Tag Archives: gold

Golden nanoglue

This starts out as a graphene story before taking an abrupt turn. From a June 5, 2018 news item on Nanowerk,

Graphene has undoubtedly been the most popular research subject of nanotechnology during recent years. Made of pure carbon, this material is in principle easy to manufacture: take ordinary graphite and peel one layer off with Scotch tape. The material thus obtained is two-dimensional, yielding unique properties, different from those in three-dimensional materials.

Graphene, however, lacks one important property, semiconductivity, which complicates its usage in electronics applications. Scientists have therefore started the quest of other two-dimensional materials with this desired property.

Molybdenum disulfide, MoS2 is among the most promising candidates. Like graphene, MoS2 consists of layers, interacting weakly with one another. In addition to being a semiconductor, the semiconducting properties of MoS2 change depending on the number of atomic layers.

A June 5, 2018 University of Oulu press release, which originated the news item,  gives more detail about the work,

For the one or few layer MoS2 to be useful in applications, one must be able to join it to other components. What is thus needed is such a metallic conductor that electric current can easily flow between the conductor and the semiconductor. In the case of MoS2, a promising conductor is provided by nickel, which also has other desired properties from the applications point of view.

However, an international collaboration, led by the Nano and molecular systems research unit at the University of Oulu has recently discovered that nanoparticles made of nickel do not attach to MoS2. One needs gold, which ‘glues’ the conductor and the component together. Says docent Wei Cao of NANOMO: “The synthesis is performed through a sonochemical method.” Sonochemistry is a method where chemical reactions are established using ultrasound. NANOMO scientist Xinying Shi adds: “The semiconductor and metal can be bridged either by the crystallized gold nanoparticles, or by the newly formed MoS2-Au-Ni ternary alloy.”

The nanojunction so established has a very small electrical resistivity. It also preserves the semiconducting and magnetic properties of MoS2. In addition, the new material has desirable properties beyond those of the original constituents. For example, it acts as a photocatalyst, which works much more efficiently than pure MoS2. Manufacturing the golden nanojunction is easy and cheap, which makes the new material attractive from the applications point of view.

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

Metallic Contact between MoS2 and Ni via Au Nanoglue by Xinying Shi, Sergei Posysaev, Marko Huttula, Vladimir Pankratov, Joanna Hoszowska, Jean‐Claude Dousse, Faisal Zeeshan, Yuran Niu, Alexei Zakharov, Taohai Li. Small Volume 14, Issue22 May 29, 2018 1704526 First published online: 24 April 2018 https://doi.org/10.1002/smll.201704526

This paper is behind a paywall.

There is a pretty illustration of the ‘golden nanojunctions’,

Golden nanoglue (Courtesy of the University of Oulu)

Create gold nanoparticles and nanowires with water droplets.

For some reason it took a lot longer than usual to find this research paper despite having the journal (Nature Communications), the title (Spontaneous formation …), and the authors’ names. Thankfully, success was wrested from the jaws of defeat (I don’t care if that is trite; it’s how I felt) and links, etc. follow at the end as usual.

An April 19, 2018 Stanford University news release (also on EurekAlert) spins fascinating tale,

An experiment that, by design, was not supposed to turn up anything of note instead produced a “bewildering” surprise, according to the Stanford scientists who made the discovery: a new way of creating gold nanoparticles and nanowires using water droplets.

The technique, detailed April 19 [2018] in the journal Nature Communications, is the latest discovery in the new field of on-droplet chemistry and could lead to more environmentally friendly ways to produce nanoparticles of gold and other metals, said study leader Richard Zare, a chemist in the School of Humanities and Sciences and a co-founder of Stanford Bio-X.

“Being able to do reactions in water means you don’t have to worry about contamination. It’s green chemistry,” said Zare, who is the Marguerite Blake Wilbur Professor in Natural Science at Stanford.

Noble metal

Gold is known as a noble metal because it is relatively unreactive. Unlike base metals such as nickel and copper, gold is resistant to corrosion and oxidation, which is one reason it is such a popular metal for jewelry.

Around the mid-1980s, however, scientists discovered that gold’s chemical aloofness only manifests at large, or macroscopic, scales. At the nanometer scale, gold particles are very chemically reactive and make excellent catalysts. Today, gold nanostructures have found a role in a wide variety of applications, including bio-imaging, drug delivery, toxic gas detection and biosensors.

Until now, however, the only reliable way to make gold nanoparticles was to combine the gold precursor chloroauric acid with a reducing agent such as sodium borohydride.

The reaction transfers electrons from the reducing agent to the chloroauric acid, liberating gold atoms in the process. Depending on how the gold atoms then clump together, they can form nano-size beads, wires, rods, prisms and more.

A spritz of gold

Recently, Zare and his colleagues wondered whether this gold-producing reaction would proceed any differently with tiny, micron-size droplets of chloroauric acid and sodium borohydide. How large is a microdroplet? “It is like squeezing a perfume bottle and out spritzes a mist of microdroplets,” Zare said.

From previous experiments, the scientists knew that some chemical reactions proceed much faster in microdroplets than in larger solution volumes.

Indeed, the team observed that gold nanoparticle grew over 100,000 times faster in microdroplets. However, the most striking observation came while running a control experiment in which they replaced the reducing agent – which ordinarily releases the gold particles – with microdroplets of water.

“Much to our bewilderment, we found that gold nanostructures could be made without any added reducing agents,” said study first author Jae Kyoo Lee, a research associate.

Viewed under an electron microscope, the gold nanoparticles and nanowires appear fused together like berry clusters on a branch.

The surprise finding means that pure water microdroplets can serve as microreactors for the production of gold nanostructures. “This is yet more evidence that reactions in water droplets can be fundamentally different from those in bulk water,” said study coauthor Devleena Samanta, a former graduate student in Zare’s lab and co-author on the paper.

