Tag Archives: silver nanoparticles

Nanocellulose sensors: 3D printed and biocompatible

I do like to keep up with nanocellulose doings, especially when there’s some Canadian involvement, and an October 8, 2019 news item on Nanowerk alerted me to a newish application for the product,

Physiological parameters in our blood can be determined without painful punctures. Empa researchers are currently working with a Canadian team to develop flexible, biocompatible nanocellulose sensors that can be attached to the skin. The 3D-printed analytic chips made of renewable raw materials will even be biodegradable in future.

The idea of measuring parameters that are relevant for our health via the skin has already taken hold in medical diagnostics. Diabetics, for example, can painlessly determine their blood sugar level with a sensor instead of having to prick their fingers.

An October 8, 2019 Empa (Swiss Federal Laboratories for Materials Science and Technology) press release, which originated the news item, provides more detail,

A transparent foil made of wood

Nanocellulose is an inexpensive, renewable raw material, which can be obtained in form of crystals and fibers, for example from wood. However, the original appearance of a tree no longer has anything to do with the gelatinous substance, which can consist of cellulose nanocrystals and cellulose nanofibers. Other sources of the material are bacteria, algae or residues from agricultural production. Thus, nanocellulose is not only relatively easy and sustainable to obtain. Its mechanical properties also make the “super pudding” an interesting product. For instance, new composite materials based on nanocellulose can be developed that could be used as surface coatings, transparent packaging films or even to produce everyday objects like beverage bottles.

Researchers at Empa’s Cellulose & Wood Materials lab and Woo Soo Kim from the Simon Fraser University [SFU] in Burnaby, Canada, are also focusing on another feature of nanocellulose: biocompatibility. Since the material is obtained from natural resources, it is particularly suitable for biomedical research.

With the aim of producing biocompatible sensors that can measure important metabolic values, the researchers used nanocellulose as an “ink” in 3D printing processes. To make the sensors electrically conductive, the ink was mixed with silver nanowires. The researchers determined the exact ratio of nanocellulose and silver threads so that a three-dimensional network could form.

Just like spaghetti – only a wee bit smaller

It turned out that cellulose nanofibers are better suited than cellulose nanocrystals to produce a cross-linked matrix with the tiny silver wires. “Cellulose nanofibers are flexible similar to cooked spaghetti, but with a diameter of only about 20 nanometers and a length of just a few micrometers,” explains Empa researcher Gilberto Siqueira.

The team finally succeeded in developing sensors that measure medically relevant metabolic parameters such as the concentration of calcium, potassium and ammonium ions. The electrochemical skin sensor sends its results wirelessly to a computer for further data processing. The tiny biochemistry lab on the skin is only half a millimeter thin.

While the tiny biochemistry lab on the skin – which is only half a millimeter thin – is capable of determining ion concentrations specifically and reliably, the researchers are already working on an updated version. “In the future, we want to replace the silver [nano] particles with another conductive material, for example on the basis of carbon compounds,” Siqueira explains. This would make the medical nanocellulose sensor not only biocompatible, but also completely biodegradable.

I like the images from Empa better than the ones from SFU,

Using a 3D printer, the nanocellulose “ink” is applied to a carrier plate. Silver particles provide the electrical conductivity of the material. Image: Empa
Empa researcher Gilberto Siqueira demonstrates the newly printed nanocellulose circuit. After a subsequent drying, the material can be further processed. Image: Empa

SFU produced a news release about this work back in February 2019. Again, I prefer what the Swiss have done because they’re explaining/communicating the science, as well as , communicating benefits. From a February 13, 2019 SFU news release (Note: Links have been removed),

Simon Fraser University and Swiss researchers are developing an eco-friendly, 3D printable solution for producing wireless Internet-of-Things (IoT) sensors that can be used and disposed of without contaminating the environment. Their research has been published as the cover story in the February issue of the journal Advanced Electronic Materials.

