Tag Archives: Reactive Oxygen Species

Using nanomagnets to remove plastic from water

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it seems Australian researchers are working hard to find ways of removing microplastics from water. I have two items, first, a November 29, 2022 news item on Nanowerk announces some of the latest work,

Researchers at RMIT University have found an innovative way to rapidly remove hazardous microplastics from water using magnets.

Lead researcher Professor Nicky Eshtiaghi said existing methods could take days to remove microplastics from water, while their cheap and sustainable invention achieves better results in just one hour.

The team says they have developed adsorbents, in the form of a powder, that remove microplastics 1,000 times smaller than those currently detectable by existing wastewater treatment plants. 

The researchers have successfully tested the adsorbents in the lab, and they plan to engage with industry to further develop the innovation to remove microplastics from waterways.

…

A November 30, 2022 RMIT University press release, which originated the news item, provides more technical detail about the work,

“The nano-pillar structure we’ve engineered to remove this pollution, which is impossible to see but very harmful to the environment, is recycled from waste and can be used multiple times,” said Eshtiaghi from RMIT’s School of Environmental and Chemical Engineering.

“This is a big win for the environment and the circular economy.”

How does this innovation work?

The researchers have developed an adsorbent using nanomaterials that they can mix into water to attract microplastics and dissolved pollutants.

Muhammad Haris, the first author and PhD candidate from RMIT’s School of Environmental and Chemical Engineering, said the nanomaterials contained iron, which enabled the team to use magnets to easily separate the microplastics and pollutants from the water.

“This whole process takes one hour, compared to other inventions taking days,” he said.

Co-lead researcher Dr Nasir Mahmood said the nano-pillar structured material was designed to attract microplastics without creating any secondary pollutants or carbon footprints.

“The adsorbent is prepared with special surface properties so that it can effectively and simultaneously remove both microplastics and dissolved pollutants from water,” said Mahmood from Applied Chemistry and Environmental Science at RMIT.

“Microplastics smaller than 5 millimetres, which can take up to 450 years to degrade, are not detectable and removable through conventional treatment systems, resulting in millions of tonnes being released into the sea every year. This is not only harmful for aquatic life, but also has significant negative impacts on human health.”

The team received scientific and technical support from the Microscopy and Microanalysis Facility and the Micro Nano Research Facility, part of RMIT’s newly expanded Advanced Manufacturing Precinct, to complete their research. 

What are the next steps?

Developing a cost-effective way to overcome these signficant challenges posed by microplastics was critical, Eshtiaghi said.

“Our powder additive can remove microplastics that are 1,000 times smaller than those that are currently detectable by existing wastewater treatment plants,” she said.

“We are looking for industrial collaborators to take our invention to the next steps, where we will be looking at its application in wastewater treatment plants.”

Eshtiaghi and her colleagues have worked with various water utilities across Australia, including with Melbourne Water and Water Corporation in Perth on a recent Australian Research Council Linkage project to optimise sludge pumping systems.

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

Self-assembly of C@FeO nanopillars on 2D-MOF for simultaneous removal of microplastic and dissolved contaminants from water by Muhammad Haris, Muhammad Waqas Khan, Ali Zavabeti, Nasir Mahmood and Nicky Eshtiaghi. Chemical Engineering Journal Available online 23 November 2022, 140390 DOI: https://doi.org/10.1016/j.cej.2022.140390

This paper is behind a paywall.

Back in 2019

Caption: This visual abstract depicts the findings of Kang et al.. Novel and robust nanocarbon springs were synthesized via solid pyrolysis with a controlled morphology, and simultaneously engineered nitrogen dopants and encapsulated magnetic nanoparticles. The carbocatalysts can effectively catalyze peroxymonosulfate to generate highly reactive radicals under hydrothermal conditions for decomposing microplastics into harmless substances in water. Credit: Kang et al/Matter

This July 31, 2019 Cell Press news release on EurekAlert announces a different approach, from an Australian team, to removing plastics from water,

Plastic waste that finds its way into oceans and rivers poses a global environmental threat with damaging health consequences for animals, humans, and ecosystems. Now, using tiny coil-shaped carbon-based magnets, researchers in Australia have developed a new approach to purging water sources of the microplastics that pollute them without harming nearby microorganisms. Their work appears July 31 in the journal Matter.

