H00102--00A, Front mat Genesis

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by Charles Baum


  novel ideas fuel origins research, though most are eventually cast

  aside—the victims of faulty chemical reasoning or failed experi-

  mental predictions. Whatever the outcome, this story epitomizes the

  exhilarating process of scientific exploration.***

  In May of 2004, Simon Nicholas (“Nick”) Platts was in trouble. After

  almost five years of fruitless graduate work, and approaching his forti-

  eth birthday, he was about to be deported to his native Australia with

  no degree and no job. [Plate 6]

  Nick’s life had defied the traditional arrow-straight science career

  path that most of us knew: college, graduate school, postdoc, and ten-

  ure track. A gifted chemist and enthusiastic educator, he went from a

  master’s degree in chemistry to teaching at Melbourne Grammar

  School. Only at the advanced age of 35 did he resolve to return to uni-

  versity, get a doctorate, and do some research. Life’s chemical origin

  was one topic that really excited him, so he applied to Rensselaer

  Polytechnic Institute in Troy, New York, to work with Jim Ferris.

  His new RPI colleagues found Nick to be outgoing and supportive,

  always ready to help others with their research, and eager to teach un-

  THE PRE-RNA WORLD

  223

  dergraduate chemistry, but progress on his thesis project suffered. Af-

  ter three years in Troy, he moved to Washington, D.C., and the Carnegie

  Institution as a NASA-sponsored predoctoral fellow, a position that

  would allow him to acquire his doctorate from RPI, but do the re-

  search in a new setting with fewer distractions. He had two years left to

  complete a thesis.

  Nick was full of ideas. Early in 2003, he came to me with plans for

  an elegant experiment on the possible influence of Earth’s magnetic

  field on the origin of biological homochirality. Could I provide some

  lab space?

  “OK, but for how long?” I asked. My lab is small and space is at a

  premium.

  “Once it’s set up, the experiment should take only a couple of

  weeks,” he assured me, so I offered him the necessary space for a few

  months.

  “No worries!” his Aussie reply.

  Nick started with a flurry of activity, marking out a good fraction

  of my lab bench with masking tape, cordoning off a sink that might

  otherwise splash onto the lab’s delicate apparatus, assembling an elabo-

  rate optical table, and filling cabinets with hardware, but his progress

  soon slowed. Crucial supplies were on back order, funds were needed

  for a special laser, other difficulties followed. More than a year later, the

  sequestered lab space, still piled high with equipment, was gathering

  dust. When pressed about his plans, Nick was vague and evasive. Many

  of us feared that he would be forced to leave the Geophysical Lab

  empty-handed at the end of June 2004. A sense of shared responsibility

  weighed heavily on George Cody, Marilyn Fogel, and me.

  EUREKA!

  Nick Platts’ life changed dramatically for the better on Tuesday, May

  25, 2004. That’s when the central idea for his PAH World scenario crys-

  tallized. Max Bernstein, a colleague of Lou Allamandola at NASA Ames,

  had planted the seeds for the concept at an RPI seminar in November

  2001. Bernstein’s talk had emphasized the occurrence of polycyclic aro-

  matic hydrocarbons in deep space, and it got Nick thinking about PAH

  chemistry. A September 2003 conference in Trieste in celebration of

  the 50th anniversary of Stanley Miller’s breakthrough experiment in-

  224

  GENESIS

  spired more progress. “On the return flight,” Nick remembers, “I

  scribbled the idea on the back of a United Airlines ticket.”

  The germ of an idea gradually developed “on the mental back

  burner,” but May 25th was the Eureka moment. “It was 5:51 p.m.,” Nick

  recalls. “That’s when I did the drawings. That’s when I realized how big

  this was.” Contrary to popular myth, there aren’t many such moments

  in science.

  Nick’s new idea follows in the tradition of other models of pre-

  RNA genetic polymers, but with an original chemical twist. PAHs

  would have been abundant among the plethora of prebiotic molecules.

  (We met them back in Chapters 3 and 5 as significant components of

  carbonaceous meteorites and, by extension, the cosmic debris that

  formed our planet.) Each of these flat sturdy molecules consists of

  fused 6-member rings of carbon atoms with hydrogen atoms around

  the edge. PAHs are relatively insoluble in ocean water, but under the

  influence of solar ultraviolet radiation they can be chemically modi-

  fied, or “functionalized”; hydrogen atoms can be stripped off, and new

  molecular fragments can take their place. If the PAH edges become

  decorated with OH, for example, then their solubility in ocean water

  increases significantly.

  By any calculation, PAHs and their functionalized variants were a

  significant repository for organic carbon on the primitive Earth. I sus-

  pect that some origins chemists thought it a shame to lock up so many

  potentially useful carbon atoms in the relatively inert, biologically use-

  less PAHs.

