridescence – changing hue and brightness with viewing angles. This project aims to mimic the nanostructures that tarantulas use to produce bright, non-iridescent blue colors to inspire next-generation, energy efficient, wide-angle color displays. Moreover, one day non-iridescent structural colorants may replace costly and toxic pigments and dyes.

What is the context of this research?

We recently discovered that some tarantulas produce vivid blue colors using unique nanostructures not found in other blue organisms like birds and Morpho butterflies. We described a number of different nanostructures that help explain how blue color evolved at least eight times within tarantulas. These colors are also remarkably non-iridescent so that they stay bright blue even at wide viewing angles, unlike the “flashy” structural colors seen in many birds and butterflies. We hypothesize that although the hue is produced by multilayer nanostructure, it is the hierarchical morphology of the hairs controls iridescence. We would like to validate our results from preliminary optical simulations by making nano-3D printed physical prototypes with and without key features of the tarantula hairs.

What is the significance of this project?

While iridescence can make a flashy signal to a mating bird or butterfly, it isn’t so useful in optical technology. This limits the application of structural colors in human contexts, even though they can be more vibrant and resist fading better than traditional pigment-based colors. For example, despite being energy efficient and viewable in direct sunlight, this butterfly-inspired color display, that utilizes principles of structural colors, has never made it into the mainstream because iridescence limits its viewing angle. We believe this limitation could be overcome using tarantula-inspired nanostructures that could be mass-produced in an economically viable way through top-down approaches. Those nanostructures may even be used to replace pigments and dyes someday!

What are the goals of the project?

We have designed five models that vary in complexity, incorporating successively more details of real tarantula hairs. We would like to fabricate those five designs by 3D nano-printing, so that we can test our hypothesis experimentally and determine which features produce blue and which remove iridescence. We’ll start making those designs as soon as we reach our goal and the project is fully funded. Once these designs are made, we will compare the angle-dependency of the colors produced by each design through angle-resolved reflectance spectrometry. We’ll also compare them visually through photography by taking series of shots from different angles similar to Fig. S4. Through those steps, we’ll be able to identify how each feature of the complex nanostructure contributes to color.

Budget
Ultra-high resolution (nano-scale) 3D printing
$6,000
To fund nano 3D printing completely
$1,700

This project has been designed using Biomimicry Thinking, and is a follow-up to our published, well-received tarantula research. In order to test our hypothesis, we are planning to use Photonic Professional GT by nanoscribe to fabricate tarantula hair-inspired prototypes by 3D printing nanostructures within millimeter sized swatches. To be able to 3D print nanostructures across these relatively large-sized swatches is critical to the success of our project. Currently, there’s no widely-accessible technology out there that meets our needs other than Photonic Professional GT. However, the estimated cost just for 3D printing those nanostructures alone is $20,000. So far, we have successfully raised and allocated $13,000 of research funds through conventional means, but we are still $7,000 short. Initial trial of our most complex prototype was a success. Therefore, we’re here, seeking your help. Please help us make this nano fabrication happen, and make this project a success! Thank you!

The researchers managed to raise $7, 708.00 in total, making this paper possible,

Tarantula-Inspired Noniridescent Photonics with Long-Range Order by Bor-Kai Hsiung, Radwanul Hasan Siddique, Lijia Jiang, Ying Liu, Yongfeng Lu, Matthew D. Shawkey, and Todd A. Blackledge. Advanced Materials DOI: 10.1002/adom.201600599 Version of Record online: 11 OCT 2016

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

This paper is behind a paywall but I did manage to get my hands on a copy. So here are a few highlights from the paper,

Pigment-based colorants are used for applications ranging from textiles to packaging to cosmetics.[1] However, structural-based alternatives can be more vibrant, durable, and eco-friendly relative to pigmentary colors.[2] Moreover, optical nanostructures are highly tunable, they can achieve a full color gamut by slight alterations to spacing.[3] However, light interference and/or diffraction from most photonic structures results in iridescence,[4] which limits their broader applications. Iridescent colors that change hue when viewed from different directions are useful for niche markets, such as security and anticounterfeiting, {emphasis mine} [5] but are not desirable for most applications, such as paints, coatings, electronic displays, and apparels. Hence, fabricating a photonic structure that minimizes iridescence is a key step to unlocking the potential applications of structural colors.

Noniridescent structural colors in nature are produced by coherent scattering of light by quasi-ordered, amorphous photonic structures (i.e., photonic glass),[6–10] or photonic polycrystals [9,11–14] that possess only short-range order. Iridescence is thought to be a fundamental component of photonic structures with long-range order, such as multilayers.[4] However, the complexity of short-range order photonic structures prohibits their design and fabrication using top-down approaches while bottom-up synthesis using colloidal suspension[15,16] or self-assembly[17–20] lack the tight controls over the spatial and temporal scales needed for industrial mass production. Photonic structures with long-range order are easier to model mathematically. Hence, long-range order photonic structures are intrinsically suitable for top-down fabrication, where precise feature placement and scalability can be guaranteed.

