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Surface passivation of CdSe-TOPO quantum dots by poly(acrylic acid): solvent sensitivity and photo-induced emission in water

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Abstract

The principal available methods for the preparation of high quality CdSe quantum dots (QDs) are based on organic ligands such as tri-n-octylphosphine oxide (TOPO) which lead to non-water soluble nanocrystal QDs. As most biological interactions take place in aqueous media, much effort has been made on preparation of water soluble QDs. In this report, the water soluble CdSe QDs were prepared via a ligand exchange process between organic soluble CdSe-TOPO quantum dots and poly(acrylic acid). The poly(acrylic acid) (PAA) can attach onto the surface of CdSe-TOPO quantum dots in a ligand exchange process to make water-soluble CdSe-PAA complexes. In spite of CdSe-TOPO QDs, the resultant CdSe-PAA QDs are soluble in polar solvents such as methanol or water. Optical properties of CdSe-PAA QDs in several solvents showed that the emission intensity of QDs was mainly decreased in protic solvents such as methanol or water. The TEM images of dots in different solvents were examined and some aggregation of dots was found in protic solvents. In comparison with PAA, the addition of PDMAEMA to the solution of CdSe-TOPO QDs in THF increased the emission intensity of QDs. Furthermore, we found that the entitled ligand exchange process was fast and conjugation process completed at short time intervals. The UV-irradiation of the CdSe-PAA conjugate in water showed that the emission was amplified by increasing the irradiation time.

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References

  1. Alivisatos AP (1996) Perspectives on the physical chemistry of semiconductor nanocrystals. J Phys Chem 100:13226–13239

    Article  CAS  Google Scholar 

  2. Quintos Vazquez AL, Torchynska TV, Casas Espinola JL, Jaramillo Gomez JA, Douda J (2013) Electronic effects in emission of core/shell CdSe/ZnS quantum dots conjugated to anti-Interleukin 10 antibodies. J Lumin 143:38–42

    Article  CAS  Google Scholar 

  3. Adamczak M, Krok M, Pamuła E, Posadowska U, Szczepanowicz K, Barbasz J, Warszynski P (2013) Linseed oil based nanocapsules as delivery system for hydrophobic quantum dots. Colloids Surf B Biointerfaces 110:1–7

    Article  CAS  Google Scholar 

  4. LeBlanc SJ, McClanahan MR, Jones M, Moyer PJ (2013) Enhancement of multiphoton emission from single CdSe quantum dots coupled to gold films. Nano Lett 13:1662–1669

    CAS  Google Scholar 

  5. Schmidtke C, Lange H, Tran H, Ostermann J, Kloust H, Bastus N, Markl JP, Thomsen C, Weller H (2013) Radical initiated reactions on biocompatible CdSe-based quantum dots: ligand cross-linking, crystal annealing, and fluorescence enhancement. J Phys Chem C 117:8570–8578

    Article  CAS  Google Scholar 

  6. Peng X, Wilson TE, Alivisatos AP, Schultz PG (1997) Synthesis and isolation of a homodimer of cadmium selenide nanocyrstals. Angew Chem Int Ed Engl 36:145–147

    Article  CAS  Google Scholar 

  7. JrM Bruchez, Moronne M, Gin P, Weiss S, Alivisatos AP (1998) Semiconductor nanocrystals as fluorescent biological labels. Science 281:2013–2016

    Article  Google Scholar 

  8. Wang X-S, Dykstra TE, Salvador MR, Manners I, Scholes GD, Winnik MA (2004) Surface passivation of luminescent colloidal quantum dots with poly(dimethylaminoethyl methacrylate) through a ligand exchange process. J Am Chem Soc 126:7784–7785

    Article  CAS  Google Scholar 

  9. Uyeda HT, Medintz IL, Jaiswal JK, Simon SM, Mattoussi H (2005) Synthesis of compact multidentate ligands to prepare stable hydrophilic quantum dot fluorophores. J Am Chem Soc 127:3870–3878

    Article  CAS  Google Scholar 

  10. Potapova I, Mruk R, Hübner C, Zentel R, Basche T, Mews A (2005) CdSe/ZnS nanocrystals with dye-functionalized polymer ligands containing many anchor groups. Angew Chem Int Ed 44:2437–2440