If the process can be scaled up, it could eliminate the need for potentially toxic reducing agents that have harmful health side effects or that can pollute waterways, Zare said.

It’s still unclear why water microdroplets are able to replace a reducing agent in this reaction. One possibility is that transforming the water into microdroplets greatly increases its surface area, creating the opportunity for a strong electric field to form at the air-water interface, which may promote the formation of gold nanoparticles and nanowires.

“The surface area atop a one-liter beaker of water is less than one square meter. But if you turn the water in that beaker into microdroplets, you will get about 3,000 square meters of surface area – about the size of half a football field,” Zare said.

The team is exploring ways to utilize the nanostructures for various catalytic and biomedical applications and to refine their technique to create gold films.

“We observed a network of nanowires that may allow the formation of a thin layer of nanowires,” Samanta said.

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

Spontaneous formation of gold nanostructures in aqueous microdroplets by Jae Kyoo Lee, Devleena Samanta, Hong Gil Nam, & Richard N. Zare. Nature Communicationsvolume 9, Article number: 1562 (2018) doi:10.1038/s41467-018-04023-z Published online: 19 April 2018

Not unsurprisingly given Zare’s history as recounted in the news release, this paper is open access.

Mixing the unmixable for all new nanoparticles

This news comes out of the University of Maryland and the discovery could led to nanoparticles that have never before been imagined. From a March 29, 2018 news item on ScienceDaily,

Making a giant leap in the ‘tiny’ field of nanoscience, a multi-institutional team of researchers is the first to create nanoscale particles composed of up to eight distinct elements generally known to be immiscible, or incapable of being mixed or blended together. The blending of multiple, unmixable elements into a unified, homogenous nanostructure, called a high entropy alloy nanoparticle, greatly expands the landscape of nanomaterials — and what we can do with them.

This research makes a significant advance on previous efforts that have typically produced nanoparticles limited to only three different elements and to structures that do not mix evenly. Essentially, it is extremely difficult to squeeze and blend different elements into individual particles at the nanoscale. The team, which includes lead researchers at University of Maryland, College Park (UMD)’s A. James Clark School of Engineering, published a peer-reviewed paper based on the research featured on the March 30 [2018] cover of Science.

A March 29, 2018 University of Maryland press release (also on EurekAlert), which originated the news item, delves further (Note: Links have been removed),

“Imagine the elements that combine to make nanoparticles as Lego building blocks. If you have only one to three colors and sizes, then you are limited by what combinations you can use and what structures you can assemble,” explains Liangbing Hu, associate professor of materials science and engineering at UMD and one of the corresponding authors of the paper. “What our team has done is essentially enlarged the toy chest in nanoparticle synthesis; now, we are able to build nanomaterials with nearly all metallic and semiconductor elements.”

The researchers say this advance in nanoscience opens vast opportunities for a wide range of applications that includes catalysis (the acceleration of a chemical reaction by a catalyst), energy storage (batteries or supercapacitors), and bio/plasmonic imaging, among others.

To create the high entropy alloy nanoparticles, the researchers employed a two-step method of flash heating followed by flash cooling. Metallic elements such as platinum, nickel, iron, cobalt, gold, copper, and others were exposed to a rapid thermal shock of approximately 3,000 degrees Fahrenheit, or about half the temperature of the sun, for 0.055 seconds. The extremely high temperature resulted in uniform mixtures of the multiple elements. The subsequent rapid cooling (more than 100,000 degrees Fahrenheit per second) stabilized the newly mixed elements into the uniform nanomaterial.

“Our method is simple, but one that nobody else has applied to the creation of nanoparticles. By using a physical science approach, rather than a traditional chemistry approach, we have achieved something unprecedented,” says Yonggang Yao, a Ph.D. student at UMD and one of the lead authors of the paper.

To demonstrate one potential use of the nanoparticles, the research team used them as advanced catalysts for ammonia oxidation, which is a key step in the production of nitric acid (a liquid acid that is used in the production of ammonium nitrate for fertilizers, making plastics, and in the manufacturing of dyes). They were able to achieve 100 percent oxidation of ammonia and 99 percent selectivity toward desired products with the high entropy alloy nanoparticles, proving their ability as highly efficient catalysts.

Yao says another potential use of the nanoparticles as catalysts could be the generation of chemicals or fuels from carbon dioxide.

“The potential applications for high entropy alloy nanoparticles are not limited to the field of catalysis. With cross-discipline curiosity, the demonstrated applications of these particles will become even more widespread,” says Steven D. Lacey, a Ph.D. student at UMD and also one of the lead authors of the paper.

This research was performed through a multi-institutional collaboration of Prof. Liangbing Hu’s group at the University of Maryland, College Park; Prof. Reza Shahbazian-Yassar’s group at University of Illinois at Chicago; Prof. Ju Li’s group at the Massachusetts Institute of Technology; Prof. Chao Wang’s group at Johns Hopkins University; and Prof. Michael Zachariah’s group at the University of Maryland, College Park.

What outside experts are saying about this research:

“This is quite amazing; Dr. Hu creatively came up with this powerful technique, carbo-thermal shock synthesis, to produce high entropy alloys of up to eight different elements in a single nanoparticle. This is indeed unthinkable for bulk materials synthesis. This is yet another beautiful example of nanoscience!,” says Peidong Yang, the S.K. and Angela Chan Distinguished Professor of Energy and professor of chemistry at the University of California, Berkeley and member of the American Academy of Arts and Sciences.

“This discovery opens many new directions. There are simulation opportunities to understand the electronic structure of the various compositions and phases that are important for the next generation of catalyst design. Also, finding correlations among synthesis routes, composition, and phase structure and performance enables a paradigm shift toward guided synthesis,” says George Crabtree, Argonne Distinguished Fellow and director of the Joint Center for Energy Storage Research at Argonne National Laboratory.

