Tag Archives: nanosilver

Could synergistic action of engineered nanoparticles have a health impact?

Synergistic action can be difficult to study especially when you’re looking at nanoparticles which could be naturally occurring and/or engineered. I believe this study is focused on engineered nanoparticles (ENPs) and I think it’s the first one I’ve seen that examines synergistic action of any kind. So, bravo to the scientists for tackling a very ambitious project.

An October 1, 2020 news item on phys.org describes this work from Denmark,

Nanoparticles are used in a wide range of products and manufacturing processes because the properties of a material can change dramatically when the material comes in nano-form.

They can be used, for example, to purify wastewater and to transport medicine around the body. They are also added to, for example, socks, pillows, mattresses, phone covers and refrigerators to supply the items with an antibacterial surface.

Much research has been done on how nanoparticles affect humans and the environment and a number of studies have shown that nanoparticles can disrupt or damage our cells.

This is confirmed by a new study that has also looked at how cells react when exposed to more than one kind of nano particle at the same time.

An October 1, 2020 University of Southern Denmark press release (also on EurekAlert) by Birgitte Svennevig, which originated the news item, provides more insight into the research,

The lead author of the study is Barbara Korzeniowska from the Department of Biochemistry and Molecular Biology at SDU. The head of research is Professor Frank Kjeldsen from the same department.

His research into metal nanoparticles is supported by a European Research Grant of DKK 14 million.

“Throughout a lifetime, we are exposed to many different kinds of nano-particles, and we should investigate how the combination of different nano-particles affects us and also whether an accumulation through life can harm us,” says Barbara Korzeniowska.

She herself became interested in the subject when her little daughter one day was going in the bathtub and got a rubber duck as a toy.

– It turned out that it had been treated with nano-silver, probably to keep it free of bacteria, but small children put their toys in their mouths, and she could thus ingest nano-silver. That is highly worrying when research shows that nano-silver can damage human cells, she says.

In her new study, she looked at nano-silver and nano-platinum. She has investigated their individual effect and whether exposure of both types of nanoparticles results in a synergy effect in two types of brain cells.

– There are almost no studies of the synergy effect of nano particles, so it is important to get started with these studies, she says.

She chose nano-silver because it is already known to be able to damage cells and nano-platinum, because nano-platinum is considered to be so-called bio-inert; i.e. has a minimal interaction with human tissue.

The nanoparticles were tested on two types of brain cells: astrocytes and endothelial cells. Astrocytes are supporter cells in the central nervous system, which i.a. helps to supply the nervous system with nutrients and repair damage to the brain. Endothelial cells sit on the inside of the blood vessels and transport substances from the bloodstream to the brain.

When the endothelial cells were exposed to nano-platinum, nothing happened. When exposed to nano-silver, their ability to divide deteriorated. When exposed to both nano-silver and nano-platinum, the effect was amplified, and they died in large numbers. Furthermore, their defense mechanisms decreased, and they had difficulty communicating with each other.

– So even though nano-platinum alone does not do harm, something drastic happens when they are combined with a different kind of nano-particle, says Frank Kjeldsen.

The astrocytes were more hardy and reacted “only” with impaired ability to divide when exposed to both types of nano-particles.

An earlier study, conducted by Frank Kjeldsen, has shown a dramatic synergy effect of silver nanoparticles and cadmium ions, which are found naturally all around us on Earth.

In that study, 72 % of the cells died (in this study it was intestinal cells) as they were exposed to both nano-silver and cadmium ions. When they were only exposed to nano-silver, 25% died. When exposed to cadmium ions only, 12% died.

We are involuntarily exposed

– Little is known about how large concentrations of nano-particles are used in industrial products. We also do not know what size particles they use – size also has an effect on whether they can enter a cell, says Barbara Korzeniowska and continues:

– But we know that a lot of people are involuntarily exposed to nano-particles, and that there can be lifelong exposure.

There are virtually no restrictions on adding nanoparticles to products. In the EU, however, manufacturers must have an approval if they want to use nanoparticles in products with antibacterial properties. In Denmark, they must also declare nano-content in such products on the label.

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

The Cytotoxicity of Metal Nanoparticles Depends on Their Synergistic Interactions by Barbara Korzeniowska, Micaella P. Fonseca, Vladimir Gorshkov, Lilian Skytte, Kaare L. Rasmussen, Henrik D. Schrøder, Frank Kjeldsen. Particle Volume 37, Issue 8, August 2020,. 2000135 DOI: https://doi.org/10.1002/ppsc.202000135 First published: 06 July 2020

This paper is behind a paywall.

Nanoparticles in combination could be more toxic

It seems that one set of nanoparticles, e.g., silver nanoparticles, in combination with another material, e.g., cadmium ions, are more dangerous than either one separately according to an August 17, 2018 University of Southern Denmark press release by Birgitte Svennevig (also on EurekAlert but dated August 20, 2018),

Researchers warn that a combination of nanoparticles and contaminants may form a cocktail that is harmful to our cells. In their study, 72 pct. of cells died after exposure to a cocktail of nano-silver and cadmium ions.

