quinta-feira, 4 de julho de 2013

O vale improvável

Estou de volta, após me dedicar a terminar a escrita de livro de Química Orgânica para ciências da vida e saúde.
Justamente procurando sobre as possíveis reações que teriam dado origem a algumas moléculas centrais como a ribose, que ocorre no RNA e nucleotídios com funções importantes, como o agente metilante SAM (S-adenosil-metionina), a coenzima-A, que atua na transferência de grupos acila (acetila, propionila, malonila, acetoacetil) e ATP, GTP, UTP.
A hipótese de Steven Benner para a síntese da ribose envolve um dos maiores contos de fada já vistos na química, onde que não somente reações de baixíssimo rendimento são tidas como de importância fundamental, propõe que a complexação de boratos seja a responsável pela estabilização de açúcares, e para remover o "problema da água" propõe a existência de um vale especial, que "chova" formamida (HCONH2) .
Leia e reflita:

"At the very least, a continuous synthesis model must deliver
RNA from CO2, H2O, and N2, without human intervention, in
steps having plausible geological context. Further, no step
may involve introducing materials with “temporal precision”.
The process must do all of the following:
1. Create bonds attaching nucleobases to ribose from
borate-moderated formose processes.
2. Introduce phosphorus, recognizing the insolubility of
phosphates in many geological settings.
3. Generating oligomeric RNA without undoing the formation
of water-sensitive bonds.
The availability of borate-stabilized carbohydrates that
escape asphaltization, if only transiently, helps. More help
comes from the developing appreciation that formamide,
the hydrolysis product of HCN, is a more useful prebiotic
reagent than HCN itself.16 Adenine, guanine, cytosine, and
uracil can be formed from formamide, ammonium formate
(its hydrolysis product), and HCHO. The aromaticity of the
nucleobases allows them to escape asphaltization (at least
transiently).
Our favored model is associated with a specific geology:
1. The environment where oligomeric RNA is synthesized
is hypothesized to be a subaerial intermountain
desert valley.35
2. Temperatures in the valley range from -20 to 60C,
with higher temperatures intermittently achieved by
geothermal activity.
3. The valley collects runoff from a watershed containing
serpentinizing olivines and igneous tourmalines,
which collect atmospheric HCHO and HCN.
4. The runoff begins as borate-rich aquifers having pH
values of 10-11. These contain borate-stabilized carbohydrates,
formamide, and ammonium formate,
representing the inventory of the atmospheric HCHO
and HCN that was rained into the watershed.
5. The pH in the valley is buffered by atmospheric CO2 to
615 but is intermittently raised as alkaline solutions are
reintroduced.
6. The redox potential is ca. -150 mV, maintained by
serpentinizing olivines and mantle minerals, allowing
phosphate to be in equilibriumwith phosphite, avoiding
the intrinsic insolubility of phosphate,36 and allowing
oligomeric phosphites and phosphates to oligomerize
on mineral surfaces, including those of phosphite, phosphate,
arsenite, arsenate, and vanadate minerals.
7. The environment frequently suffers evaporation to the
point of dehydration, followed by rehydration.A modern
analog of this environment is the Sierra Nevada. Death
Valley system, differing first because the modern atmosphere,
poor in CO2, allows the valley today to remain
alkaline. Further, in any modern valley, any microbial
community showered with formate uses formate dehydrogenase
to generate reducing power and CO2. In our
prebiotic valley, compounds accumulate (or not) depending
only on their chemical reactivities.
This means that liquids other than water were available
as solvents in this prebiotic valley. This includes organic
liquids like formamide, which boils at ∼210 C, freezes at
∼0 C (and below this if it contains some water), and displays
a hydrophobic effect (oil and formamide do not mix).

Este artigo foi publicado na renomada Accounts of Chemical Research, como uma tentativa de mostrar o atual estado da pesquisa nesta área. Este artigo é incompatível com o atual estado da síntese orgânica e a compreensão dos mecanismos de reações, em que os "deve ser" e "poderia ser" se multiplicam ao longo da publicação.
Benner et al.,Vol. 45, No. 12 ’ 2012 ’ 2025–2034 ’ ACCOUNTS OF CHEMICAL RESEARCH


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