Tag Archives: silica nanoparticles

Preserving art canvases (think Van Gogh, Picasso, Vermeer, and others) with nanomaterials

It has to be disconcerting to realize that your precious paintings are deteriorating day by day.  In a June 22, 2017 posting titled ‘Art masterpieces are turning into soap‘,

This piece of research has made a winding trek through the online science world. First it was featured in an April 20, 2017 American Chemical Society news release on EurekAlert,

A good art dealer can really clean up in today’s market, but not when some weird chemistry wreaks havoc on masterpieces [emphasis mine]. Art conservators started to notice microscopic pockmarks forming on the surfaces of treasured oil paintings that cause the images to look hazy. It turns out the marks are eruptions of paint caused, weirdly, by soap that forms via chemical reactions. Since you have no time to watch paint dry, we explain how paintings from Rembrandts to O’Keefes are threatened by their own compositions — and we don’t mean the imagery.

Here’s the video,


Now, for the latest: canavases are deteriorating too. A May 23, 2018 news item on Nanowerk announces the latest research on the ‘canvas issue’ (Note: A link has been removed),

Paintings by Vincent van Gogh, Pablo Picasso and Johannes Vermeer have been delighting art lovers for years. But it turns out that these works of art might be their own worst enemy — the canvases they were painted on can deteriorate over time.

In an effort to combat this aging process, one group is reporting in ACS Applied Nano Materials (“Combined Nanocellulose/Nanosilica Approach for Multiscale Consolidation of Painting Canvases”) that nanomaterials can provide multiple layers of reinforcement.

A May 23, 2018 American Chemical Society (ACS) news release (also on EurekAlert), which originated the news item,  expands on the theme,

One of the most important parts of a painting is the canvas, which is usually made from cellulose-based fibers. Over time, the canvas ages, resulting in discoloration, wrinkles, tears and moisture retention, all greatly affecting the artwork. To combat aging, painting conservators currently place a layer of adhesive and a lining on the back of a painting, but this treatment is invasive and difficult to reverse. In previous work, Romain Bordes and colleagues from Chalmers University of Technology, Sweden, investigated nanocellulose as a new way to strengthen painting canvases on their surfaces. In addition, together with Krzysztof Kolman, they showed that silica nanoparticles can strengthen individual paper and cotton fibers. So, they next wanted to combine these two methods to see if they could further strengthen aging canvas.

The team combined polyelectrolyte-treated silica nanoparticles (SNP) with cellulose nanofibrils (CNF) for a one-step treatment. The researchers first treated canvases with acid and oxidizing conditions to simulate aging. When they applied the SNP-CNF treatment, the SNP penetrated and strengthened the individual fibers of the canvas, making it stiffer compared to untreated materials. The CNF strengthened the surface of the canvas and increased the canvas’s flexibility. The team notes that this treatment could be a good alternative to conventional methods.

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

Combined Nanocellulose/Nanosilica Approach for Multiscale Consolidation of Painting Canvases by Krzysztof Kolman, Oleksandr Nechyporchuk, Michael Persson, Krister Holmberg, and Romain Bordes. ACS Appl. Nano Mater., Article ASAP DOI: 10.1021/acsanm.8b00262 Publication Date (Web): April 26, 2018

Copyright © 2018 American Chemical Society

This image illustrating the researchers’ solution accompanies the article,

Courtesy: ACS

The European Union’s NanoRestART project was mentioned here before they’d put together this introductory video, which provides a good overview of the research,

For more details about the problems with contemporary and modern art, there’s my April 4, 2016 posting when the NanoRestART project was first mentioned here and there’s my Jan. 10, 2017 posting which details research into 3D-printed art and some of the questions raised by the use of 3D printing and other emerging technologies in the field of contemporary art.

The devil’s (i.e., luciferase) in the bioluminescent plant

The American Chemical Society (ACS) and the Massachusetts Institute of Technology (MIT) have both issued news releases about the latest in bioluminescence.The researchers tested their work on watercress, a vegetable that was viewed in almost sacred terms in my family; it was not easily available in Vancouver (Canada) when I was child.

My father would hunt down fresh watercress by checking out the Chinese grocery stores. He could spot the fresh stuff from across the street while driving at 30 miles or more per hour. Spotting it entailed an immediate hunt for parking (my father hated to pay so we might have go around the block a few times or more) and a dash out of the car to ensure that he got his watercress before anyone else spotted it. These days it’s much more easily available and, thankfully, my father has passed on so he won’t have to think about glowing watercress.

Getting back to bioluninescent vegetable research, the American Chemical Society’s Dec. 13, 2017 news release on EurekAlert (and as a Dec. 13, 2017 news item on ScienceDaily) makes the announcement,

The 2009 film “Avatar” created a lush imaginary world, illuminated by magical, glowing plants. Now researchers are starting to bring this spellbinding vision to life to help reduce our dependence on artificial lighting. They report in ACS’ journal Nano Letters a way to infuse plants with the luminescence of fireflies.

