Tag Archives: gold nanoparticles

Single molecule nanogold-based probe for photoacoustic Imaging and SERS biosensing

As I understand it, the big deal is that A*STAR (Singapore’s Agency for Science, Rechnology and Research) scientists have found a way to make a single molecule probe do the work of a two-molecule probe when imaging tumours. From a July 29, 2015 news item on Nanowerk (Note: A link has been removed),

An organic dye that can light up cancer cells for two powerful imaging techniques providing complementary diagnostic information has been developed and successfully tested in mice by A*STAR researchers (“Single Molecule with Dual Function on Nanogold: Biofunctionalized Construct for In Vivo Photoacoustic Imaging and SERS Biosensing”).

A July 29, 2015 A*STAR news release, which originated the news item, describes the currently used multimodal imaging technique and provides details about the new single molecule technique,

Imaging tumors is vitally important for cancer research, but each imaging technique has its own limitations for studying cancer in living organisms. To overcome the limitations of individual techniques, researchers typically employ a combination of various imaging methods — a practice known as multimodal imaging. In this way, they can obtain complementary information and hence a more complete picture of cancer.

Two very effective methods for imaging tumors are photoacoustic imaging and surface-enhanced Raman scattering (SERS). Photoacoustic imaging can image deep tissue with a good resolution, whereas SERS detects miniscule amounts of a target molecule. To simultaneously use both photoacoustic imaging and SERS, a probe must produce signals for both imaging modalities.

In multimodal imaging, researchers typically combine probes for each imaging modality into a single two-molecule probe. However, the teams of Malini Olivo at the A*STAR Singapore Bioimaging Consortium and Bin Liu at the A*STAR Institute of Materials Research and Engineering, along with overseas collaborator Ben Zhong Tang from the Hong Kong University of Science and Technology, adopted a different approach — they developed single-molecule probes that can be used for both photoacoustic imaging and SERS. The probes are based on organic cyanine dyes that absorb near-infrared light, which has the advantage of being able to deeply penetrate tissue, enabling tumors deep within the body to be imaged.

Once the team had verified that the probes worked for both imaging modalities, they optimized the performances of the probes by adding gold nanoparticles to them to amplify the SERS signal and by encapsulating them in the polymer polyethylene glycol to stabilize their structures.

The researchers then deployed these optimized probes in live mice. By functionalizing the probes with an antibody that recognizes a tumor cell-surface protein, they were able to use them to target tumors. The scientists found that, in photoacoustic imaging, the tumor-targeted probes produced signals that were roughly three times stronger than those of unmodified probes. Using SERS, the team was also able to monitor the concentrations of the probes in the tumor, spleen and liver in real time with a high degree of sensitivity.

U. S. Dinish, a senior scientist in Olivo’s group, recalls the team’s “surprise at the sensitivity and potential of the nanoconstruct.” He anticipates that the probe could be used to guide surgical removal of tumors.

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

Single Molecule with Dual Function on Nanogold: Biofunctionalized Construct for In Vivo Photoacoustic Imaging and SERS Biosensing by U. S. Dinish, Zhegang Song, Chris Jun Hui Ho, Ghayathri Balasundaram, Amalina Binte Ebrahim Attia, Xianmao Lu, Ben Zhong Tang, Bin Liu, and Malini Olivo. Advanced Functional Materials, Vol 25 Issue 15
pages 2316–2325, April 15, 2015 DOI: 10.1002/adfm.201404341 Article first published online: 11 MAR 2015

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

There’s more than one black gold

‘Black gold’ is a phrase I associate with oil, signifying its importance and desirability. These days, this analogic phrase can describe a material according to a July 24, 2015 news item on Nanowerk,

If colloidal gold [gold in solution] self-assembles into the form of larger vesicles, a three-dimensional state can be achieved that is called “black gold” because it absorbs almost the entire spectrum of visible light. How this novel intense plasmonic state can be established and what its characteristics and potential medical applications are is explored by Chinese scientists and reported in the journal Angewandte Chemie …

A July 24, 2015 Wiley (Angewandte Chemie) press release, which originated the news item, provides more details,

Metal nanostructures can self-assemble into superstructures that offer intriguing new spectroscopic and mechanical properties. Plasmonic coupling plays a particular role in this context. For example, it has been found that plasmonic metal nanoparticles help to scatter the incoming light across the surface of the Si substrate at resonance wavelengths, therefore enhancing the light absorbing potential and thus the effectivity of solar cells.

