Tag Archives: Naomi Halas

Shining a light on flurocarbon bonds and robotic ‘soft’ matter research

Both of these news bits are concerned with light for one reason or another.

Rice University (Texas, US) and breaking fluorocarbon bonds

The secret to breaking fluorocarbon bonds is light according to a June 22, 2020 news item on Nanowerk,

Rice University engineers have created a light-powered catalyst that can break the strong chemical bonds in fluorocarbons, a group of synthetic materials that includes persistent environmental pollutants.

A June 22, 2020 Rice University news release (also on EurekAlert), which originated the news item, describes the work in greater detail,

In a study published this month in Nature Catalysis, Rice nanophotonics pioneer Naomi Halas and collaborators at the University of California, Santa Barbara (UCSB) and Princeton University showed that tiny spheres of aluminum dotted with specks of palladium could break carbon-fluorine (C-F) bonds via a catalytic process known as hydrodefluorination in which a fluorine atom is replaced by an atom of hydrogen.

The strength and stability of C-F bonds are behind some of the 20th century’s most recognizable chemical brands, including Teflon, Freon and Scotchgard. But the strength of those bonds can be problematic when fluorocarbons get into the air, soil and water. Chlorofluorocarbons, or CFCs, for example, were banned by international treaty in the 1980s after they were found to be destroying Earth’s protective ozone layer, and other fluorocarbons were on the list of “forever chemicals” targeted by a 2001 treaty.

“The hardest part about remediating any of the fluorine-containing compounds is breaking the C-F bond; it requires a lot of energy,” said Halas, an engineer and chemist whose Laboratory for Nanophotonics (LANP) specializes in creating and studying nanoparticles that interact with light.

Over the past five years, Halas and colleagues have pioneered methods for making “antenna-reactor” catalysts that spur or speed up chemical reactions. While catalysts are widely used in industry, they are typically used in energy-intensive processes that require high temperature, high pressure or both. For example, a mesh of catalytic material is inserted into a high-pressure vessel at a chemical plant, and natural gas or another fossil fuel is burned to heat the gas or liquid that’s flowed through the mesh. LANP’s antenna-reactors dramatically improve energy efficiency by capturing light energy and inserting it directly at the point of the catalytic reaction.

In the Nature Catalysis study, the energy-capturing antenna is an aluminum particle smaller than a living cell, and the reactors are islands of palladium scattered across the aluminum surface. The energy-saving feature of antenna-reactor catalysts is perhaps best illustrated by another of Halas’ previous successes: solar steam. In 2012, her team showed its energy-harvesting particles could instantly vaporize water molecules near their surface, meaning Halas and colleagues could make steam without boiling water. To drive home the point, they showed they could make steam from ice-cold water.

The antenna-reactor catalyst design allows Halas’ team to mix and match metals that are best suited for capturing light and catalyzing reactions in a particular context. The work is part of the green chemistry movement toward cleaner, more efficient chemical processes, and LANP has previously demonstrated catalysts for producing ethylene and syngas and for splitting ammonia to produce hydrogen fuel.

Study lead author Hossein Robatjazi, a Beckman Postdoctoral Fellow at UCSB who earned his Ph.D. from Rice in 2019, conducted the bulk of the research during his graduate studies in Halas’ lab. He said the project also shows the importance of interdisciplinary collaboration.

“I finished the experiments last year, but our experimental results had some interesting features, changes to the reaction kinetics under illumination, that raised an important but interesting question: What role does light play to promote the C-F breaking chemistry?” he said.

The answers came after Robatjazi arrived for his postdoctoral experience at UCSB. He was tasked with developing a microkinetics model, and a combination of insights from the model and from theoretical calculations performed by collaborators at Princeton helped explain the puzzling results.

“With this model, we used the perspective from surface science in traditional catalysis to uniquely link the experimental results to changes to the reaction pathway and reactivity under the light,” he said.

The demonstration experiments on fluoromethane could be just the beginning for the C-F breaking catalyst.

“This general reaction may be useful for remediating many other types of fluorinated molecules,” Halas said.

Caption: An artist’s illustration of the light-activated antenna-reactor catalyst Rice University engineers designed to break carbon-fluorine bonds in fluorocarbons. The aluminum portion of the particle (white and pink) captures energy from light (green), activating islands of palladium catalysts (red). In the inset, fluoromethane molecules (top) comprised of one carbon atom (black), three hydrogen atoms (grey) and one fluorine atom (light blue) react with deuterium (yellow) molecules near the palladium surface (black), cleaving the carbon-fluorine bond to produce deuterium fluoride (right) and monodeuterated methane (bottom). Credit: H. Robatjazi/Rice University

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

Plasmon-driven carbon–fluorine (C(sp3)–F) bond activation with mechanistic insights into hot-carrier-mediated pathways by Hossein Robatjazi, Junwei Lucas Bao, Ming Zhang, Linan Zhou, Phillip Christopher, Emily A. Carter, Peter Nordlander & Naomi J. Halas. Nature Catalysis (2020) DOI: https://doi.org/10.1038/s41929-020-0466-5 Published: 08 June 2020

This paper is behind a paywall.