Nanoparticles are becoming increasingly widespread in our environment. Thousands of products contain nanoparticles because of their unique properties. Silver nanoparticles are one example: They have an effective antibacterial effect and can be found in refrigerators, sports clothes, cosmetics, tooth brushes, water filters, etc.

There is a significant difference between how the cells react when exposed to nanosilver alone and when they are exposed to a cocktail of nanosilver and cadmium ions. Cadmium ions are naturally found everywhere around us on Earth.

In the study, 72 pct. of the cells died, when exposed to both nanosilver and cadmiun ions. When exposed to nanosilver only, 25 pct. died. When exposed to cadmium ions only, 12 pct. died.

The study was conducted on human liver cancer cells.

  • This study indicates, that we should not look at nanoparticles isolated when we investigate and discuss the effects, they may have on our health. We need to take cocktail effects into account, said Professor Frank Kjeldsen, Dept of Biochemistry and Molecular Biology, SDU, adding:
  • Products with nano particles are being developed and manufactured every day, but in most countries there are no regulations, so there is no way of knowing what and how many nanoparticles are being released into the environment. In my opinion, this should be stopped.

Other studies, led by Professor Kjeldsen have previously shown that human cells interact with metal nanoparticles.

One study showed that nano-silver leads to the formation free radicals in cells and changes in the form and amount of proteins. Many serious diseases are characterized by an overproduction of free radicals in cells. This applies to cancer and neurological diseases such as Alzheimer’s and Parkinson’s.

This is not great news but there are a few things to note about this research. First, it was conducted on cells and therefore not subject to some of the defensive systems found in complete biological organisms such as a mouse or a dandelion plant for example.

Also, since they were cancer cells one might suspect their reactions might differ from those of healthy cells. As for how the cells were exposed to the contaminants, I think (???) they were sitting in a solution of contaminants and most of us do not live in that kind of environment.. Finally, with regard to the concentrations, I have no idea if they are greater than one might expect to encounter in one’s lifecycle but it’s always worth questioning just how much exposure you might expect during yours or a mouse’s or a dandelion’s life.

These caveats aside, Professor Frank Kjeldsen’s work raises some very concerning issues and his work adds to a growing body of evidence.

Here’s a video featuring Dr. Kjeldsen talking about his work,

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

Co-exposure to silver nanoparticles and cadmium induce metabolic adaptation in HepG2 cells by Renata Rank Miranda, Vladimir Gorshkov, Barbara Korzeniowska, Stefan J. Kempf, Francisco Filipak Neto, & Frank Kjeldsen. Nanotoxicology DOI: https://doi.org/10.1080/17435390.2018.1489987 Published online: 11 Jul 2018

This paper is open access.

Panning for silver nanoparticles in your clothes washer

A March 20, 2018 news item on phys.org describes a new approach to treating wastewater (Note: Links have been removed),

Humans have known since ancient times that silver kills or stops the growth of many microorganisms. Hippocrates, the father of medicine, is said to have used silver preparations for treating ulcers and healing wounds. Until the introduction of antibiotics in the 1940s, colloidal silver (tiny particles suspended in a liquid) was a mainstay for treating burns, infected wounds and ulcers. Silver is still used today in wound dressings, in creams and as a coating on medical devices.

Since the 1990s, manufacturers have added silver nanoparticles to numerous consumer products to enhance their antibacterial and anti-odor properties. Examples include clothes, towels, undergarments, socks, toothpaste and soft toys. Nanoparticles are ultra-small particles, ranging from 1 to 100 nanometers in diameter – too small to see even with a microscope. According to a widely cited database, about one-fourth of nanomaterial-based consumer products currently marketed in the United States contain nanosilver.

Multiple studies have reported that nanosilver leaches out of textiles when they are laundered. Research also reveals that nanosilver may be toxic to humans and aquatic and marine organisms. Although it is widely used, little is understood about its fate or long-term toxic effects in the environment.

We are developing ways to convert this potential ecological crisis into an opportunity by recovering pure silver nanoparticles, which have many industrial applications, from laundry wastewater. In a recently published study, we describe a technique for silver recovery and discuss the key technical challenges. Our approach tackles this problem at the source – in this case, individual washing machines. We believe that this strategy has great promise for getting newly identified contaminants out of wastewater.

A March 20, 2018 essay by Sukalyan Sengupta, Professor of Wastewater Treatment, and Tabish Nawaz. Doctoral Student, both at University of Massachusetts at Dartmouth on The Conversation website, which originated the news item, expands on the theme (Note: Links have been removed),

Use of nanosilver in consumer products has steadily risen in the past decade. The market share of silver-based textiles rose from 9 percent in 2004 to 25 percent in 2011.

