Karolína Šišková

Topic of PhD Thesis

New active systems for surface-enhanced Raman spectral probing of molecular and biomolecular species based on laser-ablated Ag and Au nanoparticles and nanostructures

Annotation

Ag and Au nanoparticles capped by molecular species are regarded as potential components for nanoelectronic devices. Of particular interest are the optical properties of these nanoparticles and their assemblies, namely optical resonances in the visible spectral region that give rise to strong fields with nanoscale localizations. Ag and Au nanoparticles and their assemblies indeed work as electromagnetic field amplifiers, and thus provide enhancement of optical processes undergone by molecules adsorbed on their surfaces and/or within the nanoparticle assembly. Surface–enhanced Raman scattering (SERS) and surface–enhanced resonance Raman scattering (SERRS) spectroscopies are now well established analytical and bioanalytical tools based on this phenomenon. Recent reports on achievement of a single molecule sensitivity in SERS and SERRS spectral probing largely reinforced research activities on this field. Part of the efforts is targeted on new strategies of Ag and Au nanoparticles and nanostructures preparation, and on exploration of the relationship between their morphology and optical responses. Laser ablation of a metal foil in aqueous medium has recently been recognized as a promising method for metal nanoparticle preparation.

The co-tutoring laboratories at University Pierre et Marie Curie (Paris) and at Charles University (Prague) were among the first research groups who explored and recognized the advantages of laser-ablated Ag nanoparticle hydrosols as substrates for SERS and SERRS spectroscopies. The proposed PhD thesis will be devoted to exploration of a new strategy of SERS and SERS-active substrate preparation by laser ablation of Ag and Au in the presence of molecular and biomolecular species of interest. The very new aspect of this strategy is the mediation of Ag and Au nanoparticle growth by adsorption of the selected molecular and biomolecular species and immediate formation of the SERS and/or SERRS active system during the ablation procedure. This mediation of nanoparticle growth will be monitored by TEM (Transmission Electron Microscopy) imaging of the nanostructures, and the relationship between their morphology and optical responses (in particular, production of strong nanoscale optical fields) will further be explored by determination of SERS and SERRS spectral detection limits of the target adsorbates with both macro- and micro-Raman devices. The results will be compared with those obtained from Ag and Au SERS and SERRS active systems prepared by chemical reduction of metal salts in the presence of the mediating molecular species, as well as from conventional SERS and SERRS active systems in which the adsorbate is added to pre-prepared Ag and Au metal hydrosols. Selected porphyrin and metalloporphyrin species, N-bases and fullerenes will be employed as the target adsorbates. The experiments will also provide a unique information about the stability and/or a two- or multiphoton photoactivity of the target adsorbates under Nd/YAG laser illumination during laser ablation and consequently enable a straigthforward identification of the photoproducts by SERS and/or SERRS. This study will contribute to a deep understanding of the mechanisms of nanoparticle growth under laser ablation of bulk metals in aqueous media and of the mediating role of molecular species, and possibly lead to new preparative strategies of Ag and Au nanoparticle capping by selected molecules. Furthermore, a new tool for investigation of photoprocesses undergone by porphyrin molecules will be developed and possibly provide important information for porphyrin-based photodynamic therapy of cancer. The results will also contribute to further development of SERS and SERRS spectroscopies as analytical tools for selective and ultrasensitive detection of analytes in general, and of biomolecular species in particular.

Supervisor

• Assoc. Prof. Blanka Vlčková
• Prof. Pierre-Yves Turpin

State of study

On 13 Decembre 2006 she fineshed her PhD studies (called French-Czech co-tutoring) with the succesful defence at Dept. of Physical and Macromolecular Chemistry of Charles University in Prague. The international commitee consisted of Czech and French professors: Prof. Karel Prochazka, Prof. Jiri Vohlidal, Prof. Sophie Cribier, Prof. Laurent Servant, Prof. Pierre-Yves Turpin, Assoc. Prof. Jiri Fiser, Assoc. Prof. Marek Prochazka, Assoc. Prof. Blanka Vlckova, Dr. Petr Stepanek, Dr. Zdenek Tuzar.