“Microplastics adsorb organic and metal contaminants as they travel through water and release these hazardous substances into aquatic organisms when eaten, causing them to accumulate all the way up the food chain” says senior author Shaobin Wang, a professor of chemical engineering at the University of Adelaide (Australia). “Carbon nanosprings are strong and stable enough to break these microplastics down into compounds that do not pose such a threat to the marine ecosystem.”

Although often invisible to the naked eye, microplastics are ubiquitous pollutants. Some, such as the exfoliating beads found in popular cosmetics, are simply too small to be filtered out during industrial water treatment. Others are produced indirectly, when larger debris like soda bottles or tires weather amid sun and sand.

To decompose the microplastics, the researchers had to generate short-lived chemicals called reactive oxygen species, which trigger chain reactions that chop the various long molecules that make up microplastics into tiny and harmless segments that dissolve in water. However, reactive oxygen species are often produced using heavy metals such as iron or cobalt, which are dangerous pollutants in their own right and thus unsuitable in an environmental context.

To get around this challenge, the researchers found a greener solution in the form of carbon nanotubes laced with nitrogen to help boost generation of reactive oxygen species. Shaped like springs, the carbon nanotube catalysts removed a significant fraction of microplastics in just eight hours while remaining stable themselves in the harsh oxidative conditions needed for microplastics breakdown. The coiled shape increases stability and maximises reactive surface area. As a bonus, by including a small amount of manganese, buried far from the surface of the nanotubes to prevent it from leaching into water, the minute springs became magnetic.

“Having magnetic nanotubes is particularly exciting because this makes it easy to collect them from real wastewater streams for repeated use in environmental remediation,” says Xiaoguang Duan, a chemical engineering research fellow at Adelaide who also co-led the project.

As no two microplastics are chemically quite the same, the researchers’ next steps will center on ensuring that the nanosprings work on microplastics of different compositions, shapes and origins. They also intend to continue to rigorously confirm the non-toxicity of any chemical compounds occurring as intermediates or by-products during microplastics decomposition.

The researchers also say that those intermediates and byproducts could be harnessed as an energy source for microorganisms that the polluting plastics currently plague. “If plastic contaminants can be repurposed as food for algae growth, it will be a triumph for using biotechnology to solve environmental problems in ways that are both green and cost efficient,” Wang says.

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

Degradation of Cosmetic Microplastics via Functionalized Carbon Nanosprings by Jian Kang, Li Zhou, Xiaoguang Duan, Hongqi Sun, Zhimin Ao, Shaobin Wang. Matter Volume 1, Issue 3, 4 September 2019, Pages 745-758 DOI: https://doi.org/10.1016/j.matt.2019.06.004

This paper is open access.

Comments

I’m glad to see this work and as for which approach might be preferable, I don’t know if there’s a clear winner. The 2022 work removes both microplastics and pollutants in one hour! An impressive feat, which leaves us with microplastics and pollutants to deal with. By contrast , the 2019 work transforms the microplastics into materials that don’t pose harm to the aquatic environment. Great although it takes eight hours. I wish the best for all the researchers working on this microplastics problem.

Tattoo therapy for chronic disease?

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It’s good to wake up to something truly new. In this case, it’s using tattoos and nanoparticles for medical applications. From a Sept. 22, 2016 news item on ScienceDaily,

A temporary tattoo to help control a chronic disease might someday be possible, according to scientists at Baylor College of Medicine [Texas, US] who tested antioxidant nanoparticles created at Rice University [Texas, US].

