Electrochemical and Biocatalytic Signal-Controlled Payload Release from a Metal-Organic Framework.

A metal-organic framework (MOF), ZIF-8, which is stable at neutral and slightly basic pH values in aqueous solutions and destabilized/dissolved under acidic conditions, is loaded with a pH-insensitive fluorescent dye, rhodamine-B isothiocyanate, as a model payload species. Then, the MOF species are immobilized at an electrode surface. The local (interfacial) pH value is rapidly decreased by means of an electrochemically stimulated ascorbate oxidation at +0.4 V (Ag/AgCl/KCl). Oxygen reduction upon switching the applied potential to -0.8 V allows to return the local pH to the neutral/basic pH, then stopping rapidly the release process. The developed method allows electrochemical control over stimulated or inhibited payload release processes from the MOF. The pH variation proceeds in a thin film of the solution near the electrode surface. The switchable release process is realized in a buffer solution and undiluted human serum. As the second option, the pH decrease stimulating the release process is achieved upon an enzymatic reaction using esterase and ester substrate. This approach potentially allows the release activation controlled by numerous enzymes assembled in complex biocatalytic cascades. It is expected that related electrochemical or biocatalytic systems can represent novel signal-responding materials with switchable features for delivering (bio)molecules within biomedical applications.

DNA Release from a Modified Electrode Triggered by a Bioelectrocatalytic Process.

DNA release from an electrode surface was stimulated by application of a mild electrical potential (0 V vs Ag/AgCl). The release process was activated by interfacial pH increase originating from H+ consumption during O2 reduction bio-electrocatalyzed by bilirubin oxidase immobilized at the electrode surface. The pH increase resulted in a change of the electrical charge from positive to negative at the surface of SiO2 nanoparticles (200 nm) associated with the electrode surface and functionalized with trigonelline and boronic acid. While the negatively charged DNA molecules were electrostatically bound to the positively charged surface, the negative charge produced upon O2 reduction resulted in the DNA repulsion and release from the modified interface. The small electrical potential for O2 reduction resulting in the interface recharge was allowed due to the bio-electrocatalysis using bilirubin oxidase enzyme. While, in the first set of experiments, the potential was applied on the modified electrode from an electrochemical instrument, later it was generated in situ by biocatalytic or photo-biocatalytic processes at a connected electrode. A multistep biocatalytic cascade generating NADH or photosynthetic process in thylakoid membranes was used to produce in situ a small potential to stimulate the DNA release catalyzed by bilirubin oxidase. The designed system can be used for different release processes triggered by various signals (electrical, biomolecular, and light signals, etc.), thus representing a general interfacial platform for the controlled release of different biomolecules and nanosize species.

DNA Computing Systems Activated by Electrochemically-triggered DNA Release from a Polymer-brush-modified Electrode Array.

An array of four independently wired indium tin oxide (ITO) electrodes was used for electrochemically stimulated DNA release and activation of DNA-based Identity, AND and XOR logic gates. Single-stranded DNA molecules were loaded on the mixed poly(N,N-di-methylaminoethyl methacrylate) (PDMAEMA)/poly-(methacrylic acid) (PMAA) brush covalently attached to the ITO electrodes. The DNA deposition was performed at pH 5.0 when the polymer brush is positively charged due to protonation of tertiary amino groups in PDMAE-MA, thus resulting in electrostatic attraction of the negatively charged DNA. By applying electrolysis at -1.0 V(vs. Ag/AgCl reference) electrochemical oxygen reduction resulted in the consumption of hydrogen ions and local pH increase near the electrode surface. The process resulted in recharging the polymer brush to the negative state due to dissociation of carboxylic groups of PMAA, thus repulsing the negatively charged DNA and releasing it from the electrode surface. The DNA release was performed in various combinations from different electrodes in the array assembly. The released DNA operated as input signals for activation of the Boolean logic gates. The developed system represents a step forward in DNA computing, combining for the first time DNA chemical processes with electronic input signals.