    Article  CAS  Google Scholar 

  11. Wang YA, Li JJ, Chen H, Peng X (2002) Stabilization of inorganic nanocrystals by organic dendrons. J Am Chem Soc 124:2293–2298

    Article  CAS  Google Scholar 

  12. Liu Y, Kim M, Wang Y, Wang YA, Peng X (2006) Highly luminescent, stable, and water-soluble CdSe/CdS core-shell dendron nanocrystals with carboxylate anchoring groups. Langmuir 22:6341–6345

    Article  CAS  Google Scholar 

  13. Skaff H, Emrick T (2004) Reversible addition fragmentation chain transfer (RAFT) polymerization from unprotected cadmium selenide nanoparticles. Angew Chem Int Ed 43:5383–5386

    Article  CAS  Google Scholar 

  14. Fogg DE, Radzilowski LH, Blanski R, Schrock RR, Thomas EL (1997) Fabrication of quantum dot/polymer composites: phosphine-functionalized block copolymers as passivating hosts for cadmium selenide nanoclusters. Macromolecules 30:417–426

    Article  CAS  Google Scholar 

  15. Kim S, Bawendi MG (2003) Oligomeric ligands for luminescent and stable nanocrystal quantum dots. J Am Chem Soc 125:14652–14653

    Article  CAS  Google Scholar 

  16. Nann T (2005) Phase-transfer of CdSe@ZnS quantum dots using amphiphilic hyperbranched polyethylenimine. Chem Commun 1735–1736

  17. Clapp AR, Medintz IL, Mauro JM, Fisher BR, Bawendi MG, Mattoussi H (2004) Fluorescence resonance energy transfer between quantum dot donors and dye-labeled protein acceptors. J Am Chem Soc 126:301–310

    Article  CAS  Google Scholar 

  18. Dubertret B, Skourides P, Norris DJ, Noireaux V, Brivanlou AH, Libchaber A (2002) In vivo imaging of quantum dots encapsulated in phospholipid micelles. Science 298:1759–1762

    Article  CAS  Google Scholar 

  19. Potapova I, Mruk R, Prehl S, Zentel R, Basche T, Mews A (2003) Semiconductor nanocrystals with multifunctional polymer ligands. J Am Chem Soc 125:320–321

    Article  CAS  Google Scholar 

  20. Pellegrino T, Manna L, Kudera S, Liedl T, Koktysh D, Rogach AL, Keller S, Radler J, Natile G, Parak WJ (2004) Hydrophobic nanocrystals coated with an amphiphilic polymer shell: a general route to water soluble nanocrystals. Nano Lett 4:703–707

    Article  CAS  Google Scholar 

  21. Chan WCW, Nie S (1998) Quantum dot bioconjugates for ultrasensitive nonisotopic detection. Science 281:2016–2018

    Article  CAS  Google Scholar 

  22. Murray CB, Norris DJ, Bawendi MG (1993) Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites. J Am Chem Soc 115:8706–8715

    Article  CAS  Google Scholar 

  23. Hines MA, Guyot-Sionnest P (1996) Synthesis and characterization of strongly luminescing ZnS-capped CdSe nanocrystals. J Phys Chem 100:468–471

    Article  CAS  Google Scholar 

  24. Li JJ, Wang YA, Guo W, Keay JC, Mishima TD, Johnson MB, Peng X (2003) Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction. J Am Chem Soc 125:12567–12575

    Article  CAS  Google Scholar 

  25. Wu X, Liu H, Liu J, Haley KN, Treadway JA, Larson JP, Ge N, Peale F, Bruchez MP (2002) Immunofluorescent labeling of cancer marker Her2 and other cellular targets with semiconductor quantum dots. Nat Biotechnol 21:41–46

    Article  Google Scholar 

  26. Mattoussi H, Mauro JM, Goldman ER, Anderson GP, Sundar VC, Mikulec FV, Bawendi MG (2000) Self-assembly of CdSe–ZnS quantum dot bioconjugates using an engineered recombinant protein. J Am Chem Soc 122:12142–12150

