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A facile synthesis of GO/CuO-blended nanofiber sensor electrode for efficient enzyme-free amperometric determination of glucose

A facile synthesis of GO/CuO-blended nanofiber sensor electrode for efficient enzyme-free... The development of biosensors with innovative nanomaterials is crucial to enhance the sensing performance of as- prepared biosensors. In the present research work, we prepared copper (II) oxide (CuO) and graphene oxide (GO) composite nanofibers using the hydrothermal synthesis route. The structural and morphological properties of as- prepared GO/CuO nanofibers were analyzed using an X-ray diffractometer, field-emission scanning, energy dispersive X-ray analysis, Fourier transmission infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The results indicated GO/CuO nanofibers exhibit nanosized diameters and lengths in the order of micrometers. These GO/CuO nanofibers were employed to prepare non-enzymatic biosensors (GO/CuO nanofibers/ FTO (fluorine-doped tin oxide)) modified electrodes for enhanced glucose detection. The sensing performance of the biosensors was evaluated using linear sweep voltammetry (LSV) and chronoamperometry in phosphate buffer −1 −2 solution (PBS). GO/CuO/FTO biosensor achieved high sensitivity of 1274.8 μAmM cm having a linear detection range from 0.1 to 10 mM with the lower detection limit (0.13 μM). Further, the prepared biosensor showed good reproducibility repeatability, excellent selectivity, and long-time stability. Moreover, the technique used for the preparation of the GO/CuO composite is simple, rapid, cost-effective, and eco-friendly. These electrodes are employed for the detection of glucose in blood serum with RSD ~ 1.58%. Keywords: Graphene oxide, Enzyme free, Glucose, Biosensor Introduction glucose levels of diabetic patients (Makaram et al., 2014; Diabetes is a widespread disease affecting millions of Bruen et al., 2017; Gopalan et al. 2017; Gopalan et al. populations and predicted to be the major cause of 2016; Sai-Anand et al. 2014). Enzymatic electrochemical death as it can damage neural systems in humans. It is sensors suggest good selectivity and sensitivity but due essential for diabetic patients to frequently monitor and to complex mobility, lack of stability and reproducibility maintain glucose levels. Hence, an effective diagnosis of limit their performance (Gopalan et al. 2013, Haldorai diabetes and a reliable glucose monitoring system are et al. 2016). These limitations are overcome by the de- necessary. Extensive majors have been taken to control velopment of enzyme-free glucose sensor devices diabetes through several monitoring systems. Glucose through direct oxidization of glucose in the form oxi- biosensors have a great contribution in monitoring dized layer (Sai-Anand et al. 2019). Glucose oxidase is usually practiced as an enzyme in most of the glucose biosensors. Amperometry is another widely used tech- * Correspondence: adgarje@gmail.com 3 nique for glucose detection (Peter and Heineman, 1996, Department of Physics, Sir Parashurambhau College, Savitribai Phule Pune University, Pune, Maharashtra 411030, India Thévenot et al., 2001). Glucose oxidase performs a major Full list of author information is available at the end of the article © The Author(s). 2021 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 2 of 10 role in the oxidation of β-D-glucose to D-glucono-δ-lac- doped tin oxide (FTO) substrates, D (+) glucose, dopa- tone. Hydrogen peroxide (H O ) is formed as a bypro- mine, L-ascorbic acid, D (−) fructose, lactose were pur- 2 2 duct in a catalytic reaction and oxygen as an electron chased from Qualigens Fine Chemicals, India. Deionized acceptor. A simple technique, less analysis time, cost ef- (DI) water was purchased from Sharad Agencies, India. fective, and low detection capability are some advantages The phosphate buffer solution (PBS) was prepared in the of using amperometry (Thunkhamrak et al., 2020). Re- laboratory using the standard method. All the chemicals gardless of excellent sensitivity and low detection limit are of analytical research (AR) grade and used without in few nanocomposites, an enzymatic glucose sensor further purification. limits the application of sensors due to high production cost (G. Gnana kumar et al., 2017). Nowadays, graphene Synthesis of graphene oxide has attracted researchers due to the larger specific super- Graphene oxide was synthesized using an earlier re- ficial area, purity, high conductivity, and low cost (Liu ported method (Marcano et al., 2010). Graphite powder et al., 2019). It has diversified applications in various and NaNO in 2:1 proportion were mixed with concen- areas such as batteries (Ji et al., 2016), biomedical (Mal- trated H SO and H PO in the ratio of 9:1 (wt %). Fif- 2 4 3 4 lick et al., 2018), supercapacitors (Hota et al. 2020), teen grams of KMnO was slowly added while stirring printable graphene electronics (Hu Etal. 2016) gas sen- followed by the addition of the required amount of sors (Nakate et al. 2020), and biosensors (Bai et al. H O . If the mixture turns into bright yellow color, this 2 2 2020). In chemical synthesis, graphene oxide (GO) is re- represents a great oxidation level of GO. In order to 2− duced to eliminate oxygen-containing functionalities eradicate SO ions, the solution was repeatedly washed using hazardous chemicals like hydrazine as a reducing and the brownish black precipitate was collected. agent. The process of chemical reduction contains cru- cial and lengthy steps of chemical reactions, tiresome Synthesis of GO/CuO nanocomposites washing cycles, and drying of residue. Moreover, the use Initially, 0.5 g GO and 0.2 g CuO were dissolved in DI of poisonous and explosive reducing agents in the redox and the solution was constantly stirred for half an hour process makes it non-eco-friendly. Hence, functionalized by raising its temperature to 100 °C. Fifty milliliters of GO using eco-friendly reduction methods is necessary in NaOH solution was slowly added to it. The temperature biosensing applications. Copper oxide (CuO) can be of the solution was retained for 10 min and allowed to used to functionalize GO as a catalyst because of its