A Sept. 22, 2016 Rice University news release, which originated the news item, provides more information and some good explanations of the terms used (Note: Links have been removed),

A proof-of-principle study led by Baylor scientist Christine Beeton published today by Nature’s online, open-access journal Scientific Reports shows that nanoparticles modified with polyethylene glycol are conveniently choosy as they are taken up by cells in the immune system.

That could be a plus for patients with autoimmune diseases like multiple sclerosis, one focus of study at the Beeton lab. “Placed just under the skin, the carbon-based particles form a dark spot that fades over about one week as they are slowly released into the circulation,” Beeton said.

T and B lymphocyte cells and macrophages are key components of the immune system. However, in many autoimmune diseases such as multiple sclerosis, T cells are the key players. One suspected cause is that T cells lose their ability to distinguish between invaders and healthy tissue and attack both.

In tests at Baylor, nanoparticles were internalized by T cells, which inhibited their function, but ignored by macrophages. “The ability to selectively inhibit one type of cell over others in the same environment may help doctors gain more control over autoimmune diseases,” Beeton said.

“The majority of current treatments are general, broad-spectrum immunosuppressants,” said Redwan Huq, lead author of the study and a graduate student in the Beeton lab. “They’re going to affect all of these cells, but patients are exposed to side effects (ranging) from infections to increased chances of developing cancer. So we get excited when we see something new that could potentially enable selectivity.” Since the macrophages and other splenic immune cells are unaffected, most of a patient’s existing immune system remains intact, he said.

The soluble nanoparticles synthesized by the Rice lab of chemist James Tour have shown no signs of acute toxicity in prior rodent studies, Huq said. They combine polyethylene glycol with hydrophilic carbon clusters, hence their name, PEG-HCCs. The carbon clusters are 35 nanometers long, 3 nanometers wide and an atom thick, and bulk up to about 100 nanometers in globular form with the addition of PEG. They have proven to be efficient scavengers of reactive oxygen species called superoxide molecules, which are expressed by cells the immune system uses to kill invading microorganisms.

T cells use superoxide in a signaling step to become activated. PEG-HCCs remove this superoxide from the T cells, preventing their activation without killing the cells.

Beeton became aware of PEG-HCCs during a presentation by former Baylor graduate student Taeko Inoue, a co-author of the new study. “As she talked, I was thinking, ‘That has to work in models of multiple sclerosis,’” Beeton said. “I didn’t have a good scientific rationale, but I asked for a small sample of PEG-HCCs to see if they affected immune cells.

“We found they affected the T lymphocytes and not the other splenic immune cells, like the macrophages. It was completely unexpected,” she said.

The Baylor lab’s tests on animal models showed that small amounts of PEG-HCCs injected under the skin are slowly taken up by T lymphocytes, where they collect and inhibit the cell’s function. They also found the nanoparticles did not remain in T cells and dispersed within days after uptake by the cells.

“That’s an issue because you want a drug that’s in the system long enough to be effective, but not so long that, if you have a problem, you can’t remove it,” Beeton said. “PEG-HCCs can be administered for slow release and don’t stay in the system for long. This gives us much better control over the circulating half-life.”

“The more we study the abilities of these nanoparticles, the more surprised we are at how useful they could be for medical applications,” Tour said. The Rice lab has published papers with collaborators at Baylor and elsewhere on using functionalized nanoparticles to deliver cancer drugs to tumors and to quench the overproduction of superoxides after traumatic brain injuries.

Beeton suggested delivering carbon nanoparticles just under the skin rather than into the bloodstream would keep them in the system longer, making them more available for uptake by T cells. And the one drawback – a temporary but visible spot on the skin that looks like a tattoo – could actually be a perk to some.

“We saw it made a black mark when we injected it, and at first we thought that’s going to be a real problem if we ever take it into the clinic,” Beeton said. “But we can work around that. We can inject into an area that’s hidden, or use micropattern needles and shape it.

