Simultaneous detection of guanine, adenine, thymine, and cytosine at polyaniline/MnO2 modified electrode
Graphical abstract
Introduction
Deoxyribonucleic acid (DNA) is an important biological macromolecule that plays crucial roles in the storage of genetic information and protein biosynthesis [1], [2]. This genetic material is present in the cells of all living organisms. DNA is a block copolymer with four types of deoxyribonucleotide monomers differentiated by their bases [1], [2]. Purine bases (guanine (G), and adenine (A)) and pyrimidine bases (thymine (T) and cytosine (C)) are found in DNA molecular structure and they are involved in cellular energy transduction and signaling mediated by enzymatic oxidation reactions [3]. Mutation occurs due to change in the sequence of DNA. One basic mutation in mitochondrial DNA can cause heart and muscle disease [4]. Therefore, abnormal changes of DNA bases in organism lead to the deficiency of the immunity system and may indicate the presence of various diseases, including cancer, Alzheimer's, epilepsy, and HIV infection [4], [5]. The detection of DNA bases is of great significance for clinical diagnosis as well as insight into fundamental mechanism of genetic information [6], [7]. Detecting DNA mutations is important and then to find appropriate ways to prevent or treat disease. Several analytical methods have been developed to detect DNA bases [8], [9] such as, microchip capillary electrophoresis [10], [11], flow injection chemiluminescence [12], [13], ion pairing liquid chromatography [14], laser-induced fluorescence detection [15], and micellar electrokinetic chromatography [16]. Although these methods exhibit some merits, expensive instruments, complicated operations, or time-consuming sample pretreatments are usually involved [17]. Electrochemical techniques are promising for the analysis of DNA bases due to their advantages of rapidity, convenience, low-cost and ease of miniaturization for small-volume sample [18]. Among these techniques, DNA biosensor has emerged as a promising alternative for microbial detection due to the specificity of hybridization between the probe and the complementary target sequence [18], [19]. However, the non-specific adsorption in the hybridization system increases the strong demand for the development of a sensitive and specific DNA biosensor.
The electrocatalytic oxidation of purine bases has been investigated [20]. However, the electrochemical detection of pyrimidine bases is rarely reported. It is difficult to obtain accurate oxidation signals of pyrimidine bases because of their high positive oxidation potentials and slow electron transfer kinetics [21]. In order to overcome these limitations, electrode materials with a wide potential window and high electrocatalytic activities are required.
Inorganic materials, such as metals, semiconductors, and metal oxides have been the subject of intensive research because of their potential applications in electronics, photonics, and catalysis [22]. Manganese dioxide is one of the most attractive inorganic materials because of its wide range of applications in catalysts, molecular-sieves, and electromagnetic materials [23], [24], [25]. MnO2 has become the most widely used electrode material available since Leclanché first discovered its use as an additive in batteries [26]. Birnessite structure (δ-MnO2) has attracted recent interest from the point of view of its structural, morphological modification, delamination [27], and inherent lithium insertion/deinsertion properties with respect to its application as a lithium battery electrode [28], [29]. Conducting polymer containing metal oxides based nanocomposites have attracted a great deal of interest because of the unexpected properties, synergistically derived from both components [30], [31], [32]. In this area, polyaniline (PANI) is considered as the most promising conducting polymers that has many advantages such as high doping/de-doping rate during charge/discharge process, easy polymerization and high environmental stability [33], [34]. Polyaniline (PANI) is an intrinsically conductive polymer (ICP), which can conduct electric currents without the addition of any conductive (inorganic) substances [35]. However, the electroactivity (i.e., redox behavior) of polyaniline is strongly dependent on the pH value of electrolyte solution, and is greatly weakened at pH > 4. Low electrocatalytic activity at physiological pH (neutral pH environment) condition greatly limits the applications of PANI in bioelectrochemistry [36]. It is reported that doping PANI with metals/metal oxides yields a redox active polymer, which exhibits good electrocatalytic activity in neutral or basic aqueous solution [37]. Furthermore, MnO2 based nanocomposites are known to be used in neutral aqueous electrolytes that can meet the requirements of “green electrolyte” [27], [28], [29]. The oxidation activity of δ-MnO2 is mainly associated to the presence of Mn4+. Nanocomposites based on conducting polymer and MnO2 have been intensively investigated during recent years due to their potential applications as electrode material [38], [39], [40], [41].
Our research is focused on the developments of nanoporous materials such as polyanilines, metal oxides, mesoporous zeolites and find their catalytic and electrocatalytic applications [42], [43], [44], [45], [46], [47], [48], [49], [50], [51], [52]. In this study, we report the synthesis and application of PANI/MnO2 nanofibers. MnO2 was coated onto PANI nanofibers by a direct coating method via the reduction of KMnO4. PANI/MnO2 modified electrode is used in the simultaneous detection of guanine, adenine, thymine, and cytosine. In the present study based on PANI/MnO2 nanocomposite, MnO2 along with polyaniline synergistically contributes in increasing the electrochemical performance even at physiological pH condition.
Section snippets
Materials
All chemicals used in this study were of A.R. grade. Aniline, ammonium peroxydisulphate (APS), and potassium permanganate (KMnO4) were obtained from Spectrochem India Pvt. Ltd. Guanine, adenine, thymine, cytosine, valine, and Nafion (5%, v/v) were purchased from Aldrich. Aniline was vacuum distilled and stored in the dark prior to its use. Deionized water from Millipore Milli-Q system (Resistivity 18.2 MΩ cm) was used in the electrochemical studies. Deoxyribonucleic acid sodium salt from the calf
Characterization
XRD investigation confirms that MnO2 obtained under our synthesis condition belong to monoclinic potassium birnessite (δ-MnO2) (JCPDS no. 80-1098) (Fig. 1a). Two broad diffractions at 2θ of 20.5° and 25.3° were obtained in the XRD pattern of PANI, which represent the periodicities parallel (1 0 0) and perpendicular (1 1 0) to the PANI chain, respectively (Fig. 1b) [54], [55]. XRD pattern of the PANI/MnO2 shows diffraction corresponding to the monoclinic K-birnessite MnO2 (JCPDS no. 80-1098) (Fig. 1
Conclusion
Combining the advantageous features of MnO2 and PANI, organic–inorganic hybrid PANI/MnO2 was prepared. PANI/MnO2 modified electrode shows promising activity in the electrochemical oxidation of guanine, adenine, thymine, and cytosine with high sensitivity, selectivity, and antifouling properties. Influence of various electrochemical reaction parameters such as scan rate and pH were evaluated to find the optimum condition for the analysis. PANI/MnO2 modified electrode (prepared with 0.06 M KMnO4
Acknowledgments
We are pleased to acknowledge Council of Scientific and Industrial Research (CSIR), New Delhi, for financial support under CSIR (01(2423)/10/EMR-II). AP is grateful to CSIR, New Delhi for SRF fellowship. We acknowledge Director, IIT Ropar for constant encouragements.
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