cool. The GO/CuO composite was collected after electrochemical catalytic property (Khan et al. 2021). In evaporation. an electrolysis process, Cu (II) oxidizes Cu (III) by gain- ing electrons in the redox reaction. During the oxidiza- Preparation of GO/CuO nanocomposite electrode tion process, glucose gets converted into gluconolactone Ten milligrams of the GO/CuO nanocomposite was dis- (Zhang et al. 2020; Wang et al. 2014). Hence, an efficient persed in 5 ml of DI water and 5 μl of PVA using bath electron transfer in glucose oxidation can be predicted sonication for half an hour. Then, 10 μl of the suspen- through excellent support of GO to CuO. In the present sion was drop casted on the previously cleaned FTO work, an enzyme-less amperometric glucose biosensor substrate. The working area of the electrode was 1 cm . using graphene oxide (GO) and copper oxide (CuO) The electrode was annealed at 250 °C. nanocomposites was successfully prepared using a fluorine-doped tin oxide (FTO) substrate. The prepared Mechanism of GO/CuO/FTO glucose sensing sensor electrode exhibits exclusive properties such as A new decorum for the synthesis of the GO/CuO nano- large superficial area, good catalytic activity, and excel- composite by in situ hydrothermal reduction of GO and lent electrical conductivity. Moreover, the electrode pro- CuO nanobelt formation is developed as shown in Fig. 1. vides improved sensitivity, low detection limit, and With the existence of NaOH, DI water assists in the excellent recovery in human serum compared to previ- growth of Cu (OH) nanograin morphology on the GO ously reported literature. Furthermore, the preparation surface. The epitaxial growth process caused the forma- and detection procedures are simple, fast, less time con- tion of CuO nanobelts. The augmented temperature of suming, and cost effective. the above reaction mixture leads to the formation of a fiber-like GO/CuO nanostructure. A glucose sensing Methodology performance of the GO/CuO/FTO-modified electrode Natural graphite powder (S.Aldrich, 99.99%), potassium was studied in the presence of phosphate buffer solution permanganate (KMnO , 99%), hydrogen peroxide (H O , (PBS:7.4 pH). 4 2 2 30%), sulfuric acid (H SO , 99.99%), hydrochloric acid Normally, when glucose disperses in PBS, it creates D- 2 4 (HCl, 30%), phosphoric acid (H PO ,85%), copper oxide gluconolactone and hydrogen peroxide (H O ). It further 3 4 2 2 (CuO, 99.9%), polyvinyl alcohol (PVA,99%), fluorine- generates D-gluconate with H ions due to Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 3 of 10 Fig. 1 Glucose sensing mechanism of GO/CuO/FTO electrode electrooxidation of glucose at grain boundaries of CuO. and Ag/AgCl as reference electrode. The electrocatalytic Hence, gluconolactone is the key product accountable performance of the electrode was studied using linear for oxidation that hydrolyzes gluconic acid. H ions sweep voltammetry (LSV) and chronoamperometry. lessen the pre-absorbed oxygen by discharging electrons which decrease the barrier potential between successive Results and discussion grains and lifts the electrical conductivity (Wu et al., XRD analysis 2010). XRD pattern of GO and GO/CuO nanocomposite is pre- sented in Fig. 2. CuO þ H O→CuðÞ OH þ e 2 The reflection peak which occurred at (002) at 11.92° 3þ − 2þ Cu þ glucose þ e →gluconolactone þ Cu shows the occurrence of oxygen functionalities on the hydrolysis GO surface with an interlayer basal space of 0.79 nm gluconolactone → gluconic acid (Tong et al. 2011). The peak (100) at 42.56° suggested the static disorder of GO. In the case of the GO/CuO Structural and optical characterization nanocomposite, the reflection peak (002) at 24.04° For structural characterization, an XRD analysis for the showed a shift with basal spacing of 0.37 nm. The fall in synthesized GO and GO/CuO powder was done with basal space suggested that GO was converted to rGO Bruker D8-Advanced Diffractometer using Cu Kα radi- (Dhara et al. 2015). All peaks of CuO are in good ation (λ = 0.154 nm) from the range of 5 to 85° with a scanning rate of 2°/min. Surface morphology and elem- ental composition of GO and GO/CuO samples were characterized FESEM: FEI Nova NanoSEM 450, Raman analysis was done using a micro-Raman spectrometer (Jobin-Yuon HR 800 UV) using a He–Ne (633 nm) laser excitation source. XPS analysis of GO and CuO was car- ried out by Multifunctional XPS (PHI ulvac probe III Scanning Microprobe). For the FTIR study, FTIR-6100 spectrometer (JASCO) in the transmission (T) mode in −1 the wavenumber range 4000–400 cm was taken. Electrochemical measurement Wonatech potentiostat was used for voltametric and am- perometric measurements for glucose detection with a three-electrode system which comprises GO/CuO/FTO Fig. 2 XRD pattern of a GO and b GO/CuO as a working electrode along with platinum as counter Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 4 of 10 agreement with the JCPDS file: 48-1548, which confirms nanofibers of sizes in the range of 70–200 nm and sev- a high degree of purity and crystallinity of CuO. eral nanometers in length were distributed on the gra- phene layer. The formation of GO/CuO can be FESEM and EDS analysis explained as follows. The surface morphology of prepared GO and GO/CuO Due to the increase in temperature during the synthe- nanocomposites was characterized by FESEM as shown sis, quick evaporation of water molecules caused a con- in Fig. 3. traction of CuO nanoparticles and GO sheets. GO was Graphene oxide showed a thin wrinkled paper-like thermally reduced to modified graphene. The graphene structure. In the GO/CuO nanocomposite, high-density 2D material has a strong hydrophobic center and Fig. 3 FESEM of GO and GO/CuO Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 5 of 10 Fig. 4 EDS of GO and GO/CuO hydrophilic surrounding (Georgakilas et al. 2016). It was chemical composition of GO/CuO where GO was par- noted that the active GO surface lowers the internal tially reduced in presence of cuprous ions. energy. Furthermore, CuO has a monoclinic nature and excel- Raman spectroscopy lent thermal conductivity. Therefore, CuO nanoparticles Raman analysis of the GO-CuO nanocomposite is pre- together with GO formed a fiber-like