A new fluorescence turn-on sensing platform has been developed applicable for sensitive profiling of multiple chemical and biological analytes, using azobenzene-quantum dot as a new stimuli-responsive optical nanoprobe. An azobenzene-carrying compound bis [4, 4′-(dithiophenyl azo)-1, 3-benzenediamine] (DTPABDA) is for the first time reported to be used for conjugation with CdSe/ZnS core/shell quantum dots (QDs) via the ligand exchange reaction. Due to the photo-induced electron-transfer (PET) effect, the electron-withdrawing azobenzene groups of DTPABDA can significantly cause the photoluminescence (PL) of QDs quenched. The QDs’ PL can be subsequently reignited by the removal of azo moiety cleavable through three types of specific reactions: the dithionite reduction, hypochlorite oxidation, and azoreductase enzymatic catalysis, respectively. By monitoring of reaction-induced recovery of FL signals at 560 nm with an excitation of 450 nm, such azobenzene-QDs conjugates served as a new nanoprobe enabling the fluorescence turn-on sensing of dithionite, hypochlorite, and azoreductase with high sensitivity, broad linear range, and good selectivity. The successful detection of target analytes in real samples reveals the potential of our method in practical applications, such as biosensing, environmental and industrial monitoring.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Ashton TD, Jolliffe KA, Pfeffer FM (2015) Luminescent probes for the bioimaging of small anionic species in vitro and in vivo. Chem Soc Rev 44:4547–4595
Saberi Z, Rezaei B, Ensafi AA (2019) Fluorometric label-free aptasensor for detection of the pesticide acetamiprid by using cationic carbon dots prepared with cetrimonium bromide. Microchim Acta 186:273
Saad SM, Abdullah J, Rashid SA, Fen YW, Salam F, Yih LH (2019) A fluorescence quenching based gene assay for Escherichia coli O157:H7 using graphene quantum dots and gold nanoparticles. Microchim Acta 186:804
Hildebrandt N, Spillmann CM, Algar WR, Pons T, Stewart MH, Oh E, Susumu K, Diaz SA, Delehanty JB, Medintz IL (2017) Energy transfer with semiconductor quantum dot bioconjugates: a versatile platform for biosensing, energy harvesting, and other developing applications. Chem Rev 117:536–711
Ma Q, Su X (2011) Recent advances and applications in QDs-based sensors. Analyst 136:4883–4893
Zhang WH, Ma W, Long YT (2016) Redox-mediated indirect fluorescence immunoassay for the detection of disease biomarkers using dopamine-functionalized quantum dots. Anal Chem 88:5131–5136
Goryacheva OA, Mishra PK, Goryacheva IY (2018) Luminescent quantum dots for miRNA detection. Talanta 179:456–465
Nathiya D, Gurunathan K, Wilson J (2020) Size controllable, pH triggered reduction of bovine serum albumin and its adsorption behavior with SnO2/SnS2 quantum dots for biosensing application. Talanta 210:120671
Freitas M, Neves MMPS, Nouws HPA, Delerue-Matos C (2020) Quantum dots as nanolabels for breast cancer biomarker HER2-ECD analysis in human serum. 208:120430
Pehlivan ZS, Torabfam M, Kurt H, Ow-Yang C, Hildebrandt N, Yuce M (2019) Aptamer and nanomaterial based FRET biosensors: a review on recent advances (2014-2019). Microchim Acta 186:563
Saa L, Diez-Buitrago B, Briz N, Pavlov V (2019) CdS quantum dots generated in-situ for fluorometric determination of thrombin activity. Microchim Acta 186:657
Sadeghi S, Davami A (2020) CdSe quantum dots capped with a deep eutectic solvent as a fluorescent probe for copper(II) determination in various drinks. Microchim Acta 187:147
