CHEMISTRY OF IONS IN THE GAS PHASE FULLERENES

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. • 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

Investigator(s) Contribution Nobel Prize Thomson 1897 discovery of the electron, first mass spectrometer 1906 in Physics Dempster 1918 Electron ionization and magnetic focusing Aston 1919 atomic weights using MS and 1922 in isotopes study Chemistry Stephens 1946 Time-of-flight mass analysis Hipple, Sommer, and Thomas 1949 Ion cyclotron resonance Johnson and Nier 1953 Double-focusing instruments Paul and Steinwedel 1953 Quadrupole analyzers Beynon 1956 High-resolution MS 1989 in Physics

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FULLERENES DERIVATIZED (FUNCTIONALIZED) FULLERENES CARBON NANOTUBES FUNCTIONALIZED NANOTUBES • • Li@C 60, Li@C 70, Li 2@C 70 and Li 3@C 70 Fullerenol C 60(OH)16, C 60(OH)22 Fullerene bisadduct derivative C 60 C 15 H 29 N 3 O 4 Carbon nanotubes as Maldi matrix Decorated carbon nanotubes by silver clusters Endo and exo fullerenes by 99 m. Tc 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 Sample plate Extraction grids Laser Timed ion selector Reflector detector Reflector Linear detector Camera Pumping INLET ION SOURCE MASS FILTER DETECTOR Sample plate MALDI TOF “Hybrid” HPLC GC Solids probe API/Electrospray Ion. Spray EI, CI Quadrupole Ion Trap Magnetic Sector FTMS Microchannel Plate Electron Multiplier

Ion Source: MALDI (Matrix Assisted Laser Desorption Ionisation) 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

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

Mass Filter: Reflector TOF 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

MALDI-TOF Matrices 2, 5 -dihydroxybenzoic acid (2, 5 -DHB) 2 -(4 -hydroxyphenylazo)benzoic acid (HABA) Dithranol Sinapinic acid (3, 5 -Dimethoxy-4 hydroxy cinnamic acid) Carbon Clusters Peptide (0. 1 -10 pmol/ l) Protein (0. 1 -10 pmol/ l) Oligonucleotide (10 -100 pmol/ l) Polymer (10 -4 M) 3 -hydroxypicolinic acid (3 -HPA) -cyano-4 -hydroxycinnamic acid 2, 4, 6 -trihydroxy acetophenone (THAP) trans-3 -indoleacrylic acid

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 2 x C 13 C 12 : 5730. 61 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 C 60 C 15 H 29 N 3 O 4. M+ and [M-H]+ positive ions , m/z= 1035. 56 and 1036. 48, were detected using CHCA and DCTB matrices

MALDI spectra of unpurified MWCN and SEM image

The positive MALDI spectra of fullerenes C 60 with carbon nanotubes

Exo and endohedral compleves of C 60 and C 70 and C 60(OH)(22) [99 m. Tc(CO)3(H 2 O)3]@C 60(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 Neskovic 1 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

Hipervalent molecules Lin. I, n=2 -6 Knudsen efusion mass spectromety Li. I with C 70 Experimental and theoretical investigation of new hypervalent molecules Lin. F (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