Chemists performed “surgery” on a 23-gold-atom nanoparticle according to a June 12, 2017 news item on Nanowerk (Note: A link has been removed),
A team of chemists led by Carnegie Mellon University’s [CMU] Rongchao Jin has for the first time conducted site-specific surgery on a nanoparticle. The procedure, which allows for the precise tailoring of nanoparticles, stands to advance the field of nanochemistry.
The surgical technique developed by Qi Li, the study’s lead author and a 3rd year graduate student in the Jin group, will allow researchers to enhance nanoparticles’ functional properties, such as catalytic activity and photoluminescence, increasing their usefulness in a wide variety of fields including health care, electronics and manufacturing. The findings were published in Science Advances (“Molecular “surgery” on a 23-gold-atom nanoparticle”).
Here’s an image the researchers have provided,
Caption: Carnegie Mellon chemists used a two-step metal exchange method to remove two S-Au-S staples from the surface of a nanoparticle. Credit: Carnegie Mellon University
“Nanochemistry is a relatively new field, it’s only about 20 years old. We’ve been racing to catch up to fields like organic chemistry that are more than 100 years old,” said Jin, a chemistry professor in the Mellon College of Science. “Organic chemists have been able to tailor the functional groups of molecules for quite some time, like tailoring penicillin for better medical functions, for example. We dreamed that we could do something similar in nanoscience. Developing atomically precise nanoparticles has allowed us to make this dream come true.”
In order to make this “nano-surgery” a reality, researchers needed to begin with atomically precise nanoparticles that could be reliably produced time after time. Jin’s lab has been at the forefront of this research. Working with gold nanoparticles, he and his team have developed methods to precisely control the number of atoms in each nanoparticle, resulting in uniformly-sized nanoparticles with every batch. With reliably precise particles, Jin and colleagues were able to identify the particles’ structures, and begin to tease out how that structure impacted the particles’ properties and functionality.
With these well-defined nanoparticles in hand, Jin’s next step was to find a way to surgically tailor the particles in order to learn more about – and hopefully enhance – their functionality.
In their recent study, Jin and colleagues performed nano-surgery on a gold nanoparticle made up of 23 gold atoms surrounded by a protective surface of ligands in staple-like motifs. Using a two-step metal exchange method, they removed two S-Au-S staples from the particle’s surface. In doing this they revealed the structural factors that determine the particle’s optical properties and established the role that the surface plays in photoluminescence. Significantly, the surgery increased the particle’s photoluminescence by about 10-fold. Photoluminescence plays a critical role in biological imaging, cancer diagnosis and LED technology, among other applications.
Jin and coworkers are now trying to generalize this site-specific surgery method to other nanoparticles.
Here’s a link to and a citation for the paper,
Molecular “surgery” on a 23-gold-atom nanoparticle by Qi Li, Tian-Yi Luo, Michael G. Taylor, Shuxin Wang, Xiaofan Zhu, Yongbo Song, Giannis Mpourmpakis, Nathaniel L. Rosi, and Rongchao Jin. Science Advances 19 May 2017: Vol. 3, no. 5, e1603193 DOI: 10.1126/sciadv.1603193
This work is the result of an international collaboration including Russia (from a May 23, 2017 news item on Nanowerk),
Gold nanoparticles serve as catalysts for obtaining valuable chemical products based on glycerol. Scientists from Tomsk Polytechnic University and their international colleagues are developing gold catalysts to recycle one of the main byproducts of biofuel production. The obtained products are in high demand in medicine, agriculture, cosmetic industry and other sectors.
Scientists from the University of Milano (Italy), the National Autonomous University of Mexico, the Institute of Catalysis and Petrochemistry of Madrid (Spain) and the University of Porto (Portugal) take part in the study of gold nanoparticles.
Today the production of biofuels is an important area in many countries. They can be obtained from a great variety of biomasses. In Latin America it is orange and tangerine peel as well as banana skin. In USA biofuels are produced from corn, in the central part of Russia and Europe – from rape (Brassica napus). When processing these plants into biofuels a large amount of glycerol is formed. Its esters constitute the basis of oils and fats. Glycerol is widely used in cosmetic industry as an individual product. However, much more glycerol is obtained in the production of biofuels – many thousands of tons a year. As a result, unused glycerol merely becomes waste,’ describes the problem Alexey Pestryakov, the Head of the Department of Physical and Analytical Chemistry. ‘Now, a lot of research groups are engaged in this issue as to how to transform excess glycerol into other useful products. Along with our foreign colleagues we offered catalysts based on gold nanoparticles.’
The authors of the research note that catalytic oxidation on gold is one of the most effective techniques to obtain from glycerol such useful products as aldehydes, esters, carboxylic acids and other substances.
