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      Recent Advances in Polymeric Materials Used as Electron Mediators and Immobilizing Matrices in Developing Enzyme Electrodes

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          Abstract

          Different classes of polymeric materials such as nanomaterials, sol-gel materials, conducting polymers, functional polymers and biomaterials have been used in the design of sensors and biosensors. Various methods have been used, for example from direct adsorption, covalent bonding, crossing-linking with glutaraldehyde on composites to mixing the enzymes or use of functionalized beads for the design of sensors and biosensors using these polymeric materials in recent years. It is widely acknowledged that analytical sensing at electrodes modified with polymeric materials results in low detection limits, high sensitivities, lower applied potential, good stability, efficient electron transfer and easier immobilization of enzymes on electrodes such that sensing and biosensing of environmental pollutants is made easier. However, there are a number of challenges to be addressed in order to fulfill the applications of polymeric based polymers such as cost and shortening the long laboratory synthetic pathways involved in sensor preparation. Furthermore, the toxicological effects on flora and fauna of some of these polymeric materials have not been well studied. Given these disadvantages, efforts are now geared towards introducing low cost biomaterials that can serve as alternatives for the development of novel electrochemical sensors and biosensors. This review highlights recent contributions in the development of the electrochemical sensors and biosensors based on different polymeric material. The synergistic action of some of these polymeric materials and nanocomposites imposed when combined on electrode during sensing is discussed.

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          Biosorbents for heavy metals removal and their future.

          A vast array of biological materials, especially bacteria, algae, yeasts and fungi have received increasing attention for heavy metal removal and recovery due to their good performance, low cost and large available quantities. The biosorbent, unlike mono functional ion exchange resins, contains variety of functional sites including carboxyl, imidazole, sulphydryl, amino, phosphate, sulfate, thioether, phenol, carbonyl, amide and hydroxyl moieties. Biosorbents are cheaper, more effective alternatives for the removal of metallic elements, especially heavy metals from aqueous solution. In this paper, based on the literatures and our research results, the biosorbents widely used for heavy metal removal were reviewed, mainly focusing on their cellular structure, biosorption performance, their pretreatment, modification, regeneration/reuse, modeling of biosorption (isotherm and kinetic models), the development of novel biosorbents, their evaluation, potential application and future. The pretreatment and modification of biosorbents aiming to improve their sorption capacity was introduced and evaluated. Molecular biotechnology is a potent tool to elucidate the mechanisms at molecular level, and to construct engineered organisms with higher biosorption capacity and selectivity for the objective metal ions. The potential application of biosorption and biosorbents was discussed. Although the biosorption application is facing the great challenge, there are two trends for the development of the biosorption process for metal removal. One trend is to use hybrid technology for pollutants removal, especially using living cells. Another trend is to develop the commercial biosorbents using immobilization technology, and to improve the biosorption process including regeneration/reuse, making the biosorbents just like a kind of ion exchange resin, as well as to exploit the market with great endeavor.
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            Glucose oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing.

            Direct electrochemistry of a glucose oxidase (GOD)-graphene-chitosan nanocomposite was studied. The immobilized enzyme retains its bioactivity, exhibits a surface confined, reversible two-proton and two-electron transfer reaction, and has good stability, activity and a fast heterogeneous electron transfer rate with the rate constant (k(s)) of 2.83 s(-1). A much higher enzyme loading (1.12 x 10(-9)mol/cm(2)) is obtained as compared to the bare glass carbon surface. This GOD-graphene-chitosan nanocomposite film can be used for sensitive detection of glucose. The biosensor exhibits a wider linearity range from 0.08mM to 12mM glucose with a detection limit of 0.02mM and much higher sensitivity (37.93microAmM(-1)cm(-2)) as compared with other nanostructured supports. The excellent performance of the biosensor is attributed to large surface-to-volume ratio and high conductivity of graphene, and good biocompatibility of chitosan, which enhances the enzyme absorption and promotes direct electron transfer between redox enzymes and the surface of electrodes.
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              Electrochemical biosensors: recommended definitions and classification.

              Two Divisions of the International Union of Pure and Applied Chemistry (IUPAC), namely Physical Chemistry (Commission 1.7 on Biophysical Chemistry formerly Steering Committee on Biophysical Chemistry) and Analytical Chemistry (Commission V.5 on Electroanalytical Chemistry) have prepared recommendations on the definition, classification and nomenclature related to electrochemical biosensors: these recommendations could, in the future, be extended to other types of biosensors. An electrochemical biosensor is a self-contained integrated device, which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element (biochemical receptor) which is retained in direct spatial contact with an electrochemical transduction element. Because of their ability to be repeatedly calibrated, we recommend that a biosensor should be clearly distinguished from a bioanalytical system, which requires additional processing steps, such as reagent addition. A device that is both disposable after one measurement, i.e. single use, and unable to monitor the analyte concentration continuously or after rapid and reproducible regeneration, should be designated a single use biosensor. Biosensors may be classified according to the biological specificity-conferring mechanism or, alternatively, to the mode of physico-chemical signal transduction. The biological recognition element may be based on a chemical reaction catalysed by, or on an equilibrium reaction with macromolecules that have been isolated, engineered or present in their original biological environment. In the latter cases. equilibrium is generally reached and there is no further, if any, net consumption of analyte(s) by the immobilized biocomplexing agent incorporated into the sensor. Biosensors may be further classified according to the analytes or reactions that they monitor: direct monitoring of analyte concentration or of reactions producing or consuming such analytes; alternatively, an indirect monitoring of inhibitor or activator of the biological recognition element (biochemical receptor) may be achieved. A rapid proliferation of biosensors and their diversity has led to a lack of rigour in defining their performance criteria. Although each biosensor can only truly be evaluated for a particular application, it is still useful to examine how standard protocols for performance criteria may be defined in accordance with standard IUPAC protocols or definitions. These criteria are recommended for authors. referees and educators and include calibration characteristics (sensitivity, operational and linear concentration range, detection and quantitative determination limits), selectivity, steady-state and transient response times, sample throughput, reproducibility, stability and lifetime.
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                Author and article information

                Journal
                Sensors (Basel)
                Sensors (Basel, Switzerland)
                Molecular Diversity Preservation International (MDPI)
                1424-8220
                2012
                16 January 2012
                : 12
                : 1
                : 923-953
                Affiliations
                [1 ] Department of Environmental, Water, and Earth Sciences, Tshwane University of Technology, Private Bag X680, Arcadia, Pretoria 0001, South Africa; E-Mail: OkonkwoOJ@ 123456tut.ac.za
                [2 ] Department of Chemistry, University of Limpopo, P.O. Box 235, Medunsa 0204, South Africa; E-Mail: agyei@ 123456ul.ac.za
                Author notes
                [* ]Author to whom correspondence should be addressed; E-Mail: moyom@ 123456msu.ac.zw ; Tel.: +27-83-984-7553.
                Article
                sensors-12-00923
                10.3390/s120100923
                3279247
                22368503
                8d92a18f-d3f8-448b-9c63-1b7c90fe14cd
                © 2012 by the authors; licensee MDPI, Basel, Switzerland

                This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/3.0/).

                History
                : 14 December 2011
                : 15 January 2012
                : 16 January 2012
                Categories
                Review

                Biomedical engineering
                electrochemical sensor,polymeric material,biosensor,enzyme electrode,mediator

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