Research Group n. 5
UNIVERSITA’ DEGLI STUDI DI PISA
Thermodynamics and kinetics of metal-ligand interactions. The use of
metal complexes in studies of biological interest and in metal extraction
by micellar catalysis.
Maria Rosaria Tiné, Celia Duce, Tarita Biver, Lisa Ghezzi.
Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35, I-56126 Pisa;
E-mail: [email protected]
Our research interests focus on the thermodynamics and kinetics of the formation of metal
complexes and of their interaction with small molecules and biosubstrates.
The main research topics are the following ones:
1) Thermodynamics and kinetics of the interaction of metal-receptors and nucleic acids focusing
on the intercalative process.
The research is aimed in analysing the binding features of metal complexes of biological and
biomedical interest to DNAs and RNAs. The combined use of fast kinetic (T-jump, Stopped-flow)
and spectrophotometric (and eventually spectrofluorimetric) techniques enables the binding
parameters and the reaction mechanism to be determined. The binding mode is established
(external binding, groove binding and/or intercalation) and the binding effects on the
polynucleotide structure are analysed, these ranging from simple helix distortion until cleavage of
phosphodiester bonds.
2) Thermodynamics and kinetics of the interaction of metal-nanoparticles and nucleic acids
The research is aimed first in the preparation and characterisation from a stability point of view of
water soluble metal-nanoparticles of the type of those commonly used nowadays in particular in
the field of biomedicine. Second, an analysis of their binding features to DNAs and RNAs is done.
The combined use of fast kinetic (T-jump, Stopped-flow) and spectrophotometric (and eventually
spectrofluorimetric) techniques enables the binding parameters and the reaction mechanism to be
determined. The binding effects on the polynucleotide structure are also analysed.
3) Extraction/removal of specific metal ions by micellar based systems.
The research is aimed in developing micellar based systems for the selective separation and
recovery of hazardous/precious heavy metals. The main focus of the research is on the micellar
catalysis. Micellar Enhanced Ultrafiltration (MEUF) and Ligand Modified-Micellar Enhanced
Ultrafiltration (LM-MEUF) techniques will be used for extraction and recovery of both pollutant and
precious metal ions.
4) Study of interactions between proteins and inorganic pigments in cultural heritage materials.
The research is aimed in studying the degradation and ageing of proteinaceous materials in paint
layers by thermochemical techniques. Inorganic pigments can interact with proteins through the
formation of metal complexes. Thermal analysis (TA) studies are of primary importance for the
comprehension of structural changes of proteic binders during aging in the presence of inorganic
pigments. In particular the combined use of thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC) enables to verify the presence and the strength of protein-pigment
interactions.
5) Self-assembly of ß-amyloid peptides in the presence of metal ions.
The research is aimed in analysing the self-assembly of peptides of biological and biomedical interest
focusing on their interaction with metal ions. A thermodynamic, kinetics and conformational study of
the self-aggregation reaction of the ß-amyloid peptides and the interaction of the peptides with metal
ions is performed. In particular, the peptide tendency to self-assembly is evaluated using light
scattering (LS), viscosimetry, surface tension, isothermal titration calorimetry (ITC), atomic force
microscopy, fast reactions techniques (stopped-flow , T-Jump) and spectroscopic techniques (UV,
light scattering, fluorescence and FTIR).
Keywords: Inorganic pigment; Metal receptors; Metal Nanoparticles, Metal Extraction; Micellar
Catalysis; Metal Complexes; Kinetics; Self-assembly; Thermodynamics.
1. T. Biver, F. Secco, M.R. Tiné and M. Venturini, Arch. Biochem. Biophys., 2003 , 418, 63-70.
2. T. Biver, F. Secco, M.R. Tiné and M. Venturini, J. of Inorg. Biochem., 2004, 98, 33-40.
3. C. Bazzicalupi, A. Bencini, A. Bianchi, C. Duce, P. Fornasari, C. Giorgi, P. Paoletti, R. Pardini,
M.R. Tiné, B. Valtancoli, Dalton Trans., 2004, 463-469.
4. G. Monteleone, L. Morroni, B. H. Robinson, M.R. Tiné, F. Secco, M. Venturini, Coll. Surf. A,
2004, 243, 23-31.
5. L. Morroni, F. Secco, M. Venturini, J.M. Leal, Inorganic Chemistry, 2004, 43(9),3005-3012.
6. T. Biver, D. Lombardi, F. Secco, M.R..Tinè, M..Venturini, A. Bencini, A. Bianchi, B. Valtancoli,
Dalton Trans., 2006, 1524-1533.
7. L. Ghezzi, B. H. Robinson, M.R. Tiné, F. Secco, M. Venturini, Coll. Surf. A, 2007, 292, 139-147.
8. T. Biver, A. Boggioni, F. Secco, E. Turriani, M. Venturini, S. Yarmoluk, Arch. Biochem.
Biophys., 2007, 465, 90-100.
