Tag Archives: nanomaterials

European Commission has issued evaluation of nanomaterial risk frameworks and tools

Despite complaints that there should have been more, there has been some research into risks where nanomaterials are concerned. While additional research would be welcome, it’s perhaps more imperative that standardized testing and risk frameworks are developed so, for example, carbon nanotube safety research in Japan can be compared with the similar research in the Netherlands, the US, and elsewhere. This March 15, 2017 news item on Nanowerk features some research analyzing risk assessment frameworks and tools in Europe,

A recent study has evaluated frameworks and tools used in Europe to assess the potential health and environmental risks of manufactured nanomaterials. The study identifies a trend towards tools that provide protocols for conducting experiments, which enable more flexible and efficient hazard testing. Among its conclusions, however, it notes that no existing frameworks meet all the study’s evaluation criteria and calls for a new, more comprehensive framework.

A March 9, 2017 news alert in the European Commission’s Science for Environment Policy series, which originated the news item, provides more detail (Note: Links have been removed),

Nanotechnology is identified as a key emerging technology in the EU’s growth strategy, Europe 2020. It has great potential to contribute to innovation and economic growth and many of its applications have already received large investments. However,there are some uncertainties surrounding the environmental, health and safety risks of manufactured nanomaterials. For effective regulation, careful scientific analysis of their potential impacts is needed, as conducted through risk assessment exercises.

This study, conducted under the EU-funded MARINA project1, reviewed existing frameworks and tools for risk assessing manufactured nanomaterials. The researchers define a framework as a ‘conceptual paradigm’ of how a risk assessment should be conducted and understood, and give the REACH chemical safety assessment as an example. Tools are defined as implements used to carry out a specific task or function, such as experimental protocols, computer models or databases.

In all, 12 frameworks and 48 tools were evaluated. These were identified from other studies and projects. The frameworks were assessed against eight criteria which represent different strengths, such as whether they consider properties specific to nanomaterials, whether they consider the entire life cycle of a nanomaterial and whether they include careful planning and prioritise objectives before the risk assessment is conducted.

The tools were assessed against seven criteria, such as ease of use, whether they provide quantitative information and if they clearly communicate uncertainty in their results. The researchers defined the criteria for both frameworks and tools by reviewing other studies and by interviewing staff at organisations who develop tools.

The evaluation was thus able to produce a list of strengths and areas for improvement for the frameworks and tools, based on whether they meet each of the criteria. Among its many findings, the evaluation showed that most of the frameworks stress that ‘problem formulation’, which sets the goals and scope of an assessment during the planning process, is essential to avoid unnecessary testing. In addition, most frameworks consider routes of exposure in the initial stages of assessment, which is beneficial as it can exclude irrelevant exposure routes and avoid unnecessary tests.

However, none of the frameworks met all eight of the criteria. The study therefore recommends that a new, comprehensive framework is developed that meets all criteria. Such a framework is needed to inform regulation, the researchers say, and should integrate human health and environmental factors, and cover all stages of the life cycle of a product containing nanomaterials.

The evaluation of the tools suggested that many of them are designed to screen risks, and not necessarily to support regulatory risk assessment. However, their strengths include a growing trend in quantitative models, which can assess uncertainty; for example, one tool analysed can identify uncertainties in its results that are due to gaps in knowledge about a material’s origin, characteristics and use.

The researchers also identified a growing trend in tools that provide protocols for experiments, such as identifying materials and test hazards, which are reproducible across laboratories. These tools could lead to a shift from expensive case-by-case testing for risk assessment of manufactured nanomaterials towards a more efficient process based on groupings of nanomaterials; and ‘read-across’ methods, where the properties of one material can be inferred without testing, based on the known properties of a similar material. The researchers do note, however, that although read-across methods are well established for chemical substances, they are still being developed for nanomaterials. To improve nanomaterial read-across methods, they suggest that more data are needed on the links between nanomaterials’ specific properties and their biological effects.

That’s all, folks.

Investigating nanoparticles and their environmental impact for industry?

It seems the Center for the Environmental Implications of Nanotechnology (CEINT) at Duke University (North Carolina, US) is making an adjustment to its focus and opening the door to industry, as well as, government research. It has for some years (my first post about the CEINT at Duke University is an Aug. 15, 2011 post about its mesocosms) been focused on examining the impact of nanoparticles (also called nanomaterials) on plant life and aquatic systems. This Jan. 9, 2017 US National Science Foundation (NSF) news release (h/t Jan. 9, 2017 Nanotechnology Now news item) provides a general description of the work,

We can’t see them, but nanomaterials, both natural and manmade, are literally everywhere, from our personal care products to our building materials–we’re even eating and drinking them.

At the NSF-funded Center for Environmental Implications of Nanotechnology (CEINT), headquartered at Duke University, scientists and engineers are researching how some of these nanoscale materials affect living things. One of CEINT’s main goals is to develop tools that can help assess possible risks to human health and the environment. A key aspect of this research happens in mesocosms, which are outdoor experiments that simulate the natural environment – in this case, wetlands. These simulated wetlands in Duke Forest serve as a testbed for exploring how nanomaterials move through an ecosystem and impact living things.

CEINT is a collaborative effort bringing together researchers from Duke, Carnegie Mellon University, Howard University, Virginia Tech, University of Kentucky, Stanford University, and Baylor University. CEINT academic collaborations include on-going activities coordinated with faculty at Clemson, North Carolina State and North Carolina Central universities, with researchers at the National Institute of Standards and Technology and the Environmental Protection Agency labs, and with key international partners.