Exams

• Photochemical and electrochemical trasfer of electron - Prof. Antonín Vlček: 18. 12. 2003
• Modélisation a Mathematica – Prof. Jean Cognet: 10. 5. 2004
• SERS – RNDr. Marek Procházka, PhD: 14. 7. 2004

Publications

• K. Šišková, B. Vlčková, P-Y. Turpin, C. Fayet, J. Hromadková and M. Šlouf “Effect of citrate ions on laser ablation of Ag foil in aqueous medium” – J. Phys.: Conf. Ser. 2007 Vol. 59 202-205, doi:10.1088/1742-6596/59/1/044
• K. Šišková, B. Vlčková, P-Y. Turpin, C. Fayet “Ion-specific effects on laser ablation of silver in electrolyte aqueous solutions” – under revision in J. Phys. Chem. C.
• K. Sišková, B. Vlčková, P.-Y. Turpin, A. Thorel, A. Grosjean: “Porphyrins as SERRS spectral probes of chemically functionalized Ag nanoparticles” – submitted to Journal of Vibrational Spectroscopy.
• K. Šišková, J. Pfleger, B. Vlčková, P.-Y. Turpin, M. Šlouf: “New approach to donor-acceptor nanohybrids preparation: laser ablation of metal target in presence of donor/acceptor molecules” – submitted to Applied Physics A.
• Šloufová, K. Šišková, B. Vlčková, J. Štěpánek: “SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion” – submitted to Phys. Chem. Chem. Phys.
• B. Vlčková, M. Moskovits, I. Pavel , K. Šišková, M. Sládková, M. Šlouf: “Single-Molecule Surface-Enhanced Raman Spectroscopy from a Molecularly Bridged Silver Nanoparticle Dimer” – submitted to Chem. Phys. Lett.
• B. Vlčková, I. Pavel, M. Sládková, K. Šišková, M. Šlouf “Single molecule SERS: perspectives of analytical applications” – in press J. Mol. Struct. 2006
• K. Šišková, B. Vlčková, P. Mojzeš, “Spectral detection of J-aggregates of cationic porphyrin and investigation of conditions of their formation” J. Mol. Struct. 2005 Vol 744-747C, 265-272 (paper).
• P. Šmejkal, J. Pfleger, K. Šišková, B. Vlčková, O. Dammer, M. Šlouf, “In-situ study of Ag nanoparticle hydrosol optical spectra evolution during laser ablation/fragmentation” Appl.Phys. A (Materials Science & Processing), Vol.79, No. 4-6, 2004, 1307-1309 (paper).
• Šmejkal,P; Šišková,K.; Vlčková, B; Pfleger, J.; Šloufová, I.; Šlouf, M.; Mojzeš,P. “Characterization and surface-enhanced Raman spectral probing of silver hydrosols prepared by two-wavelength laser ablation and fragmentation” Spectrochim. Acta Part A 2003, 59, 14, 2321-2329 (paper).

