An electrochromic zwitterionic viologen, N,N'-bis(3-sulfonatopropyl)-4-4'-bipyridinium, has been used for the first time for doping poly (3,4-ethylenedioxythiopene) (PEDOT) films during electropolymerization. Slow and fast diffusional rates for the monomer at deposition potentials of +1.2 and +1.8 V, respectively yielded the viologen-doped PEDOT films with granular morphology and with dendrite-like shapes. The dual electrochrome formed at +1.8 V, showed enhanced coloration efficiency, larger electrochemical charge storage capacity, and superior redox activity in comparison to its analogue grown at +1.2 V, thus demonstrating the role of dendritic shapes in amplifying electrochromism. Flexible electrochromic devices fabricated with the viologen-doped PEDOT film grown at +1.8 V and Prussian blue with an ionic liquid-based gel electrolyte film showed reversible coloration between pale and dark purple with maximum coloration efficiency of 187 cm2C(-1) at lambda=693 nm. The diffusional impedance parameters and switching kinetics of the device showed the suitability of this dual electrochrome formed as a single layer for practical electrochromic cells.

Chitosan derived from chitin is one of the most abundant naturally occurring biocompatible polymers obtained from fungi and arthropods. In this work, we report the enhancement in the bactericidal efficacy of CHI in the presence of a sharp nanotopography. High-aspect ratio nanostructured surface (NSS) was fabricated using a single-step deep reactive ion etching technique (DRIE). Post fabrication, CHI coating was carried out using a layer-by-layer (LBL) dip coating process on the flat and nanostructured surfaces. Antibacterial efficacy of the flat silicon surface coated with CHI (Si_CHI) and NSS coated with CHI (NSS_CHI) was tested against both Gram-negative (G-ve) bacteria E. coli and Gram-positive (G+ve) bacteria S. aureus. NSS_CHI exhibited superior antibacterial property against G-ve and G+ve microbes as compared with Si_CHI and NSS substrates. Scanning electron microscopy (SEM) and fluorescence microscopy were used to study the morphology and viability of the bacteria on all the surfaces. Also, biofilm quantification was carried out on all the engineered surfaces for both E. coli and S. aureus using crystal violet (CV) staining. NSS_CHI was found to have the minimum biofilm formation on its surface exhibiting its superior antibacterial property. This study shows that the antibacterial and antibiofilm efficiency of CHI can be augmented by combining it with a sharp nanotopography.

The synergistic relationship between structure and the bulk properties of polyelectrolyte multilayer (PEM) films has generated tremendous interest in their application for loading and release of bioactive species. Layer-by-layer assembly is the simplest, cost effective process for fabrication of such PEMs films, leading to one of the most widely accepted platforms for incorporating biological molecules with nanometre precision. The bulk reservoir properties of PEM films render them a potential candidate for applications such as biosensing, drug delivery and tissue engineering. Various biomolecules such as proteins, DNA, RNA or other desired molecules can be incorporated into the PEM stack via electrostatic interactions and various other secondary interactions such as hydrophobic interactions. The location and availability of the biological molecules within the PEM stack mediates its applicability in various fields of biomedical engineering such as programmed drug delivery. The development of advanced technologies for biomedical applications using PEM films has seen rapid progress recently. This review briefly summarises the recent successes of PEM being utilised for diverse bio-applications.

The measurement of molecular transport within polymer films yields information about the internal structural organization of the films and is useful in applications such as the design of polymeric capsules for drug delivery. Layer-by-layer assembly of polyelectrolyte multilayer films has been widely used in such applications where the multilayer structure often exhibits anisotropic transport resulting in different diffusivities in the lateral (parallel to the film) and transverse (normal to the film) directions. Although lateral transport can be probed using techniques such as fluorescence recovery after photobleaching (FRAP), it cannot be applied to probing transverse diffusivity in polymer films smaller than the diffraction limit of light. Here we present a technique to probe the transport of molecules tagged with fluorphores in polymer films thinner than the optical diffraction limit using the modulation of fluorescence emission depending on the distance of the tagged molecules from a metal surface. We have used this technique to probe the diffusion of proteins biotin and bovine serum albumin (BSA) in polyelectrolyte multilayer films. We also studied the interdiffusion of chains in multilayer films using this technique. We observed a 3 order of magnitude increase in interdiffusion as a function of the ionic strength of the medium. This technique, along with FRAP, will be useful in studying anisotropic transport in polymer films, even those thinner than the diffraction limit, because the signal in this technique arises only from transverse and not lateral transport. Finally, this technique is also applicable to studying the diffusion of chromophore-labeled species within a polymer film. We demonstrate this aspect by measuring the transverse diffusion of methylene blue in the PAH-PAA multilayer system.

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