SFU professor Woo Soo Kim is leading the research team’s discovery, which uses a wood-derived cellulose material to replace the plastics and polymeric materials currently used in electronics.

Additionally, 3D printing can give flexibility to add or embed functions onto 3D shapes or textiles, creating greater functionality.

“Our eco-friendly, 3D-printed cellulose sensors can wirelessly transmit data during their life, and then can be disposed without concern of environmental contamination,” says Kim, a professor in the School of Mechatronic Systems Engineering. The SFU research is being carried out at PowerTech Labs in Surrey, which houses several state-of-the-art 3D printers used to advance the research.

“This development will help to advance green electronics. For example, the waste from printed circuit boards is a hazardous source of contamination to the environment. If we are able to change the plastics in PCB to cellulose composite materials, recycling of metal components on the board could be collected in a much easier way.”

Kim’s research program spans two international collaborative projects, including the latest focusing on the eco-friendly cellulose material-based chemical sensors with collaborators from the Swiss Federal Laboratories for Materials Science.

He is also collaborating with a team of South Korean researchers from the Daegu Gyeongbuk Institute of Science and Technology’s (DGIST)’s department of Robotics Engineering, and PROTEM Co Inc, a technology-based company, for the development of printable conductive ink materials.

In this second project, researchers have developed a new breakthrough in the embossing process technology, one that can freely imprint fine circuit patterns on flexible polymer substrate, a necessary component of electronic products.

Embossing technology is applied for the mass imprinting of precise patterns at a low unit cost. However, Kim says it can only imprint circuit patterns that are imprinted beforehand on the pattern stamp, and the entire, costly stamp must be changed to put in different patterns.

The team succeeded in developing a precise location control system that can imprint patterns directly resulting in a new process technology. The result will have widespread implications for use in semiconductor processes, wearable devices and the display industry.

This paper was made available online back in December 2018 and then published in print in February 2019. As to why there’d be such large gaps between the paper’s publication dates and the two institution’s news/press releases, it’s a mystery to me. In any event, here’s a link to and a citation for the paper,

3D Printed Disposable Wireless Ion Sensors with Biocompatible Cellulose Composites by Taeil Kim, Chao Bao, Michael Hausmann, Gilberto Siqueira, Tanja Zimmermann, Woo Soo Kim. Advanced Electronic Materials DOI: https://doi.org/10.1002/aelm.201970007 First published online December 19, 2018. First published in print: 08 February 2019 (Adv. Electron. Mater. 2/2109) Volume 5, Issue 2 February 2019 1970007

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.

Observing individual silver nanoparticles in real time

A new technique for better understanding how silver nanoparticles might affect the environment was announced in a July 30, 2018 news item on ScienceDaily,

Chemists at Ruhr-Universität Bochum have developed a new method of observing the chemical reactions of individual silver nanoparticles, which only measure a thousandth of the thickness of a human hair, in real time. The particles are used in medicine, food and sports items because they have an antibacterial and anti-inflammatory effect. However, how they react and degrade in ecological and biological systems is so far barely understood. The team in the Research Group for Electrochemistry and Nanoscale Materials showed that the nanoparticles transform into poorly soluble silver chloride particles under certain conditions. The group led by Prof Dr Kristina Tschulik reports on the results in the Journal of the American Chemical Society from July 11, 2018.

A July 30,2018 Ruhr-University Bochum (RUB) press release (also on EurekAlert) by Julia Weiler, which originated the news item, provides more information,

Even under well-defined laboratory conditions, current research has yielded different, sometimes contradictory, results on the reaction of silver nanoparticles. “In every batch of nanoparticles, the individual properties of the particles, such as size and shape, vary,” says Kristina Tschulik, a member of the Cluster of Excellence Ruhr Explores Solvation. “With previous procedures, a myriad of particles was generally investigated at the same time, meaning that the effects of these variations could not be recorded. Or the measurements took place in a high vacuum, not under natural conditions in an aqueous solution.”