The research in this episode was supported by NSF award #1266252, Center for the Environmental Implications of NanoTechnology.

The mention of industry is in this video by O’Brien and Kellan, which describes CEINT’s latest work ,

Somewhat similar in approach although without a direction reference to industry, Canada’s Experimental Lakes Area (ELA) is being used as a test site for silver nanoparticles. Here’s more from the Distilling Science at the Experimental Lakes Area: Nanosilver project page,

Water researchers are interested in nanotechnology, and one of its most commonplace applications: nanosilver. Today these tiny particles with anti-microbial properties are being used in a wide range of consumer products. The problem with nanoparticles is that we don’t fully understand what happens when they are released into the environment.

The research at the IISD-ELA [International Institute for Sustainable Development Experimental Lakes Area] will look at the impacts of nanosilver on ecosystems. What happens when it gets into the food chain? And how does it affect plants and animals?

Here’s a video describing the Nanosilver project at the ELA,

You may have noticed a certain tone to the video and it is due to some political shenanigans, which are described in this Aug. 8, 2016 article by Bartley Kives for the Canadian Broadcasting Corporation’s (CBC) online news.

Are there any leaders in the ‘graphene race’?

Tom Eldridge, a director and co-founder of Fullerex, has written a Jan. 5, 2017 essay titled: Is China still leading the graphene race? for Nanotechnology Now. Before getting to the essay, here’s a bit more about Fullerex and Tom Eldridge’s qualifications. From Fullerex’s LinkedIn description,

Fullerex is a leading independent broker of nanomaterials and nano-intermediates. Our mission is to support the advancement of nanotechnology in creating radical, transformative and sustainable improvement to society. We are dedicated to achieving these aims by accelerating the commercialisation and usage of nanomaterials across industry and beyond. Fullerex is active in market development and physical trading of advanced materials. We generate demand for nanomaterials across synergistic markets by stimulating innovation with end-users and ensuring robust supply chains are in place to address the growing commercial trade interest. Our end-user markets include Polymers and Polymer Composites, Coatings, Tyre and Rubber, Cementitious Composites, 3D Printing and Printed Electronics, the Energy sector, Lubricating Oils and Functional Fluids. The materials we cover: Nanomaterials: Includes fullerenes, carbon nanotubes and graphene, metal and metal oxide nanoparticles, and organic-inorganic hybrids. Supplied as raw nanopowders or ready-to-use dispersions and concentrates. Nano-intermediates: Producer goods and semi-finished products such as nano-enabled coatings, polymer masterbatches, conductive inks, thermal interface materials and catalysts.

As for Tom Eldridge, here’s more about him, his brother, and the company from the Fullerex About page,

Fullerex was founded by Joe and Tom Eldridge, brothers with a keen interest in nanotechnology and the associated emerging market for nanomaterials.

Joe has a strong background in trading with nearly 10 years’ experience as a stockbroker, managing client accounts for European Equities and FX. At University he read Mathematics at Imperial College London gaining a BSc degree and has closely followed the markets for disruptive technologies and advanced materials for a number of years.

Tom worked in the City of London for 7 years in commercial roles throughout his professional career, with an expertise in market data, financial and regulatory news. In his academic background, he earned a BSc degree in Physics and Philosophy at Kings College London and is a member of the Institute of Physics.

As a result, Fullerex has the strong management composition that allows the company to support the growth of the nascent and highly promising nanomaterials industry. Fullerex is a flexible company with drive, enthusiasm and experience, committed to aiding the development of this market.

Getting back to the matter at hand, that’s a rather provocative title for Tom Eldridge’s essay,. given that he’s a Brit and (I believe) the Brits viewed themselves as leaders in the ‘graphene race’ but he offers a more nuanced analysis than might be expected from the title. First, the patent landscape (from Eldridge’s Jan. 5, 2017 essay),

As competition to exploit the “wonder material” has intensified around the world, detailed reports have so far been published which set out an in-depth depiction of the global patent landscape for graphene, notably from CambridgeIP and the UK Intellectual Property Office, in 2013 and 2015 respectively. Ostensibly the number of patents and patent applications both indicated that China was leading the innovation in graphene technology. However, on closer inspection it became less clear as to how closely the patent figures themselves reflect actual progress and whether this will translate into real economic impact. Some of the main reasons to be doubtful included:

– 98% of the Chinese patent applications only cover China, so therefore have no worldwide monopoly.
– A large number of the Chinese patents are filed in December, possibly due to demand to meet patent quotas. The implication being that the patent filings follow a politically driven agenda, rather than a purely innovation or commercially driven agenda.
– In general, inventors could be more likely to file for patent protection in some countries rather than others e.g. for tax purposes. Which therefore does not give a truly accurate picture of where all the actual research activity is based.
– Measuring the proportion of graphene related patents to overall patents is more indicative of graphene specialisation, which shows that Singapore has the largest proportion of graphene patents, followed by China, then South Korea.

(Intellectual Property Office, 2015), (Ellis, 2015), (CambridgeIP, 2013)

Then, there’s the question of production,

Following the recent launch of the latest edition of the Bulk Graphene Pricing Report, which is available exclusively through The Graphene Council, Fullerex has updated its comprehensive list of graphene producers worldwide, and below is a summary of the number of graphene producers by country in 2017.

