Tag Archives: silver nanoparticles

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,

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.

US National Institute of Occupational Heath and Safety (NIOSH) issues a draft bulletin about silver nanoparticles

The US National Institute of Occupational Health and Safety (NIOSH) is requesting comments on a draft version of the NIOSH Current Intelligence Bulletin: Health Effects of Occupational Exposure to Silver Nanoparticles (PDF of 321 pp.) according to a Jan. 21, 2016 notice on the US Federal Register,

On December 19, 2012, the National Institute for Occupational Safety and Health, Centers for Disease Control and Prevention announced in the Federal Registerhttp://www.gpo.gov/fdsys/pkg/FR-2012-12-19/pdf/2012-30515.pdf plans to evaluate the scientific data on silver nanomaterials and to issue its findings on the potential health risks. A draft document entitled, Health Effects of Occupational Exposure to Silver Nanomaterials, has been developed which contains a review and assessment of the currently available scientific literature on the toxicological effects of exposure to silver nanoparticles in experimental animal and cellular systems, and on the occupational exposures to silver dust and fume and the associated health effects. An emphasis area of this review is evaluating the scientific evidence on the role of particle size on the toxicological effects of silver, including the evidence basis to evaluate the adequacy of the current NIOSH recommended exposure limit (REL) for silver (metal dust and soluble compounds, as Ag) [available at: http://www.cdc.gov/niosh/npg/npgd0557.html].

Recommendations are provided for the safe handling of silver nanoparticles, and research needs are proposed to fill important data gaps in the current scientific literature on the potential adverse health effects of occupational exposure to silver nanoparticles. NIOSH is seeking comments on the draft document and plans to have a public meeting to discuss the document. To view the notice and related materials, visit www.regulations.gov and enter CDC-2016-0001 in the field and click “Search.” This draft document does not have the force or effect of the law.

As of a Feb. 10, 2016 NIOSH notice on the US Federal Register (H/T Lynn Bergeson in a Feb. 11, 2016 post on Nanotechnology Now), the public comment period has been extended,

NIOSH is extending the comment period on the document published January 21, 2016 (81 FR 3425). Electronic or written comments must be received by April 22, 2016.

You may submit comments, identified by CDC-2016-0001 and docket number NIOSH-260-A, by any of the following methods:

Federal eRulemaking Portal: www.regulations.gov Follow the instructions for submitting comments.
Mail: National Institute for Occupational Safety and Health, NIOSH Docket Office, 1090 Tusculum Avenue, MS C-34, Cincinnati, Ohio 45226-1998.

There will a public meeting about this draft bulletin to be held in Ohio (from the US Federal Register Jan. 21, 2016 notice , Note: Given the recent extension for comments, it might be prudent to check periodically for a change of date)

The public meeting will be held on March 23, 2016, 9:00 a.m.-3:00 p.m. Eastern Time, or after the last public commenter has spoken, whichever occurs first. Comments must be received on or before March 21, 2016.

The public meeting will be held at the NIOSH/CDC Robert A. Taft Laboratories, Auditorium, 1150 Tusculum Avenue, Cincinnati, Ohio 45226.

Charles Geraci, NIOSH, Education and Information Division, Nanotechnology Research Center, Robert A. Taft Laboratories, 1090 Tusculum Avenue, Cincinnati, OH 45226, (513) 533-8339 (not a toll free number).

I. Background: To discuss and obtain comments on the draft document, “NIOSH Current Intelligence Bulletin: Health Effects of Occupational Exposure to Silver Nanomaterials”. Special emphasis will be placed on discussion of the following:

Whether the health hazard identification, risk estimation, and discussion of health effects of silver and silver nanomaterials are a reasonable reflection of the current understanding of the scientific literature;
Workplaces and occupations where exposure to silver and silver nanomaterials may occur; and studies on health effects associated with occupational exposure to silver dust and fume;
Current strategies for controlling or preventing exposure to silver and silver nanomaterials (e.g., engineering controls, work practices, personal protective equipment);
Current exposure measurement methods and challenges in measuring workplace exposures to silver nanomaterials; and
Areas for future collaborative efforts (e.g., research, communication, development of exposure measurement and control strategies).

II. Public Meeting: NIOSH will hold a public meeting on the NIOSH Draft Current Intelligence Bulletin: Health Effects of Occupational Exposure to Silver Nanomaterials to allow commenters to provide oral comments on the draft document, to inform NIOSH about additional relevant data or information, and to ask questions on the draft document and NIOSH recommendations.

