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C7895 Mass Spectrometry of Biomolecules Schedule of Lectures

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C7895 Mass Spectrometry of Biomolecules Schedule of Lectures C7895 Mass Spectrometry of Biomolecules Schedule of lectures For schedule, please see a separate file with the course outline. Jan Preisler Consulting The last lecture. Please contact me in advance to make an appointment. Chemistry Dept. 312A14, tel.: 54949 6629, [email protected] This material is just an outline; students are advised to print this outline and write down notes durin the lectures. The material will be updated during The course is focused on mass spectrometry of biomolecules, i.e. ionization the semester. techniques MALDI and ESI, modern mass analyzers, such as time-of-flight MS or ion traps and bioanalytical applications. However, the course covers much broader area, including inorganic ionization techniques, virtually all Supporting study material: types of mass analyzers and hardware in mass spectrometry. • J. Gross, Mass Spectrometry, 3rd ed. Springer-Verlag, 2017 • J. Greaves, J. Roboz: Mass Spectrometry for the Novice, CRC Press, 2013 • Edmond de Hoffmann, Vincent Stroobant: Mass Spectrometry: Principles and Applications, 3rd Edition, John Wiley & Sons, 2007 Mass spectrometry of biomolecules 2018 1 Mass spectrometry of biomolecules 2018 2 1 2 Content I. Introduction 1 II. Ionization methods and sample introduction III. Mass analyzers IV. Biological applications of MS V. Example problems Introduction to Mass spectrometry. Brief History of MS. A Survey of Methods and Instrumentation. Basic Concepts in MS: Resolution, Sensitivity. Isotope patterns of organic molecules. Ionization Techniques and Sample Introductin. Electron Impact Mass spectrometry of biomolecules 2018 3 Ionization (EI). Chemical Ionization (CI) 3 4 I. Introduction Study Material • Information sources about mass spectrometry Lecture notes • Brief history of mass spectrometry, a survey of methods and Advice: please take notes, but do not copy the slides; the English slides will instrumentation be provided at the end of the semester. The Czech slides can be found on the internet: http:\\bart.chemi.muni.cz • Basic concepts of mass spectrometry Additional literature • Isotope patterns of organic molecules. • Robert J. Cotter: Time-of-Flight Mass Spectrometry - Instrumentation and Applications in Biological Research, American Chemical Society, 1997. • Richard B. Cole et al.: Electrospray Ionization Mass Spectrometry - Fundamentals, Instrumentation & Applications, John Wiley & Sons, Inc., 1997. Mass spectrometry of biomolecules 2018 5 Mass spectrometry of biomolecules 2018 6 5 6 1 Additional Sources of Information Ionization Techniques and Sample Introduction Internet Glow discharge (GD) Textbook http://www.ms-textbook.com/ Electron impact ionization (EI) Comprehensive information source www.spectroscopynow.com Chemical ionization (CI) Laboratories, e.g. www.mpi-muelheim.mpg.de/stoecki/mass_server.html Field ionization (FI) Inductively coupled plasma (ICP) Protein Prospector prospector.ucsf.edu Fast atom bombardment (FAB) Proteometrics - PROWL www.proteometrics.com Secondary ion mass spectrometry (SIMS) Etc etc. Thermospray (TSI) Ionspray (IS) Specialized journals Elektrospray (ESI) International Journal of Mass Spectrometry Plasma Desorption (PD) Journal of Mass Spectrometry Laser Desorption (LD) Journal of the American Society for Mass Spectrometry Matrix-assisted laser desorption/ionization (MALDI) Mass Spectrometry Reviews Coupling of separation and mass spectrometry (on-line, off-line, microdevices) Rapid Communications in Mass Spectrometry Mass spectrometry of biomolecules 2018 7 Mass spectrometry of biomolecules 2018 8 7 8 Mass Spectrometers MS Applications Ion optics. Simulation of ion movement, Simion Analysis of biological compounds: Energy analyzers • Proteins, peptide mapping, protein databases, new methods (ICAT) Magnetic sectors • Peptide analysis (disulfide bonds, post-translational modifications) Quadrupole filter • Nucleic acids Ion cyclotron with Fourier transformation (ICR-FT-MS) • Saccharides Ion trap (IT), linear trap (LT) Time-of-flight mass spectrometer (TOFMS) New mass spectrometers: Orbitrap, TOF-TOF, LIFT-TOF Analysis of synthetic polymers Tandem mass spectrometry (MS/MS, MSn) Collision induced dissociation (CID) and more… Surface induced dissociation (SID) In source and post source fragmentation (ISF and PSD) Principles of vacuum instrumentation Detectors a detection electronics Chromatography - MS (on-line, off-line, in-line, microdevices) Mass spectrometry of biomolecules 2018 9 Mass spectrometry of biomolecules 2018 10 9 10 Brief History of Mass Spectrometry Glow Discharge Ionization 1803 Dalton atomic theory 1880’s Crookes: glow discharge “mass consists of atoms; all atoms o of a kind have the same mass” glowvrstv dischargea iontu … not really: isotopes… U ~ 700 V DC Proof of existence of isotopes: - + + - viditvisibleelný n edischargegativní výboj + - I ~ 1 mA - optical spectroscopy: a slight shift - + - p ~ 0.2 Pa + of spectral lines ... requires a very high quality instrument + + * - MS: easy determination H2 + H2 → (H2 ) + H2 * (H2) → H2 + 4 h Mass spectrometry of biomolecules 2018 11 Mass spectrometry of biomolecules 2018 12 11 12 2 The First Mass Spectrometer The First Mass Spectrometer 1911 J. J. Thompson: Parabola MS (Phil Mag. 1911, 21, 225) Photographic plate as a detector: 20Ne and 22Ne lines “Rays of positive electricity” 1913 i m a a d d o t o t r a t e k k n e a á g l t k a e u s hollow hollow cathode d m s e electrodes magnet + d - glow á doutnavý k c Ne i vdischargeýboj v Ne, f a r + 1 NeTorr g - o 1 Torr t o f photographic photographic plate vvacuumakuová pumppumpa 22Ne+ 20Ne+ Glow discharge in Ne at 1 Torr, hollow cathode, magnet Mass spectrometry of biomolecules 2018 13 Mass spectrometry of biomolecules 2018 14 13 14 Magnetic Sector with Energy Analyzer But the History of MS Goes on ... 1919 F. W. Aston: Mass Spectrograph (Phil. Mag. 1919, 38, 209) 1940 C. Berry: Electron impact ionization (EI) for ionization of organic Magnetic sector with electrostatic energy analyzer compounds 1950-70 MS applied mostly in structural analysis of organic compounds (-) sekineticlekce kienergynetické anmassalýza (+) eanalysisnergie r = f(m/z) hanalysismotnosti 1980+ Analysis of heavy molecules due to new ionization techniques: (+) FAB, PD, ESI a MALDI + + + detection detekce Today MS for qualitative,structural and quantitative analysis (-) + + + Wide scale of commercial mass spectrometers available ziondroj B source štèrbina + + + MS necessary for analysis of organic and biological molecules extrakce slit extraction, Biospectrometry a ffocusingokusace Abundance of most natural isotopes determined by 1930 In Nobel prize ceremony lecture, 1934: “MS is dead, everything's done …” Mass spectrometry of biomolecules 2018 15 Mass spectrometry of biomolecules 2018 16 15 16 Basic Concepts of Mass Spectrometry Mass Spectrum Mass spectrometer Ion signal vs. m/z instrument, in which ions are formed from analytes and their mass-to- charge ratio is analyzed Ion signal charge, current, often converted to voltage, arbitrary units Components of mass spectrometer signal normalization: intensity of the dominant peak = 100% 1. Ion source chamber (contains device for sample introduction, ion optics) 2. Mass analyzer (ion optics, electrodes, magnets, detector) normalization of ion signal 3. Vacuum pumps (rough, high and ultrahigh vacuum) %Int. 100 4. Control and data processing unit, software 90 80 70 60 50 40 30 20 10 0 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 Mass/Charge Mass spectrometry of biomolecules 2018 17 Mass spectrometry of biomolecules 2018 18 17 18 3 Mass Spectrum Selected Powers in Mass Spectrometry Mass, m Mass resolution A measure of separation of two adjacent peaks. a.m.u., u, Da (Dalton), molecular weight number of atom mass units numerically equivalent to molar weight Two definitions: m/z ... mass-to-charge ratio, Th (Thomson) 1. FWHM (full width at half maximum), R = m/m 2. Max. mass (m/z), at which two adjacent peaks with a unit mass difference may be resolved. Number of charges, z: Ion energy, W number of elemental charges of an ion Instead of Joule (J) use electronVolts (eV) and atoms or ions rather than usually ±1 moles exceptions, e.g. electrospray-generated ions: |z| >> 1 1 eV = 1.6 x 10-19 J simplicity: acceleration voltage = 100 V, charge = 1 ... W = 100 eV Pozitive and negative ions, not cations and anions. can be easily compared with ionization energy, bond energy, photon energy... Mass spectrometry, not spectroscopy. Pressure, p 1 atm = 760 Torr = 101 325 Pa = 1.01325 bar = 14.70 PSI Mass spectrometry of biomolecules 2018 19 Mass spectrometry of biomolecules 2018 20 19 20 Abbreviations Abbreviations m mass of ion, atom, molecule (u, a.m.u., Da) n numerical concentration (m-3) z number of charges; (-) I current (A), flux (m-2), intensity (-) m/z mass-to-charge ratio (Th, Thomson) T absolute temperature (K) -19 e elemental charge (1.6x10 C) p pressure (Pa, Torr) U voltage (V) R resolution (-) E intensity of electric field (V/m, N/C) f frequency (Hz) W energy, labor (eV, J) -1 v ion velocity (m/s) w angular frequency (rad/s, s ) r curvature radius (m) a direct proportion L path (m) LD detection limit, also LOD, limit of detection (mol, g, M) l mean free path of a molecule S/N signal-to-noise ratio t time (s) RSD relative standard deviation s collision diameter (m) s2 collision cross-section (m2) m reduced mass (a.m.u., Da, kg) Mass spectrometry of biomolecules 2018 21 Mass spectrometry of biomolecules 2018 22 21 22 Isotope Patterns of Organic Molecules Isotope Patterns of Organic Molecules Carbon isotopes: 99% 12C, 1% 13C Relative abundance of molecules (%): 12 C60: C60 100 12 13 Pattern as a function of number of carbon atoms in the molecule: C59 C 66 12 13 12 13 C: 99% C 1% C C58 C2 21 12 12 12 13 13 13 12 13 C2: 98% C C 2% C C 0.01% C C C57 C3 4.6 12 12 12 12 12 13 12 13 13 -4 13 13 13 12 C3: 97% C C C 3% C C C 0.04% C C C 10 % C C C C100: C100 100 12 13 C99 C 110 12 13 Binomic formula C98 C2 60 12 13 Relative abundance of the light isotope, a C97 C3 22 Relative abundance of the heavy isotope, b (normalized with respect to the monoisotopic molecule /only 12C/ = 100 %) Number of atoms, n E.g.
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