Nature has produced many bioluminescent organisms, however, plants are not among them. Most attempts so far to create glowing greenery — decorative tobacco plants in particular — have relied on introducing the genes of luminescent bacteria or fireflies through genetic engineering. But getting all the right components to the right locations within the plants has been a challenge. To gain better control over where light-generating ingredients end up, Michael S. Strano and colleagues recently created nanoparticles that travel to specific destinations within plants. Building on this work, the researchers wanted to take the next step and develop a “nanobionic,” glowing plant.

The team infused watercress and other plants with three different nanoparticles in a pressurized bath. The nanoparticles were loaded with light-emitting luciferin; luciferase, which modifies luciferin and makes it glow; and coenzyme A, which boosts luciferase activity. Using size and surface charge to control where the sets of nanoparticles could go within the plant tissues, the researchers could optimize how much light was emitted. Their watercress was half as bright as a commercial 1 microwatt LED and 100,000 times brighter than genetically engineered tobacco plants. Also, the plant could be turned off by adding a compound that blocks luciferase from activating luciferin’s glow.

Here’s a video from MIT detailing their research,

A December 13, 2017 MIT news release (also on EurekAlert) casts more light on the topic (I couldn’t resist the word play),

Imagine that instead of switching on a lamp when it gets dark, you could read by the light of a glowing plant on your desk.

MIT engineers have taken a critical first step toward making that vision a reality. By embedding specialized nanoparticles into the leaves of a watercress plant, they induced the plants to give off dim light for nearly four hours. They believe that, with further optimization, such plants will one day be bright enough to illuminate a workspace.

“The vision is to make a plant that will function as a desk lamp — a lamp that you don’t have to plug in. The light is ultimately powered by the energy metabolism of the plant itself,” says Michael Strano, the Carbon P. Dubbs Professor of Chemical Engineering at MIT and the senior author of the study

This technology could also be used to provide low-intensity indoor lighting, or to transform trees into self-powered streetlights, the researchers say.

MIT postdoc Seon-Yeong Kwak is the lead author of the study, which appears in the journal Nano Letters.

Nanobionic plants

Plant nanobionics, a new research area pioneered by Strano’s lab, aims to give plants novel features by embedding them with different types of nanoparticles. The group’s goal is to engineer plants to take over many of the functions now performed by electrical devices. The researchers have previously designed plants that can detect explosives and communicate that information to a smartphone, as well as plants that can monitor drought conditions.

Lighting, which accounts for about 20 percent of worldwide energy consumption, seemed like a logical next target. “Plants can self-repair, they have their own energy, and they are already adapted to the outdoor environment,” Strano says. “We think this is an idea whose time has come. It’s a perfect problem for plant nanobionics.”

To create their glowing plants, the MIT team turned to luciferase, the enzyme that gives fireflies their glow. Luciferase acts on a molecule called luciferin, causing it to emit light. Another molecule called co-enzyme A helps the process along by removing a reaction byproduct that can inhibit luciferase activity.

The MIT team packaged each of these three components into a different type of nanoparticle carrier. The nanoparticles, which are all made of materials that the U.S. Food and Drug Administration classifies as “generally regarded as safe,” help each component get to the right part of the plant. They also prevent the components from reaching concentrations that could be toxic to the plants.

The researchers used silica nanoparticles about 10 nanometers in diameter to carry luciferase, and they used slightly larger particles of the polymers PLGA and chitosan to carry luciferin and coenzyme A, respectively. To get the particles into plant leaves, the researchers first suspended the particles in a solution. Plants were immersed in the solution and then exposed to high pressure, allowing the particles to enter the leaves through tiny pores called stomata.

Particles releasing luciferin and coenzyme A were designed to accumulate in the extracellular space of the mesophyll, an inner layer of the leaf, while the smaller particles carrying luciferase enter the cells that make up the mesophyll. The PLGA particles gradually release luciferin, which then enters the plant cells, where luciferase performs the chemical reaction that makes luciferin glow.

The researchers’ early efforts at the start of the project yielded plants that could glow for about 45 minutes, which they have since improved to 3.5 hours. The light generated by one 10-centimeter watercress seedling is currently about one-thousandth of the amount needed to read by, but the researchers believe they can boost the light emitted, as well as the duration of light, by further optimizing the concentration and release rates of the components.

Plant transformation

Previous efforts to create light-emitting plants have relied on genetically engineering plants to express the gene for luciferase, but this is a laborious process that yields extremely dim light. Those studies were performed on tobacco plants and Arabidopsis thaliana, which are commonly used for plant genetic studies. However, the method developed by Strano’s lab could be used on any type of plant. So far, they have demonstrated it with arugula, kale, and spinach, in addition to watercress.

For future versions of this technology, the researchers hope to develop a way to paint or spray the nanoparticles onto plant leaves, which could make it possible to transform trees and other large plants into light sources.

“Our target is to perform one treatment when the plant is a seedling or a mature plant, and have it last for the lifetime of the plant,” Strano says. “Our work very seriously opens up the doorway to streetlamps that are nothing but treated trees, and to indirect lighting around homes.”

