Abstract
Copper nanoclusters (Cu-NCs) were prepared by reducing CuCl2 with ascorbic acid in the presence of the short peptide template Cys-Cys-Cys-Asp-Leu. They were characterized by UV-vis absorption and fluorescence spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The Cu-NCs have a size of ~2 nm, can be well dispersed in water and are photostable. Their fluorescence (peaking at 425 nm under 365-nm excitation) is quenched by Fe(III) ions. Based on this finding, a sensitive and selective fluorescence assay for the detection of Fe(III) was developed. Under optimized conditions and a pH value of 2.0, the assay displays a linear response in the 0.05 to 30 μM Fe(III) concentration range, with a detection limit of 20 nM based on an S/N ratio of 3. The assay was successfully applied to the determination of Fe(III) in spiked human serum where is gave recoveries that ranged from 96.2 % to 98.3 %.
References
Nandre J, Patil S, Patil V, Yu F, Chen L, Sahoo S, Prior T, Redshaw C, Mahulikar P, Patil U (2014) A novel fluorescent “turn-on” chemosensor for nanomolar detection of Fe(III) from aqueous solution and its application in living cells imaging. Biosens Bioelectron 61:612–617
Chen Y, Wu Y, Weng B, Wang B, Li C (2016) Facile synthesis of nitrogen and sulfur co-doped carbon dots and application for Fe(III) ions detection and cell imaging. Sensors Actuators B Chem 223:689–696
Wang B, Hai J, Liu Z, Wang Q, Yang Z, Sun S (2010) Selective detection of iron(III) by rhodamine-modified Fe3O4 nanoparticles. Angew Chem Int Ed 49(27):4576–4579
Cairo G, Pietrangelo A (2000) Iron regulatory proteins in pathobiology. Biochem J 352:241–250
Kim H, Rao BA, Jeong J, Angupillai S, Choi JS, Nam J-O, Lee C-S, Son Y-A (2016) A rhodamine scaffold immobilized onto mesoporous silica as a fluorescent probe for the detection of Fe (III) and applications in bio-imaging and microfluidic chips. Sensors Actuators B Chem 224:404–412
Lynch SR (1997) Interaction of iron with other nutrients. Nutr Rev 55(4):102–110
Kim J, Kim YJ, Lee R, Moon JH, Jo I (2012) Serum levels of zinc, calcium, and iron are associated with the risk of preeclampsia in pregnant women. Nutr Res 32(10):764–769
Li L, Li L, Wang C, Liu K, Zhu R, Qiang H, Lin Y (2015) Synthesis of nitrogen-doped and amino acid-functionalized graphene quantum dots from glycine, and their application to the fluorometric determination of ferric ion. Microchim Acta 182(3–4):763–770
Wang F, Hao Q, Zhang Y, Xu Y, Lei W (2016) Fluorescence quenchometric method for determination of ferric ion using boron-doped carbon dots. Microchim Acta 183(1):273–279
Gupta VK, Mergu N, Kumawat LK (2016) A new multifunctional rhodamine-derived probe for colorimetric sensing of Cu(II) and Al(III) and fluorometric sensing of Fe(III) in aqueous media. Sensors Actuators B Chem 223:101–113
Bricks JL, Kovalchuk A, Trieflinger C, Nofz M, Buschel M, Tolmachev AI, Daub J, Rurack K (2005) On the development of sensor molecules that display Fe-III-amplified fluorescence. J Am Chem Soc 127(39):13522–13529
Luo J, Rasooly A, Wang L, Zeng K, Shen C, Qian P, Yang M, Qu F (2016) Fluorescent turn-on determination of the activity of peptidases using peptide templated gold nanoclusters. Microchim Acta 183(2):605–610
Quan H, Zuo C, Li T, Liu Y, Li M, Zhong M, Zhang Y, Qi H, Yang M (2015) Electrochemical detection of carcinoembryonic antigen based on silver nanocluster/horseradish peroxidase nanocomposite as signal probe. Electrochim Acta 176:893–897
Guo Q, Li X, Shen C, Zhang S, Qi H, Li T, Yang M (2015) Electrochemical immunoassay for the protein biomarker mucin 1 and for MCF-7 cancer cells based on signal enhancement by silver nanoclusters. Microchim Acta 182(7–8):1483–1489
Pei H, Zhu S, Yang M, Kong R, Zheng Y, Qu F (2015) Graphene oxide quantumdots@silver core–shell nanocrystals as turn-on fluorescent nanoprobe for ultrasensitive detection of prostate specific antigen. Biosens Bioelectron 74:909–914
Lu Y, Chen W (2012) Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries. Chem Soc Rev 41(9):3594
Díez I, Ras RHA (2011) Fluorescent silver nanoclusters. Nanoscale 3(5):1963
Shang L, Dong S, Nienhaus GU (2011) Ultra-small fluorescent metal nanoclusters: synthesis and biological applications. Nano Today 6(4):401–418
Shen C, Xia X, Hu S, Yang M, Wang J (2015) Silver nanoclusters-based fluorescence assay of protein kinase activity and inhibition. Anal Chem 87(1):693–698
Jin R (2010) Quantum sized, thiolate-protected gold nanoclusters. Nanoscale 2(3):343–362
Chen J, Liu J, Fang Z, Zeng L (2012) Random dsDNA-templated formation of copper nanoparticles as novel fluorescence probes for label-free lead ions detection. Chem Commun 48(7):1057–1059
Kang X, Mai Z, Zou X, Cai P, Mo J (2007) A sensitive nonenzymatic glucose sensor in alkaline media with a copper nanocluster/multiwall carbon nanotube-modified glassy carbon electrode. Anal Biochem 363(1):143–150
Shen J-S, Chen Y-L, Wang Q-P, Yu T, Huang X-Y, Yang Y, Zhang H-W (2013) In situ synthesis of red emissive copper nanoclusters in supramolecular hydrogels. J Mater Chem C 1(11):2092
Vilar-Vidal N, Blanco MC, Lopez-Quintela MA, Rivas J, Serra C (2010) Electrochemical synthesis of very stable photoluminescent copper clusters. J Phys Chem C 114(38):15924–15930
Huang H, Li H, Wang A-J, Zhong S-X, Fang K-M, Feng J-J (2014) Green synthesis of peptide-templated fluorescent copper nanoclusters for temperature sensing and cellular imaging. Analyst 139(24):6536–6541
Mu X, Qi L, Dong P, Qiao J, Hou J, Nie Z, Ma H (2013) Facile one-pot synthesis of l-proline-stabilized fluorescent gold nanoclusters and its application as sensing probes for serum iron. Biosens Bioelectron 49:249–255
Zhang W, Gan J (2016) Synthesis of blue-photoluminescent graphene quantum dots/polystyrenic anion-exchange resin for Fe(III) detection. App. Surf Sci 372:145–151
Acknowledgments
The authors are grateful to the National Key Basic Research Program of China (2014CB744502), the Special Foundation for State Major Basic Research Program of China (2015FY111100), the National Natural Science Foundation of China (No. 21575165) and the Natural Science Foundation of Hunan province (No. 2015JJ1019) for supporting this work.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
The author(s) declare that they have no competing interests.
Rights and permissions
About this article
Cite this article
Tang, T., Ouyang, J., Hu, L. et al. Synthesis of peptide templated copper nanoclusters for fluorometric determination of Fe(III) in human serum. Microchim Acta 183, 2831–2836 (2016). https://doi.org/10.1007/s00604-016-1935-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00604-016-1935-z