More from the research coauthors:

“Understanding the atomic order and crystalline structure in these multi-element nanoparticles reveals how the synthesis can be tuned to optimize their performance. It would be quite interesting to further explore the underlying atomistic mechanisms of the nucleation and growth of high entropy alloy nanoparticle,” says Reza Shahbazian-Yassar, associate professor at the University of Illinois at Chicago and a corresponding author of the paper.

“Carbon metabolism drives ‘living’ metal catalysts that frequently move around, split, or merge, resulting in a nanoparticle size distribution that’s far from the ordinary, and highly tunable,” says Ju Li, professor at the Massachusetts Institute of Technology and a corresponding author of the paper.

“This method enables new combinations of metals that do not exist in nature and do not otherwise go together. It enables robust tuning of the composition of catalytic materials to optimize the activity, selectivity, and stability, and the application will be very broad in energy conversions and chemical transformations,” says Chao Wang, assistant professor of chemical and biomolecular engineering at Johns Hopkins University and one of the study’s authors.

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

Carbothermal shock synthesis of high-entropy-alloy nanoparticles by Yonggang Yao, Zhennan Huang, Pengfei Xie, Steven D. Lacey, Rohit Jiji Jacob, Hua Xie, Fengjuan Chen, Anmin Nie, Tiancheng Pu, Miles Rehwoldt, Daiwei Yu, Michael R. Zachariah, Chao Wang, Reza Shahbazian-Yassar, Ju Li, Liangbing Hu. Science 30 Mar 2018: Vol. 359, Issue 6383, pp. 1489-1494 DOI: 10.1126/science.aan5412

This paper is behind a paywall.

Gold’s origin in the universe due to cosmic collision

An hypothesis for gold’s origins was first mentioned here in a May 26, 2016 posting,

The link between this research and my side project on gold nanoparticles is a bit tenuous but this work on the origins for gold and other precious metals being found in the stars is so fascinating and I’m determined to find a connection.

An artist's impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

An artist’s impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

From a May 19, 2016 news item on phys.org,

The origin of many of the most precious elements on the periodic table, such as gold, silver and platinum, has perplexed scientists for more than six decades. Now a recent study has an answer, evocatively conveyed in the faint starlight from a distant dwarf galaxy.

In a roundtable discussion, published today [May 19, 2016?], The Kavli Foundation spoke to two of the researchers behind the discovery about why the source of these heavy elements, collectively called “r-process” elements, has been so hard to crack.

From the Spring 2016 Kavli Foundation webpage hosting the  “Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements” Roundtable ,

Astronomers studying a galaxy called Reticulum II have just discovered that its stars contain whopping amounts of these metals—collectively known as “r-process” elements (See “What is the R-Process?”). Of the 10 dwarf galaxies that have been similarly studied so far, only Reticulum II bears such strong chemical signatures. The finding suggests some unusual event took place billions of years ago that created ample amounts of heavy elements and then strew them throughout the galaxy’s reservoir of gas and dust. This r-process-enriched material then went on to form Reticulum II’s standout stars.

Based on the new study, from a team of researchers at the Kavli Institute at the Massachusetts Institute of Technology, the unusual event in Reticulum II was likely the collision of two, ultra-dense objects called neutron stars. Scientists have hypothesized for decades that these collisions could serve as a primary source for r-process elements, yet the idea had lacked solid observational evidence. Now armed with this information, scientists can further hope to retrace the histories of galaxies based on the contents of their stars, in effect conducting “stellar archeology.”

Researchers have confirmed the hypothesis according to an Oct. 16, 2017 news item on phys.org,

Gold’s origin in the Universe has finally been confirmed, after a gravitational wave source was seen and heard for the first time ever by an international collaboration of researchers, with astronomers at the University of Warwick playing a leading role.

Members of Warwick’s Astronomy and Astrophysics Group, Professor Andrew Levan, Dr Joe Lyman, Dr Sam Oates and Dr Danny Steeghs, led observations which captured the light of two colliding neutron stars, shortly after being detected through gravitational waves – perhaps the most eagerly anticipated phenomenon in modern astronomy.

Marina Koren’s Oct. 16, 2017 article for The Atlantic presents a richly evocative view (Note: Links have been removed),

Some 130 million years ago, in another galaxy, two neutron stars spiraled closer and closer together until they smashed into each other in spectacular fashion. The violent collision produced gravitational waves, cosmic ripples powerful enough to stretch and squeeze the fabric of the universe. There was a brief flash of light a million trillion times as bright as the sun, and then a hot cloud of radioactive debris. The afterglow hung for several days, shifting from bright blue to dull red as the ejected material cooled in the emptiness of space.

Astronomers detected the aftermath of the merger on Earth on August 17. For the first time, they could see the source of universe-warping forces Albert Einstein predicted a century ago. Unlike with black-hole collisions, they had visible proof, and it looked like a bright jewel in the night sky.

But the merger of two neutron stars is more than fireworks. It’s a factory.

Using infrared telescopes, astronomers studied the spectra—the chemical composition of cosmic objects—of the collision and found that the plume ejected by the merger contained a host of newly formed heavy chemical elements, including gold, silver, platinum, and others. Scientists estimate the amount of cosmic bling totals about 10,000 Earth-masses of heavy elements.

I’m not sure exactly what this image signifies but it did accompany Koren’s article so presumably it’s a representation of colliding neutron stars,

NSF / LIGO / Sonoma State University /A. Simonnet. Downloaded from: https://www.theatlantic.com/science/archive/2017/10/the-making-of-cosmic-bling/543030/

An Oct. 16, 2017 University of Warwick press release (also on EurekAlert), which originated the news item on phys.org, provides more detail,

Huge amounts of gold, platinum, uranium and other heavy elements were created in the collision of these compact stellar remnants, and were pumped out into the universe – unlocking the mystery of how gold on wedding rings and jewellery is originally formed.