Berlina AN, Taranova NA, Zherdev AV, Sankov MN, Andreev IV, Martynov AI, Dzantiev BB (2013) Quantum-dot-based immunochromatographic assay for total IgE in human serum. PLoS One 8:e77485
Tomasulo M, Yildiz I, Kaanumalle SL, Raymo FM (2006) pH-sensitive ligand for luminescent quantum dots. Langmuir 22:10284–10290
Medintz IL, Stewart MH, Trammell SA, Susumu K, Delehanty JB, Mei BC, Melinger JS, Blanco-Canosa JB, Dawson PE, Mattoussi H (2010) Quantum-dot/dopamine bioconjugates function as redox coupled assemblies for in vitro and intracellular pH sensing. Nat Mater 9:676–684
Page LE, Zhang X, Jawaid AM, Snee PT (2011) Detection of toxic mercury ions using a ratiometric CdSe/ZnS nanocrystal sensor. Chem Commun 47:7773–7775
Amelia M, Lavie-Cambot A, McClenaghan ND, Credi A (2011) A ratiometric luminescent oxygen sensor based on a chemically functionalized quantum dot. Chem Commun 47:325–327
Sandros MG, Gao D, Benson DE (2005) A modular nanoparticle-based system for reagentless small molecule biosensing. J Am Chem Soc 127:12198–12199
Bahshi L, Freeman R, Gill R, Willner I (2009) Optical detection of glucose by means of metal nanoparticles or semiconductor quantum dots. Small 5:676–680
Yildiz I, Tomasulo M, Raymo FM (2006) A mechanism to signal receptor–substrate interactions with luminescent quantum dots. P Nat Acad Sci U S A 103:11457–11460
Chevalier A, Renard PY, Romieu A (2014) Straightforward synthesis of bioconjugatable azo dyes. Part 1: Black Hole Quencher-1 (BHQ-1) scaffold. Tetrahedron Lett 55:6759–6763
Lei H, Mo M, He Y, Wu Y, Zhu W, Wu L (2019) Bioactivatable reductive cleavage of azobenzene for controlling functional dumbbell oligodeoxynucleotides. Bioorg Chem 91:103106
Yang YY, Grammel M, Raghavan AS, Charron G, Hang HC (2010) Comparative analysis of cleavable azobenzene-based affinity tags for bioorthogonal chemical proteomics. Chem Biol 17:1212–1222
Lou X, Zhang Y, Qin J, Li Z (2012) Colorimetric hypochlorite detection using an azobenzene acid in pure aqueous solutions and real application in tap water. Sensor Actuat B: Chem 161:229–234
Medina SH, Chevliakov MV, Tiruchinapally G, Durmaz YY, Kuruvilla SP, ElSayed MEH (2013) Enzyme-activated nanoconjugates for tunable release of doxorubicin in hepatic cancer cells. Biomaterials 34:4655–4666
Phillips JH Jr, Robrish SA, Bates C (1965) High efficiency coupling of diazonium ions to proteins and amino acids. J Biol Chem 240:699–704
Dai MQ, Yung LYL (2013) Ethylenediamine-assisted ligand exchange and phase transfer of oleophilic quantum dots: stripping of original ligands and preservation of photoluminescence. Chem Mater 25:2193–2201
Li N, Ye JS, Ma Y (2019) Stimuli-responsive SERS nanoprobes for multiplexing detection. Sensor Actuat B-Chem 281:977–982
Jo J, Lee HY, Liu WJ, Olasz A, Chen CH, Lee D (2012) Reactivity-based detection of copper(II) ion in water: oxidative cyclization of azoaromatics as fluorescence turn-on signaling mechanism. J Am Chem Soc 134:16000–16007
Hooker JM, Kovacs EW, Francis MB (2004) Interior surface modification of bacteriophage MS2. J Am Chem Soc 126:3718–3719
Xing P, Gao K, Wang B, Gao J, Yan H, Wen J, Li W, Xu Y, Li H, Chen J, Wang W, Sun S (2016) HEPES is not suitable for fluorescence detection of HClO: a novel probe for HClO in absolute PBS. Chem Commun 52:5064–5066
Rao JY, Khan A (2013) Enzyme sensitive synthetic polymer micelles based on the azobenzene motif. J Am Chem Soc 135:14056–14059
