Tag Archives: Rongchao Jin

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.

Synthesized nanoparticles with the complexity of protein molecules

Caption: The structure of the largest gold nanoparticle to-date, Au246(SR)80, was resolved using x-ray crystallography. Credit: Carnegie Mellon University

Carnegie Mellon University (CMU) researchers synthesized a self-assembled nanoparticle of gold as they built on their 2015 work described in my April 14, 2015 posting (Nature’s patterns reflected in gold nanoparticles). Here’s the latest from the team in a Jan. 23, 2017 news item on phys.org,

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

A Jan.  23, 2017 CMU news release on EurekAlert, which originated the news item, expands on the theme,

“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.

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

Emergence of hierarchical structural complexities in nanoparticles and their assembly by Chenjie Zeng, Yuxiang Chen, Kristin Kirschbaum, Kelly J. Lambright, Rongchao Jin. Science  23 Dec 2016: Vol. 354, Issue 6319, pp. 1580-1584 DOI: 10.1126/science.aak9750

This paper is behind a paywall.

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.