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, Kazan Scientific Center of RAS.

2. Properties of Tb-TCAS complexes. 1.Intensive and narrow emissive bands 2.Long life-time of excited state 1.Toxicity 2.Easy degradation Na + + Na Tb-TCAS Antennae effect Emission spectrum of Tb-TCAS complex. φ = 0.141+ - 2

3. The common goal of the investigation The common goal of the investigation: preparing of luminescent silica nanoparticles, their characterization, studying of properties and using. (SiO 2 ) n = 3

4. Preparation of Tb-TCAS-doped silica nanoparticles. n Si(OH) 4 NH 4 OH -H 2 O n Si(OC 2 H 5 ) 4 +H 2 O (SiO 2 ) n oil H2OH2O Si(OC 2 H 5 ) 4 4

5. Advantages of Tb-TCAS-doped silica nanoparticles. 1.Low toxicity 2.More intensive luminescence 3.High stability 4.Simple synthetic procedure 5.Easy surface modification 1.Toxicity 2.Less intensive luminescence 3.Low stability 3 days 5 3 hours

6. The covalent modification of silica nanoparticles surface. APS (3-aminopropyl)- triethoxysilane Succinic anhydride 6 Si-OH HO-Si APS Succinic anhydride NH 2 H2NH2N H2NH2N H2NH2N COOH HOOC

7. Images of the recognition of black death antigens. SiO 2 Tb-TCAS as biomarker for the Black Death antigens. 7 antigens of black death

8. The next step of our work The next step of our work is the investigation of Tb- TCAS-doped silica nanoparticles behavior in different media. Methods of investigation: 1.Luminescent spectroscopy 2.UV-Vis spectroscopy 3.Dynamic light scattering (DLS) 4.Electrophoresis 5.Transmission electron microscopy (TEM) 6.Atomic force microscopy (AFM) 8

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

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

11. Gemini 16-6-16 Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB) (CMC = 2·10 -5 mol/l) С Gemini, Md, nmPDIζ±10%, mV 1·10 -5 237 ± 20.197+36 5·10 -5 228 ± 40.182+41 1·10 -4 238 ± 140.280+38 1·10 -3 224 ± 20.159+43 1·10 -2 237 ± 60.224+53 Average diameter (d), polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO 2 Tb-TCAS at various concentrations of Gemini. 11

12. PhR aqueous solutionSiO 2 Tb-TCAS GeminiSiO 2 Tb-TCAS covered by Gemini UV-Vis spectra of Phenol Red (PhR aqueous solution) in presence of SiO 2 Tb-TCAS; Gemini and SiO 2 Tb-TCAS covered by Gemini. pK а = 8.0 Molecular form pH = 8.2 Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Red. Anionic form 12

13. Possible locations of Phenol Red - - - H2OH2O 13 Stern layer

14. - (SiO 2 ) n - - + + + + + + I 0 /I = 1 + k q C PhR Emission spectraStern-Folmer dependence UV-Vis spectra SiO 2 Tb-TCAS covered by Gemini in presence of Phenol Red k q ~ r -6 14

15. - - + - = ? - HPO 4 2- = 15 DS -

16. HPO 4 2- = - + - (SiO 2 ) n ++ + + + + + + - - - - - - ++ + + + + + + - - - С Gemini, M 5·10 -5 C HPhR, M 5·10 -6 C Na2HPO4, M 1·10 -4 1·10 -3 1·10 -2 d, nm278 ± 2314 ± 4aggregation PDI0.3110.2490.878 ζ±10%, mV 271619 16 Interaction of HPO 4 2- with SiO 2 Tb-TCAS covered by micellar layer containing Phenol Red

17. + - - = 17 Interaction of DS - with SiO 2 Tb-TCAS covered by micellar layer containing Phenol Red DS - Emission spectra Zeta-potential (ζ) dependence on SDS concentration. - - - -

18. (SiO 2 ) n I, a.u. 450500550600650 0 50000 100000 150000 200000 250000 300000, nm - - - 18 Interaction of DS - with SiO 2 Tb-TCAS covered by micellar layer containing Phenol Red on off on

19. Conclusion. 19 onoffon + Na Na + + TEOS+ Gemini + PhR+ SDS - - -

20. 20 Acknowledgements. Mustafina A.R. Fedorenko S.V. Elistratova Yu.G. Konovalov A.I. Initial substancesAntipin I.S. Solovieva S.E. AFM methodKahirov R.K RFBR project N 09-03-12260 Ofi_M for financial supporting IOPC named after A.E. Arbuzov Kazan Federal University Method of Mostovaya O.A. luminescence spectroscopyStoikov I.I. Institute of Macromolecular Compounds, St. Petersburg TEM methodMenshikova A.Yu M.M. Shemyakin and Yu.A. Ovchinnikov Institute of Bioorganic Chemistry, Moscow Bioorganic investigationsZubov V.P.

27. Nonionic surfactant Triton X-100

28. С Gemini, MC HPhR, Md, nmPDIζ±10%, mV 5·10 -5 0228 ± 40.18241 2·10 -5 226 ± 40.15042 4·10 -5 223 ± 40.20836 6·10 -5 238 ± 130.06729 8·10 -5 250 ± 500.24229

29. С Gemini, MC HPhR, MC SDS, Md, nmPDIζ±10%, mV Peak means, nm 5·10 -5 5·10 -6 1·10 -6 246 ± 40.18335 5·10 -6 236 ± 30.17942 1·10 -5 216 ± 30.16635 2·10 -5 216 ± 20.15143 3·10 -5 227 ± 40.17546 4·10 -5 271 ± 40.23746 5·10 -5 325 ± 40.22547 6·10 -5 369 ± 50.25147 7·10 -5 420 ± 40.24346 8·10 -5 494 ± 60.28743 9·10 -5 aggregation1.00018 1·10 -4 aggregation1.0000 5·10 -4 -0.462-33 296 ± 30; 47 ± 4 1·10 -3 -0.429-34 256 ± 17; 45 ± 5

30. capillary hνhν hνhν luminescence No luminescence 12

32. SiO 2 H2OH2O 60-80 nm SiO 2 40±5 nm SiO 2