Reconstituting Enzymes for Direct Electron Transfer through

Reconstituting Enzymes for Direct Electron Transfer through Surface Initiated Polymerization of Conjugated Polymers Jason Locklin, Department of Chemistry and Faculty of Engineering, University of Georgia We have made significant advances in the surfaceinitiated polymerization of conjugated polymers using a Kumada-type catalyst transfer polycondensation. Both substituted and unsubstituted poly(thiophenes) and poly(p-phenylenes) have been synthesized from aromatic bromide monolayers on gold and ITO using both Ni and Pd cross-coupling.

S

Br

Ni(COD)2

S

L

L NiBr

Fe

Fe ClMg

S

S

S

supporting ligand

We have determined the catalyst density on surfaces indirectly through monolayer coupling experiments with defined redox couple Ligand

Coverage (1013 molecules/cm2)

Yield (%)

FWHM (mV)

E1/2 (V vs. SCE)

2 equiv. PPh3

6.00

10

120

.43

dppe

4.84

8.1

116

.43

dppp

4.14

6.9

122

.41

bpy

5.16

8.6

95

.39

Schematic of the surface initiated polymerization process
P H3C P Ni(II)-Br

P P Ni(II)-Br

CH3

CH3

S

ClMg

S

Br

H3C

S

CH3 CH3

S

ClMg

S

Br

H(Br) n

S CH3

S

intramolecular transfer Si OOO

n

Si OOO

n

Si OOO

n