Abstract
We synthesized a tetra-functional fluorescence probe based on dansyl and peptide motif, dansyl-Gly-Trp (DGT, 1), that efficiently bound several metal ions and showed distinguishing optical properties. The probe 1 could respond to Hg2+ with enhanced and blue-shifted fluorescence emission but to Cu2+ with obvious fluorescence quenching. In addition, 1 was sensitive to pH ranging from 2.0 to 5.0 and precipitated in the presence of Pb2+ at neutral conditions. The combination of these intrinsic properties with the selective responses to different chemical inputs allows this system to be implemented as an ionic switch. Furthermore, 1 could penetrate the cell membrane and accumulated well in intracellular region. The underlying mechanisms of the probe to different kind of metal ion were explored successfully by using either 1H NMR, NOESY, electron paramagnetic resonance (EPR) or FT-IR spectra. In addition, to investigate the binding model of 1/Hg2+ and 1/Cu2+, simulations were also performed by using density functional theory (DFT) and reasonable binding configurations were achieved for these two complexes.
Similar content being viewed by others
References
McRae R, Bagchi P, Sumalekshmy S, Fahrni CJ (2009) In situ imaging of metals in cells and tissues. Chem Rev 109(10):4780–4827
Nolan EM, Lippard SJ (2008) Tools and tactics for the optical detectin of mercuric ion. Chem Rev 108(9):3443–3480
Que EL, Domaille DW, Chang CJ (2008) Metals in neurobiology: probing their chemistry and biology with molecular imaging. Chem Rev 108(5):1517–1549
Kou S, Lee HN, van Noort D, Swamy KMK, Kim SH, Soh JH, Lee K-M, Nam S-W, Yoon J, Park S (2008) Fluorescent molecular logic gates using microfluidic devices. Angew Chem Int Ed 47(5):872–876
Suresh M, Ghosh A, Das A (2008) A simple chemosensor for Hg2+ and Cu2+ that works as a molecular keypad lock. Chem Commun 23(33):3906–3908
Dhir A, Bhalla V, Kumar M (2008) Ratiometric sensing of Hg2+ based on the calix[4]arene of partial cone conformation possessing a dansyl moiety. Org Lett 10(21):4891–4894
Kaur N, Singh N, Cairns D, Callan JF (2009) A multifunctional tripodal fluorescent probe: “off-on” detection of sodium as well as two-input and molecular logic behavior. Org Lett 11(11):2229–2232
Ma L, Liu Y, Wu Y (2006) A tryptophan-containing fluoroionophore sensor with high sensitivity to and selectivity for lead ion in water. Chem Commun 21(25):2702–2704
Ma L, Li Y, Li L, Sun J, Tian C, Wu Y (2008) A protein-supported fluorescent reagent for the highly-sensivive and selective detection of mercuy ions in aqueous solution and live cells. Chem Commun 23(47):6345–6437
Li H-W, Li Y, Dang Y-Q, Ma L-J, Wu Y, Hou G, Wu L (2009) An easily prepared hypersensitive water-soluble fluorescent probe for mercury(II) ions. Chem Commun 24(29):4453–4455
Joshi BH, Park J, Lee WI, Lee KH (2009) Ratiometric and turn-on monitoring for heavy and transition metal ions in aqueous solution with a fluorescent peptide sensor. Talanta 78(3):903–909
Zheng Y, Leblanc RM (2002) A dansylated peptide for the selective detection of copper ions. Chem Commun 17(20):2350–2351
Berton M, Mancin F, Stocchero G, Tecilla P, Tonellato U (2001) Self-assembling in surfactant aggregates: an alternative way to the realization of fluorescence chemosensors for Cu(II) ions. Langmuir 17(24):7521–7528
Zheng Y, Leblanc RM (2003) Peptidyl fluorescent chemosensors for the detection of divalent copper. Anal Chem 75(7):1706–1712
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE Jr, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision A. 02 Gaussian, Inc., Wallingford
Taki M, Desaki M, Ojida A, Iyoshi S, Hirayama T, Hamachi I, Yamamoto Y (2008) Fluorescnece imaging of intracellular cadmium using a dual-excitation rationmetric chemosensor. J Am Chem Soc 130(38):12564–12565
Metiver R, Leray I, Valeur B (2004) Photophysics of calixarenes bearing two or four dansyl fluorophores: charge, proton and energy transfers. Photochem Photobiol Sci 3(4):374–380
Chandrasekhar V, Bag P, Pandey MD (2009) Phosphorus-supported multidentate coumarin-containing fluorescence sensor for Cu2+. Tetrahedron 65(47):9876–9883
Rurack K, Resch-Genger U (2002) Rigidization, preorientation and electronic decoupling- the ‘magic triangle’ for the design of highly efficient fluorescent sensors and switches. Chem Soc Rev 31(2):116–127
Bag B, Bharadwaj PK (2005) Perturbation of the PET process in fluorophore-spacer-receptor systems through structural modification: transition metal induced fluorescence enhancement and selectivity. J Phys Chem B 109(10):4377–4390
Bi X, Heng CH, Yang K-L (2008) A method of obtaining high selectivity for copper ions on triglycine decorated surfaces. J Phys Chem C 112(33):12887–12893
The U.S. Enviromental Protection Agency (EPA) has set the limit of copper in drinking water to be 1.3 ppm (∼20 μM)
Wang J, Wang D, Miller EK, Moses D, Bazan GC and Heeger AJ (2000) Photoluminescence of water-soluble conjugated polymers: origin of enhanced quenching by charge transfer. Macromolecules 33(14):5153–5158
Deacon GB, Phillips RH (1980) Relationships between the carbon-oxygen stretching frequencies of carboxylate complexes and the type of carboxylate coordination. Coord Chem Rev 33(3):227–250
Nakamoto K (1986) Infrared and Raman spectra. Wiley, New York
Wold CR, Ni H, Soucek MK (2001) Model reaction study on the interaction between the inorganic and organic phases in drying oil based creamer coatings. Chem Mater 13(9):3032–3037
Ren Y, Iimura KI, Ogawa A, Kato T (2001) Surface micelles of CF3(CF2)(7)(CH2)(10)COOH on aqueous La3+ subphase investigated by atomic force microscopy and infrared spectroscopy. J Phys Chem B 105(19):4305–4312
Finnie KS, Bartlett JR, Woolfrey JL (1998) Vibrational spectroscopic study of the coordination of (2,2-‘-bipyridyl-4,4’-dicarboxylic acid) ruthenium (II) complexes to the surface of nanocrystalline titania. Langmuir 14(10):2744–2749
Ma L-J, Li H-W, Wu Y (2009) A pyrene-containing fluorescent sensor with high selectivity for Lead (II) ion in water with dual illustration of ground-state dimer. Sens Actuators B 143(1):25–29
Acknowledgements
The authors are grateful to the projects of the Natural Science Foundation of China (No. 20934002 and 20973073), the National Basic Research Program (2007CB808006), the Programs for New Century Excellent Talents in University (NCET) and the 111 Project (B06009).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
Supporting Informations (DOC 1.87 mb)
Rights and permissions
About this article
Cite this article
Wang, B., Li, HW., Gao, Y. et al. A Multifunctional Fluorescence Probe for the Detection of Cations in Aqueous Solution: the Versatility of Probes Based on Peptides. J Fluoresc 21, 1921–1931 (2011). https://doi.org/10.1007/s10895-011-0891-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10895-011-0891-6