Tag Archives: surfactants

Soap and water for creating 2D nanoflakes (hexagonal boron nitride [hBN] sheets)

Rice University (Texas, US) has a pretty image illustrating the process of making 2D nanoflakes,

Caption: The image displays the exfoliation of hexagonal boron nitride into atomically thin nanosheets aided by surfactants, a process refined by chemists at Rice University. Credit: Ella Maru Studio

A January 27, 2021 news item on Nanowerk announces the Rice University news,

Just a little soap helps clean up the challenging process of preparing two-dimensional hexagonal boron nitride (hBN).

Rice University chemists have found a way to get the maximum amount [number] of quality 2D hBN nanosheets from its natural bulk form by processing it with surfactant (aka soap) and water. The surfactant surrounds and stabilizes the microscopic flakes, preserving their properties.

Experiments by the lab of Rice chemist Angel Martí identified the “sweet spot” for making stable dispersions of hBN, which can be processed into very thin antibacterial films that handle temperatures up to 900 degrees Celsius (1,652 degrees Fahrenheit).

A brief grammatical moment: I can see where someone might view it as arguable (see second paragraph of the above excerpt) but for me ‘amount’ is for something like ‘flour’ for an ‘amount of flour’. ‘Number’ is for something like a ‘number of sheets’. The difference lies in your ability to count the items. Generally speaking, you can’t count the number of flour, therefore, it’s the amount of flour, but you can count the number of sheets. Can count these hexagonal boron nitride (hBN) sheets? If not, is what makes this arguable.

A January 27, 2021 Rice University news release (also on EurekAlert), which originated the news item, delves into details,

The work led by Martí, alumna Ashleigh Smith McWilliams and graduate student Cecilia Martínez-Jiménez is detailed in the American Chemical Society journal ACS Applied Nano Materials.

“Boron nitride materials are interesting, particularly because they are extremely resistant to heat,” Martí said. “They are as light as graphene and carbon nanotubes, but you can put hBN in a flame and nothing happens to it.”

He said bulk hBN is cheap and easy to obtain, but processing it into microscopic building blocks has been a challenge. “The first step is to be able to exfoliate and disperse them, but research on how to do that has been scattered,” Martí said. “When we decided to set a benchmark, we found the processes that have been extremely useful for graphene and nanotubes don’t work as well for boron nitride.”

Sonicating bulk hBN in water successfully exfoliated the material and made it soluble. “That surprised us, because nanotubes or graphene just float on top,” Martí said. “The hBN dispersed throughout, though they weren’t particularly stable.

“It turned out the borders of boron nitride crystals are made of amine and nitric oxide groups and boric acid, and all of these groups are polar (with positive or negative charge),” he said. “So when you exfoliate them, the edges are full of these functional groups that really like water. That never happens with graphene.”

Experiments with nine surfactants helped them find just the right type and amount to keep 2D hBN from clumping without cutting individual flakes too much during sonication. The researchers used 1% by weight of each surfactant in water, added 20 milligrams of bulk hBN, then stirred and sonicated the mix.

Spinning the resulting solutions at low and high rates showed the greatest yield came with the surfactant known as PF88 under 100-gravity centrifugation, but the highest-quality nanosheets came from all the ionic surfactants under 8,000 g centrifugation, with the greatest stability from common ionic surfactants SDS and CTAC.

DTAB — short for dodecyltrimethylammonium bromide — under high centrifugation proved best at balancing the yield and quality of 2D hBN. The researchers also produced a transparent film from hBN nanosheets dispersed in SDS and water to demonstrate how they can be processed into useful products.

“We describe the steps you need to do to produce high-quality hBN flakes,” Martí said. “All of the steps are important, and we were able to bring to light the consequences of each one.”

Understanding the Exfoliation and Dispersion of Hexagonal Boron Nitride Nanosheets by Surfactants: Implications for Antibacterial and Thermally Resistant Coatings by Ashleigh D. Smith McWilliams, Cecilia Martínez-Jiménez, Asia Matatyaho Ya’akobi, Cedric J. Ginestra, Yeshayahu Talmon, Matteo Pasquali, and Angel A. Martí. ACS Appl. Nano Mater. 2021, 4, 1, 142–151 DOI: https://doi.org/10.1021/acsanm.0c02437 Publication Date: January 7, 2021 Copyright © 2021 American Chemical Society

This paper is behind a paywall.

Reliable findings on the presence of synthetic (engineered) nanoparticles in bodies of water

An Aug. 29, 2016 news item on Nanowerk announces research into determining the presence of engineered (synthetic) nanoparticles in bodies of water,

For a number of years now, an increasing number of synthetic nanoparticles have been manufactured and incorporated into various products, such as cosmetics. For the first time, a research project at the Technical University of Munich and the Bavarian Ministry of the Environment provides reliable findings on their presence in water bodies.

An Aug. 29, 2016 Technical University of Munich (TUM) press release, which originated the news item, provides more information,

Nanoparticles can improve the properties of materials and products. That is the reason why an increasing number of nanoparticles have been manufactured over the past several years. The worldwide consumption of silver nanoparticles is currently estimated at over 300 metric tons. These nanoparticles have the positive effect of killing bacteria and viruses. Products that are coated with these particles include refrigerators and surgical instruments. Silver nanoparticles can even be found in sportswear. This is because the silver particles can prevent the smell of sweat by killing the bacteria that cause it.

Previously, it was unknown whether and in what concentration these nanoparticles enter the environment and e.g. enter bodies of water. If they do, this poses a problem. That is because the silver nanoparticles are toxic to numerous aquatic organisms, and can upset sensitive ecological balances.