On the other hand, plasmonic vesicles are the promising theranostic platform for biomedical applications, a notion which inspired Yue Li and Cuncheng Li of the Chinese Academy of Science, Hefei, China, and the University of Jinan, China, as well as collaborators to prepare plasmonic colloidosomes composed of gold nanospheres.

As the method of choice, the scientists have designed an emulsion-templating approach based on monodispersed gold nanospheres as building blocks, which arranged themselves into large spherical vesicles in a reverse emulsion system.

The resulting plasmonic vesicles were of micrometer-size and had a shell composed of hexagonally close-packed colloidal nanosphere particles in bilayer or, for the very large superspheres, multilayer arrangement, which provided the enhanced stability.

“A key advantage of this system is that such self-assembly can avoid the introduction of complex stabilization processes to lock the nanoparticles together”, the authors explain.

The hollow spheres exhibited an intense plasmonic resonance in their three-dimensionally packed structure and had a dark black appearance compared to the brick red color of the original gold nanoparticles. The “black gold” was thus characterized by a strong broadband absorption in the visible light and a very regular vesicle superstructure. In medicine, gold vesicles are intensively discussed as vehicles for the drug delivery to tumor cells, and, therefore, it could be envisaged to exploit the specific light-matter interaction of such plasmonic vesicle structures for medical use, but many other applications are also feasible, as the authors propose: “The presented strategy will pave a way to achieve noble-metal superstructures for biosensors, drug delivery, photothermal therapy, optical microcavity, and microreaction platforms.” This will prove the flexibility and versatility of the noble-metal nanostructures.

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

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self-Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System by Dilong Liu, Dr. Fei Zhou, Cuncheng Li, Tao Zhang, Honghua Zhang, Prof. Weiping Cai, and Prof. Yue Li. Angewandte Chemie International Edition Article first published online: 25 JUN 2015 DOI: 10.1002/anie.201503384

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

There is an image illustrating the work but, sadly, the gold doesn’t look black,

BlackGold

© Wiley-VCH

That’s it!

Labeling 5nm gold nanoparticles with gold isotopes (soft core, hard shell)

There’s a lot of talk about using gold nanoparticles (and others) to deliver drugs to specific locations in the body but this research at Helmholtz Zentrum Muenchen (Munich, Germany) and the University of Marburg (Marburg, Germany) appears to be the first successful attempt at tracking how this potential delivery system might actually work. From a June 23, 2015 news item on Azonano,

Nanoparticles are the smallest particles capable of reaching virtually all parts of the body. Researchers use various approaches to test ways in which nanoparticles could be used in medicine – for instance, to deliver substances to a specific site in the body such as a tumor.

For this purpose, nanoparticles are generally coated with organic materials because their surface quality plays a key role in determining further targets in the body. If they have a water-repellent shell, nanoparticles are quickly identified by the body’s immune system and eliminated.

How gold particles wander through the body

The team of scientists headed by Dr. Wolfgang Kreyling, who is now an external scientific advisor at the Institute of Epidemiology II within the Helmholtz Zentrum Muenchen, and Prof. Wolfgang Parak from the University of Marburg, succeeded for the first time in tracking the chronological sequence of such particles in an animal model. To this end, they generated tiny 5 nm gold nanoparticles radioactively labeled with a gold isotope*. These were also covered with a polymer shell and tagged with a different radioactive isotope. According to the researchers, this was, technically speaking, a very demanding nanotechnological step.

A June 22, 2015 Helmholtz Zentrum Muenchen press release, which originated the news item, provides more detail,

After the subsequent intravenous injection of the particles, however, the team observed how the specially applied polymer shell disintegrated. “Surprisingly, the particulate gold accumulated mainly in the liver,” Dr. Kreyling recalls. “In contrast, the shell molecules reacted in a significantly different manner, distributing themselves throughout the body.” Further analyses conducted by the scientists explained the reason for this: so-called proteolytic enzymes** in certain liver cells appear to separate the particles from their shell. According to the researchers, this effect was hitherto unknown in vivo, since up to now the particle-conjugate had only been tested in cell cultures, where this effect had not been examined sufficiently thoroughly.

“Our results show that even nanoparticle-conjugates*** that appear highly stable can change their properties when deployed in the human body,” Dr. Kreyling notes, evaluating the results. “The study will thus have an influence on future medical applications as well as on the risk evaluation of nanoparticles in consumer products and in science and technology.”

* Isotopes are types of atoms which have different mass numbers but which represent the same element.

