Elusive ion evades discovery for decades: Dalhousie NMR facility provides the solid proof

- April 11, 2014

Left-to-right: Luke Murphy, Ulrike Werner-Zwanziger and Jason Clyburne in Dal's NMR lab. (Danny Abriel photo)

The scientific world is one step closer to understanding how nature uses carbon capture to tame poisons, thanks to the discovery of cyanoformate — a simple but fragile ion involved in the fruit-ripening process that has evaded detection for decades.

The results of the two-year study led by Jayson Clyburne of Saint Mary’s University and Heikki Tounonen of the University of Jyväskylä in Finland, were released last week in Science, the world’s preeminent scientific journal. Dalhousie’s Nuclear Magnetic Resonance Resource (NMR-3) facility played a key role in the study.

Saving plants from cyanide with carbon dioxide


At a time when carbon capture is being looked to as a strategy for managing carbon dioxide emissions caused by humans, the study offers insight into how the natural world handles carbon.

“Here we have a perfect example of nature taming a poison, and what better way to learn the chemistry of carbon capture than from nature itself?” says Dr. Clyburne, Canada Research Chair in Environmental Science and Materials and professor of Environmental Science and Chemistry at Saint Mary’s — and also a Dal alum.

“The fact that cyanoformate was undetected for so long begs the question: What other simple chemistry have we missed?” asks Dr. Tuononen, Academy of Finland research fellow and senior lecturer at University of University of Jyväskylä.

Chemists have long been aware of the role that cyanide and carbon dioxide play in fruit ripening, but they've always been observed independent of one another. This study represents the first time scientists have isolated cyanoformate anion (NCCO2) and explored its structure using crystallography, computational chemistry and spectroscopy. It shows that there's still more to learn about the chemistry of carbon dioxide in cells, and also furthers our understanding of carbon capture.

Providing the proof


The final proof that Dr. Clyburne and his team had discovered the elusive ion came from Ulrike Werner-Zwanziger, adjunct professor (Faculty of Graduate Studies) and solid-state NMR coordinator of the Nuclear Magnetic Resonance Resource (NMR-3) at Dal.

“My contribution to the study was to use solid-state NMR to show that there is a chemical bond between cyanide and carbon dioxide,” says Dr. Werner-Zwanziger, a co-author on the study. “Only when we have direct bonding can we get this type of doublet splitting proving the structure of the ion.”

Chemists routinely use NMR spectroscopy to study chemical structure of matter in liquids and solids. Located in the Chemistry Building, the NMR-3 facility at Dal is a diverse NMR centre that often acts as a point of collaboration for researchers across the Atlantic Provinces and around the world. Its spectrometers were purchased in part through the Institute for Research in Materials (IRM).

Learn more: NMR-3 website

"Taking advantage of our high field solid-state NMR spectrometers and samples prepared by Luke Murphy, a Master of Applied Science candidate at Saint Mary's University, I could determine the coupling mechanism," explains Dr. Werner-Zwanziger.

Also involved in determining the structure was research associate Katherine Robertson (also a Dal alum), in collaboration with Scott Harroun from Christa Brosseau’s laboratory at Saint Mary’s University.

Collaborating on a local and global scale


Dr. Werner-Zwanziger says that having the NMR facility in Halifax offers many benefits to the region’s research community. The facility has collaborated with scientists in the United States, Brazil, India, Singapore, Europe and beyond.

“We have an outstanding staff of two PhD scientists and instrumentation for liquids and solids ranging from 300 MHz to 700 MHz,” says Dr. Werner-Zwanziger. “Our staff is here to support academic and industrial NMR-related research and provide services that include experiment development, data acquisition and interpretation, and assistance to users.”

Discoveries like these by Dr. Clyburne and his team of scientists, with the support from the NMR-3 facility and Dr. Werner-Zwanziger at Dal, highlights that nothing happens alone in the world of scientific research.


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