‘All these substances are products of fine organic chemistry and are in demand in a wide range of industries, first of all, in the pharmaceutical and cosmetic industries. In agriculture they are applied as part of different feed additives, veterinary drugs, fertilizers, plant treatment products, etc.
Thus, unused glycerol after being processed will further be applied,’ sums up Alexey Pestryakov.
Gold catalysts are super active. They can enter into chemical reactions with other substances at room temperature (other catalysts need to be heated), in some case even under zero. However, gold can be a catalyst only at the nanolevel.
‘If you take a piece of gold, even very tiny, there will be no chemical reaction. In order to make gold become chemically active, the size of its particle should be less than two nanometers. Only then it gets its amazing properties,’ explains the scientist.
As a catalyst gold was discovered not so long ago, in the early 1990s, by Japanese chemists.
To date, TPU scientists and their colleagues are not the only ones who develop such catalysts.
Unlike their counterparts the gold catalysts developed at TPU are more stable (they retain their activity longer).
‘A great challenge in this area is that gold catalysts are very rapidly deactivated, not only during work, but even during storage. Our objective is to ensure their longer shelf life. It is also important to use oxygen as an oxidizer, since toxic and corrosive peroxide compounds are often used for such purposes,’ says Alexey Petryakov.
Getting medication directly to the brain is a worldwide medical research goal and it seems that a team of scientists at the Washington University at St. Louis (WUSTL) has taken a step forward to accomplishing the goal. From an April 12, 2017 news item on ScienceDaily,
Delivering life-saving drugs directly to the brain in a safe and effective way is a challenge for medical providers. One key reason: the blood-brain barrier, which protects the brain from tissue-specific drug delivery. Methods such as an injection or a pill aren’t as precise or immediate as doctors might prefer, and ensuring delivery right to the brain often requires invasive, risky techniques.
A team of engineers from Washington University in St. Louis has developed a new nanoparticle generation-delivery method that could someday vastly improve drug delivery to the brain, making it as simple as a sniff.
“This would be a nanoparticle nasal spray, and the delivery system could allow a therapeutic dose of medicine to reach the brain within 30 minutes to one hour,” said Ramesh Raliya, research scientist at the School of Engineering & Applied Science.
Caption: Engineers at Washington University have discovered a new technique that could change drug delivery to the brain. They were able to apply a nanoparticle aerosol spray to the antenna of locusts, then track the nanoparticles as they traveled through the olfactory nerves, crossed the blood-brain barrier and accumulated in the brain. This new, non-invasive approach could someday make drug delivery as simple as a sniff for patients with brain injuries or tumors.
“The blood-brain barrier protects the brain from foreign substances in the blood that may injure the brain,” Raliya said. “But when we need to deliver something there, getting through that barrier is difficult and invasive. Our non-invasive technique can deliver drugs via nanoparticles, so there’s less risk and better response times.”
The novel approach is based on aerosol science and engineering principles that allow the generation of monodisperse nanoparticles, which can deposit on upper regions of the nasal cavity via diffusion. Working with Assistant Vice Chancellor Pratim Biswas, chair of the Department of Energy, Environmental & Chemical Engineering and the Lucy & Stanley Lopata Professor, Raliya developed an aerosol consisting of gold nanoparticles of controlled size, shape and surface charge. The nanoparticles were tagged with fluorescent markers, allowing the researchers to track their movement.
Next, Raliya and biomedical engineering postdoctoral fellow Debajit Saha exposed locusts’ antennae to the aerosol, and observed the nanoparticles travel from the antennas up through the olfactory nerves. Due to their tiny size, the nanoparticles passed through the brain-blood barrier, reaching the brain and suffusing it in a matter of minutes.
The team tested the concept in locusts because the blood-brain barriers in the insects and humans have anatomical similarities, and the researchers consider going through the nasal regions to neural pathways as the optimal way to access the brain.
“The shortest and possibly the easiest path to the brain is through your nose,” said Barani Raman, associate professor of biomedical engineering. “Your nose, the olfactory bulb and then olfactory cortex: two relays and you’ve reached the cortex. The same is true for invertebrate olfactory circuitry, although the latter is a relatively simpler system, with supraesophageal ganglion instead of an olfactory bulb and cortex.”
To determine whether or not the foreign nanoparticles disrupted normal brain function, Saha examined the physiological response of olfactory neurons in the locusts before and after the nanoparticle delivery. Several hours after the nanoparticle uptake, no noticeable change in the electrophysiological responses was detected.
“This is only a beginning of a cool set of studies that can be performed to make nanoparticle-based drug delivery approaches more principled,” Raman said.
