Skip to main content
SpringerLink
Log in

Organic coating of 1–2-nm-size silicon nanoparticles: Effect on particle properties

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Photoluminescent silicon nanoparticles 1–2 nm in size were synthesized by a wet chemical procedure and derivatized with propylamine (NH2SiNP). Surface NH2 groups were used as linkers for additional poly(ethylene glycol) (PEG) and folic acid (Fo) attachment (PEG-NHSiNP and Fo-NHSiNP, respectively) to enable efficient targeting of the particles to tumors and inflammatory sites. The particles were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ζ potential, dynamic light scattering, and time-resolved anisotropy.

The photophysical properties and photosensitizing capacity of the particles and their interaction with proteins was dependent on the nature of the attached molecules. While PEG attachment did not alter the photophysical behavior of NH2SiNP, the attachment of Fo diminished particle photoluminescence. Particles retained the capacity for 1O2 generation; however, efficient 1O2 quenching by the attached surface groups may be a drawback when using these particles as 1O2 photosensitizers. In addition, Fo attachment provided particles with the capacity to generate the superoxide anion radical (O −2 ).

The particles were able to bind tryptophan residues of bovine serum albumin (BSA) within quenching distances. NH2SiNP and PEG–NHSiNP ground state complexes with BSA showed binding constants of (3.1 ± 0.3) × 104 and (1.3 ± 0.4) × 103 M−1, respectively. The lower value observed for PEG-NHSiNP complexes indicates that surface PEGylation leads to a reduction in protein adsorption, which is required to prevent opsonization. An increase in particle luminescence upon BSA binding was attributed to the hydrophobic environment generated by the protein. NH2SiNP-BSA complexes were also capable of resonance energy transfer.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Llansola Portolés, M. J.; David Gara, P. M.; Kotler, M. L.; Bertolotti, S.; San Román, E.; Rodríguez, H. B.; Gonzalez, M. C. Silicon nanoparticle photophysics and singlet oxygen generation. Langmuir 2010, 26, 10953–10960.

    Article  Google Scholar 

  2. Burda, C.; Chen, X. B.; Narayanan, R.; El-Sayed, M. A. Chemistry and properties of nanocrystals of different shapes. Chem. Rev. 2005, 105, 1025–1102.

    Article  Google Scholar 

  3. Llansola Portolés, M. J.; Rodriguez Nieto, F.; Soria, D. B.; Amalvy, J. I.; Peruzzo, P. J.; Mártire, D. O.; Kotler, M.; Holub, O.; Gonzalez, M. C. Photophysical properties of blueemitting silicon nanoparticles. J. Phys. Chem. C 2009, 113, 13694–13702.

    Article  Google Scholar 

  4. Sperling, R. A.; Parak, W. J. Surface modification, functionalization and bioconjugation of colloidal inorganic nanoparticles. Phil. Trans. R. Soc. A 2010, 368, 1333–1383.

    Article  Google Scholar 

  5. Wang, C. H.; Liu, C. J.; Wang, C. L.; Huang, T. E.; Obliosca, J. M.; Lee, K. H.; Hwu, Y.; Yang, C. S.; Liu, R. S.; Lin, H. M. et al. Optimizing the size and surface properties of polyethylene glycol (PEG)–gold nanoparticles by intese X-ray irradiation. J. Phys. D: Appl. Phys. 2008, 41,195301.

    Article  Google Scholar 

  6. Matsumura, Y.; Maeda, H. A new concept for macromolecular therapeutics in cancer chemotherapy: Mechanism of tumoritropic accumulation of proteins and the antitumor agent smancs. Cancer Res. 1986, 46, 6387–6392.

    Google Scholar 

  7. Paciotti, G. F.; Kingston, D. G. I.; Tamarkin, L. Colloidal gold nanoparticles: A novel nanoparticle platform for developing multifunctional tumor-targeted drug delivery vectors. Drug. Develop. Res. 2006, 67, 47–54.

    Article  Google Scholar 

  8. David Gara, P.; Garabano, N.; Llansola Portoles, M.; Moreno, M. S.; Dodat, D.; Casas, O.; Gonzalez, M.; Kotler, M. ROS enhancement by silicon nanoparticles in X-ray irradiated aqueous suspensions and in glioma C6 cells. J. Nanopart. Res. 2012, 14,741.

