Abstract
Gold nanorods (AuNRs) show high potential in electrochemical sensing owing to their excellent conductivity, electrocatalytic activity, selectivity and sensitivity. This review (with 99 refs.) summarizes the performance of AuNR-based electrochemical sensors based on the use of advanced nanocomposites. Following an introduction into the fields of biosensors and nanomaterials, the article summarizes the advantages and limitations of conventional analytical methods. A third section overviews the methods for preparation and characterization of AuNRs and nanocomposites including bimetallic nanorods, gold-metal oxide, gold-carbon nanotubes, gold-polymer, gold-graphene, gold-CNT and gold-enzymes conjugates. Their electrochemistry is treated next, with aspects related to the effects of rod size and shape, of thiol coatings on voltammetric signals, and on the behavior of 1-D AuNRs and respective arrays. Section 5 gives examples for non-enzymatic sensors for simple biomolecules, with subsections on sensors for hydrogen peroxide, nitric oxide, glucose, dopamine, NAD/NADH, cysteine, and some drugs. Section 6 covers enzyme-based sensors, with examples on sensors using peroxidases, oxidases and the like. The next sections cover DNA biosensors (such as for DNA biomarkers) and immunosensors, mainly for tumor markers. Possibilities for improving sensor performance are presented at the end of the review.
Similar content being viewed by others
References
Song S, Xu H, Fan C (2006) Potential diagnostic applications of biosensors: current and future directions. Int J Nanomedicine 1(4):433–440
Wang J (1999) Sol–gel materials for electrochemical biosensors. Anal Chim Acta 399(1):21–27
Singh P, Pandey SK, Singh J, Srivastava S, Sachan S, Singh SK (2016) Biomedical perspective of electrochemical Nanobiosensor. Nano-Micro Lett 8(3):193–203
Jayabal S, Pandikumar A, Lim HN, Ramaraj R, Sun T, Huang NM (2015) A gold Nanorods-based localized surface Plasmon resonance platform for the detection of environmentally toxic metal ions. Analyst 140:2540–2555
Prasad BB, Singh R, Kumar A (2016) Gold nanorods vs. gold nanoparticles: application in electrochemical sensing of cytosine β-D-arabinoside using metal ion mediated molecularly imprinted polymer. RSC Adv 6:80679–80691
Huang XH, Neretina S, El-Sayed MA (2009) Gold nanorods: from synthesis and properties to biological and biomedical applications. Adv Mater 21:4880–4910
Narayanan R, El-Sayed MA (2005) Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability. J Phys Chem C 109:12663–12676
Haberlen OD, Chung SC, Stener M, Rosch N (1997) From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147. J Chem Phys 106:5189
Sau TK, Rogach AL, Jackel F, Klar TA, Feldmann J (2010) Properties and applications of colloidal nonspherical noble metal nanoparticles. Adv Mater 22:1805–1825
Bastus NG, Comenge J, Puntes V (2011) Kinetically controlled seeded growth synthesis of citrate-stabilized gold nanoparticles of up to 200 nm: size focusing versus Ostwald ripening. Langmuir 27:11098–11105
Wu H-Y, Chu H-C, Kuo T-J, Kuo C-L, Huang MH (2005) Seed-mediated synthesis of high aspect ratio gold Nanorods with nitric acid. Chem Mater 17:6447–6451
Jia H, Fang C, Zhu X-M, Ruan Q, Wang Y-X J, Wang J (2015) Synthesis of absorption-dominant small gold Nanorods and their Plasmonic properties. Langmuir 31:7418–7426