The forum will include scientists and representatives from various government agencies, industry, labor, and other stakeholders, and is open to the public. Attendance is limited only by the space available. The meeting room accommodates 100 people. The meeting will be open to limited number of participants through a conference call phone number and Webcast live on the Internet. Due to the limited spaces, notification of intent to attend the meeting must be made to the NIOSH Docket Office, at nioshdocket@cdc.gov, (513) 533-8611, or fax (513) 533-8285, no later than March 9, 2016. Priority for attendance will be given to those providing oral comments. Other requests to attend the meeting will then be accommodated on a first-come, first-served basis.

Registration is required. Because this meeting is being held at a Federal site, pre-registration is required on or before March 9, 2016 and a government-issued photo ID (driver’s license, military ID or passport) will be required to obtain entrance to the facility. There will be an airport type security check. Non‐US citizens need to register by February 12, 2016 to allow sufficient time for mandatory facility security clearance procedures to be completed. Additional personal information will be required. This information will be transmitted to the CDC Security Office for approval. An email confirming registration will be sent from NIOSH for both in-person participation and audio conferencing participation.

Oral presentations will be limited to 15 minutes per presenter. If additional time becomes available, presenters will be notified. All requests to present should contain the name, address, telephone number, and relevant business affiliations of the presenter, topic of the presentation, and the approximate time requested for the presentation. An email confirming registration will be sent from the NIOSH Docket Office and will include details needed to participate. Oral comments given at the meeting will be recorded and included in the NIOSH Docket 260-A.

After reviewing the requests for presentations, NIOSH will notify the presenter that his/her presentation is scheduled. If a participant is not in attendance when his/her presentation is scheduled to begin, the remaining participants will be heard in order. After the last scheduled speaker is heard, participants who missed their assigned times may be allowed to speak, limited by time available.

Attendees who wish to speak but did not submit a request for the opportunity to make a presentation may be given this opportunity after the scheduled speakers are heard, at the discretion of the presiding officer and limited by time available.

You may submit comments, identified by CDC-2016-0001 and NIOSH 260-A, by either of the following methods:

Federal eRulemaking Portal: www.regulations.gov. Follow the instructions for submitting comments.
Mail: National Institute for Occupational Safety and Health, NIOSH Docket Office, 1090 Tusculum Avenue, MS C-34, Cincinnati, Ohio 45226-1998.

Instructions: All information received in response to this notice must include the agency name and docket number [CDC-2016-0001; NIOSH 260-A]. All relevant comments received will be posted without change to www.regulations.gov including any personal information provided. All information will be available for public examination and copying at the NIOSH Docket Office, 1150 Tusculum Avenue, Room 155, Cincinnati, Ohio 45226.

Non-U.S. Citizens: Because of CDC Security Regulations, any non-U.S. citizen wishing to attend this meeting must provide the following information in writing to the NIOSH Docket Officer at the address below no later than February 12, 2016 [emphasis mine].



Date of Birth:

Place of Birth (city, province, state, country):


Passport Number:

Date of Passport Issue:

Date of Passport Expiration:

Type of Visa:

U.S. Naturalization Number (if a naturalized citizen):

U.S. Naturalization Date (if a naturalized citizen):

Visitor’s Organization:

Organization Address:

Organization Telephone Number:

Visitor’s Position/Title within the Organization:

This information will be transmitted to the CDC Security Office for approval. Visitors will be notified as soon as approval has been obtained.

H/T Safety + Health; The Official Magazine of the NSC Congress & Expo, Feb. 10, 2016 news item for the information about the original January 2016 notice.

Pomegranates, silver nanoparticles, and Persian carpets

One of the issues with adding silver nanoparticles to textiles is that they wash off and eventually enter our water supply. According to a Dec. 14. 2015 news item on Nanotechnology Now, Iranian scientists has devised a technique for affixing silver nanoparticles,

Iranian researchers produced laboratorial samples of antibacterial woolen fabrics by using nanoparticles which are able to preserve their properties even after five times of washing.

A Dec. 12, 2015 Iran Nanotechnology Initiative Council (INIC) press release, which originated the news item, provides more detail,

Nanoparticles used in the production of fabrics have been produced through a cost-effective method and by using environmentally-friendly materials.

The aim of the research was to obtain an eco-friendly method for the production and application of silver nanoparticles in carpet weaving industry to create antibacterial properties in the final product. The interesting point in this research is the application of pomegranate skin as the reducer in the process to produce nanoparticles.

Results showed that pigment extracted from pomegranate skin is able to be used in the production of silver nanoparticles. Therefore, this method decreases the application of chemical reducers in the synthesis of these nanoparticles, and it also decreases the environmental pollution. In addition, the synthesized nanoparticles preserve their antibacterial properties after being loaded on woolen fiber samples. Therefore, carpets woven by these fibers have antibacterial properties and no bacteria will grow on them.

