Peptides on Stardust May Have Provided a Shortcut to Life


The discovery that short peptides can form spontaneously on cosmic dust hints at more of a role for them in the earliest stages of life’s origin, on Earth or elsewhere.

READ LATER
An illustration of a polyglycine molecule among the constellations.
The spontaneous formation of peptide molecules on cosmic dust in interstellar clouds could have implications for theories about the origin of life.Kristina Armitage / Quanta Magazine

Yasemin Saplakoglu

Billions of years ago, some unknown location on the sterile, primordial Earth became a cauldron of complex organic molecules from which the first cells emerged. Origin-of-life researchers have proposed countless imaginative ideas about how that occurred and where the necessary raw ingredients came from. Some of the most difficult to account for are proteins, the critical backbones of cellular chemistry, because in nature today they are made exclusively by living cells. How did the first protein form without life to make it?

Scientists have mostly looked for clues on Earth. Yet a new discovery suggests that the answer could be found beyond the sky, inside dark interstellar clouds.

Last month in Nature Astronomy, a group of astrobiologists showed that peptides, the molecular subunits of proteins, can spontaneously form on the solid, frozen particles of cosmic dust drifting through the universe. Those peptides could in theory have traveled inside comets and meteorites to the young Earth — and to other worlds — to become some of the starting materials for life.

The simplicity and favorable thermodynamics of this new space-based mechanism for forming peptides make it a more promising alternative to the known purely chemical processes that could have occurred on a lifeless Earth, according to Serge Krasnokutski, the lead author on the new paper and a researcher at the Max Planck Institute for Astronomy and the Friedrich Schiller University in Germany. And that simplicity “suggests that proteins were among the first molecules involved in the evolutionary process leading to life,” he said.

Researchers say they’ve found a shortcut to proteins — a simpler chemical pathway that reenergizes the theory that proteins were present very early in the genesis of life.

Whether those peptides could have survived their arduous trek from space and contributed meaningfully to the origin of life is very much an open question. Paul Falkowski, a professor at the School of Environmental and Biological Sciences at Rutgers University, said that the chemistry demonstrated in the new paper is “very cool” but “doesn’t yet bridge the phenomenal gap between proto-prebiotic chemistry and the first evidence of life.” He added, “There’s a spark that’s still missing.”

Still, the finding by Krasnokutski and his colleagues shows that peptides might be a much more readily available resource throughout the universe than scientists believed, a possibility that could also have consequences for the prospects for life elsewhere.

Cosmic Dust in a Vacuum

Cells make the production of proteins look easy. They manufacture both peptides and proteins extravagantly, empowered by environments rich in useful molecules like amino acids and their own stockpiles of genetic instructions and catalytic enzymes (which are themselves typically proteins).

But before cells existed, there wasn’t an easy way to do it on Earth, Krasnokutski said. Without any of the enzymes that biochemistry provides, the production of peptides is an inefficient two-step process that involves first making amino acids and then removing water as the amino acids link up into chains in a process called polymerization. Both steps have a high energy barrier, so they occur only if large amounts of energy are available to help kick-start the reaction.

Because of these requirements, most theories about the origin of proteins have either centered on scenarios in extreme environments, such as near hydrothermal vents on the ocean floor, or assumed the presence of molecules like RNA with catalytic properties that could lower the energy barrier enough to push the reactions forward. (The most popular origin-of-life theory proposes that RNA preceded all other molecules, including proteins.) And even under those circumstances, Krasnokutski says that “special conditions” would be needed to concentrate the amino acids enough for polymerization. Though there have been many proposals, it isn’t clear how and where those conditions could have arisen on the primordial Earth.

But now researchers say they’ve found a shortcut to proteins — a simpler chemical pathway that reenergizes the theory that proteins were present very early in the genesis of life.

An illustration of a polyglycine molecule among the constellations.