Recently, we found blue color produced by multilayer interference on specialized hairs from two species of blue tarantulas (Poecilotheria metallica (Figure 1a,b) and Lampropelma violaceopes) that was largely angle independent.[21] We hypothesize that the iridescent effects of the multilayer are reduced by hierarchical structuring of the hairs. Specifically, the hairs have: (1) high degrees of rotational symmetry, (2) hierarchy—with subcylindrical multilayers surrounding a larger, overarching multilayer cylinder, and (3) nanoscale surface grooves. Because all of these structures co-occur on the tarantulas, it is impossible to decouple them simply by observing nature. Here, we use optical simulation and nano-3D rapid prototyping to demonstrate that introducing design features seen in these tarantulas onto a multilayer photonic structure nearly eliminates iridescence. As far as we are aware, this is the first known example of a noniridescent structural color produced by a photonic structure with both short and long-range order. This opens up an array of new possibilities for photonic structure design and fabrication to produce noniridescent structural colors and is a key first step to achieving economically viable solutions for mass production of noniridescent structural color.  … (p. 1 PDF)

There is a Canadian security and anti-counterfeiting company (Nanotech Security Corp.), inspired by the Morpho butterfly and its iridescent blue, which got its start in Bozena Kaminska’s laboratory at Simon Fraser University (Vancouver, Canada).

Getting back to the paper, after a few twists and turns, they conclude with this,

This approach of producing noniridescent structural colors using photonic structures with long-range order (i.e., modified multilayer) has, to our knowledge, not been explored previously. Our findings reaffirm the value of using nature and the biomimetic process as a tool for innovation and our approach also may help to overcome the current inability of colloidal self-assembly to achieve pure noniridescent structural red due to single-particle scattering and/or multiple scattering.[25] As a result, our research provides a new and easy way for designing structural colorants with customizable hues (see Figure S6, Supporting Information, as one of the potential examples) and iridescent effects to satisfy the needs of different applications. While nano-3D printing of these nanostructures is not viable for mass production, it does identify the key features that are necessary for top-down fabrication. With promising nanofabrication techniques, such as preform drawing[26]—a generally scalable methodology that has been demonstrated for fabricating particles with complex internal architectures and continuously tunable diameters down to nanometer scale[27] – it is possible to mass produce these “designer structural colorants” in an economically viable manner. Our discovery of how to produce noniridescent structural colors using long-range order may therefore lead to a more sustainable future that does not rely upon toxic and wasteful synthetic pigments and dyes. (p. 5)

I’m glad to have gotten caught up with the work. Thank you, Bor-Kai Hsiung.

Art (Lawren Harris and the Group of Seven), science (Raman spectroscopic examinations), and other collisions at the 2014 Canadian Chemistry Conference (part 4 of 4)

Cultural heritage and the importance of pigments and databases

Unlike Thom (Ian Thom, curator at the Vancouver Art Gallery), I believe that the testing was important. Knowing the spectra emitted by the pigments in Hurdy Gurdy and Autumn Harbour could help to set benchmarks for establishing the authenticity of the pigments used by artists (Harris and others) in the early part of Canada’s 20th century.

Europeans and Americans are more advanced in their use of technology as a tool in the process of authenticating, restoring, or conserving a piece of art. At the Chicago Institute of Art they identified the red pigment used in a Renoir painting as per my March 24, 2014 posting,

… The first item concerns research by Richard Van Duyne into the nature of the red paint used in one of Renoir’s paintings. A February 14, 2014 news item on Azonano describes some of the art conservation work that Van Duyne’s (nanoish) technology has made possible along with details about this most recent work,

Scientists are using powerful analytical and imaging tools to study artworks from all ages, delving deep below the surface to reveal the process and materials used by some of the world’s greatest artists.

Northwestern University chemist Richard P. Van Duyne, in collaboration with conservation scientists at the Art Institute of Chicago, has been using a scientific method he discovered nearly four decades ago to investigate masterpieces by Pierre-Auguste Renoir, Winslow Homer and Mary Cassatt.

Van Duyne recently identified the chemical components of paint, now partially faded, used by Renoir in his oil painting “Madame Léon Clapisson.” Van Duyne discovered the artist used carmine lake, a brilliant but light-sensitive red pigment, on this colorful canvas. The scientific investigation is the cornerstone of a new exhibition at the Art Institute of Chicago.

There are some similarities between the worlds of science (in this case, chemistry) and art (collectors,  institutions, curators, etc.). They are worlds where one must be very careful.