After carrying out complementary tests and producing the fabrics and fibers at a large scale, the products can be used in carpet weaving industries and also in production of medical devices.

Based on the results, fabrics completed with silver nanoparticles synthesized at low ratio of pigment have antibacterial properties and they do not affect the color of samples. Fabric samples also conserve their antibacterial properties even after five times of washing. The decrease in pH value and increase in temperature improves exhaustion of silver nanoparticles on the wool.

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

Novel method for synthesis of silver nanoparticles and their application on wool by Majid Nasiri Boroumand, Majid Montazer, Frank Simon, Jolanta Liesiene, Zoran Šaponjic, Victoria Dutschk. Applied Surface Science Volume 346, 15 August 2015, Pages 477–483 doi:10.1016/j.apsusc.2015.04.047

This paper is behind a paywall.

Smaller (20nm vs 110nm) silver nanoparticles are more likely to absorbed by fish

An Oct. 8, 2015 news item on Nanowerk offers some context for why researchers at the University of California at Los Angeles (UCLA) are studying silver nanoparticles and their entry into the water system,

More than 2,000 consumer products today contain nanoparticles — particles so small that they are measured in billionths of a meter.

Manufacturers use nanoparticles to help sunscreen work better against the sun’s rays and to make athletic apparel better at wicking moisture away from the body, among many other purposes.

Of those products, 462 — ranging from toothpaste to yoga mats — contain nanoparticles made from silver, which are used for their ability to kill bacteria. But that benefit might be coming at a cost to the environment. In many cases, simply using the products as intended causes silver nanoparticles to wind up in rivers and other bodies of water, where they can be ingested by fish and interact with other marine life.

For scientists, a key question has been to what extent organisms retain those particles and what effects they might have.

I’d like to know where they got those numbers “… 2,000 consumer products …” and “… 462 — ranging from toothpaste to yoga mats — contain nanoparticles made from silver… .”

Getting back to the research, an Oct. 7, 2015 UCLA news release, which originated the news item, describes the work in more detail,

A new study by the University of California Center for Environmental Implications of Nanotechnology has found that smaller silver nanoparticles were more likely to enter fish’s bodies, and that they persisted longer than larger silver nanoparticles or fluid silver nitrate. The study, published online in the journal ACS Nano, was led by UCLA postdoctoral scholars Olivia Osborne and Sijie Lin, and Andre Nel, director of UCLA’s Center for Environmental Implications of Nanotechnology and associate director of the California NanoSystems Institute at UCLA.

Nel said that although it is not yet known whether silver nanoparticles are harmful, the research team wanted to first identify whether they were even being absorbed by fish. CEIN, which is funded by the National Science Foundation, is focused on studying the effects of nanotechnology on the environment.

In the study, researchers placed zebrafish in water that contained fluid silver nitrate and two sizes of silver nanoparticles — some measuring 20 nanometers in diameter and others 110 nanometers. Although the difference in size between these two particles is so minute that it can only be seen using high-powered transmission electron microscopes, the researchers found that the two sizes of particles affected the fish very differently.

The researchers used zebrafish in the study because they have some genetic similarities to humans, their embryos and larvae are transparent (which makes them easier to observe). In addition, they tend to absorb chemicals and other substances from water.

Osborne said the team focused its research on the fish’s gills and intestines because they are the organs most susceptible to silver exposure.

“The gills showed a significantly higher silver content for the 20-nanometer than the 110-nanometer particles, while the values were more similar in the intestines,” she said, adding that both sizes of the silver particles were retained in the intestines even after the fish spent seven days in clean water. “The most interesting revelation was that the difference in size of only 90 nanometers made such a striking difference in the particles’ demeanor in the gills and intestines.”

The experiment was one of the most comprehensive in vivo studies to date on silver nanoparticles, as well as the first to compare silver nanoparticle toxicity by extent of organ penetration and duration with different-sized particles, and the first to demonstrate a mechanism for the differences.

Osborne said the results seem to indicate that smaller particles penetrated deeper into the fishes’ organs and stayed there longer because they dissolve faster than the larger particles and are more readily absorbed by the fish.

Lin said the results indicate that companies using silver nanoparticles have to strike a balance that recognizes their benefits and their potential as a pollutant. Using slightly larger nanoparticles might help make them somewhat safer, for example, but it also might make the products in which they’re used less effective.

He added that data from the study could be translated to understand how other nanoparticles could be used in more environmentally sustainable ways.

