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Properties of Tb-TCAS complexes.

Non-covalent modification of luminescent Tb-TCAS-doped silica nanoparticles surface by surfactants. Bochkova O.D. , Fedorenko S.V. Elistratova Yu.G., Mustafina A.R., Antipin I.S., Solovieva S.E., Konovalov A.I.

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Properties of Tb-TCAS complexes.

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  1. Non-covalent modification of luminescent Tb-TCAS-doped silica nanoparticles surface by surfactants. Bochkova O.D., Fedorenko S.V.Elistratova Yu.G., Mustafina A.R., Antipin I.S., Solovieva S.E., Konovalov A.I. A.E. Arbuzov Institute of Organic and Physical Chemistry, KazanScientific Center of RAS.

  2. Properties of Tb-TCAS complexes. + Na + Na Na+ + Na Na+ + - 2 Emission spectrum of Tb-TCAS complex. Tb-TCAS φ = 0.141 Antennae effect • Intensive and narrow emissive bands • Long life-time of excited state • Toxicity • Easy degradation

  3. 3 (SiO2)n = The common goal of the investigation: preparing ofluminescent silica nanoparticles, their characterization, studying of properties and using.

  4. 4 NH4OH +H2O nSi(OH)4 (SiO2)n n Si(OC2H5)4 -H2O oil H2O Preparation of Tb-TCAS-doped silica nanoparticles. Si(OC2H5)4

  5. 5 3 days 3 hours Advantages of Tb-TCAS-doped silica nanoparticles. • Toxicity • Less intensive luminescence • Low stability • Low toxicity • More intensive luminescence • High stability • Simple synthetic procedure • Easy surface modification

  6. 6 COOH NH2 NH2 HOOC COOH H2N HO-Si Si-OH APS Succinic NH2 HO-Si Si-OH H2N anhydride NH2 COOH HOOC H2N HO-Si Si-OH COOH NH2 The covalent modification of silica nanoparticles surface. APS (3-aminopropyl)-triethoxysilane Succinic anhydride

  7. SiO2 Tb-TCAS as biomarker for the Black Death antigens. 7 antigens of black death Images of the recognition of black death antigens.

  8. 8 The next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media. • Methods of investigation: • Luminescent spectroscopy • UV-Vis spectroscopy • Dynamic light scattering (DLS) • Electrophoresis • Transmission electron microscopy (TEM) • Atomic force microscopy (AFM)

  9. Size of Tb-TCAS-doped silica nanoparticles 9 aggregation In an aqueous solution In a solid state d = 40±5 nm d = 180±5nm рН = 6-7 TEM image of Tb-TCAS doped silica nanoparticles DLS image of Tb-TCAS doped silica nanoparticles ζ = -30 mV

  10. Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB) 10 а) С CTAB = 5·10-5mol/l (CMC = 8,5·10-3 mol/l) + CTAB Nanoparticles average size and zeta-potential dependence on CTAB concentration aggregation ζ= +74,4 mV b) С CTAB = 5·10-4 - 1·10-2mol/l repulsion

  11. Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB) 11 Average diameter (d), polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini. Gemini 16-6-16 (CMC = 2·10-5 mol/l)

  12. Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Red. 12 pKа = 8.0 Molecular form Anionic form pH = 8.2 UV-Vis spectra of Phenol Red (PhR aqueous solution) in presence of SiO2 Tb-TCAS; Geminiand SiO2 Tb-TCAS covered by Gemini.

  13. 13 - - - Possible locations of Phenol Red Stern layer H2O

  14. SiO2 Tb-TCAS covered by Gemini in presence of Phenol Red 14 - + + - (SiO2)n + + - + + Emission spectra Stern-Folmer dependence I0/I = 1 + kqCPhR kq ~ r-6 UV-Vis spectra

  15. 15 - - ? + = - - = HPO42- DS-

  16. Interaction of HPO42- with SiO2 Tb-TCAS covered by micellar layer containing Phenol Red 16 - - - - - - + + + + - - (SiO2)n (SiO2)n + + + + + + + + + + - - + + + HPO42- - =

  17. Interaction of DS- with SiO2 Tb-TCAS covered by micellar layer containing Phenol Red 17 - - - - - - = + DS- Emission spectra Zeta-potential (ζ) dependence on SDS concentration.

  18. Interaction of DS- with SiO2 Tb-TCAS covered by micellar layer containing Phenol Red 18 (SiO2)n - - - 300000 250000 200000 , a.u. 150000 I 100000 50000 0 450 500 550 600 650 l , nm on on off

  19. Conclusion. 19 Na + Na + + Na + Na + TEOS + Gemini + Gemini - + PhR + SDS - - on off on

  20. 20 Acknowledgements. IOPC named after A.E. Arbuzov Mustafina A.R. Fedorenko S.V. Elistratova Yu.G. Konovalov A.I. Initial substances Antipin I.S. Solovieva S.E. AFM method Kahirov R.K Kazan Federal University Method of Mostovaya O.A. luminescence spectroscopy Stoikov I.I. Instituteof Macromolecular Compounds, St. Petersburg TEM method Menshikova A.Yu M.M. Shemyakin and Yu.A. Ovchinnikov Instituteof Bioorganic Chemistry, Moscow Bioorganic investigations Zubov V.P. RFBR project N 09-03-12260 Ofi_M for financial supporting

  21. Nonionic surfactant Triton X-100

  22. 12 capillary No luminescence luminescence hν hν

  23. SiO2 SiO2 SiO2 H2O 40±5 nm 60-80 nm

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