Several investigators have measured the silver content of textiles and found values ranging from 0.009 to 21,600 milligrams of silver per kilogram of textile. Studies show that the amount of silver leached in the wash solution depends on many factors, including interactions between detergent and other chemicals and how silver is attached to the textiles.

In humans, exposure to silver can harm liver cells, skin and lungs. Prolonged exposure or exposure to a large dose can cause a condition called Argyria, in which the victim’s skin turns permanently bluish-gray.

Once silver goes down the drain and ends up at wastewater treatment plants, it can potentially harm bacterial treatment processes, making them less efficient, and foul treatment equipment. More than 90 percent of silver nanoparticles released in wastewater end up in nutrient-rich biosolids left over at the end of sewage treatment, which often are used on land as agricultural fertilizers.

Silver is toxic in aquatic environments, a concern that’s becoming more serious with the increased use of silver nanoparticles and awareness that oceans, rivers, and lakes are dangerously stressed.

Sengupta and Nawaz go on to describe their proposed solution (Note: Links have been removed),

Our research shows that the most efficient way to remove silver from wastewater is by treating it in the washing machine. At this point silver concentrations are relatively high, and silver is initially released from treated clothing in a chemical form that is feasible to recover.

A bit of chemistry is helpful here. Our recovery method employs a widely used chemistry process called ion exchange. Ions are atoms or molecules that have an electrical charge. In ion exchange, a solid and a liquid are brought together and exchange ions with each other.

For example, household soaps do not lather well in “hard” water, which contains high levels of ions such as magnesium and calcium. Many home water filters use ion exchange to “soften” the water, replacing those materials with other ions that do not affect its properties in the same way.

For this process to work, the ions that switch places must both be either positively or negatively charged. Nanosilver is initially released from textiles as silver ion, which is a cation – an ion with a positive charge (hence the plus sign in its chemical symbol, Ag+).

Even at the source, removing silver from washwater is challenging. Silver concentrations in the wash solution are relatively low compared to other cations, such as calcium, that could interfere with the removal process. Detergent chemistry complicates the picture further because some detergent components can potentially interact with silver.

To recover silver without picking up other chemicals, the recovery process must use materials that have a chemical affinity for silver. In a previous study, we described a potential solution: Using ion-exchange materials embedded with sulfur-based chemicals, which bind preferentially with silver.

In our new study, we passed washwater through an ion-exchange resin column and analyzed how each major detergent ingredient interacted with silver in the water and affected the resin’s ability to remove silver from the water. By manipulating process conditions such as pH, temperature and concentration of nonsilver cations, we were able to identify conditions that maximized silver recovery.

We found that pH and the levels of calcium ions (Ca2+) were critical factors. Higher levels of hydrogen or calcium ions bind up detergent ingredients and prevent them from interacting with silver ions, so the ion-exchange resin can remove the silver from the solution. We also found that some detergent ingredients – particularly bleaching and water-softening agents – made the ion-exchange resin work less efficiently. Depending on these conditions, we recovered between 20 percent and 99 percent of the silver in the washwater.

The researchers go on to propose a new approach to treating wastewater (Note: A link has been removed),

Today wastewater is collected from multiple sources, such as homes and businesses, and piped over long distances to centralized wastewater treatment plants. But increasing evidence shows that these facilities are ill-equipped to keep newly identified contaminants out of the environment, since they use one common treatment scheme for many different waste streams.

We believe the future is in decentralized systems that can treat different types of wastewater with specific technologies designed specifically for the materials they contain. If wastewater from laundromats contains different contaminants than wastewater from restaurants, why treat them the same way?

Interesting, non? In any event, here’s a link to and a citation for what I believe is the researchers’ latest paper on this subject,

Silver Recovery from Laundry Washwater: The Role of Detergent Chemistry by Tabish Nawaz and Sukalyan Sengupta. ACS Sustainable Chem. Eng., 2018, 6 (1), pp 600–608 DOI: 10.1021/acssuschemeng.7b02933 Publication Date (Web): November 21, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall. For anyone who can’t get access, Karla Lant provides a bit more technical detail about the work in her February 2, 2018 article for fondriest.com.

Is there a risk of resistance to nanosilver?

Anyone who’s noticed how popular silver has become as an antibacterial, antifungal, or antiviral agent may have wondered if resistance might occur as its use becomes more common. I have two bits on the topic, one from Australia and the other from Canada.

Australia

Researchers in Australia don’t have a definitive statement on the issue but are suggesting more caution (from a March 31, 2017 news item on Nanowerk),

Researchers at the University of Technology Sydney [UTS] warn that the broad-spectrum antimicrobial effectiveness of silver is being put at risk by the widespread and inappropriate expansion of nanosilver use in medical and consumer goods.

As well as their use in medical items such as wound dressings and catheters, silver nanoparticles are becoming ubiquitous in everyday items, including toothbrushes and toothpaste, baby bottles and teats, bedding, clothing and household appliances, because of their antibacterial potency and the incorrect assumption that ordinary items should be kept “clean” of microbes.

