Electropolymerization measurements

Entrapment of biochemically reactive molecules into conductive polymer substrates is being used to develop electrochemical biosensors (212). This has proven especially useful for the incorporation of enzymes that retain their specific chemical reactivity. Electropolymerization of pyrrole in an aqueous solution containing glucose oxidase (GO) leads to a polypyrrole in which the GO enzyme is co-deposited with the polymer. These polymer-entrapped GO electrodes have been used as glucose sensors. A direct relationship is seen between the electrode response and the glucose concentration in the solution which was analyzed with a typical measurement taking between 20 to 40 s. 

One also obtains analogous findings with trace-crossing effects for the electropolymerization of thiophene and pyrrole. This cannot be explained by a simple linear reaction sequence, as presented in Scheme I, because it indicates competing homogeneous and heterogeneous electron transfer processes. Measurements carried out in a diluted solution of JV-phenylcarbazole provide a more accurate insight into the reaction mechanism (Fig. 2). 

Galvanostatic, potentiostatic as well as potentiodynamic techniques can be used to electropolymerize suitable monomeric species and form the corresponding film on the electrode. Provided that the maximum formation potentials for all three techniques are the same, the resulting porperties of the films will be broadly similar. The potentiodynamic experiment in particular provides useful information on the growth rate of conducting polymers. The increase in current with each cycle of a multisweep CV is a direct measure of the increase in the surface of the redoxactive polymer and, hence, a suitable measure of relative growth rates (Fig. 5). 

Although much less so than pyrrole polymers, indole polymers are beginning to be synthesized and studied as new materials. Electropolymerized films of indole-5-carboxylic acid are well-suited for the fabrication of micro pH sensors and they have been used to measure ascorbate and NADH levels. The three novel pyrroloindoles shown have been electrochemically polymerized, and the polymeric pyrrolocarbazole has similar physical properties to polyaniline. 

A molecularly imprinted polypyrrole film coating a quartz resonator of a QCM transducer was used for determination of sodium dodecyl sulphate (SDS) [147], Preparation of this film involved galvanostatic polymerization of pyrrole, in the presence of SDS, on the platinum-film-sputtered electrode of a quartz resonator. Typically, a 1-mA current was passed for 1 min through the solution, which was 0.1 mM in pyrrole, 1 mM in SDS and 0.1 M in the TRIS buffer (pH = 9.0). A carbon rod and the Pt-film electrode was used as the cathode and anode, respectively. The SDS template was then removed by rinsing the MlP-film coated Pt electrode with water. The chemosensor response was measured in a differential flow mode, at a flow rate of 1.2 mL min-1, with the TRIS buffer (pH = 9.0) as the reference solution. This response was affected by electropolymerization parameters, such as solution pH, electropolymerization time and monomer concentration. Apparently, electropolymerization of pyrrole at pH = 9.0 resulted in an MIP film featuring high sensitivity of 283.78 Hz per log(conc.) and a very wide linear concentration range of 10 pM to 0.1 mM SDS. 

An alkaloid pain reliever, morphine, is an often abused drug. Chronoampero-metric MIP chemosensors have been devised for its determination [204]. In these chemosensors, a poly(3,4-ethylenedioxythiophene) (PEDOT) film was deposited by electropolymerization in ACN onto an ITO electrode in the presence of the morphine template to serve as the sensing element [204], Electrocatalytic current of morphine oxidation has been measured at 0.75 V vs AglAgCllKClsat (pH = 5.0) as the detection signal. A linear dependence of the measured steady-state current on the morphine concentration extended over the range of 0.1-1 mM with LOD for morphine of 0.2 mM. The chemosensor successfully discriminated morphine and its codeine analogue. Furthermore, a microfluidic MIP system combined with the chronoamperometric transduction has been devised for the determination of morphine [182] with appreciable LOD for morphine of 0.01 mM at a flow rate of 92.3 pL min-1 (Table 6). 

Electropolymerization and cyclic voltammetric experiments are performed with an EG G PARC, Model 173 potentiostat equipped with a Model 175 universal programmer and a Model 179 digital coulometer in conjunction with a Kipp and Zonen BD 91 XY/t recorder. All experiments are carried out using a conventional three-electrode cell. Instrumental setup for amperometric measurements ... 

The electropolymerization of 3-methoxythiophene (MOT) was performed in an aqueous micellar medium containing sodium dodecylsulfate (SDS) as a surfactant. The electronic absorption spectra, the fluorescence excitation and emission spectra, and the quantum yields of 546, were measured in different solvents of various polarities and hydrogen bond abilities (89SM(28)C487 98SM(93)175 00JF107 00POLLDG4047 ... 

Apparatus and materials. All electrochemical polymerizations, amperometric measurements and cyclic voltammetry were carried out with an EG G Princeton Applied Research Potentiostat model 273. Pyrrole was purified by vacuum distillation and by passage over neutral alumina prior to electropolymerization. The polyanions (1) used as dopants are shown in Figure 1, and were purified twice by precipitation from methanol in 0.1 M HC1. Detailed information about their synthesis and catalytic... 

Through the combination of SPR with a - poten-tiostat, SPR can be measured in-situ during an electrochemical experiment (electrochemical surface plasmon resonace, ESPR). Respective setups are nowadays commercially available. Voltammetric methods, coupled to SPR, are advantageously utilized for investigations of - conducting polymers, thin film formation under influence of electric fields or potential variation, as well as - electropolymerization, or for development of -> biosensors and - modified electrodes. Further in-situ techniques, successfully used with SPR, include electrochemical - impedance measurements and -+ electrochemical quartz crystal microbalance. 

Bithiophenes were coupled to calix[4]arene scaffolds and electropolymerized to produce alternating quarterthiophene-calix[4]arene structures 192 <03JA1142>. In situ conductivity measurements with and without TEA indicate that the polymers require protonation to be highly conductive. 

Their biosensor consisted in a Pt wire on which GOD was immobilized by the electropolymerization of m-phenylenediamine. The advantage of this type of immobilization consists in creating an effective barrier against electrochemical interference due to the polymer formed onto the electrode. Moreover, an extended linearity for the glucose sensor was also obtained, and this was a requisite for the direct measurement of the subcutaneous glucose at diabetic levels, since in practice an extremely low dilution of the subcutaneous fluid was realized. 

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