The scientists/chemists choose their words with precision while offering no certainties. Even the announcement for the discovery (by physicists) of the Higgs Boson is not described in absolute terms as I noted in my July 4, 2012 posting titled: Tears of joy as physicists announce they’re pretty sure they found the Higgs Boson. As the folks from ProsPect Scientific noted,

This is why the science must be tightly coupled with art expertise for an effective analysis.  We cannot do all of that for David [Robertson]. [He] wished to show a match between several pigments to support an interpretation that the ‘same’ paints were used. The availability of Hurdy Gurdy made this plausible because it offered a known benchmark that lessened our dependency on the databases and art-expertise. This is why Raman spectroscopy more often disproves authenticity (through pigment anachronisms). Even if all of the pigments analysed showed the same spectra we don’t know that many different painters didn’t buy the same brand of paint or that some other person didn’t take those same paints and use them for a different painting. Even if all pigments were different, that doesn’t mean Lawren Harris didn’t paint it, it just means different paints were used.

In short they proved that one of the pigments used in Autumn Harbour was also used in the authenticated Harris, Hurdy Gurdy, and the other pigment was in use at that time (early 20th century) in Canada. It doesn’t prove it’s a Harris painting but, unlike the Pollock painting where they found an anachronistic pigment, it doesn’t disprove Robertson’s contention.

To contrast the two worlds, the art world seems to revel in secrecy for its own sake while the world of science (chemistry) will suggest, hint, or hedge but never state certainties. The ProSpect* Scientific representative commented on authentication, art institutions, and databases,

We know that some art institutions are extremely cautious about any claims towards authentication, and they decline to be cited in anything other than the work they directly undertake. (One director of a well known US art institution said to me that they pointedly do not authenticate works, she offered advice on how to conduct the analysis but declined any reference to her institution.) We cannot comment on any of the business plans of any of our customers but the customers we have that use Raman spectroscopy on paintings generally build databases from their collected studies as a vital tool to their own ongoing work collecting and preserving works of art.

We don’t know of anyone with a database particular to pigments used by Canadian artists and neither did David R. We don’t know that any organization is developing such a database.The database we used is a mineral database (as pigments in the early 20th century were pre-synthetic this database contains some of the things commonly used in pigments at that time) There are databases available for many things:  many are for sale, some are protected intellectual property. We don’t have immediate access to a pigments database. Some of our art institution/museum customers are developing their own but often these are not publicly available. Raman spectroscopy is new on the scene relative to other techniques like IR and X-Ray analysis and the databases of Raman spectra are less mature.

ProSpect Scientific provided two papers which illustrate either the chemists’ approach to testing and art (RAMAN VIBRATIONAL STUDY OF PIGMENTS WITH PATRIMONIAL INTEREST FOR THE CHILEAN CULTURAL HERITAGE) and/or the art world’s approach (GENUINE OR FAKE: A MICRO-RAMAN SPECTROSCOPY STUDY OF AN ABSTRACT PAINTING ATTRIBUTED TO VASILY KANDINSKY [PDF]).

Canadian cultural heritage

Whether or not Autumn Harbour is a Lawren Harris painting may turn out to be less important than establishing a means for better authenticating, restoring, and conserving Canadian cultural heritage. (In a June 13, 2014 telephone conversation, David Robertson claims he will forward the summary version of the data from the tests to the Canadian Conservation Institute once it is received.)

If you think about it, Canadians are defined by the arts and by research. While our neighbours to the south went through a revolutionary war to declare independence, Canadians have declared independence through the visual and literary arts and the scientific research and implementation of technology (transportation and communication in the 19th and 20th centuries).

Thank you to both Tony Ma and David Robertson.

Finally, Happy Canada Day on July 1, 2014!

Part 1

Part 2

Part 3

* ‘ProsPect’ changed to ‘ProSpect’ on June 30, 2014.

ETA July 14, 2014 at 1300 hours PDT: There is now an addendum to this series, which features a reply from the Canadian Conservation Institute to a query about art pigments used by Canadian artists and access to a database of information about them.

Lawren Harris (Group of Seven), art authentication, and the Canadian Conservation Insitute (addendum to four-part series)

Art (Lawren Harris and the Group of Seven), science (Raman spectroscopic examinations), and other collisions at the 2014 Canadian Chemistry Conference (part 3 of 4)

Dramatic headlines (again)

Ignoring the results entirely, Metro News Vancouver, which favours the use of the word ‘fraud’, featured it in the headline of a second article about the testing, “Alleged Group of Seven work a fraud: VAG curator” by Thandi Fletcher (June 5, 2014 print issue); happily the online version of Fletcher’s story has had its headline changed to the more accurate: “Alleged Group of Seven painting not an authentic Lawren Harris, says Vancouver Art Gallery curator.” Fletcher’s article was updated after its initial publication with some additional text (it is worth checking out the online version even if you’re already seen the print version). There had been a second Vancouver Metro article on the testing of the authenticated painting by Nick Wells but that in common, with his June 4, 2014 article about the first test, “A fraud or a find?” is no longer available online. Note: Standard mainstream media practice is that the writer with the byline for the article is not usually the author of the article’s headline.

