Stefania Rapino

During my academic career, I have gained and consolidated my expertise in several theoretical and experimental fields concerning electrochemistry, materials science, surface chemistry, scanning probe techniques (SPT) and scanning electrochemical microscopy (SECM), Bio-electrochemistry, simulation of organic-metal interactions and dynamics for nanotechnological and highly technological purposes. Moreover, I have good skills in micro-probe development and fabrication also specific for surface micro-tailoring. I have also worked in strong collaboration with the European Institute of Oncology (IEO) in Milan, developing new electrochemical micro-tools for the investigation of oxygen consumption/reactive oxygen species generation, of metabolites and of the redox state in complex system such as living cells, in order to clarify tumour cell metabolic mechanisms.

My current research interests include micro-structuring of surfaces and  their investigation at micro and sub-micrometric level; catalytic molecules, carbon nanostructures (fullerens, carbon nanotubes and graphene) and their addressing on functional surfaces; nanotechnological applications of functional molecules onto metal surfaces and nanostructures (also for energy conversion, storage and renewable energy applications); biologically-relevant molecular processes; micro- and nano-electrochemical investigations of living cell research. I contributed to the developing, publication and patenting of original procedures to produce novel materials based on carbon nanostructures and their integration in functional materials and devices for energy conversion application. 

Surface modification and characterization: My activity in the field of surface modification and characterization has concerned the investigation of the theoretical aspects, electrochemical and photochemical behaviour of molecules directly adsorbed on surfaces or attached by postfunctionalization of preformed Self Assembled Monolayer or electrografted polymer. Some example of this activity are following reported: Immobilization and investigation 1) of fullerenes based compounds [10], 2) of  interlocked molecular architectures attached to acid terminated SAM or directly adsorbed on gold [11,13]; 3) modeling and simulation of molecular processes at gold surfaces , such as: modeling the stability and the motion of DNA  nucleobases on the gold surface and simulation of the dynamics of thiolate chains on a gold nanoparticle [8,12]; 4) Investigation of the Mechanochemistry for the targeted delivery of single molecules.[9]

Along with the investigation of such nanosystems at a fundamental level, I shall be pursuing more applicative tasks mainly oriented to the preparation of micrometer and sub-micrometer patterned and nanostructured materials and electrode surfaces for the development of electrochemical devices and (bio)sensors. My accomplishments on surface micro-patterning were published recently:  1) A novel method for using scanning electrochemical microscopy to draw pre-defined patterns of reactive spots onto conducting substrates that may then be functionalized—ad hoc and at will—with any molecular species containing an amine or other nucleophilic group, including proteins and enzymes [6]  and 2) A chemical route to locally etch the native silica film on silicon, using the SECM, thus creating patterns of reactive Si−H holes, is described. The procedure is based on the alteration of the pH in the volume between the SECM tip and the pristine p-Si substrate so as to turn locally the initially inert fluoride solution into a strong etchant capable to bear holes through the SiO2 native layer in a very controlled and highly reproducible way. The direct electrochemical grafting of p-NO2−benzene diazonium cation into the etched Si−H holes and the subsequent functionalization of the electrografted organic layer by either a fluorescent probe or a redox probe (HRP) were then used to highlight the versatility of this approach for the fabrication of micropatterned functional surfaces [4].

 

References

 

1.      Electrochemical study of hydrogen peroxide formation in isolated mitochondria. Raluca Marcu*, Stefania Rapino*, Mirella Trinei, Giovanni Valenti, Massimo Marcaccio, Pier GiuseppePelicci, Francesco Paolucci, and Marco Giorgio. Bioelectrochemistry (in press) * co-first author.

 

2.      Highly electroconductive multiwalled carbon nanotubes as potentially useful tools for modulating calcium balancing in biological environments Autori:Annalucia Serafino, Anna Rita Togna,  Giuseppina I. Togna, Antonella Lisi,  Mario Ledda, Settimio Grimaldi, Julie Russier, Federica Andreola, Marc Monthioux, Francois Béguin, Massimo Marcaccio, Stefania Rapino, Francesco Paolucci, Silvana Fiorito. Source: NANOMEDICINE.  Received 8 November 2010; accepted 20 June 2011. published online 04 July 2011. (ISSN: 1549-9634 Online ISSN: 1549-9642).

