TY - JOUR A1 - Honarvarfard, Elham A1 - Gamella, Maria A1 - Channaveerappa, Devika A1 - Darie, Costel C. A1 - Poghossian, Arshak A1 - Schöning, Michael Josef A1 - Katz, Evgeny T1 - Electrochemically Stimulated Insulin Release from a Modified Graphene–functionalized Carbon Fiber Electrode JF - Electroanalysis N2 - A graphene-functionalized carbon fiber electrode was modified with adsorbed polyethylenimine to introduce amino functionalities and then with trigonelline and 4-carboxyphenylboronic acid covalently bound to the amino groups. The trigonelline species containing quarterized pyridine groups produced positive charge on the electrode surface regardless of the pH value, while the phenylboronic acid species were neutral below pH 8 and negatively charged above pH 9 (note that their pKa=8.4). The total charge on the monolayer-modified electrode was positive at the neutral pH and negative at pH > 9. Note that 4-carboxyphenylboronic acid was attached to the electrode surface in molar excess to trigonelline, thus allowing the negative charge to dominate on the electrode surface at basic pH. Negatively charged fluorescent dye-labeled insulin (insulin-FITC) was loaded on the modified electrode surface at pH 7.0 due to its electrostatic attraction to the positively charged interface. The local pH in close vicinity to the electrode surface was increased to ca. 9–10 due to consumption of H+ ions upon electrochemical reduction of oxygen proceeding at the potential of −1.0 V (vs. Ag/AgCl) applied on the modified electrode. The process resulted in recharging of the electrode surface to the negative value due to the formation of the negative charge on the phenylboronic acid groups, thus resulting in the electrostatic repulsion of insulin-FITC and stimulating its release from the electrode surface. The insulin release was characterized by fluorescence spectroscopy (using the FITC-labeled insulin), by electrochemical measurements on an iridium oxide, IrOx, electrode and by mass spectrometry. The graphene-functionalized carbon fiber electrode demonstrated significant advantages in the signal-stimulated insulin release comparing with the carbon fiber electrode without the graphene species. Y1 - 2017 U6 - http://dx.doi.org/10.1002/elan.201700095 SN - 1521-4109 VL - 29 IS - 6 SP - 1543 EP - 1553 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Gamella, Maria A1 - Zakharchenko, Andrey A1 - Guz, Nataliia A1 - Masi, Madeline A1 - Minko, Sergiy A1 - Kolpashchikov, Dmitry M. A1 - Iken, Heiko A1 - Poghossian, Arshak A1 - Schöning, Michael Josef A1 - Katz, Evgeny T1 - DNA computing system activated by electrochemically triggered DNA realease from a polymer-brush-modified electrode array JF - Electroanalysis N2 - 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-dimethylaminoethyl 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 PDMAEMA, 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. Y1 - 2017 U6 - http://dx.doi.org/10.1002/elan.201600389 SN - 1521-4109 VL - 29 IS - 2 SP - 398 EP - 408 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Honarvarfard, Elham A1 - Gamella, Maria A1 - Poghossian, Arshak A1 - Schöning, Michael Josef A1 - Katz, Evgeny T1 - An enzyme-based reversible Controlled NOT (CNOT) logic gate operating on a semiconductor transducer JF - Applied Materials Today N2 - An enzyme-based biocatalytic system mimicking operation of a logically reversible Controlled NOT (CNOT) gate has been interfaced with semiconductor electronic transducers. Electrolyte–insulator–semiconductor (EIS) structures have been used to transduce chemical changes produced by the enzyme system to an electronically readable capacitive output signal using field-effect features of the EIS device. Two enzymes, urease and esterase, were immobilized on the insulating interface of EIS structure producing local pH changes performing XOR logic operation controlled by various combinations of the input signals represented by urea and ethyl butyrate. Another EIS transducer was functionalized with esterase only, thus performing Identity (ID) logic operation for the ethyl butyrate input. Both semiconductor devices assembled in parallel operated as a logically reversible CNOT gate. The present system, despite its simplicity, demonstrated for the first time logically reversible function of the enzyme system transduced electronically with the semiconductor devices. The biomolecular realization of a CNOT gate interfaced with semiconductors is promising for integration into complex biomolecular networks and future biosensor/biomedical applications. KW - Electrolyte–insulator–semiconductor KW - Capacitive field-effect KW - CNOT KW - XOR KW - Enzyme logic gate Y1 - 2017 U6 - http://dx.doi.org/10.1016/j.apmt.2017.08.003 SN - 2352-9407 VL - 9 SP - 266 EP - 270 PB - Elsevier CY - Amsterdam ER -