Last year in Low Temperature Physics, Krasnokutski predicted through a series of calculations that a more direct way to make peptides could exist under the conditions available in space, inside the extremely dense and frigid clouds of dust and gas that linger between the stars. These molecular clouds, the nurseries of new stars and solar systems, are packed with cosmic dust and chemicals, some of the most abundant of which are carbon monoxide, atomic carbon and ammonia.

In their new paper, Krasnokutski and his colleagues showed that these reactions in the gas clouds would likely lead to the condensation of carbon onto cosmic dust particles and the formation of small molecules called aminoketenes. These aminoketenes would spontaneously link up to form a very simple peptide called polyglycine. By skipping the formation of amino acids, reactions could proceed spontaneously, without needing energy from the environment.

To test their claim, the researchers experimentally simulated the conditions found in molecular clouds. Inside an ultrahigh vacuum chamber, they mimicked the icy surface of cosmic dust particles by depositing carbon monoxide and ammonia onto substrate plates chilled to minus 263 degrees Celsius. They then deposited carbon atoms on top of this ice layer to simulate their condensation inside molecular clouds. Chemical analyses confirmed that the vacuum simulation had indeed produced various forms of polyglycines, up to chains 10 or 11 subunits long.

The researchers hypothesized that billions of years ago, as cosmic dust stuck together and formed asteroids and comets, simple peptides on the dust could have hitchhiked to Earth in meteorites and other impactors. They might have done the same on countless other worlds, too.

The Gap From Peptides to Life

The delivery of peptides to Earth and other planets “certainly would provide a head start” to forming life, said Daniel Glavin, an astrobiologist at NASA’s Goddard Space Flight Center. But “I think there’s a large jump to go from interstellar ice dust chemistry to life on Earth.”

First the peptides would have to endure the perils of their journey through the universe, from radiation to water exposure inside asteroids, both of which can fragment the molecules. Then they’d have to survive the impact of hitting a planet. And even if they made it through all that, they would still have to go through a lot of chemical evolution to get large enough to fold into proteins that are useful for biological chemistry, Glavin said.

Is there evidence that this has happened? Astrobiologists have discovered many small molecules including amino acids inside meteorites, and one study from 2002 discovered that two meteorites held extremely small, simple peptides made from two amino acids. But researchers have yet to discover other convincing evidence for the presence of such peptides and proteins in meteorites or samples returned from asteroids or comets, Glavin said. It’s unclear if the nearly total absence of even relatively small peptides in space rocks means that they don’t exist or if we just haven’t detected them yet.

But Krasnokutski’s work could encourage more scientists to really start looking for these more complex molecules in extraterrestrial materials, Glavin said. For example, next year NASA’s OSIRIS-REx spacecraft is expected to bring back samples from the asteroid Bennu, and Glavin and his team plan to look for some of these types of molecules.

The researchers are now planning to test whether bigger peptides or different types of peptides can form in molecular clouds. Other chemicals and energetic photons in the interstellar medium might be able to trigger the formation of larger and more complex molecules, Krasnokutski said. Through their unique laboratory window into molecular clouds, they hope to witness peptides getting longer and longer, and one day folding, like natural origami, into beautiful proteins that burst with potential.

Stellar corpse reveals clues to missing stardust


Stellar corpse reveals clues to missing stardust
The Butterfly Nebula, also known as the Twin Jet Nebula, is an example of a so-called bipolar planetary nebula. The object of this study, K4-47, is much less known, but may be similar in appearance. Having nothing to do with planets.

Everything around you – your desk, your laptop, your coffee cup – in fact, even you – is made of stardust, the stuff forged in the fiery furnaces of stars that died before our sun was born. Probing the space surrounding a mysterious stellar corpse, scientists at the University of Arizona have made a discovery that could help solve a long-standing mystery: Where does stardust come from?