Northwestern University (Illinois, US) brings soft robots to ‘life’

This June 22, 2020 news item on ScienceDaily reveals how scientists are getting soft robots to mimic living creatures,

Northwestern University researchers have developed a family of soft materials that imitates living creatures.

When hit with light, the film-thin materials come alive — bending, rotating and even crawling on surfaces.

A June 22, 2020 Northwestern University news release (also on EurekAlert) by Amanda Morris, which originated the news item, delves further into the details,

Called “robotic soft matter by the Northwestern team,” the materials move without complex hardware, hydraulics or electricity. The researchers believe the lifelike materials could carry out many tasks, with potential applications in energy, environmental remediation and advanced medicine.

“We live in an era in which increasingly smarter devices are constantly being developed to help us manage our everyday lives,” said Northwestern’s Samuel I. Stupp, who led the experimental studies. “The next frontier is in the development of new science that will bring inert materials to life for our benefit — by designing them to acquire capabilities of living creatures.”

The research will be published on June 22 [2020] in the journal Nature Materials.

Stupp is the Board of Trustees Professor of Materials Science and Engineering, Chemistry, Medicine and Biomedical Engineering at Northwestern and director of the Simpson Querrey Institute He has appointments in the McCormick School of Engineering, Weinberg College of Arts and Sciences and Feinberg School of Medicine. George Schatz, the Charles E. and Emma H. Morrison Professor of Chemistry in Weinberg, led computer simulations of the materials’ lifelike behaviors. Postdoctoral fellow Chuang Li and graduate student Aysenur Iscen, from the Stupp and Schatz laboratories, respectively, are co-first authors of the paper.

Although the moving material seems miraculous, sophisticated science is at play. Its structure comprises nanoscale peptide assemblies that drain water molecules out of the material. An expert in materials chemistry, Stupp linked the peptide arrays to polymer networks designed to be chemically responsive to blue light.

When light hits the material, the network chemically shifts from hydrophilic (attracts water) to hydrophobic (resists water). As the material expels the water through its peptide “pipes,” it contracts — and comes to life. When the light is turned off, water re-enters the material, which expands as it reverts to a hydrophilic structure.

This is reminiscent of the reversible contraction of muscles, which inspired Stupp and his team to design the new materials.

“From biological systems, we learned that the magic of muscles is based on the connection between assemblies of small proteins and giant protein polymers that expand and contract,” Stupp said. “Muscles do this using a chemical fuel rather than light to generate mechanical energy.”

For Northwestern’s bio-inspired material, localized light can trigger directional motion. In other words, bending can occur in different directions, depending on where the light is located. And changing the direction of the light also can force the object to turn as it crawls on a surface.

Stupp and his team believe there are endless possible applications for this new family of materials. With the ability to be designed in different shapes, the materials could play a role in a variety of tasks, ranging from environmental clean-up to brain surgery.

“These materials could augment the function of soft robots needed to pick up fragile objects and then release them in a precise location,” he said. “In medicine, for example, soft materials with ‘living’ characteristics could bend or change shape to retrieve blood clots in the brain after a stroke. They also could swim to clean water supplies and sea water or even undertake healing tasks to repair defects in batteries, membranes and chemical reactors.”

Fascinating, eh? No batteries, no power source, just light to power movement. For the curious, here’s a link to and a citation for the paper,

Supramolecular–covalent hybrid polymers for light-activated mechanical actuation by Chuang Li, Aysenur Iscen, Hiroaki Sai, Kohei Sato, Nicholas A. Sather, Stacey M. Chin, Zaida Álvarez, Liam C. Palmer, George C. Schatz & Samuel I. Stupp. Nature Materials (2020) DOI: https://doi.org/10.1038/s41563-020-0707-7 Published: 22 June 2020

This paper is behind a paywall.

Probing the physical limits of plasmons in organic molecules with fewer than 50 atoms

A Sept. 5, 2018  news item on ScienceDaily introduces the work,

Rice University [Texas, US] researchers are probing the physical limits of excited electronic states called plasmons by studying them in organic molecules with fewer than 50 atoms.