Summary Table Showing the Number of Graphene Producers by Country and Region

The total number of graphene producers identified is 142, across 27 countries. This research expands upon previous surveys of the graphene industry, such as the big data analysis performed by Nesta in 2015 (Shapira, 2015). The study by Nesta [formerly  NESTA, National Endowment for Science, Technology and the Arts) is an independent charity that works to increase the innovation capacity of the UK; see Wikipedia here for more about NESTA] revealed 65 producers throughout 16 countries but was unable to glean accurate data on producers in Asia, particularly China.

As we can now see however from the data collected by Fullerex, China has the largest number of graphene producers, followed by the USA, and then the UK.

In addition to having more companies active in the production and sale of graphene than any other country, China also holds about 2/3rds of the global production capacity, according to Fullerex.

Eldridge goes on to note that the ‘graphene industry’ won’t truly grow and develop until there are substantive applications for the material. He also suggests taking another look at the production figures,

As with the patent landscape, rather than looking at the absolute figures, we can review the numbers in relative terms. For instance, if we normalise to account for the differences in the size of each country, by looking at the number of producers as a proportion of GDP, we see the following: Spain (7.18), UK (4.48), India (3.73), China (3.57), Canada (3.28) [emphasis mine], USA (1.79) (United Nations, 2013).

Unsurprisingly, each leading country has a national strategy for economic development which involves graphene prominently.

For instance, The Spanish Council for Scientific Research has lent 9 of its institutes along with 10 universities and other public R&D labs involved in coordinating graphene projects with industry.

The Natural Sciences and Engineering Research Council of Canada [NSERC] has placed graphene as one of five research topics in its target area of “Advanced Manufacturing” for Strategic Partnership Grants.

The UK government highlights advanced materials as one of its Eight Great Technologies, within which graphene is a major part of, having received investment for the NGI and GEIC buildings, along with EPSRC and Innovate UK projects. I wrote previously about the UK punching above its weight in terms of research, ( http://fullerex.com/index.php/articles/130-the-uk-needs-an-industrial-revolution-can-graphene-deliver/ ) but that R&D spending relative to GDP was too low compared to other developed nations. It is good to see that investment into graphene production in the UK is bucking that trend, and we should anticipate this will provide a positive economic outcome.

Yes, I’m  particularly interested in the fact Canada becomes more important as a producer when the numbers are relative but it is interesting to compare the chart with Eldridge’s text and to note how importance shifts depending on what numbers are being considered.

I recommend reading Eldridge’s piece in its entirety.

A few notes about graphene in Canada

By the way, the information in Eldridge’s essay about NSERC’s placement of graphene as a target area for grants is news to me. (As I have often noted here, I get more information about the Canadian nano scene from international sources than I do from our national sources.)

Happily I do get some home news such as a Jan. 5, 2017 email update from Lomiko Metals, a Canadian junior exploration company focused on graphite and lithium. The email provides the latest information from the company (as I’m not an expert in business or mining this is not an endorsement),

On December 13, 2016 we were excited to announce the completion of our drill program at the La Loutre flake graphite property. We received very positive results from our 1550 meter drilling program in 2015 in the area we are drilling now. In that release I stated, “”The intercepts of multiple zones of mineralization in the Refractory Zone where we have reported high grade intercepts previously is a very promising sign. The samples have been rushed to the ALS Laboratory for full assay testing,” We hope to have the results of those assays shortly.

December 16, 2016 Lomiko announced a 10:1 roll back of our shares. We believe that this roll back is important as we work towards securing long term equity financing for the company. Lomiko began trading on the basis of the roll back on December 19.

We believe that Graphite has a bright future because of the many new products that will rely on the material. I have attached a link to a video on Lomiko, Graphite and Graphene.  

https://youtu.be/Y–Y_Ub6oC4

January 3, 2017 Lomiko announced the extension and modification of its option agreements with Canadian Strategic Metals Inc. for the La Loutre and Lac des Iles properties. The effect of this extension is to give Lomiko additional time to complete the required work under the agreements.

Going forward Lomiko is in a much stronger position as the result of our share roll back. Potential equity funders who are very interested in our forthcoming assay results from La Loutre and the overall prospects of the company, have been reassured by our share consolidation.

Looking forward to 2017, we anticipate the assays of the La Loutre drilling to be delivered in the next 90 days, sooner we hope. We also anticipate additional equity funding will become available for the further exploration and delineation of the La Loutre and Lac des Iles properties and deposits.

More generally, we are confident that the market for large flake graphite will become firmer in 2017. Lomiko’s strategy of identifying near surface, ready to mine, graphite nodes puts us in the position to take advantage of improvements in the graphite price without having to commit large sums to massive mine development. As we identify and analyze the graphite nodes we are finding we increase the potential resources of the company. 2017 should see significantly improved resource estimates for Lomiko’s properties.

As I wasn’t familiar with the term ‘roll back of shares’, I looked it up and found this in an April 18, 2012 posting by Dudley Pierce Baker on kitco.com,

As a general rule, we hate to see an announcement of a share rollback, however, there exceptions which we cover below. Investors should always be aware that if a company has, say over 150 million shares outstanding, in our opinion, it is a potential candidate for a rollback and the announcement should not come as a surprise.

Weak markets, a low share price, a large number of shares outstanding, little or no cash and you have a company which is an idea candidate for a rollback.

The basic concept of a rollback or consolidation in a company’s shares is rather simple.

We are witnessing a few cases of rollbacks not with the purpose of raising more money but rather to facilitate the listing of the company’s shares on the NYSE [New York Stock Exchange] Amex.

