Oxidative Spin-Spray-Assembled Coordinative Multilayers as Platforms for Capacitive Films.

The spin-spray-assisted layer-by-layer (LbL) assembly technique was used to prepare coordinative oxidative multilayers from Ce(IV), inorganic polyphosphate (PP), and graphene oxide (GO). The films consist of successive tetralayers and have a general structure (PP/Ce/GO/Ce)n. Such oxidative multilayers have been shown to be a general platform for the electrodeless generation of conducting polymer and melanin-type films. Although the incorporation of GO enhances the film growth, the conventional dip LbL method is very time consuming. We show that the spin-spray method reduces the time required to grow thick multilayers by the order of magnitude and the film growth is linear from the beginning, which implies a stratified structure. We have deposited poly(3,4-ethylenedioxothiophene), PEDOT, on the oxidative multilayers and studied these redox-active films as models for melanin-type capacitive layers for supercapacitors to be used in biodegradable electronics, both before and after the electrochemical reduction of GO to rGO. The amount of oxidant and PEDOT scales linearly with the film thickness, and the charge transfer kinetics is not mass transfer-limited, especially after the reduction of GO. The areal capacitance of the films grows linearly with the film thickness, reaching a value of ca. 1.6 mF cm-2 with 20 tetralayers, and the specific volumetric (per film volume) and mass (per mass of PEDOT) capacitances are ca. 130 F cm-3 and 65 F g-1, respectively. 5,6-Dihydroxyindole can also be polymerized to a redox-active melanin-type film on these oxidative multilayers, with even higher areal capacitance values.

Polydopamine Nanoparticles Prepared Using Redox-Active Transition Metals.

Autoxidation of dopamine to polydopamine by dissolved oxygen is a slow process that requires highly alkaline conditions. Polydopamine can be formed rapidly also in mildly acidic and neutral solutions by using redox-active transition-metal ions. We present a comparative study of polydopamine nanoparticles formed by autoxidation and aerobic or anaerobic oxidation in the presence of Ce(IV), Fe(III), Cu(II), and Mn(VII). The UV-vis spectra of the purified nanoparticles are similar, and dopaminechrome is an early intermediate species. At low pH, Cu(II) requires the presence of oxygen and chloride ions to produce polydopamine at a reasonable rate. The changes in dispersibility and surface charge take place at around pH 4, which indicates the presence of ionizable groups, especially carboxylic acids, on their surface. X-ray photoelectron spectroscopy shows the presence of three different classes of carbons, and the carbonyl/carboxylate carbons amount to 5-15 atom %. The N 1s spectra show the presence of protonated free amino groups, suggesting that these groups may interact with the π-electrons of the intact aromatic dihydroxyindole moieties, especially in the metal-induced samples. The autoxidized and Mn(VII)-induced samples do not contain metals, but the metal content is 1-2 atom % in samples prepared with Ce(IV) or Cu(II), and ca. 20 atom % in polydopamine prepared in the presence of Fe(III). These differences in the metal content can be explained by the oxidation and complexation properties of the metals using the general model developed. In addition, the nitrogen content is lower in the metal-induced samples. All of the metal oxidants studied can be used to rapidly prepare polydopamine at room temperature, but the possible influence of the metal content and nitrogen loss should be taken into account.

Effects of pH and Oxidants on the First Steps of Polydopamine Formation: A Thermodynamic Approach.

We present a general thermodynamic top-down analysis of the effects of oxidants and pH on dopamine oxidation and cyclization, supplemented with UV-vis and electrochemical studies. The model is applicable to other catecholamines and various experimental conditions. The results show that the decisive physicochemical parameters in autoxidation are the p K values of the semiquinone and the amino group in the oxidized quinone. Addition of Ce(IV) or Fe(III) enhances dopamine oxidation in acidic media in aerobic and anaerobic conditions by the direct oxidation of dopamine and, in the presence of oxygen, also by the autoxidation of the formed semiquinone. At pH 4.5, the enhancement of the one-electron oxidation of dopamine explains the overall reaction enhancement, but at a lower pH, cyclization becomes rate-determining. Oxidation by Cu(II) at reasonable rates requires the presence of oxygen or chloride ions.