Conferences

• K. Šišková, J. Pfleger, B. Vlčková, P.-Y. Turpin, M. Šlouf: “New approach to donor-acceptor nanohybrids preparation: laser ablation of metal target in presence of donor/acceptor molecules” – poster presentation, COLA'07 (= Conference on Laser Ablation), Tenerife in Spain, September 24–28, 2007.
• K. Šišková, B. Vlčková, P.-Y. Turpin, A. Thorel, A. Grosjean: “Porphyrins as SERRS spectral probes of chemically functionalized Ag nanoparticles” 4th International Conference on Advanced Vibrational Spectroscopy; June 10–15, 2007, Corfu, Greece
• K. Šišková, B. Vlčková, P.-Y. Turpin, A. Thorel, A. Grosjean: “Nové funkcionalizované nanočástice pro SERRS spektrální detekci nízkých koncentrací porfyrinů” – oral presentation
  Workshop: Detekce kinetických a strukturních charakteristik interakcí bioaktivních molekul s jejich biologickými terči, 7.-8. 12. 2006 Praha, ČR.
• Vlčková, B., Moskovits, M., I. Pavel, Siskova, K., Sladkova, M., Smejkal P., Slouf, M.: “Časový vývoj SERS signálu získaného z molekulárně-můstkovaného dimeru Ag nanočástic” – oral presentation, coauthor
  Workshop: Detekce kinetických a strukturních charakteristik interakcí bioaktivních molekul s jejich biologickými terči, 7.-8. 12. 2006 Praha, CR.
• K. Šišková, B. Vlčková, P.-Y. Turpin, C. Fayet, J. Hromádková, M. Šlouf: “A new approche to controlled preparation of chemically modified Ag nanoparticles: laser ablation of Ag in aqueous solutions and role of bulky ions” – oral presentation
  Colloque Nano-hybrides 3: Elaboration et fonctionnalisation de nano-hybrides Bio-applications, 5-9 June 2006 Porquerolles, France.
• B. Vlckova, M. Moskovits, I. Pavel, M. Sladkova, K. Siskova, M. Slouf: “Single molecule SERS: Perspectives of analytical applications” – coauthor
  Keynote and Plenary Lectures (Pl-4), European congress on molecular spectroscopy (EUCMOS), Book of Abstracts, Editors Sevim Akyuz, Elif Akalin, Sept. 3-8, 2006, Istanbul University, Istanbul, Turkey.
• K. Šišková, B. Vlčková, P.-Y. Turpin, A. Thorel, A. Grosjean: “Porphyrins used as SERRS activity probes of Ag nanoparticle surfaces prepared by LA in controlled citrate concentrations” – poster presentation
  SBE's 2nd International Conference on Bioengineering and Nanotechnology, 5-7 September 2006 Santa Barbara, California, USA.
• K. Siskova, P. Smejkal, O. Dammer, J. Pfleger, B. Vlckova, P.-Y. Turpin, C. Fayet: “Preparation of silver nanoparticles by laser ablation of silver in aqueous media: Controlling efficiency of the process by laser pulse parameters and electrolyte presence” – coauthor
  Proceedings of ICCE-14, Fourteenth annual international conference on composites/nanoengineering, Edited by David Hui, July 2-8, 2006, USA, Boulder Colorado, Section 2a, Nano2.
• B. Vlckova, M. Moskovits, I. Pavel, M. Sladkova, K. Siskova, P. Smejkal, M. Slouf: “Surface-Enhanced Raman Spectroscopy on Single Molecule Level: Perspectives of Analytical Applications” – coauthor
  Transactions of the Universities  of Kosice, 2-3/2006, p. 132-135, ISSN 1335-2334.
• K. Šišková, B. Vlčková, P-Y. Turpin, C. Fayet, J. Hromádková and M. Šlouf: “Laser ablation of Ag foil in aqueous medium: Effect of citrate ions” – oral presentation
  Conference of PhD students : Marie Curie POLYAMPHI project (GAČR 203/05/H001), September 30, 2005, Prague; Book of abstracts, p. 32.
• K. Siskova, B. Vlckova, P-Y. Turpin, C. Fayet, J. Hromadkova and M. Slouf: “Effect of citrate ions on laser ablation of Ag foil in aqueous medium” – poster presentation
  Cola'05 (= Conference on Laser Ablation), September 11-16, 2005, Banff Centre in Canada, Journal of Physics – special issue p.xxx.
• Participation in Or-Nano congres, Paris, 30.6.-1.7. 2005.
• K. Šišková, B. Vlčková, P-Y. Turpin, C. Fayet: “Ag nanoparticles formation by laser ablation in presence of salts” – oral presentation
  NANO´04 – Book of abstracts, International Conference, VUT Brno, FSI, ed.: Šandera, P.; p.11.
• B. Vlčková, K. Šišková, I. Šloufová, M. Michl, P. Šmejkal,M. Šlouf,P. Mojzeš: “Surface-enhanced Raman spectral probing of hybrid nanomaterials constituted by silver or gold nanoparticles and porphyrin molecules” – poster presentation
  XXVII European congress on molecular spectroscopy = EUCMOS; September 2004; Editors: M. Handke, M. Hasik, C. Paluszkiewicz; Krakow.
• K. Šišková, B. Vlčková, P. Mojzeš, M. Šlouf: “New SERS-active systems based on adsorbate-mediated growth of silver nanoparticles” – oral presentation
  XXVII European congress on molecular spectroscopy = EUCMOS; September 2004; Editors: M. Handke, M. Hasik, C. Paluszkiewicz; Krakow; p. 114.
• K. Šišková, I. Šloufová-Srnová, B. Vlčková, P. Mojzeš: “Croissance de nanoparticules d´argent et formation d´Ag-2,2´-bipyridine de surface possédant des propriétés de transfert de charge photoinduit” – poster presentation
  Congres des jeunes chercheures; Association des Doctorants de l´Institut Curie; Paris;
• Šišková, K.; Vlčková, B.; Mojzeš, P.; Šlouf, M.: “Adsorbate-mediated growth of silver nanoparticles” – oral presentation
  Nano’03, International Conference, VUT Brno, FSI, ed.: Šandera, P.; October 21-23. p. 19.
• Šišková, K.; Vlčková, B.; Mojzeš, P.; Šlouf, M.: “SERS spectra of systems prepared by Ag nanoparticle growth in the presence of adsorbate” – oral presentation
  12. spectroscopic conference; ed.: Fara, M.; VŠCHT Prague, 10.-12. 6. 2003. p. 30.
• Šišková, K.; Srnová–Šloufová, I; Vlčková, B.; Mojzeš, P.: “Role of Ag nanoparticles growth in formation of Ag-2,2'-bipyridine surface species exhibiting photoinduced charge transfer” – poster presentation
  Book of Abstracts, XXXV th International Conference on Coordination Chemistry (ICCC 35) 21-26 July 2002, Heidelberg, Germany. University of Heidelberg, 2002, p. 936.

