Is the system best represented by a single step transfer or a multistep transport process. Pdf structural analysis of intact monoclonal antibodies. Electron transfer dissociation etd utilizes radical anions produced in a chemical ionization ci source external to the trap. What links here related changes upload file special pages permanent link page. Ms approach combining collisioninduced dissociation cid, electrontransfer dissociation etd, and cid of an isolated chargereduced species for the tracelevel characterization of proteins with posttranslational modifications. While cid remains the major fragmentation method for peptide sequencing, electron transfer dissociation etd is emerging as a. May 01, 2008 electron transfer dissociation collisionactivated dissociation cad, the most widely used peptide ion fragmentation technique for peptide sequence analysis by tandem mass spectrometry, works great for small peptides but is problematic for labile posttranslational modifications ptms. Figure s7, baseloss fragmentation by product ion type pdf. Etd abbreviation stands for electron transfer dissociation.
Tandem mass spectrometry, also known as msms or ms 2, is a technique in instrumental analysis where two or more mass analyzers are coupled together using an additional reaction step to increase their abilities to analyse chemical samples. Electron transfer dissociation of peptide anions sciencedirect. Atomic scale investigation of dye sensitized solar cells. Electron transfer dissociation of amide nitrogen methylated polypeptide cations, journal of the american society for mass spectrometry, 2011, pp. The oxidizing agent that gains electrons is chlorine, and the reducing agent that loses electrons is zinc. Welcome to professor donald hunts tutorial on peptide sequence analysis by electron transfer dissociation etd mass spectrometry.
Here are links to additional resources that might be useful in interpreting etd spectra. We show that these sites can be revealed by photoinduced electron transfer dissociation, which produces characteristic c and z ions only if zwitterionic species are present. The cid spectrum shows a few b and y ions, but is dominated by a peak corresponding to the loss of phosphoric acid. Interface structure and dynamics wei ma, fan zhang and sheng meng 1beijing national laboratory for condensed matter physics, and institute of physics.
Electron transfer dissociation how is electron transfer. Similar to electron capture dissociation, etd induces fragmentation of large, multiplycharged cations by transferring electrons to them. Enhanced electron transfer dissociation of peptides modified at cterminus with fixed charges article pdf available in journal of the american society for mass spectrometry 2311. Electrontransfer dissociation etd is a method of fragmenting multiplycharged gaseous. Electron transfer versus proton transfer in gasphase ion. In order to determine which orbitals are involved in the electron transfer, use the print keyword mulliken ao which prints the mulliken population of each basis function. Mass spectrometry has rapidly evolved to become the platform of choice for proteomic analysis. In this method, multiply protonated peptides or proteins are confined in the penning trap of. The tutorial is designed to teach you how to interpret and identify etd spectra manually. The electron transfer dissociation product ions produced by the present method can be subjected to mass mz analysis. Electron capture dissociation ecd and electron transfer dissociation etd in metalpeptide complexes are dependent on the metal cation in the complex.
Chapter 1 introduction to charge transfer and charge. Electron transfer dissociation is a supremely useful tool for the analysis of posttranslationally modified proteins. The term pcet was used to distinguish it from sequential etpt or ptet, and hatom transfer proposed mechanisms ph 29 proton transfer is coupled with electron transfer. The negative mode proteome with activated ion negative electron transfer dissociation ainetd. Pdf in the nearly fifteen years since electron transfer dissociation etd was introduced,1 bioanalytical mass spectrometry ms and. Jul 01, 2008 electron transfer dissociation etd is a recently introduced mass spectrometric technique which has proven to be an excellent tool for the elucidation of labile posttranslational modifications such as phosphorylation and oglcnacylation of serine and threonine residues. It requires multiplycharged gasphase cations z2 and therefore it is typically limited to an electron spray ion source. Electrontransfer dissociation etd is a variation of ecd, in which an ionion reaction, for example, between an anthracene anion and a multiprotonated peptide cation, is used to transfer an electron to the peptide ion. The net charge for a gaseous ion is easily identified by mass spectrometry, but the presence of zwitterionic pairs or salt bridges has previously been more difficult to detect. Proton coupled electron transfer university of tokyo. Hunt lab, department of chemistry, university of virginia. Probing the mechanism of electron capture and electron. Electron attachment step in electron capture dissociation.
Electron capture dissociation ecd and electron transfer dissociation etd in metalpeptide complexes are dependent on the metal cation in. Electron transfer through gasphase ionion reactions has led to the widespread application of electronbased techniques once only capable in ion trapping. Photoelectron transfer dissociation reveals surprising. Electron transfer dissociation and multistage activation. The model peptide fqpseeqqqtedelqdk, containing a phosphoserine residue, was converted to eatuned peptides via. Electron transfer dissociation mass spectrometry in proteomics. Fundamentals of electron capture dissociation fourier. Over what molecular distance is transport feasible. Top and side view of a light harvesting complex ii from rh. Electron attachment step in electron capture dissociation ecd and electron transfer dissociation etd iwona anusiewicz, joanna berdyskochanska, and jack simons chemistry department and henry eyring center for theoretical chemistry, university of utah, salt lake city, utah 84112 received. Negative electron transfer dissociation fourier transform mass. Pdf electroncapture and transfer dissociation of peptides. Remote nickelcatalyzed crosscoupling arylation via. Chapter 1 basic operation and maintenance this chapter describes basic operation and maintenance of the etd source.