structure. The dis- sented in Fig. 6. tribution of chemical elements present in the composite The fundamental vibrations of GO and GO/CuO were −1 was examined using the energy dispersive spectrum observed in the sequence of 1200 to 1700 cm . The D (EDS) as shown in Fig. 4. (disorder bands) and G (tangential bands) were formed at breathing mode A symmetry and first-order scatter- ing of E photons by Sp carbon (C-C bond) respect- FTIR analysis ively (AC Ferrari et al. 2006). A broad 2D band of GO −1 FTIR spectra for GO and GO/CuO nanocomposite is as with a higher wavenumber was located at 2918 cm shown in Fig. 5. confirming the multilayered nature of GO. The 2D band The bending and stretching modes of O-H groups of GO/CuO predicted the reduction of GO to rGO were represented as broad spectra present around 3203 caused GO/CuO to stack. The ID/IG ratio of GO/CuO −1 −1 cm and the peak at 1734cm Showed C=O stretching was slightly decreased specifiying that there were some vibrations on the surface of GO. The C-O stretching vi- structural changes that occurred during thermal −1 brations were assigned to the peak at 1054 cm (Xu reduction. Zhu et al. 2012). This surface functional group exhibited the probable bonding of CuO on the GO surface. The XPS analysis −1 peaks at low frequencies below 1000 cm in GO/CuO XPS spectrum of GO and GO/CuO nanocomposite is spectra could be ascribed to Cu-O-Cu and Cu-O-C vi- presented in Fig. 7. The peaks centered at C, O, and brations (Q Chen et al. 2012). This demonstrated the Fig. 5 FTIR of a GO and b GO/CuO Fig. 6 Raman Spectrum of a GO and b GO/CuO nanocomposite Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 6 of 10 CuO are core-level regions associated with C1s, O1s, During the oxidation process, CuO was oxidized to and Cu2p peaks respectively. CuOOH and glucose to gluconolactone by Cu (III) (Wei H et al. 2009). Deconvoluted spectrum of GO/CuO Further, the electrochemical effect on GO/CuO/FTO A deconvoluted spectrum of GO/CuO is shown in Fig. with a variable scan rate was examined using LSV as 8. shown in Fig. 10. The electrode was scanned from 10 to Carbon in the nanocomposite was identified by the 300 mv/s (a to h) in PBS electrolyte in the presence of 5 high-resolution spectrum of C1s. The major peak at mM D (+) glucose. The oxidation occurred at + 0.6 V 283.5 eV exhibited sp (C-C, C=C) bonding and the for each scan and the oxidation peak current was in- shoulder peaks revealed C=O and O-C=O bonding. The creased with an increase in scan rate. This revealed that chemical bonding states of C-OH and C-O-C were lo- electrochemical reaction takes place on GO/CuO nano- cated at characteristic peaks 286.8 eV. The presence of composite demonstrating its ability towards enzyme CuO and Cu O was confirmed using high-resolution sensing (Wang et al. 2012). Hence, further electrochem- O1s spectra. The characteristic peaks observed at 530.2 ical and amperometric measurements were carried out eV belong to Cu-O, -C=O bonding in GO/CuO. The at the optimized potential of + 0.6 V vs. Ag/AgCl. peak shown at 532.9 eV was assigned to oxygen present in GO. The XPS spectrum of Cu 2p showed a peak at Amperometric measurements 932.5 eV for Cu 2p and confirmed the presence of The amperometric response of the GO/CuO/FTO elec- 3/2 CuO as a catalyst. A binding energy peak at 952.2 eV trode was measured and presented in Fig. 11a. The pro- was allocated to Cu 2p (Wu J et al. 2018). posed electrode revealed that the electron transport 1/2 between PBS solution and electrode in the redox process Electrochemical measurements is enhanced due to the high electrical conductivity and Linear sweep voltammogram to study the electrocata- electrocatalytic activity of the GO/CuO nanocomposite lytic activity of the modified electrodes is represented in (Hsu et al. 2012). The calibration curve in Fig.11b dis- Fig. 9. played two linear ranges corresponding to low glucose The electrodes were scanned at 100 mv/s in presence concentration (0.1–1 mM) and high concentration (1– of 5 mM D (+) glucose. There was no signal response 10 mM). detected for bare FTO (curve a). GO/FTO (curve b) and The corresponding linear regression equations were I CuO/FTO (curve c) showed a small increase in back- = 424.95c + 569.22 with R = 0.9984 (N =9)and I = ground current due to the large superficial area of GO 27.666c + 826 with R = 0.9963 (N = 9) respectively. For and electrocatalytic capability for glucose oxidation of low glucose concentration the sensitivity was 1274.8 μA −1 −2 CuO respectively. A well-defined glucose oxidation peak mM cm (S/N = 3) whereas for high concentration −1 −2 was observed for GO/CuO/FTO (curve d) in the pres- was 830 μAmM cm along with a low detection limit ence of 5 mM glucose at + 0.6 V. This indicates that the of 0.13 μM. A comparative study of performance of vari- GO/CuO/FTO composite electrode is necessary to ob- ous glucose biosensors is displayed in Table 1. tain high sensitivity and better electrocatalytic activity. Selectivity, stability, and reproducibility The selectivity and stability of the GO/CuO/FTO sensor electrode are presented in Fig. 12. The biological range of glucose concentration in hu- man serum is 3–8 mM, which is quite greater compared to other interfering substances like ascorbic acid, dopa- mine, etc. Hence, the electrode amperometric responses were examined with 1 mM D (+) glucose with the abovementioned interfering species (0.1 mM) in PBS (7.4) solution. It was observed that the glucose sensing ability of the proposed sensor was unaffected by the interfering substances. The reproducibility of the sensor was studied using 10 similar sensors. The current re- sponse was observed for 1 mM glucose concentration for each sensor. RSD of 2.7% confirms the significant re- producibility. The aging effect (stability) of the samples was also tested periodically for 30 days with of 1 mM Fig. 7 XPS spectrum of a GO b GO/CuO glucose concentration and an RSD of 2.64% was Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 7 of 10 Fig. 8 Deconvoluted spectrum of GO/CuO a C1s, b O1s, and c Cu2p achieved. This demonstrates that the GO/CuO/FTO folds) using the standard dilution method before ana- electrode has good repeatability, reproducibility, and