 

3.      Tailored Functionalization of Carbon Nanotubes for Electrocatalytic Water Splitting and Sustainable Energy Applications. Autori: Francesca Maria Toma, Andrea Sartorel,  Matteo Iurlo, Mauro Carraio,  Stefania Rapino, Lena Hoober-Burkhardt, Tatiana Da Ros, Massimo Marcaccio, Gianfranco Scorrano, Francesco Paolucci, Marcella Tonchio, Maurizio Prato. CHEMSUSCHEM. Volume 4, Issue 10, pages 1447–1451, October 17, 2011. (Article first published online: 7 JUL 2011 DOI: 10.1002/cssc.201100089, Print ISSN: 1864-5631, Online ISSN: 1864-564X)

 

 

4.      Creation of Reactive Micro Patterns on Silicon by Scanning Electrochemical Microscopy. G. Valenti, L. Bardini, D. Bonazzi, S. Rapino, M. Marcaccio, F. Paolucci J.Phys. Chem C, 2010, 114(50), 22165-22170. DOI: 10.1021/jp1067928 (Casa Editrice American Chemical Society, Washington DC, ISSN:1932-7447; Pubblicato on line il 02/12/2010)

 

5.      Intense and Tunable Electrochemiluminescence of Corannulene.  G. Valenti, C. Bruno, S. Rapino, A. Fiorani, E. A. Jackson, L. T. Scott, F. Paolucci, M. Marcaccio J.Phys. Chem C, 2010, 114 (45), 19467–19472. (Casa Editrice American Chemical Society, Washington DC, ISSN:1932-7447; Pubblicato il 26/10/2010)

 

6.      Efficient water oxidation at carbon nanotube–polyoxometalate electrocatalytic interfaces. F. M. Toma, A. Sartore, M. Iurlo, Mauro Carraro, P. Parisse, C. Maccato, S. Rapino, B. Rodriguez Gonzalez, H. Amenitsch, T. Da Ros, L. Casalis, A. Goldoni, M. Marcaccio, G. Scorrano, G. Scoles, F. Paolucci, M. Prato, M. Tonchio. Nature Chemistry, 2010, 2, 826-831 (8 August 2010) doi:10.1038/nchem.761 (Nature Group Publishing, London, ISSN:1755-4330)

 

7.      Microdrawing and highlighting a reactive surface. Stefania Rapino, Giovanni Valenti, Raluca Marcu, Marco Giorgio, Massimo Marcaccio,  Francesco Paolucci. J. Mater. Chem. (2010), 20 ,34, 7272-7275. DOI: 10.1039/c0jm00818d (Royal Society of Chemistry, Cambridge, ISSN: 0959-9428 Pubblicato il 24/03/2010)

 

8.      Dynamics of Thiol Chains on Gold Nanoparticle.  Stefania Rapino, Francesco Zerbetto. Small, 2007, 3 (3), 386-388. (Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim, DOI: 10.1002/smll.200600456, ISSN: 1613-6810, pubblicato on-line: 5/02/2007)

9.      Mechanochemistry: targeted delivery of single molecules. Anne-Sophie Duwez, Stéphane Cuenot, Christine Jérôme, Sabine Gabriel, Robert Jérôme, Stefania Rapino and Francesco Zerbetto. Nature Nanotechnology (2006), 1, 122-125. (doi:10.1038/nnano.2006.92, Nature Publishing group, London, Published online: 29 October 2006; ISSN:1748-3387; Pubblicato on-line: pubblicato on-line: 29/10/2006)

 

10.  Structural and electrochemical characterization of fullerene-based surfaces of C60 mono- or bis-adducts grafted onto self-assembled monolayers.      Cecchet, Francesca; Rapino, Stefania; Margotti, Massimo; Da Ros, Tatiana; Prato, Maurizio; Paolucci, Francesco; Rudolf, Petra.  Carbon  (2006),  44 (14),  3014-3021. (doi:10.1016/j.carbon.2006.05.024, Elsevier Ltd., ISSN: 0008-6223, London - New York; pubblicato on line: 10/07/2006)

 