** Proteolytic enzymes split protein structures and are used, for example, to nourish or detoxify the body.

*** Conjugates are several types of molecules that are bound in one particle.

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

In vivo integrity of polymer-coated gold nanoparticles by Wolfgang G. Kreyling, Abuelmagd M. Abdelmonem, Zulqurnain Ali, Frauke Alves, Marianne Geiser, Nadine Haberl, Raimo Hartmann, Stephanie Hirn, Dorleta Jimenez de Aberasturi, Karsten Kantner, Gülnaz Khadem-Saba, Jose-Maria Montenegro, Joanna Rejman, Teofilo Rojo, Idoia Ruiz de Larramendi, Roser Ufartes, Alexander Wenk, & Wolfgang J. Parak. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.111 Published online 15 June 2015

This paper is behind a paywall.

Metallic nanoparticles: measuring their discrete quantum states

I tend to forget how new nanotechnology is and unconsciously take for granted stunning feats such as measuring a metallic nanoparticle’s electronic properties. A June 15, 2015 news item on Nanowerk provides a reminder with its description of the difficulties and a new technique to make it easier (Note:  A link has been removed),

How do you measure the electronic properties of individual nanoparticles or molecules that are only a few nanometers in size? Conventional methods using electron transport spectroscopy rely on contacting a material with two contacts, a source and a drain electrode. By applying a small potential difference over the electrodes and monitoring the resulting current, valuable information about the electronic properties are extracted. For example if a material is metallic or semiconducting.
But this becomes quite a challenge if the material is only a few nm in size. Even the most sophisticated fabrication tools such as electron-beam lithography have a resolution of about 10 nm at best, which is not precise enough. Scientists have developed workarounds such as creating small gaps in narrow metallic wires in which a nanoparticle can be trapped if it matches the gap size. However, even though there have been some notable successes using this approach, this method has a low yield and is not very reproducible.

Now an international collaboration including researchers in Japan, the university [sic] of Cambridge and the LCN [London Centre for Nanotechnology] in the UK have approached this in a different way as described in a paper in Nature’s Scientific Reports (“Radio-frequency capacitance spectroscopy of metallic nanoparticles”). Their method only requires a single electrode to be in direct contact with a nanoparticle or molecule, thus significantly simplifying fabrication.

A June 15, 2015 (?) LCN press release, which originated the news item, describes the achievement,

The researchers demonstrated the potential of the radio-frequency reflectometry technique by measurements on Au nanoparticles of only 2.7 nm in diameter. For such small particles, the electronic spectrum is discrete which was indeed observed in the measurements and in very good agreement with theoretical models. The researchers now plan to extend these measurements to other nanoparticles and molecules with applications in a range of areas such as biomedicine, spintronics and quantum information processing.

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

Radio-frequency capacitance spectroscopy of metallic nanoparticles by James C. Frake, Shinya Kano, Chiara Ciccarelli, Jonathan Griffiths, Masanori Sakamoto,  Toshiharu Teranishi, Yutaka Majima, Charles G. Smith & Mark R. Buitelaar. Scientific RepoRts 5:10858 DOi: 10.1038/srep10858 Published June 4, 2015

This is an open access paper.

Using stevia to synthesize gold nanoparticles?

The research into using stevia as a greener alternative to synthesize gold nanoparticles is from Iran (from a June 2, 2015 news item on Nanotechology Now),

Iranian researchers suggested the extract of stevia plant as a replacement for chemical solvents and reducers in the synthesis of gold nanoparticles.

A May 31, 2015 Iran Nanotechnology Initiative Council news release, which originated the news item, provides a little more detail,

Various chemical methods have been proposed for the synthesis of gold nanoparticles as the application of these particles has increased. These methods cause some problems, including environmental pollution and difficulty in synthesis. This research studied the possibility of using stevia leaf extract to reduce gold ions into atomic nanoparticles.

According to the researchers, the extract of stevia plant is biocompatible and it acts as a reducing and stabilizing agent. In addition, the simplicity of the method easily makes possible the quick biosynthesis of gold nanoparticles in different sizes.

Since the antibacterial effect of gold nanoparticles has been proved, these materials can be used in the production of detergents, packaging industry and production of medical drugs.

Gold nanoparticles stabilized with stevia extract in this research are absorbed by cells more than nanoparticles coated with chemical stabilizers (polymers). The reason is that nanoparticles stabilized with herbal extract contain various proteins and fibers on their surface. Therefore, the nanoparticles are more probable to diffuse into the cells through the multiple receivers of protein in comparison with the dual receiver of protein and chemical polymer. Therefore, it is expected that the transfer of protein and drugs into the cells can be adjusted by changing the size and shape of the nanoparticles.