sta- lysis. The results obtained using the GO/CuO/FTO sen- bility as a glucose biosensor. sor were compared with the certified values received from the pathology laboratory (Table 2). The average re- Determination of glucose concentration in human serum covery rate was 99.17% along with an RSD of 1.58% The blood glucose level in human serum samples was which assured the reliability and applicability of the GO/ determined using the proposed glucose biosensor. The CuO/FTO sensor to determine the glucose concentra- human serum samples were received from a standard tion in a real sample. pathology laboratory. The samples were diluted (100 Fig. 9 LSV of a FTO, b GO/FTO, c CuO/FTO, and d GO/CuO/FTO at 100 mv/s scan rate Fig. 10 LSV of GO/CuO/FTO electrode with variable scan rate Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 8 of 10 Fig. 11 a Chronoamperometric response of GO/CuO/FTO. b Calibration curve Table 1 Comparison of the enzyme-free GO-based glucose sensor with its composites −1 −2 Electrode Method of detection Potential (V) Sensitivity (μAmM cm ) Linear range (mM) LOD (μM) Ref. GO/CuO/FTO Amp 0.6 830, 1274.8 0.1–1 0.13 Present work 1–10 PDDA/Ch/GOx/PtAuNPs/ Amp 0.5 110, 62.3 0.5–2 0.2 Sridara et al. (2020) 2–5 Cu/Cu O/CSs on GCE Amp 0.65 63.8, 22.6 0.01–0.69 0.005 Yin et al. (2016) 1.19–3.69 Au/GO on GCE Amp 0 5.20, 4.56 0.1–2 0.025 Shu et al. (2015) 2–16 GR–CuO NPs Amp 0.6 1065 1 μM–8 mM 1 Hsu et al. (2012) GOx/CdS/Gr/GCE CV – 1.76 2–16 0.7 Wang et al., 2011) GO–CuONPs Amp 0.7 162.52 2.79μM–2.03 mM 0.69 Song et al., 2013) The prepared GO/CuO/FTO enzyme-free glucose biosensor exhibit good linearity, high sensitivity, low detection limit, and fast response time of 5 s Fig. 12 a Selectivity and b stability of GO/CuO/FTO glucose sensor Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 9 of 10 Table 2 Analysis of the glucose sensing performance of GO/CuO/FTO electrode Sample Certified method (mM) Proposed method (mM) RSD (%) Recovery rate (%) 1 4.5 4.59 2 102 2 6.11 6.00 1.81 98.19 3 5.22 5.3 1.5 101.5 4 5 4.75 1 95 Conclusion carbohydrates. Anal Chem. 2012;84(1):171–8. https://doi.org/10.1021/ac2022 The GO/CuO/FTO electrode was successfully prepared Dhara K, Ramachandran T, Nair BG, SatheeshBabu TG. Single step synthesis of using the hydrothermal method and employed as a glu- au–CuO nanoparticles decorated reduced graphene oxide for high cose biosensor. The developed sensor has numerous ad- performance disposable nonenzymatic glucose sensor. J Electroanal Chem. 2015;743:1–9. https://doi.org/10.1016/j.jelechem.2015.02.005. vantages, such as a simple, eco-friendly method, quick Ferrari AC, Meyer JC, Scardaci V, Casiraghi C, Lazzeri M, Mauri F, et al. Raman detection with LOD 0.13 μM, fast analysis, high sensitiv- spectrum of graphene and graphene layers. Phys Rev Lett. 2006;97:187401. −1 −2 ity of 1274.8 μAmM cm (S/N = 3), good selectivity, https://doi.org/10.1103/PhysRevLett.97.187401. Georgakilas V, Tiwari JN, Kemp KC, Perman JA, Bourlinos AB, Kim KS, et al. excellent reproducibility, and good stability. The RSD of Noncovalent functionalization of graphene and graphene oxide for energy 1.58% obtained in human serum samples supports the materials, biosensing, catalytic, and biomedical applications. Chem Rev. 2016; reliability of the developed biosensor 116(9):5464–519. https://doi.org/10.1021/acs.chemrev.5b00620. Gopalan AI, Komathi S, Sai Anand G, Lee KP. Nanodiamond based sponges with entrapped enzyme: a novel electrochemical probe for hydrogen peroxide. Abbreviations Biosens Bioelectron. 2013;46:136–41. https://doi.org/10.1016/j.bios.2013.02.03 GO: Graphene oxide; CuO: Copper oxide; FTO: Fluorine-doped tin oxide; PVA: Polyvinyl alcohol; PBS: Phosphate buffer solution; LSV: Linear sweep Gopalan AI, Muthuchamy N, Komathi S, Lee KP. A novel multicomponent redox voltammetry; LOD: Limit of detection; RSD: Relative standard deviation polymer nanobead based high performance non-enzymatic glucose sensor. Biosens Bioelectron. 2016;84:53–63. https://doi.org/10.1016/j.bios.2015.10.079. Acknowledgements Gopalan AI, Muthuchamy N, Lee KP. A novel bismuth oxychloride-graphene Not applicable hybrid nanosheets based non-enzymatic photoelectrochemical glucose sensing platform for high performances. Biosens Bioelectron. 2017;89(Pt 1): Authors’ contributions 352–60. https://doi.org/10.1016/j.bios.2016.07.017. Medha Gijare: First author, Conceptualization, Methodology, Data curation, Haldorai Y, Hwang SK, Gopalan AI, Huh YS, Han YK, Voit W, Sai-Anand G, Lee K. P Writing—original draft preparation, Investigation. Sharmila Chaudhari: (2016) Direct electrochemistry of cytochrome c immobilized on titanium Supervision and review. Satish Ekar: Visualization, Investigation, Supervision. nitride/multi-walled carbon nanotube composite for amperometric nitrite Anil Garje: Corresponding author, Writing—reviewing and editing, Validation. biosensor. Biosens Bioelectron 79:543–552. https://doi.org/10.1016/j.bios.201 All authors read and approved the final manuscript. 5.12.054 Hota P, Miah M, Bose S, Dinda D, Ghorai KU, Su Y, et al. Ultra-small amorphous Availability of data and materials MoS decorated reduced graphene oxide for supercapacitor application. J The datasets used and/or analyzed during the current study are available Mater Sci Technol. 2020;40:196–203. https://doi.org/10.1016/j.jmst.2019.08. from the corresponding author on reasonable request. Hsu YW, Hsu TK, Sun CL, Nien YT, Pu NW, Ger MD. Synthesis of CuO/graphene Declarations nanocomposites for nonenzymatic electrochemical glucose biosensor applications. Electrochimca Acta. 2012;82:152–7. https://doi.org/10.1016/j. Competing interests electacta.2012.03.094. The authors declare that they have no competing interests. Hu A, Li R, Bridges D, Zhou W, Bai S, Ma D, et al. Photonic nanomanufacturing of high-performance energy devices on flexible substrates. J Laser Applications. Author details 2016;28(2):022602. https://doi.org/10.2351/1.4944449. Department of Physics, Baburaoji Gholap College, Savitribai Phule Pune Ji L, Praveen M, Victor A, Xingcheng X, Mataz. A graphene-based University, Pune, Maharashtra 411027, India. Department of Physics, nanocomposites for energy storage. Adv Energy Mater. 