Quoted message said:From: "Perplexed in Peoria" <[email hidden]> In
your writing on this, you use the word "catalyst", but you
don't use the word "precursor". This creates the picture
in my mind that each catalyst in your cycle is producing
its product from food molecules.
Well each catalyst is simply enhancing a reaction so that it
occurs at a fast rate while at reasonable temperatures. Each
such reaction takes a small number of "food" or "reactant"
molecules and rearranges them to form a small number of
"product" molecules. The thing about a catalyst is that it
goes in and comes out basically the same, or that it has a
small number of forms and switches from one form to another
form after each reaction, or that it switches from one form
to another after a reaction then spontaneously reverts to
original form after a while, etc.
You wish to use the word "precursor"? To mean the same thing
as "food" or "reactant", or to mean something else, for
example in some *other* reaction where our friend the
catalyst wasn't playing a role as a catalyst but was in fact
the product of that reaction, which involved some *other*
catalyst to make *that* reaction occur? In that case there
may be more than one precursor to our friend-catalyst in
that other reaction. But in the context of a catalytic loop,
there would be one precursor in the loop, the rest of the
precursors being merely food going into the loop.
Quoted message said:no large organic molecule can be built from scratch by a
single catalyst.
That's a strawman! Let me rephrase so you understand:
There's this random chemical that happens to have catalytic
capability, that is it enhances a bunch of different
reactions without itself being consumed in those reactions.
One of these reactions happens to take readily available
materials from natural sources, and produce some products,
one of which would virtually never occur except with the
aid of some catalyst. So thanks to the chance occurrance of
this one molecule with catalytic ability, and thanks to the
abundance of the reactants it works on in this one
reaction, this one reaction occurs several times before
that one molecule gets accidently broken apart. (Or if the
catalyst is just a metal ion etc., it might catalyze
gazillions of individual chemical reactions over a period
of millions of years before by chance it gets snagged in a
tektonic plate that is subducting into the mantle and that
metal ion or whatever is taken out of service for hundreds
of millions of years.)
All this catalyst (metal ion, or actual molecule) does is
enable some tiny change such as bonding two molecules or
splitting a molecule or moving a sidechain from one molecule
to another etc. At the small end of the range of reactant
size, there's not much splitting possible, so most reactions
make larger molecules. At slighter larger reactant size,
some reactions make smaller molecules and some make larger
molecules. As long sequences of catalyzed reactions happen,
it's somewhat a random walk how large the molecules get, but
every so often a moderately large molecules is built from a
slightly smaller one or from two pieces totalling the large
size. If it's energetically favorable to polymerize, and if
a suitable catalyst for polymerization is available, very
long polymers might form rather quickly. Otherwise I'd
expect only small to medium-size molecules.
Quoted message said:But the main point is that to produce anything, you need
both a precursor and a catalyst.
Yes. In most cases the precursors would be abundantly
available, and the product from the catalyzed reaction would
be something new but which builds up in quantity if the
catalyst stays around a while.
Occasionally there'd be a reaction where all but one of the
reactants are common, but one reactant is rare. So that rare
reactant would be all used up to make the product. Not much
of interest there.
Occasionally a long-lived catalyst would catalyze a reaction
from common ingredients, and the reaction product would be
something with catalytic ability, which would then start to
build up in quantity, significantly increasting the rate of
all the reactions it catalyzes (where the reactants are
common), causing large amounts of its reaction products to
occur, among which there might be yet another chemical with
catalytic ability, whose quantity would build up, causing
yet another bloom of catalyzed reactions and build-up of
reaction products, etc.
At this point, the question that needs to be answered is:
For a given catalyst (either long-lived such as metal ion,
or re-generated in great quantity such as product of
reactions using former), of all the reactions it catalyzes,
how many reaction products of them all have catalytic
capability of their own? If on the average each catalyst
causes the production of significant quantities of more than
one other catalyst, then already we have a branching tree of
catalyst-begats-catalyst, and surely we'll get a catalytic
loop within a relatively short time geologically speaking.
Or if polymerization happens readily, then surely among the
various polymers created there would be a whole lot of
different catalysts, and a good chance of completing a loop
somewhere. The Miller-Urey result, lots of tarry stuff,
indicates some sort of polymerization happens readily.
