ASU team shows evidence for one mineral affecting the most fundamental process in organic chemistry: Carbon-hydrogen bond breaking and making
Reactions among minerals and organic compounds in hydrothermal environments are critical components of the Earth's deep carbon cycle, they provide energy for the deep biosphere, and may have implications for the origins of life. However, very little is known about how minerals influence organic reactions. A team of researchers from Arizona State University have demonstrated how a common mineral acts as a catalysts for specific hydrothermal organic reactions – negating the need for toxic solvents or expensive reagents.
At the heart of organic chemistry, aka carbon chemistry, is the covalent carbon-hydrogen bond (C–H bond) ─ a fundamental link between carbon and hydrogen atoms found in nearly every organic compound.
The essential ingredients controlling chemical reactions of organic compounds in hydrothermal systems are the organic molecules, hot pressurized water, and minerals, but a mechanistic understanding of how minerals influence hydrothermal organic reactivity has been virtually nonexistent.
The ASU team set out to understand how different minerals affect hydrothermal organic reactions and found that a common sulfide mineral (ZnS, or Sphalerite) cleanly catalyzes a fundamental chemical reaction – the making and breaking of a C-H bond.
Their findings are published in the July 28 issue of the Proceedings of the National Academy of Sciences. The paper was written by a transdisciplinary team of ASU researchers that includes: Jessie Shipp (2013 PhD in Chemistry & Biochemistry), Ian Gould, Lynda Williams, Everett Shock, and Hilairy Hartnett. The work was funded by the National Science Foundation.
"Typically you wouldn't expect water and an organic hydrocarbon to react. If you place an alkane in water and add some mineral it's probably just going to sit there and do nothing," explains first author Shipp. "But at high temperature and pressure, water behaves more like an organic solvent, the thermodynamics of reactions change, and suddenly reactions that are impossible on the bench-top start becoming possible. And it's all using naturally occurring components at conditions that can be found in past and present hydrothermal systems."
A mineral in the mix
Previously, the team had found they could react organic molecules in hot pressurized water to produce many different types of products, but reactions were slow and conversions low. This work, however, shows that in the presence of sphalerite, hydrothermal reaction rates increased dramatically, the reaction approached equilibrium, and only one product formed. This very clean, very simple reaction was unexpected.
"We chose sphalerite because we had been working with iron sulfides and realized that we couldn't isolate the effects of iron from the effects of sulfur. So we tried a mineral with sulfur but not iron. Sphalerite is a common mineral in hydrothermal systems so it was a pretty good choice. We really didn't expect it to behave so differently from the iron sulfides," says Hartnett, an associate professor in the School of Earth and Space Exploration, and in the Department of Chemistry and Biochemistry at ASU.
This research provides information about exactly how the sphalerite mineral surface affects the breaking and making of the C-H bond. Sphalerite is present in marine hydrothermal systems i.e., black smokers, and has been the focus of recent origins-of-life investigations.
For their experiments, the team needed high pressures (1000 bar - nearly 1000 atm) and high temperatures (300°C) in a chemically inert container. To get these conditions, the reactants (sphalerite, water, and an organic molecule) are welded into a pure gold capsule and placed in a pressure vessel, inside a furnace. When an experiment is done, the gold capsule is frozen in liquid nitrogen to stop the reaction, opened and allowed to thaw while submerged in dichloromethane to extract the organic products.
"This research is a unique collaboration because Dr. Gould is an organic chemist and you combine him with Dr. Hartnett who studies carbon cycles and environmental geochemistry, Dr. Shock who thinks in terms of thermodynamics and about high temperature environments, and Dr. Williams who is the mineral expert, and you get a diverse set of brains thinking about the same problems," says Shipp.
Hydrothermal organic reactions affect the formation, degradation, and composition of petroleum, and provide energy and carbon sources for microbial communities in deep sedimentary systems. The results have implications for the carbon cycle, astrobiology, prebiotic organic chemistry, and perhaps even more importantly for Green Chemistry (a philosophy that encourages the design of products and processes that minimize the use and generation of hazardous substances).
"This C-H bond activation is a fundamental step that is ultimately necessary to produce more complex molecules – in the environment those molecules could be food for the deep biosphere – or involved in the production of petroleum fuels," says Hartnett. "The green chemistry side is potentially really cool – since we can conduct reactions in just hot water with a common mineral that ordinarily would require expensive or toxic catalysts or extremely harsh – acidic or oxidizing – conditions."
Nikki Cassis | Eurek Alert!
High-arctic butterflies shrink with rising temperatures
07.10.2015 | Aarhus University
Long-term contraception in a single shot
07.10.2015 | California Institute of Technology
The MICADO camera, a first light instrument for the European Extremely Large Telescope (E-ELT), has entered a new phase in the project: by agreeing to a Memorandum of Understanding, the partners in Germany, France, the Netherlands, Austria, and Italy, have all confirmed their participation. Following this milestone, the project's transition into its preliminary design phase was approved at a kick-off meeting held in Vienna. Two weeks earlier, on September 18, the consortium and the European Southern Observatory (ESO), which is building the telescope, have signed the corresponding collaboration agreement.
As the first dedicated camera for the E-ELT, MICADO will equip the giant telescope with a capability for diffraction-limited imaging at near-infrared...
Self-driving cars will be on our streets in the foreseeable future. In Graz, research is currently dedicated to an innovative driver assistance system that takes over control if there is a danger of collision. It was nature that inspired Dr Manfred Hartbauer from the Institute of Zoology at the University of Graz: in dangerous traffic situations, migratory locusts react around ten times faster than humans. Working together with an interdisciplinary team, Hartbauer is investigating an affordable collision detector that is equipped with artificial locust eyes and can recognise potential crashes in time, during both day and night.
Inspired by insects
An interdisciplinary team of researchers has built the first prototype of a miniature particle accelerator that uses terahertz radiation instead of radio...
At present, tiny magnetic whirls – so called skyrmions – are discussed as promising candidates for bits in future robust and compact data storage devices. At...
In cooperation with the Center for Nano-Optics of Georgia State University in Atlanta (USA), scientists of the Laboratory for Attosecond Physics of the Max Planck Institute of Quantum Optics and the Ludwig-Maximilians-Universität have made simulations of the processes that happen when a layer of carbon atoms is irradiated with strong laser light.
Electrons hit by strong laser pulses change their location on ultrashort timescales, i.e. within a couple of attoseconds (1 as = 10 to the minus 18 sec). In...
01.10.2015 | Event News
30.09.2015 | Event News
17.09.2015 | Event News
08.10.2015 | Earth Sciences
08.10.2015 | Information Technology
08.10.2015 | Physics and Astronomy