Tag Archives: gold

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.

The origins of gold and other precious metals

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 ,

RESEARCHERS HAVE SOLVED a 60-year-old mystery regarding the origin of the heaviest elements in nature, conveyed in the faint starlight from a distant dwarf galaxy.

Most of the chemical elements, composing everything from planets to paramecia, are forged by the nuclear furnaces in stars like the Sun. But the cosmic wellspring for a certain set of heavy, often valuable elements like gold, silver, lead and uranium, has long evaded scientists.

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.”

The Kavli Foundation recently spoke with three astrophysicists about how this discovery can unlock clues about galactic evolution as well as the abundances of certain elements on Earth we use for everything from jewelry-making to nuclear power generation. The participants were:

  • Alexander Ji – is a graduate student in physics at the Massachusetts Institute of Technology (MIT) and a member of the MIT Kavli Institute for Astrophysics and Space Research (MKI). He is lead author of a paper in Nature describing this discovery.
  • Anna Frebel – is the Silverman Family Career Development Assistant Professor in the Department of Physics at MIT and also a member of MKI. Frebel is Ji’s advisor and coauthored the Nature paper. Her work delves into the chemical and physical conditions of the early universe as conveyed by the oldest stars.
  • Enrico Ramirez-Ruiz – is a Professor of Astronomy and Astrophysics at the University of California, Santa Cruz. His research explores violent events in the universe, including the mergers of neutron stars and their role in generating r-process elements.

Here’s a link to and citation for Ji’s and Frebel’s paper about r-process elements in the stars,

R-process enrichment from a single event in an ancient dwarf galaxy by Alexander P. Ji, Anna Frebel, Anirudh Chiti, & Joshua D. Simon. Nature 531, 610–613 (31 March 2016) doi:10.1038/nature17425 Published online 21 March 2016

This paper is behind a paywall but you can read an edited transcript of the roundtable discussion on the Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements webpage (keep scrolling past the introductory text).

As for my side project, Steep (2) on gold nanoparticles, that’s still in the planning stages but if there’s a way to include this information, I’ll do it.

Gold nanoparticles and two different collective oscillations

An April 27, 2016 news item on phys.org describes research into gold nanoparticles and Surface Plasmon Resonance at Hokkaido University and the University of Tsukuba (Japan),

The research group of Professor Hiroaki Misawa of Research Institute for Electronic Science, Hokkaido University and Assistant Professor Atsushi Kubo of the Faculty of Pure and Applied Sciences, University of Tsukuba, have successfully observed the dephasing time of the two different types of collective motions of electrons generated on the surface of a gold nanoparticle for the first time in the world, by combining a laser that emits ultrashort light pulses with a photoemission electron microscope.

An April 26, 2016 Hokkaido University press release, which originated the news item, explains further,

When gold is reduced to the size in nanometer scale, its color is red instead of gold. When gold nanoparticles are exposed to light, the collective oscillations of electrons existing on the localized surface of the gold causes red light to be strongly absorbed and dispersed.

This phenomenon is called Surface Plasmon Resonance. The red color of stained glass is also a result of this phenomenon. Recently, gold nanoparticles have been widely used in various fields, such as application in pregnancy tests.

This collective oscillations of electrons on the surface of gold nanoparticles caused by light was considered to be a phenomenon that sustained only for an extremely short time, and difficult to measure due to this shortness.

Our research group developed a methodology to measure the dephasing time of the collective oscillations of electrons occurring on the surface of gold nanoparticles by combining a laser that emits ultrashort light pulses of a few femtoseconds (1 femtosecond: 1´10-15 seconds), and a photoemission electron microscope in high spatial resolution.

When measured by this technique, the different dephasing times of the two different collective oscillations, namely dipole and quadrupole surface plasmon modes, could be resolved and identified as 5 femtoseconds and 9 femtoseconds, respectively.

Research using gold nanoparticles as optical antennae to harvest light for photovoltaic cell and an artificial photosynthesis system that can split water to obtain hydrogen is progressing. The successful measurement of the dephasing time of the collective oscillations of electrons is considered to be a useful guideline in developing these systems.

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

Dissecting the Few-Femtosecond Dephasing Time of Dipole and Quadrupole Modes in Gold Nanoparticles Using Polarized Photoemission Electron Microscopy by Quan Sun†, Han Yu, Kosei Ueno, Atsushi Kubo, Yasutaka Matsuo, and Hiroaki Misawa. ACS Nano, 2016, 10 (3), pp 3835–3842 DOI: 10.1021/acsnano.6b00715Publication Date (Web): February 15, 2016

Copyright © 2016 American Chemical Society

This paper appears to be open access.