Islam MS, Honma M, Nakabayashi T, Kinjo M, Ohta N (2013) pH dependence of the fluorescence lifetime of FAD in solution and in cells. Int J Mol Sci 14:1952–1963
Szajewski RP, Whitesides GM (1980) Rate constants and equilibrium constants for thiol-disulfide interchange reactions involving oxidized glutathione. J Am Chem Soc 102:2011–2026
Cingarapu S, Yang ZQ, Sorensen CM, Klabunde KJ (2012) Synthesis of CdSe/ZnS and CdTe/ZnS quantum dots: refined digestive ripening. J Nanomater 2:7
Chen S, Bao L, Ou EC, Peng C, Wang WM, Xu WJ (2015) A cationic azobenzene-surfactant-modified graphene hybrid: unique photoresponse and electrochemical behavior. Nanoscale 7:19673–19686
Crisalli P, Kool ET (2011) Multi-path quenchers: efficient quenching of common fluorophores. Bioconjug Chem 22:2345–2354
Kilroy WP (1983) Analysis of mixtures of sulphide, thiosulphate, dithionite and sulphite. Talanta 30:419–422
De Wael K, Westbroek P, Temmerman E (2005) Electrocatalytic oxidation of dithionite at a cobalt(II)tetrasulfonated phthalocyanine and 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin cobalt(II) modified gold electrode in alkaline solution. Electroanalysis 17:263–268
Zhu H, Fan J, Wang J, Mu H, Peng X (2014) An “enhanced PET”-based fluorescent probe with ultrasensitivity for imaging basal and elesclomol-induced HClO in cancer cells. J Am Chem Soc 136:12820–12823
Xiao HD, Xin K, Dou HF, Yin G, Quan YW, Wang RY (2015) A fast-responsive mitochondria-targeted fluorescent probe detecting endogenous hypochlorite in living RAW 264.7 cells and nude mouse. Chem Commun 51:1442–1445
Kiyose K, Hanaoka K, Oushiki D, Nakamura T, Kajimura M, Suematsu M, Nishimatsu H, Yamane T, Terai T, Hirata Y, Nagano T (2010) Hypoxia-sensitive fluorescent probes for in vivo real-time fluorescence imaging of acute ischemia. J Am Chem Soc 132:15846–15848
Cao J, Campbell J, Liu L, Mason RP, Lippert AR (2016) In vivo chemiluminescent imaging agents for nitroreductase and tissue oxygenation. Anal Chem 88:4995–5002
Xie D, King TL, Banerjee A, Kohli V, Que EL (2016) Exploiting copper redox for 19F magnetic resonance-based detection of cellular hypoxia. J Am Chem Soc 138:2937–2940
Li YH, Sun Y, Li JC, Su QQ, Yuan W, Dai Y, Han CM, Wang QH, Feng W, Li FY (2015) Ultrasensitive near-infrared fluorescence-enhanced probe for in vivo nitroreductase imaging. J Am Chem Soc 137:6407–6416
Liu JN, Liu Y, Bu WB, Bu JW, Sun Y, Du JL, Shi JL (2014) Ultrasensitive nanosensors based on upconversion nanoparticles for selective hypoxia imaging in vivo upon near-infrared excitation. J Am Chem Soc 136:9701–9709
This work was supported by the Guangdong Basic and Applied Basic Research Foundation (2020A1515010957), the Fundamental Research Funds for the Central Universities (No. 21618414), the Open Funds of the State Key Laboratory of Electroanalytical Chemistry (No. SKLEAC201903), and the Guangdong Innovative and Entrepreneurial Research Team Program (No. 2014ZT05S136).
Conflict of interest
The author(s) declare that they have no competing interests.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
About this article
Cite this article
Zha, Y., Xin, R., Zhang, M. et al. Stimuli-responsive azobenzene-quantum dots for multi-sensing of dithionite, hypochlorite, and azoreductase. Microchim Acta 187, 481 (2020). https://doi.org/10.1007/s00604-020-04455-9
- Quantum dots
- Fluorescent nanoprobe
- Chemical sensors