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

A simple definition of a Mass Spectrometer A Mass Spectrometer is an analytical instrument that can separate charged molecules according to their mass–to–charge ratio.A Mass Spectrometer is an analytical instrument that can separate charged molecules according to their mass–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 sensitivityMass 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

Investigator(s)ContributionNobel Prize Thomson1897 discovery of the electron, first mass spectrometer 1906 in Physics Dempster1918 Electron ionization and magnetic focusing Aston1919 atomic weights using MS and isotopes study 1922 in Chemistry Stephens1946 Time-of-flight mass analysis Hipple, Sommer, and Thomas 1949 Ion cyclotron resonance Johnson and Nier1953 Double-focusing instruments Paul and Steinwedel 1953 Quadrupole analyzers1989 in Physics Beynon 1956 High-resolution MS

Mass Spectrometry VINCA Advanced Mass Spectrometry Facility Picture Gallery

Mass Spectrometry

Maldi TOF Mass Spectromerer

Mass Spectrometry Magnetic Mass Spectrometer MS-1-MT

Mass Spectrometry Quadrupole Mass Spectrometer

Mass Spectrometry Mass Spectrometry Group

FULLERENES DERIVATIZED (FUNCTIONALIZED) FULLERENES CARBON NANOTUBES FUNCTIONALIZED NANOTUBES and 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

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

Components of a Mass Spectrometer INLETION SOURCEMASS FILTERDETECTOR Sample plate HPLC GC Solids probe MALDI API/Electrospray IonSpray EI, CI TOF Quadrupole Ion Trap Magnetic Sector FTMS “Hybrid” Microchannel Plate Electron Multiplier

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 Ion Source: MALDI (Matrix Assisted Laser Desorption Ionisation)

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

The electrical field applied within the reflector produces an ion mirror effect directing the ions towards a second detector Mass Filter: Reflector TOF 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

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

CHCA and DCTB matrices

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)

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

MALDI TOF mass spectrum of the fullerenol C 60 (OH) 16 containing sample using DCTB as a matrix and the corresponding negative-ion results

Novel fullerene bisadduct derivative

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

MALDI spectra of unpurified MWCN and SEM image

The positive MALDI spectra of fullerenes C60 with carbon nanotubes

Exo and endohedral compleves of C60 and C70 and C60(OH)(22)

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

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

Mass spectrum of silver clusters

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 1Figure 2 Figure 1: Implication of functionalized CNTS in the human lymphocyte cell Figure 2: STM picture of functionalized CNTS by sequence of DNA

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)

Mass Spectrometry Group Vinča 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