What is the answer to Life, the Universe and Everything?
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Transcript of What is the answer to Life, the Universe and Everything?
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Hadean Archean Proterozoic
Mesozoic
Cenozo
ic
Paleozoic
inthe beginning…
Nov. 9 2005
today1 bya2 bya3 bya4 bya
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3.5 bya!
Oldest fossils: stromatolites = Calcium carbonate deposits from blue-green algae or cyanobacteria.
0.5 bya
N2 + 3 H2 --> 2 NH3
BANG!
Hadean4.5 -3.8 bya
Archean3.8 -2.5 bya
Oldest rocks?
Most famous characteristic?Nitrogen “fixing” bacteria:
4.5 bya!
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What do we find deep withincyanobacteria’samazing N2-fixing machinery?
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MoMolybdenum
(Greek ‘molybdos’ ) lead-like
“Moly”
# 42
The Answer to Life, the Universe, and Everything (?)
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540 mya
Mesozoic2.5 -0.6 mya
Global catastrophe!
Cenozoic65 mya - today!
“age of mammals”
“age of dinosaurs”
quagga
Paleozoic540 - 250 mya
250 mya 65 mya
Plants!!
Animals!!Anotherextinction!!
Has evolution moved on without #42 - Mo?
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Grown without MoGrown with Mo
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Tobacco plants (Arabidopsis thaliana)
Healthy(wild type)
Sick(mutant)
All plants requirethe molybdoenzymeNitrate Reductase
nitrate nitrite
Nitrate
Nitrite
Proteins
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inthe Beginningof Life…
1 bya2 bya3 bya4 bya
CyanobacteriaNeed
Mo
PlantsNeed
Mo
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What about the animals?
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sulfite oxidase
xanthine oxidase
enzyme in mammalian milk
Got Mo?
aldehyde oxidase
two enzymes in liversof mammals and avians
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Why the correct oxidation state matters
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MRI of brain of deceased babywith Sulfite Oxidase Deficiency MRI of healthy brain
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The baby died because this reaction didn’t happen:
SO32- + H2O ---> SO4
2- + 2H+ + 2e- Sulfite SulfateS4+ S6+
The baby has a genetic defect in the enzyme that catalyzes this reaction.Babies with this genetic disease die within hours.The enzyme is Sulfite Oxidase.
You have it in your liver.
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Oxidation SO32- + H2O ---> SO4
2- + 2H+ + 2e- half reaction S4+ in Sulfite S6+ in Sulfate
Reduction Mo6+ + 2e- ---> Mo4+ half reaction
Net redox reactionSO3
2- + H2O + Mo6+ ---> SO42- + 2H+ + Mo4+
Review the terms:
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aldehyde oxidase sulfite oxidasexanthine dehydrogenase
Human Molybdenum Cofactor Disorder: Combined Oxidase Deficiency
sulfite sulfate
•Mental/motor retardation•Epileptic seizures•Brain atrophy•Dislocated ocular lens•death
xanthine uric acid
•xanthinuria•(gout)
hypoxanthine xanthine
•No detoxification of heterocycles
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+ Mo
defective molybdoenzymes
Human Molybdoenzyme Deficiencies: Cured with more Mo?
Not repaired by adding Mo alone
Non-functional enzyme
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Bioinorganic Chemistry
1. Not having the structure or organization of living bodies2. Not characterized by vital processes3. Not fundamental or related; extraneous 4. Pertaining to compounds that are not hydrocarbons5. Mineral
1. (Gr. “bios” ‘life, course or way of living’). In compounds formed in Greek itself, as biography; and in modernscientific words in which bio- is extended to mean ‘organic life.’
2. A prefix meaning “life” Websters, OED
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Bioinorganic ChemistryMolybdenum Enzymes Hemoglobin (Fe)
Manganese Enzymes
Zinc Enzymes (Zn)
Auranofin (Au) arthritisCis-platin (Pt) cancer
Copper Enzymes (Cu)Vitamin B12 (Co) Iron enzymes
Tungsten Enzymes
Therapeutics
V, Ti, Cr
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Bioinorganic ChemistryMolybdenum Enzymes Hemoglobin (Fe)
Manganese Enzymes
Zinc Enzymes (Zn)
Aurial (Au) arthritisCis-platin (Pt) cancer
Copper Enzymes (Cu)Vitamin B12 (Co) Iron enzymes
Tungsten Enzymes
Therapeutic s
V, Ti, Cr
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Questions asked of molybdoenzymes and their model compounds:
-What is the redox potential ( energy of) Mo redox reactions?
- What are the structural details? What is bond order? (angles, bond distances)
-How well do models mimic reactions of Mo in enzymes? in structure in reactivity
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Mo Chemistry1.Oxidation states
Mo occurs in oxidation states from 0 +6Project 1 will generate complexes in states +4 –
6, same as enzymes
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Mo Chemistry2. Geometries: Mo complexes have Coordination Numbers
from CN 4 8 Project 1 uses reagents or makes products
with CN 4 7
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3. Reaction Chemistry Mo S; dtc ligand
Mo O; Mo=O ligands
Mo Chemistry
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What do you get if you multiply nine by six?
Molybdenum, atomic # 42: is it the answer to Life, the Universe and Everything?
What’s the Ultimate Question?
Adams speculates in “The Restaurant at the End of the Universe”:
Sure looks like it!
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O
Mo+6
OS
S
O
MoOS
S
O
Mo+4
S
S
O
Mo+4OS
S
SO
OO
OSO
OO
O
Mo+4
S
SH
H
O
Mo+5OHS
S
a
- H+, - e -
- H+, - e -
+ SO32-
- SO42-
+ H2O
oxygen
atom
transfer
coupled
proton
electron
transfer
A proposed catalytic cycle for how Mo oxidizes SO32-
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Mo
molybdopterinpterin
dithiolene
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Mo
Ball and stick diagram Chemical structure diagram
S
S
O
HN NH
HNNO
O
NH2
MoO NN
NH2
O
HO
P OP O
O
O
OO
OH
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S
S
O
HN NH
HNNO
O
NH2
MoO NN
NH2
O
HO
P OP O
O
O
OO
OH
S
S
O
HN NH
HNNO
O
NH2
MoO NN
NH2
O
HO
P OP O
O
O
OO
OH
Protein structuredestroyed
Mo compoundreleased (isolated)
rapid decomposition
HS
SH
HO
HN
NH
HN
N
O
O
H2N
Mo
P
O
O
O
N
N
HN
N
O
H2N S
S
CHOHCH2OH
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