Whether this is just an activated chemical fragment
attaching itself to a molecule and then grabbing another
nearby molecule to glue them together, or an actual
polymerization catalyst that got formed spontaneously, I
don't know. But in either case I belive the tarry stuff was
formed in the early-Earth seas, and wind/wave action sloshed
it around to break it apart to expose inner bonds to fresh
water to allow it to catalyze new reactions, resulting in a
very rich assortment of medium-length molecules, many of
which had catalytic ability (not a large fraction, just a
large number of catalysts among a vastly larger total number
of different kinds of molecules).
Quoted message said:you need more than one or two chemical species to be
infectuous
Consider seventeen kinds of molecules (a1 a2 b1 b2 b3 c1 ...
g3) naturally occurring in large quantities, which are
reactants in a 7-link catalytic loop (A -> B -> ... -> G ->
A), producing various waste products (m n o ... u): A + a1 +
a2 -> A + B + m B + b1 + b2 + b3 -> B + C + n + o C + c1 +
c2 -> C + D D + d1 + d2 + d3 -> D + E + p E + e1 + e2 -> E +
F + q + r F + f1 + f2 -> F + G + s G + g1 + g2 + g3 -> G + A
+ t + u Suppose e2 is a lipid which is part of some bag that
supports a nice colony. Suppose one molecule of E happens by
and attaches to that bag and grabs a molecule of e2, and
finds an e1 floating by in the water, and does its reaction.
Then it finds another e2 nearby on the bag, grabs it, finds
another e1 floating by, and does its reaction again. q and r
drift away, but some of the molecules of F that are created
do their thing while still nearby, making G which does its
thing, etc. around the loop until a bunch of E are made, any
of which still nearby quickly attach to e2's of the bag.
Before long all the e2 of the bag is eaten away, and the
large quantity of E that was created will now diffuse away
to infect other e2-lipid bags.
Quoted message said:I agree that growth is more urgent than reproduction.
However, an organism that grows without reproducing leaves
all its eggs in one basket, and natural selection seems to
favor multiple, geographically dispersible, baskets.
I agree. But these lipid-bag colonies are very flexible as
to the size of the bag, not like for example like elephants
which if fifty times as large would crush their lungs and
suffocate. If a lipid bag merely grows as large as possible,
sooner or later shear will stretch it apart, and its "eggs"
will now be in more than one basket. So these lipid-bag
colonies could survive for a nice long time, and have "eggs"
in many baskets, without any explicit mechanism to split.
At such time as any two species of bag have different bag
strengths, caused by differences in their "genome" (set of
replicators in them), then natural selection would favor
whichever is optimum for longterm survival.
Quoted message said:Quoted message said:... Also if the main purpose of the replicators residing
in lipid bags is for protection against extremes of
temperature and against too-highly-active chemicals, ...
Quoted message said:In my viewpoint, the main "purpose" is in residing near
your symbiotes,
Per my idea, in these early lipid-bag colonies of
replicators, each replicator (catalytic loop) originated in
a different environment, and later these came together and
any that consumed the same scarce "food" competed for it and
only one survived, and the set that remained was a set which
happened to all use different foods (except for very common
foods where sharing a food wouldn't be limiting). None of
the waste of one cycle was food for another, so there was no
specific value in being near a different kind of replicator
except maybe that other replicators damped some kinds of
harsh chemicals by reacting with them first.
Quoted message said:You ought to learn the chemical distinction between ions
and free radicals if you are going to use the word
radical.
In high-school chemistry I learned that an ion is a
single atom which is charged, whereas a radical is more
than one atom but not a whole molecule, which may be
either charged or not. For example Na+ is just an ion
whereas SO4-- is a radical, and -NH2 (the initial -
denoting a dangling place where a covalent bond should
be, not a negative charge) is also a radical, although we
were doing only inorganic chemistry so didn't deal with
covalent bonds explicitly. Please correct my use of
terminology if that's not current usage.
Quoted message said:In any case, my speculations tend to discount the role of
free radicals from the global environment as a food for my
organisms. I would see such radicals as too dangerous.