“I can see doing this for a child who wants a tattoo and could never get her parents to go along,” she said. “This will be a good way to convince them.”

The research was supported by Baylor College of Medicine, the National Multiple Sclerosis Society, National Institutes of Health, the Dan L. Duncan Cancer Center, John S. Dunn Gulf Coast Consortium for Chemical Genomics and the U.S. Army-funded Traumatic Brain Injury Consortium.

That’s an interesting list of funders at the end of the news release.

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

Preferential uptake of antioxidant carbon nanoparticles by T lymphocytes for immunomodulation by Redwan Huq, Errol L. G. Samuel, William K. A. Sikkema, Lizanne G. Nilewski, Thomas Lee, Mark R. Tanner, Fatima S. Khan, Paul C. Porter, Rajeev B. Tajhya, Rutvik S. Patel, Taeko Inoue, Robia G. Pautler, David B. Corry, James M. Tour, & Christine Beeton. Scientific Reports 6, Article number: 33808 (2016) doi:10.1038/srep33808 Published online: 22 September 2016

This paper is open access.

Here’s an image provided by the researchers,

Polyethylene glycol-hydrophilic carbon clusters developed at Rice University were shown to be selectively taken up by T cells, which inhibits their function, in tests at Baylor College of Medicine. The researchers said the nanoparticles could lead to new strategies for controlling autoimmune diseases like multiple sclerosis. (Credit: Errol Samuel/Rice University) - See more at: http://news.rice.edu/2016/09/22/tattoo-therapy-could-ease-chronic-disease/#sthash.sIfs3b0S.dpuf

Polyethylene glycol-hydrophilic carbon clusters developed at Rice University were shown to be selectively taken up by T cells, which inhibits their function, in tests at Baylor College of Medicine. The researchers said the nanoparticles could lead to new strategies for controlling autoimmune diseases like multiple sclerosis. (Credit: Errol Samuel/Rice University)

Breathing nanoparticles into your brain

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Thanks to Dexter Johnson and his Sept. 8, 2016 posting (on the Nanoclast blog on the IEEE [Institute for Electrical and Electronics Engineers]) for bringing this news about nanoparticles in the brain to my attention (Note: Links have been removed),

An international team of researchers, led by Barbara Maher, a professor at Lancaster University, in England, has found evidence that suggests that the nanoparticles that were first detected in the human brain over 20 years ago may have an external rather an internal source.

…

These magnetite nanoparticles are an airborne particulate that are abundant in urban environments and formed by combustion or friction-derived heating. In other words, they have been part of the pollution in the air of our cities since the dawn of the Industrial Revolution.

However, according to Andrew Maynard, a professor at Arizona State University, and a noted expert on the risks associated with nanomaterials,  the research indicates that this finding extends beyond magnetite to any airborne nanoscale particles—including those deliberately manufactured.

“The findings further support the possibility of these particles entering the brain via the olfactory nerve if inhaled.  In this respect, they are certainly relevant to our understanding of the possible risks presented by engineered nanomaterials—especially those that are iron-based and have magnetic properties,” said Maynard in an e-mail interview with IEEE Spectrum. “However, ambient exposures to airborne nanoparticles will typically be much higher than those associated with engineered nanoparticles, simply because engineered nanoparticles will usually be manufactured and handled under conditions designed to avoid release and exposure.”

A Sept. 5, 2016 University of Lancaster press release made the research announcement,

Researchers at Lancaster University found abundant magnetite nanoparticles in the brain tissue from 37 individuals aged three to 92-years-old who lived in Mexico City and Manchester. This strongly magnetic mineral is toxic and has been implicated in the production of reactive oxygen species (free radicals) in the human brain, which are associated with neurodegenerative diseases including Alzheimer’s disease.