The proton transfer reaction mainly reduced the charge of the peptide eq 1, with only a small amount of fragmentation, co 2 loss. Negative electron transfer dissociation of glycosaminoglycans. Structural analysis of intact monoclonal antibodies by electron transfer dissociation mass spectrometry. While cid remains the major fragmentation method for peptide sequencing, electron transfer dissociation etd is emerging as a complementary method for characterization of peptides and posttranslational modifications ptms. In addition to classical crosscouplings involving preformed or preactivated coupling partners, more recently breakthroughs have been made in the selective, direct coupling of abundant aliphatic carbonhydrogen bonds using hydrogen atom transfer reactions in which the bond dissociation energy is the thermodynamic driving force. Leveraging electron transfer dissociation for site selective radical. Etd is defined as electron transfer dissociation frequently. Electron capture dissociation ecd and electron transfer dissociation etd of doubly protonated electron affinity eatuned peptides were studied to further illuminate the mechanism of these processes. Electron transfer dissociation etd is a method of fragmenting multiplycharged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry msms.
New ion fragmentation technologieselectron capture dissociation ecd and electrontransfer dissociation etdare based on interaction of multiply charged polypeptides with either free electrons ecd or anionic species etd. In much earlier work, mcluckey and coworkers reported gasphase electron transfer reactions of multiply deprotonated nucleic acids with rare gas cations 4. Electron shuttling in electron transfer dissociation. In typical etd experiments, multiply protonated peptides are produced by electrospray ionization, stored in a radiofrequency ion trap, and partially discharged by electron transfer from a molecular anion donor. To study proton transfer reactions of peptide anions, we introduced another cationprotonated fluoranthene. Electron shuttling in electron transfer dissocia tion article in international journal of mass spectrometry 2831. The negative mode proteome with activated ion negative. Comprehensive comparison of collision induced dissociation. Electroncapture and transfer dissociation of peptides tagged with tunable fixedcharge groups. Files available from the acs website may be downloaded for personal use only. Electron transfer dissociation etd user guide 3 in this guide this guide provides information about your etd source.
Electron transfer dissociation the scientist magazine. Jan 20, 2011 electron transfer dissociation etd is one of the newer ion activation methods that is particularly useful for peptide sequencing. Since its discovery in 1998, electron capture dissociation ecd has been broadly applied to the structural characterization of a wide variety of biomolecules, including proteinspeptides, dnasrnas, carbohydrates, lipids, and protein complexes. In a sense, etd is the ionion analog of electron capture dissociation 3the reagent anion is simply a vehicle for electron delivery. Electrontransfer dissociation etd is a method of fragmenting multiplycharged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry msms.
Because chemists have defined oxidation in terms of electron transfer, it is quite unnecessary for redox reactions to have oxygen as the oxidizing agent. Electrontransfer and dissociation cross sections of. The dissociation of the bond may follow or be concerted to the et itself, as. Implementation of electrontransfer dissociation on a hybrid. Pdf enhanced electron transfer dissociation of peptides. Application of electron transfer dissociation etd for the analysis of. Electron transfer dissociation nci source tuning ncisource ionization chamber transfer hexapole unit transfer octopole reactant. Electron capturetransfer versus collisionally activated. A newly developed fragmentation technique, namely electron transfer dissociation etd, supports both, ptm.
This introductory chapter details basic electron transfer theory and describes some. Hornshaw1 and nick morrice2 1thermo fisher scientific, hemel hempstead, uk and 2mrc protein phosphorylation unit, dundee, uk. Electron transfer dissociation and multistage activation analysis of human kinase sites of phosphorylation martin p. Many of the ions that form have eight electrons in their valence shell. Easyetd coupled with orbitrap fusion platform offers increased efficiency, usability, and functionality for electron transfer dissociation and parallel scan modes.
Etd capability can be added to many thermo scientific ion trap and orbitrap mass spectrometers. Electron transfer versus proton transfer in gasphase ionion reactions of polyprotonated peptides harsha p. Study the next example of metallic zinc reacting with chlorine gas to form zinc chloride. Negative electron transfer dissociation netd has proven valuable in. Ribonucleic acid sequence characterization by negative electron. Aug 28, 2015 electron transfer dissociation is a popular peptide fragmentation technique in mass spectrometry.
Mcluckey contribution from the department of chemistry, purdue university, west lafayette, indiana 479072084. What is the abbreviation for electron transfer dissociation. In contrast, the etd spectrum displays a rich fragmentation pattern of c and z ions that reveals the exact location of the phosphorylation t. Sep 01, 2010 the remaining electron transfer dissociation product ions are then subjected to lowenergy, offresonance collisional activation such that the activation generates less than about 20% or less than about 5% of total ion products. Difference of electron capture and transfer dissociation. Pdf the role of electron transfer dissociation in modern.
Peptide and protein sequence analysis by electron transfer. Meyer first coined the term protoncoupled electron transfer and applied it to the reaction below. Electrontransfer dissociation an overview sciencedirect. Sep 21, 2011 to verify the localization of the electron in the calculation of the vectors, carefully examine the mulliken population analysis.
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