South Africa, energy, and nanotechnology

South African academics Nosipho Moloto, Associate Professor, Department of Chemistry, University of the Witwatersrand and Siyabonga P. Ngubane, Lecturer in Chemistry, University of the Witwatersrand have written a Feb. 17, 2016 article for The Conversation (also available on the South African Broadcasting Corporation website) about South Africa’s energy needs and its nanotechnology efforts (Note: Links have been removed),

Energy is an economic driver of both developed and developing countries. South Africa over the past few years has faced an energy crisis with rolling blackouts between 2008 and 2015. Part of the problem has been attributed to mismanagement by the state-owned utility company Eskom, particularly the shortcomings of maintenance plans on several plants.

But South Africa has two things going for it that could help it out of its current crisis. By developing a strong nanotechnology capability and applying this to its rich mineral reserves the country is well-placed to develop new energy technologies.

Nanotechnology has already shown that it has the potential to alleviate energy problems. …

It can also yield materials with new properties and the miniaturisation of devices. For example, since the discovery of graphene, a single atomic layer of graphite, several applications in biological engineering, electronics and composite materials have been identified. These include economic and efficient devices like solar cells and lithium ion secondary batteries.

Nanotechnology has seen an incredible increase in commercialisation. Nearly 10,000 patents have been filed by large corporations since its beginning in 1991. There are already a number of nanotechnology products and solutions on the market. Examples include Miller’s beer bottling composites, Armor’s N-Force line bulletproof vests and printed solar cells produced by Nanosolar – as well as Samsung’s nanotechnology television.

The advent of nanotechnology in South Africa began with the South African Nanotechnology Initiative in 2002. This was followed by the a [sic] national nanotechnology strategy in 2003.

The government has spent more than R450 million [Rand] in nanotechnology and nanosciences research since 2006. For example, two national innovation centres have been set up and funding has been made available for equipment. There has also been flagship funding.

The country could be globally competitive in this field due to the infancy of the technology. As such, there are plenty of opportunities to make novel discoveries in South Africa.

Mineral wealth

There is another major advantage South Africa has that could help diversify its energy supply. It has an abundance of mineral wealth with an estimated value of US$2.5 trillion. The country has the world’s largest reserves of manganese and platinum group metals. It also has massive reserves of gold, diamonds, chromite ore and vanadium.

Through beneficiation and nanotechnology these resources could be used to cater for the development of new energy technologies. Research in beneficiation of minerals for energy applications is gaining momentum. For example, Anglo American and the Department of Science and Technology have embarked on a partnership to convert hydrogen into electricity.

The Council for Scientific and Industrial research also aims to develop low cost lithium ion batteries and supercapacitors using locally mined manganese and titanium ores. There is collaborative researchto use minerals like gold to synthesize nanomaterials for application in photovoltaics.

The current photovoltaic market relies on importing solar cells or panels from Europe, Asia and the US for local assembly to produce arrays. South African UV index is one of the highest in the world which reduces the lifespan of solar panels. The key to a thriving and profitable photovoltaic sector therefore lies in local production and research and development to support the sector.

It’s worth reading the article in its entirety if you’re interested in a perspective on South Africa’s energy and nanotechnology efforts.

Not the same old gold: there’s a brand new phase

A Dec. 7, 2015 news item on ScienceDaily announces a new phase for gold has been identified,

A new and stable phase of gold with different physical and optical properties from those of conventional gold has been synthesized by Agency for Science, Technology and Research (A*STAR) researchers [1], Singapore, and promises to be useful for a wide range of applications, including plasmonics and catalysis.

Many materials exist in a variety of crystal structures, known as phases or polymorphs. These different phases have the same chemical composition but different physical structures, which give rise to different properties. For example, two well-known polymorphs of carbon, graphite and diamond, arranged differently, have radically different physical properties, despite being the same element.

Gold has been used for many purposes throughout history, including jewelry, electronics and catalysis. Until now it has always been produced in one phase ― a face-centered cubic structure in which atoms are located at the corners and the center of each face of the constituent cubes.

