Tag Archives: nickel

Nanoparticles from tattoo inks circulate through your body

English: Tattoo of Hand of Fatima,. Model: Casini. Date: 4 July 2017, 18:13:41. Source : Own work. Author: Stephencdickson.

For those who like their news in video format, there’s this Canadian Broadcasting Corporation (CBC) news item broadcast on Sep. 11, 2017 (after the commercials),

For those who like text and more detail, scientists at the European Synchrotron Radiation Facility (ESRF) have produced a study of the (at the nanoparticle scale) inks in tattoos. From a Sept. 12, 2017 news item on phys.org,

The elements that make up the ink in tattoos travel inside the body in micro and nanoparticle forms and reach the lymph nodes, according to a study published in Scientific Reports on 12 September [2017] by scientists from Germany and the ESRF, the European Synchrotron, Grenoble (France). It is the first time researchers have found analytical evidence of the transport of organic and inorganic pigments and toxic element impurities as well as in depth characterization of the pigments ex vivo in tattooed tissues. Two ESRF beamlines were crucial in this breakthrough.

A Sept. 12, 2017 ESRF press release (also on EurkeAlert), which originated the news item, explains further,

The reality is that little is known about the potential impurities in the colour mixture applied to the skin. Most tattoo inks contain organic pigments, but also include preservatives and contaminants like nickel, chromium, manganese or cobalt. Besides carbon black, the second most common ingredient used in tattoo inks is titanium dioxide (TiO2), a white pigment usually applied to create certain shades when mixed with colorants. Delayed healing, along with skin elevation and itching, are often associated with white tattoos, and by consequence with the use of TiO2. TiO2 is also commonly used in food additives, sun screens and paints. Scientists from the ESRF, the German Federal Institute for Risk Assessment, Ludwig-Maximilians University, and the Physikalisch-Technische Bundesanstalt have managed to get a very clear picture on the location of titanium dioxide once it gets in the tissue. This work was done on the ESRF beamlines ID21 and ID16B.

drawing tattookinetics.jpg

Translocation of tattoo particles from skin to lymph nodes. Upon injection of tattoo inks, particles can be either passively transported via blood and lymph fluids or phagocytized by immune cells and subsequently deposited in regional lymph nodes. After healing, particles are present in the dermis and in the sinusoids of the draining lymph nodes. Credits: C. Seim.

The hazards that potentially derive from tattoos were, until now, only investigated by chemical analysis of the inks and their degradation products in vitro. “We already knew that pigments from tattoos would travel to the lymph nodes because of visual evidence: the lymph nodes become tinted with the colour of the tattoo. It is the response of the body to clean the site of entrance of the tattoo. What we didn’t know is that they do it in a nano form, which implies that they may not have the same behaviour as the particles at a micro level. And that is the problem: we don’t know how nanoparticles react”, explains Bernhard Hesse, one of the two first authors of the study (together with Ines Schreiver, from the German Federal Institute for Risk Assessment) and ESRF visiting scientist.


Particle mapping and size distribution of different tattoo pigment elements.  a, d) Ti and the Br containing pigment phthalocyanine green 36 are located next to each other. b, e) Log scale mappings of Ti, Br and Fe in the same areas as displayed in a) and d) reveal primary particle sizes of different pigment species. c, f) Magnifications of the indicated areas in b) and e), respectively. Credits: C. Seim.

X-ray fluorescence measurements on ID21 allowed the team to locate titanium dioxide at the micro and nano range in the skin and the lymphatic environment. They found a broad range of particles with up to several micrometres in size in human skin, but only smaller (nano) particles transported to the lymph nodes. This can lead to the chronic enlargement of the lymph nodes and lifelong exposure. Scientists also used the technique of Fourier transform infrared spectroscopy to assess biomolecular changes in the tissues in the proximity of the tattoo particles.


Ines Schreiver doing experiments on ID16B with Julie Villanova. Credits: B. Hesse.

Altogether the scientists report strong evidence for both migration and long-term deposition of toxic elements and tattoo pigments as well as for conformational alterations of biomolecules that are sometimes linked to cutaneous adversities upon tattooing.

Then next step for the team is to inspect further samples of patients with adverse effects in their tattoos in order to find links with chemical and structural properties of the pigments used to create these tattoos.