Pontifex GH, Zhang P, Wang Z, Haslett TL, AlMawlawi D, Moskovits M (1991) STM imaging of the surface of small metal particles formed in anodic oxide pores. J Phys Chem 95:9989–9993
Gole A, Murphy CJ (2004) Seed-mediated synthesis of gold Nanorods: role of the size and nature of the seed. Chem Mater 16:3633–3640
Nikoobakht B, El-Sayed MA (2003) Preparation and growth mechanism of gold Nanorods (NRs) using seed-mediated growth method. Chem Mater 15:1957–1962
Lamprect G, Pichlmayer F, Schmid ER (1994) Determination of the authenticity of vanilla extracts by stable isotope ratio analysis and component analysis by HPLC. J Agric Food Chem 42:1722–1727
Ni Y, Zhang G, Kokot S (2005) Simultaneous spectrophotometric determination of maltol, ethyl maltol, vanillin and ethyl vanillin in foods by multivariate calibration and artificial neural networks. Food Chem 89:465–473
Boyce MC, Haddad PR, Sostaric T (2003) Determination of flavour components in natural vanilla extracts and synthetic flavourings by mixed micellar electrokinetic capillary chromatography. Anal Chim Acta 485:179–186
Sostaric T, Boyce MC, Spickett EE (2000) Analysis of the volatile components in vanilla extracts and flavorings by solid-phase microextraction and gas chromatography. J Agric Food Chem 48:5802–5807
Peng H, Wang S, Zhang Z, Xiong H, Li J, Chen L, Li Y (2012) Molecularly imprinted photonic hydrogels as colorimetric sensors for rapid and label-free detection of vanillin. J Agric Food Chem 60:1921–1928
Yusoff N, Pandikumar A, Ramaraj R, Huang NM, Lim HN (2015) Gold nanoparticles based optical and electrochemical sensing of dopamine. Microchim Acta 182:2091–2114
Pandikumar A, How GTS, Teo PS, Fatin SO, Jayabal S, Kamali KZ, Yusoff N, Asilah J, Ramaraj R, Abraham John S, Lim HN, Huang NM (2014) Graphene and its nanocomposite material based electrochemical sensor platform for dopamine. RSC Adv 4:63296–63323
Pandikumar A, How GTS, See TP, Omar FS, Jayabal S, Kamali KZ, Yusoff N, Jamil A, Ramaraj R, John SA, Limbe HN, Huang NM (2014) Graphene and its nanocomposite material based electrochemical sensor platform for dopamine. RSC Adv 4:63296
Yu Y, Chang SS, Lee CL, Wang CRC (1997) Gold Nanorods: electrochemical synthesis and optical properties. J Phys Chem B 101:6661–6664
Chang SS, Shih CW, Chen CD, Lai WC, Wang CRC (1999) The shape transition of gold Nanorods. Langmuir 15:701–709
Vigderman L, Khanal BP, Eugene RZ (2012) Functional gold Nanorods: synthesis, self-assembly, and sensing applications. Adv Mater 24:4811–4841
Jana NR, Gearheart L, Murphy CJ (2001) Seed-mediated growth approach for shape-controlled synthesis of spheroidal and rod-like gold nanoparticles using a surfactant template. Adv Mater 13:1389–1393
Zweifel DA, Wei A (2005) Sulfide-arrested growth of gold Nanorods. Chem Mater 17:4256–4261
Dickson W, Evans PR, Wurtz GA, Hendren W, Atkinson R, Pollard RJ, Zayatz AV (2008) Towards nonlinear plasmonic devices based on metallic nanorods. J Microsc 229:415–420
Van der Zande BMI, MBoehmer R, Fokkink LGJ, Schoenenberger C (2000) Colloidal dispersions of gold rods: synthesis and optical properties. Langmuir 16:451–458
Grand J, Kostcheev S, Bijeon JL, de la Chapelle ML, Adam PM, Rumyantseva A, Lerondel G, Royer P (2003) Optimization of SERS-active substrates for near-field Raman spectroscopy. Synth Met 139:621