The team led by Kristina Tschulik thus developed a method that enables individual silver particles to be investigated in a natural environment. “Our aim is to be able to record the reactivity of individual particles,” explains the researcher. This requires a combination of electrochemical and spectroscopic methods. With optical and hyperspectral dark-field microscopy, the group was able to observe individual nanoparticles as visible and coloured pixels. Using the change in the colour of the pixels, or more precisely their spectral information, the researchers were able to follow what was happening in an electrochemical experiment in real time.

Degradation of the particles slowed down

In the experiment, the team replicated the oxidation of silver in the presence of chloride ions, which often takes place in ecological and biological systems. “Until now, it was generally assumed that the silver particles dissolve in the form of silver ions,” describes Kristina Tschulik. However, poorly soluble silver chloride was formed in the experiment – even if only a few chloride ions were present in the solution.

“This extends the lifespan of the nanoparticles to an extreme extent and their breakdown is slowed down in an unexpectedly drastic manner,” summarises Tschulik. “This is equally important for bodies of water and for living beings because this mechanism could cause the heavy metal silver to accumulate locally, which can be toxic for many organisms.”

Further development planned

The Bochum-based group now wants to further improve its technology for analysing individual nanoparticles in order to better understand the ageing mechanisms of such particles. The researchers thus want to obtain more information about the biocompatibility of the silver particles and the lifespan and ageing of catalytically active nanoparticles in the future.

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

Simultaneous Opto- and Spectro-Electrochemistry: Reactions of Individual Nanoparticles Uncovered by Dark-Field Microscopy by Kevin Wonner, Mathies V. Evers, and Kristina Tschulik. J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.8b02367 Publication Date (Web): July 11, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Algae outbreaks (dead zones) in wetlands and waterways

It’s been over seven years since I first started writing about Duke University’s  Center for the Environmental Implications of Nanotechnology and mesocosms (miniature ecosystems) and the impact that nanoparticles may have on plants and water (see August 11, 2011 posting). Since then, their focus has shifted from silver nanoparticles and their impact on plants, fish, bacteria, etc. to a more general examination of metallic nanoparticles and water. A June 25, 2018 news item on ScienceDaily announces some of their latest work,

The last 10 years have seen a surge in the use of tiny substances called nanomaterials in agrochemicals like pesticides and fungicides. The idea is to provide more disease protection and better yields for crops, while decreasing the amount of toxins sprayed on agricultural fields.

But when combined with nutrient runoff from fertilized cropland and manure-filled pastures, these “nanopesticides” could also mean more toxic algae outbreaks for nearby streams, lakes and wetlands, a new study finds.

A June 25, 2018 Duke University news release (also on EurekAlert) by Robin A. Smith, which originated the news item, provides more detail,

Too small to see with all but the most powerful microscopes, engineered nanomaterials are substances manufactured to be less than 100 nanometers in diameter, many times smaller than a hair’s breadth.

Their nano-scale gives them different chemical and physical properties from their bulk counterparts, including more surface area for reactions and interactions.

Those interactions could intensify harmful algal blooms in wetlands, according to experiments led by Marie Simonin, a postdoctoral associate with biology professor Emily Bernhardt at Duke University.

Carbon nanotubes and teeny tiny particles of silver, titanium dioxide and other metals are already added to hundreds of commercial products to make everything from faster, lighter electronics, self-cleaning fabrics, and smarter food packaging that can monitor food for spoilage. They are also used on farms for slow- or controlled-release plant fertilizers and pesticides and more targeted delivery, and because they are effective at lower doses than conventional products.

These and other applications have generated tremendous interest and investment in nanomaterials. However the potential risks to human health or the environment aren’t fully understood, Simonin said.

