1. Medicinal Chemistry: Technetium and Nuclear Medicine ICIS - CNR - Padova, Italy

4. Group 7 metals relevant to Nuclear Medicine - 1 4576891011 transition metals Tc Re MnFe W Ir Rh Co Os Ru Ni Pd PtTa Cr Au Ag Cu Nb V Mo Hf Zr Ti 1st row 2nd row 3rd row

7. Group 7 metals relevant to Nuclear Medicine - 2 radiodiagnosis 99m Tc t 1/2 = 6.0 h E  = 142 keV inorganic chemistry 99 Tc t 1/2 = 2.12x10 5 y E  = 292 keV inorganic chemistry ’cold’ 185/187 Re radiometabolic theraphy 188 Re t 1/2 = 16.9 h E  = 2.0 MeV 186 Re t 1/2 = 90.0 h E  = 1.1 MeV

8. Inorganic Chemistry vs Nuclear Medicine inorganic chemistry: 10 -3 – 10 -5 M (millimolar conc) nuclear medicine: 10 -7 – 10 -9 M (micro/nanomolar conc) Conventional physico-chemical characterization NMR, IR, UV-vis spectroscopies Mass spectrometry (EI, ESI) X-ray crystal structure determination TLC & HPLC chromatography Radiometric characterization TLC & HPLC chromatography

10. The 99 Mo/ 99m Tc generator 99 Mo 99m Tc 99 Tc t 1/2 = 66.7 h; E  - = 1.37 MeV t 1/2 = 6 h; E  - = 142 KeV

17. The bifunctional approach in mixed nitrido-Tc heterocomplexes Tc N P P N O S O N O S N N O H HH MW = 913

18. The substitution-inert [Tc(N)(PXP] synthon Tc N X Cl P P Y Z P P Tc N X Bolzati et al., J. Am. Chem. Soc. 124, 2002, 11468

19. Crystal structure of [Re(N)(dedc)(pnp2)] + pseudo-octahedron cis-P co-ordination P(1)-Re-P(2) = 101.2(1)° trans-N co-ordination N(1)-Re-N(2) = 164.5(5)° Re-N(2) = 2.73(1) Å

20. From aryl- to alkyl-diphosphines P N P O pnp2 S S N dedc S S N O O dbodc P O O N P O O O pnp5

21. ESI - MS of [ 99 Tc(dbodc)(pnp5)] + 100200300400500600700800900100011001200130014001500 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Relative Abundance 846.6 848.6 640.6 527.4 849.5 844.7 279.4 552.8 306.5641.6 371.4 862.5 788.5413.5 185.3 961.81049.9130.61139.01183.9 1401.21314.21454.4 M+M+ [Tc(N)Cl 2 (PPh 3 ) 2 ] DCM i) pnp5 ii) dbodc yellow oil E. Marotta et al, RCM, 2003, submitted

23. Collisional experiments on [ 99 Tc(N)(bdodc)(pnp5)] + - MS 2 - -

24. Collisional experiments on [ 99 Tc(N)(bdodc)(pnp5)] + - MS 3 - - -

25. Collisionally induced fragmentation pattern of [ 99 Tc(N)(dbodc)(pnp5)] +

26. 1 H NMR of [ 99 Tc(N)(dbodc)(pnp5)] + S S N O O dbodc 99 Tc-complex P O O N P O O O pnp5

27. 1 H- 1 H COSY-45 of [ 99g Tc(N)(dbodc)(pnp5)] + dbodc  N-CH 2 -CH 2 -O- dbodc -O-CH 2 -CH 3 pnp5 -O-CH 2 -CH 3 pnp5  N-CH 2 -CH 2 -O-

28. 31 P and 13 C NMR of [ 99 Tc(N)(dbodc)(pnp5)] + -C-CH 3 -O-CH 3 various CH 2 30.2 ppm impurity oxidized pnp5

29. 1 H - 13 C HMQC of [ 99 Tc(N)(dbodc)(PNP5)] + C-CH 3 C-C and P-C O- CH 3 N-C region O-C region P-…CH 2 -O- Tc N P P N S S N O O O O O O O +

30. Nitrido- 99m Tc(V) hetero-complexes: heart uptake in rats %ID/g time (min) 230 5 102012060 1 2 3 4 6 5 Myoview 99m Tc-Myoview Cardiolite 99m Tc-Cardiolite DBODC5 99m Tc-DBODC5 A. Boschi et al., J. Nucl. Med. 2003, in press

31. Nitrido- 99m Tc(V) hetero-complexes: heart/liver ratio in rats time (min) Myoview 99m Tc-Myoview Cardiolite 99m Tc-Cardiolite DBODC5 99m Tc-DBODC5 h/lh/l 230 25 102012060 5 10 15 20 30 5 35

32. Nitrido-99mTc(V) hetero-complexes: micro-SPET analysis

33. Cardiolite® by Dupont NOEt by Cis-Schering Tc(N)DBODC5 by Nihon Medi-Physics