Simultaneous Electropolymerization and Electro-Click Functionalization for Highly Versatile Surface Platforms

Simple preparation methods of chemically versatile and highly functionalizable surfaces remain rare and present a challenging research objective. Here, we demonstrate a simultaneous electropolymerization and electro-click functionalization process (SEEC) for one-pot self-construction of aniline- and naphthalene-based functional polymer films where both polymerization and click functionalization are triggered by applying electrochemical stimuli. Cyclic voltammetry (CV) can be applied for the simultaneous oxidation of 4-azido­aniline and the reduction of Cu(II) ions, resulting in polymerization of the former, and the Cu(I)-catalyzed alkyne/azide cycloaddition (“click” chemistry). Properties of the films obtained can be tuned by varying their morphology, their chemically “clicked” content, or by postconstruction functionalization. To demonstrate this, the CV scan rates, component monomers, and “clicked” molecules were varied. Covalent postconstruction immobilization of horseradish peroxidase was also performed. Consequently, pseudo­capacitance and enzyme activity were affected. SEEC provides surface scientists an easy access to a wide range of functionalization possibilities in several fields including sensors, fuel cells, photovoltaics, and biomaterials

Dynamic Disorder in Single-Enzyme Experiments: Facts and Artifacts

Using a single-molecule fluorescence approach, the time series of catalytic events of an enzymatic reaction can be monitored, yielding a sequence of fluorescent “on”- and “off”-states. An accurate on/off-assignment is complicated by the intrinsic and extrinsic noise in every single-molecule fluorescence experiment. Using simulated data, the performance of the most widely employed binning and thresholding approach was systematically compared to change point analysis. It is shown that the underlying on- and off-histograms as well as the off-autocorrelation are not necessarily extracted from the “signal’’ buried in noise. The shapes of the on- and off-histograms are affected by artifacts introduced by the analysis procedure and depend on the signal-to-noise ratio and the overall fluorescence intensity. For experimental data where the background intensity is not constant over time we consider change point analysis to be more accurate. When using change point analysis for data of the enzyme α-chymotrypsin, no characteristics of dynamic disorder was found. In light of these results, dynamic disorder might not be a general sign of enzymatic reactions