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Electrostatically controlled fluorometric assay for differently charged biotargets based on the use of silver/copper bimetallic nanoclusters modified with polyethyleneimine and graphene oxide

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Abstract

An electrostatically controlled fluorometric assay is described that is based on the use of silver/copper bimetallic nanoclusters. The nanoclusters were coated with polyethyleneimine (PEI-Ag/CuNCs). At pH 7.4, these particles are positively charged. Their blue fluorescence (with excitation/emission peaks at 341/464 nm) depends on local pH values and temperature. If graphene oxide (which is negatively charged at pH 7.4) is introduced, the fluorescence of the PEI-Ag/CuNCs is quenched. Based on various electrostatic interactions, three kinds of biomacromolecules were detected by fluorometry. These include (negatively charged) heparin, (positively charged) protamine, and (virtually uncharged) trypsin. Heparin is detected by using GO/PEI-Ag/CuNCs, protamine by using GO/heparin/PEI-Ag/CuNCs, and trypsin by using GO/protamine/heparin/PEI-Ag/CuNC. The detection limits and linear ranges are 4.8 nM and 10–450 nM for heparin, 0.09 μg·mL−1 and 0.25–5 μg·mL−1 for protamine, and 0.03 μg·mL−1 and 0.05–1 μg·mL−1 for trypsin. Zeta potentials of the various substances in the system were determined to elucidate the detection mechanism. Comceivably, the method provides a widely applicable approach for electrostatically controlled biomolecular assays.

Schematic presentation of electrostatically controlled fluorometric assay for the detection of heparin, protamine, and trypsin based on the silver/copper bimetallic nanoclusters modified with polyethyleneimine and graphene oxide.

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References

  1. Chen LJ, Ren YY, Wu NW, Sun B, Ma JQ, Zhang L, Tan H, Liu M, Li X, Yang HB (2015) Hierarchical self-assembly of discrete organoplatinum(II) metallacycles with polysaccharide via electrostatic interactions and their application for heparin detection. J Am Chem Soc 137:11725–11735

    Article  CAS  PubMed  Google Scholar 

  2. Lee DN, Bae S, Han K, Shin IS, Kim SK, Hong JI (2017) Electrostatic modification for promotion of flavin-mediated oxidation of a probe for flavin detection. Chem Eur J 23:16078–16084

    Article  CAS  PubMed  Google Scholar 

  3. Wu Y, Huang S, Zeng F, Wang J, Yu C, Huang J, Xie H, Wu S (2015) A ratiometric fluorescent system for carboxylesterase dtection with AIE dots as FRET donors. Chem Commun 51:12791–12794

    Article  CAS  Google Scholar 

  4. Fan X, Zhang D, Li H, Sun S, Xu Y (2017) A BSA-squaraine hybrid system for selectively detecting ag+ in absolute PBS and sequential construction of logic functions. Sensors Actuators B Chem 245:290–296

    Article  CAS  Google Scholar 

  5. Jiang G, Wang J, Yang Y, Zhang G, Liu Y, Lin H, Zhang G, Li Y, Fan X (2016) Fluorescent turn-on sensing of bacterial lipopolysaccharide in artificial urine sample with sensitivity down to nanomolar by tetraphenylethylene based aggregation induced emission molecule. Biosens Bioelectron 85:62–67

    Article  CAS  PubMed  Google Scholar 

  6. Liu J, Liu G, Liu W, Wang Y, Xu M, Wang B (2016) Turn-on fluorometric β-carotene assay based on competitive host-guest interaction between rhodamine 6G and β-carotene with a graphene oxide functionalized with a β-cyclodextrin-modified polyethyleneimine. Microchim Acta 183:1161–1168

    Article  CAS  Google Scholar 

  7. Liu G, Huang X, Zheng S, Li L, Xu D, Xu X, Zhang Y, Lin H (2018) Novel triadimenol detection assay based on fluorescence resonance energy transfer between gold nanoparticles and cadmium telluride quantum dots. Dyes Pigments 149:229–235

    Article  CAS  Google Scholar 

  8. Xie H, Bei F, Hou J, Ai S (2018) A highly sensitive dual-signaling assay via inner filter effect between g-C3N4 and gold nanoparticles for organophosphorus pesticides. Sensors Actuators B Chem 55:2232–2239