The next phase of research involves fusing the gold nanoparticles with various medicines, and using ultrasound to target a more precise dose to specific areas of the brain, which would be especially beneficial in brain-tumor cases.
“We want to drug target delivery within the brain using this non-invasive approach,” Raliya said. “In the case of a brain tumor, we hope to use focused ultrasound so we can guide the particles to collect at that particular point.”
I featured another team working on delivering drugs directly to the brain via the olfactory system, except their nanoparticles were gelatin and they were testing stroke medication on rats, in my Sept. 24, 2014 posting.
An April 26, 2017 news item on Nanowerk announces research that may explain the link between heart disease and air pollution (Note: A link has been removed),
Tiny particles in air pollution have been associated with cardiovascular disease, which can lead to premature death. But how particles inhaled into the lungs can affect blood vessels and the heart has remained a mystery.
Now, scientists have found evidence in human and animal studies that inhaled nanoparticles can travel from the lungs into the bloodstream, potentially explaining the link between air pollution and cardiovascular disease. Their results appear in the journal ACS Nano (“Inhaled Nanoparticles Accumulate at Sites of Vascular Disease”).
The World Health Organization estimates that in 2012, about 72 percent of premature deaths related to outdoor air pollution were due to ischemic heart disease and strokes. Pulmonary disease, respiratory infections and lung cancer were linked to the other 28 percent. Many scientists have suspected that fine particles travel from the lungs into the bloodstream, but evidence supporting this assumption in humans has been challenging to collect. So Mark Miller and colleagues at the University of Edinburgh in the United Kingdom and the National Institute for Public Health and the Environment in the Netherlands used a selection of specialized techniques to track the fate of inhaled gold nanoparticles.
In the new study, 14 healthy volunteers, 12 surgical patients and several mouse models inhaled gold nanoparticles, which have been safely used in medical imaging and drug delivery. Soon after exposure, the nanoparticles were detected in blood and urine. Importantly, the nanoparticles appeared to preferentially accumulate at inflamed vascular sites, including carotid plaques in patients at risk of a stroke. The findings suggest that nanoparticles can travel from the lungs into the bloodstream and reach susceptible areas of the cardiovascular system where they could possibly increase the likelihood of a heart attack or stroke, the researchers say.
Here’s a link to and a citation for the paper,
Inhaled Nanoparticles Accumulate at Sites of Vascular Disease by Mark R. Miller, Jennifer B. Raftis, Jeremy P. Langrish, Steven G. McLean, Pawitrabhorn Samutrtai, Shea P. Connell, Simon Wilson, Alex T. Vesey, Paul H. B. Fokkens, A. John F. Boere, Petra Krystek, Colin J. Campbell, Patrick W. F. Hadoke, Ken Donaldson, Flemming R. Cassee, David E. Newby, Rodger Duffin, and Nicholas L. Mills. ACS Nano, Article ASAP DOI: 10.1021/acsnano.6b08551 Publication Date (Web): April 26, 2017
I have two news bits (dated almost one month apart) about the use of graphene in neural probes, one from the European Union and the other from Korea.
European Union (EU)
This work is being announced by the European Commission’s (a subset of the EU) Graphene Flagship (one of two mega-funding projects announced in 2013; 1B Euros each over ten years for the Graphene Flagship and the Human Brain Project).
According to a March 27, 2017 news item on ScienceDaily, researchers have developed a graphene-based neural probe that has been tested on rats,
Measuring brain activity with precision is essential to developing further understanding of diseases such as epilepsy and disorders that affect brain function and motor control. Neural probes with high spatial resolution are needed for both recording and stimulating specific functional areas of the brain. Now, researchers from the Graphene Flagship have developed a new device for recording brain activity in high resolution while maintaining excellent signal to noise ratio (SNR). Based on graphene field-effect transistors, the flexible devices open up new possibilities for the development of functional implants and interfaces.
The research, published in 2D Materials, was a collaborative effort involving Flagship partners Technical University of Munich (TU Munich; Germany), Institut d’Investigacions Biomèdiques August Pi i Sunyer (IDIBAPS; Spain), Spanish National Research Council (CSIC; Spain), The Biomedical Research Networking Center in Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN; Spain) and the Catalan Institute of Nanoscience and Nanotechnology (ICN2; Spain).
Caption: Graphene transistors integrated in a flexible neural probe enables electrical signals from neurons to be measured with high accuracy and density. Inset: The tip of the probe contains 16 flexible graphene transistors. Credit: ICN2
The devices were used to record the large signals generated by pre-epileptic activity in rats, as well as the smaller levels of brain activity during sleep and in response to visual light stimulation. These types of activities lead to much smaller electrical signals, and are at the level of typical brain activity. Neural activity is detected through the highly localised electric fields generated when neurons fire, so densely packed, ultra-small measuring devices is important for accurate brain readings.