Professor Barbara Maher, from Lancaster Environment Centre, and colleagues (from Oxford, Glasgow, Manchester and Mexico City) used spectroscopic analysis to identify the particles as magnetite. Unlike angular magnetite particles that are believed to form naturally within the brain, most of the observed particles were spherical, with diameters up to 150 nm, some with fused surfaces, all characteristic of high-temperature formation – such as from vehicle (particularly diesel) engines or open fires.

The spherical particles are often accompanied by nanoparticles containing other metals, such as platinum, nickel, and cobalt.

Professor Maher said: “The particles we found are strikingly similar to the magnetite nanospheres that are abundant in the airborne pollution found in urban settings, especially next to busy roads, and which are formed by combustion or frictional heating from vehicle engines or brakes.”

Other sources of magnetite nanoparticles include open fires and poorly sealed stoves within homes. Particles smaller than 200 nm are small enough to enter the brain directly through the olfactory nerve after breathing air pollution through the nose.

“Our results indicate that magnetite nanoparticles in the atmosphere can enter the human brain, where they might pose a risk to human health, including conditions such as Alzheimer’s disease,” added Professor Maher.

Leading Alzheimer’s researcher Professor David Allsop, of Lancaster University’s Faculty of Health and Medicine, said: “This finding opens up a whole new avenue for research into a possible environmental risk factor for a range of different brain diseases.”

Damian Carrington’s Sept. 5, 2016 article for the Guardian provides a few more details,

“They [the troubling magnetite particles] are abundant,” she [Maher] said. “For every one of [the crystal shaped particles] we saw about 100 of the pollution particles. The thing about magnetite is it is everywhere.” An analysis of roadside air in Lancaster found 200m magnetite particles per cubic metre.

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Other scientists told the Guardian the new work provided strong evidence that most of the magnetite in the brain samples come from air pollution but that the link to Alzheimer’s disease remained speculative.

For anyone who might be concerned about health risks, there’s this from Andrew Maynard’s comments in Dexter Johnson’s Sept. 8, 2016 posting,

“In most workplaces, exposure to intentionally made nanoparticles is likely be small compared to ambient nanoparticles, and so it’s reasonable to assume—at least without further data—that this isn’t a priority concern for engineered nanomaterial production,” said Maynard.

While deliberate nanoscale manufacturing may not carry much risk, Maynard does believe that the research raises serious questions about other manufacturing processes where exposure to high concentrations of airborne nanoscale iron particles is common—such as welding, gouging, or working with molten ore and steel.

It seems everyone is agreed that the findings are concerning but I think it might be good to remember that the percentage of people who develop Alzheimer’s Disease is much smaller than the population of people who have crystals in their brains. In other words, these crystals might (they don’t know) be a factor and likely there would have to be one or more factors to create the condition for developing Alzheimer’s.

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

Magnetite pollution nanoparticles in the human brain by Barbara A. Maher, Imad A. M. Ahmed, Vassil Karloukovski, Donald A. MacLaren, Penelope G. Fouldsd, David Allsop, David M. A. Mann, Ricardo Torres-Jardón, and Lilian Calderon-Garciduenas. PNAS [Proceedings of the National Academy of Sciences] doi: 10.1073/pnas.1605941113

This paper is behind a paywall but Dexter’s posting offers more detail for those who are still curious.

Disinfectants without chemicals for the food industry

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Michael Berger in his March 16, 2015 Nanowerk Spotlight article profiles some very interesting research into replacing chemicals with water nanostructures,

The burden of foodborne diseases worldwide is huge, with serious economic and public health consequences. The CDC [US Centers for Disease Control] estimates that each year in the USA approximately 48 million people get sick, 128,000 get hospitalized and 3,000 die from the consumption of food contaminated with pathogenic microorganisms. The food industry is in search of effective intervention methods that can be applied from ‘farm to fork’ to ensure the safety of the food chain and be consumer and environment friendly at the same time.