There are two points to be made here. First, Robertson has not attempted to represent ‘Autumn Harbour’ as an authentic Lawren Harris painting other than in a misguided headline for his 2011 news release.  From Robertson’s July 26, 2011 news release (published by Reuters and published by Market Wired) where he crossed a line by stating that Autumn Harbour is a Harris in his headline (to my knowledge the only time he’s done so),

Lost Lawren Harris Found in Bala, Ontario

Unknown 24×36 in. Canvas Piques a Storm of Controversy

VANCOUVER, BRITISH COLUMBIA–(Marketwire – July 26, 2011) –
Was Autumn Harbour painted by Lawren Harris in the fall of 1912? That summer Lawren Harris was 26 years old and had proven himself as an accomplished and professional painter. He had met J.E.H. MacDonald in November of 1911. They became fast friends and would go on to form the Group of Seven in 1920 but now in the summer of 1912 they were off on a sketching expedition to Mattawa and Temiscaming along the Quebec-Ontario border. Harris had seen the wilderness of the northern United States and Europe but this was potentially his first trip outside the confines of an urban Toronto environment into the Canadian wilderness.

By all accounts he was overwhelmed by what he saw and struggled to find new meaning in his talents that would capture these scenes in oil and canvas. There are only two small works credited to this period, archived in the McMichael gallery in Kleinburg, Ontario. Dennis Reid, Assistant Curator of the National Gallery of Canada stated in 1970 about this period: “Both Harris and (J.E.H.) MacDonald explored new approaches to handling of colour and overall design in these canvases. Harris in particular was experimenting with new methods of paint handling, and Jackson pointed out the interest of the other painters in these efforts, referring to the technique affectionately as ‘Tomato Soup’.” For most authorities the summer and fall of 1912 are simply called his ‘lost period’ because it was common for Harris to destroy, abandon or give away works that did not meet his standards. The other trait common to Harris works, is the lack of a signature and some that are signed were signed on his behalf. The most common proxy signatory was Betsy Harris, his second wife who signed canvases on his behalf when he could no longer do so.

So the question remains. Can an unsigned 24×36 in. canvas dated to 1900-1920 that was found in a curio shop in Bala, Ontario be a long lost Lawren Harris? When pictures were shown to Charles C. Hill, Curator of Canadian Art, National Gallery of Canada, he replied: “The canvas looks like no Harris I have ever seen…” A similar reply also came from Ian Thom, Head Curator for the Vancouver Art Gallery: “I do not believe that your work can be connected with Harris in any way.” [emphases mine] Yet the evidence still persists. The best example resides within the National Art Gallery. A 1919, 50.5 X 42.5 in. oil on rough canvas shows Harris’s style of under painting, broad brush strokes and stilled composition. Shacks, painted in 1919 and acquired the Gallery in 1920 is an exact technique clone of Autumn Harbour. For a list of comparisons styles with known Harris works and a full list of the collected evidence please consult www.1912lawrenharris.ca/ and see for yourself.

If Robertson was intent on perpetrating a fraud, why would he include the negative opinions from the curators or attempt to authenticate his purported Harris? The 2011 website is no longer available but Robertson has established another website, http://autumnharbour.ca/.

It’s not a crime (fraud) to have strong or fervent beliefs. After all, Robertson was the person who contacted ProSpect* Scientific to arrange for a test.

Second, Ian Thom, the VAG curator did not call ‘Autumn Harbour’ or David Robertson, a fraud. From the updated  June 5, 2014 article sporting a new headline by Thandi Fletcher,

“I do not believe that the painting … is in fact a Lawren Harris,” said Ian Thom, senior curator at the Vancouver Art Gallery, “It’s that simple.”

It seems Thom feels as strongly as Robertson does; it’s just that Thom holds an opposing opinion.

Monetary value was mentioned earlier as an incentive for Robertson’s drive to prove the authenticity of his painting, from the updated June 5, 2014 article with the new headline by Thandi Fletcher,

Still, Robertson, who has carried out his own research on the painting, said he is convinced the piece is an authentic Harris. If it were, he said it would be worth at least $3 million. [emphasis mine]

“You don’t have to have a signature on the canvas to recognize brushstroke style,” he said.