The researchers have also demonstrated that they can turn the light off by adding nanoparticles carrying a luciferase inhibitor. This could enable them to eventually create plants that shut off their light emission in response to environmental conditions such as sunlight, the researchers say.

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

A Nanobionic Light-Emitting Plant by Seon-Yeong Kwak, Juan Pablo Giraldo, Min Hao Wong, Volodymyr B. Koman, Tedrick Thomas Salim Lew, Jon Ell, Mark C. Weidman, Rosalie M. Sinclair, Markita P. Landry, William A. Tisdale, and Michael S. Strano. Nano Lett., 2017, 17 (12), pp 7951–7961 DOI: 10.1021/acs.nanolett.7b04369 Publication Date (Web): November 17, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

Liquid circuitry, shape-shifting fluids and more

I’d have to see it to believe it but researchers at the US Dept. of Energy (DOE) Lawrence Berkeley National Laboratory (LBNL) have developed a new kind of ‘bijel’ which would allow for some pretty nifty robotics. From a Sept. 25, 2017 news item on ScienceDaily,

A new two-dimensional film, made of polymers and nanoparticles and developed by researchers at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), can direct two different non-mixing liquids into a variety of exotic architectures. This finding could lead to soft robotics, liquid circuitry, shape-shifting fluids, and a host of new materials that use soft, rather than solid, substances.

The study, reported today in the journal Nature Nanotechnology, presents the newest entry in a class of substances known as bicontinuous jammed emulsion gels, or bijels, which hold promise as a malleable liquid that can support catalytic reactions, electrical conductivity, and energy conversion.

A Sept. 25, 2017 LBNL news release (also on EurekAlert), which originated the news item, expands on the theme,

Bijels are typically made of immiscible, or non-mixing, liquids. People who shake their bottle of vinaigrette before pouring the dressing on their salad are familiar with such liquids. As soon as the shaking stops, the liquids start to separate again, with the lower density liquid – often oil – rising to the top.

Trapping, or jamming, particles where these immiscible liquids meet can prevent the liquids from completely separating, stabilizing the substance into a bijel. What makes bijels remarkable is that, rather than just making the spherical droplets that we normally see when we try to mix oil and water, the particles at the interface shape the liquids into complex networks of interconnected fluid channels.

Bijels are notoriously difficult to make, however, involving exact temperatures at precisely timed stages. In addition, the liquid channels are normally more than 5 micrometers across, making them too large to be useful in energy conversion and catalysis.

“Bijels have long been of interest as next-generation materials for energy applications and chemical synthesis,” said study lead author Caili Huang. “The problem has been making enough of them, and with features of the right size. In this work, we crack that problem.”

Huang started the work as a graduate student with Thomas Russell, the study’s principal investigator, at Berkeley Lab’s Materials Sciences Division, and he continued the project as a postdoctoral researcher at DOE’s Oak Ridge National Laboratory.

Creating a new bijel recipe

The method described in this new study simplifies the bijel process by first using specially coated particles about 10-20 nanometers in diameter. The smaller-sized particles line the liquid interfaces much more quickly than the ones used in traditional bijels, making the smaller channels that are highly valued for applications.

Illustration shows key stages of bijel formation. Clockwise from top left, two non-mixing liquids are shown. Ligands (shown in yellow) with amine groups are dispersed throughout the oil or solvent, and nanoparticles coated with carboxylic acids (shown as blue dots) are scattered in the water. With vigorous shaking, the nanoparticles and ligands form a “supersoap” that gets trapped at the interface of the two liquids. The bottom panel is a magnified view of the jammed nanoparticle supersoap. (Credit: Caili Huang/ORNL)

“We’ve basically taken liquids like oil and water and given them a structure, and it’s a structure that can be changed,” said Russell, a visiting faculty scientist at Berkeley Lab. “If the nanoparticles are responsive to electrical, magnetic, or mechanical stimuli, the bijels can become reconfigurable and re-shaped on demand by an external field.”

The researchers were able to prepare new bijels from a variety of common organic, water-insoluble solvents, such as toluene, that had ligands dissolved in it, and deionized water, which contained the nanoparticles. To ensure thorough mixing of the liquids, they subjected the emulsion to a vortex spinning at 3,200 revolutions per minute.

“This extreme shaking creates a whole bunch of new places where these particles and polymers can meet each other,” said study co-author Joe Forth, a postdoctoral fellow at Berkeley Lab’s Materials Sciences Division. “You’re synthesizing a lot of this material, which is in effect a thin, 2-D coating of the liquid surfaces in the system.”

The liquids remained a bijel even after one week, a sign of the system’s stability.

Russell, who is also a professor of polymer science and engineering at the University of Massachusetts-Amherst, added that these shape-shifting characteristics would be valuable in microreactors, microfluidic devices, and soft actuators.

Nanoparticle supersoap

Nanoparticles had not been seriously considered in bijels before because their small size made them hard to trap in the liquid interface. To resolve that problem, the researchers coated nano-sized particles with carboxylic acids and put them in water. They then took polymers with an added amine group – a derivative of ammonia – and dissolved them in the toluene.