I have no idea what situation Lomiko finds itself in but it should be noted that graphere research has been active since 2004 when the first graphene sheets were extracted from graphite. This is a relatively new field of endeavour and Lomiko (along with other companies) is in the position of pioneering the effort here in Canada. That said, there are many competitors to graphene and major international race to commercialize nanotechnology-enabled products.

Are there any leaders in the ‘graphene race?

Getting back to the question in the headline, I don’t think there are any leaders at the moment. No one seems to have what they used to call “a killer app,” that one application/product that everyone wants and which drive demand for graphene.

Carbon nanotubes: faster, cheaper, easier, and more consistent

One of the big problems with nanomaterials has to do with production issues such as: consistent size and shape. It seems that scientists at the US National Institute of Standards and Technology (NIST) have developed a technique for producing carbon nanotubes (CNTs) which addresses these issues. From a July 19, 2016 news item on Nanotechnology Now,

Just as many of us might be resigned to clogged salt shakers or rush-hour traffic, those working to exploit the special properties of carbon nanotubes have typically shrugged their shoulders when these tiniest of cylinders fill with water during processing. But for nanotube practitioners who have reached their Popeye threshold and “can’t stands no more,” the National Institute of Standards and Technology (NIST) has devised a cheap, quick and effective strategy that reliably enhances the quality and consistency of the materials–important for using them effectively in applications such as new computing technologies.

To prevent filling of the cores of single-wall carbon nanotubes with water or other detrimental substances, the NIST researchers advise intentionally prefilling them with a desired chemical of known properties. Taking this step before separating and dispersing the materials, usually done in water, yields a consistently uniform collection of nanotubes. In quantity and quality, the results are superior to water-filled nanotubes, especially for optical applications such as sensors and photodetectors.

A July 15, 2016 NIST news release, which originated the news item, expands on the theme,

The approach opens a straightforward route for engineering the properties of single-wall carbon nanotubes—rolled up sheets of carbon atoms arranged like chicken wire or honey combs—with improved or new properties.

“This approach is so easy, inexpensive and broadly useful that I can’t think of a reason not to use it,” said NIST chemical engineer Jeffrey Fagan.

In their proof-of-concept experiments, the NIST team inserted more than 20 different compounds into an assortment of single-wall carbon nanotubes with an interior diameter that ranged from more than 2 down to about 0.5 nanometers. Led by visiting researcher Jochen Campo, the scientists tested their strategy by using hydrocarbons called alkanes as fillers.

The alkanes, which include such familiar compounds as propane and butane, served to render the nanotube interiors unreactive. In other words, the alkane-filled nanotubes behaved almost as if they were empty—precisely the goal of Campo, Fagan and colleagues.

Compared with nanotubes filled with water and possibly ions, acids and other unwanted chemicals encountered during processing, empty nanotubes possess far superior properties. For example, when stimulated by light, empty carbon nanotubes fluoresce far brighter and with sharper signals.

Yet, “spontaneous ingestion” of water or other solvents by the nanotubes during processing is an “endemic but often neglected phenomenon with strong implications for the development of nanotube applications,” the NIST team wrote in a recent article in Nanoscale Horizons.

Perhaps because of the additional cost and effort required to filter out and gather nanotubes, researchers tend to tolerate mixed batches of unfilled (empty) and mostly filled single-wall carbon nanotubes. Separating unfilled nanotubes from these mixtures requires expensive ultracentrifuge equipment and, even then, the yield is only about 10 percent, Campo estimates.

“If your goal is to use nanotubes for electronic circuits, for example, or for fluorescent anti-cancer image contrast agents, then you require much greater quantities of materials of consistent composition and quality,” Campo explained, who was exploring these applications while doing postdoctoral research at the University of Antwerp. “This particular need inspired development of the new prefilling method by asking the question, can we put some passive chemical into the nanotube instead to keep the water out.”

From the very first simple experiments, the answer was yes. And the benefits can be significant. In fluorescence experiments, alkane-filled nanotubes emitted signals two to three times stronger than those emitted by water-filled nanotubes. Performance approached that of empty nanotubes—the gold standard for these comparisons.

As important, the NIST-developed prefilling strategy is controllable, versatile and easily incorporated into existing methods for processing single-wall carbon nanotubes, according to the researchers.

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

Enhancing single-wall carbon nanotube properties through controlled endohedral filling by J. Campo, Y. Piao, S. Lam, C. M. Stafford, J. K. Streit, J. R. Simpson, A. R. Hight Walker, and J. A. Fagan. Nanoscale Horiz., 2016,1, 317-324 DOI: 10.1039/C6NH00062B First published online 10 May 2016

This paper is open access but you do need to register on the site (it is a free registration).

Study nanomaterial toxicity without testing animals

The process of moving on from testing on animals is laborious as new techniques are pioneered and, perhaps more arduously, people’s opinions and habits are changed. The People for the Ethical Treatment of Animals (PETA) organization focusing the research end of things has announced a means of predicting carbon nanotube toxicity in lungs according to an April 25, 2016 news item on Nanowerk (Note: A link has been removed),

A workshop organized last year [2015] by the PETA International Science Consortium Ltd has resulted in an article published today in the journal Particle and Fibre Toxicology (“Aerosol generation and characterization of multi-walled carbon nanotubes [MWCNTs] exposed to cells cultured at the air-liquid interface”). It describes aerosol generation and exposure tools that can be used to predict toxicity in human lungs following inhalation of nanomaterials.