Note: In a June 13, 2014 telephone conversation, Robertson used the figure of $1M to denote his valuation of Autumn Harbour and claimed a degree in Geography with a minor in Fine Arts from the University of Waterloo. He also expressed the hope that Autumn Harbour would prove to be a* Rosetta Stone of sorts for art pigments used in the early part of the 20th century.

As for the owner of Hurdy Gurdy and the drama that preceded its test on June 4, 2014, Fletcher had this in her updated and newly titled article,

Robertson said the painting’s owner, local Vancouver businessman Tony Ma, had promised to bring the Harris original to the chemistry conference but pulled out after art curator Thom told him not to participate.

While Thom acknowledged that Ma did ask for his advice, he said he didn’t tell him to pull out of the conference.

“It was more along the lines of, ‘If I were you, I wouldn’t do it, because I don’t think it’s going to accomplish anything,’” said Thom, adding that the final decision is up to Ma. [emphasis mine]

A request for comment from Ma was not returned Wednesday [June 5, 2014].

Thom, who already examined Robertson’s painting a year ago [in 2013? then, how is he quoted in a 2011 news release?], said he has no doubt Harris did not paint it.

“The subject matter is wrong, the handling of the paint is wrong, and the type of canvas is wrong,” he said, adding that many other art experts agree with him.

Part 1

Part 2

Part 4

* ‘ProsPect’ changed to ‘ProSpect’ on June 30, 2014. Minor grammatical change made to sentence: ‘He also expressed the hope that Autumn Harbour would prove to a be of Rosetta Stone of sorts for art pigments used in the early part of the 20th century.’ to ‘He also expressed the hope that Autumn Harbour would prove to be a* Rosetta Stone of sorts for art pigments used in the early part of the 20th century.’ on July 2, 2014.

ETA July 14, 2014 at 1300 hours PDT: There is now an addendum to this series, which features a reply from the Canadian Conservation Institute to a query about art pigments used by Canadian artists and access to a database of information about them.

Lawren Harris (Group of Seven), art authentication, and the Canadian Conservation Insitute (addendum to four-part series)

Art (Lawren Harris and the Group of Seven), science (Raman spectroscopic examinations), and other collisions at the 2014 Canadian Chemistry Conference (part 2 of 4)

Testing the sample and Raman fingerprints

The first stage of the June 3, 2010 test of David Robertson’s Autumn Harbour, required taking a tiny sample from the painting,. These samples are usually a fleck of a few microns (millionths of an inch), which can then be tested to ensure the lasers are set at the correct level assuring no danger of damage to the painting. (Robertson extracted the sample himself prior to arriving at the conference. He did not allow anyone else to touch his purported Harris before, during, or after the test.)

Here’s how ProSpect* Scientific describes the ‘rehearsal’ test on the paint chip,

Tests on this chip were done simply to ensure we knew what power levels were safe for use on the painting.  While David R stated he believed the painting was oil on canvas without lacquer, we were not entirely certain of that.  Lacquer tends to be easier to burn than oil pigments and so we wanted to work with this chip just to be entirely certain there was no risk to the painting itself.

The preliminary (rehearsal) test resulted in a line graph that showed the frequencies of the various pigments in the test sample. Titanium dioxide, for example, was detected and its frequency (spectra) reflected on the graph.

I found this example of a line graph representing the spectra (fingerprint) for a molecule of an ultramarine (blue) pigment along with a general explanation of a Raman ‘fingerprint’. There is no indication as to where the ultramarine pigment was obtained. From the  WebExhibits.org website featuring a section on Pigments through the Ages and a webpage on Spectroscopy,

raman-ArtPigment

Ultramarine [downloaded from http://www.webexhibits.org/pigments/intro/spectroscopy.html]

Raman spectra consist of sharp bands whose position and height are characteristic of the specific molecule in the sample. Each line of the spectrum corresponds to a specific vibrational mode of the chemical bonds in the molecule. Since each type of molecule has its own Raman spectrum, this can be used to characterize molecular structure and identify chemical compounds.

Most people don’t realize that the chemical signature (spectra) for pigment can change over time with new pigments being introduced. Finding a pigment that was on the market from 1970 onwards in a painting by Jackson Pollock who died in 1956 suggests strongly that the painting couldn’t have come from Pollock’s hand. (See Michael Shnayerson’s May 2012 article, A Question of Provenance, in Vanity Fair for more about the Pollock painting. The article details the fall of a fabled New York art gallery that had been in business prior to the US Civil War.)