11.  Adsorption of Fumaramide [2]Rotaxane and Its Components on a Solid Substrate: A Coverage-Dependent Study.      Whelan, Caroline M.; Gatti, Francesco; Leigh, David A.; Rapino, Stefania; Zerbetto, Francesco; Rudolf, Petra.  Journal of Physical Chemistry B  (2006),  110 (34),  17076-17081. (10.1021/jp061836c, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; Pubblicato on-line 10/8/2006)

 

12.  Redox Mediation at 11-Mercaptoundecanoic Acid Self-Assembled Monolayers on Gold.      Cecchet, Francesca; Marcaccio, Massimo; Margotti, Massimo; Paolucci, Francesco; Rapino, Stefania; Rudolf, Petra. Journal of Physical Chemistry B  (2006),  110 (5),  2241-2248. (10.1021/jp054290n, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 14/01/2006)

13.  Electrode Surface Modification by a Spirobifluorene Derivative. An XPS and Electrochemical Investigation.      Cecchet, Francesca; Fioravanti, Giulia; Marcaccio, Massimo; Margotti, Massimo; Mattiello, Leonardo; Paolucci, Francesco; Rapino, Stefania; Rudolf, Petra. Journal of Physical Chemistry B  (2005),  109 (39),  18427-18432. (doi: 10.1021/jp051786w, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 08/09/2005)

 

14.  Modeling the Stability and the Motion of DNA Nucleobases on the Gold Surface.      Rapino, Stefania; Zerbetto, Francesco.  Langmuir  (2005),  21 (6),  2512-2518. (doi: 10.1021/la047091o, American Chemical Society, Washington, DC, ISSN:0743-7463; pubblicato on-line: 08/02/2005)

 

15.  Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer.      Cecchet, Francesca; Rudolf, Petra; Rapino, Stefania; Margotti, Massimo; Paolucci, Francesco; Baggerman, Jacob; Brouwer, Albert M.; Kay, Euan R.; Wong, Jenny K. Y.; Leigh, David A.      Journal of Physical Chemistry B  (2004),  108 (39),  15192-15199. (Doi:10.1021/jp048621s, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 08/09/2004)

During my academic career, I have gained and consolidated my expertise in several theoretical and experimental fields concerning electrochemistry, materials science, surface chemistry, scanning probe techniques (SPT) and scanning electrochemical microscopy (SECM), Bio-electrochemistry, simulation of organic-metal interactions and dynamics for nanotechnological and highly technological purposes. Moreover, I have good skills in micro-probe development and fabrication also specific for surface micro-tailoring. I have also worked in strong collaboration with the European Institute of Oncology (IEO) in Milan, developing new electrochemical micro-tools for the investigation of oxygen consumption/reactive oxygen species generation and of the redox state in complex system such as living cells, in order to clarify tumour cell metabolic mechanisms. 

My current research interests include micro-structuring of surfaces and  their investigation at micro and sub-micrometric level; catalytic molecules, carbon nanostructures (fullerens, carbon nanotubes and graphene) and their addressing on functional surfaces; nanotechnological applications of functional molecules onto metal surfaces and nanostructures (also for energy conversion, storage and renewable energy applications); biologically-relevant molecular processes; micro- and nano-electrochemical living cell research. I contributed to the developing, publication and patenting of original procedures to produce novel materials based on carbon nanostructures and their integration in functional materials and devices for energy conversion application. [3,6]

Surface modification and characterization: My activity in the field of surface modification and characterization has concerned the investigation of the theoretical aspects, electrochemical and photochemical behaviour of molecules directly adsorbed on surfaces or attached by postfunctionalization of preformed Self Assembled Monolayer or electrografted polymer. Some example of this activity are following reported: Immobilization and investigation 1) of fullerenes based compounds [10], 2) of  interlocked molecular architectures attached to acid terminated SAM or directly adsorbed on gold [11,13]; 3) modeling and simulation of molecular processes at gold surfaces , such as: modeling the stability and the motion of DNA  nucleobases on the gold surface and simulation of the dynamics of thiolate chains on a gold nanoparticle [8,12]; 4) Investigation of the Mechanochemistry for the targeted delivery of single molecules.[9]