When stars die, they seed the cosmos around them with the elements that go on to coalesce into , planets, asteroids and comets. Most everything that makes up Earth, even life itself, consists of elements made by previous stars, including silicon, carbon, nitrogen and oxygen. But this is not the whole story. Meteorites commonly contain traces of a type of stardust that, until now, was believed to form only in exceptionally violent, explosive events of stellar death known as novae or supernovae – too rare to account for the abundance preserved in meteorites.

Researchers at the UA used radio telescopes in Arizona and Spain to observe gas clouds in the young planetary nebula K4-47, an enigmatic object approximately 15,000 light-years from Earth. Classified as a nebula, K4-47 is a stellar remnant, which astronomers believe was created when a star not unlike our sun shed some of its material in a shell of outflowing gas before ending its life as a white dwarf.

To their surprise, the researchers found that some of the elements that make up the nebula – carbon, nitrogen and oxygen – are highly enriched with certain variants that match the abundances seen in some meteorite particles but are otherwise rare in our solar system: so-called heavy isotopes of carbon, nitrogen and oxygen, or 13C, 15N and 17O, respectively. These isotopes differ from their more common forms by containing an extra neutron inside their nucleus.

Fusing an additional neutron onto an atomic nucleus requires in excess of 200 million degrees Fahrenheit, leading scientists to conclude those isotopes could only be formed in novae – violent outbursts of energy in aging binary star systems – and supernovae, in which a star blows itself apart in one cataclysmic explosion.

“The models invoking only novae and supernovae could never account for the amounts of 15N and 17O we observe in ,” said Lucy Ziurys, senior author of the paper, which is published in the Dec. 20 issue of the journal Nature. “The fact that we’re finding these isotopes in K4-47 tells us that we don’t need strange exotic stars to explain their origin. It turns out your average garden variety stars are capable of producing them as well.”

In lieu of cataclysmic explosive events forging heavy isotopes, the team suggests they could be produced when an average-size star such as our sun becomes unstable toward the end of its life and undergoes a so-called helium flash, in which super-hot helium from the star’s core punches through the overlaying hydrogen envelope.

“This process, during which the material has to be spewed out and cooled quickly, produces 13C, 15N and 17O,” explained Ziurys, a professor with dual appointments in the UA’s Steward Observatory and Department of Chemistry and Biochemistry. “A helium flash doesn’t rip the star apart like a supernova does. It’s more like a stellar eruption.”

Stellar corpse reveals clues to missing stardust
At 15,000 light-years, object K4-47 is about seven times farther away than the Twin Jet nebula, making it much more difficult to image. Based on what scientists have learned about K4-47 so far, it may have a similar structure of two lobes .

The findings have implications for the identification of stardust and the understanding of how common stars create elements such as oxygen, nitrogen and carbon, the authors said.

The discovery was made possible through a collaboration between disciplines that traditionally have remained relatively separate: astronomy and cosmochemistry. The team used at the Arizona Radio Observatory and Institut de Radioastronomie Millimetrique (IRAM) to observe rotational spectra emitted by the molecules in the K4-47 nebula, which reveal clues about their mass distribution and their identity.

“When Lucy and I started collaborating on this project, we realized that we could reconcile what we found in meteorites and what we observe in space,” said co-author Tom Zega, associate professor of cosmochemistry, planetary materials and astrobiology in the UA’s Lunar and Planetary Laboratory.

The researchers are eagerly awaiting the discoveries that lie ahead for NASA’s OSIRIS-REx asteroid sample return mission, which is led by the UA. Just two weeks ago, the spacecraft arrived at its target asteroid, Bennu, from which it will collect a sample of pristine material in 2020. One of the mission’s major goals is to understand the evolution of Bennu and the origins of the solar system.

“You can think of the grains we find in meteorites as stellar ashes, left behind by stars that had long died when our formed,” Zega said. “We expect to find those pre-solar grains on Bennu – they are part of the puzzle of the history of this asteroid, and this research will help define where the material on Bennu came from.”

“We can now trace where those ashes came from,” Ziurys added. “It’s like an archeology of stardust.”