Light-driven artificial enzymes for selective oxidation of guanosine triphosphate using water-soluble POSS network polymers

Abstract

The light-driven artificial enzymes were constructed to realize unnatural reactions concerning bio-significant molecules. In this manuscript, the guanosine triphosphate (GTP)-selective oxidation is reported using the network polymers composed of polyhedral oligomeric silsesquioxane (POSS). We synthesized the water-soluble POSS network polymer containing the naphthyridine ligands to capture GTP inside the networks and the ruthenium complexes to oxidize the captured GTP under light irradiation. Initially, the binding affinities of the guanosine nucleosides to the naphthyridine ligand inside the POSS network polymer were evaluated from the emission quenching experiments. Accordingly, it was observed that the naphthyridine ligand can form the stable complex only with GTP (K(a) = 5.5 × 10(6) M(-1)). These results indicate that only GTP can be captured by the network polymer. Next, the photo-catalytic activity of the ruthenium complex-modified POSS network polymer was investigated. Finally, it was revealed that the network polymer can decompose GTP efficiently under light irradiation. This is the first example, to the best of our knowledge, to offer not only the GTP-selective host polymers but also the light-driven artificial enzyme for GTP oxidation.

New Polymeric Materials Based on Element-Blocks

“…37 The naphthyridine ligand was tethered to the POSS network polymers with a covalent bond. From similar emission quenching experiments, it was observed that the naphthyridine ligand can form a stable complex with GTP (K a = 5.5 © 10 6 M…”

High Refractive-Index Hybrids Consisting of Water-Soluble Matrices with Bipyridine-Modified Polyhedral Oligomeric Silsesquioxane and Lanthanoid Cations

“…However, it is necessary to inhibit aggregation for maintaining transparency of materials. Therefore, we designed the SSQ matrices with the bipyridine linker to preserve dispersion states of metal cations homogeneously for obtaining good transparency as well as high RIs [ 40 , 41 ]. Furthermore, molecular assembly is easily accomplished by adsorption to SSQ [ 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 ].…”

Synthesis of single component element‐block materials based on siloxane‐based cage frameworks

“…Their use as molecular fillers is an attractive strategy to control functional properties such as refractive index, dielectric constant, mechanical properties and thermal stability. Another method of using siloxane‐based cage compounds involves direct crosslinking with small organic molecules to form three‐dimensional networks …”