The neural probes are placed directly on the surface of the brain, so safety is of paramount importance for the development of graphene-based neural implant devices. Importantly, the researchers determined that the graphene-based probes are non-toxic, and did not induce any significant inflammation.
Devices implanted in the brain as neural prosthesis for therapeutic brain stimulation technologies and interfaces for sensory and motor devices, such as artificial limbs, are an important goal for improving quality of life for patients. This work represents a first step towards the use of graphene in research as well as clinical neural devices, showing that graphene-based technologies can deliver the high resolution and high SNR needed for these applications.
First author Benno Blaschke (TU Munich) said “Graphene is one of the few materials that allows recording in a transistor configuration and simultaneously complies with all other requirements for neural probes such as flexibility, biocompability and chemical stability. Although graphene is ideally suited for flexible electronics, it was a great challenge to transfer our fabrication process from rigid substrates to flexible ones. The next step is to optimize the wafer-scale fabrication process and improve device flexibility and stability.”
Jose Antonio Garrido (ICN2), led the research. He said “Mechanical compliance is an important requirement for safe neural probes and interfaces. Currently, the focus is on ultra-soft materials that can adapt conformally to the brain surface. Graphene neural interfaces have shown already great potential, but we have to improve on the yield and homogeneity of the device production in order to advance towards a real technology. Once we have demonstrated the proof of concept in animal studies, the next goal will be to work towards the first human clinical trial with graphene devices during intraoperative mapping of the brain. This means addressing all regulatory issues associated to medical devices such as safety, biocompatibility, etc.”
Caption: The graphene-based neural probes were used to detect rats’ responses to visual stimulation, as well as neural signals during sleep. Both types of signals are small, and typically difficult to measure. Credit: ICN2
Here’s a link to and a citation for the paper,
Mapping brain activity with flexible graphene micro-transistors by Benno M Blaschke, Núria Tort-Colet, Anton Guimerà-Brunet, Julia Weinert, Lionel Rousseau, Axel Heimann, Simon Drieschner, Oliver Kempski, Rosa Villa, Maria V Sanchez-Vives. 2D Materials, Volume 4, Number 2 DOI https://doi.org/10.1088/2053-1583/aa5eff Published 24 February 2017
While this research from Korea was published more recently, the probe itself has not been subjected to in vivo (animal testing). From an April 19, 2017 news item on ScienceDaily,
Electrodes placed in the brain record neural activity, and can help treat neural diseases like Parkinson’s and epilepsy. Interest is also growing in developing better brain-machine interfaces, in which electrodes can help control prosthetic limbs. Progress in these fields is hindered by limitations in electrodes, which are relatively stiff and can damage soft brain tissue.
Designing smaller, gentler electrodes that still pick up brain signals is a challenge because brain signals are so weak. Typically, the smaller the electrode, the harder it is to detect a signal. However, a team from the Daegu Gyeongbuk Institute of Science & Technology [DGIST} in Korea developed new probes that are small, flexible and read brain signals clearly.
This is a pretty interesting way to illustrate the research,
Caption: Graphene and gold make a better brain probe. Credit: DGIST
The probe consists of an electrode, which records the brain signal. The signal travels down an interconnection line to a connector, which transfers the signal to machines measuring and analysing the signals.
The electrode starts with a thin gold base. Attached to the base are tiny zinc oxide nanowires, which are coated in a thin layer of gold, and then a layer of conducting polymer called PEDOT. These combined materials increase the probe’s effective surface area, conducting properties, and strength of the electrode, while still maintaining flexibility and compatibility with soft tissue.
Packing several long, thin nanowires together onto one probe enables the scientists to make a smaller electrode that retains the same effective surface area of a larger, flat electrode. This means the electrode can shrink, but not reduce signal detection. The interconnection line is made of a mix of graphene and gold. Graphene is flexible and gold is an excellent conductor. The researchers tested the probe and found it read rat brain signals very clearly, much better than a standard flat, gold electrode.
“Our graphene and nanowires-based flexible electrode array can be useful for monitoring and recording the functions of the nervous system, or to deliver electrical signals to the brain,” the researchers conclude in their paper recently published in the journal ACS Applied Materials and Interfaces.
The probe requires further clinical tests before widespread commercialization. The researchers are also interested in developing a wireless version to make it more convenient for a variety of applications.
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.
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 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.
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.
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.”