Most of the 260,000 to 309,000 metric tons of nanomaterials produced worldwide each year are eventually disposed in landfills, according to a previous study. But of the remainder, up to 80,400 metric tons per year are released into soils, and up to 29,200 metric tons end up in natural bodies of water.

“And these emerging contaminants don’t end up in water bodies alone,” Simonin said. “They probably co-occur with nutrient runoff. There are likely multiple stressors interacting.”

Algae outbreaks already plague polluted waters worldwide, said Steven Anderson, a research analyst in the Bernhardt Lab at Duke and one of the authors of the research.

Nitrogen and phosphorous pollution makes its way into wetlands and waterways in the form of agricultural runoff and untreated wastewater. The excessive nutrients cause algae to grow out of control, creating a thick mat of green scum or slime on the surface of the water that blocks sunlight from reaching other plants.

These nutrient-fueled “blooms” eventually reduce oxygen levels to the point where fish and other organisms can’t survive, creating dead zones in the water. Some algal blooms also release toxins that can make pets and people who swallow them sick.

To find out how the combined effects of nutrient runoff and nanoparticle contamination would affect this process, called eutrophication, the researchers set up 18 separate 250-liter tanks with sandy sloped bottoms to mimic small wetlands.

Each open-air tank was filled with water, soil and a variety of wetland plants and animals such as waterweed and mosquitofish.

Over the course of the nine-month experiment, some tanks got a weekly dose of algae-promoting nitrates and phosphates like those found in fertilizers, some tanks got nanoparticles — either copper or gold — and some tanks got both.

Along the way the researchers monitored water chemistry, plant and algae growth and metabolism, and nanoparticle accumulation in plant tissues.

“The results were surprising,” Simonin said. The nanoparticles had tiny effects individually, but when added together with nutrients, even low concentrations of gold and copper nanoparticles used in fungicides and other products turned the once-clear water a murky pea soup color, its surface covered with bright green smelly mats of floating algae.

Over the course of the experiment, big algal blooms were more than three times more frequent and more persistent in tanks where nanoparticles and nutrients were added together than where nutrients were added alone. The algae overgrowths also reduced dissolved oxygen in the water.

It’s not clear yet how nanoparticle exposure shifts the delicate balance between plants and algae as they compete for nutrients and other resources. But the results suggest that nanoparticles and other “metal-based synthetic chemicals may be playing an under-appreciated role in the global trends of increasing eutrophication,” the researchers said.

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

Engineered nanoparticles interact with nutrients to intensify eutrophication in a wetland ecosystem experiment by Marie Simonin, Benjamin P. Colman, Steven M. Anderson, Ryan S. King, Matthew T. Ruis, Astrid Avellan, Christina M. Bergemann, Brittany G. Perrotta, Nicholas K. Geitner, Mengchi Ho, Belen de la Barrera, Jason M. Unrine, Gregory V. Lowry, Curtis J. Richardson, Mark R. Wiesner, Emily S. Bernhardt. Ecological Applications, 2018; DOI: 10.1002/eap.1742 First published: 25 June 2018

This paper is behind a paywall.

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.

“Living” bandages made from biocompatible anti-burn nanofibers

A February 16, 2018 news item on Nanowerk announces research from a Russian team about their work on “living” bandages,

In regenerative medicine, and particularly in burn therapy, the effective regeneration of damaged skin tissue and the prevention of scarring are usually the main goals. Scars form when skin is badly damaged, whether through a cut, burn, or a skin problem such as acne or fungal infection.

Scar tissue mainly consists of irreversible collagen and significantly differs from the tissue it replaces, having reduced functional properties. For example, scars on skin are more sensitive to ultraviolet radiation, are not elastic, and the sweat glands and hair follicles are not restored in the area.

The solution of this medical problem was proposed by the researchers from the NUST MISIS [National University of Science and Technology {formerly Moscow Institute of Steel and Alloys State Technological University})] Inorganic Nanomaterials Laboratory, led by PhD Anton Manakhov, a senior researcher. The team of nanotechnology scientists has managed to create multi-layer ‘bandages’ made of biodegradable fibers and multifunctional bioactive nanofilms, which [the bandages] prevent scarring and accelerate tissue regeneration.