A Sept. 4, 2018 Rice University news release (also on EurekAlert published on Sept. 5, 2018), which originated the news item, explains what plasmons are and why this research is being undertaken,

Plasmons are oscillations in the plasma of free electrons that constantly swirl across the surface of conductive materials like metals. In some nanomaterials, a specific color of light can resonate with the plasma and cause the electrons inside it to lose their individual identities and move as one, in rhythmic waves. Rice’s Laboratory for Nanophotonics (LANP) has pioneered a growing list of plasmonic technologies for applications as diverse as color-changing glass, molecular sensing, cancer diagnosis and treatment, optoelectronics, solar energy collection and photocatalysis.

Reporting online in the Proceedings of the National Academy of Sciences, LANP scientists detailed the results of a two-year experimental and theoretical study of plasmons in three different polycyclic aromatic hydrocarbons (PAHs). Unlike the plasmons in relatively large metal nanoparticles, which can typically be described with classical electromagnetic theory like Maxwell’s [James Clerk Maxwell] equations, the paucity of atoms in the PAHs produces plasmons that can only be understood in terms of quantum mechanics, said study co-author and co-designer Naomi Halas, the director of LANP and the lead researcher on the project.

“These PAHs are essentially scraps of graphene that contain five or six fused benzene rings surrounded by a perimeter of hydrogen atoms,” Halas said. “There are so few atoms in each that adding or removing even a single electron dramatically changes their electronic behavior.”

Halas’ team had experimentally verified the existence of molecular plasmons in several previous studies. But an investigation that combined side by side theoretical and experimental perspectives was needed, said study co-author Luca Bursi, a postdoctoral research associate and theoretical physicist in the research group of study co-designer and co-author Peter Nordlander.

“Molecular excitations are a ubiquity in nature and very well studied, especially for neutral PAHs, which have been considered as the standard of non-plasmonic excitations in the past,” Bursi said. “Given how much is already known about PAHs, they were an ideal choice for further investigation of the properties of plasmonic excitations in systems as small as actual molecules, which represent a frontier of plasmonics.”

Lead co-author Kyle Chapkin, a Ph.D. student in applied physics in the Halas research group, said, “Molecular plasmonics is a new area at the interface between plasmonics and molecular chemistry, which is rapidly evolving. When plasmonics reach the molecular scale, we lose any sharp distinction of what constitutes a plasmon and what doesn’t. We need to find a new rationale to explain this regime, which was one of the main motivations for this study.”

In their native state, the PAHs that were studied — anthanthrene, benzo[ghi]perylene and perylene — are charge-neutral and cannot be excited into a plasmonic state by the visible wavelengths of light used in Chapkin’s experiments. In their anionic form, the molecules contain an additional electron, which alters their “ground state” and makes them plasmonically active in the visible spectrum. By exciting both the native and anionic forms of the molecules and comparing precisely how they behaved as they relaxed back to their ground states, Chapkin and Bursi built a solid case that the anionic forms do support molecular plasmons in the visible spectrum.

The key, Chapkin said, was identifying a number of similarities between the behavior of known plasmonic particles and the anionic PAHs. By matching both the timescales and modes for relaxation behaviors, the LANP team built up a picture of a characteristic dynamics of low-energy plasmonic excitations in the anionic PAHs.

“In molecules, all excitations are molecular excitations, but select excited states show some characteristics that allow us to draw a parallel with the well-established plasmonic excitations in metal nanostructures,” Bursi said.

“This study offers a window on the sometimes surprising behavior of collective excitations in few-atom quantum systems,” Halas said. “What we’ve learned here will aid our lab and others in developing quantum-plasmonic approaches for ultrafast color-changing glass, molecular-scale optoelectronics and nonlinear plasmon-mediated optics.”

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

Lifetime dynamics of plasmons in the few-atom limit by Kyle D. Chapkin, Luca Bursi, Grant J. Stec, Adam Lauchner, Nathaniel J. Hogan, Yao Cui, Peter Nordlander, and Naomi J. Halas. PNAS September 11, 2018 115 (37) 9134-9139; published ahead of print August 27, 2018 DOI: https://doi.org/10.1073/pnas.1805357115

This paper is behind a paywall.

Using only sunlight to desalinate water

The researchers seem to believe that this new desalination technique could be a game changer. From a June 20, 2017 news item on Azonano,

An off-grid technology using only the energy from sunlight to transform salt water into fresh drinking water has been developed as an outcome of the effort from a federally funded research.

The desalination system uses a combination of light-harvesting nanophotonics and membrane distillation technology and is considered to be the first major innovation from the Center for Nanotechnology Enabled Water Treatment (NEWT), which is a multi-institutional engineering research center located at Rice University.

