Electroactive Nanostructured Membranes (ENM): Synthesis and Electrochemical Properties of Redox Mediator-Modified Gold Nanoparticles Using a Dendrimer Layer-by-Layer Approach

The layer-by-layer (LbL) self-assembly process has become an important tool in the fabrication of nanostructured devices for electrochemical applications, especially in those cases where control at the molecular level is required. In this paper we present a system based on electroactive nanostructured membranes (ENM) with ITO-PVS/PAMAM-Au LbL electrodes, in which a redox mediator (Me) is electrodeposited around the Au nanoparticles to form an ITO-PVS/PAMAM-Au@Me system. The redox mediators used were Co, Fe, Ni and Cu hexacyanoferrates. The 3-bilayer ITO-PVS/PAMAM-Au@Me system was characterized electrochemically by cyclic voltammetry and electrochemical impedance spectroscopy. All hexacyanoferrate modified electrodes showed electrocatalytic activity towards hydrogen peroxide, thus demonstrating that this new approach can be used in biosensors and nanodevices, where a redox mediator is required

Impact of Collagen/Heparin Multilayers for Regulating Bone Cellular Functions

Bone cell interaction with extracellular matrix (ECM) microenvironment is of critical importance when engineering surface interfaces for bone regeneration. In this work layer-by-layer films of type I collagen (coll), the major constituent of bone ECM, and heparin (hep), a glycosaminoglycan, were assembled on poly(l-lactic acid) (PLLA) substrates to evaluate the impact of the biomacromolecular coating on cell activity. The surface modification of PLLA demonstrated that the hep/coll multilayer is stable after 10 bilayers (confirmed by contact angle, infrared spectroscopy, and morphological analysis). This simple approach provided novel information on the effect of heparin on type I collagen hierarchical organization and subsequent cell response of osteoblast-like (MC3T3-E1) and human bone marrow-derived mesenchymal stem cells (hMSCs). Interestingly, the number of deposited heparin layers (1 or 10) appeared to play an important role in the self-assembly of collagen into fibrils, stabilizing the fibrous collagen layer, and potentially impacting hMSCs activity.Ana M. Ferreira thanks the Lagrange CRT for financing her researc

Interaction of Fe3+ meso-tetrakis (2,6-dichloro-3-sulfonatophenyl) porphyrin with cationic bilayers: magnetic switching of the porphyrin and magnetic induction at the interface

An organized multilayer was constructed by the layer-by-layer technique in which alternating layers of metalloporphyrin and dioctadecyldimethylammonium bromide bilayers were deposited onto an indium tin oxide surface electrode. The porphyrin molecules that are organized in the different layers showed a strong electroactivity with a well-defined electrochemical process. In LbL, electroactivity could be explained only by the occurrence of electron hoping. Thus, total Kohn–Sham density functional theory (KS-DFT) was performed to better understand the conditions responsible for the electroactivity of the metalloporphyrin layers intercalated by an insulating material. Total KS-DFT theory involves local density approximation energy calculations based on spin-polarized variant of KS-DFT theory. The results revealed a magnetization switching of the metalloporphyrin induced by the interaction with the surfactant bilayer accompanied by spin polarization of the porphyrin-interacting surfactant molecule. Although discrete, the surfactant magnetization had significant repercussions on the electron conductivity. Calculations also demonstrated loss of porphyrin symmetry promoted by a parent surfactant with a shorter hydrocarbon chain, ditetradecyldimethylammonium bromide. The calculation results were corroborated by experimental results obtained by the electron paramagnetic resonance and magnetic circular dichroism techniques.FAPESPCNPqCAPE

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc}n and {Chit-SWCNTs/CoTsPc}n (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E1/2 at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]5-/[CoTsPc(II)]4- and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc}5 multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.FAPEPICNPq (472369/2008-3)CAPESRede NanoBioMednBioNet Films & Sensor

Enhanced Charge Transport and Incorporation of Redox Mediators in Layer-by-Layer Films Containing PAMAM-Encapsulated Gold Nanoparticles