Analytical challenge

In the past, however, nanoparticles have not been easy to detect. That is because they measure only 1 to 100 nanometers across [nanoparticles may be larger than 100nm or smaller than 1nm but the official definitions usually specify up to 100nm although some definitions go up to 1000nm] – a nanometer is a millionth of a millimeter. “In order to know if a toxicological hazard exists, we need to know how many of these particles enter the environment, and in particular bodies of water”, explains Michael Schuster, Professor for Analytical Chemistry at the TU Munich.

This was an analytical challenge for the researchers charged with solving the problem on behalf of the Bavarian Ministry of the Environment. In order to overcome this issue, they used a well-known principle that utilizes the effect of surfactants to separate and concentrate the particles. “Surfactants are also found in washing and cleaning detergents”, explains Schuster. “Basically, what they do is envelop grease and dirt particles in what are called micelles, making it possible for them to float in water.” One side of the surfactant is water-soluble, the other fat-soluble. The fat-soluble ends collect around non-polar, non-water soluble compounds such as grease or around particles, and “trap” them in a micelle. The water-soluble, polar ends of the surfactants, on the other hand, point towards the water molecules, allowing the microscopically small micelle to float in water.

A box of sugar cubes in the Walchensee lake

The researchers applied this principle to the nanoparticles. “When the micelles surrounding the particles are warmed slightly, they start to clump”, explains Schuster. This turns the water cloudy. Using a centrifuge, the surfactants and the nanoparticles trapped in them can then be separated from the water. This procedure is called cloud point extraction. The researchers then use the surfactants that have been separated out in this manner – which contain the particles in an unmodified, but highly concentrated form – to measure how many silver nanoparticles are present. To do this, they use a highly sensitive atomic spectrometer configured to only detect silver. In this manner, concentrations in a range of less than one nanogram per liter can be detected. To put this in perspective, this would be like detecting a box of sugar cubes that had dissolved in the Walchensee lake.

With the help of this analysis procedure, it is possible to gain new insight into the concentration of nanoparticles in drinking and waste water, sewage sludge, rivers, and lakes. In Bavaria, the measurements yielded good news: The concentrations measured in the water bodies were extremely low. In was only in four of the 13 Upper Bavarian lakes examined that the concentration even exceeded the minimum detection limit of 0.2 nanograms per liter. No measured value exceeded 1.3 nanograms per liter. So far, no permissible values have been established for silver nanoparticles.

Representative for watercourses, the Isar river was examined from its source to its mouth at around 30 locations. The concentration of silver nanoparticles was also measured in the inflow and outflow of sewage treatment plants. The findings showed that at least 94 percent of silver nanoparticles are filtered out by the sewage treatment plants.

Unfortunately, the researchers have not published their results.

Injectable medicine made safer?

The lede for this May 19, 2016 news item on Nanowerk is great,

Bring the drugs, hold the suds.

The May 19, 2016 University of Buffalo news release (also on EurekAlert) by Cory Nealon, which originated the news item, quickly gets to the point,

That summarizes a promising new drug-making technique designed to reduce serious allergic reactions and other side effects from anti-cancer medicine, testosterone and other drugs that are administered with a needle.

Developed by University at Buffalo researchers, the breakthrough removes potentially harmful additives – primarily soapy substances known as surfactants – from common injectable drugs.

“We’re excited because this process can be scaled up, which could make existing injectable drugs safer and more effective for millions of people suffering from serious diseases and ailments,” says Jonathan F. Lovell, a biomedical engineer at UB and the study’s corresponding author.

Pharmaceutical companies use surfactants to dissolve medicine into a liquid solution, a process that makes medicine suitable for injection. While effective, the process is seldom efficient. Solutions loaded with surfactant and other nonessential ingredients can carry the risk of causing anaphylactic shock, blood clotting, hemolysis and other side effects.

Researchers have tried to address this problem in two ways, each with varying degrees of success.

Some have taken the so-called “top down” approach, in which they shrink drug particles to nanoscale sizes to eliminate excess additives. While promising, the method doesn’t work well in injectable medicine because the drug particles are still too large to safely inject.

Other researchers work from the “bottom up” using nanotechnology to build new drugs from scratch. This may yield tremendous results; however, developing new drug formulations takes years, and drugs are coupled with new additives that create new side effects.

The technique under development at UB differs because it improves existing injectable drug-making methods by taking the unusual step of stripping away all of the excess surfactant.

In laboratory experiments, researchers dissolved 12 drugs – cabazitaxel (anti-cancer), testosterone, cyclosporine (an immunosuppressant used during organ transplants) and others – one at a time into a surfactant called Pluronic. Then, by lowering the solution’s temperature to 4 degrees Celsius (most drugs are made at room temperature), they were able to remove the excess Pluronic via a membrane.

The end result are drugs that contain 100 to 1,000 times less excess additives.

“For the drugs we looked at, this is as close as anyone has gotten to introducing pure, injectable medicine into the body,” says Lovell, PhD, assistant professor in the Department of Biomedical Engineering in UB’s School of Engineering and Applied Sciences. “Essentially, it’s a new way to package drugs.”

The findings are significant, he says, because they show that many injectable drug formulations may be improved through an easy-to-adopt process. Future experiments are planned to further refine the method, he says.

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

Therapeutic surfactant-stripped frozen micelles by Yumiao Zhang, Wentao Song, Jumin Geng, Upendra Chitgupi, Hande Unsal, Jasmin Federizon, Javid Rzayev, Dinesh K. Sukumaran, Paschalis Alexandridis, & Jonathan F. Lovell. Nature Communications 7, Article number: 11649 doi:10.1038/ncomms11649 Published 19 May 2016

This is an open access paper.

A few years back, a friend got a flu shot and became ill (not the flu). Suspicions  (my friend is a doctor) centered on the additives in the shot as that particular year a number of people got sick from the shot.