NEWT’s “nanophotonics-enabled solar membrane distillation” technology (NESMD) integrates tried-and-true water treatment methods with cutting-edge nanotechnology capable of transforming sunlight to heat. …

A June 19, 2017 Rice University news release, which originated the news item, expands on the theme,

More than 18,000 desalination plants operate in 150 countries, but NEWT’s desalination technology is unlike any other used today.

“Direct solar desalination could be a game changer for some of the estimated 1 billion people who lack access to clean drinking water,” said Rice scientist and water treatment expert Qilin Li, a corresponding author on the study. “This off-grid technology is capable of providing sufficient clean water for family use in a compact footprint, and it can be scaled up to provide water for larger communities.”

The oldest method for making freshwater from salt water is distillation. Salt water is boiled, and the steam is captured and run through a condensing coil. Distillation has been used for centuries, but it requires complex infrastructure and is energy inefficient due to the amount of heat required to boil water and produce steam. More than half the cost of operating a water distillation plant is for energy.

An emerging technology for desalination is membrane distillation, where hot salt water is flowed across one side of a porous membrane and cold freshwater is flowed across the other. Water vapor is naturally drawn through the membrane from the hot to the cold side, and because the seawater need not be boiled, the energy requirements are less than they would be for traditional distillation. However, the energy costs are still significant because heat is continuously lost from the hot side of the membrane to the cold.

“Unlike traditional membrane distillation, NESMD benefits from increasing efficiency with scale,” said Rice’s Naomi Halas, a corresponding author on the paper and the leader of NEWT’s nanophotonics research efforts. “It requires minimal pumping energy for optimal distillate conversion, and there are a number of ways we can further optimize the technology to make it more productive and efficient.”

NEWT’s new technology builds upon research in Halas’ lab to create engineered nanoparticles that harvest as much as 80 percent of sunlight to generate steam. By adding low-cost, commercially available nanoparticles to a porous membrane, NEWT has essentially turned the membrane itself into a one-sided heating element that alone heats the water to drive membrane distillation.

“The integration of photothermal heating capabilities within a water purification membrane for direct, solar-driven desalination opens new opportunities in water purification,” said Yale University ‘s Menachem “Meny” Elimelech, a co-author of the new study and NEWT’s lead researcher for membrane processes.

In the PNAS study, researchers offered proof-of-concept results based on tests with an NESMD chamber about the size of three postage stamps and just a few millimeters thick. The distillation membrane in the chamber contained a specially designed top layer of carbon black nanoparticles infused into a porous polymer. The light-capturing nanoparticles heated the entire surface of the membrane when exposed to sunlight. A thin half-millimeter-thick layer of salt water flowed atop the carbon-black layer, and a cool freshwater stream flowed below.

Li, the leader of NEWT’s advanced treatment test beds at Rice, said the water production rate increased greatly by concentrating the sunlight. “The intensity got up 17.5 kilowatts per meter squared when a lens was used to concentrate sunlight by 25 times, and the water production increased to about 6 liters per meter squared per hour.”

Li said NEWT’s research team has already made a much larger system that contains a panel that is about 70 centimeters by 25 centimeters. Ultimately, she said, NEWT hopes to produce a modular system where users could order as many panels as they needed based on their daily water demands.

“You could assemble these together, just as you would the panels in a solar farm,” she said. “Depending on the water production rate you need, you could calculate how much membrane area you would need. For example, if you need 20 liters per hour, and the panels produce 6 liters per hour per square meter, you would order a little over 3 square meters of panels.”

Established by the National Science Foundation in 2015, NEWT aims to develop compact, mobile, off-grid water-treatment systems that can provide clean water to millions of people who lack it and make U.S. energy production more sustainable and cost-effective. NEWT, which is expected to leverage more than $40 million in federal and industrial support over the next decade, is the first NSF Engineering Research Center (ERC) in Houston and only the third in Texas since NSF began the ERC program in 1985. NEWT focuses on applications for humanitarian emergency response, rural water systems and wastewater treatment and reuse at remote sites, including both onshore and offshore drilling platforms for oil and gas exploration.

There is a video but it is focused on the NEWT center rather than any specific water technologies,

For anyone interested in the technology, here’s a link to and a citation for the researchers’ paper,

Nanophotonics-enabled solar membrane distillation for off-grid water purification by Pratiksha D. Dongare, Alessandro Alabastri, Seth Pedersen, Katherine R. Zodrow, Nathaniel J. Hogan, Oara Neumann, Jinjian Wu, Tianxiao Wang, Akshay Deshmukh,f, Menachem Elimelech, Qilin Li, Peter Nordlander, and Naomi J. Halas. PNAS {Proceedings of the National Academy of Sciences] doi: 10.1073/pnas.1701835114 June 19, 2017

This paper appears to be open access.

