1. Free and Encapsulated (TiO 2 ) 2 Dimers into Carbon Nanotubes Presented by Prof. TANGOUR Bahoueddine University of Tunis-El Manar, Tunisia S. Dargouthi, S. Boughdiri, B. Tangour ICMCC2015 JUNE 15-16 TORONTO - CANADA

2. 1- Introduction to Nanotechnology

3. Nanotechnologies are concerned with: Controlledproduction, design, characterization and application of structures, devices, and systems presenting size and shape at the nanometer scale and exhibiting at least one novel/superior characteristic or property. ICMCC2015 JUNE 15-16 TORONTO - CANADA3

4. The nanometer scale Humanhair fragment and a network of single-walled carbon nanotubes. ICMCC2015 JUNE 15-16 TORONTO - CANADA4

5. The gold color ICMCC2015 JUNE 15-16 TORONTO - CANADA5

6. 2- Phenomenological Description of Single Walled Carbon nanotubes (SWNT) 6

7. ICMCC2015 JUNE 15-16 TORONTO - CANADA SWNT are conceptuallyconsidered as rolled-up graphite sheet even it does not related to the real fabrication way. 7

8. Schematic description ICMCC2015 JUNE 15-16 TORONTO - CANADA8

9. Different types of Carbon SWNT Chiral Θ ≠ 0 and 30° (n,m) type Semi-conductor Gap = [2-4] eV Achiral θ=30° Armchair (n,n)type Semi-metallic Gap = [0,2 - 1,4] eV Achiral θ=0° Zigzag (n,0) type Metallic 9

10. 3- Confined molecules inside carbon nanotubes ICMCC2015 JUNE 15-16 TORONTO - CANADA10

11. fullerenes encapsulated into CNT C60@CNT Nanotubes offer a unique opportunity for investigation of physical and chemical processes in confined systems ICMCC2015 JUNE 15-16 TORONTO - CANADA11

12. Release of carboplatin from CNT. ICMCC2015 JUNE 15-16 TORONTO - CANADA Representative HRTEM pictures were shown after incubation of CNT-Carboplatin A) 30min B) 24h in cell culture medium at 37°C. NanomedicineNanomedicine April 2008, Vol. 3, No. 2, Pages 175-182 12

13. 4- THEORETICAL CALCULATIONS CONFINED TiO 2 SPECIES into CNT noted molecule@CNT

14. ICMCC2015 JUNE 15-16 TORONTO - CANADA Calculation details DFT B3LYP calculations Different basis sets 6-311G and 6-311G (d). Hundreds of atoms Thousands of basis functions 14

15. TiO 2 ICMCC2015 JUNE 15-16 TORONTO - CANADA R Ti-O (Å)=1.629 (exp. =1.704)  O-Ti-O (°)=111.4 (exp.=113.0) TiO 2 molecule is only detected into noble gas matrix at very low temperature of some Kelvin. 15 CNTs with different diameters

16. TiO 2 @CNT ICMCC2015 JUNE 15-16 TORONTO - CANADA16

17. Different Confinement interactions Chemical Interactions Physical Interactions Without confinement effect Energy Variation (in arbitrary units) CNT Diameter in Á ICMCC2015 JUNE 15-16 TORONTO - CANADA17

18. TiO 2 @CNT (8,0) D=6.267 Å Stabilisation of the molecule by roughly 50 kcal/mol ICMCC2015 JUNE 15-16 TORONTO - CANADA R Ti-O (Å)=1.612 (1.629 in free molecule)  O-Ti-O (°)=94.6 (111.4 in free molecule ) Confinement of TiO 2 molecule will help its manipulation at room temperature 18

19. 3 possible Dimers (TiO 2 ) 2 ICMCC2015 JUNE 15-16 TORONTO - CANADA Trans DIMER (T) Cis DIMER (C) Tetrahedron/ Pyramidal DIMER (T/P) 19 Optimized Structures

20. Stabily Comparison ICMCC2015 JUNE 15-16 TORONTO - CANADA 20

21. CONFINED DIMERS

22. T- (TiO 2 ) 2 @(12,0 ICMCC2015 JUNE 15-16 TORONTO - CANADA 22 Few and non signifiant changes Before Confinement After

23. C- (TiO 2 ) 2 @(12,0 ICMCC2015 JUNE 15-16 TORONTO - CANADA 23 Few and non signifiant changes Before Confinement After

24. T/P- (TiO 2 ) 2 @(12,0 ICMCC2015 JUNE 15-16 TORONTO - CANADA 24 T/P transforms in Trans Before Confinement After

25. Separated Dimers

26. Parallele position (P) ICMCC2015 JUNE 15-16 TORONTO - CANADA26 Transitory specie

27. Orthogonal position (O) ICMCC2015 JUNE 15-16 TORONTO - CANADA 27 Transitory specie

28. Confined (P) Dimer ICMCC2015 JUNE 15-16 TORONTO - CANADA 28 (P) Transforms in (O) and stays in iteraction with CNT’s edge Before Confinement After

29. Confined (O) Dimer ICMCC2015 JUNE 15-16 TORONTO - CANADA 29 The dimer keeps his structure when confined so Stabilizing of the transitory species (TiO2)2 by encapsulation into carbon nanotubes. Before Confinement After

30. Stabilisation by confinement ICMCC2015 JUNE 15-16 TORONTO - CANADA 30 Dargouthi Sarra a, Boughdiri Salima and Tangour Bahoueddine, 2015 Acta Chimica Slovenica, 61, in press

31. THANK YOU FOR YOUR ATTENTION ICMCC2015 JUNE 15-16 TORONTO - CANADA31