Nanostructures of the conducting polymer poly(3,4-ethylenedioxythiophene) with large surface areas enhance the performance of energy storage devices such as electrochemical supercapacitors. However, until now, high aspect ratio nanofibers of this polymer could only be deposited from the vapor-phase, utilizing extrinsic hard templates such as electrospun nanofibers and anodized aluminum oxide. These routes result in low conductivity and require postsynthetic template removal, conditions that stifle the development of conducting polymer electronics. Here we introduce a simple process that overcomes these drawbacks and results in vertically directed high aspect ratio poly(3,4-ethylenedioxythiophene) nanofibers possessing a high conductivity of 130 S/cm. Nanofibers deposit as a freestanding mechanically robust film that is easily processable into a supercapacitor without using organic binders or conductive additives and is characterized by excellent cycling stability, retaining more than 92% of its initial capacitance after 10,000 charge/discharge cycles. Deposition of nanofibers on a hard carbon fiber paper current collector affords a highly efficient and stable electrode for a supercapacitor exhibiting gravimetric capacitance of 175 F/g and 94% capacitance retention after 1000 cycles.

No abstract

The authors wish to dedicate this paper to the memory of Officer Sean Collier for his caring service to the MIT community and for his sacrifice.

Viologens, either as anions in solution or as pendant substituents to pyrrole, were incorporated as dopants to electrodeposited films of polypyrrole. The resulting polymer films exhibited redox activity at -0.5 V vs Ag/AgCl. The film consisting of polypyrrole with pendant viologens exhibited the best charge-discharge behavior with a maximum capacity of 55 mAh/g at a discharge current of 0.25 mA/cm(2). An anode consisting of polypyrrole (pPy) doped with viologen (V) was coupled to a cathode consisting of pPy doped with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) to yield a polymer-based battery with a cell electromotive force (emf) of 1.0 V, maximum capacity of 16 mAh/g, and energy density of 15 Wh/kg.

Rapid fabrication of layer-by-layer (LbL) electrodes is essential to expand their utility in energy storage applications. Herein, we address challenges in developing thick LbL electrodes of multi-wall carbon nanotubes (MWNTs) using conventional dip-and spray-LbL processes, and present a solution to overcome these challenges. The vacuum-assisted spray-LbL process using porous carbon substrates enabled a linear growth of LbL-MWNT electrodes with a 600 time decrease in their fabrication time.This result was attributed to the enhanced surface interactions between MWNTs and substrate via increased surface areas, enhanced capillary forces, physical entrapment in pores, and changes in hydrodynamic drag forces. Scanning electron microscopy (SEM) revealed high surface area carbon nanotube networks comprised of individual MWNT's. The spray MWNT electrodes delivered a high gravimetric energy of 100 W h kg À1 at high gravimetric power of 50 kW kg À1 , which is higher than those of most carbon nanotube electrodes reported. Moreover, the spray MWNT electrodes delivered the highest energy capacity per unit area (up to 300 mW h cm À2 at 0.4 mW cm À2 among the LbL electrodes reported, and showed excellent retention of energy capacity up to 100 mW h cm À2 at high power capacity of 200 mW cm À2 . These performance values are higher or comparable to the most advanced battery electrodes for high energy capacity per unit area. Broader contextWith emerging applications of Li-ion batteries such as electrical vehicles, load-leveling, and new electronic devices, the demand for improving both the gravimetric and areal energy and power output of battery electrodes is ever increasing. Although the previously reported battery electrodes assembled via layerby-layer (LbL) assembly have been shown to provide high gravimetric energy and power densities, the LbL electrodes deliver only limited total energy (per area) because of the long fabrication time required by traditional LbL processes. In this work, we demonstrate a rapid fabrication of thick LbL electrodes of multi-wall carbon nanotubes (MWNTs) via the modied spray-LbL method; the fabrication time decreased 600 times compared with traditional processes. The spray LbL-MWNT electrode showed both high gravimetric energy (100 W h kg electrode À1 ) and areal energy (100 mW h cm À2 ) without the expense of gravimetric or areal power density (50 kW kg electrode À1 or 200 mW cm À2 ). Our method can be easily expanded to different combinations of energy storage materials, substrates with different structures, and spray conditions, allowing us to efficiently fabricate novel energy storage electrodes via LbL assembly.

Tailoring cell response on an electrode surface is essential in the application of neural interfaces. In this paper, a method of controlling neuron adhesion on the surface of an electrode was demonstrated using a conducting polymer composite as an electrode coating. The electrodeposited coating was functionalized further with biomolecules-of-interest (BOI), with their surface concentration controlled via repetition of carbodiimide chemistry. The result was an electrode surface that promoted localized adhesion of primary neurons, the density of which could be controlled quantitatively via changes in the number of layers of BOI added. Important to neural interfaces, it was found that additional layers of BOI caused an insignificant increase in the electrical impedance, especially when compared to the large drop in impedance upon coating of the electrode with the conducting polymer composite.

Biomaterials derived via programmable supramolecular protein assembly provide a viable means of constructing precisely defined structures. Here, we present programmed superstructures of AuPt nanoparticles (NPs) on carbon nanotubes (CNTs) that exhibit distinct electrocatalytic activities with respect to the nanoparticle positions via rationally modulated peptide-mediated assembly. De novo designed peptides assemble into six-helix bundles along the CNT axis to form a suprahelical structure. Surface cysteine residues of the peptides create AuPt-specific nucleation site, which allow for precise positioning of NPs onto helical geometries, as confirmed by 3-D reconstruction using electron tomography. The electrocatalytic model system, i.e., AuPt for oxygen reduction, yields electrochemical response signals that reflect the controlled arrangement of NPs in the intended assemblies. Our design approach can be expanded to versatile fields to build sophisticated functional assemblies.

The effects of ascorbic acid on the riboflavin-sensitized photochemical changes in beta-lactoglobulin in an aqueous buffer solution as determined by high performance gel permeation liquid chromatography (HPGPLC), insoluble protein content, and individual amino acid content during fluorescent light illumination were studied. The riboflavin-sensitized photochemical degradation of beta-lactoglobulin was effectively inhibited by ascorbic acid, and its inhibitory effectiveness was concentration dependent. The 0.1% ascorbic acid treatment showed 74.4% inhibition of beta-lactoglobulin degradation as determined by a HPGPLC during 6 h light illumination. Insolubility of beta-lactoglobulin in a buffer solution during light illumination was also effectively decreased by ascorbic acid treatment. The riboflavin-sensitized photochemical reduction of cysteine, histidine, lysine, methionine, and tryptophan in beta-lactoglobulin was high during 6 h fluorescent light illumination. The 0.1% ascorbic acid treatment exhibited 20.8% inhibition of total amino acid degradation in beta-lactoglobulin during 6 h light illumination, showing strong inhibitory activity against the degradation of arginine, aspartic acid, cystein, glycine, histidine, phenylalanine, proline, serine, and tryptophan.