Nel said the team’s next step is to determine whether silver particles are potentially harmful. “Our research will continue in earnest to determine what the long-term effects of this exposure can be,” he said.

Here’s an image illustrating the findings,

Courtesy ACS Nano

Courtesy ACS Nano

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

Organ-Specific and Size-Dependent Ag Nanoparticle Toxicity in Gills and Intestines of Adult Zebrafish by Olivia J. Osborne, Sijie Lin, Chong Hyun Chang, Zhaoxia Ji, Xuechen Yu, Xiang Wang, Shuo Lin, Tian Xia, and André E. Nel. ACS Nano, Article ASAP DOI: 10.1021/acsnano.5b04583 Publication Date (Web): September 1, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Nano-alchemy: silver nanoparticles that look like and act like gold

This work on ‘nano-alchemy’ comes out of the King Abduhllah University of Science and Technology (KAUST) according to a Sept. 22, 2015 article by Lisa Zynga for phys.org (Note: A link has been removed),

In an act of “nano-alchemy,” scientists have synthesized a silver (Ag) nanocluster that is virtually identical to a gold (Au) nanocluster. On the outside, the silver nanocluster has a golden yellow color, and on the inside, its chemical structure and properties also closely mimic those of its gold counterpart. The work shows that it may be possible to create silver nanoparticles that look and behave like gold despite underlying differences between the two elements, and could lead to creating similar analogues between other pairs of elements.

“In some aspects, this is very similar to alchemy, but we call it ‘nano-alchemy,'” Bakr [Osman Bakr, Associate Professor of Materials Science and Engineering at King Abdullah University of Science and Technology (KAUST) in Saudi Arabia] told Phys.org. “When we first encountered the optical spectrum of the silver nanocluster, we thought that we may have inadvertently switched the chemical reagents for silver with gold, and ended up with gold nanoparticles instead. But repeated synthesis and measurements proved that the clusters were indeed silver and yet show properties akin to gold. It was really surprising to us as scientists to find not only similarities in the color and optical properties, but also the X-ray structure.”

In their study, the researchers performed tests demonstrating that the silver and gold nanoclusters have very similar optical properties. Typically, silver nanoclusters are brown or red in color, but this one looks just like gold because it emits light at almost the same wavelength (around 675 nm) as gold. The golden color can be explained by the fact that both nanoclusters have virtually identical crystal structures.

The question naturally arises: why are these silver and gold nanoclusters so similar, when individual atoms of silver and gold are very different, in terms of their optical and structural properties? As Bakr explained, the answer may have to do with the fact that, although larger in size, the nanoclusters behave like “superatoms” in the sense that their electrons orbit the entire nanocluster as if it were a single giant atom. These superatomic orbitals in the silver and gold nanoclusters are very similar, and, in general, an atom’s electron configuration contributes significantly to its properties.

Here’s one of the images used to illustrate Zynga’s article and the paper published by the American Chemical Society,

(Left) Optical properties of the silver and gold nanoclusters, with the inset showing photographs of the actual color of the synthesized nanoclusters. The graph shows the absorption (solid lines) and normalized emission (dotted lines) spectra. (Right) Various representations of the X-ray structure of the silver nanocluster. Credit: Joshi, et al. ©2015 American Chemical Society

(Left) Optical properties of the silver and gold nanoclusters, with the inset showing photographs of the actual color of the synthesized nanoclusters. The graph shows the absorption (solid lines) and normalized emission (dotted lines) spectra. (Right) Various representations of the X-ray structure of the silver nanocluster. Credit: Joshi, et al. ©2015 American Chemical Society

I encourage you to read Zynga’s article in its entirety. For the more technically inclined, here’s a link to and a citation for the researchers’ paper,

[Ag25(SR)18]: The “Golden” Silver Nanoparticle by Chakra P. Joshi, Megalamane S. Bootharaju, Mohammad J. Alhilaly, and Osman M. Bakr.J. Am. Chem. Soc., 2015, 137 (36), pp 11578–11581 DOI: 10.1021/jacs.5b07088 Publication Date (Web): August 31, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Wound healing with cellulose acetate nanofibres

This work on cellulose acetate nanofibres and wound healing (tested on mice) comes from Egypt according to an Aug. 10, 2015 news item on ScienceDaily,

People with diabetes mellitus often suffer from impaired wound healing. Now, scientists in Egypt have developed antibacterial nanofibres of cellulose acetate loaded with silver that could be used in a new type of dressing to promote tissue repair.