The ability to identify a pigment’s molecular fingerprint means that an examination by Raman spectroscopy can be part of an authentication, a restoration, or a conservation process. Here is how a representative from ProSpect Scientific describes the process,

Raman spectroscopy is non-destructive (when conducted at the proper power levels) and identifies the molecular components in the pigments, allowing characterization of the pigments for proper restoration or validation by comparison with other pigments of the same place/time. It is valuable to art institutions and conservators because it can do this.  In most cases of authentication Raman spectroscopy is one of many tools used and not the first in line. A painting would be first viewed by art experts for technique, format etc, then most often analysed with IR or X-Ray, then perhaps Raman spectroscopy. It is impossible to use Raman spectroscopy to prove authenticity as paint pigments are usually not unique to any particular painter.  Most often Raman spectroscopy is used by conservators to determine proper pigments for appropriate restoration.  Sometimes Raman will tell us that the pigment isn’t from the time/era the painting is purported to be from (anachronisms).

Autumn Harbour test

Getting back to the June 3, 2014 tests, once the levels were set then it was time to examine Autumn Harbour itself to determine the spectra for the various pigments.  ProSpect Scientific has provided an explanation of the process,

This spectrometer was equipped with an extension that allowed delivery of the laser and collection of the scattered light at a point other than directly under the microscope. We could also have used a flexible fibre optic probe for this, but this device is slightly more efficient. This allowed us to position the delivery/collection point for the light just above the painting at the spot we wished to test. For this test, we don’t sweep across the surface, we test a small pinpoint that we feel is a pigment of the target colour.

We only use one laser at a time. The system is built so we can easily select one laser or another, depending on what we wish to look at. Some researchers have 3 or 4 lasers in their system because different lasers provide a better/worse raman spectrum depending on the nature of the sample. In this case we principally used the 785nm laser as it is better for samples that exhibit fluorescence at visible wavelengths. 532nm is a visible wavelength.  For samples that didn’t produce good signal we tried the 532nm laser as it produces better signal to noise than 785nm, generally speaking. I believe the usable results in our case were obtained with the 785nm laser.

The graphed Raman spectra shows peaks for the frequency of scattered light that we collect from the laser-illuminated sample (when shining a laser on a sample the vast majority of light is scattered in the same frequency of the laser, but a very small amount is scattered at different frequencies unique to the molecules in the sample). Those frequencies correspond to and identify molecules in the sample. We use a database (on the computer attached to the spectrometer) to pattern match the spectra to identify the constituents.

One would have thought ‘game over’ at this point. According to some informal sources, Canada has a very small (almost nonexistent) data bank of information about pigments used in its important paintings. For example, the federal government’s Canadian Conservation Institute (CCI) has a very small database of pigments and nothing from Lawren Harris paintings [See the CCI’s response in this addendum], so the chances that David Robertson would have been able to find a record of pigments used by Lawren Harris roughly in the same time period that Autumn Harbour seems to have been painted are not good.

Everything changes

In a stunning turn of events and despite the lack of enthusiasm from Vancouver Art Gallery (VAG) curator, Ian Thom, on Wednesday, June 4, 2014 the owner of the authenticated Harris, Hurdy Gurdy, relented and brought the painting in for tests.

Here’s what the folks from ProSpect Scientific had to say about the comparison,

Many pigments were evaluated. Good spectra were obtained for blue and white. The blue pigment matched on both paintings, the white didn’t match. We didn’t get useful Raman spectra from other pigments. We had limited time, with more time we might fine tune and get more data.

One might be tempted to say that the results were 50/50 with one matching and the other not, The response from the representative of ProSpect Scientific is more measured,

We noted that the mineral used in the pigment was the same.  Beyond that is interpretation:  Richard offered the view that lapis-lazuli was a typical and characteristic component for blue in that time period (early 1900’s).   We saw different molecules in the whites used in the two paintings, and Richard offered that both were characteristic of the early 1900’s.

Part 1

Part 3

Part 4

* ‘ProsPect’ changed to ‘ProSpect’ on June 30, 2014.

ETA July 14, 2014 at 1300 hours PDT: There is now an addendum to this series, which features a reply from the Canadian Conservation Institute to a query about art pigments used by Canadian artists and access to a database of information about them.

Lawren Harris (Group of Seven), art authentication, and the Canadian Conservation Insitute (addendum to four-part series)

 

Art (Lawren Harris and the Group of Seven), science (Raman spectroscopic examinations), and other collisions at the 2014 Canadian Chemistry Conference (part 1 of 4)

One wouldn’t expect the 97th Canadian Chemistry Conference held in Vancouver, Canada from  June 1 – 5, 2014 to be an emotional rollercoaster. One would be wrong. Chemists and members of the art scene are not only different from thee and me, they are different from each other.

Setting the scene

It started with a May 30, 2014 Simon Fraser University (SFU) news release,

During the conference, ProSpect Scientific has arranged for an examination of two Canadian oil paintings; one is an original Lawren Harris (Group of Seven) titled “Hurdy Gurdy” while the other is a painting called “Autumn Harbour” that bears many of Harris’s painting techniques. It was found in Bala, Ontario, an area that was known to have been frequented by Harris.