Other scientific activities and/or events

• 21. 8.–15. 9. 2000 – 9th Summer School of Vibrational spectroscopy in biophysics and biochemistry at the Faculty of Mathematics and Physics of Charles university in Prague – active presence
• September 2001 – 9thECSB (European conference on spectroscopy of biomolecules) hold in Prague (main organizer: Prof. Josef Štěpánek, Institut of Biophysics at the Faculty of Mathematics and Physics of Charles university in Prague) – as a student staff support
• December 2003 – 1st place in the competition for the best Diploma Thesis of the year
• September 2005 – member of organizing team of PhD students‘ conference hold in Prague on the Department of Physical and Macromolecular Chemistry at the Faculty of Science at Charles University in Prague
• 26.–28. 6. 2007 – Summer school of SPM (Scanning probe microscopy), VUT, Brno.
• 30. 10. 2007 – Kelvin probe AFM, Institute of Physics AS CR, Cukrovarnická 122/10, Praha 6.
• Receiving of Fulbright grant for the long-term stay in the US, at the University of California at Santa Barbara from September 2008 to June 2009 – prof. Nguyen laboratory.

Stays abroad

• 21-26 July 2002, Heidelberg, Germany
• 7. 1.–30. 6. 2004, Paris, France
• September 2004, Krakow, Poland
• 9. 1.–6. 7. 2005, Paris, France
• September 11–16, 2005, Banff Centre in Canada
• 3. 1.–24. 6. 2006, Paris, France

Pedagogical activities

• Winter semestre 2003/2004 – assistant in the subject “Practice of Physical Chemistry” for students of 3th schoolyear of their Master degree in Chemistry-Biology education for grammar schools
• Winter semestre 2004/2005 – assistant in the subject “Practice of Physical Chemistry” for students of 5th schoolyear of their Master degree in Chemistry education for grammar schools
• September 2004, Krakow, Poland
• 13. 6.–1. 7. 2005 – education of two French students on the topic of metal nanoparticles preparation by laser ablation
• November 2007 – lecture about STM at the Dept. of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague

Participation in other grants and projects

• AV0Z4050913
• 203/04/0688

Contact

e-mail: ksiskova (na) seznam (tečka) cz