Nanobiologist Dr Cindy Gunawan, from the ithree institute at UTS and lead researcher on the investigation, said alarm bells should be ringing at the commercialisation of nanosilver use because of a “real threat” that resistance to nanosilver will develop and spread through microorganisms in the human body and the environment.

A March 31 (?), 2017 University of Technology Sydney press release by Fiona McGill, which originated the news item, expands on the theme,

Dr Gunawan and ithree institute director Professor Liz Harry, in collaboration with researchers at UNSW [University of New South Wales] and abroad, investigated more than 140 commercially available medical devices, including wound dressings and tracheal and urinary catheters, and dietary supplements, which are promoted as immunity boosters and consumed by throat or nasal spray.

Their perspective article in the journal ACS Nano concluded that the use of nanosilver in these items could lead to prolonged exposure to bioactive silver in the human body. Such exposure creates the conditions for microbial resistance to develop.

E. coli bacteria. Photo: Flickr/NIAID

 

The use of silver as an antimicrobial agent dates back centuries. Its ability to destroy pathogens while seemingly having low toxicity on human cells has seen it widely employed, in treating burns or purifying water, for example. More recently, ultra-small (less than 10,000th of a millimetre) silver nanoparticles have been engineered for antimicrobial purposes.  Their commercial appeal lies in superior potency at lower concentrations than “bulk” silver.

“Nanosilver is a proven antimicrobial agent whose reliability is being jeopardised by the commercialisation of people’s fear of bacteria,” Dr Gunawan said.

“Our use of it needs to be far more judicious, in the same way we need to approach antibiotic usage. Nanosilver is a useful tool but we need to be careful, use it wisely and only when the benefit outweighs the risk.

“People need to be made aware of just how widely it is used, but more importantly they need to be made aware that the presence of nanosilver has been shown to cause antimicrobial resistance.”

What is also needed, Dr Gunawan said, is a targeted surveillance strategy to monitor for any occurrence of resistance.

Professor Harry said the findings were a significant contribution to addressing the global antimicrobial resistance crisis.

“This research emphasises the threat posed to our health and that of the environment by the inappropriate use of nanosilver as an antibacterial, particularly in ordinary household and consumer items,” she said.

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

Widespread and Indiscriminate Nanosilver Use: Genuine Potential for Microbial Resistance by Cindy Gunawan, Christopher P. Marquis, Rose Amal, Georgios A. Sotiriou, Scott A. Rice⊥, and Elizabeth J. Harry. ACS Nano, Article ASAP DOI: 10.1021/acsnano.7b01166 Publication Date (Web): March 24, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

Meanwhile, researchers at the University Calgary (Alberta, Canada) may have discovered what could cause resistance to silver.

Canada

This April 25, 2017 news release on EurekAlert is from the Experimental Biology Annual Meeting 2017,

Silver and other metals have been used to fight infections since ancient times. Today, researchers are using sophisticated techniques such as the gene-editing platform Crispr-Cas9 to take a closer look at precisely how silver poisons pathogenic microbes–and when it fails. The work is yielding new insights on how to create effective antimicrobials and avoid the pitfalls of antimicrobial resistance.

Joe Lemire, a postdoctoral fellow at the University of Calgary, will present his work in this area at the American Society for Biochemistry and Molecular Biology annual meeting during the Experimental Biology 2017 meeting, to be held April 22-26 in Chicago.

“Our overarching goal is to deliver the relevant scientific evidence that would aid policymakers in developing guidelines for when and how silver could be used in the clinic to combat and control infectious pathogens,” said Lemire. “With our enhanced mechanistic understanding of silver toxicity, we also aim to develop novel silver-based antimicrobial therapies, and potentially rejuvenate other antibiotic therapies that bacteria have come to resist, via silver-based co-treatment strategies.”

Lemire and his colleagues are using Crispr-Cas9 genome editing to screen for and delete genes that allow certain bacterial species to resist silver’s antimicrobial properties. [emphasis mine] Although previous methods allowed researchers to identify genes that confer antibiotic resistance or tolerance, Crispr-Cas9 is the first technology to allow researchers to cleanly delete these genes from the genome without leaving behind any biochemical markers or “scars.”

The team has discovered many biological pathways involved in silver toxicity and some surprising ways that bacteria avoid succumbing to silver poisoning, Lemire said. While silver is used to control bacteria in many clinical settings and has been incorporated into hundreds of commercial products, gaining a more complete understanding of silver’s antimicrobial properties is necessary if we are to make the most of this ancient remedy for years to come.

###

Joe Lemire will present this research at 12-2:30 p.m. Tuesday, April 25, [2017] in Hall F, McCormick Place Convention Center (poster B379 939.2) (abstract). Contact the media team for more information or to obtain a free press pass to attend the meeting.