An April 25, 2016 PETA press release on EurekAlert, which originated the news item, explains further without much more detail,

Nanomaterials are increasingly being used in consumer products such as paints, construction materials, and food packaging, making human exposure to these materials more likely. One of the common ways humans may be exposed to these substances is by inhalation, therefore, regulatory agencies often require the toxicity of these materials on the lungs to be tested. These tests usually involve confining rats to small tubes the size of their bodies and forcing them to breathe potentially toxic substances before they are killed. However, time, cost, scientific and ethical issues have led scientists to develop methods that do not use animals. The tools described in the new article are used to deposit nanomaterials (or other inhalable substances) onto human lung cells grown in a petri dish.

Co-authors of the Particle and Fibre Toxicology article are scientists from the PETA Science Consortium , The Dow Chemical Company, Baylor University, and the U.S. NTP Interagency Center for the Evaluation of Alternative Toxicological Methods (NICEATM).

“Promoting non-animal methods to assess nanotoxicity has been a focus of the PETA International Science Consortium”, said Dr. Monita Sharma, co-author of the publication and Nanotechnology Specialist at the Consortium, “we organized an international workshop last year on inhalation testing of nanomaterials and this review describes some of the tools that can be used to provide a better understanding of what happens in humans after inhaling these substances.” During the workshop, experts provided recommendations on the design of an in vitro test to assess the toxicity of nanomaterials (especially multi-walled carbon nanotubes) in the lung, including cell types, endpoints, exposure systems, and dosimetry considerations. Additional publications summarizing the outcomes of the workshop are forthcoming.

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

Aerosol generation and characterization of multi-walled carbon nanotubes exposed to cells cultured at the air-liquid interface by William W. Polk, Monita Sharma, Christie M. Sayes, Jon A. Hotchkiss, and Amy J. Clippinger. Particle and Fibre Toxicology201613:20 DOI: 10.1186/s12989-016-0131-y Published: 23 April 2016

This is an open access paper.

Use of nanomaterials in food for animals: the US Food and Drug Administration (FDA) issues a final guidance

Bureaucratese is not my first language so the US Food and Drug Administration’s final guidance on the use of nanomaterials in animal food seems a little vague to me. That said, here’s the Aug. 5, 2015 news item on Nanowerk, which announced the guidance (Note: A link has been removed),

The U.S. Food and Drug Administration has issued a final guidance for industry, ‘Use of Nanomaterials in Food for Animals’ (pdf), which is intended to assist industry and other stakeholders in identifying potential issues related to safety or regulatory status of food for animals containing nanomaterials or otherwise involving the application of nanotechnology. This guidance is applicable to food ingredients intended for use in animal food which (1) consist entirely of nanomaterials, (2) contain nanomaterials as a component or (3) otherwise involve the application of nanotechnology.

An Aug. 4, 2015 FDA announcement, which originated the news item, provides more detail,

This final guidance addresses the legal framework for adding nanomaterial substances to food for animals and includes recommendations for submitting a Food Additive Petition (FAP) for a nanomaterial animal food ingredient. This guidance also recommends manufacturers consult with FDA early in the development of their nanomaterial animal food ingredient and before submitting an FAP. At this time, we are not aware of any animal food ingredient engineered on the nanometer scale for which there is generally available safety data sufficient to serve as the foundation for a determination that the use of such an animal food ingredient is generally recognized as safe (GRAS).

Nanotechnology is an emerging technology that allows scientists to create, explore, and manipulate materials on a scale measured in nanometers – particles so small that they cannot be seen with a regular microscope. These particles can have chemical, physical, and biological properties that differ from those of their larger counterparts, and nanotechnology has a broad range of potential applications.

Guidance documents represent the FDA’s current thinking on particular topics, policies, and regulatory issues. While “guidance for industry” documents are prepared primarily for industry, they also are used by FDA staff and other stakeholders to understand the agency’s interpretation of laws and policies.

Although this guidance has been finalized, you can submit comments at any time. To submit comments to the docket by mail, use the following address. Be sure to include docket number FDA-2013-D-1009 on each page of your written comments.

Division of Dockets Management
HFA-305
Food and Drug Administration
5630 Fishers Lane, Room 1061
Rockville, MD 20852

You can find the guidance here.

Carbon dioxide as a source for new nanomaterials

Polish researchers have made a startling suggestion (from a Jan. 23, 2014 news item on Nanowerk),

In common perception, carbon dioxide is just a greenhouse gas, one of the major environmental problems of mankind. For Warsaw chemists CO2 became, however, something else: a key element of reactions allowing for creation of nanomaterials with unprecedented properties.

In reaction with carbon dioxide, appropriately designed chemicals allowed researchers from the Institute of Physical Chemistry of the Polish Academy of Sciences (IPC PAS) in Warsaw and the Faculty of Chemistry, Warsaw University of Technology, (WUT) for production of unprecedented nanomaterials.

Here’s an image the researchers use to illustrate their work,

Yellow tennis balls, spatially integrated in an adamant-like structure, symbolise crystal lattice of the microporous material resulting from self-assembly of nanoclusters. Orange balls imitate gas molecules that can adsorb in this material. The presentation is performed by Katarzyna Sołtys, a doctoral student from the Institute of Physical Chemistry of the Polish Academy of Sciences in Warsaw. (Source: IPC PAS, Grzegorz Krzyżewski).