An Aug. 10, 2015 Inderscience Publishers press release on the Alpha Galileo website, which originated the news item, provides more detail about the research,

Thanaa Ibrahim Shalaby and colleagues, Nivan Mahmoud Fekry, Amal Sobhy El Sodfy, Amel Gaber El Sheredy and Maisa El Sayed Sayed Ahmed Moustafa, at Alexandria University, prepared nanofibres from cellulose acetate, an inexpensive and easily fabricated, semisynthetic polymer used in everything from photographic film to coatings for eyeglasses and even cigarette filters. It can be spun into fibres and thus used to make an absorbent and safe wound dressing. Shalaby and co-workers used various analytical techniques including scanning electron microscope (SEM) and Fourier-transform infrared (FTIR) spectroscopy to characterise their fibres in which they incorporated silver nanoparticles.

Having characterised the material the team then successfully tested its antibacterial activity against various strains of bacteria that might infect an open wound. They next used the material as a dressing on skin wounds on mice with diabetes and determined how quickly the wound healed with and without the nano dressing. The dressing absorbs fluids exuded by the wound, but also protects the wound from infectious agents while being permeable to air and moisture, the team reports. The use of this dressing also promotes collagen production as the wound heals, which helps to recreate normal skin strength and texture something that is lacking in unassisted wound healing in diabetes mellitus.

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

Preparation and characterisation of antibacterial silver-containing nanofibres for wound healing in diabetic mice by Thanaa Ibrahim Shalaby; Nivan Mahmoud Fekry; Amal Sobhy El Sodfy; Amel Gaber El Sheredy; Maisa El Sayed Sayed Ahmed Moustafa. International Journal of Nanoparticles (IJNP), Vol. 8, No. 1, p. 82 2015 DOI: 10.1504/IJNP.2015.070346

This paper is behind a paywall although there are some exceptions.

Saving silver; a new kind of electrode

An Aug. 1, 2015 news item on Nanotechnology Now highlights work from Germany’s Helmholtz-Zentrum Berlin für Materialien und Energie (Helmholtz Zentrum Berlin),

The electrodes for connections on the “sunny side” of a solar cell need to be not just electrically conductive, but transparent as well. As a result, electrodes are currently made either by using thin strips of silver in the form of a coarse-meshed grid squeegeed onto a surface, or by applying a transparent layer of electrically conductive indium tin oxide (ITO) compound. Neither of these are ideal solutions, however. This is because silver is a precious metal and relatively expensive, and silver particles with nanoscale dimensions oxidise particularly rapidly; meanwhile, indium is one of the rarest elements on earth crust and probably will only continue to be available for a few more years.

Manuela Göbelt on the team of Prof. Silke Christiansen has now developed an elegant new solution using only a fraction of the silver and entirely devoid of indium to produce a technologically intriguing electrode. The doctoral student initially made a suspension of silver nanowires in ethanol using wet-chemistry techniques. She then transferred this suspension with a pipette onto a substrate, in this case a silicon solar cell. As the solvent is evaporated, the silver nanowires organise themselves into a loose mesh that remains transparent, yet dense enough to form uninterrupted current paths.

A July 31, 2015 Helmholtz Zentrum Berlin press release (also on EurekAlert), which originated the news item, describes the work in more detail,

Subsequently, Göbelt used an atomic layer deposition technique to gradually apply a coating of a highly doped wide bandgap semiconductor known as AZO. AZO consists of zinc oxide that is doped with aluminium. It is much less expensive than ITO and just as transparent, but not quite as electrically conductive. This process caused tiny AZO crystals to form on the silver nanowires, enveloped them completely, and finally filled in the interstices. The silver nanowires, measuring about 120 nanometres in diameter, were covered with a layer of about 100 nanometres of AZO and encapsulated by this process.

Quality map calculated

Measurements of the electrical conductivity showed that the newly developed composite electrode is comparable to a conventional silver grid electrode. However, its performance depends on how well the nanowires are interconnected, which is a function of the wire lengths and the concentration of silver nanowires in the suspension. The scientists were able to specify the degree of networking in advance with computers. Using specially developed image analysis algorithms, they could evaluate images taken with a scanning electron microscope and predict the electrical conductivity of the electrodes from them.

“We are investigating where a given continuous conductive path of nanowires is interrupted to see where the network is not yet optimum”, explains Ralf Keding. Even with high-performance computers, it still initially took nearly five days to calculate a good “quality map” of the electrode. The software is now being optimised to reduce the computation time. “The image analysis has given us valuable clues about where we need to concentrate our efforts to increase the performance of the electrode, such as increased networking to improve areas of poor coverage by changing the wire lengths or the wire concentration in solution”, says Göbelt.