Along with the investigation of such nanosystems at a fundamental level, I shall be pursuing more applicative tasks mainly oriented to the preparation of micrometer and sub-micrometer patterned and nanostructured materials and electrode surfaces for the development of electrochemical devices and (bio)sensors. My accomplishments on surface micro-patterning were published recently:  1) A novel method for using scanning electrochemical microscopy to draw pre-defined patterns of reactive spots onto conducting substrates that may then be functionalized—ad hoc and at will—with any molecular species containing an amine or other nucleophilic group, including proteins and enzymes [6]  and 2) A chemical route to locally etch the native silica film on silicon, using the SECM, thus creating patterns of reactive Si−H holes, is described. The procedure is based on the alteration of the pH in the volume between the SECM tip and the pristine p-Si substrate so as to turn locally the initially inert fluoride solution into a strong etchant capable to bear holes through the SiO2 native layer in a very controlled and highly reproducible way. The direct electrochemical grafting of p-NO2−benzene diazonium cation into the etched Si−H holes and the subsequent functionalization of the electrografted organic layer by either a fluorescent probe or a redox probe (HRP) were then used to highlight the versatility of this approach for the fabrication of micropatterned functional surfaces [4].

 

References

 

1.      Electrochemical study of hydrogen peroxide formation in isolated mitochondria. Raluca Marcu*, Stefania Rapino*, Mirella Trinei, Giovanni Valenti, Massimo Marcaccio, Pier GiuseppePelicci, Francesco Paolucci, and Marco Giorgio. Bioelectrochemistry (in press) * co-first author.

 

2.      Highly electroconductive multiwalled carbon nanotubes as potentially useful tools for modulating calcium balancing in biological environments Autori:Annalucia Serafino, Anna Rita Togna,  Giuseppina I. Togna, Antonella Lisi,  Mario Ledda, Settimio Grimaldi, Julie Russier, Federica Andreola, Marc Monthioux, Francois Béguin, Massimo Marcaccio, Stefania Rapino, Francesco Paolucci, Silvana Fiorito. Source: NANOMEDICINE.  Received 8 November 2010; accepted 20 June 2011. published online 04 July 2011. (ISSN: 1549-9634 Online ISSN: 1549-9642).

 

3.      Tailored Functionalization of Carbon Nanotubes for Electrocatalytic Water Splitting and Sustainable Energy Applications. Autori: Francesca Maria Toma, Andrea Sartorel,  Matteo Iurlo, Mauro Carraio,  Stefania Rapino, Lena Hoober-Burkhardt, Tatiana Da Ros, Massimo Marcaccio, Gianfranco Scorrano, Francesco Paolucci, Marcella Tonchio, Maurizio Prato. CHEMSUSCHEM. Volume 4, Issue 10, pages 1447–1451, October 17, 2011. (Article first published online: 7 JUL 2011 DOI: 10.1002/cssc.201100089, Print ISSN: 1864-5631, Online ISSN: 1864-564X)

 

 

4.      Creation of Reactive Micro Patterns on Silicon by Scanning Electrochemical Microscopy. G. Valenti, L. Bardini, D. Bonazzi, S. Rapino, M. Marcaccio, F. Paolucci J.Phys. Chem C, 2010, 114(50), 22165-22170. DOI: 10.1021/jp1067928 (Casa Editrice American Chemical Society, Washington DC, ISSN:1932-7447; Pubblicato on line il 02/12/2010)

 

5.      Intense and Tunable Electrochemiluminescence of Corannulene.  G. Valenti, C. Bruno, S. Rapino, A. Fiorani, E. A. Jackson, L. T. Scott, F. Paolucci, M. Marcaccio J.Phys. Chem C, 2010, 114 (45), 19467–19472. (Casa Editrice American Chemical Society, Washington DC, ISSN:1932-7447; Pubblicato il 26/10/2010)

 

6.      Efficient water oxidation at carbon nanotube–polyoxometalate electrocatalytic interfaces. F. M. Toma, A. Sartore, M. Iurlo, Mauro Carraro, P. Parisse, C. Maccato, S. Rapino, B. Rodriguez Gonzalez, H. Amenitsch, T. Da Ros, L. Casalis, A. Goldoni, M. Marcaccio, G. Scorrano, G. Scoles, F. Paolucci, M. Prato, M. Tonchio. Nature Chemistry, 2010, 2, 826-831 (8 August 2010) doi:10.1038/nchem.761 (Nature Group Publishing, London, ISSN:1755-4330)