In the world before any catalytic cycles existed, free
radicals etc. were the spur that triggered the formation of
a wide variety of really strange molecular species, many of
which were highly reactive. This great variety of molecule,
and great activity, resulted in both molecular catalysts and
reactants for them to catalyze reactions upon. This is how
the first catalytic cycles formed.
In the atmosphere, UV strikes a molecule, such as NH3, and
either knocks an electron off producing a charged molecule,
or severs a bond producing fragements which may or may not
be charged. The free electron sticks to another random
molecule creating an oppositely charged molecule. A fragment
collides with a molecule and grabs a bond and either joins
with it to make a bigger fragment or exchanges something.
Charged molecules collide and stick for a moment to
neutralize their charge, possibly overcoming activation
energy to react during that moment. The variety of new
molecules thereby created rains down to the ocean.
At the surface of the ocean, UV does all those things except
the temporary products have a chance to react with organic
soup before deactivating, increaseing both the destructive
capability and the random-new-molecule-forging capability.
The same argument applies to geothermal vents.
The first catalytic cycles probably occurred very close to
the surface of the ocean or inside a volcanic vent, just
because of the greater variety of things going on there. But
once a stable catalytic cycle formed, if it stayed there it
probably got disrupted whereas if it diffused away it had a
better chance to survive, so among the many copies of each
catalyst in a cycle, some randomly survived by diffusing
slightly away and the rest stayed too close and got
disrupted. Since these catalytic cycles depended on "food"
from the danger zone, any that diffused too far away became
inactive until they randomly wandered back into the food
zone again. (Note that each molecule undergoes random-walk
independently of others in the same cycle. All it takes is
one molecule wandering back into a good-food region to start
the cycle going there again.)
Quoted message said:You are definitely talking about a heterotrophic theory
here, rather than an autotrophic one.
Well I'm *not* talking about eating food that comes from
some other living being, only eating raw chemicals that
happen to form naturally. So your use of that word might be
misleading.
Quoted message said:My main objection to heterotrophy is this: any environment
that produces high energy organic chemicals that you can
use will also produce a smorgasbord of high energy organic
chemicals that you can't use - that would be actively
disruptive if you tried to use them.
I agree. That's why the catalytic cycles would have to form
very close to the disruptive zone where a small amount of
very active chemicals, maybe only one or two species in any
significant quantity, drift down (from surface) or out (from
vent). So the early catalytic cycle would be dependent on a
big "roller coaster lift" from that one highly active
chemical, relying on more tame chemicals for the rest of the
cycle. It'd reside in that narrow layer of water where every
so often an active molecule of the right species comes in
and preferentially finds the catalyst that takes it as food,
immediately removing it from the water so other catalysts
that might be damaged by it don't touch it. (Note the one
catalyst that uses it would [censored] it whenever it drifted
nearby, whereas the other catalysts would not [censored] it so
wouldn't be damaged unless they ventured too close.)
Possibly that one highly-active chemical would be scarce in
the zone where the catalytic cycle resides, so there'd be a
build-up of whatever precursors were needed with it, and a
deficiency of whatever was produced from it, until one
molecule of the highly-active species arrived, at which time
it'd immediately react with the appropriate catalyst and the
rest of the cycle would complete in rapid succession
yielding more of that one catalyst again. (All molecular
catalysts decompose naturally, hence decline in quantity
when not renewed, so perhaps most of the catalytic cycle
would nearly disappear while waiting for the highly-active
chemical to appear. For example, if G -> A was the big
roller coaster lift, and A -> B -> ... -> G were the
downward coast, with food for G -> A scarse, A would decay
fastest, and with it mostly gone B would start to decay, and
with B mostly gone C would start to decay, etc. until only
maybe F and G remained, and if still no active chemical then
F would be gone and G would start to decay. With F&G still
around, if the active molecule arrives and hits F it'd
damage it, but if it hits G it'd kick-start the ride again.
Maybe most of the decay is caused by the active chemical
coming in and striking the wrong catalyst anyway.)
The roller coaster metaphor might be a little misleading.