Multicolor, electrochromic glass

Electrochromic (changes color to block light and heat) glass could prove to be a significant market by 2020 according to a March 8, 2017 news item on phys.org,

Rice University’s latest nanophotonics research could expand the color palette for companies in the fast-growing market for glass windows that change color at the flick of an electric switch.

In a new paper in the American Chemical Society journal ACS Nano, researchers from the laboratory of Rice plasmonics pioneer Naomi Halas report using a readily available, inexpensive hydrocarbon molecule called perylene to create glass that can turn two different colors at low voltages.

“When we put charges on the molecules or remove charges from them, they go from clear to a vivid color,” said Halas, director of the Laboratory for Nanophotonics (LANP), lead scientist on the new study and the director of Rice’s Smalley-Curl Institute. “We sandwiched these molecules between glass, and we’re able to make something that looks like a window, but the window changes to different types of color depending on how we apply a very low voltage.”

Adam Lauchner, an applied physics graduate student at Rice and co-lead author of the study, said LANP’s color-changing glass has polarity-dependent colors, which means that a positive voltage produces one color and a negative voltage produces a different color.

“That’s pretty novel,” Lauchner said. “Most color-changing glass has just one color, and the multicolor varieties we’re aware of require significant voltage.”

Glass that changes color with an applied voltage is known as “electrochromic,” and there’s a growing demand for the light- and heat-blocking properties of such glass. The projected annual market for electrochromic glass in 2020 has been estimated at more $2.5 billion.

A March 8, 2017 Rice University news release (also on EurekAlert), which originated the news item, provides more detail about the research,

Lauchner said the glass project took almost two years to complete, and he credited co-lead author Grant Stec, a Rice undergraduate researcher, with designing the perylene-containing nonwater-based conductive gel that’s sandwiched between glass layers.

“Perylene is part of a family of molecules known as polycyclic aromatic hydrocarbons,” Stec said. “They’re a fairly common byproduct of the petrochemical industry, and for the most part they are low-value byproducts, which means they’re inexpensive.”

Grant Stec and Adam Lauchner

Grant Stec and Adam Lauchner of Rice University’s Laboratory for Nanophotonics have used an inexpensive hydrocarbon molecule called perylene to create a low-voltage, multicolor, electrochromic glass. (Photo by Jeff Fitlow/Rice University)

There are dozens of polycyclic aromatic hydrocarbons (PAHs), but each contains rings of carbon atoms that are decorated with hydrogen atoms. In many PAHs, carbon rings have six sides, just like the rings in graphene, the much-celebrated subject of the 2010 Nobel Prize in physics.

“This is a really cool application of what started as fundamental science in plasmonics,” Lauchner said.

A plasmon is [a] wave of energy, a rhythmic sloshing in the sea of electrons that constantly flow across the surface of conductive nanoparticles. Depending upon the frequency of a plasmon’s sloshing, it can interact with and harvest the energy from passing light. In dozens of studies over the past two decades, Halas, Rice physicist Peter Nordlander and colleagues have explored both the basic physics of plasmons and potential applications as diverse as cancer treatment, solar-energy collection, electronic displays and optical computing.

The quintessential plasmonic nanoparticle is metallic, often made of gold or silver, and precisely shaped. For example, gold nanoshells, which Halas invented at Rice in the 1990s, consist of a nonconducting core that’s covered by a thin shell of gold.

Grant Stec, Naomi Halas and Adam Lauchner

Student researchers Grant Stec (left) and Adam Lauchner (right) with Rice plasmonics pioneer Naomi Halas, director of Rice University’s Laboratory for Nanophotonics. (Photo by Jeff Fitlow/Rice University)

“Our group studies many kinds of metallic nanoparticles, but graphene is also conductive, and we’ve explored its plasmonic properties for several years,” Halas said.

She noted that large sheets of atomically thin graphene have been found to support plasmons, but they emit infrared light that’s invisible to the human eye.

“Studies have shown that if you make graphene smaller and smaller, as you go down to nanoribbons, nanodots and these little things called nanoislands, you can actually get graphene’s plasmon closer and closer to the edge of the visible regime,” Lauchner said.

In 2013, then-Rice physicist Alejandro Manjavacas, a postdoctoral researcher in Nordlander’s lab, showed that the smallest versions of graphene — PAHs with just a few carbon rings — should produce visible plasmons. Moreover, Manjavacas calculated the exact colors that would be emitted by different types of PAHs.

“One of the most interesting things was that unlike plasmons in metals, the plasmons in these PAH molecules were very sensitive to charge, which suggested that a very small electrical charge would produce dramatic colors,” Halas said.