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

GC–MS analysis of bioactive components and synthesis of gold nanoparticle using Chloroxylon swietenia DC leaf extract and its larvicidal activity by Govindasamy Balasubramani, Rajendiran Ramkumar, Narayanaswamy Krishnaveni, Rajamani Sowmiya, Paramasivam Deepak, Dhayalan Arul, & Pachiappan Perumal. Journal of Photochemistry and Photobiology B: Biology Volume 148, July 2015, Pages 1–8  doi:10.1016/j.jphotobiol.2015.03.016

This paper is behind a paywall.

Gold detection down to the nanoparticle?

It appears that detecting gold, presumably for mining purposes, isn’t as easy as one might think especially at the nanoscale. Researchers at Australia’s University of Adelaide have devised a new method according to an April 29, 2015 news item on Nanowerk (Note: A link has been removed),

University of Adelaide researchers are developing a portable, highly sensitive method for gold detection that would allow mineral exploration companies to test for gold on-site at the drilling rig.

Using light in two different processes (fluorescence and absorption), the researchers from the University’s Institute for Photonics and Advanced Sensing (IPAS), have been able to detect gold nanoparticles at detection limits 100 times lower than achievable under current methods.

An April 29, 2015 University of Adelaide news release details Australia’s interest in gold and offers a high level explanation of the need for better gold detection (Note: Links have been removed),

Australia is the world’s second largest gold producer, worth $13 billion in export earnings.

“Gold is not just used for jewellery, it is in high demand for electronics and medical applications around the world, but exploration for gold is extremely challenging with a desire to detect very low concentrations of gold in host rocks,” says postdoctoral researcher Dr Agnieszka Zuber, working on the project with Associate Professor Heike Ebendorff-Heidepriem.

“The presence of gold deep underground is estimated by analysis of rock particles coming out of the drilling holes. But current portable methods for detection are not sensitive enough, and the more sensitive methods require some weeks before results are available.

“This easy-to-use sensor will allow fast detection right at the drill rig with the amount of gold determined within an hour, at much lower cost.”

The researchers have been able to detect less than 100 parts per billion of gold in water. They are now testing using samples of real rock with initial promising results. The work is funded by the Deep Exploration Technologies Cooperative Research Centre.

The gold detection project is one of a series of projects which will be presented at the IPAS Minerals and Energy Sector Workshop today [April 29, 2015], aimed at linking resources specific research to local companies.

You can find out more about the University of Adelaide’s Institute of Photonics and Advanced Sensing here.

Gold nanoparticle clusters: four new models

This research is being done at the University of Nebraska-Lincoln (UNL) which seems to be on a publishing tear lately. From an April 27, 2015 news item on Nanowerk, here’s the latest,

They may deal in gold, atomic staples and electron volts rather than cement, support beams and kilowatt-hours, but chemists have drafted new nanoscale blueprints for low-energy structures capable of housing pharmaceuticals and oxygen atoms.

Led by UNL’s Xiao Cheng Zeng and former visiting professor Yi Gao, new research has revealed four atomic arrangements of a gold nanoparticle cluster. The arrangements exhibit much lower potential energy and greater stability than a standard-setting configuration reported last year by a Nobel Prize-winning team from Stanford University.

The modeling of these arrangements could inform the cluster’s use as a transporter of pharmaceutical drugs and as a catalyst for removing pollutants from vehicular emissions or other industrial byproducts, Zeng said.

An April 24, 2015 UNL news release (also on EurekAlert), which originated the news item, provides more technical details about the work,

Led by UNL’s Xiao Cheng Zeng and former visiting professor Yi Gao, new research has revealed four atomic arrangements of a gold nanoparticle cluster. The arrangements exhibit much lower potential energy and greater stability than a standard-setting configuration reported last year by a Nobel Prize-winning team from Stanford University.

The modeling of these arrangements could inform the cluster’s use as a transporter of pharmaceutical drugs and as a catalyst for removing pollutants from vehicular emissions or other industrial byproducts, Zeng said.

Zeng and his colleagues unveiled the arrangements for a molecule featuring 68 gold atoms and 32 pairs of bonded sulfur-hydrogen atoms. Sixteen of the gold atoms form the molecule’s core; the remainder bond with the sulfur and hydrogen to form a protective coating that stems from the core.