At left is a vial of bijel stabilized with nanoparticle surfactants. On the right is the same vial after a week of inversion, showing that the nanoparticle kept the liquids from moving. (Credit: Caili Huang/ORNL)

This configuration took advantage of the amine group’s affinity to water, a characteristic that is comparable to surfactants, like soap. Their nanoparticle “supersoap” was designed so that the nanoparticles join ligands, forming an octopus-like shape with a polar head and nonpolar legs that get jammed at the interface, the researchers said.

“Bijels are really a new material, and also excitingly weird in that they are kinetically arrested in these unusual configurations,” said study co-author Brett Helms, a staff scientist at Berkeley Lab’s Molecular Foundry. “The discovery that you can make these bijels with simple ingredients is a surprise. We all have access to oils and water and nanocrystals, allowing broad tunability in bijel properties. This platform also allows us to experiment with new ways to control their shape and function since they are both responsive and reconfigurable.”

The nanoparticles were made of silica, but the researchers noted that in previous studies they used graphene and carbon nanotubes to form nanoparticle surfactants.

“The key is that the nanoparticles can be made of many materials,” said Russell.  “The most important thing is what’s on the surface.”

This is an animation of the bijel

3-D rendering of the nanoparticle bijel taken by confocal microscope. (Credit: Caili Huang/ORNL [Oak Ridge National Laboratory] and Joe Forth/Berkeley Lab)

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

Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants by Caili Huang, Joe Forth, Weiyu Wang, Kunlun Hong, Gregory S. Smith, Brett A. Helms & Thomas P. Russell. Nature Nanotechnology (2017) doi:10.1038/nnano.2017.182 25 September 2017

This paper is behind a paywall.

Nano with green tea for sensitive teeth

The future will be beautiful if scientists are successful with a new DNA (deoxyribonucleic acid) sunscreen (my Aug. 3, 2017 posting) and a new dental material for people with sensitive teeth. From an Aug. 2, 2017 news item on phys.org,

An ice cold drink is refreshing in the summer, but for people with sensitive teeth, it can cause a painful jolt in the mouth. This condition can be treated, but many current approaches don’t last long. Now researchers report in the journal ACS [American Chemical Society] Applied Materials & Interfaces the development of a new material with an extract from green tea that could fix this problem—and help prevent cavities in these susceptible patients.

An Aug. 2, 2017 ACS news release, which originated the news item, describes the problem and the work in more detail,

Tooth sensitivity commonly occurs when the protective layers of teeth are worn away, revealing a bony tissue called dentin. This tissue contains microscopic hollow tubes that, when exposed, allow hot and cold liquids and food to contact the underlying nerve endings in the teeth, causing pain. Unprotected dentin is also vulnerable to cavity formation. Plugging these tubes with a mineral called nanohydroxyapatite is a long-standing approach to treating sensitivity. But the material doesn’t stand up well to regular brushing, grinding, erosion or acid produced by cavity-causing bacteria. Cui Huang and colleagues wanted to tackle sensitivity and beat the bacteria at the same time.

The researchers encapsulated nanohydroxyapatite and a green tea polyphenol — epigallocatechin-3-gallate, or EGCG — in silica nanoparticles, which can stand up to acid and wear and tear. EGCG has been shown in previous studies to fight Streptococcus mutans, which forms biofilms that cause cavities. Testing on extracted wisdom teeth showed that the material plugged the dentin tubules, released EGCG for at least 96 hours, stood up to tooth erosion and brushing and prevented biofilm formation. It also showed low toxicity. Based on these findings, the researchers say the material could indeed be a good candidate for combating tooth sensitivity and cavities.

The authors acknowledge funding from the National Natural Science Foundation of China, the Natural Science Foundation of Hubei Province of China and the Fundamental Research Funds for the Central Universities.

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

Development of Epigallocatechin-3-gallate-Encapsulated Nanohydroxyapatite/Mesoporous Silica for Therapeutic Management of Dentin Surface by Jian Yu, Hongye Yang, Kang Li, Hongyu Ren, Jinmei Lei, and Cui Huang. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.7b06597 Publication Date (Web): July 13, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

The Canadian nano scene as seen by the OECD (Organization for Economic Cooperation and Development)

I’ve grumbled more than once or twice about the seemingly secret society that is Canada’s nanotechnology effort (especially health, safety, and environment issues) and the fact that I get most my information from Organization for Economic Cooperation and Development (OECD) documents. That said, thank you to Lynne Bergeson’s April 8, 2016 post on Nanotechnology Now for directions to the latest OECD nano document,

The Organization for Economic Cooperation and Development recently posted a March 29, 2016, report entitled Developments in Delegations on the Safety of Manufactured Nanomaterials — Tour de Table. … The report compiles information, provided by Working Party on Manufactured Nanomaterials (WPMN) participating delegations, before and after the November 2015 WPMN meeting, on current developments on the safety of manufactured nanomaterials.

It’s an international roundup that includes: Australia, Austria, Belgium, Canada, Germany, Japan, Korea, the Netherlands, Switzerland, Turkey, United Kingdom, U.S., and the European Commission (EC), as well as the Business and Industry Advisory Committee to the OECD (BIAC) and International Council on Animal Protection in OECD Programs (ICAPO).

