1. Blood is red because of the iron in hemoglobin.
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.

2. 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

4. Wikipedia’s dynamic picture

5. 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

6. One example: Cytochrome c Oxidase
Where dioxygen is reduced to water during respiration
Note all the hemes!

7. How to draw a porphyrin:

8. The Adler synthesis of simple, symmetrically substituted porphyrins:
Meso position
R = phenyl (TPP)
toluyl (TTP)
p-chlorophenyl (TClPP)

9. Metallation of porphyrin
Anything change at Fe?
How do you know when
the reaction is done?
Porphyrin substituents
on heme in hemoglobin

10. 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).

11. 1H NMR Characterization:
Challenges….
and how to meet them

13. L- keto

15. Ru(L-amino)
Ru(L-keto)
Ru(L-allox)
ppm

16. Complicated spectrum?
Try 2-D COSY NMR
(correlation spectroscopy)

19. from Ben Williams

20. from Ben Williams

21. from Ben Williams

22. from Ben Williams
,aʹ b
a,bʹ c cʹ 1 2
ppm

23. from Alex Gaudette. BMC’12

24. Ru(L-amino) Ru(L-keto) Ru(L-allox) ppm d a,b,bʹ c cʹ 3 aʹ d ,aʹ a b,bʹ

25. 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

26. 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

27. Ru(L-aap) Ru(L-amino) Ru(L-keto) ppm ,aʹ b a,bʹ c cʹ 1 2 d a,b,bʹ c cʹ3 aʹ
Ru(L-amino) d
,aʹ a
b,bʹ
c cʹ
Ru(L-keto)
ppm

28. Ru(L-aap) Ru(L-amino) Ru(L-keto) Ru(L-allox) ppm ,aʹ b a,bʹ c cʹ 1 2 d
a,b,bʹ
Ru(L-amino) c cʹ 3 aʹ d
,aʹ a
b,bʹ
Ru(L-keto)
c cʹ
,aʹ
Ru(L-allox)
c cʹ a
b,bʹ
ppm