A February 14, 2018 NUST MISIS press release, which originated the news item, provides more detail,

The addition of the antibacterial effect by the introduction of silver nanoparticles or joining antibiotics, as well as the increase of biological activity to the surface of hydrophilic groups (-COOH) and the blood plasma proteins have provided unique healing properties to the material.

A significant acceleration of the healing process, the successful regeneration of normal skin covering tissue, and the prevention of scarring on the site of burnt or damaged skin have been observed when applying these bandages made of the developed material to an injured area. The antibacterial components of multifunctional nanofibers decrease inflammation, and the blood plasma with an increased platelet level — vital and multi-purposed for every element in the healing process — stimulates the regeneration of tissues. The bandages should not be removed or changed during treatment as it may cause additional pain to the patient. After a certain period of time, the biodegradable fiber simply “dissolves” without any side effects.

“With the help of chemical bonds, we were able to create a stable layer containing blood plasma components (growth factors, fibrinogens, and other important proteins that promote cell growth) on a polycaprolactone base. The base fibers were synthesized by electroforming. Then, with the help of plasma treatment, to increase the material`s hydrophilic properties, a polymer layer containing carboxyl groups was applied to the surface. The resulting layer was enriched with antibacterial and protein components”, noted Elizabeth Permyakova, one of the project members and laboratory scientists.

The researchers have made images of their work available including this one,

Courtesy NUST MISS [downloaded from http://en.misis.ru/university/news/science/2018-02/5219/]

There is doesn’t appear to be an accompanying published paper.

Taking spectroscopy to a new dimension with silver nanoparticles

This latest move towards better detection at the nanoscale comes from India (from a January 2, 2018 news item on ScienceDaily),

As medicine and pharmacology investigate nanoscale processes, it has become increasingly important to identify and characterize different molecules. Raman spectroscopy, a technique that leverages the scattering of laser light to identify molecules, has a limited capacity to detect molecules in diluted samples because of low signal yield.

A team of researchers from the University of Hyderabad in India has improved molecular detection at low concentration levels by arranging nanoparticles on nanowires to enhance Raman spectroscopy. Surface-enhanced Raman spectroscopy (SERS) uses electromagnetic fields to improve Raman scattering and boost sensitivity in standard dyes such as R6G by more than one billionfold.

Here’s an image illustrating the work,

Caption: Detection of a low concentration analyte molecule using silicon nanowires decorated with silver nanoparticles and surface enhanced Raman scattering measurements. Credit: V.S. Vendamani

A January 2, 2017 American Institute of Physics press release on EurekAlert, which originated the news item, explains further,

The team decorated vertically aligned silicon nanowires with varying densities of silver nanoparticles, utilizing and enhancing the structure’s 3-D shape. Their results, published in the Journal of Applied Physics, from AIP [American Institute of Physics] Publishing, show that their device was able to enhance the Raman signals for cytosine protein and ammonium perchlorate by a factor of 100,000.

“The beauty is that we can improve the density of these nanowires using simple chemistry,” said Soma Venugopal Rao, one of the paper’s authors. “If you have a large density of nanowires, you can put more silver nanoparticles into the substrate and can increase the sensitivity of the substrate.”

Applying the necessary nanostructures to SERS devices remains a challenge for the field. Building these structures in three dimensions with silicon nanowires has garnered attention for their higher surface area and superior performance, but silicon nanowires are still expensive to produce.

Instead, the team was able to find a cheaper way to make silicon nanowires and used a technique called electroless etching to make a wide range of nanowires. They “decorated” these wires with silver nanoparticles with variable and controlled densities, which increased the nanowires’ surface area.