As usual, I’m focusing on Canada. From the DEVELOPMENTS IN DELEGATIONS ON THE SAFETY OF MANUFACTURED NANOMATERIALS – TOUR DE TABLE Series on the Safety of Manufactured Nanomaterials No. 67,

CANADA
National  developments  on  human  health  and  environmental  safety  including  recommendations, definitions, or discussions related to adapting or applying existing regulatory systems or the drafting of new laws/ regulations/amendments/guidance materials A consultation document on a Proposed Approach to Address Nanoscale Forms of Substances on the Domestic  Substances  List was  published  with  a  public  comment  period  ending on  May  17,  2015. The proposed approach outlines the Government’s plan to address nanomaterials considered in commerce in Canada (on  Canada’s  public inventory).  The  proposal is a stepwise  approach to  acquire  and  evaluate information,  followed  by  any  necessary  action. A  follow-up  stakeholder  workshop  is  being  planned  to discuss  next  steps  and  possible  approaches  to prioritize  future  activities. The  consultation document  is available at: http://www.ec.gc.ca/lcpe-cepa/default.asp?lang=En&n=1D804F45-1

A mandatory information gathering survey was published on July 25, 2015. The purpose of the survey is to collect information to determine the commercialstatus of certain nanomaterials in Canada. The survey targets  206  substances  considered  to  be  potentially  in commerce  at  the  nanoscale. The  list  of  206 substances was developed using outcomes from the Canada-United States Regulatory Cooperation Council (RCC)  Nanotechnology  Initiative  to  identify nanomaterial  types. These  nanomaterial  types  were  cross-referenced  with  the Domestic  Substances  List to  develop  a  preliminary  list  of  substances  which are potentially intentionally manufactured at the nanoscale. The focus of the survey aligns with the Proposed Approach to  Address  Nanoscale  Forms  of  Substances  on  the Domestic  Substances  List (see  above)  and certain  types  of  nanomaterials  were  excluded  during the  development  of  the  list  of  substances. The information  being  requested  by  the  survey  includes substance  identification,  volumes,  and  uses.  This information will feed into the Government’s proposed approach to address nanomaterials on the Domestic Substances List. Available at: http://gazette.gc.ca/rp-pr/p1/2015/2015-07-25/html/notice-avis-eng.php

Information on:

a.risk  assessment  decisions, including  the  type  of:  (a)  nanomaterials  assessed; (b) testing recommended; and (c) outcomes of the assessment;

Four substances were notified to the program since the WPMN14 – three surface modified substances and  one  inorganic  substance.  No  actions,  including  additional  data requests,  were  taken  due  to  low expected  exposures  in  accordance  with  the New  Substances  Notifications  Regulations  (Chemicals and Polymers) (NSNR) for two of the substances.  Two of the substances notified were subject to a Significant New Activity Notice. A Significant New Activity notice is an information gathering tool used to require submission  of  additional  information  if  it  is suspected  that  a  significant  new  activity  may  result in  the substance becoming toxic under the Canadian Environmental Protection Act, 1999.

b.Proposals, or modifications to previous regulatory decisions

As  part  of  the  Government’s  Chemicals  Management Plan,  a  review  is  being  undertaken  for  all substances  which  have  been  controlled through  Significant  New  Activity  (SNAc)  notices (see  above).  As part  of  this  activity,  the  Government  is  reviewing past  nanomaterials  SNAc  notices  to  see  if  new information  is  available  to  refine  the  scope  and information  requirements.    As  a  result  of  this  review, 9 SNAc  notices  previously  in  place  for  nanomaterials have  been  rescinded.    This  work  is  ongoing,  and  a complete review of all nanomaterial SNAcs is currently planned to be completed in 2016.

Information related to good practice documents

The Canada-led,  ISO  standards project, ISO/DTR  19716 Nanotechnologies — Characterization  of cellulose  nanocrystals, [emphasis mine] initiated  in  April 2014, is  now at Committee  Draft  (CD)  3-month  ISO ballot, closing    Aug 31, 2015. Ballot comments will be addressed during JWG2 Measurement and Characterization working  group meetings  at  the 18th Plenary  of  ISO/TC229, Nanotechnologies,  being held in Edmonton, Alberta, Sep. 28 – Oct. 2, 2015.

Research   programmes   or   strategies   designed   to  address   human   health   and/   or environmental safety aspects of nanomaterials

Scientific research

Environment Canada continues to support various academic and departmental research projects. This research has to date included studying fate and effects of nanomaterials in the aquatic, sediment, soil, and air  compartments. Funding  in  fiscal  2015-16  continues  to  support  such  projects,  including  sub-surface transportation, determining key physical-chemical parameters to predict ecotoxicity, and impacts of nano-silver [silver nanoparticles]  addition  to  a  whole  lake  ecosystem [Experimental Lakes Area?]. Environment  Canada  has  also  partnered  with  the National Research  Council  of  Canada  recently  to  initiate  a project  on  the  development  of  test  methods  to identify surfaces of nanomaterials for the purposes of regulatory identification and to support risk assessments. In addition,  Environment  Canada  is  working  with  academic laboratories in  Canada  and  Germany  to  prepare guidance to support testing of nanoparticles using the OECD Test Guideline for soil column leaching.