Practical aternative to conventional electrodes

“We have developed a practical, cost-effective alternative to conventional screen-printed grid electrodes and to the common ITO type that is threatened however by material bottlenecks”, says Christiansen, who heads the Institute of Nanoarchitectures for Energy Conversion at HZB and additionally directs a project team at the Max Planck Institute for the Science of Light (MPL).

Only a fraction of silver, nearly no shadow effects

The new electrodes can actually be made using only 0.3 grams of silver per square metre, while conventional silver grid electrodes require closer to between 15 and 20 grams of silver. In addition, the new electrode casts a considerably smaller shadow on the solar cell. “The network of silver nanowires is so fine that almost no light for solar energy conversion is lost in the cell due to the shadow”, explains Göbelt. On the contrary, she hopes “it might even be possible for the silver nanowires to scatter light into the solar cell absorbers in a controlled fashion through what are known as plasmonic effects.”

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

Encapsulation of silver nanowire networks by atomic layer deposition for indium-free transparent electrodes by Manuela Göbelt, Ralf Keding, Sebastian W. Schmitt, Björn Hoffmann, Sara Jäckle, Michael Latzel, Vuk V. Radmilović, Velimir R. Radmilović,  Erdmann Spiecker, and Silke Christiansen. Nano Energy Volume 16, September 2015, Pages 196–206 doi:10.1016/j.nanoen.2015.06.027

This paper is behind a paywall.

Greening silver nanoparticles with lignin

A July 13, 2015 news item on phys.org highlights a new approach to making silver nanoparticles safer in the environment,

North Carolina State University researchers have developed an effective and environmentally benign method to combat bacteria by engineering nanoscale particles that add the antimicrobial potency of silver to a core of lignin, a ubiquitous substance found in all plant cells. The findings introduce ideas for better, greener and safer nanotechnology and could lead to enhanced efficiency of antimicrobial products used in agriculture and personal care.

A July 13, 2015 North Carolina State University (NCSU) news release (also on EurekAlert), which originated the news item, adds a bit more information,

As the nanoparticles wipe out the targeted bacteria, they become depleted of silver. The remaining particles degrade easily after disposal because of their biocompatible lignin core, limiting the risk to the environment.

“People have been interested in using silver nanoparticles for antimicrobial purposes, but there are lingering concerns about their environmental impact due to the long-term effects of the used metal nanoparticles released in the environment,” said Velev, INVISTA Professor of Chemical and Biomolecular Engineering at NC State and the paper’s corresponding author. “We show here an inexpensive and environmentally responsible method to make effective antimicrobials with biomaterial cores.”

The researchers used the nanoparticles to attack E. coli, a bacterium that causes food poisoning; Pseudomonas aeruginosa, a common disease-causing bacterium; Ralstonia, a genus of bacteria containing numerous soil-borne pathogen species; and Staphylococcus epidermis, a bacterium that can cause harmful biofilms on plastics – like catheters – in the human body. The nanoparticles were effective against all the bacteria.

The method allows researchers the flexibility to change the nanoparticle recipe in order to target specific microbes. Alexander Richter, the paper’s first author and an NC State Ph.D. candidate who won a 2015 Lemelson-MIT prize, says that the particles could be the basis for reduced risk pesticide products with reduced cost and minimized environmental impact.

“We expect this method to have a broad impact,” Richter said. “We may include less of the antimicrobial ingredient without losing effectiveness while at the same time using an inexpensive technique that has a lower environmental burden. We are now working to scale up the process to synthesize the particles under continuous flow conditions.”

I don’t quite understand how the silver nanoparticles/ions are rendered greener. I gather the lignin is harmless but where do the silver nanoparticles/ions go after they’ve been stripped of their lignin cover and have killed the bacteria? I did try reading the paper’s abstract (not much use for someone with my science level),

Silver nanoparticles have antibacterial properties, but their use has been a cause for concern because they persist in the environment. Here, we show that lignin nanoparticles infused with silver ions and coated with a cationic polyelectrolyte layer form a biodegradable and green alternative to silver nanoparticles. The polyelectrolyte layer promotes the adhesion of the particles to bacterial cell membranes and, together with silver ions, can kill a broad spectrum of bacteria, including Escherichia coli, Pseudomonas aeruginosa and quaternary-amine-resistant Ralstonia sp. Ion depletion studies have shown that the bioactivity of these nanoparticles is time-limited because of the desorption of silver ions. High-throughput bioactivity screening did not reveal increased toxicity of the particles when compared to an equivalent mass of metallic silver nanoparticles or silver nitrate solution. Our results demonstrate that the application of green chemistry principles may allow the synthesis of nanoparticles with biodegradable cores that have higher antimicrobial activity and smaller environmental impact than metallic silver nanoparticles.