In the food industry, chemicals are routinely used to clean and disinfect product contact surfaces as well as the outer surface of the food itself. These chemicals provide a necessary and required step to ensure that the foods produced and consumed are as free as possible from microorganisms that can cause foodborne illness.

Food activists are concerned that some of the chemicals used by the food industry for disinfection can cause health issues for consumers. A prime example is the current discussion in Europe about ‘American chlorine chicken’. …

Berger goes on to highlight the research being conducted at the Harvard T. Chan School of Public Health (Harvard University). The team announced a new technique called Engineered Water Nanostructures (EWNS), which is generated by electrospraying water. The team published this paper in 2014,

A chemical free, nanotechnology-based method for airborne bacterial inactivation using engineered water nanostructures by Georgios Pyrgiotakis, James McDevitt, Andre Bordini, Edgar Diaz, Ramon Molina, Christa Watson, Glen Deloid, Steve Lenard, Natalie Fix, Yosuke Mizuyama, Toshiyuki Yamauchi, Joseph Brain and Philip Demokritou. Environ. Sci.: Nano, 2014,1, 15-26 DOI: 10.1039/C3EN00007A

First published online 28 Nov 2013

This paper is open access.

More recently, the team has proved the efficacy of this technique on stainless steel surfaces and tomatoes. A Feb. 25, 2015 Harvard T. Chan School of Public Health news release provides information about the costs of foodborne diseases and goes on to describe the technique and the latest experiments,

The burden of foodborne diseases worldwide is huge, with serious economic and public health consequences. The U.S. Department of Agriculture’s (USDA’s) Economic Research Service reported in 2014 that foodborne illnesses are costing the economy more than $15.6 billion and about 53,245 Americans visit the hospital annually due to foodborne illnesses. The food industry is in search of effective intervention methods that can be applied form “farm to fork” to ensure the safety of the food chain and be consumer and environment friendly at the same time.

Researchers at the Center for Nanotechnology and Nanotoxicology of the Harvard T. Chan School of Public Health are currently exploring the effectiveness of a nanotechnology based, chemical free, intervention method for the inactivation of foodborne and spoilage microorganisms on fresh produce and on food production surfaces. This method utilizes Engineered Water Nanostructures (EWNS) generated by electrospraying of water. EWNS possess unique properties; they are 25 nm in diameter, remain airborne in indoor conditions for hours, contain Reactive Oxygen Species (ROS), have very strong surface charge (on average 10e/structure) and have the ability to interact and inactivate pathogens by destroying their membrane.

In a study funded by the USDA and just published this week in the premier Environmental Science and Technology journal, the efficacy of these tiny water nanodroplets, in inactivating representative foodborne pathogens such as Escherichia coli, Salmonella enterica and Listeria innocua, on stainless steel surfaces and on tomatoes, was assessed showing significant log reductions in inactivation of select food pathogens. These promising results could open up the gateway for further exploration into the dynamics of this method in the battle against foodborne disease. More importantly this novel, chemical-free, cost effective and environmentally friendly intervention method holds great potential for development and application in the food industry, as a ‘green’ alternative to existing inactivation methods.

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

Inactivation of Foodborne Microorganisms Using Engineered Water Nanostructures (EWNS) by Georgios Pyrgiotakis, Archana Vasanthakumar, Ya Gao, Mary Eleftheriadou, Eduardo Toledo, Alice DeAraujo, James McDevitt, Taewon Han, Gediminas Mainelis, Ralph Mitchell, and Philip Demokritou. Environ. Sci. Technol., Article ASAP DOI: 10.1021/es505868a Publication Date (Web): February 19, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall. The researchers have made this image illustrating a ‘water shell’s’ effect on a bacterium located on a tomato,

Courtesy: Researchers and the American Chemical Society

Courtesy: Researchers and the American Chemical Society

I’m not sure how chemical companies are going to feel but this is very exciting news. Still, one has to wonder just how much water this technique would require for full scale adoption and would it be reusable?