Plasmonic printing produces resolutions several times greater than conventional printing methods. In plasmonic printing, colours are formed on the surfaces of tiny metallic particles when light excites their electrons to oscillate. Researchers at the Max Planck Institute for Intelligent Systems in Stuttgart have now shown how the colours of such metallic particles can be altered with hydrogen (Nature Communications, “Dynamic plasmonic colour display”).
The technique could open the way for animating ultra-high-resolution images and for developing extremely sharp displays. At the same time, it provides new approaches for encrypting information and detecting counterfeits.
Glass artisans in medieval times exploited the effect long before it was even known. They coloured the magnificent windows of gothic cathedrals with nanoparticles of gold, which glowed red in the light. It was not until the middle of the 20th century that the underlying physical phenomenon was given a name: plasmons. These collective oscillations of free electrons are stimulated by the absorption of incident electromagnetic radiation. The smaller the metallic particles, the shorter the wavelength of the absorbed radiation. In some cases, the resonance frequency, i.e., the absorption maximum, falls within the visible light spectrum. The unabsorbed part of the spectrum is then scattered or reflected, creating an impression of colour. The metallic particles, which usually appear silvery, copper-coloured or golden, then take on entirely new colours.
A resolution of 100,000 dots per inch
Researchers are also taking advantage of the effect to develop plasmonic printing, in which tailor-made square metal particles are arranged in specific patterns on a substrate. The edge length of the particles is in the order of less than 100 nanometres (100 billionths of a metre). This allows a resolution of 100,000 dots per inch – several times greater than what today’s printers and displays can achieve.
For metallic particles measuring several 100 nanometres across, the resonance frequency of the plasmons lies within the visible light spectrum. When white light falls on such particles, they appear in a specific colour, for example red or blue. The colour of the metal in question is determined by the size of the particles and their distance from each other. These adjustment parameters therefore serve the same purpose in plasmonic printing as the palette of colours in painting.
The trick with the chemical reaction
The Smart Nanoplasmonics Research Group at the Max Planck Institute for Intelligent Systems in Stuttgart also makes use of this colour variability. They are currently working on making dynamic plasmonic printing. They have now presented an approach that allows them to alter the colours of the pixels predictably – even after an image has been printed. “The trick is to use magnesium. It can undergo a reversible chemical reaction in which the metallic character of the element is lost,” explains Laura Na Liu, who leads the Stuttgart research group. “Magnesium can absorb up to 7.6% of hydrogen by weight to form magnesium hydride, or MgH2”, Liu continues. The researchers coat the magnesium with palladium, which acts as a catalyst in the reaction.
During the continuous transition of metallic magnesium into non-metallic MgH2, the colour of some of the pixels changes several times. The colour change and the speed of the rate at which it proceeds follow a clear pattern. This is determined both by the size of and the distance between the individual magnesium particles as well as by the amount of hydrogen present.
In the case of total hydrogen saturation, the colour disappears completely, and the pixels reflect all the white light that falls on them. This is because the magnesium is no longer present in metallic form but only as MgH2. Hence, there are also no free metal electrons that can be made to oscillate.
Minerva’s vanishing act
The scientists demonstrated the effect of such dynamic colour behaviour on a plasmonic print of Minerva, the Roman goddess of wisdom, which also bore the logo of the Max Planck Society. They chose the size of their magnesium particles so that Minerva’s hair first appeared reddish, the head covering yellow, the feather crest red and the laurel wreath and outline of her face blue. They then washed the micro-print with hydrogen. A time-lapse film shows how the individual colours change. Yellow turns red, red turns blue, and blue turns white. After a few minutes all the colours disappear, revealing a white surface instead of Minerva.
The scientists also showed that this process is reversible by replacing the hydrogen stream with a stream of oxygen. The oxygen reacts with the hydrogen in the magnesium hydride to form water, so that the magnesium particles become metallic again. The pixels then change back in reverse order, and in the end Minerva appears in her original colours.
In a similar manner the researchers first made the micro image of a famous Van Gogh painting disappear and then reappear. They also produced complex animations that give the impression of fireworks.
The principle of a new encryption technique
Laura Na Liu can imagine using this principle in a new encryption technology. To demonstrate this, the group formed various letters with magnesium pixels. The addition of hydrogen then caused some letters to disappear over time, like the image of Minerva. “As for the rest of the letters, a thin oxide layer formed on the magnesium particles after exposing the sample in air for a short time before palladium deposition,” Liu explains. This layer is impermeable to hydrogen. The magnesium lying under the oxide layer therefore remains metallic − and visible − because light is able to excite the plasmons in the magnesium.
In this way it is possible to conceal a message, for example by mixing real and nonsensical information. Only the intended recipient is able to make the nonsensical information disappear and filter out the real message. For example, after decoding the message “Hartford” with hydrogen, only the words “art or” would remain visible. To make it more difficult to crack such encrypted messages, the group is currently working on a process that would require a precisely adjusted hydrogen concentration for deciphering.