2016;6(16):1502159. Anantrao Pawar College, Pirangut, Savitribai Phule Pune University, Pune, https://doi.org/10.1002/aenm.201502159. Maharashtra 412115, India. Department of Physics, Sir Parashurambhau Khan M, Nagal V, Nakate UT, Khan MR, Khosla A, Ahmad R. Engineered CuO College, Savitribai Phule Pune University, Pune, Maharashtra 411030, India. nanofibers with boosted non-enzymatic glucose sensing performance. J Electrochem Soc. 2021;168(6):067507. https://doi.org/10.1149/1945-7111/ac030d. Received: 22 April 2021 Accepted: 26 July 2021 Liu F, Wang C, Sui X, Adi M, Riaz MA, Xu M, et al. Synthesis of graphene materials by electrochemical exfoliation: recent progress and future potential. Carbon Energy. 2019;1:173–99. https://doi.org/10.1002/cey2.14. References Makaram P, Owens D, Aceros J. 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A facile synthesis of GO/CuO-blended nanofiber sensor electrode for efficient enzyme-free amperometric determination of glucose

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Abstract

The development of biosensors with innovative nanomaterials is crucial to enhance the sensing performance of as- prepared biosensors. In the present research work, we prepared copper (II) oxide (CuO) and graphene oxide (GO) composite nanofibers using the hydrothermal synthesis route. The structural and morphological properties of as- prepared GO/CuO nanofibers were analyzed using an X-ray diffractometer, field-emission scanning, energy dispersive X-ray analysis, Fourier transmission infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The results indicated GO/CuO nanofibers exhibit nanosized diameters and lengths in the order of micrometers. These GO/CuO nanofibers were employed to prepare non-enzymatic biosensors (GO/CuO nanofibers/ FTO (fluorine-doped tin oxide)) modified electrodes for enhanced glucose detection. The sensing performance of the biosensors was evaluated using linear sweep voltammetry (LSV) and chronoamperometry in phosphate buffer −1 −2 solution (PBS). GO/CuO/FTO biosensor achieved high sensitivity of 1274.8 μAmM cm having a linear detection range from 0.1 to 10 mM with the lower detection limit (0.13 μM). Further, the prepared biosensor showed good reproducibility repeatability, excellent selectivity, and long-time stability. Moreover, the technique used for the preparation of the GO/CuO composite is simple, rapid, cost-effective, and eco-friendly. These electrodes are employed for the detection of glucose in blood serum with RSD ~ 1.58%. Keywords: Graphene oxide, Enzyme free, Glucose, Biosensor Introduction glucose levels of diabetic patients (Makaram et al., 2014; Diabetes is a widespread disease affecting millions of Bruen et al., 2017; Gopalan et al. 2017; Gopalan et al. populations and predicted to be the major cause of 2016; Sai-Anand et al. 2014). Enzymatic electrochemical death as it can damage neural systems in humans. It is sensors suggest good selectivity and sensitivity but due essential for diabetic patients to frequently monitor and to complex mobility, lack of stability and reproducibility maintain glucose levels. Hence, an effective diagnosis of limit their performance (Gopalan et al. 2013, Haldorai diabetes and a reliable glucose monitoring system are et al. 2016). These limitations are overcome by the de- necessary. Extensive majors have been taken to control velopment of enzyme-free glucose sensor devices diabetes through several monitoring systems. Glucose through direct oxidization of glucose in the form oxi- biosensors have a great contribution in monitoring dized layer (Sai-Anand et al. 2019). Glucose oxidase is usually practiced as an enzyme in most of the glucose biosensors. Amperometry is another widely used tech- * Correspondence: adgarje@gmail.com 3 nique for glucose detection (Peter and Heineman, 1996, Department of Physics, Sir Parashurambhau College, Savitribai Phule Pune University, Pune, Maharashtra 411030, India Thévenot et al., 2001). Glucose oxidase performs a major Full list of author information is available at the end of the article © The Author(s). 2021 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 2 of 10 role in the oxidation of β-D-glucose to D-glucono-δ-lac- doped tin oxide (FTO) substrates, D (+) glucose, dopa- tone. Hydrogen peroxide (H O ) is formed as a bypro- mine, L-ascorbic acid, D (−) fructose, lactose were pur- 2 2 duct in a catalytic reaction and oxygen as an electron chased from Qualigens Fine Chemicals, India. Deionized acceptor. A simple technique, less analysis time, cost ef- (DI) water was purchased from Sharad Agencies, India. fective, and low detection capability are some advantages The phosphate buffer solution (PBS) was prepared in the of using amperometry (Thunkhamrak et al., 2020). Re- laboratory using the standard method. All the chemicals gardless of excellent sensitivity and low detection limit are of analytical research (AR) grade and used without in few nanocomposites, an enzymatic glucose sensor further purification. limits the application of sensors due to high production cost (G. Gnana kumar et al., 2017). Nowadays, graphene Synthesis of graphene oxide has attracted researchers due to the larger specific super- Graphene oxide was synthesized using an earlier re- ficial area, purity, high conductivity, and low cost (Liu ported method (Marcano et al., 2010). Graphite powder et al., 2019). It has diversified applications in various and NaNO in 2:1 proportion were mixed with concen- areas such as batteries (Ji et al., 2016), biomedical (Mal- trated H SO and H PO in the ratio of 9:1 (wt %). Fif- 2 4 3 4 lick et al., 2018), supercapacitors (Hota et al. 2020), teen grams of KMnO was slowly added while stirring printable graphene electronics (Hu Etal. 2016) gas sen- followed by the addition of the required amount of sors (Nakate et al. 2020), and biosensors (Bai et al. H O . If the mixture turns into bright yellow color, this 2 2 2020). In chemical synthesis, graphene oxide (GO) is re- represents a great oxidation level of GO. In order to 2− duced to eliminate oxygen-containing functionalities eradicate SO ions, the solution was repeatedly washed using hazardous chemicals like hydrazine as a reducing and the brownish black precipitate was collected. agent. The