Electrochromic glass that glass that turns from clear to black

Rice University researchers demonstrated a new type of glass that turns from clear to black when a low voltage is applied. The glass uses a combination of molecules that block almost all visible light when they each gain a single electron. (Photo by Jeff Fitlow/Rice University)

Lauchner said the project really took off after Stec joined the research team in 2015 and created a perylene formulation that could be sandwiched between sheets of conductive glass.

In their experiments, the researchers found that applying just 4 volts was enough to turn the clear window greenish-yellow and applying negative 3.5 volts turned it blue. It took several minutes for the windows to fully change color, but Halas said the transition time could easily be improved with additional engineering.

Stec said the team’s other window, which turns from clear to black, was produced later in the project.

“Dr. Halas learned that one of the major hurdles in the electrochromic device industry was making a window that could be clear in one state and completely black in another,” Stec said. “We set out to do that and found a combination of PAHs that captured no visible light at zero volts and almost all visible light at low voltage.”

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

Multicolor Electrochromic Devices Based on Molecular Plasmonics by Grant J. Stec, Adam Lauchner, Yao Cui, Peter Nordlander, and Naomi J. Halas. ACS Nano, Article ASAP DOI: 10.1021/acsnano.7b00364 Publication Date (Web): February 22, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

‘Stained glass nanotechnology’ for color displays

From a Dec. 4, 2015 news item on ScienceDaily,

A new method for building “drawbridges” between metal nanoparticles may allow electronics makers to build full-color displays using light-scattering nanoparticles that are similar to the gold materials that medieval artisans used to create red stained-glass.

“Wouldn’t it be interesting if we could create stained-glass windows that changed colors at the flip of a switch?” said Christy Landes, associate professor of chemistry at Rice and the lead researcher on a new study about the drawbridge method that appears this week in the open-access journal Science Advances.

The research by Landes and other experts at Rice University’s Smalley-Curl Institute could allow engineers to use standard electrical switching techniques to construct color displays from pairs of nanoparticles that scatter different colors of light.

For centuries, stained-glass makers have tapped the light-scattering properties of tiny gold nanoparticles to produce glass with rich red tones. Similar types of materials could increasingly find use in modern electronics as manufacturers work to make smaller, faster and more energy-efficient components that operate at optical frequencies.

A Dec. 4, 2015 Rice University news release (also on EurekAlert), which originated the news item, describes the research in more detail,

Though metal nanoparticles scatter bright light, researchers have found it difficult to coax them to produce dramatically different colors, Landes said.

Rice’s new drawbridge method for color switching incorporates metal nanoparticles that absorb light energy and convert it into plasmons, waves of electrons that flow like a fluid across a particle’s surface. Each plasmon scatters and absorbs a characteristic frequency of light, and even minor changes in the wave-like sloshing of a plasmon shift that frequency. The greater the change in plasmonic frequency, the greater the difference between the colors observed.

“Engineers hoping to make a display from optically active nanoparticles need to be able to switch the color,” Landes said. “That type of switching has proven very difficult to achieve with nanoparticles. People have achieved moderate success using various plasmon-coupling schemes in particle assemblies. What we’ve shown though is variation of the coupling mechanism itself, which can be used to produce huge color changes both rapidly and reversibly.”

To demonstrate the method, Landes and study lead author Chad Byers, a graduate student in her lab, anchored pairs of gold nanoparticles to a glass surface covered with indium tin oxide (ITO), the same conductor that’s used in many smartphone screens. By sealing the particles in a chamber filled with a saltwater electrolyte and a silver electrode, Byers and Landes were able form a device with a complete circuit. They then showed they could apply a small voltage to the ITO to electroplate silver onto the surface of the gold particles. In that process, the particles were first coated with a thin layer of silver chloride. By later applying a negative voltage, the researchers caused a conductive silver “drawbridge” to form. Reversing the voltage caused the bridge to withdraw.

“The great thing about these chemical bridges is that we can create and eliminate them simply by applying or reversing a voltage,” Landes said. “This is the first method yet demonstrated to produce dramatic, reversible color changes for devices built from light-activated nanoparticles.”

This research has its roots in previous work (from the news release),

Byers said his research into the plasmonic behavior of gold dimers began about two years ago.

“We were pursuing the idea that we could make significant changes in optical properties of individual particles simply by altering charge density,” he said. “Theory predicts that colors can be changed just by adding or removing electrons, and we wanted to see if we could do that reversibly, simply by turning a voltage on or off.”

The experiments worked. The color shift was observed and reversible, but the change in the color was minute.

“It wasn’t going to get anybody excited about any sort of switchable display applications,” Landes said.

But she and Byers also noticed that their results differed from the theoretical predictions.

