Their approach offers a significant advantage over routine methods for analyzing gold nanoparticles because it can determine whether the nanoparticles exist in a both right-handed and left-handed configuration, a phenomenon called chirality. Determining a nanoparticle's chirality is an important step toward developing them as chiral catalysts — tools that are highly sought-after by the pharmaceutical industry. Their results are published online at ACS Nano.
Pictured above is the crystal structure of a pair of gold nanoparticles that exist in a right-handed (bottom) and left-handed (top) configuration. These nanoparticles hold great promise as a chiral catalyst—a tool highly sought-after by the pharmaceutical industry.gol
Many drugs on the market today contain at least one molecule that is chiral. Often only one of the configurations, or isomers, is effective in the body. In some cases, the other isomer may even be harmful. A striking example is the drug thalidomide, which consisted of two isomers: one of which helped pregnant women control nausea while the other caused damage to the developing fetus. In an effort to create safer, more effective drugs, drug manufacturers are looking for ways to produce purer substances that contain only the left- or right-handed isomer.
Huifeng Qian, a fourth-year graduate student working with Jin, created a gold nanoparticle that has the potential to catalyze chemical reactions that will produce one isomer rather than the other. The nanoparticle is comprised of precisely 38 gold atoms and measures a mere 1.4 nanometers. Qian worked diligently for nearly a year to grow the nanoparticles into high-quality crystals so that he could study their structure using x-ray crystallography.
"Growing a pure crystal from nanoparticles is very challenging, and you may not even be able to get a crystal at all," said Jin, an assistant professor of chemistry in CMU's Mellon College of Science. "In the nanoparticle community, the crystal structures of only three nanoparticles have been reported."
In Jin's case, x-ray crystallography revealed that the gold nanoparticle is chiral. Chemists typically probe the internal chiral structure of gold nanoparticles using a technique called circular dichoism spectroscopy. When pure chiral molecules are exposed to circularly polarized light, each isomer absorbs the light differently, resulting in a unique — and of opposite sign — spectrum for each isomer. The process of creating the gold nanoparticles, however, often results in a 50/50 mix of each isomer, known as racemates.
"Because the spectrum is of opposite sign for each isomer, they cancel each other out and the net optical response is zero. This makes circular dichoism (CD) spectroscopy useless when it comes to determining the chirality of gold nanoparticles in 50/50 mixtures," said Gil, associate research professor of chemistry and director of the Department of Chemistry's NMR Facility.
Since Jin couldn't use circular dichoism spectroscopy, Gil was able to use NMR to help Jin distinguish between his gold nanoparticles' left- and right-handed isomers.
NMR spectroscopy takes advantage of the physical phenomenon wherein some nuclei wobble and spin like tops, emitting and absorbing a radio frequency signal in a magnetic field. By observing the behavior of these spinning nuclei, scientists can piece together the chemical structure of the compound.
In 1957, scientists observed that the hydrogen atoms of a freely rotating methylene (CH2) group produced two different frequencies if they were close to a chiral center. Jin's gold nanoparticles, which have a chiral core, are cushioned by several chemical groups, including freely rotating methylene groups. Gil reasoned that the nanoparticles' chiral core should induce the methylene group's two hydrogen atoms to give off different frequencies, a phenomenon known as diastereotopicity.
Gil and Jin compared the NMR signal from the hydrogen atoms in a non-chiral gold nanoparticle with the NMR signal from the hydrogen atoms in chiral gold nanoparticle. The non-chiral nanoparticle's NMR spectrum did not reveal any differences, but the chiral nanoparticle's NMR spectrum revealed two different hydrogen signals, providing a simple and efficient way of telling whether the particle is chiral or not, even for a 50/50 mixture of isomers.
"NMR is an alternative — and very efficient — method for providing useful information about how the atoms in nanoparticles form the molecular structure. Because NMR can determine chirality in some cases, it can readily be used to determine the purity of a nanoparticle mixture," Jin said.
In current work, Jin and Qian are striving to turn their 50/50 mixture of right- and left-handed isomers into a pure solution of one or the other.
By: Jocelyn Duffy, email@example.com, 412-268-9982
Jocelyn Duffy | EurekAlert!
Scientists channel graphene to understand filtration and ion transport into cells
11.12.2017 | National Institute of Standards and Technology (NIST)
Successful Mechanical Testing of Nanowires
07.12.2017 | Helmholtz-Zentrum Geesthacht - Zentrum für Material- und Küstenforschung
Tiny pores at a cell's entryway act as miniature bouncers, letting in some electrically charged atoms--ions--but blocking others. Operating as exquisitely sensitive filters, these "ion channels" play a critical role in biological functions such as muscle contraction and the firing of brain cells.
To rapidly transport the right ions through the cell membrane, the tiny channels rely on a complex interplay between the ions and surrounding molecules,...
The miniaturization of the current technology of storage media is hindered by fundamental limits of quantum mechanics. A new approach consists in using so-called spin-crossover molecules as the smallest possible storage unit. Similar to normal hard drives, these special molecules can save information via their magnetic state. A research team from Kiel University has now managed to successfully place a new class of spin-crossover molecules onto a surface and to improve the molecule’s storage capacity. The storage density of conventional hard drives could therefore theoretically be increased by more than one hundred fold. The study has been published in the scientific journal Nano Letters.
Over the past few years, the building blocks of storage media have gotten ever smaller. But further miniaturization of the current technology is hindered by...
With innovative experiments, researchers at the Helmholtz-Zentrums Geesthacht and the Technical University Hamburg unravel why tiny metallic structures are extremely strong
Light-weight and simultaneously strong – porous metallic nanomaterials promise interesting applications as, for instance, for future aeroplanes with enhanced...
An interdisciplinary group of researchers interfaced individual bacteria with a computer to build a hybrid bio-digital circuit - Study published in Nature Communications
Scientists at the Institute of Science and Technology Austria (IST Austria) have managed to control the behavior of individual bacteria by connecting them to a...
Physicists in the Laboratory for Attosecond Physics (run jointly by LMU Munich and the Max Planck Institute for Quantum Optics) have developed an attosecond electron microscope that allows them to visualize the dispersion of light in time and space, and observe the motions of electrons in atoms.
The most basic of all physical interactions in nature is that between light and matter. This interaction takes place in attosecond times (i.e. billionths of a...
11.12.2017 | Event News
08.12.2017 | Event News
07.12.2017 | Event News
11.12.2017 | Information Technology
11.12.2017 | Power and Electrical Engineering
11.12.2017 | Event News