Yellow tennis balls, spatially integrated in an adamant-like structure, symbolise crystal lattice of the microporous material resulting from self-assembly of nanoclusters. Orange balls imitate gas molecules that can adsorb in this material. The presentation is performed by Katarzyna Sołtys, a doctoral student from the Institute of Physical Chemistry of the Polish Academy of Sciences in Warsaw. (Source: IPC PAS, Grzegorz Krzyżewski).

The Jan. 23, 2014 IPC news release, which originated the news item, describes the work in more detail,

Carbon dioxide (CO2) is a natural component of Earth’s atmosphere. It is the most abundant carbon-based building block, and is involved in the synthesis of glucose, an energy carrier and building unit of paramount importance for living organisms.

“Carbon dioxide has been for years used in industrial synthesis of polymers. On the other hand, there has been very few research papers reporting fabrication of inorganic functional materials using CO2”, says Kamil Sokołowski, a doctoral student in IPC PAS.

Prof. Lewiński’s [Janusz Lewiński (IPC PAS, WUT)] group has shown that appropriately designed precursor compounds in reaction with carbon dioxide lead to fabrication of a microporous material (with pore diameters below 2 nm) resulting from self-assembly of luminescent nanoclusters. Novel microporous material, composed of building blocks with zinc carbonate core encapsulated in appropriately designed organic shell (hydroxyquinoline ligands), is highly luminescent, with photoluminescence quantum yield significantly higher than those of classical fluorescent compounds used in state-of-the-art OLEDs.

“Using carbon dioxide as a building block we were able to construct a highly porous and really highly luminescent material. Can it be used for construction of luminescent diodes or sensing devices? The discovery is new, the research work on the novel material is in progress, but we are deeply convinced that the answer is: yes”, says Sokołowski.

Already now it can be said that the novel material enjoys considerable interest. Polish and international patent applications were filed for the invention and the implementation work in cooperation with a joint venture company is in progress.

The design of precursors was inspired by nature, in particular by the binding of carbon dioxide in enzymatic systems of carbonic anhydrase, an enzyme responsible for fast metabolism of CO2 in human body. Effective enzyme activity is based on its active centre, where a hydroxyzinc (ZnOH) type reaction system is located.

“A hydroxyzinc reaction system occurs also in molecules of alkylzinc compounds, designed by us and used for fixation of carbon dioxide”, explains Sokołowski and continues: “These compounds are of particular interest for us, because in addition to hydroxyl group they contain also a reactive metal-carbon bond. It means that both the first and the second reaction system can participate in consecutive chemical transformations of such precursors”.

The research related to the chemistry of alkylhydroxyzinc compounds has an over 150 years of history and its roots are directly connected to the birth of organometallic chemistry. It was, however, only in 2011 and 2012 when Prof. Lewiński’s group has presented the first examples of stable alkylhydroxyzinc compounds obtained as a result of rationally designed synthesis.

The strategy for materials synthesis using carbon dioxide and appropriate alkylhydroxyzinc precursors, discovered by the researchers from Warsaw, seems to be a versatile tool for production of various functional materials. Depending on the composition of the reagents and the process conditions, a mesoporous material (with pore diameter from 2 to 50 nm) composed of zinc carbonate nanoparticles or multinuclear zinc nanocapsules for prospective applications in supramolecular chemistry can be obtained in addition to the material described above.

Further research of Prof. Lewiński’s group has shown that the mesoporous materials based on ZnCO3-nanoparticles can be transformed into zinc oxide (ZnO) aerogels. Mesoporous materials made of ZnO nanoparticles with extended surface can be used as catalytic fillings, allowing for and accelerating reactions of various gaseous reagents. Other potential applications are related to semiconducting properties of zinc oxide. That’s why the novel materials can be used in future in photovoltaic cells or as a major component of semiconductor sensing devices.

Good luck to the researchers as they find ways to turn a greenhouse gas into something useful.

US National Insitute for Occupational Health and Safety issues report on strategies for handling nanomaterials

A Dec. 19, 2013 news item on Nanowerk announces the release of a recent publication about the safe handling of nanomaterials from the US National Institute of Occupational Health and Safety (NIOSH), Note: A link has been removed,

Occupational health risks associated with manufacturing and using nanomaterials are not yet clearly understood. However, initial toxicological data indicate that there is reason for caution. NIOSH is committed to promoting the responsible development and advancement of nanotechnology through its research and communication efforts to protect workers. NIOSH has taken a leading role in conducting research and making recommendations for nanotechnology safety in work settings. See the nanotechnology topic page for a list of documents and resources.

Recently, NIOSH has released a document titled, Current Strategies for Engineering Controls in Nanomaterial Production and Downstream Handling Processes, which provides information on how to control exposures for many of the most common processes seen in facilities that use or produce nanomaterials or nano-enabled products.

A Nov.8, 2013 NIOSH news release provides some additional insight into NIOSH’s strategy,,

Engineering controls are favored over administrative controls and personal protective equipment for lowering worker exposures, because they are designed to remove the hazard at the source, before it comes into contact with the worker. However, evidence showing the effectiveness of controls during the manufacture and downstream use of engineered nanomaterials in specific applications has been scarce.

The NIOSH recommendations fill a gap for science-based guidance that employers and workers can apply now, as research continues for better understanding of nanomaterial characteristics, and ways in which workers may be exposed, that may pose the risk of adverse health effects.

The consumer products market currently has more than 1,000 nanomaterial-containing products including makeup, sunscreen, food storage products, appliances, clothing, electronics, computers, sporting goods, and coatings. As more nanomaterials are introduced into the workplace and nano-enabled products enter the market, it is essential that producers and users of engineered nanomaterials ensure a safe and healthy work environment, the new document states.

