CHEMISTRY OF IONS IN THE GAS PHASE: FULLERENES AND ATOMIC CLUSTERS

1. CHEMISTRY OF IONS IN THE GAS PHASE: FULLERENES AND ATOMIC CLUSTERS Olivera Nešković Vinča Institute of Nuclear Sciences

2. A simple definition of a Mass Spectrometer • A Mass Spectrometer is an analytical instrument that can separate charged molecules according to theirmass–to–charge ratio. • Mass spectrometer can answer the questions “what is in the sample” (qualitative structural information) and “how much is present” (quantitative determination) for a very wide range of samples at high sensitivity

5. Mass Spectrometry Mass Spectrometry VINCA Advanced Mass Spectrometry Facility Picture Gallery Mass Spectrometry Mass Spectrometry

6. Mass Spectrometry Mass Spectrometry Mass Spectrometry Mass Spectrometry

7. Mass Spectrometry Mass Spectrometry Mass Spectrometry Maldi TOF Mass Spectromerer

8. Mass Spectrometry Mass Spectrometry Mass Spectrometry Magnetic Mass Spectrometer MS-1-MT

9. Mass Spectrometry Mass Spectrometry Mass Spectrometry Quadrupole Mass Spectrometer

10. Mass Spectrometry Mass Spectrometry Mass Spectrometry Mass Spectrometry Group

11. FULLERENESDERIVATIZED (FUNCTIONALIZED) FULLERENESCARBON NANOTUBESFUNCTIONALIZED NANOTUBES • Li@C60, Li@C70, Li2@C70 and Li3@C70 • Fullerenol C60(OH)16, C60(OH)22 • Fullerene bisadduct derivative C60C15H29N3O4 • Carbon nanotubes as Maldi matrix • Decorated carbon nanotubes by silver clusters • Endo and exo fullerenes by 99mTc • Carbon nanotubes derocated by DNA • Sequencing DNA by carbon nanotubes

12. The personal review (the limiting range of topics): • Prof. Dr. T.D. Märk, Institut für Ionenphysik, Innsbruck, Austria • Prof. Dr. Chava Lifshictz, The Hebrew University of Jerusalem, Israel • Prof. Dr. Lev Sidorov, Moscow State University, Russia • Prof. Dr. Thomas Drewello, University of Warwick, UK • Prof. Dr. Maurizio Prato, University of Trieste, Italy

13. Sample plate Extraction grids Reflector detector Linear detector Timed ion selector Reflector Laser Camera Pumping Pumping INLET ION SOURCE MASS FILTER DETECTOR Sample plate HPLC GC Solids probe MALDI API/Electrospray IonSpray EI, CI TOF Quadrupole Ion Trap Magnetic Sector FTMS “Hybrid” Microchannel Plate Electron Multiplier Components of a Mass Spectrometer

14. Ion Source:MALDI (MatrixAssistedLaserDesorptionIonisation) Laser flash produces matrix (M) neutrals, positive, negative ions and sample neutrals. M M*, MH+, (M-H)- Sample molecules (A) are ionised by gas phase proton transfer MH++A AH++M (M-H)-+A AH-+M + + + +

15. Ions of same mass, different velocities + + + + + + + + + + + + 0 kV 150 nsec Detector 2: Expansion of the ion cloud in the absence of an electric field. +20 kV 3: Field applied. Gradient accelerates slow ions more than fast ones. + +20 kV 4: Slow ions catch up with faster ones at the detector. DelayedExtraction(DE) 0 kV 0 nsec 1: Laser fired. Formed ions detach from plate in the absence of an electric field.

16. Mass Filter:ReflectorTOF The electrical field applied within the reflector produces an ion mirror effect directing the ions towards a second detector • Improvement in resolution by • Increasing the effective flight length of the tube • Re-focusing of analogous ions having slight different energy due to initial spread in the ion source

17. MALDI-TOFMatrices Sinapinic acid (3,5-Dimethoxy-4-hydroxy cinnamic acid) -cyano-4-hydroxycinnamic acid 2,5-dihydroxybenzoic acid (2,5-DHB) Carbon Clusters Peptide (0.1-10 pmol/l) Protein (0.1-10 pmol/ l) Oligonucleotide (10-100 pmol/ l) Polymer (10-4M) 2,4,6-trihydroxy acetophenone (THAP) 2-(4-hydroxyphenylazo)-benzoic acid (HABA) trans-3-indoleacrylic acid Dithranol 3-hydroxypicolinic acid (3-HPA)

18. CHCA and DCTB matrices

19. Isotopic Resolution • What benefit is high resolution • Improved identification of peptides • Indication of potential modification • Greater degree of mass accuracy • Resolution is defined as : Mass / (peak width at half peak height)

20. 2 x C13 C13 C12 : 5730.61 High Resolution - Too much data?Monoisotopic resolution of Insulin In compounds with more than 100 carbon atoms the height of the 13C isotope peak exceeds the height of the 12C peak

23. MALDI TOF mass spectrum of the fullerenol C60(OH)16containing sample using DCTB as a matrix and the corresponding negative-ion results

24. Novel fullerene bisadduct derivative

25. MALDI TOF mass spectrum of the novel fullerene bisadduct derivative C60C15H29N3O4. M+ and [M-H]+ positive ions , m/z= 1035.56 and 1036.48, were detected using CHCA and DCTB matrices

30. MALDI spectra of unpurified MWCN and SEM image

31. The positive MALDI spectra of fullerenes C60 with carbon nanotubes

32. Exo and endohedral compleves of C60 and C70 and C60(OH)(22) [99mTc(CO)3(H2O)3]@C60(OH)(22)

34. Silver clusters on carbon nanotubes Figure 1. TEM images of Ag/polymer MWCNT, (a) in the atmosphere of Ar, (b) in the

35. Figure 4: (a) STM image of MWCNT, (b) STM image of Ag/MWCNT Figure 5. STM image of Ag cluster

36. Mass spectrum of silver clusters

37. Using carbon nanotubes to induce micronuclei and double strand breaks of the DNA in human cells Jelena Cveticanin, Gordana Joksic, Andreja Leskovac, Sandra Petrovic, Ana Valenta Sobot and Olivera Neskovic1 Vinca Institute of Nuclear Sciences, PO Box 522, Belgrade, Serbia Figure 1 Figure 2 Figure 1: Implication of functionalized CNTS in the human lymphocyte cell Figure 2: STM picture of functionalized CNTS by sequence of DNA

38. Hipervalent molecules LinI, n=2-6 Knudsen efusion mass spectromety LiI with C70 Experimental and theoretical investigation of new hypervalent molecules LinF (n = 2–4)

39. Mass Spectrometry GroupVinča Institute of Nuclear Sciences • Thermal Ionization Mass Spectrometry (TIMS) • Maldi-Tof Mass Spectrometry (Maldi-Tof MS) Olivera Nešković Miomir Veljković Suzana Veličković Vesna Đorđević Jelena Cvetićanin Jasmina Đustebek Aleksandra Đerić Đorđe Trpkov