Cubukcu E, Kort EA, Crozier KB, Capasso F (2006) Plasmonic laser antenna. Appl Phys Lett 89:093120
Taub N, Krichevski O, Markovich G (2003) Growth of gold Nanorods on surfaces. J Phys Chem B 107:11579–11582
Wei Z, Mieszawska AJ, Zamborini FP (2004) Synthesis and manipulation of high aspect ratio gold Nanorods grown directly on surfaces. Langmuir 20:4322
Liao H, Hafner JH (2004) Monitoring gold Nanorod synthesis on surfaces. J Phys Chem B 108:19276–19280
Shopova SI, Blackledge CW, Rosenberg AT (2006) Gold nanorods grown from HgTe nanoparticles directly on various surfaces. Appl Phys Lett 89:023120
Mieszawska AJ, Zamborini FP (2005) Gold Nanorods grown directly on surfaces from microscale patterns of gold seeds. Chem Mater 17:3415–3420
Xia H, Li L, Yin Z, Hou X, Zhu JJ (2015) Biobar-coded gold nanoparticles and DNAzyme-based dual signal amplification strategy for ultrasensitive detection of protein by Electrochemiluminescence. ACS Appl Mater Interfaces 7:696–703
Liu J, He X, Wang K, He D, Wang Y, Mao Y, Shi H, Wen L (2015) A highly sensitive electrochemiluminescence assay for protein kinase based on double-quenching of graphene quantum dots by G-quadruplex–hemin and gold nanoparticles. Biosens Bioelectron 70:54–60
Chirea M, Cruz A, Pereira CM, Silva AF (2009) Size-dependent electrochemical properties of gold Nanorods. J Phys Chem C 113:13077–13087
Chirea M, Garcia-Morales V, Manzanares JA, Pereira C, Gulaboski R, Silva FJ (2005) Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes. Phys Chem B 109:21808–21817
Chirea M, Pereira CM, Silva F (2007) Catalytic effect of gold nanoparticles self-assembled in multilayered polyelectrolyte films. J Phys Chem C 111:9255–9266
Chirea M, Borges J, Pereira CM, Silva AF (2010) Density-dependent electrochemical properties of vertically aligned gold Nanorods. J Phys Chem C 114:9478–9488
Gooding JJ, Chou A, Liu JQ, Losic D, Shapter JG, Hibbert DB (2007) The effects of the lengths and orientations of single-walled carbon nanotubes on the electrochemistry of nanotube-modified electrodes. Electrochem Commun 9:1677–1683
Chidsey CED (1991) Free energy and temperature dependence of electron transfer at the metal-electrolyte Interface. Science 251:919–922
Lin CC, Juo TJ, Chen YJ, Chiou CH, Wang HW, Liu YL (2008) Enhanced cyclic voltammetry using 1-D gold nanorods synthesized via AAO template electrochemical deposition. Desalination 233:113–119
Munshi AM, Ho D, Saunders M, Agarwal V, Raston CL, Iyer KS (2016) Influence of aspect ratio of magnetite coated gold nanorods in hydrogen peroxide sensing. Sensors Actuators B Chem 235:492–497
Jayabal S, Ramaraj R (2013) Synthesis of core/shell au/ag nanorods embedded in functionalized silicate sol–gel matrix and their applications in electrochemical sensors. Electrochim Acta 88:51–58
Xun F, Hongyan XL, Hao S, Xiaochun H, Song WW (2014) Highly accessible Pt nanodots homogeneously decorated on au nanorods surface for sensing. Anal Chim Acta 852:37–44
Pang P, Yang Z, Xiao S, Xie J, Zhang Y, Gao Y (2014) Nonenzymatic amperometric determination of hydrogen peroxide by graphene and gold nanorods nanocomposite modified electrode. J Electroanal Chem 727:27–33
Wang C, Zou X, Wang Q, Shi K, Tan J, Zhao X, Chaia Y, Yuan R (2014) A nitrite and hydrogen peroxide sensor based on Hb adsorbed on au nanorods and graphene oxide coated by polydopamine. Anal Methods 6:758