  But what if PAHs played a key role in the ancient ocean? What

  Nick realized was that a functionalized PAH with OH around the edges

  is an amphiphile—a molecule that both loves and hates water, similar

  to Dave Deamer’s lipids (see Chapter 11). The flat surfaces of the car-

  bon rings repel water (they’re hydrophobic), but the OH-bearing edges

  of the PAHs attract water (they’re hydrophilic). So what happens when

  lots of functionalized PAHs are placed in seawater? How might the

  hydrophobic parts stay away from water, while the hydrophilic parts

  remain in contact with the wet surroundings? The simple answer is to

  assemble a pile of PAHs like a stack of plates in the cupboard. The flat

  hydrophobic parts shield each other from water, while the edges form

  the water-bathed outside of the stack. The PAHs self-organize.

  Platts predicted that, once stacked, the system would preferentially

  bind small flat molecules, like the DNA bases, to the PAH edges and

  THE PRE-RNA WORLD

  225

  thus concentrate them from the surrounding prebiotic soup. These

  baselike molecules would attach and break free in a constant game of

  molecular musical chairs. Gradually, however, a selection process

  would take place. Because the PAHs are loosely stacked, adjacent flat

  PAH molecules would slide back and forth and rotate next to each

  other, like your hands do when you rub them together on a cold day.

  This mechanical action would tend to break off any edge-bound mol-

  ecule that isn’t, itself, as flat as a PAH. Consequently, the small, flat,

  ring-shaped base molecules (the A, C, G, and U of RNA, for example)

  would bind preferentially around the edges of the stack. What’s more,

  these RNA bases are also amphiphilic, so they might have a tendency

  to line up more or less on top of each other, forming a kind of

  ministack. Remarkably, the spacing between the PAH layers (and hence

&
nbsp; the vertical separation between bases) is 0.34 billionths of a meter—

  exactly the same spacing as found between the bases of DNA and RNA.

  The result of all this self-organization, according to Nick’s PAH

  World hypothesis, would be a stack of PAHs decorated along the side

  by an array of small flat molecules, including bases—an arrangement

  that looks for all the world like the information-rich genetic sequence

  of DNA or RNA.

  Once bases are effectively stacked, Platts suspects, other small mol-

  ecules would start to form a backbone linking the bases together into a

  true information-rich molecule, though those key chemical steps re-

  main fuzzy. Then a change in the ocean water’s acidity, as might be

  experienced by moving from a deep hydrothermal environment to a

  more shallow zone, might allow the sequence of bases to break free as a

  true pre-RNA genetic molecule that could fold back on itself to match

  up base pairs. Eventually, complex assemblies of these polymers might

  act as catalysts for self-replication and growth.

  Nick’s proposal lacked any experimental support. Nevertheless, the

  PAH World hypothesis seemed to provide a geochemically plausible,

  self-consistent, conceptually simple, and seamless chemical path from

  the dilute soup to an RNA-like genetic sequence.

  SHARING

  Nick Platts’ model crystallized in a flash, but was it reasonable? Did it

  make sense? He decided the best strategy was to bounce the idea off

  other people.

  226

  GENESIS

  A

  B

  C

  THE PRE-RNA WORLD

  227

  D

  E

  (A) Nick Platts’ PAH World hypothesis rests on the ability of polycyclic molecules to self-organize into stacks. (B) Once stacked, the PAHs would tend to attract small flat molecules (notably the bases of DNA and RNA) to the edges. (C) A molecular backbone forms to link the bases into a long chain. (D) The RNA-like chain of bases

  separates from the PAHs and folds into a molecule that carries information. (E) Complex assemblages of these chains have the potential to catalyze reactions. These drawings are adapted from Nick Platts’ unpublished manuscript.

  228

  GENESIS

  I must have been about tenth on his list. Nick appeared at my of-

  fice door on the afternoon of Thursday, May 27th. “You got a few min-

  utes?” he asked, taking a seat. I nodded, hoping for a progress report on

  the stalled thesis experiments. “I’ve found something extraordinary,”

  he began. “I think I’ve discovered how life began.”

  And so he described his hypothesis—the self-assembly of

  functionalized PAHs, the selection of flat molecules along the edges,

  the fortuitous spacing of the bases. He sat on the edge of his chair,

  leaning toward me and gesticulating as he spoke. Nick was clearly ex-

  hausted from almost two days without sleep; his voice took on a manic

  intensity. “This is a once-in-a-lifetime moment! I’ve never been part of

  anything this big!”

  I was a bit taken aback by what sounded like a wildly speculative

  idea. It seemed at first like another distraction, just weeks before his

  scheduled doctoral defense.

  “I told Dave Deamer and he loves the idea.” Nick rattled off the

  names of half a dozen other origin-of-life experts he’d already con-

  tacted. “No one can think of an objection.” Then, paradoxically, “We’ve

  got to keep this secret. Someone else will be sure to steal the idea, so

  don’t tell anyone.”

  “Can you propose any experimental tests?” I asked him. A safe,

  neutral question, while I considered how else to respond.

  He deflected the question. “There’s lots we can do, but we have to

  get this out fast. I’ve been drafting a manuscript. I’d like you to be a

  coauthor. Where do you think we should submit it?”