Differences in atomic arrangements can alter molecular energy and stability, with less potential energy making for a more stable molecule. The team calculates that one of the arrangements may represent the most stable possible structure in a molecule with its composition.

“Our group has helped lead the front on nano-gold research over the past 10 years,” said Zeng, an Ameritas University Professor of chemistry. “We’ve now found new coating structures of much lower energy, meaning they are closer to the reality than (previous) analyses. So the deciphering of this coating structure is major progress.”

The structure of the molecule’s gold core was previously detailed by the Stanford team. Building on this, Zeng and his colleagues used a computational framework dubbed “divide-and-protect” to configure potential arrangements of the remaining gold atoms and sulfur-hydrogen pairs surrounding the core.

The researchers already knew that the atomic coating features staple-shaped linkages of various lengths. They also knew the potential atomic composition of each short, medium and long staple — such as the fact that a short staple consists of two sulfur atoms bonded with one gold.

By combining this information with their knowledge of how many atoms reside outside the core, the team reduced the number of potential arrangements from millions to mere hundreds.

“We divided 32 into the short, middle and long (permutations),” said Zeng, who helped develop the divide-and-protect approach in 2008. “We lined up all those possible arrangements, and then we computed their energies to find the most stable ones.

“Without those rules, it’s like finding a needle in the Platte River. With them, it’s like finding a needle in the fountain outside the Nebraska Union. It’s still hard, but it’s much more manageable. You have a much narrower range.”

The researchers resorted to the computational approach because of the difficulty of capturing the structure via X-ray crystallography or single-particle transmission electron microscopy, two of the most common imaging methods at the atomic scale.

Knowing the nanoparticle’s most stable configurations, Zeng said, could allow biomedical engineers to identify appropriate binding sites for drugs used to treat cancer and other diseases. The findings could also optimize the use of gold nanoparticles in catalyzing the oxidation process that transforms dangerous carbon monoxide emissions into the less noxious carbon dioxide, he said.

Here’s an image illustrating the work,

This rendering shows the atomic arrangements of a gold nanocluster as reported in a new study led by UNL chemist Xiao Cheng Zeng. The cluster measures about 1.7 nanometers long -- roughly the same length that a human fingernail grows in two seconds. (Joel Brehm/Office of Research and Economic Development)

This rendering shows the atomic arrangements of a gold nanocluster as reported in a new study led by UNL chemist Xiao Cheng Zeng. The cluster measures about 1.7 nanometers long — roughly the same length that a human fingernail grows in two seconds. (Joel Brehm/Office of Research and Economic Development)

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

Unraveling structures of protection ligands on gold nanoparticle Au68(SH)32 by Wen Wu Xu, Yi Gao, and Xiao Cheng Zeng. Science Advances 24 Apr 2015: Vol. 1 no. 3 e1400211 DOI: 10.1126/sciadv.1400211

This is an open access article.

As for the Stanford University team’s work mentioned in the news release, I believe it’s from the Roger Kornberg (Nobel laureate) Laboratory. There’s more about that team’s work in an Aug. 21, 2014 article (A new gold standard for nano; Note: A link has been removed) by David Bradley for Chemistry World,

Characterising gold nanoparticles at atomic resolution might improve our understanding of the catalytic activity of these materials, according to an international team. These researchers have now demonstrated that it is possible to use electron microscopy to obtain data on at least one gold cluster of greater than 1nm diameter and to validate the results by comparison with small-angle x-ray scattering data, infrared absorption spectra and density functional theory calculations.

Here’s a link to and a citation for the 2014 paper,

Electron microscopy of gold nanoparticles at atomic resolution by Maia Azubel, Jaakko Koivisto, Sami Malola, David Bushnell, Greg L. Hura, Ai Leen Koh, Hironori Tsunoyama, Tatsuya Tsukuda, Mika Pettersson, Hannu Häkkinen, & Roger D. Kornberg. Science 22 August 2014: Vol. 345 no. 6199 pp. 909-912 DOI: 10.1126/science.1251959

This paper is behind a paywall.

The most recent posting here about gold nanoparticles is an April 14, 2015 piece titled: Gold atoms: sometimes they’re a metal and sometimes they’re a molecule.

Liquid nanolaser: the first one

According to an April 24, 2015 news item on Nanowerk, there has been a big discovery at Northwestern University (located in Chicago, Illinois, US),

Northwestern University scientists have developed the first liquid nanoscale laser. And it’s tunable in real time, meaning you can quickly and simply produce different colors, a unique and useful feature. The laser technology could lead to practical applications, such as a new form of a “lab on a chip” for medical diagnostics.