The collision produced as much gold as the mass of the Earth. [emphasis mine]

This discovery has also confirmed conclusively that short gamma-ray bursts are directly caused by the merging of two neutron stars.

The neutron stars were very dense – as heavy as our Sun yet only 10 kilometres across – and they collided with each other 130 million years ago, when dinosaurs roamed the Earth, in a relatively old galaxy that was no longer forming many stars.

They drew towards each other over millions of light years, and revolved around each other increasingly quickly as they got closer – eventually spinning around each other five hundred times per second.

Their merging sent ripples through the fabric of space and time – and these ripples are the elusive gravitational waves spotted by the astronomers.

The gravitational waves were detected by the Advanced Laser Interferometer Gravitational-Wave Observatory (Adv-LIGO) on 17 August this year [2017], with a short duration gamma-ray burst detected by the Fermi satellite just two seconds later.

This led to a flurry of observations as night fell in Chile, with a first report of a new source from the Swope 1m telescope.

Longstanding collaborators Professor Levan and Professor Nial Tanvir (from the University of Leicester) used the facilities of the European Southern Observatory to pinpoint the source in infrared light.

Professor Levan’s team was the first one to get observations of this new source with the Hubble Space Telescope. It comes from a galaxy called NGC 4993, 130 million light years away.

Andrew Levan, Professor in the Astronomy & Astrophysics group at the University of Warwick, commented: “Once we saw the data, we realised we had caught a new kind of astrophysical object. This ushers in the era of multi-messenger astronomy, it is like being able to see and hear for the first time.”

Dr Joe Lyman, who was observing at the European Southern Observatory at the time was the first to alert the community that the source was unlike any seen before.

He commented: “The exquisite observations obtained in a few days showed we were observing a kilonova, an object whose light is powered by extreme nuclear reactions. This tells us that the heavy elements, like the gold or platinum in jewellery are the cinders, forged in the billion degree remnants of a merging neutron star.”

Dr Samantha Oates added: “This discovery has answered three questions that astronomers have been puzzling for decades: what happens when neutron stars merge? What causes the short duration gamma-ray bursts? Where are the heavy elements, like gold, made? In the space of about a week all three of these mysteries were solved.”

Dr Danny Steeghs said: “This is a new chapter in astrophysics. We hope that in the next few years we will detect many more events like this. Indeed, in Warwick we have just finished building a telescope designed to do just this job, and we expect it to pinpoint these sources in this new era of multi-messenger astronomy”.

Congratulations to all of the researchers involved in this work!

Many, many research teams were  involved. Here’s a sampling of their news releases which focus on their areas of research,

University of the Witwatersrand (South Africa)

https://www.eurekalert.org/pub_releases/2017-10/uotw-wti101717.php

Weizmann Institute of Science (Israel)

https://www.eurekalert.org/pub_releases/2017-10/wios-cns101717.php

Carnegie Institution for Science (US)

https://www.eurekalert.org/pub_releases/2017-10/cifs-dns101217.php

Northwestern University (US)

https://www.eurekalert.org/pub_releases/2017-10/nu-adc101617.php

National Radio Astronomy Observatory (US)

https://www.eurekalert.org/pub_releases/2017-10/nrao-ru101317.php

Max-Planck-Gesellschaft (Germany)

https://www.eurekalert.org/pub_releases/2017-10/m-gwf101817.php

Penn State (Pennsylvania State University; US)

https://www.eurekalert.org/pub_releases/2017-10/ps-stl101617.php

University of California – Davis

https://www.eurekalert.org/pub_releases/2017-10/uoc–cns101717.php

The American Association for the Advancement of Science’s (AAAS) magazine, Science, has published seven papers on this research. Here’s an Oct. 16, 2017 AAAS news release with an overview of the papers,

https://www.eurekalert.org/pub_releases/2017-10/aaft-btf101617.php

I’m sure there are more news releases out there and that there will be many more papers published in many journals, so if this interests, I encourage you to keep looking.

Two final pieces I’d like to draw your attention to: one answers basic questions and another focuses on how artists knew what to draw when neutron stars collide.

Keith A Spencer’s Oct. 18, 2017 piece on salon.com answers a lot of basic questions for those of us who don’t have a background in astronomy. Here are a couple of examples,

What is a neutron star?

Okay, you know how atoms have protons, neutrons, and electrons in them? And you know how protons are positively charged, and electrons are negatively charged, and neutrons are neutral?

Yeah, I remember that from watching Bill Nye as a kid.

Totally. Anyway, have you ever wondered why the negatively-charged electrons and the positively-charged protons don’t just merge into each other and form a neutral neutron? I mean, they’re sitting there in the atom’s nucleus pretty close to each other. Like, if you had two magnets that close, they’d stick together immediately.

I guess now that you mention it, yeah, it is weird.

Well, it’s because there’s another force deep in the atom that’s preventing them from merging.

It’s really really strong.

The only way to overcome this force is to have a huge amount of matter in a really hot, dense space — basically shove them into each other until they give up and stick together and become a neutron. This happens in very large stars that have been around for a while — the core collapses, and in the aftermath, the electrons in the star are so close to the protons, and under so much pressure, that they suddenly merge. There’s a big explosion and the outer material of the star is sloughed off.

Okay, so you’re saying under a lot of pressure and in certain conditions, some stars collapse and become big balls of neutrons?

Pretty much, yeah.

So why do the neutrons just stick around in a huge ball? Aren’t they neutral? What’s keeping them together? 

Gravity, mostly. But also the strong nuclear force, that aforementioned weird strong force. This isn’t something you’d encounter on a macroscopic scale — the strong force only really works at the type of distances typified by particles in atomic nuclei. And it’s different, fundamentally, than the electromagnetic force, which is what makes magnets attract and repel and what makes your hair stick up when you rub a balloon on it.

