The Photochemical Activation of Enzymes

Figure 11.16 Assembly of CdS NP/AChE modified electrode used for the photochemical detection of enzyme activity. Reprinted with permission from Ref. 55.

Albeit the substantial progress in the bioelectrochemical activation of enzymes, one could identify two important future challenges in the field (i) The active relay units wiring the redox centers of the enzymes with the electrodes could be generated by photoinduced electron transfer. This could pave the way to the photochemical wiring of enzymes and to the development of photobiofuel cells, (ii) DNA scaffolds provide unique templates for the ordered self-assembly of molecular or biomolecular units through dictated hybridization. The ordering of relay units and enzymes, or of relay units photosystems, on DNA templates associated with electrodes may yield attractive new supramolecular nanostructures for bioelectronics and optobioelec tronic s. 

Photoswitchable enzymes could have an important role in controlling biochemical transformations in bioreactors. Various biotechnological processes generate an inhibitor, or alter the environmental conditions (pH, for example) of the reaction medium. Photochemical activation of enzymes that adjust environmental conditions or deplete the inhibitor to a low concentration may maintain the bioreactor at optimal performance. More specifically, integration of the photoswitchable biocataly-tic matrix with a sensory electrode might yield a feedback mechanism in which the sensor element triggers the light-induced activation/deactivation of the photosensitive biocatalyst. 

Photochemical Activation of Enzymes Using Dyes Covalently Tethered to the Protein Backbone... 

It has been found that the catalytic activity of PKC is enhanced by a lipid component of the cell membrane, namely phosphatidylserine. This activity is further stimulated by sn-1,2-diacylglycerol. Oleic acid also activates the enzyme in the presence of 1,2-diacylglycerol, and thus it is presumed to mimic phosphatidylserine. In order to identify that modulating binding site for oleic acid on PKC, a photoaffinity analogue was devised. A carbene generating photophore, diazirine was placed in the apolar terminus of the unsaturated fatty acid ligand (30, Fig. 12). The synthesis and the photochemical activation properties were reported by Ruhmann and Wentrup [113]. 

Redox enzymes are the active component in many electrochemical enzyme electrode biosensor devices.1821 The integration of two different redox enzymes with an electrode support, in which one of the biocatalysts is photoswitchable between ON and OFF states, can establish a composite multisensor array. The biomaterial interface that includes the photoswitchable enzyme in the OFF state electrochemi-cally transduces the sensing event of the substrate corresponding to the nonphoto-switchable enzyme. Photochemical activation of the light-active enzyme leads to the full electrochemical response, corresponding to the analysis of the substrates of the two enzymes. As a result, the processing of the signals transduced by the composite biomaterial interface in the presence of the two substrates permits the assay of the... 

---