Now, Lin Wu and colleagues at the Institute of the A*STAR Institute of High Performance Computing have modeled the optical and plasmonic properties of nanoscale ribbons of a new phase of gold — the 4H hexagonal phase (…) — produced and characterized by collaborators at other institutes in Singapore, China and the USA. The team synthesized nanoribbons of the new phase by simply heating the gold (III) chloride hydrate (HAuCl4) with a mixture of three organic solvents and then centrifuging and washing the product. This gave a high yield of about 60 per cent.

Here’s an image supplied by the researchers,

The atomic structure of the new phase of gold synthesized by A*STAR researchers. Reproduced from Ref. 1 and licensed under CC BY 4.0 © 2015 Z. Fan et al.

The atomic structure of the new phase of gold synthesized by A*STAR researchers. Reproduced from Ref. 1 and licensed under CC BY 4.0 © 2015 Z. Fan et al.

A Dec. 2, 2015 A*STAR news release, which originated the news item, provides more details,

The researchers also produced 4H hexagonal phases of the precious metals silver, platinum and palladium by growing them on top of the gold 4H hexagonal phase.

The cubic phase looks identical when viewed front on, from one side or from above. In contrast, the new 4H hexagonal phase lacks this cubic symmetry and hence varies more with direction — a property known as anisotropy. This lower symmetry gives it more directionally varying optical properties, which may make it useful for plasmonic applications. “Our finding is not only is of fundamental interest, but it also provides a new avenue for unconventional applications of plasmonic devices,” says Wu.

The team is keen to explore the potential of their new phase. “In the future, we hope to leverage the unconventional anisotropic properties of the new gold phase and design new devices with excellent performances not achievable with conventional face-centered-cubic gold,” says Wu. The synthesis method also gives rise to the potential for new strategies for controlling the crystalline phase of nanomaterials made from the noble metals.

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

Stabilization of 4H hexagonal phase in gold nanoribbons by Zhanxi Fan, Michel Bosman, Xiao Huang, Ding Huang, Yi Yu, Khuong P. Ong, Yuriy A. Akimov, Lin Wu, Bing Li, Jumiati Wu, Ying Huang, Qing Liu, Ching Eng Png, Chee Lip Gan, Peidong Yang & Hua Zhang. Nature Communications 6, Article number: 7684 doi:10.1038/ncomms8684 Published 28 July 2015

This is an open access paper.

Combining gold and palladium for catalytic and plasmonic octopods

Hopefully I did not the change meaning when I made the title for this piece more succinct. In any event, this research comes from the always prolific Rice University in Texas, US (from a Nov. 30, 2015 news item on Nanotechnology Now),

Catalysts are substances that speed up chemical reactions and are essential to many industries, including petroleum, food processing and pharmaceuticals. Common catalysts include palladium and platinum, both found in cars’ catalytic converters. Plasmons are waves of electrons that oscillate in particles, usually metallic, when excited by light. Plasmonic metals like gold and silver can be used as sensors in biological applications and for chemical detection, among others.

Plasmonic materials are not the best catalysts, and catalysts are typically very poor for plasmonics. But combining them in the right way shows promise for industrial and scientific applications, said Emilie Ringe, a Rice assistant professor of materials science and nanoengineering and of chemistry who led the study that appears in Scientific Reports.

“Plasmonic particles are magnets for light,” said Ringe, who worked on the project with colleagues in the U.S., the United Kingdom and Germany. “They couple with light and create big electric fields that can drive chemical processes. By combining these electric fields with a catalytic surface, we could further push chemical reactions. That’s why we’re studying how palladium and gold can be incorporated together.”

The researchers created eight-armed specks of gold and coated them with a gold-palladium alloy. The octopods proved to be efficient catalysts and sensors.

A Nov. 30, 2015 Rice University news release (also on EurekAlert), which originated the news item, expands on the theme,

“If you simply mix gold and palladium, you may end up with a bad plasmonic material and a pretty bad catalyst, because palladium does not attract light like gold does,” Ringe said. “But our particles have gold cores with palladium at the tips, so they retain their plasmonic properties and the surfaces are catalytic.”

Just as important, Ringe said, the team established characterization techniques that will allow scientists to tune application-specific alloys that report on their catalytic activity in real time.

The researchers analyzed octopods with a variety of instruments, including Rice’s new Titan Themis microscope, one of the most powerful electron microscopes in the nation. “We confirmed that even though we put palladium on a particle, it’s still capable of doing everything that a similar gold shape would do. That’s really a big deal,” she said.