About Experimental Biology 2017

Experimental Biology is an annual meeting comprised of more than 14,000 scientists and exhibitors from six host societies and multiple guest societies. With a mission to share the newest scientific concepts and research findings shaping clinical advances, the meeting offers an unparalleled opportunity for exchange among scientists from across the U.S. and the world who represent dozens of scientific areas, from laboratory to translational to clinical research. http://www.experimentalbiology.org #expbio

About the American Society for Biochemistry and Molecular Biology (ASBMB)

ASBMB is a nonprofit scientific and educational organization with more than 12,000 members worldwide. Founded in 1906 to advance the science of biochemistry and molecular biology, the society publishes three peer-reviewed journals, advocates for funding of basic research and education, supports science education at all levels, and promotes the diversity of individuals entering the scientific workforce. http://www.asbmb.org

Lemire’s co-authors for the work presented at the 2017 annual meeting are: Kate Chatfield-Reed (The University of Calgary), Lindsay Kalan (Perelman School of Medicine), Natalie Gugala (The University of Calgary), Connor Westersund (The University of Calgary), Henrik Almblad (The University of Calgary), Gordon Chua (The University of Calgary), Raymond Turner (The University of Calgary).

For anyone who wants to pursue this research a little further, the most recent paper I can find is this one from 2015,

Silver oxynitrate: An Unexplored Silver Compound with Antimicrobial and Antibiofilm Activity by Joe A. Lemire, Lindsay Kalan, Alexandru Bradu, and Raymond J. Turner. Antimicrobial Agents and Chemotherapy 05177-14, doi: 10.1128/AAC.05177-14 Accepted manuscript posted online 27 April 2015

This paper appears to be open access.

First Canadian Governor-General’s innovation award goes to professor Robert Burrell (nanoscientist) at the University of Alberta

The first innovation award ever given by the Canadian Governor General* has gone to a nanomedicine pioneer at the University of Alberta. From a May 12, 2016 news article by Marc Montgomery for Radio Canada International*, Note: A link has been removed,

Professor Robert Burrell of the University of Alberta has won a prestigious Governor-General’s Innovation Award for the world’s first therapeutic use of nanotechnology.

Professor Burrell used nano-technology on a wound bandage that has already begun transforming treatment of wounds in situations around the world.

Robert Burrell,  Professor in the Faculty of Chemical and Mechanical Engineering at the University of Alberta, is also Canada Research Chair in Nanostructured Biomaterials, and Chair, Biomedical Engineering at the university.

Burrell’s development called Acticoat came from research into nano-forms of silver.  When silver is reduced to nano scale it’s properties and chemical activity change.

In his research prior to joining the University in 2002, Burrell created a coating of nano-crystals of silver which not only kills bacteria but also has anti-inflammatory properties.

A May 9, 2016 University of Alberta news release has a bit more information,

… The chair of the U of A Department of Biomedical Engineering has been awarded a new national innovation prize in recognition of an invention that transformed wound care around the world.

Rob Burrell PhD, FCAHS, who holds the Canada Research Chair in Nanostructure Biomaterials and leads the Department of Biomedical Engineering, is one of six Canadians to win the inaugural round of the Governor General’s Innovation Awards. The awards recognize “exceptional and transformative work” that has helped “shape our future and positively impact our quality of life.”

“It was a nice surprise,” Burrell says of receiving the award. “I got an email in April—and was wondering why the Secretary to the Governor General of Canada [David Johnston is the current Governor General] wanted to talk to me. When we had our phone call he congratulated me on winning the award.”

Burrell invented Acticoat, a new wound dressing that uses nanocrystalline silver to fight bacteria and inflammation in wounds, while working for Westaim Biomedical, later Nucryst Pharmaceuticals. He joined the Faculty of Engineering in 2002.

The dressing was the world’s first therapeutic use of nanotechnology and has saved thousands of lives and limbs, transforming the treatment of burns and wounds.

“We have three projects on the go now. We’ve developed a new dressing and applied for a patent on it for scar control and we’re looking at commercializing that,” he said. “I have two of my grad students—and this summer we will have three summer students—working on a diagnostic tool that will allow a surgeon in an operating room to assess a tumour in 10 to 15 minutes. The analysis of the tumour can determine the type of surgery and post-surgical care the patient receives.”

You can find out more about the Governor General awards, which include, in addition to the new innovation category, the arts,  the sciences and humanities, and more here.

* I have a couple of explanatory notes for those unfamiliar with the concept of a Governor General and/or those who may be curious about Radio Canada International.

The Governor General is the Queen’s or the British monarch’s representative in Canada. Here’s another more general definition from a Wikipedia entry,

Governor-general or governor general, in modern usage, is the title of an office-holder appointed to represent the monarch of a sovereign state in the governing of an independent realm. Governors-general have also previously been appointed in respect of major colonial states or other territories held by either a monarchy or republic, such as French Indochina.

