Microchimica Acta

, Volume 181, Issue 13–14, pp 1529–1539 | Cite as

Hybrid fluorescent nanoparticles fabricated from pyridine-functionalized polyfluorene-based conjugated polymer as reversible pH probes over a broad range of acidity-alkalinity

Original Paper

Abstract

Conjugated polymer nanoparticles (CPNs) were developed based on a polyfluorene-based conjugated polymer with thiophene units carrying pyridyl moieties incorporated in the backbone of polymer chains (PFPyT). Hybrid CPNs fabricated from PFPyT and an amphiphilic polymer (NP1) displayed pH-sensitive fluorescence emission features in the range from pH 4.8 to 13, which makes them an attractive nanomaterial for wide range optical sensing of pH values. The fluorescence of hybrid CPNs based on chemically close polyfluorene derivatives without pyridyl moieties (NP3), in contrast, remains virtually unperturbed by pH values in the same range. The fluorescence emission features of NP1 underwent fully reversible changes upon alternating acidification/basification of aqueous dispersions of the CPNs and also displayed excellent repeatability. The observed pH sensing properties of NP1 are attributed to protonation/deprotonation of the nitrogen atoms of the pyridine moieties. This, in turn, leads to the redistribution of electron density of pyridine moieties and their participation in the π-conjugation within the polymer main chains. The optically transparent amphiphilic polymers also exerted significant influence on the pH sensing features of the CPNs, likely by acting as proton sponge and/or acid chaperone.

Figure

pH-sensitive fluorescent nanoparticles were fabricated from pyridine-functionalized conjugated polymer; protonation/deprotonation of the nitrogen atoms of pyridine moieties upon pH changes, which leads to the redistribution of electron density of pyridine moieties and their participation in the π-conjugation with polymer chains, were confirmed.

Keywords

Conjugated polymer nanoparticles Fluorescence pH sensing Protonation 

Notes

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant no. 21173262, 21373218) and the “Hundred-Talent Program” of CAS to Z. Tian.