“If you shine a light on these nanoparticles, it creates strong electric fields. Those fields enhance the catalysis, but they also report on the catalysis and the molecules present at the surface of the particles,” Ringe said.

The researchers used electron energy loss spectroscopy, cathodoluminescence and energy dispersive X-ray spectroscopy to make 3-D maps of the electric fields produced by exciting the plasmons. They found that strong fields were produced at the palladium-rich tips, where plasmons were the least likely to be excited.

Ringe expects further research will produce multifunctional nanoparticles in a variety of shapes that can be greatly refined for applications. Her own Rice lab is working on a metal catalyst to turn inert petroleum derivatives into backbone molecules for novel drugs.

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

Resonances of nanoparticles with poor plasmonic metal tips by Emilie Ringe, Christopher J. DeSantis, Sean M. Collins, Martial Duchamp, Rafal E. Dunin-Borkowski, Sara E. Skrabalak, & Paul A. Midgley.  Scientific Reports 5, Article number: 17431 (2015)  doi:10.1038/srep17431 Published online: 30 November 2015

This is an open access paper,

Solid gold smoke?

Aerogels seem to enchant even scientists who sometimes call it ‘solid smoke’ (my Aug. 20, 2012 posting). This latest aerogel is made of gold according to a Nov. 25, 2015 news item on Nanowerk,

 A nugget of real 20 carats gold, so light that it does not sink in a cappuccino, floating instead on the milk foam – what sounds unbelievable has actually been accomplished by researchers from ETH Zurich. Scientists led by Raffaele Mezzenga, Professor of Food and Soft Materials, have produced a new kind of foam out of gold, a three-dimensional mesh of gold that consists mostly of pores. It is the lightest gold nugget ever created. “The so-called aerogel is a thousand times lighter than conventional gold alloys. It is lighter than water and almost as light as air,” says Mezzenga.

A Nov. 25, 2015 ETH Zurich press release (also on EurekAlert), which originated the news item, provides more information about the ‘gold smoke’,

The new gold form can hardly be differentiated from conventional gold with the naked eye – the aerogel even has a metallic shine. But in contrast to its conventional form, it is soft and malleable by hand. It consists of 98 parts air and only two parts of solid material. Of this solid material, more than four-fifths are gold and less than one-fifth is milk protein fibrils. This corresponds to around 20 carat gold.

Here’s what it looks like,

Caption: Even when it seems unbelievable: these are genuine photographs, in which nothing has been faked. E.g. the 20 carats gold foam is lighter than milk foam. Credit: Gustav Nyström and Raffaele Mezzenga / (copyright) ETH Zurich

Caption: Even when it seems unbelievable: these are genuine photographs, in which nothing has been faked. E.g. the 20 carats gold foam is lighter than milk foam.
Credit: Gustav Nyström and Raffaele Mezzenga / (copyright) ETH Zurich

The press release provides more technical details,

The scientists created the porous material by first heating milk proteins to produce nanometre-fine protein fibres, so-called amyloid fibrils, which they then placed in a solution of gold salt. The protein fibres interlaced themselves into a basic structure along which the gold simultaneously crystallised into small particles. This resulted in a gel-like gold fibre network.

“One of the big challenges was how to dry this fine network without destroying it,” explains Gustav Nyström, postdoc in Mezzenga’s group and first author of the corresponding study in the journal Advanced Materials. As air drying could damage the fine gold structure, the scientists opted for a gentle and laborious drying process using carbon dioxide. They did so in an interdisciplinary effort assisted by researchers in the group of Marco Mazzotti, Professor of Process Engineering.

Dark-red gold

The method chosen, in which the gold particles are crystallised directly during manufacture of the aerogel protein structure (and not, for example, added to an existing scaffold) is new. The method’s biggest advantage is that it makes it easy to obtain a homogeneous gold aerogel, perfectly mimicking gold alloys.

The manufacturing technique also offers scientists numerous possibilities to deliberately influence the properties of gold in a simple manner. ” The optical properties of gold depend strongly on the size and shape of the gold particles,” says Nyström. “Therefore we can even change the colour of the material. When we change the reaction conditions in order that the gold doesn’t crystallise into microparticles but rather smaller nanoparticles, it results in a dark-red gold.” By this means, the scientists can influence not only the colour, but also other optical properties such as absorption and reflection.