    Article  Google Scholar 

  9. Klein, S.; Dell’Arciprete, M. L.; Wegmann, M.; Distel, L. V. R.; Neuhuber, W.; Gonzalez, M. C.; Kryschi, C. Oxidized silicon nanoparticles for radiosensitization of cancer and tissue cells. Biochem. Bioph. Res. Commun. 2013, 434, 217–222.

    Article  Google Scholar 

  10. Huang, P.; Xu, C.; Lin, J.; Wang, C.; Wang, X. S.; Zhang, C. L.; Zhou, X. J.; Guo, S. W.; Cui, D. X. Folic acidconjugated graphene oxide loaded with photosensitizers for targeting photodynamic therapy. Theranostics 2011, 1, 240–250.

    Article  Google Scholar 

  11. Lu, Y. J.; Low, P. S. Folate-mediated delivery of macromolecular anticancer therapeutic agents. Adv. Drug Deliver. Rev. 2002, 54, 675–693.

    Article  Google Scholar 

  12. Romero, J. J.; Llansola Portolés, M. J.; Dell’Arciprete, M. L.; Rodríguez, H. B.; Moore, A. L.; Gonzalez, M. C. Photoluminescent 1–2 nm sized silicon nanoparticles: A surface-dependent system. Chem. Mater. 2013, 25, 3488–3498.

    Article  Google Scholar 

  13. Bhattacharjee, S.; Rietjens, I. M. C. M.; Singh, M. P.; Atkins, T. M.; Purkait, T. K.; Xu, Z. J.; Regli, S.; Shukaliak, A.; Clark, R. J.; Mitchell, B. S. et al. Cytotoxicity of surface-functionalized silicon and germanium nanoparticles: The dominant role of surface charges. Nanoscale 2013, 5, 4870–4883.

    Article  Google Scholar 

  14. Nel, A. E.; Mädler, L.; Velegol, D.; Xia, T.; Hoek, E. M. V.; Somasundaran, P.; Klaessig, F.; Castranova, V.; Thompson, M. Understanding biophysicochemical interactions at the nano-bio interface. Nat. Mater. 2009, 8, 543–557.

    Article  Google Scholar 

  15. Erogbogbo, F.; Tien, C. A.; Chang, C. W.; Yong, K. T.; Law, W. C.; Ding, H.; Roy, I.; Swihart, M. T.; Prasad, P. N. Bioconjugation of luminescent silicon quantum dots for selective uptake by cancer cells. Bioconjugate Chem. 2011, 22, 1081–1088.

    Article  Google Scholar 

  16. Doshi, N.; Mitragotri, S. Designer biomaterials for nanomedicine. Adv. Funct. Mater. 2009, 19, 3843–3854.

    Article  Google Scholar 

  17. Ausubel, F. M.; Brent, R.; Kingston, R. E.; Seidman, J. G.; Smith, J. A.; Struhl, K. Current Protocols in Molecular Biology. John Wiley & Sons: New York, 2003.

    Google Scholar 

  18. Lakowicz, J. R. Principles of Fluorescence Spectroscopy, 3rd ed.; Springer Science+Business Media: New York, 2006.

    Book  Google Scholar 

  19. Frauenheim, T.; Seifert, G.; Elstner, M.; Niehaus, T.; Köhler, C.; Amkreutz, M.; Sternberg, M.; Hajnal, Z.; Di Carlo, A.; Suhai, S. Atomistic simulations of complex materials: Groundstate and excited-state properties. J. Phys.: Condens. Matter 2002, 14, 3015–3047.

    Google Scholar 

  20. Steinbeck, M. J.; Khan, A. U.; Karnovsky, M. J. Extracellular production of singlet oxygen by stimulated macrophages quantified using 9,10-diphenylanthracene and perylene in a polystyrene film. J. Biol. Chem. 1993, 268, 15649–15654.

    Google Scholar 

  21. Llansola Portolés, M. J.; Pis Diez, R.; Dell’Arciprete, M. L.; Caregnato, P.; Romero, J. J.; Mártire, D. O.; Azzaroni, O.; Ceolín, M.; Gonzalez, M. C. Understanding the parameters affecting the photoluminescence of silicon nanoparticles. J. Phys. Chem. C 2012, 116, 11315–11325.

    Google Scholar 

  22. Warner, J. H.; Hoshino, A.; Yamamoto, K.; Tilley, R. D. Water-soluble photoluminescent silicon quantum dots. Angew. Chem. 2005, 117, 4626–4630.

