Control of bioelectrocatalytic transformations on DNA scaffolds.
The spatial organization of biomolecules on a DNA scaffold linked to an electrode leads to programmed biocatalytic transformations. This is exemplified by the electrical contacting of glucose oxidase (GOx) linked to the DNA scaffold with the electrode. A nucleic acid functionalized with a ferrocene relay unit was hybridized with the DNA scaffold at a position adjacent to the electrode, and GOx functionalized with nucleic acid units complementary to the specific domain of the DNA template was hybridized with the DNA scaffold in a position remote from the electrode. Under these conditions, ferrocene-mediated oxidation of the redox center of GOx occurred, and the effective bioelectrocatalytic oxidation of glucose was activated. Exchange of the position of GOx and the electron-mediator groups prohibited the bioelectrocatalytic oxidation of glucose. In another system, a nucleic acid-functionalized microperoxidase-11 (MP-11) and the nucleic acid-modified GOx were hybridized with the adjacent and remote sites, respectively, on the DNA scaffold associated with the electrode. In this configuration, effective MP-11-catalyzed reduction of H(2)O(2) generated by the GOx-catalyzed oxidation of glucose occurred, and the resulting bioelectrocatalytic cathodic currents were controlled by the concentration of glucose. Exchanging the positions of MP-11 and GOx on the DNA scaffold eliminated the MP-11-electrocatalyzed reduction of H(2)O(2).
Piperberg
Gilad
G
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Wilner
Ofer I
OI
Yehezkeli
Omer
O
Tel-Vered
Ran
R
Willner
Itamar
I
D055162:Biocatalysis; D015374:Biosensing Techniques / Q000379:methods; D004247:DNA / Q000737:chemistry* / Q000378:metabolism*; D004563:Electrochemistry / Q000379:methods*; D004566:Electrodes; D004800:Enzymes, Immobilized / Q000737:chemistry / Q000378:metabolism; D005296:Ferrous Compounds / Q000737:chemistry*; D005947:Glucose / Q000378:metabolism; D005949:Glucose Oxidase / Q000737:chemistry* / Q000378:metabolism*; D006861:Hydrogen Peroxide / Q000378:metabolism; D000075163:Metallocenes; D009693:Nucleic Acid Hybridization; D009696:Nucleic Acids / Q000737:chemistry / Q000378:metabolism; D010084:Oxidation-Reduction; D010544:Peroxidases / Q000737:chemistry / Q000378:metabolism
D004800:Enzymes, Immobilized; D005296:Ferrous Compounds; D000075163:Metallocenes; D009696:Nucleic Acids; D004247:DNA; D006861:Hydrogen Peroxide; D005949:Glucose Oxidase; D010544:Peroxidases; C021799:microperoxidase; D005947:Glucose; C004998:ferrocene