Using Raman Spectroscopy equipment manufactured by Renishaw (Canada), Dr. Richard Bormett will determine whether the paint from both works of art was painted from the same tube of paint.

As it turns out, the news release got it somewhat wrong. Raman spectroscopy testing does not make it possible to* determine whether the paints came from the same tube, the same batch, or even the same brand. Nonetheless, it is an important tool for art authentication, restoration and/or conservation and both paintings were scheduled for testing on Tuesday, June 3, 2014. But that was not to be.

The owner of the authenticated Harris (Hurdy Gurdy) rescinded permission. No one was sure why but the publication of a June 2, 2014 article by Nick Wells for Metro News Vancouver probably didn’t help in a situation that was already somewhat fraught. The print version of the Wells article titled, “A fraud or a find?” showed only one painting “Hurdy Gurdy” and for anyone reading quickly, it might have seemed that the Hurdy Gurdy painting was the one that could be “a fraud or a find.”

The dramatically titled article no longer seems to be online but there is one (also bylined by Nick Wells) dated June 1, 2014 titled, Chemists in Vancouver to use lasers to verify Group of Seven painting. It features (assuming it is still available online) images of both paintings, the purported Harris (Autumn Harbour) and the authenticated Harris (Hurdy Gurdy),

"Autumn Harbour" [downloaded from http://metronews.ca/news/vancouver/1051693/chemists-in-vancouver-to-use-lasers-to-verify-group-of-seven-painting/]

“Autumn Harbour” [downloaded from http://metronews.ca/news/vancouver/1051693/chemists-in-vancouver-to-use-lasers-to-verify-group-of-seven-painting/]

Heffel Fine Art Auction

Lawren Harris’‚ Hurdy Gurdy, a depiction of Toronto’s Ward district is shown in this handout image. [downloaded from http://metronews.ca/news/vancouver/1051693/chemists-in-vancouver-to-use-lasers-to-verify-group-of-seven-painting/]

David Robertson who owns the purported Harris (Autumn Harbour) and is an outsider vis à vis the Canadian art world, has been trying to convince people for years that the painting he found in Bala, Ontario is a “Lawren Harris” painting. For anyone unfamiliar with the “Group of Seven” of which Lawren Harris was a founding member, this group is legendary to many Canadians and is the single most recognized name in Canadian art history (although some might argue that status for Emily Carr and/or Tom Thomson; both of whom have been, on occasion, honorarily included in the Group).  Robertson’s incentive to prove “Autumn Harbour” is a Harris could be described as monetary and/or prestige-oriented and/or a desire to make history.

The owner of the authenticated Harris “Hurdy Gurdy” could also be described as an outsider of sorts [unconfirmed at the time of publication; a June 26, 2014 query is outstanding], gaining entry to that select group of people who own a ‘Group of Seven’ painting at a record-setting price in 2012 with the purchase of a piece that has a provenance as close to unimpeachable as you can get. From a Nov. 22, 2012 news item on CBC (Canadian Broadcasting Corporation) news online,

Hurdy Gurdy, one of the finest urban landscapes ever painted by Lawren Harris, sold for $1,082,250, a price that includes a 17 per cent buyer’s premium. The pre-sale estimate suggested it could go for $400,000 to $600,000 including the premium.

The Group of Seven founder kept the impressionistic painting of a former Toronto district known as the Ward in his own collection before bequeathing it to his daughter. It has remained in the family ever since.

Occasionally, Harris “would come and say, ‘I need to borrow this back for an exhibition,’ and sometimes she wouldn’t see [the paintings] again,” Heffel vice-president Robert Heffel said. “Harris asked to have this painting back for a show…and she said ‘No, dad. Not this one.’ It was a painting that was very, very dear to her.”

It had been a coup to get access to an authenticated Harris for comparison testing so Hurdy Gurdy’s absence was a major disappointment. Nonetheless, Robertson went through with the scheduled June 3, 2014 testing of his ‘Autumn Harbour’.

Chemistry, spectroscopy, the Raman system, and the experts

Primarily focused on a technical process, the chemists (from ProSpect* Scientific and Renishaw) were unprepared for the drama and excitement that anyone associated with the Canadian art scene might have predicted.  From the chemists’ perspective, it was an opportunity to examine a fabled piece of Canadian art (Hurdy Gurdy) and, possibly, play a minor role in making Canadian art history.

The technique the chemists used to examine the purported Harris, Autumn Harbour, is called Raman spectroscopy and its beginnings as a practical technique date back to the 1920s. (You can get more details about Raman spectroscopy in this Wikiipedia entry then will be given here after the spectroscopy description.)