If you can explain what happens to the silver nanoparticles, please let me know.

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

An environmentally benign antimicrobial nanoparticle based on a silver-infused lignin core by Alexander P. Richter, Joseph S. Brown, Bhuvnesh Bharti, Amy Wang, Sumit Gangwal, Keith Houck, Elaine A. Cohen Hubal, Vesselin N. Paunov, Simeon D. Stoyanov, & Orlin D. Velev. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.141 Published online 13 July 2015

This paper is behind a paywall.

Silver nanoparticle production at room temperature

I hadn’t thought silver nanoparticles were important to electronics but it seems I was wrongish. A July 2, 2015 news item on Nanowerk describes a breakthrough in silver nanoparticle production, which could increase its possible impact on electronics,

Engineers at Oregon State University [OSU] have invented a way to fabricate silver, a highly conductive metal, for printed electronics that are produced at room temperature.

There may be broad applications in microelectronics, sensors, energy devices, low emissivity coatings and even transparent displays.

A patent has been applied for on the technology, which is now available for further commercial development. The findings were reported in Journal of Materials Chemistry C. …

A July 1, 2015 OSU news release (also on EurekAlert), which originated the news item, expands on the theme of silver nanoparticles and electronics,

Silver has long been considered for the advantages it offers in electronic devices. Because of its conductive properties, it is efficient and also stays cool. But manufacturers have often needed high temperatures in the processes they use to make the devices, adding to their cost and complexity, and making them unsuitable for use on some substrates, such as plastics that might melt or papers that might burn.

This advance may open the door to much wider use of silver and other conductors in electronics applications, researchers said.

“There’s a great deal of interest in printed electronics, because they’re fast, cheap, can be done in small volumes and changed easily,” said Chih-hung Chang, a professor in the OSU College of Engineering. “But the heat needed for most applications of silver nanoparticles has limited their use.”

OSU scientists have solved that problem by using a microreactor to create silver nanoparticles at room temperatures without any protective coating, and then immediately printing them onto almost any substrate with a continuous flow process.

“Because we could now use different substrates such as plastics, glass or even paper, these electronics could be flexible, very inexpensive and stable,” Chang said. “This could be quite important and allow us to use silver in many more types of electronic applications.”

Among those, he said, could be solar cells, printed circuit boards, low-emissivity coatings, or transparent electronics. A microchannel applicator used in the system will allow the creation of smaller, more complex electronics features.

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

Room temperature fabrication and patterning of highly conductive silver features using in situ reactive inks by microreactor-assisted printing by Chang-Ho Choi, Elizabeth Allan-Cole, and Chih-hung Chang. J. Mater. Chem. C, 2015, Advance Article DOI: 10.1039/C5TC00947B First published online 26 May 2015

I believe this paper is behind a paywall.

Silver nanoparticles and wormwood tackle plant-killing fungus

I’m back in Florida (US), so to speak. Last mentioned here in an April 7, 2015 post about citrus canker and zinkicide, a story about a disease which endangers citrus production in the US, this latest story concerns a possible solution to the problem of a fungus, which attacks ornamental horticultural plants in Florida. From a May 5, 2015 news item on Azonano,

Deep in the soil, underneath more than 400 plant and tree species, lurks a lethal fungus threatening Florida’s $15 billion a year ornamental horticulture industry.

But University of Florida plant pathologist G. Shad Ali has found an economical and eco-friendly way to combat the plant destroyer known as phytophthora before it attacks the leaves and roots of everything from tomato plants to oak trees.

Ali and a team of researchers with UF’s Institute of Food and Agricultural Sciences, along with the University of Central Florida and the New Jersey Institute of Technology, have found that silver nanoparticles produced with an extract of wormwood, an herb with strong antioxidant properties, can stop several strains of the deadly fungus.

A May 4, 2015 University of Florida news release, which originated the news item, describes the work in more detail,

“The silver nanoparticles are extremely effective in eliminating the fungus in all stages of its life cycle,” Ali said. “In addition, it has no adverse effects on plant growth.” [emphasis mine]

The silver nanoparticles measure 5 to 100 nanometers in diameter – about one one-thousandth the width of a human hair. Once the nanoparticles are sprayed onto a plant, they shield it from fungus. Since the nanoparticles display multiple ways of inhibiting fungus growth, the chances of pathogens developing resistance to them are minimized, Ali said. Because of that, they may be used for controlling fungicide-resistant plant pathogens more effectively.