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

Synchrotron-based ν-XRF mapping and μ-FTIR microscopy enable to look into the fate and effects of tattoo pigments in human skin by Ines Schreiver, Bernhard Hesse, Christian Seim, Hiram Castillo-Michel, Julie Villanova, Peter Laux, Nadine Dreiack, Randolf Penning, Remi Tucoulou, Marine Cotte, & Andreas Luch. Scientific Reports 7, Article number: 11395 (2017) doi:10.1038/s41598-017-11721-z Published online: 12 September 2017

This paper is open access.

Ultimate discovery tool?

For anyone familiar with the US nanomedicine scene, Chad Mirkin’s appearance in this announcement from Northwestern University isn’t much of a surprise.  From a June 23, 2016 news item on ScienceDaily,

The discovery power of the gene chip is coming to nanotechnology. A Northwestern University research team is developing a tool to rapidly test millions and perhaps even billions or more different nanoparticles at one time to zero in on the best particle for a specific use.

When materials are miniaturized, their properties—optical, structural, electrical, mechanical and chemical—change, offering new possibilities. But determining what nanoparticle size and composition are best for a given application, such as catalysts, biodiagnostic labels, pharmaceuticals and electronic devices, is a daunting task.

“As scientists, we’ve only just begun to investigate what materials can be made on the nanoscale,” said Northwestern’s Chad A. Mirkin, a world leader in nanotechnology research and its application, who led the study. “Screening a million potentially useful nanoparticles, for example, could take several lifetimes. Once optimized, our tool will enable researchers to pick the winner much faster than conventional methods. We have the ultimate discovery tool.”

A June 23, 2016 Northwestern University news release (also on EurekAlert), which originated the news item, describes the work in more detail,

Using a Northwestern technique that deposits materials on a surface, Mirkin and his team figured out how to make combinatorial libraries of nanoparticles in a very controlled way. (A combinatorial library is a collection of systematically varied structures encoded at specific sites on a surface.) Their study will be published June 24 by the journal Science.

The nanoparticle libraries are much like a gene chip, Mirkin says, where thousands of different spots of DNA are used to identify the presence of a disease or toxin. Thousands of reactions can be done simultaneously, providing results in just a few hours. Similarly, Mirkin and his team’s libraries will enable scientists to rapidly make and screen millions to billions of nanoparticles of different compositions and sizes for desirable physical and chemical properties.

“The ability to make libraries of nanoparticles will open a new field of nanocombinatorics, where size — on a scale that matters — and composition become tunable parameters,” Mirkin said. “This is a powerful approach to discovery science.”

“I liken our combinatorial nanopatterning approach to providing a broad palette of bold colors to an artist who previously had been working with a handful of dull and pale black, white and grey pastels,” said co-author Vinayak P. Dravid, the Abraham Harris Professor of Materials Science and Engineering in the McCormick School of Engineering.

Using five metallic elements — gold, silver, cobalt, copper and nickel — Mirkin and his team developed an array of unique structures by varying every elemental combination. In previous work, the researchers had shown that particle diameter also can be varied deliberately on the 1- to 100-nanometer length scale.

Some of the compositions can be found in nature, but more than half of them have never existed before on Earth. And when pictured using high-powered imaging techniques, the nanoparticles appear like an array of colorful Easter eggs, each compositional element contributing to the palette.

To build the combinatorial libraries, Mirkin and his team used Dip-Pen Nanolithography, a technique developed at Northwestern in 1999, to deposit onto a surface individual polymer “dots,” each loaded with different metal salts of interest. The researchers then heated the polymer dots, reducing the salts to metal atoms and forming a single nanoparticle. The size of the polymer dot can be varied to change the size of the final nanoparticle.

This control of both size and composition of nanoparticles is very important, Mirkin stressed. Having demonstrated control, the researchers used the tool to systematically generate a library of 31 nanostructures using the five different metals.

To help analyze the complex elemental compositions and size/shape of the nanoparticles down to the sub-nanometer scale, the team turned to Dravid, Mirkin’s longtime friend and collaborator. Dravid, founding director of Northwestern’s NUANCE Center, contributed his expertise and the advanced electron microscopes of NUANCE to spatially map the compositional trajectories of the combinatorial nanoparticles.

Now, scientists can begin to study these nanoparticles as well as build other useful combinatorial libraries consisting of billions of structures that subtly differ in size and composition. These structures may become the next materials that power fuel cells, efficiently harvest solar energy and convert it into useful fuels, and catalyze reactions that take low-value feedstocks from the petroleum industry and turn them into high-value products useful in the chemical and pharmaceutical industries.