9. C. Bazzicalupi, A. Bencini, A. Bianchi, T. Biver, A. Boggioni, S. Bonacchi, A. Danesi, C. Giorgi,
P. Gratteri, A. Marchal Ingraín, F. Secco, C. Sissi, B. Valtancoli, M. Venturini, Chem – Eur. J.,
2008, 14(1), 184-196.
10. L. Ghezzi,G. Monteleone, B. H. Robinson, M.R. Tiné, F. Secco, M. Venturini, Coll. Surf. A,
2008, 717-723.
11. T. Biver, F. Secco, M. Venturini, Coordination Chemistry Reviews, 2008, 252, 1163-1177.
12. A. Bencini, V. Bambagioni, D. Bani, T. Biver, R. Chelli, L. Cinci, P. Failli, L. Ghezzi, C. Giorgi,
S. Nappini, F. Secco, M. Tine, M. Venturini, B. Valtancoli, M. Cantore, Journal of Medicinal
Chemistry, 2008, 51, 2350-2360.
13. T. Biver, R. Friani, C. Gattai, F. Secco, M.R. Tiné, M. Venturini, J. Phys. Chem. B, 2008,
112(38), 12168-12173.
14. T. Biver, A. Boggioni, F. Secco, M. Venturini, Langmuir, 2008, 24(1), 36-42.
15. T. Biver, M. Venturini, E. A. Jares-Erijman, T. M. Jovin, F. Secco. Biochemistry.
2009, 48(1), 173-179.
16. T. Biver, L. Ghezzi, V. Malvaldi, F. Secco, M. R. Tine´, M. Venturini. J. Phys. Chem. B.
2009, 113(6), 1598-1606.
17. A. Desii, C. Duce, L. Ghezzi, S. Monti, R. Solaro, M. R. Tiné, Journal of Thermal Analysis and
Calorimetry (2009), 97, (3), 791-796.
18. C. Duce, S. Monti, R. Solaro, M. R. Tiné, Journal of Thermal Analysis and Calorimetry (2009), 113,
2433-2442.
19. A. Desii, C. Duce, F. Chiellini, L. Ghezzi, S. Monti, R. Solaro, M. R. Tiné, Journal of Polymer
Science, Part A: Polymer Chemistry (2010), 48, 889-896.
20. A. Desii, F. Chiellini, R. Di Stefano, R. Solaro, M. R. Tiné, Journal of Polymer Science, Part A:
Polymer Chemistry (2010), 48, 986-990.
21. S. Aydinoglu, T. Biver, F. Secco*, M. Venturini. Int. J. Chem. Kin., 2010, 42(2), 79-89.
22. Z. Atay, T. Biver*, A. Corti, N. Eltugral, E. Lorenzini, M. Masini, A. Paolicchi, A. Pucci, G.
Ruggeri, F. Secco, M. Venturini.”, J. Nanopart. Res., 2010, 12(6), 2241-2253.
23. T. Biver, A. Boggioni, B. García, J. M. Leal, R. Ruiz, F. Secco, M. Venturini. Nucleic Acids
Research, 2010, 38(5), 1697-1710.
24. F. Secco, M. Venturini, T. Biver, F. Sanchez, R. Prado-Gotor, E. Grueso. J. Phys. Chem. B,
2010, 114(13), 4686-4691.
25. B. García, J. M. Leal, R. Ruiz, T. Biver, F. Secco, M. Venturini. J. Phys. Chem. B, 2010,
114(25), 8555-8564.
26. T. Biver, B. García, J. M. Leal, F. Secco, E. Turriani. Phys. Chem. Chem. Phys., 2010,
12(40), 13309-13317.
27. C. Bazzicalupi, S. Biagini, A. Bianchi, T. Biver, A. Boggioni, C. Giorgi, P. Gratteri, M. Malavolti,
F. Secco, B. Valtancoli, M. Venturini, Dalton Trans., 2010, 39, 9838-9850.
28. S. Biagini, A. Bianchi, T. Biver, A. Boggioni, I.V. Nikolayenko, F. Secco, M. Venturini, J. Inorg.
Biochem, 2011, 105, 558-562.
29. C. Duce, L. Ghezzi, A. Michele, R. Solaro, M. R. Tiné, Journal of Thermal Analysis and
Calorimetry (2011), 103, 75-80.
30. T. Biver, N. Eltugral, A. Pucci, G. Ruggeri, A. Schena, F. Secco, M. Venturini, Dalton Trans.,
in stampa.
31. I. Bonaduce, L. Carlyle, M.P.Colombini, C. Duce, C. Ferrari, E. Ribechini, P. Selleri, M.R. Tiné, J.
H.Townsend, submitted to Journal of Thermal Analysis and Calorimetry.