Liu believes that the technology could also be used some day in the fight against counterfeiting. “For example, plasmonic security features could be printed on banknotes or pharmaceutical packs, which could later be checked or read only under specific conditions unknown to counterfeiters.”
It doesn’t necessarily have to be hydrogen
Laura Na Liu knows that the use of hydrogen makes some applications difficult and impractical for everyday use such as in mobile displays. “We see our work as a starting shot for a new principle: the use of chemical reactions for dynamic printing,” the Stuttgart physicist says. It is certainly conceivable that the research will soon lead to the discovery of chemical reactions for colour changes other than the phase transition between magnesium and magnesium dihydride, for example, reactions that require no gaseous reactants.
Here’s a link to and a citation for the paper,
Dynamic plasmonic colour display by Xiaoyang Duan, Simon Kamin, & Na Liu. Nature Communications 8, Article number: 14606 (2017) doi:10.1038/ncomms14606 Published online: 24 February 2017
Chemists at Carnegie Mellon University have demonstrated that synthetic nanoparticles can achieve the same level of structural complexity, hierarchy and accuracy as their natural counterparts – biomolecules. The study, published in Science, also reveals the atomic-level mechanisms behind nanoparticle self-assembly.
The findings from the lab of Chemistry Professor Rongchao Jin provide researchers with an important window into how nanoparticles form, and will help guide the construction of nanoparticles, including those that can be used in the fabrication of computer chips, creation of new materials, and development of new drugs and drug delivery devices.
Caption: By resolving the structure of Au246, Carnegie Mellon researchers were able to visualize its hierarchical assembly into artificial solid. Credit: Carnegie Mellon University
“Most people think that nanoparticles are simple things, because they are so small. But when we look at nanoparticles at the atomic level, we found that they are full of wonders,” said Jin.
Nanoparticles are typically between 1 and 100 nanometers in size. Particles on the larger end of the nanoscale are harder to create precisely. Jin has been at the forefront of creating precise gold nanoparticles for a decade, first establishing the structure of an ultra-small Au25 nanocluster and then working on larger and larger ones. In 2015, his lab used X-ray crystallography to establish the structure of an Au133 nanoparticle and found that it contained complex, self-organized patterns that mirrored patterns found in nature.
In the current study, they sought to find out the mechanisms that caused these patterns to form. The researchers, led by graduate student Chenjie Zeng, established the structure of Au246, one of the largest and most complex nanoparticles created by scientists to-date and the largest gold nanoparticle to have its structure determined by X-ray crystallography. Au246 turned out to be an ideal candidate for deciphering the complex rules of self- assembly because it contains an ideal number of atoms and surface ligands and is about the same size and weight as a protein molecule.
Analysis of Au246’s structure revealed that the particles had much more in common with biomolecules than size. They found that the ligands in the nanoparticles self-assembled into rotational and parallel patterns that are strikingly similar to the patterns found in proteins’ secondary structure. This could indicate that nanoparticles of this size could easily interact with biological systems, providing new avenues for drug discovery.
The researchers also found that Au246 particles form by following two rules. First, they maximize the interactions between atoms, a mechanism that had been theorized but not yet seen. Second the nanoparticles match symmetric surface patterns, a mechanism that had not been considered previously. The matching, which is similar to puzzle pieces coming together, shows that the components of the particle can recognize each other by their patterns and spontaneously assemble into the highly ordered structure of a nanoparticle.
“Self-assembly is an important way of construction in the nanoworld. Understanding the rules of self-assembly is critical to designing and building up complex nanoparticles with a wide-range of functionalities,” said Zeng, the study’s lead author.
In future studies, Jin hopes to push the crystallization limits of nanoparticles even farther to larger and larger particles. He also plans to explore the particles’ electronic and catalytic power.
The ‘artificial nose’ is not a newcomer to this blog. The most recent post prior to this is a March 15, 2016 piece about Disney using an artificial nose for art conservation. Today’s (Jan. 9, 2016) piece concerns itself with work from Israel and ‘sniffing out’ disease, according to a Dec. 30, 2016 news item in Sputnik News,
A team from the Israel Institute of Technology has developed a device that from a single breath can identify diseases such as multiple forms of cancer, Parkinson’s disease, and multiple sclerosis. While the machine is still in the experimental stages, it has a high degree of promise for use in non-invasive diagnoses of serious illnesses.