So these neutrons in a big ball are bound by gravity, but also sticking together by virtue of the strong nuclear force. 

So basically, the new ball of neutrons is really small, at least, compared to how heavy it is. That’s because the neutrons are all clumped together as if this neutron star is one giant atomic nucleus — which it kinda is. It’s like a giant atom made only of neutrons. If our sun were a neutron star, it would be less than 20 miles wide. It would also not be something you would ever want to get near.

Got it. That means two giant balls of neutrons that weighed like, more than our sun and were only ten-ish miles wide, suddenly smashed into each other, and in the aftermath created a black hole, and we are just now detecting it on Earth?

Exactly. Pretty weird, no?

Spencer does a good job of gradually taking you through increasingly complex explanations.

For those with artistic interests, Neel V. Patel tries to answer a question about how artists knew what draw when neutron stars collided in his Oct. 18, 2017 piece for Slate.com,

All of these things make this discovery easy to marvel at and somewhat impossible to picture. Luckily, artists have taken up the task of imagining it for us, which you’ve likely seen if you’ve already stumbled on coverage of the discovery. Two bright, furious spheres of light and gas spiraling quickly into one another, resulting in a massive swell of lit-up matter along with light and gravitational waves rippling off speedily in all directions, towards parts unknown. These illustrations aren’t just alluring interpretations of a rare phenomenon; they are, to some extent, the translation of raw data and numbers into a tangible visual that gives scientists and nonscientists alike some way of grasping what just happened. But are these visualizations realistic? Is this what it actually looked like? No one has any idea. Which is what makes the scientific illustrators’ work all the more fascinating.

“My goal is to represent what the scientists found,” says Aurore Simmonet, a scientific illustrator based at Sonoma State University in Rohnert Park, California. Even though she said she doesn’t have a rigorous science background (she certainly didn’t know what a kilonova was before being tasked to illustrate one), she also doesn’t believe that type of experience is an absolute necessity. More critical, she says, is for the artist to have an interest in the subject matter and in learning new things, as well as a capacity to speak directly to scientists about their work.

Illustrators like Simmonet usually start off work on an illustration by asking the scientist what’s the biggest takeaway a viewer should grasp when looking at a visual. Unfortunately, this latest discovery yielded a multitude of papers emphasizing different conclusions and highlights. With so many scientific angles, there’s a stark challenge in trying to cram every important thing into a single drawing.

Clearly, however, the illustrations needed to center around the kilonova. Simmonet loves colors, so she began by discussing with the researchers what kind of color scheme would work best. The smash of two neutron stars lends itself well to deep, vibrant hues. Simmonet and Robin Dienel at the Carnegie Institution for Science elected to use a wide array of colors and drew bright cracking to show pressure forming at the merging. Others, like Luis Calcada at the European Southern Observatory, limited the color scheme in favor of emphasizing the bright moment of collision and the signal waves created by the kilonova.

Animators have even more freedom to show the event, since they have much more than a single frame to play with. The Conceptual Image Lab at NASA’s [US National Aeronautics and Space Administration] Goddard Space Flight Center created a short video about the new findings, and lead animator Brian Monroe says the video he and his colleagues designed shows off the evolution of the entire process: the rising action, climax, and resolution of the kilonova event.

The illustrators try to adhere to what the likely physics of the event entailed, soliciting feedback from the scientists to make sure they’re getting it right. The swirling of gas, the direction of ejected matter upon impact, the reflection of light, the proportions of the objects—all of these things are deliberately framed such that they make scientific sense. …

Do take a look at Patel’s piece, if for no other reason than to see all of the images he has embedded there. You may recognize Aurore Simmonet’s name from the credit line in the second image I have embedded here.

Gold at the nanoscale in medieval textiles

It takes a while (i.e., you have to read the abstract for the paper) to get to the nanoscale part of the story. In the meantime, here are the broad brushstrokes (as it were) from a group of researchers in Hungary, from an Oct. 11, 2017 American Chemical Society (ACS) news release (also on EurekAlert),

Gold has long been valued for its luxurious glitter and hue, and threads of the gleaming metal have graced clothing and tapestries for centuries. Determining how artisans accomplished these adornments in the distant past can help scientists restore, preserve and date artifacts, but solutions to these puzzles have been elusive. Now scientists, reporting in ACS’ journal Analytical Chemistry, have revealed that medieval artisans used a gilding technology that has endured for centuries.

Researchers can learn a lot about vanished cultures from objects left behind. But one detail that has escaped understanding has been the manufacturing method of gold-coated silver threads found in textiles from the Middle Ages. Four decades of intensive research yielded some clues, but the findings have been very limited. Study of the materials has been hindered by their extremely small size: A single metal thread is sometimes only as thick as a human hair, and the thickness of its gold coating is a hundredth of that. Tamás G. Weiszburg, Katalin Gherdán and colleagues set out to fill this gap.

Using a suite of lab techniques, the researchers examined medieval gilded silver threads, and silver and gold strips produced during and after the Middle Ages. The items come from European cultures spanning the 13th to 17th centuries. The researchers characterized the chemistry of the silver thread, its gold coating, the interactions between the two and the shape of metal strips’ edges. To characterize the threads and strips, the researchers combined high-resolution scanning electron microscopy, electron back-scattered diffraction with energy-dispersive electron probe microanalysis and other analytical methods. Though previous studies indicated that these tiny objects were manufactured by a mercury-based method in fashion at that time, the new results suggest that the threads were gilded exclusively by using an ancient method that survived for a millennium. The goldsmiths simply heated and hammered the silver sheets and the gold foil together, and then cut them into strips. It was also possible to determine whether scissor- or knife-like tools were used for cutting. The results also show that this process was used widely in the region well into the 17th century.