Processes discussed in the document and for which controls are recommended and described include reactor operations and cleanout processes, small-scale weighing and handling of nanopowders, intermediate and finishing processes, and maintenance tasks. The document also includes recommendations for evaluating the performance of control technologies and control systems.

There’s a Dec. 9, 2013 NIOSH blog posting written by Jennifer L. Topmiller and Kevin H. Dunn which provides more detail about workers’ exposure to nanomaterials,,

Engineered nanomaterials are materials that are intentionally produced and have at least one primary dimension less than 100 nanometers (nm). Nanomaterials have properties different from those of larger particles of the same material, making them unique and desirable for specific product applications.  The consumer products market currently has more than 1,000 nanomaterial-containing products including makeup, sunscreen, food storage products, appliances, clothing, electronics, computers, sporting goods, and coatings [WWICS 2011].

It is difficult to estimate how many workers are involved in this field. By one estimate, there are 400,000 workers worldwide in the field of nanotechnology, with an estimated 150,000 of those in the United States [Roco et al. 2010]. The National Science Foundation has estimated that approximately 6 million workers will be employed in nanotechnology industries worldwide by 2020.

Occupational health risks associated with manufacturing and using nanomaterials are not yet clearly understood.  However, initial toxicological data indicate that there is reason for caution. NIOSH is committed to promoting the responsible development and advancement of nanotechnology through its research and communication efforts to protect workers. NIOSH has taken a leading role in conducting research and making recommendations for nanotechnology safety in work settings. …

The greatest exposures to raw nanomaterials are likely to occur in the workplace during production, handling, secondary processing, and packaging. In a review of exposure assessments conducted at nanotechnology plants and laboratories, Dr. Derk Brouwer determined that activities which resulted in exposures included harvesting (e.g., scraping materials out of reactors), bagging, packaging, and reactor cleaning [Brouwer 2010]. Downstream activities that may release nanomaterials include bag dumping, manual transfer between processes, mixing or compounding, powder sifting, and machining of parts that contain nanomaterials.  Similar to controlling hazards in traditional macro-scale manufacturing, engineering controls are recommended to reduce exposures to nanomaterials.

… Because little has been published on exposure controls in the production and use of nanomaterials, this document focuses on applications that have relevance to the field of nanotechnology and on engineering control technologies currently used, and known to be effective, in other industries.

Assessing how well the exposure control works is also essential for verifying that the exposure goals of the facility have been successfully met. This document covers a range of control evaluation tools including airflow visualization and measurement and containment test methods, such as tracer gas testing. Additional methods, such as video exposure monitoring, also provide information on critical task-based exposures and helps identify high-exposure activities and help provide the basis for interventions.

intriguingly, there’s also a plea for partnership at the end of this Dec. 9, 2013 NIOSH posting,

Producers and users of engineered nanomaterials are invited and encouraged to partner with NIOSH. Companies that have installed exposure controls, such as local exhaust ventilation, or are interested in assessing and reducing worker exposures can work with NIOSH engineers to develop and evaluate exposure mitigation options. Partnering with NIOSH not only benefits your company by providing an assessment of process emissions and recommending effective exposure control approaches  but also expands the knowledge base that benefits the industry as a whole.  Please feel free to contact us through the comment section below or by sending an e-mail to nioshblog@cdc.gov.  Thank for your interest in protecting workers!

You can find the NIOSH report, Current Strategies for Engineering Controls in Nanomaterial Production and Downstream Handling Processes here.

NanoDefine: a project for implementing the European Union’s definition for nanomaterials

Here”s an excerpt from the Dec. 13, 2013 news item on Azonano about a new consortium focused on measuring nanomaterials and, if I understand the news item rightly, refining the definition so that it can be implemented,

A 29-partner consortium of top European RTD [?] performers, metrology institutes, and nanomaterials and instrument manufacturers, gathered at a launch meeting in Wageningen, NL, [Netherlands] last month to begin the mobilisation of the critical mass of expertise required to establish the measurement tools and scientific data that help to implement the EU recommendation on the definition of a nanomaterial.

We have come a long way in exploring the full potential of nano as a key enabling technology, yet, there are still uncertainties surrounding environment, health and safety (EHS) issues and the questions that need to be addressed: what is or isn’t a nanomaterial. One challenge consists in the development of methods that reliably identify, characterize and measure nanomaterials (NM) both as substance and in various products and matrices. In responses, the European Commission has recently recommended a definition of NM as a reference to determine this (2011/696/EU).

The NanoDefine project will explicitly address this question over the next four years.

I have written about the European Union’s definition of nanomaterials in an Oct, 18, 2011 posting,

After all the ‘sturm und drang’ in the last few months (my Sept. 8, 2011 posting summarizing some of the lively discussion), a nanomaterials definition for Europe has been adopted. It is the first ‘cross-cutting’ nanomaterials definition to date according to the Oct. 18, 2011 news item on Nanowerk,

“Nanomaterials” are materials whose main constituents have a dimension of between 1 and 100 billionth of a metre, according to a Recommendation on the definition of nanomaterial (pdf) adopted by the European Commission today. The announcement marks an important step towards greater protection for citizens, clearly defining which materials need special treatment in specific legislation.

I also featured some specific critiques of the then newly proclaimed definition in an Oct. 19, 2011 posting and again in an Oct. 20, 2011 posting.