    Article  CAS  Google Scholar 

  27. Pinaud F, King D, Moore H-P, Weiss S (2004) Bioactivation and cell targeting of semiconductor CdSe/ZnS nanocrystals with phytochelatin-related peptides. J Am Chem Soc 126:6115–6123

    Article  CAS  Google Scholar 

  28. Gerion D, Pinaud F, Williams SC, Parak WJ, Zanchet D, Weiss S, Alivisatos AP (2001) Synthesis and properties of biocompatible water-soluble silica-coated CdSe/ZnS semiconductor quantum dots. J Phys Chem B 105:8861–8871

    Article  CAS  Google Scholar 

  29. Gerion D, Parak WJ, Williams SC, Zanchet D, Micheel CM, Alivisatos AP (2002) Sorting fluorescent nanocrystals with DNA. J Am Chem Soc 124:7070–7074

    Article  CAS  Google Scholar 

  30. Rezanejade Bardajee G, Hooshyar Z, Rezanezhad H, Guerin G (2012) Optical properties of water-soluble CdTe quantum dots passivated by a biopolymer based on poly((2-dimethyl-aminoethyl) methacrylate) grafted onto κ-carrageenan. Acs Appl Mater Interf 4:3517–3525

    Article  CAS  Google Scholar 

  31. Pathak S, Choi S-K, Arnheim N, Thompson ME (2001) Hydroxylated quantum dots as luminescent probes for in situ hybridization. J Am Chem Soc 123:4103–4104

    Article  CAS  Google Scholar 

  32. Skaff H, Emrick T (2003) The use of 4-substituted pyridines to afford amphiphilic, pegylated cadmium selenide nanoparticles. Chem Commun 9:52–53

    Article  Google Scholar 

  33. Rosenthal SJ, Tomlinson I, Adkins EM, Schroeter S, Adams S, Swafford L, McBride J, Wang Y, Defelice LJ, Blakely RD (2002) Targeting cell surface receptors with ligand-conjugated nanocrystals. J Am Chem Soc 124:4586–4594

    Article  CAS  Google Scholar 

  34. Xie M, Liu H–H, Chen P, Zhang Z, Wang X, Xie Z, Du Y, Pan B, Pang D (2005) CdSe/ZnS-labeled carboxymethyl chitosan as a bioprobe for live cell imaging. Chem Commun 5518–5520

  35. Manna L, Scher EC, Alivisatos AP (2000) Synthesis of soluble and processable rod-, arrow-, teardrop-, and tetrapod-shaped CdSe nanocrystals. J Am Chem Soc 122:12700–12706

    Article  CAS  Google Scholar 

  36. Myung N, Bae Y, Bard AJ (2003) Enhancement of the photoluminescence of CdSe nanocrystals dispersed in CHCl3 by oxygen passivation of surface states. Nano Lett 3:747–749

    Article  CAS  Google Scholar 

  37. Gao X, Chan WCW, Nie S (2002) Quantum-dot nanocrystals for ultrasensitive biological labeling and multicolor optical encoding. J Biomed Opt 7:532–538

    Article  CAS  Google Scholar 

  38. Katari JEB, Colvin VL, Alivisatos AP (1994) X-Ray photoelectron spectroscopy of CdSe nanocrystals with applications to studies of the nanocrystal surface. J Phys Chem 98:4109–4117

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Payame Noor University, P.O. Box: 19395-3697, Tehran, Iran

    Ghasem Rezanejade Bardajee

  2. Polymer Science and Technology Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

    Rouhollah Soleyman

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  1. Ghasem Rezanejade Bardajee
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  2. Rouhollah Soleyman
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Correspondence to Ghasem Rezanejade Bardajee.

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Bardajee, G.R., Soleyman, R. Surface passivation of CdSe-TOPO quantum dots by poly(acrylic acid): solvent sensitivity and photo-induced emission in water. Iran Polym J 22, 885–890 (2013). https://doi.org/10.1007/s13726-013-0187-6

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  • DOI: https://doi.org/10.1007/s13726-013-0187-6

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