To understand the concept, imagine a laser pointer whose color can be changed simply by changing the liquid inside it, instead of needing a different laser pointer for every desired color.

In addition to changing color in real time, the liquid nanolaser has additional advantages over other nanolasers: it is simple to make, inexpensive to produce and operates at room temperature.

An April 24, 2015 Northwestern University news release by Megan Fellman (also on EurekAlert), which originated the news item, offers a little history buttressed by some technical details (Note: Links have been removed),

Nanoscopic lasers — first demonstrated in 2009 — are only found in research labs today. They are, however, of great interest for advances in technology and for military applications.

“Our study allows us to think about new laser designs and what could be possible if they could actually be made,” said Teri W. Odom, who led the research. “My lab likes to go after new materials, new structures and new ways of putting them together to achieve things not yet imagined. We believe this work represents a conceptual and practical engineering advance for on-demand, reversible control of light from nanoscopic sources.”

The liquid nanolaser in this study is not a laser pointer but a laser device on a chip, Odom explained. The laser’s color can be changed in real time when the liquid dye in the microfluidic channel above the laser’s cavity is changed.

The laser’s cavity is made up of an array of reflective gold nanoparticles, where the light is concentrated around each nanoparticle and then amplified. (In contrast to conventional laser cavities, no mirrors are required for the light to bounce back and forth.) Notably, as the laser color is tuned, the nanoparticle cavity stays fixed and does not change; only the liquid gain around the nanoparticles changes.

The main advantages of very small lasers are:

• They can be used as on-chip light sources for optoelectronic integrated circuits;

• They can be used in optical data storage and lithography;

• They can operate reliably at one wavelength; and

• They should be able to operate much faster than conventional lasers because they are made from metals.

Some technical background

Plasmon lasers are promising nanoscale coherent sources of optical fields because they support ultra-small sizes and show ultra-fast dynamics. Although plasmon lasers have been demonstrated at different spectral ranges, from the ultraviolet to near-infrared, a systematic approach to manipulate the lasing emission wavelength in real time has not been possible.

The main limitation is that only solid gain materials have been used in previous work on plasmon nanolasers; hence, fixed wavelengths were shown because solid materials cannot easily be modified. Odom’s research team has found a way to integrate liquid gain materials with gold nanoparticle arrays to achieve nanoscale plasmon lasing that can be tuned dynamical, reversibly and in real time.

The use of liquid gain materials has two significant benefits:

• The organic dye molecules can be readily dissolved in solvents with different refractive indices. Thus, the dielectric environment around the nanoparticle arrays can be tuned, which also tunes the lasing wavelength.

• The liquid form of gain materials enables the fluid to be manipulated within a microfluidic channel. Thus, dynamic tuning of the lasing emission is possible simply by flowing liquid with different refractive indices. Moreover, as an added benefit of the liquid environment, the lasing-on-chip devices can show long-term stability because the gain molecules can be constantly refreshed.

These nanoscale lasers can be mass-produced with emission wavelengths over the entire gain bandwidth of the dye. Thus, the same fixed nanocavity structure (the same gold nanoparticle array) can exhibit lasing wavelengths that can be tuned over 50 nanometers, from 860 to 910 nanometers, simply by changing the solvent the dye is dissolved in.

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

Real-time tunable lasing from plasmonic nanocavity arrays by Ankun Yang, Thang B. Hoang, Montacer Dridi, Claire Deeb, Maiken H. Mikkelsen, George C. Schatz, & Teri W. Odom. Nature Communications 6, Article number: 6939 doi:10.1038/ncomms7939 Published 20 April 2015

This paper is open access.

Gold atoms: sometimes they’re a metal and sometimes they’re a molecule

Fascinating work out of Finland shows that a minor change in the number of gold atoms in your gold nanoparticle can mean the difference between a metal and a molecule (coincidentally, this phenomenon is alluded to in my April 14, 2015 post (Nature’s patterns reflected in gold nanoparticles); more about that at the end of this piece. Getting back to Finland and when gold is metal and when it’s a molecule, here’s more from an April 10, 2015 news item on ScienceDaily,

Researchers at the Nanoscience Center at the University of Jyväskylä, Finland, have shown that dramatic changes in the electronic properties of nanometre-sized chunks of gold occur in well-defined size range. Small gold nanoclusters could be used, for instance, in short-term storage of energy or electric charge in the field of molecular electronics. Funded by the Academy of Finland, the researchers have been able to obtain new information which is important, among other things, in developing bioimaging and sensing based on metal-like clusters.