Radio Canada International is a little complicated. Radio Canada is the French language arm of the Canadian Broadcasting Corporation (CBC) and the name ‘Radio Canada’ refers to its radio, television, and internet services.

Interestingly Radio Canada International is the global outreach for both Radio Canada and CBC, presumably, uniting the English and French language services under one banner.

New model to track flow of nanomaterials through our air, earth, and water

Just how many tons of nanoparticles are making their way through the environment? Scientists at the Swiss Federal Laboratories for Materials Science and Technology (Empa) have devised a new model which could help answer that question. From a May 12, 2016 news item on phys.org,

Carbon nanotubes remain attached to materials for years while titanium dioxide and nanozinc are rapidly washed out of cosmetics and accumulate in the ground. Within the National Research Program “Opportunities and Risks of Nanomaterials” (NRP 64) a team led by Empa scientist Bernd Nowack has developed a new model to track the flow of the most important nanomaterials in the environment.

A May 12, 2016 Empa press release by Michael Hagmann, which also originated the news item, provides more detail such as an estimated tonnage for titanium dioxide nanoparticles produced annually in Europe,

How many man-made nanoparticles make their way into the air, earth or water? In order to assess these amounts, a group of researchers led by Bernd Nowack from Empa, the Swiss Federal Laboratories for Materials Science and Technology, has developed a computer model as part of the National Research Program “Opportunities and Risks of Nanomaterials” (NRP 64). “Our estimates offer the best available data at present about the environmental accumulation of nanosilver, nanozinc, nano-tinanium dioxide and carbon nanotubes”, says Nowack.

In contrast to the static calculations hitherto in use, their new, dynamic model does not just take into account the significant growth in the production and use of nanomaterials, but also makes provision for the fact that different nanomaterials are used in different applications. For example, nanozinc and nano-titanium dioxide are found primarily in cosmetics. Roughly half of these nanoparticles find their way into our waste water within the space of a year, and from there they enter into sewage sludge. Carbon nanotubes, however, are integrated into composite materials and are bound in products such as which are immobilized and are thus found for example in tennis racquets and bicycle frames. It can take over ten years before they are released, when these products end up in waste incineration or are recycled.

39,000 metric tons of nanoparticles

The researchers involved in this study come from Empa, ETH Zurich and the University of Zurich. They use an estimated annual production of nano-titanium dioxide across Europe of 39,000 metric tons – considerably more than the total for all other nanomaterials. Their model calculates how much of this enters the atmosphere, surface waters, sediments and the earth, and accumulates there. In the EU, the use of sewage sludge as fertilizer (a practice forbidden in Switzerland) means that nano-titanium dioxide today reaches an average concentration of 61 micrograms per kilo in affected soils.

Knowing the degree of accumulation in the environment is only the first step in the risk assessment of nanomaterials, however. Now this data has to be compared with results of eco-toxicological tests and the statutory thresholds, says Nowack. A risk assessment has not been carried out with his new model so far. Earlier work with data from a static model showed, however, that the concentrations determined for all four nanomaterials investigated are not expected to have any impact on the environment.

But in the case of nanozinc at least, its concentration in the environment is approaching the critical level. This is why this particular nanomaterial has to be given priority in future eco-toxicological studies – even though nanozinc is produced in smaller quantities than nano-titanium dioxide. Furthermore, eco-toxicological tests have until now been carried out primarily with freshwater organisms. The researchers conclude that additional investigations using soil-dwelling organisms are a priority.

Here are links to and citations for papers featuring the work,

Dynamic Probabilistic Modeling of Environmental Emissions of Engineered Nanomaterials by Tian Yin Sun†, Nikolaus A. Bornhöft, Konrad Hungerbühler, and Bernd Nowack. Environ. Sci. Technol., 2016, 50 (9), pp 4701–4711 DOI: 10.1021/acs.est.5b05828 Publication Date (Web): April 04, 2016

Copyright © 2016 American Chemical Society

Probabilistic environmental risk assessment of five nanomaterials (nano-TiO2, nano-Ag, nano-ZnO, CNT, and fullerenes) by Claudia Coll, Dominic Notter, Fadri Gottschalk, Tianyin Sun, Claudia Som, & Bernd Nowack. Nanotoxicology Volume 10, Issue 4, 2016 pages 436-444 DOI: 10.3109/17435390.2015.1073812 Published online: 10 Nov 2015

The first paper, which is listed in Environmental Science & Technology, appears to be open access while the second paper is behind a paywall.

Research into nanosilver’s antibiotic properties and nanogold’s detection skills

There is a puzzling and exciting announcement from the Canadian Light Source in a May 27, 2015 news item on Nanowerk,

Precious metals like silver and gold have biomedical properties that have been used for centuries, but how do these materials effectively combat the likes of cancer and bacteria without contaminating the patient and the environment?

These are the questions that researchers from Dalhousie University and the Canadian Light Source are trying to find out.