The authors acknowledge funding from the European Social Fund.

Here’s an image of medieval bling,

Caption: A new study unravels how medieval artisans embellished textiles with gold. Credit: The American Chemical Society

Finally, here’s the abstract with the information about the nanoscale elements (link to paper follows abstract),

Although gilt silver threads were widely used for decorating historical textiles, their manufacturing techniques have been elusive for centuries. Contemporary written sources give only limited, sometimes ambiguous information, and detailed cross-sectional study of the microscale soft noble metal objects has been hindered by sample preparation. In this work, to give a thorough characterization of historical gilt silver threads, nano- and microscale textural, chemical, and structural data on cross sections, prepared by focused ion beam milling, were collected, using various electron-optical methods (high-resolution scanning electron microscopy (SEM), wavelength-dispersive electron probe microanalysis (EPMA), electron backscattered diffraction (EBSD) combined with energy-dispersive electron probe microanalysis (EDX), transmission electron microscopy (TEM) combined with EDX, and micro-Raman spectroscopy. The thickness of the gold coating varied between 70–400 nm [emphasis mine]. Data reveal nano- and microscale metallurgy-related, gilding-related and corrosion-related inhomogeneities in the silver base. These inhomogeneities account for the limitations of surface analysis when tracking gilding methods of historical metal threads, and explain why chemical information has to be connected to 3D texture on submicrometre scale. The geometry and chemical composition (lack of mercury, copper) of the gold/silver interface prove that the ancient gilding technology was diffusion bonding. The observed differences in the copper content of the silver base of the different thread types suggest intentional technological choice. Among the examined textiles of different ages (13th–17th centuries) and provenances narrow technological variation has been found.

Here’s a link to the paper,

Medieval Gilding Technology of Historical Metal Threads Revealed by Electron Optical and Micro-Raman Spectroscopic Study of Focused Ion Beam-Milled Cross Sections by Tamás G. Weiszburg, Katalin Gherdán, Kitti Ratter, Norbert Zajzon, Zsolt Bendő, György Radnóczi, Ágnes Takács, Tamás Váczi, Gábor Varga and György Szakmány. Anal. Chem., Article ASAP DOI: 10.1021/acs.analchem.7b01917 Publication Date (Web): September 19, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

One final comment, if you read the abstract, you’ll see how many technologies the researchers needed to use to examine the textiles. How did medieval artisans create nanoscale and microscale gilding when they couldn’t see it? I realize there are now some optical microscopes that can provide a view of the nanoscale but presumably those artisans of the Middle Ages did not have access to that kind of equipment. So, how did they create those textiles with the technology of the day?

Nanomesh for hypoallergenic wearable electronics

It stands to reason that sensors and monitoring devices held against the skin (wearable electronics) for long periods of time could provoke an allergic reaction. Scientists at the University of Tokyo have devised a possible solution according to a July 17, 2017 news item on ScienceDaily,

A hypoallergenic electronic sensor can be worn on the skin continuously for a week without discomfort, and is so light and thin that users forget they even have it on, says a Japanese group of scientists. The elastic electrode constructed of breathable nanoscale meshes holds promise for the development of noninvasive e-skin devices that can monitor a person’s health continuously over a long period.

Here’s an image illustrating the hypoallergenic electronics,

Caption: The electric current from a flexible battery placed near the knuckle flows through the conductor and powers the LED just below the fingernail. Credit: 2017 Someya Laboratory.

A University of Tokyo press release on EurekAlert, which originated the news item, expands on the theme,

Wearable electronics that monitor heart rate and other vital health signals have made headway in recent years, with next-generation gadgets employing lightweight, highly elastic materials attached directly onto the skin for more sensitive, precise measurements. However, although the ultrathin films and rubber sheets used in these devices adhere and conform well to the skin, their lack of breathability is deemed unsafe for long-term use: dermatological tests show the fine, stretchable materials prevent sweating and block airflow around the skin, causing irritation and inflammation, which ultimately could lead to lasting physiological and psychological effects.

“We learned that devices that can be worn for a week or longer for continuous monitoring were needed for practical use in medical and sports applications,” says Professor Takao Someya at the University of Tokyo’s Graduate School of Engineering whose research group had previously developed an on-skin patch that measured oxygen in blood.

In the current research, the group developed an electrode constructed from nanoscale meshes containing a water-soluble polymer, polyvinyl alcohol (PVA), and a gold layer–materials considered safe and biologically compatible with the body. The device can be applied by spraying a tiny amount of water, which dissolves the PVA nanofibers and allows it to stick easily to the skin–it conformed seamlessly to curvilinear surfaces of human skin, such as sweat pores and the ridges of an index finger’s fingerprint pattern.

The researchers next conducted a skin patch test on 20 subjects and detected no inflammation on the participants’ skin after they had worn the device for a week. The group also evaluated the permeability, with water vapor, of the nanomesh conductor–along with those of other substrates like ultrathin plastic foil and a thin rubber sheet–and found that its porous mesh structure exhibited superior gas permeability compared to that of the other materials.

Furthermore, the scientists proved the device’s mechanical durability through repeated bending and stretching, exceeding 10,000 times, of a conductor attached on the forefinger; they also established its reliability as an electrode for electromyogram recordings when its readings of the electrical activity of muscles were comparable to those obtained through conventional gel electrodes.

“It will become possible to monitor patients’ vital signs without causing any stress or discomfort,” says Someya about the future implications of the team’s research. In addition to nursing care and medical applications, the new device promises to enable continuous, precise monitoring of athletes’ physiological signals and bodily motion without impeding their training or performance.