An April 10, 2015 news release (also on EurekAlert) on the Academy of Finland (Suomen Akatemia) website, which originated the news item, describes the work in more detail,

Two recent papers by the researchers at Jyväskylä (1, 2) demonstrate that the electronic properties of two different but still quite similar gold nanoclusters can be drastically different. The clusters were synthesised by chemical methods incorporating a stabilising ligand layer on their surface. The researchers found that the smaller cluster, with up to 102 gold atoms, behaves like a giant molecule while the larger one, with at least 144 gold atoms, already behaves, in principle, like a macroscopic chunk of metal, but in nanosize.

The fundamentally different behaviour of these two differently sized gold nanoclusters was demonstrated by shining a laser light onto solution samples containing the clusters and by monitoring how energy dissipates from the clusters into the surrounding solvent.

“Molecules behave drastically different from metals,” said Professor Mika Pettersson, the principal investigator of the team conducting the experiments. “The additional energy from light, absorbed by the metal-like clusters, transfers to the environment extremely rapidly, in about one hundred billionth of a second, while a molecule-like cluster is excited to a higher energy state and dissipates the energy into the environment with a rate that is at least 100 times slower. This is exactly what we saw: the 102-gold atom cluster is a giant molecule showing even a transient magnetic state while the 144-gold atom cluster is already a metal. We’ve thus managed to bracket an important size region where this fundamentally interesting change in the behaviour takes place.”

“These experimental results go together very well with what our team has seen from computational simulations on these systems,” said Professor Hannu Häkkinen, a co-author of the studies and the scientific director of the nanoscience centre. “My team predicted this kind of behaviour back in 2008-2009 when we saw big differences in the electronic structure of exactly these nanoclusters. It’s wonderful that robust spectroscopic experiments have now proved these phenomena. In fact, the metal-like 144-atom cluster is even more interesting, since we just published a theoretical paper where we saw a big enhancement of the metallic properties of just a few copper atoms mixed with gold.” (3)

Here are links to and citation for the papers,

Ultrafast Electronic Relaxation and Vibrational Cooling Dynamics of Au144(SC2H4Ph)60 Nanocluster Probed by Transient Mid-IR Spectroscopy by Satu Mustalahti, Pasi Myllyperkiö, Tanja Lahtinen, Kirsi Salorinne, Sami Malola, Jaakko Koivisto, Hannu Häkkinen, and Mika Pettersson. J. Phys. Chem. C, 2014, 118 (31), pp 18233–18239 DOI: 10.1021/jp505464z Publication Date (Web): July 3, 2014

Copyright © 2014 American Chemical Society

Copper Induces a Core Plasmon in Intermetallic Au(144,145)–xCux(SR)60 Nanoclusters by Sami Malola, Michael J. Hartmann, and Hannu Häkkinen. J. Phys. Chem. Lett., 2015, 6 (3), pp 515–520 DOI: 10.1021/jz502637b Publication Date (Web): January 22, 2015

Copyright © 2015 American Chemical Society

Molecule-like Photodynamics of Au102(pMBA)44 Nanocluster by Satu Mustalahti, Pasi Myllyperkiö, Sami Malola, Tanja Lahtinen, Kirsi Salorinne, Jaakko Koivisto, Hannu Häkkinen, and Mika Pettersson. ACS Nano, 2015, 9 (3), pp 2328–2335 DOI: 10.1021/nn506711a Publication Date (Web): February 22, 2015

Copyright © 2015 American Chemical Society

These papers are behind paywalls.

As for my April 14, 2015 post (Nature’s patterns reflected in gold nanoparticles), researchers at Carnegie Mellon University were researching patterns in different sized gold nanoparticles when this was noted in passing,

… Normally, gold is one of the best conductors of electrical current, but the size of Au133 is so small that the particle hasn’t yet become metallic. …

Nature’s patterns reflected in gold nanoparticles

A 133 atom gold nanoparticle bears a resemblance to the Milky Way and to DNA’s (deoxyribonucleic acid) double helix according to an April 9, 2015 news item on ScienceDaily,

Our world is full of patterns, from the twist of a DNA molecule to the spiral of the Milky Way. New research from Carnegie Mellon chemists has revealed that tiny, synthetic gold nanoparticles exhibit some of nature’s most intricate patterns.