    Article  CAS  Google Scholar 

  9. Zhang Y, Li Y, Zhang C, Zhang Q, Huang X, Yang M, Shahzad SA, Lo KK, Yu C, Jiang S (2017) Fluorescence turn-on detection of alkaline phosphatase activity based on controlled release of PEI-capped cu nanoclusters from MnO2 nanosheets. Anal Bioanal Chem 409:4771–4778

    Article  CAS  Google Scholar 

  10. Chen J, Liao D, Wang Y, Zhou H, Li W, Yu C (2013) Real-time fluorometric assay for acetylcholinesterase activity and inhibitor screening through the pyrene probe monomer-excimer transition. Org Lett 15(9):2132–2135

    Article  CAS  PubMed  Google Scholar 

  11. Hu Q, Zeng F, Wu S (2016) A ratiometric fluorescent probe for hyaluronidase detection via hyaluronan-induced formation of red-light emitting excimers. Biosens Bioelectron 79:776–783

    Article  CAS  PubMed  Google Scholar 

  12. Fang J, Zhang B, Yao Q, Yang Y, Xie J, Yan N (2016) Recent advances in the synthesis and catalytic applications of ligand-protected, atomically precise metal nanoclusters. Coord Chem Rev 322:1–29

    Article  CAS  Google Scholar 

  13. Yue D, Wang M, Deng F, Yin W, Zhao H, Zhao X, Xu Z (2018) Biomarker-targeted fluorescent probes for breast cancer imaging. Chinese Chem Lett 29:648–656

    Article  CAS  Google Scholar 

  14. Zhou TY, Lin LP, Rong MC, Jiang YQ, Chen X (2013) Silver-gold alloy nanoclusters as a fluorescence-enhanced probe for aluminum ion sensing. Anal Chem 85:9839–9844

    Article  CAS  PubMed  Google Scholar 

  15. Yao Q, Feng Y, Fung V, Yu Y, Jiang DE, Yang J, Xie J (2017) Precise control of alloying sites of bimetallic nanoclusters via surface motif exchange reaction. Nat Commun 8:1555

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Wang C, Cheng H, Sun Y, Xu Z, Lin H, Lin Q, Zhang C (2014) Nanoclusters prepared from a silver/gold alloy as a fluorescent probe for selective and sensitive determination of lead(II). Microchim Acta 182:695–701

    Article  CAS  Google Scholar 

  17. Zhang N, Si Y, Sun Z, Chen L, Li R, Qiao Y, Wang H (2014) Rapid, selective, and ultrasensitive fluorimetric analysis of mercury and copper levels in blood using bimetallic gold-silver nanoclusters with "silver effect"-enhanced red fluorescence. Anal Chem 86:11714–11721

    Article  CAS  PubMed  Google Scholar 

  18. Sun J, Yang F, Zhao D, Chen C, Yang X (2015) Integrated logic gate for fluorescence turn-on detection of histidine and cysteine based on ag/au bimetallic nanoclusters-Cu2+ ensemble. ACS Appl Mater Interfaces 7:6860–6866

    Article  CAS  PubMed  Google Scholar 

  19. Li W, Li W, Hu Y, Xia Y, Shen Q, Nie Z, Huang Y, Yao S (2013) A fluorometric assay for acetylcholinesterase activity and inhibitor detection based on DNA-templated copper/silver nanoclusters. Biosens Bioelectron 47:345–349

    Article  CAS  PubMed  Google Scholar 

  20. Mehta PK, Lee H, Lee KH (2017) Highly sensitive ratiometric detection of heparin and its oversulfated chondroitin sulfate contaminant by fluorescent peptidyl probe. Biosens Bioelectron 91:545–552

    Article  CAS  PubMed  Google Scholar 

  21. Rao H, Ge H, Wang X, Zhang Z, Liu X, Yang Y, Liu Y, Liu W, Zou P, Wang Y (2017) Colorimetric and fluorometric detection of protamine by using a dual-mode probe consisting of carbon quantum dots and gold nanoparticles. Microchim Acta 184:3017–3025

    Article  CAS  Google Scholar 

  22. Kim D, Kim J, Lee TS (2018) Dual-signal detection of trypsin using controlled aggregation of conjugated polymer dots and magnetic nanoparticles. Sensors Actuators B Chem 264:45–51

    Article  CAS  Google Scholar 

  23. Liu Q, Lai Q, Li N, Su X (2018) Copper nanoclusters capped with tannic acid as a fluorescent probe for real-time determination of the activity of pyrophosphatase. Microchim Acta 185:182