Health  Canada  continues  its  research  efforts  to  investigate  the  effects  of  surface-modified  silica nanoparticles. The   aims   of   these   projects   are  to:   (1) study the importance of size and surface functionalization;  and  (2)  provide a genotoxic profile and  to  identify  mechanistic  relationships  of  particle properties  to  elicited  toxic  responses.  A manuscript reporting  the in  vitro genotoxic,  cytotoxic and transcriptomic  responses  following  exposure  to  silica  nanoparticles  has  recently  been  submitted to  a  peer reviewed journal and is currently undergoing review. Additional manuscripts reporting the toxicity results obtained to date are in preparation.

Information on public/stakeholder consultations;

A consultation document on a Proposed Approach to Address Nanoscale Forms of Substances on the Domestic  Substances  List was  published  with a  public  comment  period ending  on May  17,  2015  (see Question  1).  Comments  were  received  from approximately  20  stakeholders  representing  industry and industry  associations,  as  well  as  non-governmental  organizations. These  comments  will  inform  decision making to address nanomaterials in commerce in Canada.

Information on research or strategies on life cycle aspects of nanomaterials

Canada, along with Government agencies in the United States, Non-Governmental Organizations and Industry,  is  engaged  in  a  project  to  look  at releases  of  nanomaterials  from  industrial  consumer  matrices (e.g., coatings). The objectives of the NanoRelease Consumer Products project are to develop protocols or
methods (validated  through  interlaboratory  testing) to  measure  releases  of  nanomaterials  from  solid matrices as a result of expected uses along the material life cycle for consumer products that contain the nanomaterials. The  project  is  currently  in  the  advanced  stages  of Phase  3  (Interlaboratory  Studies).  The objectives of Phase 3 of the project are to develop robust methods for producing and collecting samples of CNT-epoxy  and  CNT-rubber  materials  under  abrasion  and  weathering scenarios,  and  to  detect  and quantify, to the extent possible, CNT release fractions. Selected laboratories in the US, Canada, Korea and the European Community are finalising the generation and analysis of sanding and weathering samples and the    results    are    being    collected    in    a   data    hub    for    further    interpretation    and    analysis.

Additional details about the project can be found at the project website: http://www.ilsi.org/ResearchFoundation/RSIA/Pages/NanoRelease1.aspx

Under the OECD Working Party on Resource Productivity and Waste (WPRPW), the expert group on waste containing nanomaterials has developed four reflection papers on the fate of nanomaterials in waste treatment  operations.  Canada  prepared the  paper  on  the  fate  of  nanomaterials in  landfills;  Switzerland on the  recycling  of  waste  containing  nanomaterials;  Germany  on  the  incineration  of  waste  containing nanomaterials;  and  France  on  nanomaterials  in wastewater  treatment.  The  purpose  of  these  papers is to provide  an  overview  of  the  existing  knowledge  on the  behaviour  of  nanomaterials  during  disposal operations and identify the information gaps. At the fourth meeting of the WPRPW that took place on 12-14 November 2013, three of the four reflection papers were considered by members. Canada’s paper was presented and discussed at the fifth meeting of the WPRPRW that took place on 8-10 December 2014. The four  papers  were  declassified  by  EPOC  in  June  2015, and  an  introductory  chapter  was  prepared  to  draw these  papers  together. The introductory  chapter  and accompanying  papers  will  be  published in  Fall  2015. At  the sixth  meeting  of  the  WPRPW  in  June – July  2015,  the  Secretariat  presented  a  proposal  for an information-sharing  platform  that  would  allow  delegates  to  share research  and  documents  related  to nanomaterials. During a trial phase, delegates will be asked to use the platform and provide feedback on its use at the next meeting of the WPRPW in December 2015. This information-sharing platform will also be accessible to delegates of the WPMN.

Information related to exposure measurement and exposure mitigation.

Canada and the Netherlands are co-leading a project on metal impurities in carbon nanotubes. A final version  of  the  report  is  expected  to  be ready for WPMN16. All  research has  been completed (e.g. all components are published or in press and there was a presentation by Pat Rasmussen to SG-08 at the Face-to-Face Meeting in Seoul June 2015). The first draft will be submitted to the SG-08 secretariat in autumn 2015. Revisions  will  be  based  on  early  feedback  from  SG-08  participants.  The  next  steps  depend  on  this feedback and amount of revision required.

Information on past, current or future activities on nanotechnologies that are being done in co-operation with non-OECD countries.

A webinar between ECHA [European Chemicals Agency], the US EPA [Environmental Protection Agency] and Canada was hosted by Canada on April 16, 2015. These are  regularly  scheduled  trilateral  discussions  to keep  each  other  informed  of  activities  in  respective jurisdictions.