Yang X, Wang Y, Liu Y, Jiang X (2013) A sensitive hydrogen peroxide and glucose biosensor based on gold/silver core–shell nanorods. Electrochim Acta 108:39–44
Dang X, Hu H, Wang S, Hu S (2015) Nanomaterial-based electrochemical sensors for nitric oxide. Microchim Acta 182:455–467
Vasilescu A, Gheorghiu M, Peteu S (2017) Nanomaterial-based electrochemical sensors and optical probes for detection and imaging of peroxynitrite: a review. Microchim Acta 184:649–676
Jayabal S, Viswanathan P, Ramaraj R (2014) Reduced graphene oxide–gold nanorods composite material stabilized in silicate sol–gel matrix for nitric oxide sensor. RSC Adv 4:33541
Marlinda AR, Pandikumar A, Jayabal S, Yusoff N, Suriani AB, Huang NM (2016) Voltammetric determination of nitric oxide using a glassy carbon electrode modified with a nanohybrid consisting of myoglobin, gold nanorods, and reduced graphene oxide. Microchim Acta 183:3077–3085
Zhao Y, Fang X, Yan X, Zhang X, Kang Z, Zhang G, Zhang Y (2015) Nanorod arrays composed of zinc oxide modified with gold nanoparticles and glucose oxidase for enzymatic sensing of glucose. Microchim Acta 182(3–4):605–610
Zhang C, Ni H, Chen R, Zhan W, Zhang B, Lei R, Zha Y (2015) Enzyme-free glucose sensing based on Fe3O4 nanorod arrays. Microchim Acta 182(9–10):1811–1818
Tamer U, Seckin AI, Temur E, Torul H (2011) Fabrication of biosensor based on polyaniline/gold Nanorod composite. Int J Electrochem 2011:7
Yingying L, Xiaoxia W, Xiang D, Zhipeng H, Haiqian Z (2010) Amperometric glucose biosensor based on gold nanorods and chitosan comodified au electrode. Rare Metals 29:238–242
Ciftci H, Tamer U (2012) Functional gold nanorod particles on conducting polymer poly(3-octylthiophene) as non-enzymatic glucose sensor. React Funct Polym 72:127–132
Ren X, Chen D, Meng X, Tang F, Du A, Zhang L (2009) Amperometric glucose biosensor based on a gold nanorods/cellulose acetate composite film as immobilization matrix. Colloids Surf B 72:188–192
Hsu CW, JenWang G (2014) Highly sensitive glucose biosensor based on au–Ni coaxial nanorod array having high aspect ratio. Biosens Bioelectron 56:204–209
Liu H, Chen D, Yang L, Ren X, Tang F, Ren J (2010) A study of the electron transfer and photothermal effect of gold nanorods on a glucose biosensor. Nanotechnology 21:185504
Ahn M, Kim J (2012) Electrochemical behavior of dopamine and ascorbic acid at dendritic au rod surfaces: selective detection of dopamine in the presence of high concentration of ascorbic acid. J Electroanal Chem 683:75–79
Deng C, Chen J, Yang M, Nie Z, Si S (2011) Electrochemical determination of dopamine in the presence of ascorbic acid based on the gold nanorods/carbon nanotubes composite film. Electrochim Acta 56:8851–8856
Jia Z, Liu J, Shen Y (2007) Fabrication of a template-synthesized gold nanorod-modified electrode for the detection of dopamine in the presence of ascorbic acid. Electrochem Commun 9:2739–2743
Li L, Lu H, Deng L (2013) A sensitive NADH and ethanol biosensor based on graphene-au nanorods nanocomposites. Talanta 113:1–6
Jayabal S, Ramaraj R (2015) Amperometric sensing of NADH at gold nanorods stabilized in amine-functionalized silicate sol–gel matrix modified electrode. J Appl Electrochem 45:881–888