    Article  Google Scholar 

  23. Atkins, T. M.; Louie, A. Y.; Kauzlarich, S. M. An efficient microwave-assisted synthesis method for the production of water soluble amine-terminated Si nanoparticles. Nanotechnology 2012, 23, 294006.

    Article  Google Scholar 

  24. Hua, F. J.; Swihart, M. T.; Ruckenstein, E. Efficient surface grafting of luminescent silicon quantum dots by photoinitiated hydrosilylation. Langmuir 2005, 21, 6054–6062.

    Article  Google Scholar 

  25. Elstner, M.; Porezag, D.; Jungnickel, G.; Elsner, J.; Haugk, M.; Frauenheim, T.; Suhai, S.; Seifert, G. Self-consistentcharge density-functional tight-binding method for simulations of complex materials properties. Phys. Rev. B 1998, 58, 7260–7268.

    Article  Google Scholar 

  26. Aradi, B.; Hourahine, B.; Frauenheim, T. DFTB+, a sparse matrix-based implementation of the DFTB method. J. Phys. Chem. A 2007, 111, 5678–5684.

    Article  Google Scholar 

  27. Rosso-Vasic, M.; Spruijt, E.; van Lagen, B.; De Cola, L.; Zuilhof, H. Alkyl-functionalized oxide-free silicon nanoparticles: Synthesis and optical properties. Small 2008, 4, 1835–1841.

    Article  Google Scholar 

  28. Wilcoxon, J. P.; Samara, G. A.; Provencio, P. N. Optical and electronic properties of Si nanoclusters synthesized in inverse micelles. Phys. Rev. B 1999, 60, 2704–2714.

    Article  Google Scholar 

  29. Wahab, M. A.; Kim, I.; Ha, C. S. Bridged aminefunctionalized mesoporous organosilica materials from 1,2-bis(triethoxysilyl)ethane and bis[(3-trimethoxysilyl) propyl]amine. J. Solid. State Chem. 2004, 177, 3439–3447.

    Article  Google Scholar 

  30. Coates, J. Interpretation of infrared spectra, a practical approach. In Encyclopedia of Analytical Chemistry. Meyer, R. A., Ed. John Wiley & Sons Ltd: Chinchester, 2000; pp10815–10837.

    Google Scholar 

  31. Alexander, M. R.; Short, R. D.; Jones, F. R.; Michaeli, W.; Blomfield, C. J. A study of HMDSO/O2 plasma deposits using a high-sensitivity and -energy resolution XPS instrument: Curve fitting of the Si 2p core level. Appl. Surf. Sci. 1999, 137, 179–183.

    Article  Google Scholar 

  32. Hairdary, S. M.; Córcoles, E. P.; Ali, N. K. Folic acid delivery device based on porous silicon nanoparticles synthesized by electrochemical etching. Int. J. Electrochem. Sci. 2013, 8, 9956–9966.

    Google Scholar 

  33. Wu, Z. P.; Zuo, F.; Zheng, Z. H.; Ding, X. B.; Peng, Y. X. A novel approach to molecular recognition surface of magnetic nanoparticles based on host–guest effect. Nanoscale Res. Lett. 2009, 4, 738–747.

    Article  Google Scholar 

  34. Mattoussi, S. H.; Cumming, A. W.; Murray, C. B.; Bawendi, M. G. Properties of CdSe nanocrystal dispersions in the dilute regime: Structure and interparticle interactions. Phys. Rev. B 1998, 58, 7850–7863.

    Article  Google Scholar 

  35. Smith, A.; Yamani, Z. H.; Roberts, N.; Turner, J.; Habbal, S. R.; Granick, S.; Nayfeh, M. H. Observation of strong directlike oscillator strength in the photoluminescence of Si nanoparticles. Phys. Rev. B 2005, 72, 205307.

    Article  Google Scholar 

  36. Xiao, L.; Gu, L.; Howell, S. B.; Sailor, M. J. Porous silicon nanoparticle photosensitizers for singlet oxygen and their phototoxicity against cancer cells. ACS Nano 2011, 5, 3651–3659.

    Article  Google Scholar 

  37. Timoshenko, V. Light-induced generation of singlet oxygen in porous silicon. In Sensors for Environment, Health and Security. Baraton, M. I., Ed. Springer: the Netherlands, 2009; pp125–139.

    Chapter  Google Scholar 

  38. Fumon, H; Nojiri, M.; Fujii, M. Hayashi, S.; Akamatsu, K. Sensitized generation of singlet oxygen by allylamineterminated hydrophillic porous Si. Trans. Mat. Res. Soc. Jpn. 2008, 33, 165–168.