Here’s a diagram illustrating the work,

 Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

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

Polyelemental nanoparticle libraries by Peng-Cheng Chen, Xiaolong Liu, James L. Hedrick, Zhuang Xie, Shunzhi Wang, Qing-Yuan Lin, Mark C. Hersam, Vinayak P. Dravid, Chad A. Mirkin. Science  24 Jun 2016: Vol. 352, Issue 6293, pp. 1565-1569 DOI: 10.1126/science.aaf8402

This paper is behind a paywall.

Platinum catalysts and their shortcomings

The problem boils down to the fact that platinum isn’t cheap and so US Dept. of Energy research laboratories are looking for alternatives to or ways of making more efficient use of platinum according to a June 16, 2015 news item on Nanowerk,

Visions of dazzling engagement rings may pop to mind when platinum is mentioned, but a significant share of the nearly half a million pounds of the rare metalExternal link [sic] mined each year ends up in vehicle emission systems and chemical manufacturing plants. The silvery white metal speeds up or enhances reactions, a role scientists call serving as a catalyst, and platinum is fast and efficient performing this function.

Because of its outstanding performance as a catalyst, platinum plays a major role in fuel cells. Inside a fuel cell, tiny platinum particles break apart hydrogen fuel to create electricity. Leftover protons are combined with oxygen ions to create pure water.

Fuel cells could let scientists turn wind into fuel. Right now, electricity generated by wind turbines is not stored. If that energy could be converted into hydrogen to power fuel cells, it would turn a sporadic source into a continuous one.

The problem is the platinum – a scarce and costly metal. Scientists funded by the U.S. Department of Energy’s Office of Science are seeing if something more readily available, such as iron or nickel, could catalyze the reaction.

But, earth-abundant metals cannot simply be used in place of platinum and other rare metals. Each metal works differently at the atomic level. It takes basic research to understand the interactions and use that knowledge to create the right catalysts.

A June 15, 2015 US Department of Energy Office of Science news release, which originated the news item, describes various efforts,

At the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, scientists are gaining new understanding of catalysts based on common metals and how they move protons, the positively charged, oft-ignored counterpart to the electron.

Center Director Morris Bullock and his colleagues showed that protons’ ability to move through the catalyst greatly influences the catalyst’s speed and efficiency. Protons move via relays — clusters of atoms that convey protons to or from the active site of catalysts, where the reaction of interest occurs. The constitution, placement, and number of relays can let a reaction zip along or grind to a halt. Bullock and his colleagues are creating “design guidelines” for building relays.

Further, the team is expanding the guidelines to examine proton movement related to the solutions and surfaces where the catalyst resides. For example, matching the proton-donating abilityExternal link [sic] of a nickel-based catalyst to that of the surrounding liquid, much like matching your clothing choice with the event you’re attending, eases protons’ travels. The benefit? Speed. A coordinated catalyst pumped out 96,000 hydrogen molecules a second — compared to just 27,000 molecules a second without the adjustment.

This and other research at the Energy Frontier Research Center is funded by the DOE Office of Science’s Office of Basic Energy Sciences. The Center is led by Pacific Northwest National Laboratory.

At two other labs, research shows how changing the catalyst’s superstructure, which contains the proton relays and wraps around the active site, can also increase the speed of the reaction. Led by Argonne National Lab’s Vojislav Stamenkovic and Berkeley Lab’s Peidong Yang, researchers created hollow platinum and nickel nanoparticles, a thousand times smaller in diameter than a human hair. The 12-sided particles split oxygen molecules into charged oxygen ions, a reaction that’s needed in fuel cells. The new catalyst is far more active and uses far less platinum than conventional platinum-carbon catalysts.

Building the catalysts begins with tiny structures made of platinum and nickel held in solution. Oxygen from the air dissolves into the liquid and selectively etches away some of the nickel atoms. The result is a hollow framework with a highly active platinum skin over the surface. The open design of the catalyst allows the oxygen to easily access the platinum. The new catalyst has a 36-fold increase in activity compared to traditional platinum–carbon catalysts. Further, the new hollow structure continues to work far longer in operating fuel cells than traditional catalysts.

I think we’re entering the ‘slow’ season newswise so there are likely to be more of these ’roundup’ pieces being circulated in the online nanosciencesphere and, consequently, here. too.