Perhaps I’m misreading the announcement but the statement that nanosilver and nanogold don’t contaminate the patient or the environment is a bit exuberant. There are published studies examining questions about whether or not nanosilver may affect the environment and health and the answer is that no one is certain yet. You can read more about two studies highlighted in my February 28, 2013 posting titled:  Silver nanoparticles, water, the environment, and toxicity. As for nanosilver and nanogold not contaminating patients, that too is a problematic statement. For example, I have this paper which cites several studies on nanogold and possible toxicity. The paper itself is a plea to standardize testing and protocols so researchers can do a better job of establishing toxicity issues with nanogold.

GoldNP_ToxicityMar2015

Reservations aside, it’s good to learn of some Canadian research in this area. From a May 26, 2015 Canadian Light Source news release, which originated the news item, provides more details about the research and its current focus on nanosilver,

“Gold and silver are both exciting materials,” said Peng Zhang, Associate Professor of Chemistry at Dalhousie. “We can use gold to either detect or kill cancer cells. Silver is also excited and a very promising material as an antibacterial agents.”

Zhang said that if you compare silver to current antibiotics, silver does not show drug-resistant behaviour. “But with silver, so far, we are not finding that,” he added.

Finding out why silver is such a great antibacterial agent is the focus of Zhang’s research, recently published in the journal Langmuir.

“We want to understand the relationship between the atomic structure and bioactivity of nanosilver as to why it is so efficient at inhibiting bacterial activity. It’s a big puzzle.”

Zhang said it is very hard to understand what is happening at the atomic level. Using small nanosilver particles is the most effective way, because when you make silver small, you can expect higher activity because of the increased surface area.

This poses another problem however, as the nanosilver needs to be stabilized with a coating or the silver particles will bond together forming large pieces of silver that do not efficiently interact with the bacteria.

Zhang’s group used two different coatings to compare the effectiveness of the silver as an antibacterial agent. The first was a small amino acid coating and the other was a larger polymer coating. And after testing the interactions between the nanosilver and the bacteria, and looking at the atomic structure of nanosilver using the CLS and the Advanced Photon Source, the researchers were surprised to find that the thicker, larger polymer coating actually created a better delivery method for sliver to inhibit the bacteria.

“We proposed that the small amino acid coating would bind so tightly to the silver surface that it would be difficult for  the silver atoms to interact with the bacteria, whereas the polymers are actually very good at staying in place and still releasing sufficient amount of silver with the bacteria.”

Zhang said the next steps will be to find out if the nanosilver is actually attacking good cells in living systems before they can make any further progress on determining whether nanosilver is an effective and efficient antibactieral agent that could be used to cure human and animal diseases.

Here’s an illustration provided by the researchers,

The atomic structure of nanosilver, revealed by synchrotron X-ray spectroscopy, is proving to be a determinant of silver’s antibacterial activity. Padmos, J. Daniel, et al. "Impact of Protecting Ligands on Surface Structure and Antibacterial Activity of Silver Nanoparticles." Langmuir 31.12 (2015): 3745-3752.

The atomic structure of nanosilver, revealed by synchrotron X-ray spectroscopy, is proving to be a determinant of silver’s antibacterial activity.
Padmos, J. Daniel, et al. “Impact of Protecting Ligands on Surface Structure and Antibacterial Activity of Silver Nanoparticles.” Langmuir 31.12 (2015): 3745-3752.

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

Impact of Protecting Ligands on Surface Structure and Antibacterial Activity of Silver Nanoparticles by J. Daniel Padmos, Robert T. M. Boudreau, Donald F. Weaver, and Peng Zhang. Langmuir, 2015, 31 (12), pp 3745–3752
DOI: 10.1021/acs.langmuir.5b00049 Publication Date (Web): March 15, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

rePOOPulate, silver nanoparticles, your gut, and Queen’s University (Canada)

A Nov. 19, 2014 Queen’s University (Ontario, Canada) news release by Anne Craig (also on EurekAlert), describes some research into nanosilver’s effects on the human (more or less) gut,

Queen’s University biologist Virginia Walker and Queen’s SARC Awarded Postdoctoral Fellow Pranab Das have shown nanosilver, which is often added to water purification units, can upset your gut. The discovery is important as people are being exposed to nanoparticles every day.

“We were surprised to see significant upset of the human gut community at the lowest concentration of nanosilver in this study,” says Dr. Das. “To our knowledge, this is the first time anyone has looked at this. It is important as we are more and more exposed to nanoparticles in our everyday lives through different routes such as inhalation, direct contact or ingestion.”

To conduct the research, Drs. Walker and Das utilized another Queen’s discovery, rePOOPulate, created by Elaine Petrof (Medicine). rePOOPulate is a synthetic stool substitute, which Dr. Petrof designed to treat C. difficile infections. In this instance, rather than being used as therapy, the synthetic stool was used to examine the impact of nanoparticles on the human gut.