Silva FDADS, Silva MGAD, Lima PR, Meneghetti MR, Kubota LT, Goulart MOF (2013) A very low potential electrochemical detection of L-cysteine based on a glassy carbon electrode modified with multi-walled carbon nanotubes/gold nanorods. Biosens Bioelectron 50:202–209
Jagriti N, Nitesh M, Gajendra S, Pundir CS (2015) Electrochemical impediometric detection of anti-HIV drug taking gold nanorods as a sensing interface. Biosens Bioelectron 66:332–337
Bai W, Huang H, Li Y, Zhang H, Liang B, Guo R, Du L, Zhang Z (2014) Direct preparation of well-dispersed graphene/gold nanorodcomposites and their application in electrochemical sensors for determination of ractopamine. Electrochim Acta 117:322–328
Rahi A, Sattarahmady N, Vais RD, Heli H (2015) Sonoelectrodeposition of gold nanorods at a gold surface – Applicationfor electrocatalytic reduction and determination of nitrofurazone. Sensors Actuators B Chem 210:96–102
Mengdong W, Yitao H, Xingxing L, Zhou N, Chunyan D, Manli G, Shouzhuo Y (2011) Assembly of layer-by-layer films of superoxide dismutase and gold nanorods: a third generation biosensor for superoxide anion. Sci China Mater 54:1284–1291
Arvand M, Gholizadeh TM (2013) Gold nanorods-graphene oxide nanocomposite incorporated carbonnanotube paste modified glassy carbon electrode for voltammetric determination of indomethacin. Sensors Actuators B Chem 186:622–632
Komathi S, Gopalan AI, Kim SK, Anand GS, Lee KP (2013) Fabrication of horseradish peroxidase immobilized poly(N-[3-(trimethoxy silyl)propyl]aniline) gold nanorods film modified electrode and electrochemical hydrogen peroxide sensing. Electrochim Acta 92:71–78
Zhang S, Han L, Hou C, Li C, Lang Q, Han L, Liu A (2015) Novel glucose sensor with au@ag heterogeneous nanorods based on electrocatalytic reduction of hydrogen peroxide at negative potential and neutral pH. J Electroanal Chem 742:84–89
Li Y, Wang F, Huang F, Li Y, Feng S (2012) Direct electrochemistry of glucose oxidase and its biosensing to glucose based on the chit-MWCNTs–AuNRs modified gold electrode. J Electroanal Chem 685:86–90
Nirala NR, Abraham S, Kumar V, Pandey SA, Yadav U, Srivastava M, Srivastava SK, Singh VN, Kayastha AM, Srivastava A, Saxena PS (2015) Partially reduced graphene oxide-gold nanorods composite based bioelectrode of improved sensing performance. Talanta 144:745–754
Rasheed PA, Sandhyarani N (2017) Electrochemical DNA sensors based on the use of gold nanoparticles: a review on recent developments. Microchim Acta 84:981–1000
Han X, Fang X, Shi A, Wang J, Zhang Y (2013) An electrochemical DNA biosensor based on gold nanorods decorated graphene oxide sheets for sensing platform. Anal Biochem 443:117–123
Huang H, Bai W, Dong C, Guo R, Liu Z (2015) An ultrasensitive electrochemical DNA biosensor based on graphene/ au nanorod/polythionine for human papillomavirus DNA detection. Biosens Bioelectron 68:442–446
Azimzadeh M, Rahaiea M, Navid Nasirizadeh N, Ashtari K, Manesh HN (2016) An electrochemical nanobiosensor for plasma miRNA-155, based on graphene oxide and gold nanorod, for early detection of breast cancer. Biosens Bioelectron 77:99–106
Zhang Y, Ge L, Li M, Yan M, Ge S, Yu J, Song X, Cao B (2014) Flexible paper-based ZnO nanorod light-emitting diodes induced multiplexed photoelectrochemical immunoassay. Chem Commun 50:1417–1419