    Google Scholar 

  39. Schweitzer, C.; Schmidt, R. Physical mechanisms of generation and deactivation of singlet oxygen. Chem. Rev. 2003, 103, 1685–1758.

    Article  Google Scholar 

  40. Wilkinson, F.; Helman, W. P.; Ross, A. B. Rate constants for the decay and reactions of the lowest electronically excited singlet state of molecular oxygen in solution. An expanded and revised compilation. J. Phys. Chem. Ref. Data 1995, 24, 663–677.

    Google Scholar 

  41. Darmanyan, A. P.; Jenks, W. S.; Jardon, P. Charge-transfer quenching of singlet oxygen O2(1Δg) by amines and aromatic hydrocarbons. J. Phys. Chem. A 1998, 102, 7420–7426.

    Article  Google Scholar 

  42. Thomas, A. H.; Lorente, C.; Capparelli, A. L.; Martinez, C. G.; Braun, A. M.; Oliveros, E. Singlet oxygen (1Δg) production by pterin derivatives in aqueous solutions. Photochem. Photobio. Sci. 2003, 2, 245–250.

    Article  Google Scholar 

  43. Cabrerizo, F. M.; Laura Dántola, M.; Petroselli, G.; Capparelli, A. L.; Thomas, A. H.; Braun, A. M.; Lorente, C.; Oliveros, E. Reactivity of conjugated and unconjugated pterins with singlet oxygen (O2(1Δg)): Physical quenching and chemical reaction. Photochem. Photobiol. 2007, 83, 526–534.

    Article  Google Scholar 

  44. Alarcón, E.; Aspée, A.; Abuin, E. B.; Lissi, E. A. Evaluation of solute binding to proteins and intra-protein distances from steady state fluorescence measurements. J. Photochem. Photobiol. B 2012, 106, 1–17.

    Article  Google Scholar 

  45. Rahman, M.; Laurent, S.; Tawil, N.; Yahia, L.; Mahmoundi, M. Protein–Nanoparticle Interactions—The Bio-Nano Interface; Springer-Verlag Berlin Heidelberg: Berlin, 2013.

    Google Scholar 

  46. Ying, P. Q.; Jin, G.; Tao, Z. L. Competitive adsorption of collagen and bovine serum albumin—Effect of the surface wettability. Colloid. Surf. B 2004, 33, 259–263.

    Article  Google Scholar 

  47. Lynch, I.; Dawson, K. A. Protein–nanoparticle interactions. Nano Today 2008, 3, 40–47.

    Article  Google Scholar 

  48. Chatterjee, S.; Mukherjee, T. K. Spectroscopic investigation of interaction between bovine serum albumin and aminefunctionalized silicon quantum dots. Phys. Chem. Chem. Phys. 2014, 16, 8400–8408.

    Article  Google Scholar 

  49. Valeur, B. Resonance energy transfer and its applications. In Molecular Fluorescence: Principles and Applications. Valeur, B., Ed.; Wiley-VCH Verlag GmbH: Weinhelm, 2001; pp247–272.

    Chapter  Google Scholar 

Download references

Author information

Author notes

  1. Manuel Llansola Portolés

    Present address: Department of Chemistry and Biochemistry, Center for Bioenergy and Photosynthesis, Arizona State University, Tempe, Arizona, USA

Authors and Affiliations

  1. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CCT-La Plata-CONICET, Facultad de Ciencias, Universidad Nacional de La Plata, cc 16, Suc. 4, 1900, La Plata, Argentina

    Cristian R. Lillo, Juan J. Romero, Manuel Llansola Portolés, Paula Caregnato & Mónica C. Gonzalez

  2. CEQUINOR, CCT-La Plata-CONICET, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, cc 962, 1900, La Plata, Argentina

    Reinaldo Pis Diez

Authors
  1. Cristian R. Lillo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Juan J. Romero
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Manuel Llansola Portolés
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Reinaldo Pis Diez
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Paula Caregnato
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Mónica C. Gonzalez
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mónica C. Gonzalez.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lillo, C.R., Romero, J.J., Portolés, M.L. et al. Organic coating of 1–2-nm-size silicon nanoparticles: Effect on particle properties. Nano Res. 8, 2047–2062 (2015). https://doi.org/10.1007/s12274-015-0716-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-015-0716-z

Keywords

Search

Navigation