Landes said that was because the predictions were based upon using an inert electrode made of a metal like palladium that isn’t subject to oxidation. But silver is not inert. It reacts easily with oxygen in air or water to form a coat of unsightly silver oxide. This oxidizing layer can also form from silver chloride, and Landes said that is what was occurring when the silver counter electrode was used in Byers’ first experiments.

The scientists decided to embrace imperfection (from the news release),

“It was an imperfection that was throwing off our results, but rather than run away from it, we decided to use it to our advantage,” Landes said.

Rice plasmonics pioneer and study co-author Naomi Halas, director of the Smalley-Curl Institute, said the new research shows how plasmonic components could be used to produce electronically switchable color-displays.

“Gold nanoparticles are particularly attractive for display purposes,” said Halas, Rice’s Stanley C. Moore Professor of Electrical and Computer Engineering and professor of chemistry, bioengineering, physics and astronomy, and materials science and nanoengineering. “Depending upon their shape, they can produce a variety of specific colors. They are also extremely stable, and even though gold is expensive, very little is needed to produce an extremely bright color.”

In designing, testing and analyzing the follow-up experiments on dimers, Landes and Byers engaged with a brain trust of Rice plasmonics experts that included Halas, physicist and engineer Peter Nordlander, chemist Stephan Link, materials scientist Emilie Ringe and their students, as well as Paul Mulvaney of the University of Melbourne in Australia.

Together, the team confirmed the composition and spacing of the dimers and showed how metal drawbridges could be used to induce large color shifts based on voltage inputs.

Nordlander and Hui Zhang, the two theorists in the group, examined the device’s “plasmonic coupling,” the interacting dance that plasmons engage in when they are in close contact. For instance, plasmonic dimers are known to act as light-activated capacitors, and prior research has shown that connecting dimers with nanowire bridges brings about a new state of resonance known as a “charge-transfer plasmon,” which has its own distinct optical signature.

“The electrochemical bridging of the interparticle gap enables a fully reversible transition between two plasmonic coupling regimes, one capacitive and the other conductive,” Nordlander said. “The shift between these regimes is evident from the dynamic evolution of the charge transfer plasmon.”

Halas said the method provides plasmonic researchers with a valuable tool for precisely controlling the gaps between dimers and other multiparticle plasmonic configurations.

“In an applied sense, gap control is important for the development of active plasmonic devices like switches and modulators, but it is also an important tool for basic scientists who are conducting curiosity-driven research in the emerging field of quantum plasmonics.”

I’m glad the news release writer included the background work leading to this new research and to hint at the level of collaboration needed to achieve the scientists’ new understanding of color switching.

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

From tunable core-shell nanoparticles to plasmonic drawbridges: Active control of nanoparticle optical properties by Chad P. Byers, Hui Zhang, Dayne F. Swearer, Mustafa Yorulmaz, Benjamin S. Hoener, Da Huang, Anneli Hoggard, Wei-Shun Chang, Paul Mulvaney, Emilie Ringe, Naomi J. Halas, Peter Nordlander, Stephan Link, and Christy F. Landes. Science Advances  04 Dec 2015: Vol. 1, no. 11, e1500988 DOI: 10.1126/sciadv.1500988

In case you missed it in the news release, this is an open access paper.

Cow blood declumps (stabilizes) gold nanoparticles in a solution

Rice University (Texas, US) researchers have discovered a means of stabilizing gold nanoparticles in a variety of solutions including one of the harshest, salt solutions. From the May 14, 2013 news item on Nanowerk (Note: A link has been removed),

A protein from cow blood has the remarkable ability to keep gold nanoparticles from clumping in a solution. The discovery could lead to improved biomedical applications and contribute to projects that use nanoparticles in harsh environments.

Bovine serum albumin (BSA) forms a protein “corona” around gold nanoparticles that keeps them from aggregating, particularly in high-salt environments like seawater. The new research by the Rice University labs of chemists Stephan Link and Christy Landes was published by the American Chemical Society journal ACS Sustainable Chemistry and Engineering (“Adsorption of a Protein Monolayer via Hydrophobic Interactions Prevents Nanoparticle Aggregation under Harsh Environmental Conditions”).

The May 13, 2012 Rice University news release by Mike Williams, which originated the news item, describes the researchers and the nature of their work,

Link’s primary interest is in the plasmonic properties of nanoparticles. Landes’ work incorporates protein binding and molecular transport. The BSA research combines their unique talents with those of Sergio Dominguez-Medina, a graduate student in Link’s lab who studied to be a physicist at Monterrey Tech and was drawn to this interdisciplinary project during an undergraduate fellowship at Link’s Rice lab.