“Optimizing these vertically aligned structures took a lot of time in the beginning,” said Nageswara Rao, another of the paper’s authors. “We increased the surface area and to do this we needed to change the aspect ratio.”

After optimizing their system to detect Rhodamine dye on a nanomolar level, these new substrates the team built enhanced Raman sensitivity by a factor of 10,000 to 100,000. The substrates detected concentrations of cytosine, a nucleotide found in DNA, and ammonium perchlorate, a molecule with potential for detecting explosives, in as dilute concentrations as 50 and 10 micromolar, respectively.

The results have given the team reason to believe that it might soon be possible to detect compounds in concentrations on the scale of nanomolar or even picomolar, Nageswara Rao said. The team’s work has opened several avenues for future research, from experimenting with different nanoparticles such as gold, increasing the sharpness of the nanowires or testing these devices across several types of molecules.

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

Three-dimensional hybrid silicon nanostructures for surface enhanced Raman spectroscopy based molecular detection featured by V. S. Vendamani, S. V. S. Nageswara Rao, S. Venugopal Rao, D. Kanjilal, and A. P. Pathak. Journal of Applied Physics 123, 014301 (2018); Published Online: January 2018 https://doi.org/10.1063/1.5000994

This paper is open access.

Light-based computation made better with silver

It’s pretty amazing to imagine a future where computers run on light but according to a May 16, 2017 news item on ScienceDaily the idea is not beyond the realms of possibility,

Tomorrow’s computers will run on light, and gold nanoparticle chains show much promise as light conductors. Now Ludwig-Maximilians-Universitaet (LMU) in Munich scientists have demonstrated how tiny spots of silver could markedly reduce energy consumption in light-based computation.

Today’s computers are faster and smaller than ever before. The latest generation of transistors will have structural features with dimensions of only 10 nanometers. If computers are to become even faster and at the same time more energy efficient at these minuscule scales, they will probably need to process information using light particles instead of electrons. This is referred to as “optical computing.”

The silver serves as a kind of intermediary between the gold particles while not dissipating energy. Capture: Liedl/Hohmann (NIM)

A March 15, 2017 LMU press release (also one EurekAlert), which originated the news item, describes a current use of light in telecommunications technology and this latest research breakthrough (the discrepancy in dates is likely due to when the paper was made available online versus in print),

Fiber-optic networks already use light to transport data over long distances at high speed and with minimum loss. The diameters of the thinnest cables, however, are in the micrometer range, as the light waves — with a wavelength of around one micrometer — must be able to oscillate unhindered. In order to process data on a micro- or even nanochip, an entirely new system is therefore required.

One possibility would be to conduct light signals via so-called plasmon oscillations. This involves a light particle (photon) exciting the electron cloud of a gold nanoparticle so that it starts oscillating. These waves then travel along a chain of nanoparticles at approximately 10% of the speed of light. This approach achieves two goals: nanometer-scale dimensions and enormous speed. What remains, however, is the energy consumption. In a chain composed purely of gold, this would be almost as high as in conventional transistors, due to the considerable heat development in the gold particles.

A tiny spot of silver

Tim Liedl, Professor of Physics at LMU and PI at the cluster of excellence Nanosystems Initiative Munich (NIM), together with colleagues from Ohio University, has now published an article in the journal Nature Physics, which describes how silver nanoparticles can significantly reduce the energy consumption. The physicists built a sort of miniature test track with a length of around 100 nanometers, composed of three nanoparticles: one gold nanoparticle at each end, with a silver nanoparticle right in the middle.

The silver serves as a kind of intermediary between the gold particles while not dissipating energy. To make the silver particle’s plasmon oscillate, more excitation energy is required than for gold. Therefore, the energy just flows “around” the silver particle. “Transport is mediated via the coupling of the electromagnetic fields around the so-called hot spots which are created between each of the two gold particles and the silver particle,” explains Tim Liedl. “This allows the energy to be transported with almost no loss, and on a femtosecond time scale.”