Every step in the catalytic cycle needs a source of
negentropy to drive it. It's just that one of the steps
needs a big kick and would ignore any little nudge, while
the rest of the steps need only a little nudge and would be
damaged by a big kick. So most of the time little-nudge food
is coming in, and the rest of the cycle is building up huge
quantities of G from large quantities of F from medium
quantities of E from small quanties of D from tiny
quantities of C not yet destroyed, all of B and A gone by
now. Then one highly-active module needed by G comes in and
most of the time the first thing it hits is indeed G because
of such large quantities of G built up, making one molecule
of A, which during the next lull makes several molecules of
B, which rebuilds the supply of C, etc.
Quoted message said:Thermodynamic free energy for driving the cycles has to
come from redox, perhaps with photo-assist.
Indirect photo-assist, from UV making highly-active stuff,
per my "just so story".
Quoted message said:No "fermentations".
Agreed. There is nothing complex enough to ferment
initially. (The Miller-Urey tar stuff has too much variety
and not enough bound energy to be fermentable, by my guess
anyway.) Fermentation is parasitical/preditory upon products
of other life, mostly large concentrations of specific
sugars, which doesn't yet exist at this point in our
scenerios.
Quoted message said:... Miller experiments ... They produce soup or tars,
depending on your prejudices. I don't like that direction
- that way lies chaos, ... I want life to start simple and
then slowly add complexity - not to start complex and then
somehow find order in that chaos.
They are not *complex* in the sense of lots of purposeful
order, such as fractally-nested hierarchies of structure, as
current life is. They are merely complex in the sense of
having lots of mathematical entropy in the sense of having
lots of purposeless variety. Each chemical reaction is
simple: A random bunch of chemicals react with the aid of
some random catalyst. The reactants and the catalyst simply
drift in from who knows where, and then the reaction
products and released catalyst simply drift away to who
knows where. That's a very simple system which can be
modeled almost entirely statistically with the whole equal
to the sum of its individual parts, no need to take any
organization of the parts into consideration, only need to
take into account that the statistics vary with geography,
partly due to forcing conditions (UV on surface, geothermal
energy in vents, different temperatures by latitude and
ocean depth) and partly due to sudden accumulations of
particular replicators in one locale which take a long time
to diffuse worldwide due to other replicators that have
consumed almost all available food in other locales.
Before the first replicators (catalytic cycles with
fecundity greater than one) form, a high amount of
purposeless random variety is exactly what is needed to "let
a thousand flowers bloom" and see which "flower" chances
upon a closed loop of catalysts in some locale, then see
which other "flower" chances upon likewise in another
locale, etc.
Each closed loop is very simple, just a chance implication
cycle. No regulatory mechanisms, no very specific catalytic
capability, just general catalytic capability that happens
to form a loop in some locale with such-and-such food
abundantly available. So my "just so story" has the initial
simplicity of mechanism you desire, it just has a lot more
different experiments running in parallel then you can
comfortably imagine.
One feature you might like, if you really like ultra-simple
starts to life on Earth: As soon as a catalytic cycle gets
really going in one locale, it gobbles up much of the
"food" there, reducing input to other dead-end catalytic
chains, reducing the total amount of variety in chemical
species in that locale. Also the particular "foods" it
consumes are probably the most active species of chemicals
around, so actually the amount of reduction in the
"thousand flowers" process is probably immensely starved.
It does produce large quantities of its particular waste
products, but these are limited in variety, and most or all
low-energy chemicals, so they only re-boost the "thousand
flowers" randomness a little bit if any. So the local
region would resemble a very simple ecosystem with a single
species dominating all chemical processes, and that one
species being very simple itself.
Once several catalytic cycles have occupied all the major
niches where lots of negentropy (free energy) is available,
there's no longer any place where new catalytic experiments
can take place, and the Miller-Urey era is all finished
(until the next huge rain of comets or asteroids boils away
the oceans, so there's no liquid water to percolate down
into pores in rock to keep any catalytic cycles going even
there, and later when the oceans re-form all this has to
start over; perhaps this happened several times; but let's
talk now only about the last Miller-Urey era, the one which
didn't get obliterated, the one which evolved to what we
have today, below🙂.
Maybe one of these first catalytic loops had at least one
catalyst which had handedness. Maybe this handedness was
preserved through all the evolutionary transformations
from then to now. Or maybe two different catalytic loops
involved handedness, and one of them eventually yielded
the handedness of amino acids and the other eventually
yielded the opposite handedness of something else that I
forget what.