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

Inflammation-free, gas-permeable, lightweight, stretchable on-skin electronics with nanomeshes by Akihito Miyamoto, Sungwon Lee, Nawalage Florence Cooray, Sunghoon Lee, Mami Mori, Naoji Matsuhisa, Hanbit Jin, Leona Yoda, Tomoyuki Yokota, Akira Itoh, Masaki Sekino, Hiroshi Kawasaki, Tamotsu Ebihara, Masayuki Amagai, & Takao Someya. Nature Nanotechnology (2017) doi:10.1038/nnano.2017.125 Published online 17 July 2017

This paper is behind a paywall.

Shades of the Nokia Morph: a smartphone than conforms to your wrist

A March 16, 2017 news item on Nanowerk brought back some memories for me,

Some day, your smartphone might completely conform to your wrist, and when it does, it might be covered in pure gold, thanks to researchers at Missouri University of Science and Technology.

Nokia, a Finnish telecommunications company, was promoting its idea for a smartphone ‘and more’ that could be worn around your wrist in a concept called the Morph. It was introduced in 2008 at the Museum of Modern Art in New York City (see my March 20, 2010 posting for one of my last updates on this moribund project). Here’s Nokia’s Morph video (almost 6 mins.),

Getting back to the present day, here’s what the Missouri researchers are working on,

An example of a gold foil peeled from single crystal silicon. Reprinted with permission from Naveen Mahenderkar et al., Science [355]:[1203] (2017)

A March 16, 2017 Missouri University of Science and Technology news release, by Greg Katski, which originated the news item, provides more details about this Missouri version (Note: A link has been removed),

Writing in the March 17 [2017] issue of the journal Science, the S&T researchers say they have developed a way to “grow” thin layers of gold on single crystal wafers of silicon, remove the gold foils, and use them as substrates on which to grow other electronic materials. The research team’s discovery could revolutionize wearable or “flexible” technology research, greatly improving the versatility of such electronics in the future.

According to lead researcher Jay A. Switzer, the majority of research into wearable technology has been done using polymer substrates, or substrates made up of multiple crystals. “And then they put some typically organic semiconductor on there that ends up being flexible, but you lose the order that (silicon) has,” says Switzer, Donald L. Castleman/FCR Endowed Professor of Discovery in Chemistry at S&T.

Because the polymer substrates are made up of multiple crystals, they have what are called grain boundaries, says Switzer. These grain boundaries can greatly limit the performance of an electronic device.

“Say you’re making a solar cell or an LED,” he says. “In a semiconductor, you have electrons and you have holes, which are the opposite of electrons. They can combine at grain boundaries and give off heat. And then you end up losing the light that you get out of an LED, or the current or voltage that you might get out of a solar cell.”

Most electronics on the market are made of silicon because it’s “relatively cheap, but also highly ordered,” Switzer says.

“99.99 percent of electronics are made out of silicon, and there’s a reason – it works great,” he says. “It’s a single crystal, and the atoms are perfectly aligned. But, when you have a single crystal like that, typically, it’s not flexible.”

By starting with single crystal silicon and growing gold foils on it, Switzer is able to keep the high order of silicon on the foil. But because the foil is gold, it’s also highly durable and flexible.

“We bent it 4,000 times, and basically the resistance didn’t change,” he says.

The gold foils are also essentially transparent because they are so thin. According to Switzer, his team has peeled foils as thin as seven nanometers.

Switzer says the challenge his research team faced was not in growing gold on the single crystal silicon, but getting it to peel off as such a thin layer of foil. Gold typically bonds very well to silicon.

“So we came up with this trick where we could photo-electrochemically oxidize the silicon,” Switzer says. “And the gold just slides off.”

Photoelectrochemical oxidation is the process by which light enables a semiconductor material, in this case silicon, to promote a catalytic oxidation reaction.

Switzer says thousands of gold foils—or foils of any number of other metals—can be made from a single crystal wafer of silicon.

The research team’s discovery can be considered a “happy accident.” Switzer says they were looking for a cheap way to make single crystals when they discovered this process.

“This is something that I think a lot of people who are interested in working with highly ordered materials like single crystals would appreciate making really easily,” he says. “Besides making flexible devices, it’s just going to open up a field for anybody who wants to work with single crystals.”

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

Epitaxial lift-off of electrodeposited single-crystal gold foils for flexible electronics by Naveen K. Mahenderkar, Qingzhi Chen, Ying-Chau Liu, Alexander R. Duchild, Seth Hofheins, Eric Chason, Jay A. Switzer. Science  17 Mar 2017: Vol. 355, Issue 6330, pp. 1203-1206 DOI: 10.1126/science.aam5830

This paper is behind a paywall.

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.

‘Golden’ protein crystals

Yet another use for gold. From a March 14, 2017 news item on Nanowerk (Note: A link has been removed),

Scientists from the London Centre for Nanotechnology (LCN) have revealed how materials such as gold can help create protein crystals. The team hope their findings, published in the journal Scientific Reports (“Protein crystal nucleation in pores”), could aid the discovery of new medicines and treatments. The Lead author; Professor Naomi Chayen states that “Gold doesn’t react with proteins, due to its inert nature, which makes it an ideal material to create crystals”.

Image: Crystals of an antibody peptide complex related to AIDS research Courtesy: LCN

A March 14, 2017 (?) LCN press release, which originated the news item, expands on the theme,

Proteins are crucial to numerous functions in the body – yet scientists are still in the dark about what most of them look like. This is because the most powerful way of revealing the structure of proteins is to turn them into crystals, and then analyse these with X-rays. However, persuading proteins to turn into useful crystals is notoriously difficult. All crystals start from a conception stage when the first molecules come together; this is called nucleation. But reaching nucleation is often difficult as it requires a lot of energy – and many proteins simply can’t overcome this barrier. Scientists also struggle to create medicines that bind to particular proteins – for instance a protein involved in cancer formation, if they don’t know the protein’s structure.