The new material could be used in many of the applications where gold is currently being used, says Mezzenga. The substance’s properties, including its lighter weight, smaller material requirement and porous structure, have their advantages. Applications in watches and jewellery are only one possibility. Another application demonstrated by the scientists is chemical catalysis: since the highly porous material has a huge surface, chemical reactions that depend on the presence of gold can be run in a very efficient manner. The material could also be used in applications where light is absorbed or reflected. Finally, the scientists have also shown how it becomes possible to manufacture pressure sensors with it. “At normal atmospheric pressure the individual gold particles in the material do not touch, and the gold aerogel does not conduct electricity,” explains Mezzenga. “But when the pressure is increased, the material gets compressed and the particles begin to touch, making the material conductive.”

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

Amyloid Templated Gold Aerogels by Gustav Nyström, Maria P. Fernandez-Ronco, Sreenath Bolisetty, Marco Mazzotti, Raffaele Mezzenaga. Advanced Materials DOI: 10.1002/adma.201503465 First published: 23 November 2015

This paper is behind a paywall.

Gold, acetic acid, and proton shuttles

I think the information has been taken from Russian to English by a machine translator, as well, I’m not a chemist, so please bear with my interpretation. It seems that Russian researchers have determined why gold, inert at the macroscale, is a good catalyst at the nanoscale. From a July 28, 2015 news item on Azonano,

Being found mostly in the native state, gold is one of the oldest elements known to man. The affection to gold was determined by it’s unusual properties – heft, shine and ability to withstand oxidation and corrosion.

The combination of properties determined gold use in the jewelry and as a coinage metal. The ancient alchemists working with gold were struggled by utmost chemical resistance of this element – it did not react with concentrated acids or alkali solutions even at high temperatures. Actually, it is the chemical inertness that makes gold to appear in a native form and not as a part of a mineral.

Later analysis established that gold compounds can not only compete with traditional nickel and palladium-based catalysts in the common reactions, but to surpass them. Besides that, gold compounds often demonstrated principally novel types of reactivity compared to well-established catalysts. This allowed chemists to discover a bunch of new chemical reactions and predetermined a fascinating boom in gold catalysis that we have observed in the recent years.

A July 24, 2015 Institute of Organic Chemistry, Russian Academy of Sciences press release on EurekAlert, which also originated the news item, reveals more about the study,

Professor Ananikov and co-workers introduced gold into well-known catalytic system which led to dramatic change of the reactivity and furnished the formation of novel gold-containing complexes. The complexes appeared to be air stable and were isolated in the individual state. A single crystal X-Ray diffraction study ascertained the existence of unique structural motif in the molecule, which can not be explained within conventional mechanistic framework.

The study was carried out using both theoretical and experimental approaches. Dedicated labeling of the reagents allowed observation of molecular re-organizations. Variation of reaction conditions helped to estimate key factors governing the discovered transformation. In addition, computational study of the reaction provided the models of certain intermediate steps, which were invisible for experimental investigation. The theoretical data obtained was in excellent agreement with experiment, proposing the reaction mechanism, where a molecule of acetic acid serves as a proton shuttle, transferring the hydrogen atom between the reaction centers.

The belief of gold inactivity towards chemical transformations resulted in the fact, that organometallic chemistry of gold was developed significantly later compared to other coinage metals (like silver, nickel or copper). Today, our goal is to “introduce gold catalysis as a valuable practical tool in fine organic chemistry, competitive with other transition metal catalysts”, says Prof. Ananikov.

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

Carboxylic Group-Assisted Proton Transfer in Gold-Mediated Thiolation of Alkynes by Sergey S. Zalesskiy, Victor N. Khrustalev, Alexandr Yu. Kostukovich, and Valentine P. Ananikov. Organometallics, Article ASAP DOI: 10.1021/acs.organomet.5b00210 Publication Date (Web): July 22, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

At a distance of less than a light wave, nanocamera takes pictures

A July 17, 2014 University of Illinois College of Engineering news release (also on EurekAlert) features a research breakthrough,

How is it possible to record optically encoded information for distances smaller than the wavelength of light?

Researchers at the University of Illinois at Urbana-Champaign have demonstrated that an array of novel gold, pillar-bowtie nanoantennas (pBNAs) can be used like traditional photographic film to record light for distances that are much smaller than the wavelength of light (for example, distances less than ~600 nm for red light). A standard optical microscope acts as a “nanocamera” whereas the pBNAs are the analogous film.