The research showed that the addition of nanosilver reduced metabolic activity in the synthetic stool sample, perturbed fatty acids and significantly changed the population of bacteria. This information can help lead to an understanding of how nanoparticles could impact our “gut ecosystem.” [emphasis mine]

“There is no doubt that the nanosilver shifted the bacterial community, but the impact of nanosilver ingestion on our long-term health is currently unknown,” Dr. Walker says. “This is another area of research we need to explore.”

The findings by Drs. Das and Walker, Julie AK McDonald (Kingston General Hospital), Dr. Petrof (KGH)  and Emma Allen-Vercoe (University of Guelph) were published in the Journal of Nanomedicine and Nanotechnology.

It’s perturbing news. And, I notice the news release is carefully worded, “This information can help lead to an understanding of how nanoparticles could impact our ‘gut ecosystem.'”

The news release notes this about the ubiquity of nanosilver use,

Nanosilver is also used in biomedical applications, toys, sunscreen, cosmetics, clothing and other items.

I’m a little surprised by the reference to sunscreens; most of the material I’ve seen cites titanium dioxide and/or zinc oxide at the nanoscale.

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

Nanosilver-Mediated Change in Human Intestinal Microbiota by Pranab Das, Julie AK McDonald, Elaine O Petrof, Emma Allen-Vercoe, and Virginia K Walker. Nanomed Nanotechnol 5: 235. doi: 10.4172/2157-7439.1000235

The link takes you to a PDF version of the research paper,

Note: Queen’s University is located in Kingston, Ontario, Canada.

Danish scientists provide insights into celllular response to silver nanoparticles

The conclusions are concerning but the scientists at the University of Southern Denmark are careful to note that this research on silver nanopartices was performed in a laboratory setting which does not necessarily predict what might happen under real life conditions.

As for the research itself, a Feb. 28, 2014 news item on Azonano has this to say,

Endocrine disrupters are not the only worrying chemicals that ordinary consumers are exposed to in everyday life. Also nanoparticles of silver, found in e.g. dietary supplements, cosmetics and food packaging, now worry scientists. A new study from the University of Southern Denmark shows that nano-silver can penetrate our cells and cause damage.

Silver has an antibacterial effect and therefore the food and cosmetic industry often coat their products with silver nanoparticles. Nano-silver can be found in e.g. drinking bottles, cosmetics, band aids, toothbrushes, running socks, refrigerators, washing machines and food packagings.

“Silver as a metal does not pose any danger, but when you break it down to nano-sizes, the particles become small enough to penetrate a cell wall. If nano-silver enters a human cell, it can cause changes in the cell”, explain Associate Professor Frank Kjeldsen and PhD Thiago Verano-Braga, Department of Biochemistry and Molecular Biology at the University of Southern Denmark.

A Feb. 27, 2014 University of Southern Denmark news release, which originated the news item, provides more detail about the research,

The researchers examined human intestinal cells, as they consider these to be most likely to come into contact with nano-silver, ingested with food.

“We can confirm that nano-silver leads to the formation of harmful, so called free radicals in cells. We can also see that there are changes in the form and amount of proteins. This worries us”, say Frank Kjeldsen and Thiago Verano-Braga.

A large number of serious diseases are characterized by the fact that there is an overproduction of free radicals in cells. This applies to cancer and neurological diseases such as Alzheimer’s and Parkinson’s.

Kjeldsen and Verano-Braga emphasizes that their research is conducted on human cells in a laboratory, not based on living people. They also point out that they do not know how large a dose of nano-silver, a person must be exposed to for the emergence of cellular changes.

“We don’t know how much is needed, so we cannot conclude that nano-silver can make you sick. But we can say that we must be very cautious and worried when we see an overproduction of free radicals in human cells”, they say.

Nano-silver is also sold as a dietary supplement, promising to have an antibacterial, anti-flu and cancer-inhibatory effect. The nano-silver should also help against low blood counts and bad skin. In the EU, the marketing of dietary supplements and foods with claims to have medical effects is not allowed. But the nano-silver is easy to find and buy online.

In the wake of the SDU-research, the Danish Veterinary and Food Administration now warns against taking dietary supplements with nano-silver.

“The recent research strongly suggests that it can be dangerous”, says Søren Langkilde from the Danish Veterinary and Food Administration to the Danish Broadcasting Corporation (DR).

The researchers supplied this image to illustrate the abstract for their paper (link and citation to follow),

Courtesy University of Southern Denmark

Courtesy University of Southern Denmark

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

Insights into the Cellular Response Triggered by Silver Nanoparticles Using Quantitative Proteomics by Thiago Verano-Braga, Rona Miethling-Graff, Katarzyna Wojdyla, Adelina Rogowska-Wrzesinska, Jonathan R. Brewer, Helmut Erdmann, and Frank Kjeldsen. ACS Nano, Article ASAP DOI: 10.1021/nn4050744 Publication Date (Web): February 10, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.