Shan J, Ma Z (2017) A review on amperometric immunoassays for tumor markers based on the use of hybrid materials consisting of conducting polymers and noble metal nanomaterials. Microchim Acta 184:969–979
Hasanzadeh M, Shadjou N (2017) Advanced nanomaterials for use in electrochemical and optical immunoassays for the carcinoembryonic antigen. A review. Microchim Acta 184:389–414
Sun Z, Deng L, Gan H, Shen R, Yang M, Zhang Y (2013) Sensitive immunosensor for tumor necrosis factor based on dual signal amplification of ferrocene modified self-assembled peptide nanowire and glucose oxidase functionalized gold nanorods. Biosens Bioelectron 39:215–219
Zang S, Liu Y, Lin M, Kang J, Sun Y, Lei H (2013) A dual amplified electrochemical immunosensor for ofloxacin: Polypyrrole film-au nanocluster as the matrix and multi-enzyme-antibody functionalized gold nanorod as the label. Electrochim Acta 90:246–253
Sun G, Liu H, Zhang Y, Yu J, Yan M, Song X, He W (2015) Gold nanorods-paper electrode based enzyme-free electrochemical immunoassay of prostate specific antigen using porous zinc oxide spheres-silver nanoparticles nanocomposites as labels. New J Chem 39:6062–6067
Du D, Wang J, Lu D, Dohnalkova A, Lin Y (2011) Multiplexed electrochemical immunoassay of phosphorylated proteins based on enzyme-functionalized gold Nanorod labels and electric field-driven acceleration. Anal Chem 83:6580–6585
Cheng AKH, Sen D, Yu HZ (2009) Design and testing of aptamer-based electrochemical biosensors for proteins and small molecules. Bioelectrochemistry 77:1–12
Liu Y, Tuleouva N, Ramanculov E, Revzin A (2010) Aptamer-based electrochemical biosensor for interferon gamma detection. Anal Chem 82:8131–8136
Shakoori Z, Salimian S, Kharrazi S, Adabi M, Saber R (2015) Electrochemical DNA biosensor based on gold nanorods for detecting hepatitis B virus. Anal Bioanal Chem 407:455–461
Wen W, Huang JY, Bao T, Zhou J, Xia HX, Zhang XH, Wang SF, Zhao YD (2016) Increased electrocatalyzed performance through hairpin oligonucleotide aptamer-functionalized gold nanorods labels and graphene-streptavidin nanomatrix: highly selective and sensitive electrochemical biosensor of carcinoembryonic antigen. Biosens Bioelectron 83:142–148
Gallina ME, Zhou Y, Johnson CJ, Harris-Birtill D, Singh M, Zhao H, Ma D, Cass T, Elson DS (2016) Aptamer-conjugated, fluorescent gold nanorods as potential cancer theradiagnostic agents. Mater Sci Eng C 59:324–332
Noiphung J, Songjaroen T, Dungchai W, Henry CS, Chailapakul O, Laiwattanapaisal W (2013) Electrochemical detection of glucose from whole blood using paper-based microfluidic devices. Anal Chim Acta 788:39–45
Cate DM, Adkins JA, Mettakoonpitak J, Henry CS (2015) Recent developments in paper-based microfluidic devices. Anal Chem 87(1):19–41
Acknowledgments
PR and AP dedicated this article to Professor R.Ramaraj, CSIR-Emeritus Scientist, School of Chemistry, Madurai Kamaraj University for his pioneer contribution in electrocatalysis and sensors.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
The author(s) declare that they have no competing interests.
Rights and permissions
About this article
Cite this article
Alagiri, M., Rameshkumar, P. & Pandikumar, A. Gold nanorod-based electrochemical sensing of small biomolecules: A review. Microchim Acta 184, 3069–3092 (2017). https://doi.org/10.1007/s00604-017-2418-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00604-017-2418-6