Unveiling the kaleidoscope of these patterns was a Herculean task, and it marks the first time that a nanoparticle of this size has been crystallized and its structure mapped out atom by atom. The researchers report their work in the March 20  [2015] issue of Science Advances.

“As you broadly think about different research areas or even our everyday lives, these kinds of patterns, these hierarchical patterns, are universal,” said Rongchao Jin, associate professor of chemistry. “Our universe is really beautiful and when you see this kind of information in something as small as a 133-atom nanoparticle and as big as the Milky Way, it’s really amazing.”

An April 8, 2015 Carnegie Mellon University news release (also on EurekAlert but dated April 9) by Jocelyn Duffy, which originated the news release, offers a description of gold nanoparticles along with details about the research,

Gold nanoparticles, which can vary in size from 1 to 100 nanometers, are a promising technology that has applications in a wide range of fields including catalysis, electronics, materials science and health care. But, in order to use gold nanoparticles in practical applications, scientists must first understand the tiny particles’ structure.

“Structure essentially determines the particle’s properties, so without knowing the structure, you wouldn’t be able to understand the properties and you wouldn’t be able to functionalize them for specific applications,” said Jin, an expert in creating atomically precise gold nanoparticles.

With this latest research, Jin and his colleagues, including graduate student Chenjie Zeng, have solved the structure of a nanoparticle, Au133, made up of 133 gold atoms and 52 surface-protecting molecules—the biggest nanoparticle structure ever resolved with X-ray crystallography. While microscopy can reveal the size, shape and the atomic lattice of nanoparticles, it can’t discern the surface structure. X-ray crystallography can, by mapping out the position of every atom on the nanoparticles’ surface and showing how they bond with the gold core. Knowing the surface structure is key to using the nanoparticles for practical applications, such as catalysis, and for uncovering fundamental science, such as the basis of the particle’s stability.

The crystal structure of the Au133 nanoparticle divulged many secrets.

“With X-ray crystallography, we were able to see very beautiful patterns, which was a very exciting discovery. These patterns only show up when the nanoparticle size becomes big enough,” Jin said.

During production, the Au133 particles self-assemble into three layers within each particle: the gold core, the surface molecules that protect it and the interface between the two. In the crystal structure, Zeng discovered that the gold core is in the shape of an icosahedron. At the interface between the core and the surface-protecting molecules is a layer of sulfur atoms that bind with the gold atoms. The sulfur-gold-sulfur combinations stack into ladder-like helical structures. Finally, attached to the sulfur molecules is an outer layer of surface-protecting molecules whose carbon tails self-assemble into fourfold swirls.

“The helical features remind us of a DNA double helix and the rotating arrangement of the carbon tails is reminiscent of the way our galaxy is arranged. It’s really amazing,” Jin said.

These particular patterns are responsible for the high stability of Au133 compared to other sizes of gold nanoparticles. The researchers also tested the optical and electronic properties of Au133 and found that these gold nanoparticles are not metallic. [emphasis mine] Normally, gold is one of the best conductors of electrical current, but the size of Au133 is so small that the particle hasn’t yet become metallic. Jin’s group is currently testing the nanoparticles for use as catalysts, substances that can increase the rate of a chemical reaction.

*ETA April 14, 2015 at 9015 PDT: Coincidentally, researchers in Finland have been examining gold nanoparticles and the size at which they are considered metals and at which they are considered molecules (mentioned in my April 14, 2015 posting [Gold atoms: sometimes they’re a metal and sometimes they’re a molecule]).*

Getting back to patterns, the researchers have provided an A-ray image of Au133,

 Caption: The X-ray crystallographic structure of the gold nanoparticle is shown. Gold atoms = magenta; sulfur atoms = yellow; carbon atoms = gray; hydrogen atoms = white. Credit: Carnegie Mellon


Caption: The X-ray crystallographic structure of the gold nanoparticle is shown. Gold atoms = magenta; sulfur atoms = yellow; carbon atoms = gray; hydrogen atoms = white.
Credit: Carnegie Mellon

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

Structural patterns at all scales in a nonmetallic chiral Au133(SR)52 nanoparticle* by Chenjie Zeng, Yuxiang Chen, Kristin Kirschbaum, Kannatassen Appavoo, Matthew Y. Sfeir, Rongchao Jin. Science Advances 20 Mar 2015: Vol. 1 no. 2 e1500045 DOI: 10.1126/sciadv.1500045

This paper appears to be open access.

* Link updated June 26, 2015.