process of chemical reduction contains cru- cial and lengthy steps of chemical reactions, tiresome Synthesis of GO/CuO nanocomposites washing cycles, and drying of residue. Moreover, the use Initially, 0.5 g GO and 0.2 g CuO were dissolved in DI of poisonous and explosive reducing agents in the redox and the solution was constantly stirred for half an hour process makes it non-eco-friendly. Hence, functionalized by raising its temperature to 100 °C. Fifty milliliters of GO using eco-friendly reduction methods is necessary in NaOH solution was slowly added to it. The temperature biosensing applications. Copper oxide (CuO) can be of the solution was retained for 10 min and allowed to used to functionalize GO as a catalyst because of its cool. The GO/CuO composite was collected after electrochemical catalytic property (Khan et al. 2021). In evaporation. an electrolysis process, Cu (II) oxidizes Cu (III) by gain- ing electrons in the redox reaction. During the oxidiza- Preparation of GO/CuO nanocomposite electrode tion process, glucose gets converted into gluconolactone Ten milligrams of the GO/CuO nanocomposite was dis- (Zhang et al. 2020; Wang et al. 2014). Hence, an efficient persed in 5 ml of DI water and 5 μl of PVA using bath electron transfer in glucose oxidation can be predicted sonication for half an hour. Then, 10 μl of the suspen- through excellent support of GO to CuO. In the present sion was drop casted on the previously cleaned FTO work, an enzyme-less amperometric glucose biosensor substrate. The working area of the electrode was 1 cm . using graphene oxide (GO) and copper oxide (CuO) The electrode was annealed at 250 °C. nanocomposites was successfully prepared using a fluorine-doped tin oxide (FTO) substrate. The prepared Mechanism of GO/CuO/FTO glucose sensing sensor electrode exhibits exclusive properties such as A new decorum for the synthesis of the GO/CuO nano- large superficial area, good catalytic activity, and excel- composite by in situ hydrothermal reduction of GO and lent electrical conductivity. Moreover, the electrode pro- CuO nanobelt formation is developed as shown in Fig. 1. vides improved sensitivity, low detection limit, and With the existence of NaOH, DI water assists in the excellent recovery in human serum compared to previ- growth of Cu (OH) nanograin morphology on the GO ously reported literature. Furthermore, the preparation surface. The epitaxial growth process caused the forma- and detection procedures are simple, fast, less time con- tion of CuO nanobelts. The augmented temperature of suming, and cost effective. the above reaction mixture leads to the formation of a fiber-like GO/CuO nanostructure. A glucose sensing Methodology performance of the GO/CuO/FTO-modified electrode Natural graphite powder (S.Aldrich, 99.99%), potassium was studied in the presence of phosphate buffer solution permanganate (KMnO , 99%), hydrogen peroxide (H O , (PBS:7.4 pH). 4 2 2 30%), sulfuric acid (H SO , 99.99%), hydrochloric acid Normally, when glucose disperses in PBS, it creates D- 2 4 (HCl, 30%), phosphoric acid (H PO ,85%), copper oxide gluconolactone and hydrogen peroxide (H O ). It further 3 4 2 2 (CuO, 99.9%), polyvinyl alcohol (PVA,99%), fluorine- generates D-gluconate with H ions due to Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 3 of 10 Fig. 1 Glucose sensing mechanism of GO/CuO/FTO electrode electrooxidation of glucose at grain boundaries of CuO. and Ag/AgCl as reference electrode. The electrocatalytic Hence, gluconolactone is the key product accountable performance of the electrode was studied using linear for oxidation that hydrolyzes gluconic acid. H ions sweep voltammetry (LSV) and chronoamperometry. lessen the pre-absorbed oxygen by discharging electrons which decrease the barrier potential between successive Results and discussion grains and lifts the electrical conductivity (Wu et al., XRD analysis 2010). XRD pattern of GO and GO/CuO nanocomposite is pre- sented in Fig. 2. CuO þ H O→CuðÞ OH þ e 2 The reflection peak which occurred at (002) at 11.92° 3þ − 2þ Cu þ glucose þ e →gluconolactone þ Cu shows the occurrence of oxygen functionalities on the hydrolysis GO surface with an interlayer basal space of 0.79 nm gluconolactone → gluconic acid (Tong et al. 2011). The peak (100) at 42.56° suggested the static disorder of GO. In the case of the GO/CuO Structural and optical characterization nanocomposite, the reflection peak (002) at 24.04° For structural characterization, an XRD analysis for the showed a shift with basal spacing of 0.37 nm. The fall in synthesized GO and GO/CuO powder was done with basal space suggested that GO was converted to rGO Bruker D8-Advanced Diffractometer using Cu Kα radi- (Dhara et al. 2015). All peaks of CuO are in good ation (λ = 0.154 nm) from the range of 5 to 85° with a scanning rate of 2°/min. Surface morphology and elem- ental composition of GO and GO/CuO samples were characterized FESEM: FEI Nova NanoSEM 450, Raman analysis was done using a micro-Raman spectrometer (Jobin-Yuon HR 800 UV) using a He–Ne (633 nm) laser excitation source. XPS analysis of GO and CuO was car- ried out by Multifunctional XPS (PHI ulvac probe III Scanning Microprobe). For the FTIR study, FTIR-6100 spectrometer (JASCO) in the transmission (T) mode in −1 the wavenumber range 4000–400 cm was taken. Electrochemical measurement Wonatech potentiostat was used for voltametric and am- perometric measurements for glucose detection with a three-electrode system which comprises GO/CuO/FTO Fig. 2 XRD pattern of a GO and b GO/CuO as a working electrode along with platinum as counter Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 4 of 10 agreement with the JCPDS file: 48-1548, which confirms nanofibers of sizes in the range of 70–200 nm and sev- a high degree of purity and crystallinity of CuO. eral nanometers in length were distributed on the gra- phene layer. The formation of GO/CuO can be FESEM and EDS analysis explained as follows. The surface morphology of prepared GO and GO/CuO Due to the increase in temperature during the synthe- nanocomposites was characterized by FESEM as shown sis, quick evaporation of water molecules caused a con- in Fig. 3. traction of CuO nanoparticles and GO sheets. GO was