The international team demonstrated that a medical theory first proposed by the Greek physician Hippocrates some 2400 years ago is true, certain diseases leave a “breathprint” on the exhalations of those afflicted. The researchers created a prototype for a machine that can pick up on those diseases using the outgoing breath of a patient. The machine, called the Na-Nose, tests breath samples for the presence of trace amounts of chemicals that are indicative of 17 different illnesses.
An international team of 56 researchers in five countries has confirmed a hypothesis first proposed by the ancient Greeks – that different diseases are characterized by different “chemical signatures” identifiable in breath samples. …
Diagnostic techniques based on breath samples have been demonstrated in the past, but until now, there has not been scientific proof of the hypothesis that different and unrelated diseases are characterized by distinct chemical breath signatures. And technologies developed to date for this type of diagnosis have been limited to detecting a small number of clinical disorders, without differentiation between unrelated diseases.
The study of more than 1,400 patients included 17 different and unrelated diseases: lung cancer, colorectal cancer, head and neck cancer, ovarian cancer, bladder cancer, prostate cancer, kidney cancer, stomach cancer, Crohn’s disease, ulcerative colitis, irritable bowel syndrome, Parkinson’s disease (two types), multiple sclerosis, pulmonary hypertension, preeclampsia and chronic kidney disease. Samples were collected between January 2011 and June 2014 from in 14 departments at 9 medical centers in 5 countries: Israel, France, the USA, Latvia and China.
The researchers tested the chemical composition of the breath samples using an accepted analytical method (mass spectrometry), which enabled accurate quantitative detection of the chemical compounds they contained. 13 chemical components were identified, in different compositions, in all 17 of the diseases.
According to Prof. Haick, “each of these diseases is characterized by a unique fingerprint, meaning a different composition of these 13 chemical components. Just as each of us has a unique fingerprint that distinguishes us from others, each disease has a chemical signature that distinguishes it from other diseases and from a normal state of health. These odor signatures are what enables us to identify the diseases using the technology that we developed.”
With a new technology called “artificially intelligent nanoarray,” developed by Prof. Haick, the researchers were able to corroborate the clinical efficacy of the diagnostic technology. The array enables fast and inexpensive diagnosis and classification of diseases, based on “smelling” the patient’s breath, and using artificial intelligence to analyze the data obtained from the sensors. Some of the sensors are based on layers of gold nanoscale particles and others contain a random network of carbon nanotubes coated with an organic layer for sensing and identification purposes.
The study also assessed the efficiency of the artificially intelligent nanoarray in detecting and classifying various diseases using breath signatures. To verify the reliability of the system, the team also examined the effect of various factors (such as gender, age, smoking habits and geographic location) on the sample composition, and found their effect to be negligible, and without impairment on the array’s sensitivity.
“Each of the sensors responds to a wide range of exhalation components,” explain Prof. Haick and his previous Ph.D student, Dr. Morad Nakhleh, “and integration of the information provides detailed data about the unique breath signatures characteristic of the various diseases. Our system has detected and classified various diseases with an average accuracy of 86%.
This is a new and promising direction for diagnosis and classification of diseases, which is characterized not only by considerable accuracy but also by low cost, low electricity consumption, miniaturization, comfort and the possibility of repeating the test easily.”
“Breath is an excellent raw material for diagnosis,” said Prof. Haick. “It is available without the need for invasive and unpleasant procedures, it’s not dangerous, and you can sample it again and again if necessary.”
Here’s a schematic of the study, which the researchers have made available,
Diagram: A schematic view of the study. Two breath samples were taken from each subject, one was sent for chemical mapping using mass spectrometry, and the other was analyzed in the new system, which produced a clinical diagnosis based on the chemical fingerprint of the breath sample. Courtesy: Tech;nion
There is also a video, which covers much of the same ground as the press release but also includes information about the possible use of the Na-Nose technology in the European Union’s SniffPhone project,
Here’s a link to and a citation for the paper,
Diagnosis and Classification of 17 Diseases from 1404 Subjects via Pattern Analysis of Exhaled Molecules by Morad K. Nakhleh, Haitham Amal, Raneen Jeries, Yoav Y. Broza, Manal Aboud, Alaa Gharra, Hodaya Ivgi, Salam Khatib, Shifaa Badarneh, Lior Har-Shai, Lea Glass-Marmor, Izabella Lejbkowicz, Ariel Miller, Samih Badarny, Raz Winer, John Finberg, Sylvia Cohen-Kaminsky, Frédéric Perros, David Montani, Barbara Girerd, Gilles Garcia, Gérald Simonneau, Farid Nakhoul, Shira Baram, Raed Salim, Marwan Hakim, Maayan Gruber, Ohad Ronen, Tal Marshak, Ilana Doweck, Ofer Nativ, Zaher Bahouth, Da-you Shi, Wei Zhang, Qing-ling Hua, Yue-yin Pan, Li Tao, Hu Liu, Amir Karban, Eduard Koifman, Tova Rainis, Roberts Skapars, Armands Sivins, Guntis Ancans, Inta Liepniece-Karele, Ilze Kikuste, Ieva Lasina, Ivars Tolmanis, Douglas Johnson, Stuart Z. Millstone, Jennifer Fulton, John W. Wells, Larry H. Wilf, Marc Humbert, Marcis Leja, Nir Peled, and Hossam Haick. ACS Nano, Article ASAP DOI: 10.1021/acsnano.6b04930 Publication Date (Web): December 21, 2016
As for SniffPhone, they’re hoping that Na-Nose or something like it will allow them to modify smartphones in a way that will allow diseases to be detected.