  A manuscript? Coauthorship? Nick had just raised the stakes. I

  was uncomfortable with being an author unless I could contribute

  something original to the paper, but I was happy to discuss publication

  strategy. I thought the ideal forum for a short, high-impact outline

  would be a 700-word “Brief Communication” in Nature or a similarly

  concise “Brevia” in Science. Proceedings of the National Academy of Sciences was another option, but PNAS articles are generally longer, and Nick had no data yet with which to flesh out his hypothesis. He agreed

  to adopt the short Nature format, while I promised to read his paper

  and comment quickly.

  The next day, Nick e-mailed me a 700-word draft for “Edge-

  derivatised and stacked polycyclic aromatic hydrocarbons (PAHs) as

  essential scaffolding at the origin of life.” I could tell from the title that

  THE PRE-RNA WORLD

  229

  the paper was going to need some work. Even so, as I read the text I

  warmed to the elegant theory.

  The hallmark of any useful scientific hypothesis is that it makes

  unambiguous predictions. Nick’s hypothesis made testable predictions

  by the bundle. First, functionalized PAHs must self-assemble into

  stacks. The stacked PAHs, furthermore, must be of similar size and

  shape. PAH edges must attract a variety of molecules, but there must

  be a preferential selection for flat, baselike molecules. And the bases

  must also be aligned vertically. If only we could confirm at least one of

  these predictions.

  George Cody provided the chemical evidence that made me a be-

  liever. Coal, George’s specialty, is loaded with PAHs. It turns out that

  there’s already an extensive scientific literature on the ability of

  functionalized PAHs to self-organize into stacks—a process known as

  discotic organization. A quarter-century of publications had already

  elaborated on Nick Platts’ prediction. Neither Nick nor I had ever heard

  the word “discotic” until Cody mentioned it, drawing on seminars he’d

  heard on the subject while working at Exxon. I returned to Nick’s

  manuscript with a red pen and renewed intensity. My principal contri-

  bution was to come up with a catchier title, “The PAH World.”

  By Tuesday, June 1st, Nick had received comments from more than

  a dozen scientists from around the world and the draft manuscript was

  taking final form. He called a meeting of Carnegie coauthors—nine of

  us in all—at the Lab’s library. We sat around a massive mission oak

  table and worked through the paper one last time. Should we talk about

  the common mineral graphite, which also has flat carbon rings? Had

  we included the most appropriate references? Should we propose spe-

  cific experiments? Our biggest concern was Nick’s figure, which needed

  to make the essentials of the model as clear as possible, and he agreed

  to redo it. He submitted the PAH World paper to Nature on Thursday,

  June 3rd, just nine days after his epiphany.

  OPINIONS

  Nick had no time to relax. Whether or not Nature accepted the paper,

  he wanted us to stake a claim. We began e-mailing the manuscript,

  designated “in review,” to a dozen astrobiologists and origins experts

  to request their comments. We focused on leading RNA World propo-

  230<
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  GENESIS

  nents—Jerry Joyce, Leslie Orgel, Jack Szostak—figuring they would

  have the most to gain from the novel idea.

  Responses came quickly and with varying degrees of enthusiasm.

  A few scientists who were good friends of the Lab were warmly con-

  gratulatory, but most respondents remained cautious, and almost ev-

  eryone cited the need for experimental evidence. Jack Szostak

  responded in less than an hour with some skepticism, adding “I think

  it’s worth pursuing experimentally—it would certainly be cool if an

  effect could be demonstrated.” The next day Leslie Orgel chimed in,

  “An experimental demonstration of your scheme might be interesting,

  but I wouldn’t advise publishing without showing that it works well.”

  “I thought it was interesting and certainly appealing,” echoed Jerry

  Joyce. “However, it would help tremendously if there were some ex-

  perimental support.”

  Andy Knoll joined the chorus: “For now it is fascinating specula-

  tion, but the ideas seem amenable to what you guys do best—careful

  experimentation.”

  Evidently the editors at Nature agreed. We received the form re-

  jection letter a week later. “Thank you for submitting your contribu-

  tion, . . . which we are unable to consider for publication.” Boilerplate

  didn’t make their decision any easier to swallow. “Because of severe

  space constraints . . . we are unable to return individual explanations

  to authors. . . .”

  EXPERIMENTS

  Experimental evidence seemed the obvious key to securing support

  for the PAH World hypothesis. Unfortunately, experiments take time,

  and that was one commodity of which Nick Platts had precious little at

  this stage in his graduate work.

  In such circumstances, it’s best to think boldly. Nick envisioned a

  single sequence of experiments that might validate every facet of his

  theory. His plan: First obtain a sample of a modest-sized PAH, one

  with a dozen or so interlocking rings. He settled on the elegant, sym-

  metrical hexabenzocoronene (HBC), with its starlike pattern of 13

  rings. Put the HBC into a flask with some water, functionalize the mol-

  ecules by irradiation with an ultraviolet lamp, then measure the system

  for discotic organization. That much we were pretty confident would

  work, based on a survey of the discotics literature. Then add base mol-

 

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