Graphene oxide showed a thin wrinkled paper-like thermally reduced to modified graphene. The graphene structure. In the GO/CuO nanocomposite, high-density 2D material has a strong hydrophobic center and Fig. 3 FESEM of GO and GO/CuO Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 5 of 10 Fig. 4 EDS of GO and GO/CuO hydrophilic surrounding (Georgakilas et al. 2016). It was chemical composition of GO/CuO where GO was par- noted that the active GO surface lowers the internal tially reduced in presence of cuprous ions. energy. Furthermore, CuO has a monoclinic nature and excel- Raman spectroscopy lent thermal conductivity. Therefore, CuO nanoparticles Raman analysis of the GO-CuO nanocomposite is pre- together with GO formed a fiber-like structure. The dis- sented in Fig. 6. tribution of chemical elements present in the composite The fundamental vibrations of GO and GO/CuO were −1 was examined using the energy dispersive spectrum observed in the sequence of 1200 to 1700 cm . The D (EDS) as shown in Fig. 4. (disorder bands) and G (tangential bands) were formed at breathing mode A symmetry and first-order scatter- ing of E photons by Sp carbon (C-C bond) respect- FTIR analysis ively (AC Ferrari et al. 2006). A broad 2D band of GO −1 FTIR spectra for GO and GO/CuO nanocomposite is as with a higher wavenumber was located at 2918 cm shown in Fig. 5. confirming the multilayered nature of GO. The 2D band The bending and stretching modes of O-H groups of GO/CuO predicted the reduction of GO to rGO were represented as broad spectra present around 3203 caused GO/CuO to stack. The ID/IG ratio of GO/CuO −1 −1 cm and the peak at 1734cm Showed C=O stretching was slightly decreased specifiying that there were some vibrations on the surface of GO. The C-O stretching vi- structural changes that occurred during thermal −1 brations were assigned to the peak at 1054 cm (Xu reduction. Zhu et al. 2012). This surface functional group exhibited the probable bonding of CuO on the GO surface. The XPS analysis −1 peaks at low frequencies below 1000 cm in GO/CuO XPS spectrum of GO and GO/CuO nanocomposite is spectra could be ascribed to Cu-O-Cu and Cu-O-C vi- presented in Fig. 7. The peaks centered at C, O, and brations (Q Chen et al. 2012). This demonstrated the Fig. 5 FTIR of a GO and b GO/CuO Fig. 6 Raman Spectrum of a GO and b GO/CuO nanocomposite Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 6 of 10 CuO are core-level regions associated with C1s, O1s, During the oxidation process, CuO was oxidized to and Cu2p peaks respectively. CuOOH and glucose to gluconolactone by Cu (III) (Wei H et al. 2009). Deconvoluted spectrum of GO/CuO Further, the electrochemical effect on GO/CuO/FTO A deconvoluted spectrum of GO/CuO is shown in Fig. with a variable scan rate was examined using LSV as 8. shown in Fig. 10. The electrode was scanned from 10 to Carbon in the nanocomposite was identified by the 300 mv/s (a to h) in PBS electrolyte in the presence of 5 high-resolution spectrum of C1s. The major peak at mM D (+) glucose. The oxidation occurred at + 0.6 V 283.5 eV exhibited sp (C-C, C=C) bonding and the for each scan and the oxidation peak current was in- shoulder peaks revealed C=O and O-C=O bonding. The creased with an increase in scan rate. This revealed that chemical bonding states of C-OH and C-O-C were lo- electrochemical reaction takes place on GO/CuO nano- cated at characteristic peaks 286.8 eV. The presence of composite demonstrating its ability towards enzyme CuO and Cu O was confirmed using high-resolution sensing (Wang et al. 2012). Hence, further electrochem- O1s spectra. The characteristic peaks observed at 530.2 ical and amperometric measurements were carried out eV belong to Cu-O, -C=O bonding in GO/CuO. The at the optimized potential of + 0.6 V vs. Ag/AgCl. peak shown at 532.9 eV was assigned to oxygen present in GO. The XPS spectrum of Cu 2p showed a peak at Amperometric measurements 932.5 eV for Cu 2p and confirmed the presence of The amperometric response of the GO/CuO/FTO elec- 3/2 CuO as a catalyst. A binding energy peak at 952.2 eV trode was measured and presented in Fig. 11a. The pro- was allocated to Cu 2p (Wu J et al. 2018). posed electrode revealed that the electron transport 1/2 between PBS solution and electrode in the redox process Electrochemical measurements is enhanced due to the high electrical conductivity and Linear sweep voltammogram to study the electrocata- electrocatalytic activity of the GO/CuO nanocomposite lytic activity of the modified electrodes is represented in (Hsu et al. 2012). The calibration curve in Fig.11b dis- Fig. 9. played two linear ranges corresponding to low glucose The electrodes were scanned at 100 mv/s in presence concentration (0.1–1 mM) and high concentration (1– of 5 mM D (+) glucose. There was no signal response 10 mM). detected for bare FTO (curve a). GO/FTO (curve b) and The corresponding linear regression equations were I CuO/FTO (curve c) showed a small increase in back- = 424.95c + 569.22 with R = 0.9984 (N =9)and I = ground current due to the large superficial area of GO 27.666c + 826 with R = 0.9963 (N = 9) respectively. For and electrocatalytic capability for glucose oxidation of low glucose concentration the sensitivity was 1274.8 μA −1 −2 CuO respectively. A well-defined glucose oxidation peak mM cm (S/N = 3) whereas for high concentration −1 −2 was observed for GO/CuO/FTO (curve d) in the pres- was 830 μAmM cm along with a low detection limit ence of 5 mM glucose at + 0.6 V. This indicates that the of 0.13 μM. A comparative study of performance of vari- GO/CuO/FTO composite electrode is necessary to ob- ous glucose biosensors is displayed in Table 1. tain high sensitivity and better electrocatalytic activity. Selectivity, stability, and reproducibility The selectivity and stability of the GO/CuO/FTO sensor electrode are presented in Fig. 12. The biological range of glucose concentration in hu- man serum is 3–8 mM, which is quite greater compared to other interfering substances like ascorbic acid, dopa- mine, etc. Hence, the electrode amperometric responses were examined with 1 mM D (+) glucose with the abovementioned interfering species (0.1 mM) in PBS (7.4) solution. It was observed that the glucose sensing