Mapping the nanoscale elastic property modulations of polypyrrole thin films in liquid electrolyte with EC-AFM.

Linking structure to mechanical and elastic properties is a major concern for the development of novel electroactive materials. This work reports on the potential-induced changes in thickness and Young modulus of a substrate supported, perchlorate doped polypyrrole thin film (<100 nm) investigated with electrochemical atomic force microscopy (AFM) under in situ conditions. This was accomplished by nanomechanical mapping of potentiodynamically electropolymerized polypyrrole film in electrolyte solution with AFM during redox cycling. The polypyrrole film thickness and Young modulus follow the electrical potential nearly linearly, increasing due to solvent and ion influx as the film is oxidized, and decreasing during reduction. Our measurements also confirm the presence of a potential-independent, passive swelling which is accompanied by softening of the film, likely caused by osmotic effects. Additionally, the heterogeneous distribution of the Young modulus can be directly traced to the typical nodular surface topography of polypyrrole, with the top of the nodular area possessing lower modulus, thus highlighting the complex relationship between topography and elastic properties.

Reversible Ultrathin PtOx Formation at the Buried Pt/YSZ(111) Interface Studied In Situ under Electrochemical Polarization.

Three different platinum oxides are observed by in situ X-ray diffraction during electrochemical potential cycles of platinum thin film model electrodes on yttria-stabilized zirconia (YSZ) at a temperature of 702 K in air. Scanning electron microscopy and atomic force microscopy performed before and after the in situ electrochemical X-ray experiments indicate that approximately 20% of the platinum electrode has locally delaminated from the substrate by forming pyramidlike blisters. The oxides and their locations are identified as (1) an ultrathin PtOx at the buried Pt/YSZ interface, which forms reversibly upon anodic polarization; (2) polycrystalline ß-PtO2, which forms irreversibly upon anodic polarization on the inside of the blisters; and (3) an ultrathin α-PtO2 at the Pt/air interface, which forms by thermal oxidation and which does not depend on the electrochemical polarization. Thermodynamic and kinetic aspects are discussed to explain the coexistence of multiple phases at the same electrochemical conditions.

Probing the Electrolyte Transfer in Ultrathin Polypyrrole Films by In Situ X-ray Reflectivity and Electrochemistry.

This study reports on the potential-induced charge and mass transfer between an ultrathin polypyrrole (PPy) film and an electrolyte by simultaneous in situ X-ray reflectivity (XRR) and electrochemistry (EC) utilizing their sensitivity to electrons. An about 30 nm thin PPy film was deposited on a silicon single crystal by fast potential cycling, providing a dense film of an extraordinary small surface roughness. XRR was recorded from the PPy film in an aqueous 0.1 M perchloric acid at electric potentials between -0.2 V and +0.5 V vs Ag/AgCl. The PPy film shows typical reversible and linear changes in film thickness and electron density arising from the potential-dependent electrolyte incorporation. By introducing EC-XRR, a comprehensive analysis combining in situ XRR and EC, the net number of electrons passing through the PPy-electrolyte interface was deduced along with the potential-induced thickness variations, indicating a complex exchange mechanism. Evidently, along with the anion transfer, parallel charge compensation by protons and a volume and electron compensating counterflow of solvent molecules take place. Complementary time-dependent EC-XRR scans indicate that these exchange mechanisms are individual in two potential ranges. The low actuation along with a high pseudocapacitance suggest the fast potentiodynamically deposited PPy film as a promising supercapacitor material.

Giant electrochemical actuation in a nanoporous silicon-polypyrrole hybrid material.

The absence of piezoelectricity in silicon makes direct electromechanical applications of this mainstream semiconductor impossible. Integrated electrical control of the silicon mechanics, however, would open up new perspectives for on-chip actuorics. Here, we combine wafer-scale nanoporosity in single-crystalline silicon with polymerization of an artificial muscle material inside pore space to synthesize a composite that shows macroscopic electrostrain in aqueous electrolyte. The voltage-strain coupling is three orders of magnitude larger than the best-performing ceramics in terms of piezoelectric actuation. We trace this huge electroactuation to the concerted action of 100 billions of nanopores per square centimeter cross section and to potential-dependent pressures of up to 150 atmospheres at the single-pore scale. The exceptionally small operation voltages (0.4 to 0.9 volts), along with the sustainable and biocompatible base materials, make this hybrid promising for bioactuator applications.

Applying phasor approach analysis of multiphoton FLIM measurements to probe the metabolic activity of three-dimensional in vitro cell culture models.

Fluorescence lifetime imaging microscopy (FLIM) can measure and discriminate endogenous fluorophores present in biological samples. This study seeks to identify FLIM as a suitable method to non-invasively detect a shift in cellular metabolic activity towards glycolysis or oxidative phosphorylation in 3D Caco-2 models of colorectal carcinoma. These models were treated with potassium cyanide or hydrogen peroxide as controls, and epidermal growth factor (EGF) as a physiologically-relevant influencer of cell metabolic behaviour. Autofluorescence, attributed to nicotinamide adenine dinucleotide (NADH), was induced by two-photon laser excitation and its lifetime decay was analysed using a standard multi-exponential decay approach and also a novel custom-written code for phasor-based analysis. While both methods enabled detection of a statistically significant shift of metabolic activity towards glycolysis using potassium cyanide, and oxidative phosphorylation using hydrogen peroxide, employing the phasor approach required fewer initial assumptions to quantify the lifetimes of contributing fluorophores. 3D Caco-2 models treated with EGF had increased glucose consumption, production of lactate, and presence of ATP. FLIM analyses of these cultures revealed a significant shift in the contribution of protein-bound NADH towards free NADH, indicating increased glycolysis-mediated metabolic activity. This data demonstrate that FLIM is suitable to interpret metabolic changes in 3D in vitro models.