Here’s an image the researchers have provided to illustrate their work,

We demonstrate the plasmonic equivalent of photographic film for recording optical intensity in the near field. The plasmonic structure is based on gold bowtie nanoantenna arrays fabricated on SiO2 pillars. We show that it can be employed for direct laser writing of image data or recording the polarization structure of optical vector beams.[downloaded from http://pubs.acs.org/doi/abs/10.1021/nl501788a]

We demonstrate the plasmonic equivalent of photographic film for recording optical intensity in the near field. The plasmonic structure is based on gold bowtie nanoantenna arrays fabricated on SiO2 pillars. We show that it can be employed for direct laser writing of image data or recording the polarization structure of optical vector beams.[downloaded from http://pubs.acs.org/doi/abs/10.1021/nl501788a]

The news release describes the technique,

“Unlike conventional photographic film, the effect (writing and curing) is seen in real time,” explained Kimani Toussaint, an associate professor of mechanical science and engineering, who led the research. “We have demonstrated that this multifunctional plasmonic film can be used to create optofluidic channels without walls. Because simple diode lasers and low-input power densities are sufficient to record near-field optical information in the pBNAs, this increases the potential for optical data storage applications using off-the-shelf, low-cost, read-write laser systems.”

“Particle manipulation is the proof-of-principle application,” stated Brian Roxworthy, first author of the group’s paper, “Multifunctional Plasmonic Film for Recording Near-Field Optical Intensity,” published in the journal, Nano Letters. “Specifically, the trajectory of trapped particles in solution is controlled by the pattern written into the pBNAs. This is equivalent to creating channels on the surface for particle guiding except that these channels do not have physical walls (in contrast to those optofluidics systems where physical channels are fabricated in materials such as PDMS).”

To prove their findings, the team demonstrated various written patterns—including the University’s “Block I” logo and brief animation of a stick figure walking—that were either holographically transferred to the pBNAs or laser-written using steering mirrors (see video).

The news release concludes with,

“We wanted to show the analogy between what we have made and traditional photographic film,” Toussaint added. “There’s a certain cool factor with this. However, we know that we’re just scratching the surface since the use of plasmonic film for data storage at very small scales is just one application. Our pBNAs allow us to do so much more, which we’re currently exploring.”

The researchers noted that the fundamental bit size is currently set by the spacing of the antennas at 425-nm. However, the pixel density of the film can be straightforwardly reduced by fabricating smaller array spacing and a smaller antenna size, as well as using a more tightly focusing lens for recording.

“For a standard Blu-ray/DVD disc size, that amounts to a total of 28.6 gigabites per disk,” Roxworthy added. “With modifications to array spacing and antenna features, it’s feasible that this value can be scaled to greater than 75 gigabites per disk. Not to mention, it can be used for other exciting photonic applications, such as lab-on-chip nanotweezers or sensing.”

“In our new technique, we use controlled heating via laser illumination of the nanoantennas to change the plasmonic response instantaneously, which shows an innovative but easy way to fabricate spatially changing plasmonic structures and thus opens a new avenue in the field of nanotech-based biomedical technologies and nano optics,”  said Abdul Bhuiya, a co-author and member of the research team.

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

Multifunctional Plasmonic Film for Recording Near-Field Optical Intensity by Brian J. Roxworthy, Abdul M. Bhuiya, V. V. G. Krishna Inavalli, Hao Chen, and Kimani C. Toussaint , Jr. Nano Lett., Article ASAP DOI: 10.1021/nl501788a Publication Date (Web): July 14, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.

You probably can’t poison yourself by eating too many nanoparticles

Researchers, Ingrid Bergin in the Unit for Laboratory Animal Medicine, at the University of Michigan in Ann Arbor and Frank Witzmann in the Department of Cellular and Integrative Physiology, at Indiana University School of Medicine, in Indianapolis, have stated that ingesting food and beverage (translated by me from the more scientific description) with nanoparticles (at today’s current levels) is unlikely to prove toxic. A June 26, 2013 Inderscience news release on EurekAlert describes the researchers’ research and their conclusions,

Writing in a forthcoming issue of the International Journal of Biomedical Nanoscience and Nanotechnology, researchers have compared existing laboratory and experimental animal studies pertaining to the toxicity of nanoparticles most likely to be intentionally or accidentally ingested. Based on their review, the researchers determined ingestion of nanoparticles at likely exposure levels is unlikely to cause health problems, at least with respect to acute toxicity. Furthermore, in vitro laboratory testing, which often shows toxicity at a cellular level, does not correspond well with in vivo testing, which tends to show less adverse effects.