“Initially, we wanted to look at nanoparticles in solution with something they would encounter frequently in blood: serum albumin,” Landes said. “In our first experiments, Sergio reported the very efficient, reasonably fast and irreversible binding the moment he put nanoparticles into a solution that contained serum albumin.”

“It turned out the salt is actually driving this binding,” Dominguez-Medina said.

Without BSA, gold nanoparticles in a salty solution quickly aggregate and fall to the bottom. “That by itself is undesirable for biomedical or industrial applications, because it could lead to toxicity issues,” he said. “The nanoparticles get more hydrophobic because in the presence of salts, the excess charges on the surface (which discourage clumping) are actually removed.” But if BSA is present, the proteins are drawn to the nanoparticles faster than the particles are drawn to each other.

“Once the protein is bound, it gives a super protection against any type of salt-induced aggregation. We think this could be used for the stabilization of nanoparticles in environments where, right now, it hasn’t been achieved,” Dominguez-Medina said.

He said the discovery also offers the possibility that nanoparticles might be made more compatible for treating humans by using a patient’s own albumin. “Albumin is really easy to purify and the process is well-established,” he said.

Here’s a little more about the plasmonics of the situation and how this discovery about cow blood protein might apply in biomedical and other applications (from the news release),

The ability of gold nanoparticles to absorb and redirect light is at the heart of several breakthrough technologies being developed at Rice and elsewhere. Most notable are a nanoparticle-based cancer treatment now in human testing that was developed by Professor Naomi Halas and former Rice colleague Jennifer West, and Halas’ project to convert solar energy directly into steam for sanitation and water purification.

“The only way nanoparticles exhibit their really nice optical properties in very specific optical frequencies is if they’re separated,” Landes said.

The key words in Landes comment is ‘separated’ (from the news release),

Because pure gold nanoparticles are so hydrophobic, they naturally clump together in a solution unless chemically treated. “A lot of industrial effort goes into keeping stuff off of surfaces, like contact lenses and ship hulls,” she said. “That involves chemically altering the surfaces to prevent unwanted adsorption, or in the case of nanoparticles, unwanted aggregation.”

Protecting the surface is costly, Link said. “But we found we could take nanoparticles prepared in the cheapest way, with a sodium citrate coating that stabilizes the particles by electrostatic repulsion, and add BSA, which coats the particles and makes them really stable.”

Adding the BSA seems logical when one of the scientists explains the reasoning (from the news release),

Albumin is the most common protein in blood, and the bovine version shares 98 percent of its amino acid sequence with human serum albumin. “One of its main purposes, biologically, is to take things that aren’t water-soluble, bind to them and make them soluble,” Landes said. “When you combine it with gold nanoparticles, BSA trades places with the cheap citrate, which isn’t a good protective layer, to form the monolayer corona, which is very strong and protective.”

Aside from obvious biomedical applications (e.g. implants and joint replacements), there are desalination and fuel cell applications (from the news release),

Seawater is the very definition of a harsh environment, Landes said. “One of the problems with desalination applications and, similarly, with fuel cells, is that saline or acidic conditions are very corrosive,” she said. “That’s why you have to use platinum electrodes in fuel cells – not because they’re better than cheaper materials at catalysis, but because they don’t corrode in a harsh environment.” She sees promise for BSA-treated gold nanoparticles in both applications.

The researchers have other plans as well (from the news release),

The researchers are now looking at how well gold nanoparticles retain their albumin corona with repeated use. “Gold is expensive,” Landes said. “But the beauty of it is that if you can reuse it, it only costs you once.”

They also want to use spectroscopy to see how the binding mechanism works in real time, Link said. “We want to study what’s happening at the interface of nanoparticles and biologically relevant media” that may eventually include DNA, RNA and drugs for delivery to cells, he said.

Link plans to see how BSA can be used in combination with gold nanorods. Because nanorods’ plasmonic properties can be tuned, “we can get them into the biological window, which is near-infrared light,” he said. Near-IR from lasers is used to activate, by heating, Halas’ and West’s cancer-killing nanoshells. Nanorods may also offer ways to combine BSA and other useful proteins by coating the tips and sides separately.

For interested parties, here’s a link to and a citation for the published paper,

Adsorption of a Protein Monolayer via Hydrophobic Interactions Prevents Nanoparticle Aggregation under Harsh Environmental Conditions by Sergio Dominguez-Medina, Jan Blankenburg, Jana Olson, Christy F. Landes, and Stephan Link. ACS Sustainable Chem. Eng., Article ASAP DOI: 10.1021/sc400042h
Publication Date (Web): April 3, 2013
Copyright © 2013 American Chemical Society

Unusually for the American Chemical Society (ACS), this paper appears to be open access; I was able to access the full HTML version today, May 14, 2013 at 10:10 am PDT.