ability of the proposed sensor was unaffected by the interfering substances. The reproducibility of the sensor was studied using 10 similar sensors. The current re- sponse was observed for 1 mM glucose concentration for each sensor. RSD of 2.7% confirms the significant re- producibility. The aging effect (stability) of the samples was also tested periodically for 30 days with of 1 mM Fig. 7 XPS spectrum of a GO b GO/CuO glucose concentration and an RSD of 2.64% was Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 7 of 10 Fig. 8 Deconvoluted spectrum of GO/CuO a C1s, b O1s, and c Cu2p achieved. This demonstrates that the GO/CuO/FTO folds) using the standard dilution method before ana- electrode has good repeatability, reproducibility, and sta- lysis. The results obtained using the GO/CuO/FTO sen- bility as a glucose biosensor. sor were compared with the certified values received from the pathology laboratory (Table 2). The average re- Determination of glucose concentration in human serum covery rate was 99.17% along with an RSD of 1.58% The blood glucose level in human serum samples was which assured the reliability and applicability of the GO/ determined using the proposed glucose biosensor. The CuO/FTO sensor to determine the glucose concentra- human serum samples were received from a standard tion in a real sample. pathology laboratory. The samples were diluted (100 Fig. 9 LSV of a FTO, b GO/FTO, c CuO/FTO, and d GO/CuO/FTO at 100 mv/s scan rate Fig. 10 LSV of GO/CuO/FTO electrode with variable scan rate Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 8 of 10 Fig. 11 a Chronoamperometric response of GO/CuO/FTO. b Calibration curve Table 1 Comparison of the enzyme-free GO-based glucose sensor with its composites −1 −2 Electrode Method of detection Potential (V) Sensitivity (μAmM cm ) Linear range (mM) LOD (μM) Ref. GO/CuO/FTO Amp 0.6 830, 1274.8 0.1–1 0.13 Present work 1–10 PDDA/Ch/GOx/PtAuNPs/ Amp 0.5 110, 62.3 0.5–2 0.2 Sridara et al. (2020) 2–5 Cu/Cu O/CSs on GCE Amp 0.65 63.8, 22.6 0.01–0.69 0.005 Yin et al. (2016) 1.19–3.69 Au/GO on GCE Amp 0 5.20, 4.56 0.1–2 0.025 Shu et al. (2015) 2–16 GR–CuO NPs Amp 0.6 1065 1 μM–8 mM 1 Hsu et al. (2012) GOx/CdS/Gr/GCE CV – 1.76 2–16 0.7 Wang et al., 2011) GO–CuONPs Amp 0.7 162.52 2.79μM–2.03 mM 0.69 Song et al., 2013) The prepared GO/CuO/FTO enzyme-free glucose biosensor exhibit good linearity, high sensitivity, low detection limit, and fast response time of 5 s Fig. 12 a Selectivity and b stability of GO/CuO/FTO glucose sensor Gijare et al. Journal of Analytical Science and Technology (2021) 12:40 Page 9 of 10 Table 2 Analysis of the glucose sensing performance of GO/CuO/FTO electrode Sample Certified method (mM) Proposed method (mM) RSD (%) Recovery rate (%) 1 4.5 4.59 2 102 2 6.11 6.00 1.81 98.19 3 5.22 5.3 1.5 101.5 4 5 4.75 1 95 Conclusion carbohydrates. Anal Chem. 2012;84(1):171–8. https://doi.org/10.1021/ac2022 The GO/CuO/FTO electrode was successfully prepared Dhara K, Ramachandran T, Nair BG, SatheeshBabu TG. Single step synthesis of using the hydrothermal method and employed as a glu- au–CuO nanoparticles decorated reduced graphene oxide for high cose biosensor. The developed sensor has numerous ad- performance disposable nonenzymatic glucose sensor. J Electroanal Chem. 2015;743:1–9. https://doi.org/10.1016/j.jelechem.2015.02.005. vantages, such as a simple, eco-friendly method, quick Ferrari AC, Meyer JC, Scardaci V, Casiraghi C, Lazzeri M, Mauri F, et al. Raman detection with LOD 0.13 μM, fast analysis, high sensitiv- spectrum of graphene and graphene layers. Phys Rev Lett. 2006;97:187401. −1 −2 ity of 1274.8 μAmM cm (S/N = 3), good selectivity, https://doi.org/10.1103/PhysRevLett.97.187401. Georgakilas V, Tiwari JN, Kemp KC, Perman JA, Bourlinos AB, Kim KS, et al. excellent reproducibility, and good stability. The RSD of Noncovalent functionalization of graphene and graphene oxide for energy 1.58% obtained in human serum samples supports the materials, biosensing, catalytic, and biomedical applications. Chem Rev. 2016; reliability of the developed biosensor 116(9):5464–519. https://doi.org/10.1021/acs.chemrev.5b00620. Gopalan AI, Komathi S, Sai Anand G, Lee KP. Nanodiamond based sponges with entrapped enzyme: a novel electrochemical probe for hydrogen peroxide. Abbreviations Biosens Bioelectron. 2013;46:136–41. https://doi.org/10.1016/j.bios.2013.02.03 GO: Graphene oxide; CuO: Copper oxide; FTO: Fluorine-doped tin oxide; PVA: Polyvinyl alcohol; PBS: Phosphate buffer solution; LSV: Linear sweep Gopalan AI, Muthuchamy N, Komathi S, Lee KP. A novel multicomponent redox voltammetry; LOD: Limit of detection; RSD: Relative standard deviation polymer nanobead based high performance non-enzymatic glucose sensor. Biosens Bioelectron. 2016;84:53–63. https://doi.org/10.1016/j.bios.2015.10.079. Acknowledgements Gopalan AI, Muthuchamy N, Lee KP. A novel bismuth oxychloride-graphene Not applicable hybrid nanosheets based non-enzymatic photoelectrochemical glucose sensing platform for high performances. Biosens Bioelectron. 2017;89(Pt 1): Authors’ contributions 352–60. https://doi.org/10.1016/j.bios.2016.07.017. Medha Gijare: First author, Conceptualization, Methodology, Data curation, Haldorai Y, Hwang SK, Gopalan AI, Huh YS, Han YK, Voit W, Sai-Anand G, Lee K. P Writing—original draft preparation, Investigation. Sharmila Chaudhari: (2016) Direct electrochemistry of cytochrome c immobilized on titanium Supervision and review. Satish Ekar: Visualization, Investigation, Supervision. nitride/multi-walled carbon nanotube composite for amperometric nitrite Anil Garje: Corresponding author, Writing—reviewing and editing, Validation. biosensor. Biosens Bioelectron 79:543–552. https://doi.org/10.1016/j.bios.201 All authors read and approved the final manuscript. 5.12.054 Hota P, Miah M, Bose S, Dinda D, Ghorai KU, Su Y, et al. Ultra-small amorphous Availability of data and materials MoS decorated reduced graphene oxide for supercapacitor application. 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Journal

"Journal of Analytical Science and Technology" – Springer Journals

Published: Sep 1, 2021

Keywords: Graphene oxide; Enzyme free; Glucose; Biosensor

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