The Institute of Nanotechnology Dec. 12, 2013 news release, which originated the news item, provides more details about the NanoDefine project,

Based on a comprehensive evaluation of existing methodologies and a rigorous intra-lab and inter-lab comparison, validated measurement methods and instruments will be developed that are robust, readily implementable, cost-effective and capable to reliably measure the size of particles in the range of 1 – 100 nm, with different shapes, coatings and for the widest possible range of materials, in various complex media and products. Practical case studies will assess their applicability for various sectors, including food/feed, cosmetics etc.

One major outcome of the project will be the establishment of an integrated tiered approach including validated rapid screening methods (tier 1) and validated in depth methods (tier 2), with a user manual to guide end-users, such as manufacturers, regulatory bodies and contract laboratories, to implement the developed methodology.

NanoDefine will closely collaborate with its sister projects in the NanoSafety Cluster (www.nanosafetycluster.eu) as well as engage with international EHS, RTD and metrology initiatives. NanoDefine will also be strongly linked to main standardization bodies, such as CEN, ISO and OECD, by actively participating in Technical Commissions and Working Groups, and by proposing specific ISO/CEN work items, to integrate the developed and validated methodology into the current standardization work.

For more information:
NanoDefine: ‘Development of an integrated approach based on validated and standardized methods to support the implementation of the EC recommendation for a definition of nanomaterial’ receives funding from the European Community’s Seventh Framework Programme under grant agreement n°604347 and runs from 1/11/2013 – 31/10/2017

Visit the project website: www.nanodefine.eu (currently under construction) [as of Dec. 13, 2013 there is no landing page]
Contact the Project Coordinators:
hans.marvin@wur.nl
wim.beek@wur.nl
stefan.weigel@wur.nl
rudolf.reuther@enas-online.com

Visit the NanoSafety Cluster website: www.nanosafetycluster.eu

I have searched on this blog to see if I’ve stumbled across the Institute of Nanotechnology, located in the UK, previously but cannot find any other mentions (which may be due to the search function and my impatience for paging through apparently irrelevant search results). At any rate, here’s more about the institute from its About Us webpage (Note: Links have been removed),

Background

The Institute of Nanotechnology (IoN) was founded by Ottilia Saxl in January 1997. It is a registered Charity, whose core activities are focused on education and training in nanotechnology. It grew out of the Centre for Nanotechnology, part funded by the DTI through the UK’s National Initiative on Nanotechnology (NION). The Institute was one of the world’s first nanotechnology information providers and is now a global leader.

The Institute works closely with governments, universities, researchers, companies and the general public to educate and inform on all aspects of nanotechnology. It also organises various international scientific events, conferences and educational courses that examine the implications of nanotechnology across a wide variety of themes and sectors.

As most people know (except maybe policymakers), implementation is the tricky part of any rule, policy, and/or law and  the definitions are crucial.

Danish evaluate research on absorption of nanomaterials through the skin

An Oct. 3, 2013 news item on Azonano announces a report produced by the Danish Environmental Protection Agency on the state of research into dermal absorption of nanomaterials  (Note: A link has been removed),

 A new report published by the Danish Environmental Protection Agency (EPA) provides a comprehensive evaluation of the knowledge base regarding the dermal absorption of nanomaterials.

The report is the final output of the project “Dermal absorption of Nanomaterials”, which forms part of the “Better Control of Nano” initiative 2012 – 2015 conducted by the Danish EPA with the aim of further clarifying possible risks to consumers and the environment from nanomaterials.

The overall objectives of the project – which was led by the Institute of Occupational Medicine (IOM) working with COWI A/S – were to:  i) gather and evaluate the existing knowledge concerning the dermal absorption of nanomaterials, ii) assess the need to generate new knowledge, and iii) develop recommendations for the most suitable skin models, measurement methods and relevant candidate nanomaterials for future experimental testing.

The report: Dermal Absorption of Nanomaterials Part of the ”Better control of nano” initiative 2012 – 2015 Environmental Project No. 1504, 2013 gives a good description of skin and a good technical overview of the literature and the state of the research which, for the interested reader, could supply the basis for a better understanding of how to read research papers on this topic.  The report does not offer consumer information about nano sunscreens, etc.

Here’ are some of the conclusions from the Executive Summary,

One of the key challenges in assessing the literature on the physicochemical properties influencing dermal penetration/absorption of nanomaterials is that it is difficult to draw conclusions due to either: i) limitations in the reporting of physicochemical data, and/or, ii) the alteration of multiple experimental parameters in a non-systematic way. The issue of a lack of information on nanoparticle physicochemical properties is common, yet the most challenging aspect is the alteration of multiple experimental parameters whereby multiple characteristics such as shape, charge, coating, size can all be changed. This means that little meaningful comparison of results can be made within a single experimental study, let alone between studies.

Despite such challenges, some key conclusions can be drawn. [emphasis mine] Whilst there are many conflicting results, on balance the literature seems to suggest that absorption of particles in the nano-range through the skin is possible although occurs to a very low degree and that the level of penetration, depending on chemistry and experimental conditions, may be greater than for larger particles. The role of size is considered a critical component of dermal absorption but this in itself does not seem to guarantee absorption or lack of as other properties can also influence dermal absorption markedly. In addition, particle size is not necessarily a constant parameter as agglomeration of particles can occur over time and also in relation to experimental conditions (e.g. presence of surfactants within particle vehicle formulation). However, whilst this issue of agglomeration has been suggested as being important (as well as an important experimental variable), agglomeration state is often not reported within studies.