In this work, we exploit the molecular engineering capability of the layer-by-layer (LbL) method to immobilize layers of gold nanoparticles on indium tin oxide (ITO) substrates, which exhibit enhanced charge transfer and may incorporate mediating redox substances. Polyamidoamine (PAMAM generation 4) dendrimers were used as template/stabilizers for Au nanoparticle growth, with PAMAM-Au nanoparticles serving as cationic polyelectrolytes to produce LbL films with poly(vinylsulfonic acid) (PVS). The cyclic voltammetry (CV) of ITO-PVS/PAMAM-Au electrodes in sulfuric acid presented a redox pair attributed to Au surface oxide formation. The maximum kinetics adsorption is first-order, 95% of the current being achieved after only 5 min of adsorption. Electron hopping can be considered as the charge transport mechanism between the PVS/PAMAM-Au layers within the LbL films. This charge transport was faster than that for nonmodified electrodes, shown by employing hexacyanoferrate(III) as the surface reaction marker. Because the enhanced charge transport may be exploited in biosensors requiring redox mediators, we demonstrate the formation of Prussian blue (PB) around the Au nanoparticles as a proof of principle. PAMAM-Au@PB could be easily prepared by electrodeposition, following the ITO-PVS/ PAMAM-Au LbL film preparation procedure. Furthermore, the coverage of Au nanoparticles by PB may be controlled by monitoring the oxidation current

Enzyme immobilisation on electroactive nanostructured membranes (ENM): Optimised architectures for biosensing

Electroactive nanostructured membranes have been produced by the layer-by-layer (LbL) technique, and used to make electrochemical enzyme biosensors for glucose by modification with cobalt hexacyanoferrate redox mediator and immobilisation of glucose oxidase enzyme. Indium tin oxide (ITO) glass electrodes were modified with up to three bilayers of polyamidoamine (PAMAM) dendrimers containing gold nanoparticles and poly(vinylsulfonate) (PVS). The gold nanoparticles were covered with cobalt hexacyanoferrate that functioned as a redox mediator, allowing the modified electrode to be used to detect H2O2, the product of the oxidase enzymatic reaction, at 0.0 V vs. SCE. Enzyme was then immobilised by cross-linking with glutaraldehyde. Several parameters for optimisation of the glucose biosensor were investigated, including the number of deposited bilayers, the enzyme immobilisation protocol and the concentrations of immobilised enzyme and of the protein that was crosslinked with PAMAM. The latter was used to provide glucose oxidase with a friendly environment, in order to preserve its bioactivity. The optimised biosensor, with three bilayers, has high sensitivity and operational stability, with a detection limit of 6.1 [mu]M and an apparent Michaelis-Menten constant of 0.20 mM. It showed good selectivity against interferents and is suitable for glucose measurements in natural samples.http://www.sciencedirect.com/science/article/B6THP-4SDPX4X-3/1/4f9bf4e20f357feac1d3435f51b9823

Multiplex Infrared Spectroscopy Imaging for Monitoring Spatially Resolved Redox Chemistry

IR spectroscopy is an excellent method for understanding surface redox chemistry. However, obtaining sufficient spatial resolution to analyze in situ surface redox reactions is difficult because the aqueous sampling environments provide some challenges for IR spectroscopy. These challenges arise because of the vibrational contribution of water. In this letter, we demonstrate a solution to this problem, where the key development enabling the coupling of spectromicroscopy with electrochemical measurements is a CaF₂/electrolyte/Au sandwich IR-sensitive sample holder that acts as an electrochemical cell. In this system, there is a very thin layer of aqueous electrolyte (∼10 μm), and it is possible to monitor, in real time, the vibrational maps and changes to the Au surface modified with iron­(II, III) hexacyanoferrate­(II, III) by varying the electrochemical potential. By selecting specific vibrational modes with a focal plane array detector, which allows the simultaneous collection of IR spectra from 4096 microscopic regions, chemical maps showing the surface changes were obtained and analyzed using color, providing new insights into how the charge transfer processes affect the chemical composition in specific 2D spatially resolved regions