That’s good news for the horticulture industry. Worldwide crop losses due to phytophthora fungus diseases are estimated to be in the multibillion dollar range, with $6.7 billion in losses in potato crops due to late blight – the cause of the Irish Potato Famine in the mid-1800s when more than 1 million people died – and $1 billion to $2 billion in soybean loss.

Silver nanoparticles are being investigated for applications in various industries, including medicine, diagnostics, cosmetics and food processing.  They already are used in wound dressings, food packaging and in consumer products such as textiles and footwear for fighting odor-causing microorganisms.

Other members of the UF research team were Mohammad Ali, a visiting doctoral student from the Quaid-i-Azam University, Islamabad, Pakistan; David Norman and Mary Brennan with the University of Florida’s Plant Pathology-Mid Florida Research and Education Center; Bosung Kim with the University of Central Florida’s chemistry department; Kevin Belfield with the College of Science and Liberal Arts at the New Jersey Institute of Technology and the University of Central Florida’s chemistry department.

Ali’s comment about silver nanoparticles not having any adverse effects on plant growth is in contrast to findings by Mark Wiesner and other researchers at  Duke University (North Carolina, US). From my Feb. 28, 2013 posting (which also features a Finnish-Estonia study showing no adverse effects from silver nanoparticles  in crustaceans),

… there’s a study from Duke University suggests that silver nanoparticles in wastewater which is later put to agricultural use may cause problems. From the Feb. 27, 2013 news release on EurekAlert,

In experiments mimicking a natural environment, Duke University researchers have demonstrated that the silver nanoparticles used in many consumer products can have an adverse effect on plants and microorganisms.

The main route by which these particles enter the environment is as a by-product of water and sewage treatment plants. [emphasis] The nanoparticles are too small to be filtered out, so they and other materials end up in the resulting “sludge,” which is then spread on the land surface as a fertilizer.

The researchers found that one of the plants studied, a common annual grass known as Microstegium vimeneum, had 32 percent less biomass in the mesocosms treated with the nanoparticles. Microbes were also affected by the nanoparticles, Colman [Benjamin Colman, a post-doctoral fellow in Duke’s biology department and a member of the Center for the Environmental Implications of Nanotechnology (CEINT)] said. One enzyme associated with helping microbes deal with external stresses was 52 percent less active, while another enzyme that helps regulate processes within the cell was 27 percent less active. The overall biomass of the microbes was also 35 percent lower, he said.

“Our field studies show adverse responses of plants and microorganisms following a single low dose of silver nanoparticles applied by a sewage biosolid,” Colman said. “An estimated 60 percent of the average 5.6 million tons of biosolids produced each year is applied to the land for various reasons, and this practice represents an important and understudied route of exposure of natural ecosystems to engineered nanoparticles.”

“Our results show that silver nanoparticles in the biosolids, added at concentrations that would be expected, caused ecosystem-level impacts,” Colman said. “Specifically, the nanoparticles led to an increase in nitrous oxide fluxes, changes in microbial community composition, biomass, and extracellular enzyme activity, as well as species-specific effects on the above-ground vegetation.”

Getting back to Florida, you can find Ali’s abstract here,

Inhibition of Phytophthora parasitica and P. capsici by silver nanoparticles synthesized using aqueous extract of Artemisia absinthium by Mohammad Ali, Bosung Kim, Kevin Belfield, David J. Norman, Mary Brennan, & Gul Shad Ali. Phytopathology  http://dx.doi.org/10.1094/PHYTO-01-15-0006-R Published online April 14, 2015

This paper is behind a paywall.

For anyone who recognized that wormwood is a constituent of Absinthe, a liquor that is banned in many parts of the world due to possible side effects associated with the wormwood, here’s more about it from the Wormwood overview page on WebMD (Note: Links have been removed),

Wormwood is an herb. The above-ground plant parts and oil are used for medicine.

Wormwood is used in some alcoholic beverages. Vermouth, for example, is a wine beverage flavored with extracts of wormwood. Absinthe is another well-known alcoholic beverage made with wormwood. It is an emerald-green alcoholic drink that is prepared from wormwood oil, often along with other dried herbs such as anise and fennel. Absinthe was popularized by famous artists and writers such as Toulouse-Lautrec, Degas, Manet, van Gogh, Picasso, Hemingway, and Oscar Wilde. It is now banned in many countries, including the U.S. But it is still allowed in European Union countries as long as the thujone content is less than 35 mg/kg. Thujone is a potentially poisonous chemical found in wormwood. Distilling wormwood in alcohol increases the thujone concentration.

Returning to the matter at hand, as I’ve noted previously elsewhere, research into the toxic effects associated with nanomaterials (e.g. silver nanoparticles) is a complex process.