References

  1. 1.
    Roos A, Boron WF (1981) Intracellular pH. Physiol Rev 61:296–434Google Scholar
  2. 2.
    Young BP, Shin JJH, Orij R, Chao JT, Li SC, Guan XL, Khong A, Jan E, Wenk MR, Prinz WA, Smits GJ, Loewen CJR (2010) Phosphatidic acid is a pH biosensor that links membrane biogenesis to metabolism. Science 329:1085–1088CrossRefGoogle Scholar
  3. 3.
    Roy I, Gupta MN (2003) Smart polymeric materials: emerging biochemical applications. Chem Biol 10:1161–1171CrossRefGoogle Scholar
  4. 4.
    Fog A, Buck RP (1984) Electronic semiconducting oxides as pH sensors. Sensors Actuators 5:137–146CrossRefGoogle Scholar
  5. 5.
    Swindlehurst BR, Narayanaswamy R (2004) Optical sensing of pH in low ionic strength waters. In: Narayanaswamy R, Wolfbeis OS (ed) Optical sensors industrial environmental and diagnostic applications. Springer-Verlag, Berlin Heidelberg 12, pp 281–308Google Scholar
  6. 6.
    Johnson I, Spencer MTZ (2010) The molecular probes handbook, 11th edn. Life Technologies, CaliforniaGoogle Scholar
  7. 7.
    Lakowicz JR (2006) Principles of fluorescence spectroscopy. Springer, BerlinCrossRefGoogle Scholar
  8. 8.
    Krulwich TA, Sachs G, Padan E (2011) Molecular aspects of bacterial pH sensing and homeostasis. Nat Rev Microbiol 9:330–343CrossRefGoogle Scholar
  9. 9.
    Miesenböck G, Angelis DAD, Rothman JE (1998) Visualizing secretion and synaptic transmission with pH-sensitive green fluorescent proteins. Nature 394:192–195CrossRefGoogle Scholar
  10. 10.
    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 9:676–684CrossRefGoogle Scholar
  11. 11.
    Wang XD, Stolwijk JA, Lang T, Sperber M, Meier RJ, Wegener J, Wolfbeis OS (2012) Ultra-Small, highly stable and sensitive dual nanosensors for imaging intracellular oxygen and pH in cytosol. J Am Chem Soc 134:17011–17014CrossRefGoogle Scholar
  12. 12.
    Han JY, Burgess K (2010) Fluorescent indicators for intracellular pH. Chem Rev 110:2709–2728CrossRefGoogle Scholar
  13. 13.
    Smith AM, Duan HW, Mohs AM, Nie SM (2008) Bioconjugated quantum dots for in vivo molecular and cellular imaging. Adv Drug Deliv Rev 60:1226–1240CrossRefGoogle Scholar
  14. 14.
    Lewinski N, Colvin V, Drezek R (2008) Cytotoxicity of nanoparticles. Small 4:26–49CrossRefGoogle Scholar
  15. 15.
    Albertazzi L, Storti B, Marchetti L, Beltram F (2010) Delivery and subcellular targeting of dendrimer-based fluorescent pH sensors in living cells. J Am Chem Soc 132:18158–18167CrossRefGoogle Scholar
  16. 16.
    Gao XH, Yang LL, Petros JA, Marshal FF, Simons JW, Nie SM (2005) In vivo molecular and cellular imaging with quantum dots. Curr Opin Biotechnol 16:63–72CrossRefGoogle Scholar
  17. 17.
    Kim HN, Guo ZQ, Zhu WH, Yoon J, Tian H (2011) Recent progress on polymer-based fluorescent and colorimetric chemosensors. Chem Soc Rev 40:79–93CrossRefGoogle Scholar
  18. 18.
    Thomas SW, Joly GD, Swager TM (2007) Chemical sensors based on amplifying fluorescent conjugated polymers. Chem Rev 107:1339–1386CrossRefGoogle Scholar
  19. 19.
    Feng XL, Liu LB, Wang S, Zhu DB (2010) Water-soluble fluorescent conjugated polymers and their interactions with biomacromolecules for sensitive biosensors. Chem Soc Rev 39:2411–2419CrossRefGoogle Scholar
  20. 20.
    Tian ZY, Yu JB, Wu CF, Szymanski C, McNeill J (2010) Amplified energy transfer in conjugated polymer nanoparticle tags and sensors. Nanoscale 2:1999–2011CrossRefGoogle Scholar
  21. 21.
    Wu CF, Chiu DT (2013) Highly fluorescent semiconducting polymer dots for biology and medicine. Angew Chem Int Ed 52:3086–3109CrossRefGoogle Scholar
  22. 22.
    Chan YH, Wu CF, Ye FM, Jin YH, Smith PB, Chiu DT (2011) Development of ultrabright semiconducting polymer dots for ratiometric pH sensing. Anal Chem 83:1448–1455CrossRefGoogle Scholar
  23. 23.
    Zhang Y, Hörnfeldt AB, Gronowitz S (1995) Pyridine-substituted hydroxythiophenes. IV. Preparation of 3- and 4-(2-, 3- and 4- Pyridyl)-2-hydroxythiophenes. J Heterocycl Chem 32:435–444CrossRefGoogle Scholar
  24. 24.
    Lu G, Usta H, Risko C, Wang L, Facchetti A, Ratner MA, Marks TJ (2008) Synthesis, characterization, and transistor response of semiconducting silole polymers with substantial hole mobility and air stability. Experiment and theory. J Am Chem Soc 130:7670–7685CrossRefGoogle Scholar
  25. 25.
    Liu H, Hao X, Duan CH, Yang H, Lv Y, Xu HJ, Wang HD, Huang F, Xiao DB, Tian ZY (2013) Al3+-induced far-red fluorescence enhancement of conjugated polymer nanoparticles and its application in live cell imaging. Nanoscale 5:9340–9347CrossRefGoogle Scholar
  26. 26.
    Yang H, Duan CH, Wu YS, Lv Y, Liu H, Lv YL, Xiao DB, Huang F, Fu HB, Tian ZY (2013) Conjugated polymer nanoparticles with Ag+-sensitive fluorescence emission: a new insight into the cooperative recognition mechanism. Part Part Syst Charact 30:972–980CrossRefGoogle Scholar
  27. 27.
    Huynh HV, He XM, Baumgartner T (2013) Halo chromic generation of white light emission using a single dithienophosphole luminophore. Chem Commun 49:4899–4901CrossRefGoogle Scholar
  28. 28.
    Stolar M, Baumgartner T (2012) Synthesis and unexpected halochromism of carbazole-functionalized dithienophospholes. New J Chem 36:1153–1160CrossRefGoogle Scholar
  29. 29.
    Romero-Nieto C, Durben S, Kormos IM, Baumgartner T (2009) Simple and efficient generation of white light emission from organophosphorus building blocks. Adv Funct Mater 19:3625–3631CrossRefGoogle Scholar
  30. 30.
    Zalar P, Henson ZB, Welch GC, Bazan GC, Nguyen TQ (2012) Color tuning in polymer light-emitting diodes with lewis acids. Angew Chem Int Ed 124:7613–7616CrossRefGoogle Scholar
  31. 31.
    Zhang X, Rehm S, Safont-Sempere MM, Würthner F (2009) Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems. Nat Chem 1:623–629CrossRefGoogle Scholar
  32. 32.
    Peng HS, Stolwijk JA, Sun LN, Wegener J, Wolfbeis OS (2010) A nanogel for ratiometric fluorescent sensing of intracellular pH values. Angew Chem Int Ed 49:4246–4249CrossRefGoogle Scholar
  33. 33.
    Yang ZY, Qin W, Lam JWY, Chen SJ, Sung HHY, Williams ID, Tang BZ (2013) Fluorescent pH sensor constructed from a heteroatom-containing luminogen with tunable AIE and ICT characteristics. Chem Sci 4:3725–3730CrossRefGoogle Scholar
  34. 34.
    Wen QS, Liu LB, Yang Q, Lv FT, Wang S (2013) Dopamine-modified cationic conjugated polymer as a new platform for pH sensing and autophagy imaging. Adv Funct Mater 23:764–769CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Wien 2014

Authors and Affiliations

  1. 1.School of Chemistry & Chemical EngineeringUniversity of Chinese Academy of Sciences (UCAS)BeijingChina
  2. 2.Laboratory for Nanomaterials, National Center for Nanoscience and TechnologyBeijingChina
  3. 3.Beijing National Laboratory for Molecular Science (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, and Key Laboratory for Photochemistry, Institute of ChemistryChinese Academy of SciencesBeijingChina

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