In  March 2015, Health  Canada  hosted  3  nanotechnology knowledge  transfer sessions  targeting Canadian  government  research  and  regulatory  communities  working  in  nanotechnology.  These  sessions were  an  opportunity  to  share  information  and perspectives  on  the  current  state  of  science supporting  the regulatory  oversight  of  nanomaterials with  Government.  Presenters  provided  detailed  outputs  from  the OECD WPMN including: updates on OECD test methods and guidance documents; overviews of physical-chemical properties, as well as their relevance to toxicological testing and risk assessment; ecotoxicity and fate   test   methods;   human   health   risk   assessment   and   alternative   testing   strategies;   and exposure measurement  and  mitigation.  Guest  speakers  included  Dr  Richard  C.  Pleus  Managing  Director  and  Director of Intertox, Inc and Dr. Vladimir Murashov Special Assistant on Nanotechnology to the Director of National Institute for Occupational Safety and Health (NIOSH).

On   March   4-5, 2015, Industry   Canada   and   NanoCanada co-sponsored  “Commercializing Nanotechnology  in  Canada”,  a  national  workshop  that brought  together  representatives  from  industry, academia and government to better align Canada’s efforts in nanotechnology.  This workshop was the first of  its  kind  in  Canada. It  also  marked  the  official  launch  of  NanoCanada (http://nanocanada.com/),  a national  initiative  that  is  bringing  together stakeholders  from  across  Canada  to  bridge  the  innovation  gap and stimulates emerging technology solutions.

It’s nice to get an update about what’s going on. Despite the fact this report was published in 2016 the future tense is used in many of the verbs depicting actions long since accomplished. Maybe this was a cut-and-paste job?

Moving on, I note the mention of the Canada-led,  ISO  standards project, ISO/DTR  19716 Nanotechnologies — Characterization  of cellulose  nanocrystals (CNC). For those not familiar with CNC, the Canadian government has invested hugely in this material derived mainly from trees, in Canada. Other countries and jurisdictions have researched nanocellulose derived from carrots, bananas, pineapples, etc.

Finally, it was interesting to find out about the existence of  NanoCanada. In looking up the Contact Us page, I noticed Marie D’Iorio’s name. D’Iorio, as far as I’m aware, is still the Executive Director for Canada’s National Institute of Nanotechnology (NINT) or here (one of the National Research Council of Canada’s institutes). I have tried many times to interview someone from the NINT (Nils Petersen, the first NINT ED and Martha Piper, a member of the advisory board) and more recently D’Iorio herself only to be be met with a resounding silence. However, there’s a new government in place, so I will try again to find out more about the NINT, and, this time, NanoCanada.

Ceramic firefighting foam: better at extinguishing fires and nontoxic

A Dec. 14, 2015 news item on Nanowerk announces a new ceramic firefighting foam developed in Russia,

A team of chemists from ITMO University, in collaboration with research company SOPOT, has developed a novel type of firefighting foam based on inorganic silica nanoparticles. The new foam beats existing analogues in fire extinguishing capacity, thermal and mechanical stability and biocompatibility.

A Dec. 14, 2015 ITMO University press release on EurekAlert, which originated the news item, provides more details,

Fighting large-scale fires usually involves firefighting foams based on synthetic substances, such as prefluorinated surfactants, that, despite their effectiveness, are extremely toxic for living organisms. Complete biodegradation of such foams can last for more than 200 years [emphasis mine], with residues quickly penetrating deep into soil and surface water. This leads to the the accumulation of toxic elements in living organisms, such as plants, animals and men. Many countries have declined the use of such fire extinguishing agents or opted for reducing the production of such substances despite the absence of any decent alternatives.

A group of scientists from the International Laboratory of Advanced Materials and Technologies (SCAMT) at ITMO University in Saint Petersburg and research company SOPOT devised a foam, which was awarded full biodegradability and whose fire extinguishing capacity is higher than that of any existing analogue currently in use by fire fighters. After the fire is extinguished, the substance actively absorbs water, softens and falls apart into bioinert silica particles. And even when the foam accidentally enters living organisms, it does not not pose any danger to them.

“Our foam is based on silica nanoparticles, which create a polymer network when exposed to air,” says Alexander Vinogradov, deputy head of the SCAMT laboratory. “Such a network embraces and adheres to the burning object and momentarily cools it down. At the same time, the foam itself hardens. The inorganic origin of this polymer network allows it to resist temperatures above 1000 degrees Celsius, which ensures gigantic stability from the aggressive environment in the midst of a raging fire.”

“Most existing foams are made of organic materials and quickly deteriorate when temperature approaches 300 degrees Celsius. In our case, the foam creates a hard frame that not only puts out the fire, but also protects the object from re-ignition. With ordinary foams, re-ignition occurs within seconds after flame is applied to the object again.”

The scientists conducted a series of large-scale experiments of the hardening foam, including the imitation of an actual forest fire. The foam was used to create a flame retardant belt that was supposed stop the spread of the fire. The tests demonstrated that the foam easily localizes the forest fire seat and can stay active during the whole fire season.