Textbook quantum model

The decisive precondition for the experiments was the fact that Tim Liedl and his colleagues are experts in the exquisitely exact placement of nanostructures. This is done by the DNA origami method, which allows different crystalline nanoparticles to be placed at precisely defined nanodistances from each other. Similar experiments had previously been conducted using conventional lithography techniques. However, these do not provide the required spatial precision, in particular where different types of metals are involved.

In parallel, the physicists simulated the experimental set-up on the computer – and had their results confirmed. In addition to classical electrodynamic simulations, Alexander Govorov, Professor of Physics at Ohio University, Athens, USA, was able to establish a simple quantum-mechanical model: “In this model, the classical and the quantum-mechanical pictures match very well, which makes it a potential example for the textbooks.”

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

Hotspot-mediated non-dissipative and ultrafast plasmon passage by Eva-Maria Roller, Lucas V. Besteiro, Claudia Pupp, Larousse Khosravi Khorashad, Alexander O. Govorov, & Tim Liedl. Nature Physics (2017) doi:10.1038/nphys4120 Published online 15 May 2017

This paper is behind a paywall.

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.

Plasmonic ‘Goldfinger’: antifungal nail polish with metallic nanoparticles

A March 29,.2017 news item on Nanowerk announces a new kind of nanopolish,

Since ancient times, people have used lustrous silver, platinum and gold to make jewelry and other adornments. Researchers have now developed a new way to add the metals to nail polish with minimal additives, resulting in durable, tinted — and potentially antibacterial — nail coloring.

Using metal nanoparticles in clear nail polish makes it durable and colorful without extra additives.
Credit: American Chemical Society

A March 29, 2017 American Chemical Society (ACS) news release (also on EurekAlert), which originated the news item, adds a little more detail (Note: A link has been removed),

Nail polish comes in a bewildering array of colors. Current coloring techniques commonly incorporate pigment powders and additives. Scientists have recently started exploring the use of nanoparticles in polishes and have found that they can improve their durability and, in the case of silver nanoparticles, can treat fungal toenail infections. Marcus Lau, Friedrich Waag and Stephan Barcikowski wanted to see if they could come up with a simple way to integrate metal nanoparticles in nail polish.

The researchers started with store-bought bottles of clear, colorless nail polish and added small pieces of silver, gold, platinum or an alloy to them. To break the metals into nanoparticles, they shone a laser on them in short bursts over 15 minutes. Analysis showed that the method resulted in a variety of colored, transparent polishes with a metallic sheen. The researchers also used laser ablation to produce a master batch of metal nanoparticles in ethyl acetate, a polish thinner, which could then be added to individual bottles of polish. This could help boost the amount of production for commercialization. The researchers say the technique could also be used to create coatings for medical devices.

The authors acknowledge funding from the INTERREG-Program Germany-Netherlands.

A transparent nail varnish can be colored simply and directly with laser-generated nanoparticles. This does not only enable coloring of the varnish for cosmetic purposes, but also gives direct access to nanodoped varnishes to be used on any solid surface. Therefore, nanoparticle properties such as plasmonic properties or antibacterial effects can be easily adapted to surfaces for medical or optical purposes. The presented method for integration of metal (gold, platinum, silver, and alloy) nanoparticles into varnishes is straightforward and gives access to nanodoped polishes with optical properties, difficult to be achieved by dispersing powder pigments in the high-viscosity liquids. Courtesy: Industrial and Engineering & Chemistry Research

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

Direct Integration of Laser-Generated Nanoparticles into Transparent Nail Polish: The Plasmonic “Goldfinger” by Marcus Lau, Friedrich Waag, and Stephan Barcikowski. Ind. Eng. Chem. Res., 2017, 56 (12), pp 3291–3296 DOI: 10.1021/acs.iecr.7b00039 Publication Date (Web): March 7, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.