Spectroscopy (borrowing heavily from this Wikipedia entry) is the process where one studies the interaction between matter and radiated energy and which can be measured as frequencies and/or wavelengths. Raman spectroscopy systems can be used to examine radiated energy with low frequency emissions as per this description in the Raman spectroscopy Wikipedia entry,

Raman spectroscopy (/ˈrɑːmən/; named after Sir C. V. Raman) is a spectroscopic technique used to observe vibrational, rotational, and other low-frequency modes in a system.[1] It relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range. The laser light interacts with molecular vibrations, phonons or other excitations in the system, resulting in the energy of the laser photons being shifted up or down.

The reason for using Raman spectroscopy for art authentication, conservation, and/or restoration purposes is that the technique, as noted earlier, can specify the specific chemical composition of the pigments used to create the painting. It is a technique used in many fields as a representative from ProSpect Scientific notes,

Raman spectroscopy is a vital tool for minerologists, forensic investigators, surface science development, nanotechnology research, pharmaceutical research and other applications.  Most graduate level university labs have this technology today, as do many government and industry researchers.  Raman spectroscopy is now increasingly available in single purpose hand held units that can identify the presence of a small number of target substances with ease-of-use appropriate for field work by law enforcers, first responders or researchers in the field.

About the chemists and ProSpect Scientific and Renishaw

There were two technical experts attending the June 3, 2014 test for the purported Harris painting, Autumn Harbour, Dr. Richard Bormett of Renishaw and Dr. Kelly Akers of ProSpect Scientific.

Dr. Kelly Akers founded ProSpect Scientific in 1996. Her company represents Renishaw Raman spectroscopy systems for the most part although other products are also represented throughout North America. Akers’ company is located in Orangeville, Ontario. Renishaw, a company based in the UK. offers a wide line of products including Raman spectroscopes. (There is a Renishaw Canada Ltd., headquartered in Mississauga, Ontario, representing products other than Raman spectroscopes.)

ProSpect Scientific runs Raman spectroscopy workshops, at the Canadian Chemistry Conferences as a regular occurrence, often in conjunction with Renishaw’s Bormett,. David Robertson, on learning the company would be at the 2014 Canadian Chemistry Conference in Vancouver, contacted Akers and arranged to have his purported Harris and Hurdy Gurdy, the authenticated Harris, tested at the conference.

Bormett, based in Chicago, Illinois, is Renishaw’s business manager for the Spectroscopy Products Division in North America (Canada, US, & Mexico).  His expertise as a spectroscopist has led him to work with many customers throughout the Americas and, as such, has worked with several art institutions and museums on important and valuable artifacts.  He has wide empirical knowledge of Raman spectra for many things, including pigments, but does not claim expertise in art or art authentication. You can hear him speak at a 2013 US Library of Congress panel discussion titled, “Advances in Raman Spectroscopy for Analysis of Cultural Heritage Materials,” part of the Library of Congress’s Topics in Preservation Series (TOPS), here on the Library of Congress website or here on YouTube. The discussion runs some 130 minutes.

Bormett has a PhD in analytical chemistry from the University of Pittsburgh. Akers has a PhD in physical chemistry from the University of Toronto and is well known in the Raman spectroscopy field having published in many refereed journals including “Science” and the “Journal of Physical Chemistry.”  She expanded her knowledge of industrial applications of Raman spectroscopy substantive post doctoral work in Devon, Alberta at the CANMET Laboratory (Natural Resources Canada).

About Renishaw InVia Reflex Raman Spectrometers

The Raman spectroscopy system used for the examination, a Renishaw InVia Reflex Raman Spectrometer, had

  • two lasers (using 785nm [nanometres] and 532nm lasers for this application),
  • two cameras,
    (ProSpect Scientific provided this description of the cameras: The system has one CCD [Charged Coupled Device] camera that collects the scattered laser light to produce Raman spectra [very sensitive and expensive]. The system also has a viewing camera mounted on the microscope to allow the user to visually see what the target spot on the sample looks like. This camera shows on the computer what is visible through the eyepieces of the microscope.)
  • a microscope,
  • and a computer with a screen,

all of which fit on a tabletop, albeit a rather large one.

For anyone unfamiliar with the term CCD (charged coupled device), it is a sensor used in cameras to capture light and convert it to digital data for capture by the camera. (You can find out more here at TechTerms.com on the CCD webpage.)

Part 2

Part 3

Part 4

* ‘to’ added to sentence on June 27, 2014 at 1340 hours (PDT). ‘ProsPect’ corrected to ‘ProSpect’ on June 30, 2014.

ETA July 14, 2014 at 1300 hours PDT: There is now an addendum to this series, which features a reply from the Canadian Conservation Institute to a query about art pigments used by Canadian artists and access to a database of information about them.

Lawren Harris (Group of Seven), art authentication, and the Canadian Conservation Insitute (addendum to four-part series)