    Article  CAS  Google Scholar 

  24. Liu C, Ding Y, Li Q, Lin Y (2017) Photochemical synthesis of glutathione-stabilized silver nanoclusters for fluorometric determination of hydrogen peroxide. Microchim Acta 184:2497–2503

    Article  CAS  Google Scholar 

  25. Huang X, Shahzad SA, Li Y, Zhang Y, Sang L, Zhou H, Jiang H, Kam-Wing Lo K, Yu C (2017) Silver nanoclusters capped silica nanoparticles as a ratiometric photoluminescence nanosensor for the selective detection of I and S2−. Anal Chim Acta 988:74–80

    Article  CAS  PubMed  Google Scholar 

  26. Liu ZC, Qi JW, Hu C, Zhang L, Song W, Liang RP, Qiu JD (2015) Cu nanoclusters-based ratiometric fluorescence probe for ratiometric and visualization detection of copper ions. Anal Chim Acta 895:95–103

    Article  CAS  PubMed  Google Scholar 

  27. Qu F, Zou X, Kong R, You J (2016) A tunable pH-sensing system based on ag nanoclusters capped by hyperbranched polyethyleneimine with different molecular weights. Talanta 146:549–555

    Article  CAS  PubMed  Google Scholar 

  28. Kong L, Chu X, Wang C, Zhou H, Wu Y, Liu W (2018) D-penicillamine-coated cu/ag alloy nanocluster superstructures: aggregation-induced emission and tunable photoluminescence from red to orange. Nanoscale 10:1631–1640

    Article  CAS  PubMed  Google Scholar 

  29. Xiong H, Wang W, Liang J, Wen W, Zhang X, Wang S (2017) A convenient purification method for metal nanoclusters based on pH-induced aggregation and cyclic regeneration and its applications in fluorescent pH sensors. Sensors Actuators B Chem 239:988–992

    Article  CAS  Google Scholar 

  30. Qu F, Li NB, Luo HQ (2013) Highly sensitive fluorescent and colorimetric pH sensor based on polyethylenimine-capped silver nanoclusters. Langmuir 29:1199–1205

    Article  CAS  PubMed  Google Scholar 

  31. Lan J, Zou H, Liu Z, Gao M, Chen B, Li Y, Huang C (2015) A visual physiological temperature sensor developed with gelatin-stabilized luminescent silver nanoclusters. Talanta 143:469–473

    Article  CAS  PubMed  Google Scholar 

  32. Sailapu SK, Sahoo AK, Ghosh SS, Chattopadhyay A (2014) Hierarchical logic structures based on responsive fluorescent gold nanoclusters. Small 10:4067–4071

    Article  CAS  PubMed  Google Scholar 

  33. Zu F, Yan F, Bai Z, Xu J, Wang Y, Huang Y, Zhou X (2017) The quenching of the fluorescence of carbon dots: a review on mechanisms and applications. Microchim Acta 184:1899–1914

    Article  CAS  Google Scholar 

  34. Ling Y, Gao ZF, Zhou Q, Li NB, Luo HQ (2015) Multidimensional optical sensing platform for detection of heparin and reversible molecular logic gate operation based on the phloxine B/polyethyleneimine system. Anal Chem 87:1575–1581

    Article  CAS  PubMed  Google Scholar 

  35. Cai L, Zhan R, Pu KY, Qi X, Zhang H, Huang W, Liu B (2011) Butterfly-shaped conjugated oligoelectrolyte/graphene oxide integrated assay for light-up visual detection of heparin. Anal Chem 83:7849–7855

    Article  CAS  PubMed  Google Scholar 

  36. Chen H, Fang A, Zhang Y, Yao S (2017) Silver triangular nanoplates as an high efficiently FRET donor-acceptor of upconversion nanoparticles for ultrasensitive "turn on-off" protamine and trypsin sensor. Talanta 174:148–155

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

The project was supported by State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, China (2019-4).

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Correspondence to Qiong Jia.

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Yang, J., Song, N. & Jia, Q. Electrostatically controlled fluorometric assay for differently charged biotargets based on the use of silver/copper bimetallic nanoclusters modified with polyethyleneimine and graphene oxide. Microchim Acta 186, 70 (2019). https://doi.org/10.1007/s00604-018-3179-6

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