True or false?
Blood is red because of the iron in hemoglobin.
“Red blood cells”
A close-up of red blood
cells within a capillary.
Over 99 percent
of the blood vessels in the body
are capillaries,
even though they only hold 5
percent of the body’s blood.
False
por·phy·rin
Function: noun
Etymology: from Greek porphyra purple
-any of various compounds with a macrocyclic structure that consists essentially of four
pyrrole rings joined by four =CH- groups; especially : one (as chlorophyll or hemoglobin)
containing a central metal atom and usually exhibiting biological activity
Wikipedia’s dynamic picture
There are many
different hemes
used in
biochemistry as:
• Electron
transfer
cofactors as
Fe(3+) / Fe(2+)
• Catalytic
Cofactors as
cytochrome
P450
• Besides O2
transport as
hemoglobin
One example:
Cytochrome c
Oxidase
Where dioxygen
is reduced to
water during
respiration
Note all the
hemes!
How to draw a porphyrin:
The Adler synthesis of simple, symmetrically substituted porphyrins:
Meso position
R = phenyl (TPP)
toluyl (TTP)
p-chlorophenyl (TClPP)
Metallation of porphyrin
Anything change at Fe?
Porphyrin substituents
on heme in hemoglobin
How do you know when
the reaction is done?
Absorption Spectrum of a Porphyrin
Figure 1. Typical UV-Vis absorption spectrum of a porphyrin. The highly
conjugated porphyrin macrocycle shows intense absorption (extinction
coefficient > 200,000 M-1cm-1) at around 400 nm (the "Soret" band), followed
by several weaker absorption bands (Q Bands) at higher wavelengths (450 to
700 nm).
1H
NMR Characterization:
Challenges….
and how to meet them
L- keto
Ru(L-amino)
9.6
9.1
8.6
8.1
7.6
7.1
10.1
9.6
9.1
8.6
8.1
7.6
7.1
10.1
9.6
9.1
8.6
8.1
7.6
7.1
Ru(L-allox)
Ru(L-keto)
10.1
ppm
Complicated spectrum?
Try 2-D COSY NMR
(correlation spectroscopy)
from Ben Williams
from Ben Williams
from Ben Williams
from Ben Williams
,aʹ
b
a,bʹ
c
cʹ
1
2
10.1
9.6
9.1
ppm
8.6
8.1
7.6
7.1
from Alex Gaudette. BMC’12
Ru(L-amino)
d
c
10.1
a,b,bʹ
3
cʹ
9.6
aʹ
9.1
8.6
8.1
Ru(L-keto)
d
7.6
7.1
7.6
7.1
7.6
7.1
,aʹ
a
b,bʹ
c cʹ
10.1
9.6
9.1
8.6
8.1
Ru(L-allox)
,aʹ
a
c cʹ
10.1
9.6
9.1
8.6
ppm
b,bʹ
8.1
For Thursday, Sept. 27:
• Do heme synthesis using your prophyrin, TPP, TTP or TClPP,
determining reaction completion by fluorescence
• Filter Ru complex (if necessary); obtain MS of product
• Observe 2D COSY NMR process
• Obtain UV/vis spectrum of your Fe(porphyrin)Cl complex
Writing Assignments
• Goal = writing a full synthesis and characterization
manuscript on the Ru complex you made
• Structure like those we discussed on first day
• Includes, synthesis, 1D NMR and 2D COSY, and CV
• Due dates
• Draft 1 on Wednesday Oct.3 of the Experimental Section
with outline form of introduction
• Draft 2 on Wednesday Oct. 10: Introduction, revised
Expermental and Results section with NMR Results
,aʹ
cʹ
Ru(L-aap)
c
b
a,bʹ
1
2
d
Ru(L-amino)
10.1
c
9.6
cʹ
a,b,bʹ
9.1
8.6
3
9.6
7.6
aʹ
d
10.1
8.1
,aʹ
9.1
a
8.6
b,bʹ8.1
7.6
7.1
9.1
8.6
8.1
7.6
7.1
Ru(L-keto)
c cʹ
10.1
9.6
7.1
Ru(L-aap)
,aʹ
c
a,bʹ
cʹ
1
2
10.1
9.6
9.1
8.6
8.1
Ru(L-amino)
d
c
10.1
3
cʹ
9.6
Ru(L-keto)
7.6
7.1
7.6
7.1
7.6
7.1
a,b,bʹ
aʹ
9.1
8.6
8.1
d
,aʹ
a
b,bʹ
c cʹ
10.1
9.6
9.1
8.6
8.1
,aʹ
-allox)
b
c cʹ
a