“How can you target a protein if you have no idea what it looks like? It’s like recognising a face in a crowd – you need a picture,” explained Professor Naomi Chayen, lead author of the research.

Forcing molecules together with gold

One technique for allowing proteins to reach their nucleation point is to trap them in tiny holes. This forces the molecules together, which helps them overcome the energy barrier needed to trigger the first crystal. One material that scientists have found to be effective at growing crystals is gold. Creating many holes in the metal creates a substance called porous gold, which acts as a perfect environment for growing crystals, explained Professor Chayen: “Gold doesn’t react with proteins, due to its inert nature, which makes it an ideal material to create crystals. Creating holes in the metal enable it to act a bit like coral, with each hole providing an ideal environment to harbour crystals.”

Creating crystals

In the latest research, the team investigated the best size hole needed to create crystals. They found that a variety of different sized holes produced the highest quality crystals. Most holes were around 5-10nm, just slightly larger than the width of a human hair. Professor Chayen explained: “Imagine walking down a street with many potholes – some of the holes will be big enough for me to step out of, while some will be too small for my foot to fall into. “However, some will be the exact size of my foot, and will trap me in them. This is the same principle as having different pore sizes – it allows us to trap different size protein molecules, enabling them to form crystals.”

She added that the findings which give a simple explanation of why, and under what conditions porous materials can induce protein crystal nucleation may help scientists design porous materials that would produce the highest quality crystals.

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

Protein crystal nucleation in pores by Christo N. Nanev, Emmanuel Saridakis & Naomi E. Chayen. Scientific Reports 7, Article number: 35821 (2017) doi:10.1038/srep35821 Published online: 16 January 2017

This is an open access article.

Pure gold nanostructures

This Nov. 4, 2016 news item on ScienceDaily features another ‘alchemy’ story although this one is truer to the source material than some of the other stories,

The idea is reminiscent of the ancient alchemists’ attempts to create gold from worthless substances: Researchers have discovered a novel way to fabricate pure gold nanostructures using an additive direct-write lithography technique. An electron beam is used to turn an auriferous organic compound into pure gold. This new technique can now be used to create nanostructures, which are needed for many applications in electronics and sensor technology. Just like with a 3D-printer on the nanoscale, almost any arbitrary shape can be created.

Caption: Nanostructure made of gold. Credit: TU Wien

Caption: Nanostructure made of gold. Credit: TU Wien

A Nov. 3, 2016 Technical University of Vienna (Technische Universität Wien) press release (also so on EurekAlert), which originated the news item, expands on the theme,

“Gold is not only a noble metal of exceptional beauty, but also a highly desired material for functional nanostructures”, says Professor Heinz Wanzenböck from TU Wien. Especially patterned gold nanostructures are key enabling structures in plasmonic devices, for biosensors with immobilized antibodies and as electrical contacts. For decades the fabrication of pure gold nanostructures on non-planar surfaces as well as of 3-dimensional gold nanostructures has been the bottleneck. Up to now, only 2-dimensional gold nanostructures on planar surfaces were achievable by resist based lithography.

The new technology, developed at TU Wien, can now solve this problem. The principle is the local decomposition of a metalorganic precursor by the focused electron beam of an electron microscope. With extremely high precision, the electron beam can decompose the organic compound at exactly the right position, leaving behind a 3D-trail of solid gold.

The final obstacle was getting the material purity right, as the electron-induced decomposition of metalorganic precursors has typically yielded metals with high carbon contaminations. This last bottleneck on the road to custom-designed, pure gold nanostructures has now been overcome as described in the work on “Highly conductive and pure gold nanostructures grown by electron beam induced deposition” published in Scientific Reports.

While conventional gold deposition usually contains about 70 atomic % carbon and only 30 atomic % gold, the new approach developed by a research group lead by Dr. Heinz Wanzenboeck at TU Wien has allowed to fabricate pure gold structures by in-situ addition of an oxidizing agent during the gold deposition. “The whole community has been working hard for the last 10 years to directly deposit pure gold nanostructures”, says Heinz Wanzenböck. At last, the group’s expertise in engineering and chemical reactions paid off and direct deposition of pure gold was successful. “It’s a bit like discovering the legendary philosopher’s stone that turns common, ignoble material into gold” joked Wanzenboeck.

This deposited pure gold structure exhibits extremely low resistivity near that of bulk gold. Generally, a FEBID gold structure has a resistivity around 1-Ohm-cm which is about 1 million times worse than the resistivity of purest bulk gold. However, this specially enhanced FEBID process produces a resistivity of 8.8 micro-Ohm-cm which is only a factor 4 away from the bulk resistivity of purest gold (2.4 micro-Ohm-cm).

The authors of the paper Dr. Mostafa Moonir Shawrav and Dipl.Ing. Philipp Taus stated, “This highly conductive and pure gold structure will open a new door for novel nanoelectronic devices. For example, it will be easier to produce pure gold structures for nanoantennas and biomolecule immobilization which will change our everyday life”. Dr. Shawrav added “it is remarkable how a regular SEM (Scanning Electron Microscope) nowadays can deposit nanostructures compared to 20 years back when it was only a characterization device”. And with pure gold direct deposition available now, he expects nanodevices to be deposited directly and utilized in many different applications for technological revolution. Concluding, this work is a giant leap forward for 3D nano-printing of gold structures which will be the core part of nanoplasmonics and bioelectronics devices.

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

Highly conductive and pure gold nanostructures grown by electron beam induced deposition by Mostafa M. Shawrav, Philipp Taus, Heinz D. Wanzenboeck, M. Schinnerl, M. Stöger-Pollach, S. Schwarz, A. Steiger-Thirsfeld, & Emmerich Bertagnolli. Scientific Reports 6, Article number: 34003 (2016)  doi:10.1038/srep34003 Published online: 26 September 2016

This paper is open access.