New Carbosilane Polymers with Interacting Ferrocenes as Support and Bioelectrocatalysts of Oxidases to Develop Versatile and Specific Amperometric Biodevices

Abstract

In this work, the bioelectrocatalytical properties and kinetic characteristics of new oxidase amperometric biosensors based on two different ferrocene functionalized carbosilane polymers, polydiallylmethylsilane (PDAMS) and polymethyldiundecenylsilane (PMDUS) are described. In the development of these biodevices, glucose oxidase has been used as example of oxidase enzyme, and two different immobilization procedures have been studied. The polymer-modified electrodes act as efficient transducers for glucose sensing in anodic and cathodic aerobic conditions and also in anodic anaerobic conditions, and this fact turns them into useful devices for a wide field of applications. PMDUS has shown to be the bioelectrocatalyst with best kinetic and analytical properties in aerobic media while PDAMS was better in anaerobic conditions. The best aerobic biosensor developed displayed a strictly linear range from 0 to 3.0 mM, a detection limit of 7.8 μM and a response time less than 2 s in an ascorbate interference free work potential interval. The apparent Michaelis-Menten constant was calculated to be 1.36 mM according to the Lineweaver-Burk equation.

Polyferrocenyl Polycyclosiloxane/Gold Nanoparticles: An Efficient Electrocatalytic Platform for Immobilization and Direct Electrochemistry of HRP

“…The average linear intervals were 0-200 μM and 0.2-6.8 mM, with linear fit equations I (μA) = −(0.048 ± 0.004) C (μM) -(0.11 ± 0.06) with average correlation coefficient R 2 = 0.9980; and I (μA) = −(18.62 ± 0.26) C (mM) -(8.40 ± 0.80) with the same average correlation coefficient R 2 = 0.9980 respectively. This behavior has been observed by us earlier 27 with a dehydrogenase biosensor and also by other authors, 33,47 and it is increasingly common as more sensitive devices are developed. In the first dynamic range, the sensitivity was determined to be 685.71 μA mM −1 cm −2 and the detection limit was 69 nM (S/N = 3), thus improving the more recent biosensors based on direct electrochemistry of HRP.…”

“…On the other hand, ferrocene and its derivatives have been widely used as mediators in oxidase-peroxidase-modified electrodes 4,[25][26][27] and ferrocenyl dendrimers and polymers have demonstrated their capacities for the enhancement of electronic transfer in several electrochemical devices. [28][29][30] These conducting polymers and dendrimers are easily electrodeposited on electrode surfaces allowing the control of the thickness of films and the quantity of electroactive sites.…”

Molecular Recognition and Sensing Based on Ferrocene Derivatives and Ferrocene-Based Polymers

“…Dendrons and dendrimers with ferrocenyl terminal groups (Fc-dendrons and Fc-dendrimers) are useful materials for biosensors. 111,112 When they were deposited onto electrodes, they showed good mechanical stability and provided large areas for enzyme immobilization. Ferrocenyl silicon based dendrimers showed better operational stabilities than monomeric mediators and higher sensitivity than polymeric mediators in amperometric biosensors for glucose.…”

“…Dendrons and dendrimers with ferrocenyl terminal groups (Fc-dendrons and Fc-dendrimers) are useful materials for biosensors. , When they were deposited onto electrodes, they showed good mechanical stability and provided large areas for enzyme immobilization.…”

Thiolated DAB Dendrimers-Gold Nanoparticles as Self-Assembled Layers for the Direct Electrochemistry of HRP

“…Because of their molecular uniformity, multifunctional surface and internal holes, dendrimers have potential applications in a variety of biomedical, chemical or industrial fields. [29][30][31][32][33][34] Some interesting applications of dendrimers are the preparation of catalytic surfaces with electroactive ferrocenyl dendrimers [35][36][37] or with metallic nanoparticles obtained from dendrimers as templates. 8,[38][39][40][41][42] z E-mail: pilar.garcia.armada@upm.es Thiol functionalized dendrimers have been successfully used as anchor structures for nanomaterials as quantum dots with different nanotechnology applications.…”