Tag Archives: Giannis Mpourmpakis

Building metal nanoparticles: one step closer

University of Pittsburgh scientists have researched why metal nanoparticles form, a necessary first step before developing techniques for synthesizing them commercially. From a July 10, 2017 news item on ScienceDaily,

Although scientists have for decades been able to synthesize nanoparticles in the lab, the process is mostly trial and error, and how the formation actually takes place is obscure. A new study explains how metal nanoparticles form.

Caption: This is a structure of a ligand-protected Au25 nanocluster. Credit: Computer-Aided Nano and Energy Lab (C.A.N.E.LA.)

A July 10, 2017 University of Pittsburgh news release (also on EurekAlert), which originated the news item, expands on the theme (Note: A link has been removed),

“Even though there is extensive research into metal nanoparticle synthesis, there really isn’t a rational explanation why a nanoparticle is formed,” Dr. Mpourmpakis [Giannis Mpourmpakis, assistant professor of chemical and petroleum engineering] said. “We wanted to investigate not just the catalytic applications of nanoparticles, but to make a step further and understand nanoparticle stability and formation. This new thermodynamic stability theory explains why ligand-protected metal nanoclusters are stabilized at specific sizes.”

A ligand is a molecule that binds to metal atoms to form metal cores that are stabilized by a shell of ligands, and so understanding how they contribute to nanoparticle stabilization is essential to any process of nanoparticle application. Dr. Mpourmpakis explained that previous theories describing why nanoclusters stabilized at specific sizes were based on empirical electron counting rules – the number of electrons that form a closed shell electronic structure, but show limitations since there have been metal nanoclusters experimentally synthesized that do not necessarily follow these rules.

“The novelty of our contribution is that we revealed that for experimentally synthesizable nanoclusters there has to be a fine balance between the average bond strength of the nanocluster’s metal core, and the binding strength of the ligands to the metal core,” he said. “We could then relate this to the structural and compositional characteristic of the nanoclusters, like size, number of metal atoms, and number of ligands.

“Now that we have a more complete understanding of this stability, we can better tailor the nanoparticle morphologies and in turn properties, to applications from biolabeling of individual cells and targeted drug delivery to catalytic reactions, thereby creating more efficient and sustainable production processes.”

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

Thermodynamic stability of ligand-protected metal nanoclusters by Michael G. Taylor & Giannis Mpourmpakis. Nature Communications 8, Article number: 15988 (2017) doi:10.1038/ncomms15988 Published online: 07 July 2017

This paper is open access.

Surgery on nanoparticles?

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

A June 12, 2017 CMU press release (also on EurekAlert), which originated the news item, provides more details about the research,

“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 paper is open access.