Tag Archives: nanobeads

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.

A new lens (made from nanobeads) for seeing subwavelength images at visible frequencies

The image which illustrates the research is quite intriguing but I don’t think it makes much sense until you read about the research. From an Aug. 12, 2016 news item on ScienceDaily,

Nanobeads are all around us- and are, some might argue, used too frequently in everything from sun-screen to white paint, but a new ground-breaking application is revealing hidden worlds.

A paper in Science Advances provides proof of a new concept, using new solid 3D superlenses to break through the scale of things previously visible through a microscope.

Illustrating the strength of the new superlens, the scientists describe seeing for the first time, the actual information on the surface of a Blue Ray DVD. That shiny surface is not as smooth as we think. Current microscopes cannot see the grooves containing the data- but now even the data itself is revealed.

Now the image,

(a) Conceptual drawing of nanoparticle-based metamaterial solid immersion lens (mSIL) (b) Lab made mSIL (c) SEM image of 60 nm sized imaging sample (d) corresponding superlens imaging of the 60 nm samples by the developed mSIL. Courtesy: Bangor University

(a) Conceptual drawing of nanoparticle-based metamaterial solid immersion lens (mSIL) (b) Lab made mSIL (c) SEM image of 60 nm sized imaging sample (d) corresponding superlens imaging of the 60 nm samples by the developed mSIL. Credit: ©BangorUniversity Fudan University

An Aug. 13, 2016 Bangor University press release (also on EurekAlert with an Aug. 12, 2016 publication date), which originated the news item, describes the work in more detail,

Led by Dr Zengbo Wang at Bangor University UK and Prof Limin Wu at Fudan University, China, the team created minute droplet-like lens structures on the surface to be examined. These act as an additional lens to magnify the surface features previously invisible to a normal lens.

Made of millions of nanobeads, the spheres break up the light beam. Each bead refracts the light, acting as individual torch-like minute beam. It is the very small size of each beam of light which illuminate the surface, extending the resolving ability of the microscope to record-breaking levels. The new superlens adds 5x magnification on top of existing microscopes.

Extending the limit of classical microscope’s resolution has been the ‘El Dorado’ or ‘Holy Grail’ of microscopy for over a century. Physical laws of light make it impossible to view objects smaller than 200 nm – the smallest size of bacteria, using a normal microscope alone. However, superlenses have been the new goal since the turn of the millennium, with various labs and teams researching different models and materials.

“We’ve used high-index titanium dioxide (TiO2) nanoparticles as the building element of the lens. These nanoparticles are able to bend light to a higher degree than water. To explain, when putting a spoon into a cup of this material, if it were possible, you’d see a larger bend where you spoon enters the material than you would looking at the same spoon in a glass of water,” Dr Wang says.

Nanoparticles splitting single incident beam into multiple=Nanoparticles splitting single incident beam into multiple beams which provides optical super-resolution in imaging.“Each sphere bends the light to a high magnitude and splits the light beam, creating millions of individual beams of light. It is these tiny light beams which enable us to view previously unseen detail.”

Wang believes that the results will be easily replicable and that other labs will soon be adopting the technology and using it for themselves.

The advantages of the technology is that the material, titanium dioxide, is cheap and readily available, and rather than buying a new microscope, the lenses are applied to the material to be viewed, rather than to the microscope.

“We have already viewed details to a far greater level than was previously possible. The next challenge is to adapt the technology for use in biology and medicine. This would not require the current use of a combination of dyes and stains and laser light- which change the samples being viewed. The new lens will be used to see germs and viruses not previously visible.”

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

Three-dimensional all-dielectric metamaterial solid immersion lens for subwavelength imaging at visible frequencies by Wen Fan, Bing Yan, Zengbo Wang, and Limin Wu. Science Advances  12 Aug 2016: Vol. 2, no. 8, e1600901 DOI: 10.1126/sciadv.1600901

This paper is open access.