Ingrid Bergin in the Unit for Laboratory Animal Medicine, at the University of Michigan in Ann Arbor and Frank Witzmann in the Department of Cellular and Integrative Physiology, at Indiana University School of Medicine, in Indianapolis, explain that the use of particles that are in the nano size range (from 1 billionth to 100 billionths of a meter in diameter, 1-100 nm, other thereabouts) are finding applications in consumer products and medicine. These include particles such as nano-silver, which is increasingly used in consumer products and dietary supplements for its purported antimicrobial properties. Nanoparticles can have some intriguing and useful properties because they do not necessarily behave in the same chemical and physical ways as non-nanoparticle versions of the same material.

Nanoparticles are now used as natural flavor enhancers in the form of liposomes and related materials, food pigments and in some so-called “health supplements”. They are also used in antibacterial toothbrushes coated with silver nanoparticles, for instance in food and drink containers and in hygienic infant feeding equipment. They are also used to carry pharmaceuticals to specific disease sites in the body to reduce side effects. Nanoparticles actually encompass a very wide range of materials from pure metals and alloys, to metal oxide nanoparticles, and carbon-based and plastic nanoparticles. Because of their increasing utilization in consumer products, there has been concern over whether these small scale materials could have unique toxicity effects when compared to more traditional versions of the same materials.

Difficulties in assessing the health risks of nanoparticles include the fact that particles of differing materials and shapes can have different properties. Furthermore, the route of exposure (e.g. ingestion vs. inhalation) affects the likelihood of toxicity. The U.S. researchers evaluated the current literature specifically with respect to toxicity of ingested nanoparticles. They point out that, in addition to intentional ingestion as with dietary supplements, unintentional ingestion can occur due to nanoparticle presence in water or as a breakdown product from coated consumer goods. Inhaled nanoparticles also represent an ingestion hazard since they are coughed up, swallowed, and eliminated through the intestinal tract.

Based on their review, the team concludes that, “Ingested nanoparticles appear unlikely to have acute or severe toxic effects at typical levels of exposure.” Nevertheless, they add that the current literature is inadequate to assess whether nanoparticles can accumulate in tissues and have long-term effects or whether they might cause subtle alterations in gut microbial populations. The researchers stress that better methods are needed for correlating particle concentrations used for cell-based assessment of toxicity with the actual likely exposure levels to body cells. Such methods may lead to better predictive value for laboratory in vitro testing, which currently over-predicts toxicity of ingested nanoparticles as compared to in vivo testing.

The researchers focused specifically on ingestion via the gastrointestinal tract which I take to mean that they focused largely on nanoparticles in food (eaten) and liquid (swallowed).

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

Nanoparticle toxicity by the gastrointestinal route: evidence and knowledge gaps by Ingrid L. Bergin; Frank A. Witzmann.  Int. J. of Biomedical Nanoscience and Nanotechnology, 2013 Vol.3, No.1/2, pp.163 – 210.  DOI: 10.1504/IJBNN.2013.054515

I think the abstract further helps to understand the research focus,

The increasing interest in nanoparticles for advanced technologies, consumer products, and biomedical applications has led to great excitement about potential benefits but also concern over the potential for adverse human health effects. The gastrointestinal tract represents a likely route of entry for many nanomaterials, both directly through intentional ingestion or indirectly via nanoparticle dissolution from food containers or by secondary ingestion of inhaled particles. Additionally, increased utilisation of nanoparticles may lead to increased environmental contamination and unintentional ingestion via water, food animals, or fish. The gastrointestinal tract is a site of complex, symbiotic interactions between host cells and the resident microbiome. Accordingly, evaluation of nanoparticles must take into consideration not only absorption and extraintestinal organ accumulation but also the potential for altered gut microbes and the effects of this perturbation on the host. The existing literature was evaluated for evidence of toxicity based on these considerations. Focus was placed on three categories of nanomaterials: nanometals and metal oxides, carbon-based nanoparticles, and polymer/dendrimers with emphasis on those particles of greatest relevance to gastrointestinal exposures.

The article is behind a paywall.

I last mentioned Frank Witzmann here in a May 8, 2013 posting titled, US multicenter (Nano GO Consortium) study of engineered nanomaterial toxicology.