 

7.      Microdrawing and highlighting a reactive surface. Stefania Rapino, Giovanni Valenti, Raluca Marcu, Marco Giorgio, Massimo Marcaccio,  Francesco Paolucci. J. Mater. Chem. (2010), 20 ,34, 7272-7275. DOI: 10.1039/c0jm00818d (Royal Society of Chemistry, Cambridge, ISSN: 0959-9428 Pubblicato il 24/03/2010)

 

8.      Dynamics of Thiol Chains on Gold Nanoparticle.  Stefania Rapino, Francesco Zerbetto. Small, 2007, 3 (3), 386-388. (Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim, DOI: 10.1002/smll.200600456, ISSN: 1613-6810, pubblicato on-line: 5/02/2007)

9.      Mechanochemistry: targeted delivery of single molecules. Anne-Sophie Duwez, Stéphane Cuenot, Christine Jérôme, Sabine Gabriel, Robert Jérôme, Stefania Rapino and Francesco Zerbetto. Nature Nanotechnology (2006), 1, 122-125. (doi:10.1038/nnano.2006.92, Nature Publishing group, London, Published online: 29 October 2006; ISSN:1748-3387; Pubblicato on-line: pubblicato on-line: 29/10/2006)

 

10.  Structural and electrochemical characterization of fullerene-based surfaces of C60 mono- or bis-adducts grafted onto self-assembled monolayers.      Cecchet, Francesca; Rapino, Stefania; Margotti, Massimo; Da Ros, Tatiana; Prato, Maurizio; Paolucci, Francesco; Rudolf, Petra.  Carbon  (2006),  44 (14),  3014-3021. (doi:10.1016/j.carbon.2006.05.024, Elsevier Ltd., ISSN: 0008-6223, London - New York; pubblicato on line: 10/07/2006)

 

11.  Adsorption of Fumaramide [2]Rotaxane and Its Components on a Solid Substrate: A Coverage-Dependent Study.      Whelan, Caroline M.; Gatti, Francesco; Leigh, David A.; Rapino, Stefania; Zerbetto, Francesco; Rudolf, Petra.  Journal of Physical Chemistry B  (2006),  110 (34),  17076-17081. (10.1021/jp061836c, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; Pubblicato on-line 10/8/2006)

 

12.  Redox Mediation at 11-Mercaptoundecanoic Acid Self-Assembled Monolayers on Gold.      Cecchet, Francesca; Marcaccio, Massimo; Margotti, Massimo; Paolucci, Francesco; Rapino, Stefania; Rudolf, Petra. Journal of Physical Chemistry B  (2006),  110 (5),  2241-2248. (10.1021/jp054290n, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 14/01/2006)

13.  Electrode Surface Modification by a Spirobifluorene Derivative. An XPS and Electrochemical Investigation.      Cecchet, Francesca; Fioravanti, Giulia; Marcaccio, Massimo; Margotti, Massimo; Mattiello, Leonardo; Paolucci, Francesco; Rapino, Stefania; Rudolf, Petra. Journal of Physical Chemistry B  (2005),  109 (39),  18427-18432. (doi: 10.1021/jp051786w, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 08/09/2005)

 

14.  Modeling the Stability and the Motion of DNA Nucleobases on the Gold Surface.      Rapino, Stefania; Zerbetto, Francesco.  Langmuir  (2005),  21 (6),  2512-2518. (doi: 10.1021/la047091o, American Chemical Society, Washington, DC, ISSN:0743-7463; pubblicato on-line: 08/02/2005)

 

15.  Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer.      Cecchet, Francesca; Rudolf, Petra; Rapino, Stefania; Margotti, Massimo; Paolucci, Francesco; Baggerman, Jacob; Brouwer, Albert M.; Kay, Euan R.; Wong, Jenny K. Y.; Leigh, David A.      Journal of Physical Chemistry B  (2004),  108 (39),  15192-15199. (Doi:10.1021/jp048621s, American Chemical Society, Washington, D.C., ISSN: 1520-6106, ISSN rivista on-line 1520-5215; pubblicato on-line: 08/09/2004)