“The flame retardant belt made of our foam will prevent the spread of any forest fire, regardless of its strength and level of complexity,” says Gennady Kuprin, head of SOPOT. “We can localize the fire and be sure that the adjacent territories will be safe. This is crucial to organize evacuation works during forest fires, where 9 of 10 people die in our and other countries.”

The standard firefighting foam can take up to 200 years before completely degrading? I hope this new foam is all they say it is and that they can get it to market. In the meantime, here’s a link to and a citation for the researchers’ paper,

Silica foams for fire prevention and firefighting by Alexander V. Vinogradov, Denis Kuprin, Iosif Abduragimov, Gennadii Kuprin, Evgeniy Serebriyakov, and Vladimir V. Vinogradov. ACS Appl. Mater. Interfaces, DOI: 10.1021/acsami.5b08653
Publication Date (Web): October 22, 2015

Copyright © 2015 American Chemical Society

This is paper is behind a paywall. But, the researchers have made an image of the foam available,

Caption: This is an electronic microscope image of hybrid silica foam. Credit: ITMO University

Caption: This is an electronic microscope image of hybrid silica foam. Credit: ITMO University

For anyone curious about SOPOT, here’s more from the company’s About page,

  “NPO Sopot” was founded in 1994 in St. Petersburg. Its creation was preceded by many years of scientific research and experimental design work done in person at the head of the firm basis of the Ministry of Defence and the Ministry of Internal Affairs of Russia, as well as, with the participation and cooperation with representatives of several institutions of the defense industry (the Sukhoi Design Bureau, Institute TRANSMASH, Academy. Zhukovsky etc.), the Ministry of Civil aviation, Fire Prevention Russian Interior Ministry, the Russian Interior Ministry VIPTSH

General Director of JSC “NPO” Sopot “Gennady Kuprin. Winner of the National Industry Award” Bison-2006 “, the grand prize Emergencies Ministry in 2005 and 2006., Awarded the” Golden Shield of the Russian economy, “international diploma” European quality “member of the International Academy of Patronage, the World Academy of Integrated Security.

Repairing sensitive teeth with silica nanoparticles

Don’t rush out to talk to your dentist yet but researchers at the University of Birmingham (UK) have devised a promising technique for repairing sensitive teeth according to a Sept. 16, 2015 news item on ScienceDaily,

Researchers at the University of Birmingham have shown how the development of coated silica nanoparticles could be used in restorative treatment of sensitive teeth and preventing the onset of tooth decay.

The study, published in the Journal of Dentistry, shows how sub-micron silica particles can be prepared to deliver important compounds into damaged teeth through tubules in the dentine.

The tiny particles can be bound to compounds ranging from calcium tooth building materials to antimicrobials that prevent infection.

A Sept. 16, 2015 university of Birmingham press release (also on EurekAlert), which originated the news item, expands on the research,

Professor Damien Walmsley, from the School of Dentistry at the University of Birmingham, explained, “The dentine of our teeth have numerous microscopic holes, which are the entrances to tubules that run through to the nerve. When your outer enamel is breached, the exposure of these tubules is really noticeable. If you drink something cold, you can feel the sensitivity in your teeth because these tubules run directly through to the nerve and the soft tissue of the tooth.”

“Our plan was to use target those same tubules with a multifunctional agent that can help repair and restore the tooth, while protecting it against further infection that could penetrate the pulp and cause irreversible damage.”

The aim of restorative agents is to increase the mineral content of both the enamel and dentine, with the particles acting like seeds for further growth that would close the tubules.

Previous attempts have used compounds of calcium fluoride, combinations of carbonate-hydroxypatite nanocrystals and bioactive glass, but all have seen limited success as they are liable to aggregate on delivery to the tubules. This prevents them from being able to enter the opening which is only 1 to 4 microns in width.

However, the Birmingham team turned to sub-micron silica particles that had been prepared with a surface coating to reduce the chance of aggregation.

When observed using high definition SEM (Scanning Electron Microsopy), the researchers saw promising signs that suggested that the aggregation obstacle had been overcome.

Professor Zoe Pikramenou, from the School of Chemistry at the University of Birmingham, said, “These silica particles are available in a range of sizes, from nanometre to sub-micron, without altering their porous nature. It is this that makes them an ideal container for calcium based compounds to restore the teeth, and antibacterial compounds to protect them. All we needed to do was find the right way of coating them to get them to their target.  We have found that different coatings does change the way that they interact with the tooth surface.”

“We tested a number of different options to see which would allow for the highest level particle penetration into the tubules, and identified a hydrophobic surface coating that provides real hope for the development of an effective agent.”

Our next steps are to optimise the coatings and then see how effective the particles are blocking the communication with the inside of the tooth.  The ultimate aim is to provide relief from the pain of sensitivity.

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

The deposition and imaging of silica sub-micron particles in dentine by Sunil Claire, Anthony Damien Walmsley, Sophie Glinton, Hayley Floyd, Rachel Sammons, Zoe Pikramenou. Journal of Dentistry October 2015 Volume 43, Issue 10, Pages 1242–1248 DOI: http://dx.doi.org/10.1016/j.jdent.2015.08.002
Published Online: August 07, 2015

This paper is behind a paywall.