I can’t help wondering who will own the data if your smartphone detects a disease. If you think that’s an idle question, here’s an excerpt from Sue Halpern’s Dec. 22, 2016 review of two books (“Weapons of Math Destruction: How Big Data Increases Inequality and Threatens Democracy” by Cathy O’Neil and “Virtual Competition: The Promise and Perils of the Algorithm-Driven Economy” by Ariel Ezrachi and Maurice E. Stucke) for the New York Times Review of Books,
We give our data away. We give it away in drips and drops, not thinking that data brokers will collect it and sell it, let alone that it will be used against us. There are now private, unregulated DNA databases culled, in part, from DNA samples people supply to genealogical websites in pursuit of their ancestry. These samples are available online to be compared with crime scene DNA without a warrant or court order. (Police are also amassing their own DNA databases by swabbing cheeks during routine stops.) In the estimation of the Electronic Frontier Foundation, this will make it more likely that people will be implicated in crimes they did not commit.
Or consider the data from fitness trackers, like Fitbit. As reported in The Intercept:
During a 2013 FTC panel on “Connected Health and Fitness,” University of Colorado law professor Scott Peppet said, “I can paint an incredibly detailed and rich picture of who you are based on your Fitbit data,” adding, “That data is so high quality that I can do things like price insurance premiums or I could probably evaluate your credit score incredibly accurately.”
Halpern’s piece is well worth reading in its entirety.
For centuries, scientists believed that light, like all waves, couldn’t be focused down smaller than its wavelength, just under a millionth of a metre. Now, researchers led by the University of Cambridge have created the world’s smallest magnifying glass, which focuses light a billion times more tightly, down to the scale of single atoms.
If they’ve created is a ‘magnifying glass’ as they call it in the news item, then I suppose you could call the ‘pico-cavity’ mentioned in the following press release, a lens.
In collaboration with European colleagues, the team used highly conductive gold nanoparticles to make the world’s tiniest optical cavity, so small that only a single molecule can fit within it. The cavity – called a ‘pico-cavity’ by the researchers – consists of a bump in a gold nanostructure the size of a single atom, and confines light to less than a billionth of a metre. The results, reported in the journal Science, open up new ways to study the interaction of light and matter, including the possibility of making the molecules in the cavity undergo new sorts of chemical reactions, which could enable the development of entirely new types of sensors.
According to the researchers, building nanostructures with single atom control was extremely challenging. “We had to cool our samples to -260°C in order to freeze the scurrying gold atoms,” said Felix Benz, lead author of the study. The researchers shone laser light on the sample to build the pico-cavities, allowing them to watch single atom movement in real time.
“Our models suggested that individual atoms sticking out might act as tiny lightning rods, but focusing light instead of electricity,” said Professor Javier Aizpurua from the Center for Materials Physics in San Sebastian in Spain, who led the theoretical section of this work.
“Even single gold atoms behave just like tiny metallic ball bearings in our experiments, with conducting electrons roaming around, which is very different from their quantum life where electrons are bound to their nucleus,” said Professor Jeremy Baumberg of the NanoPhotonics Centre at Cambridge’s Cavendish Laboratory, who led the research.
The findings have the potential to open a whole new field of light-catalysed chemical reactions, allowing complex molecules to be built from smaller components. Additionally, there is the possibility of new opto-mechanical data storage devices, allowing information to be written and read by light and stored in the form of molecular vibrations.
Here’s a link to and a citation for the paper,
Single-molecule optomechanics in “picocavities” by Felix Benz, Mikolaj K. Schmidt, Alexander Dreismann, Rohit Chikkaraddy, Yao Zhang, Angela Demetriadou, Cloudy Carnegie, Hamid Ohadi, Bart de Nijs, Ruben Esteban, Javier Aizpurua, Jeremy J. Baumberg. Science 11 Nov 2016: Vol. 354, Issue 6313, pp. 726-729 DOI: 10.1126/science.aah5243