Further, ionion chemistry, namely electron transfer reactions, presents a. 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. Jackson1,2 1department of forensic and investigative science, west virginia university, morgantown, wv 26506, usa 2c. The model peptide fqpseeqqqtedelqdk, containing a phosphoserine residue, was converted to eatuned peptides via. Electron transfer dissociation is complementary to cad and can be especially useful for sequencing peptides containing posttranslational modification ptm 28 36.
Numerous biological processes involve et reactions. View enhanced pdf access article on wiley online library html view download pdf for offline viewing. Photoelectron transfer dissociation reveals surprising. In these experiments, electron transfer to a protonated site is initiated by. Probing the mechanism of electron capture and electron. In the nearly fifteen years since electron transfer dissociation etd was introduced,1 bioanalytical mass spectrometry ms and msdriven proteomics have continued to develop as the premier tools. Activatedion electron transfer dissociation on an orbitrap fusion lumos mass spectrometer. 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. Zic hilic stationary phase in a micropipette tip format protea biosciences. In the second part, the electron transfer process in the single quantum dot fluorescence blinking phenomenon is studied. Electron transfer dissociation is a supremely useful tool for the analysis of posttranslationally modified proteins.
Many of the ions that form have eight electrons in their valence shell. Longlived charge separation at heterojunctions between. Fundamentals of electron capture dissociation fourier. Improving collision induced dissociation cid, high. The molecular structures of six openshell z 3ions resulting from electron transfer dissociation mass spectrometry etd ms were investigated using infrared ion spectroscopy in the 8001850 and 32003700 cm. Gaskella a michael barber centre for mass spectrometry, school of chemistry and. Electron transfer dissociation of itraq labeled peptide. Ho w ev er, the symmetry b et een pro jectile and target states together with the large exo or endothermicit y of the v arious one.
Electron transfer dissociation of peptide anions sciencedirect. Here are links to additional resources that might be useful in interpreting etd spectra. Natural and engineered electron transfer of nitrogenase. In a sense, etd is the ionion analog of electron capture dissociation 3the reagent anion is simply a vehicle for electron delivery. It is one of the most widely used techniques for activation and dissociation of mass selected precursor ion in msms.
It requires multiplycharged gasphase cations z2 and therefore it is typically limited to an electron spray ion source. Fragmentation spectra generated by electron transfer dissociation, for a large. Ion mobilityresolved collisioninduced dissociation and electron. 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. Triply and doubly charged itraq isobaric tagging for relative and absolute quantitation labeled peptide cations from a tryptic peptide mixture of bovine carbonic anhydrase ii were subjected to electron transfer ionion reactions to investigate the effect of charge bearing modifications associated with itraq on the fragmentation pattern. Performance characteristics of electron transfer dissociation mass. Electroncapture dissociation ecd is a method of fragmenting gasphase ions for structure elucidation of peptides and proteins in tandem mass spectrometry. Middledown electron capture dissociation and electron. The partitioning of products among all the possible competing processes is examined closely to study the role of amide nitrogen methylation on the competition between electron transfer and proton transfer, the tendency for electron transfer to result in spontaneous fragmentation i.
Investigation of the position of the radical in z3ions. Electrontransfer dissociation etd is a method of fragmenting multiplycharged gaseous. Armstrong sd, duncan hlr, cheetham sa, hurst jl,beynon rj. We show that etd combined with ion mobilitymass spectrometry. The cid spectrum shows a few b and y ions, but is dominated by a peak corresponding to the loss of phosphoric acid. Principal investigators meeting, year 2, june 2016, bethesda, md. Hunt lab, department of chemistry, university of virginia.
Charge transfer dissociation ctd mass spectrometry of peptide cations using kiloelectronvolt helium cations william d. The sample, usually in solution, is first ionized by electrospray. Type ions formed by electron transfer dissociation of. For reagent anions in reactions with protonated peptides, proton transfer is usually significantly more exothermic than electron transfer. It was noted that electron transfer dissociation etd. These processes include oxygen binding, photosynthesis, respiration, and. Ion mobilityresolved collisioninduced dissociation and electron transfer. In much earlier work, mcluckey and coworkers reported gasphase electron transfer reactions of multiply deprotonated nucleic acids with rare gas cations 4.
Articles analysis of the trypanosome flagellar proteome using a combined electron transfercollisionally activated dissociation strategy sarah r. University of groningen molecular dissociation induced by. In contrast, the etd spectrum displays a rich fragmentation pattern of c and z ions that reveals the exact location of the phosphorylation t. To understand the exciton dissociation process at the molecular level, one needs to resolve the evolution of the charge transfer ct excitons an interfacial exciton with its electron and hole residing in the electron acceptor and donor materials, respectively in the temporal, spatial and energy domains.
What links here related changes upload file special pages permanent link page. Electron capture dissociation ecd and electron transfer dissociation etd in metalpeptide complexes are dependent on the metal cation in. We assess in particular the question of whether the. Infrared multiphoton dissociation irmpd electron capture dissociation ecd electron transfer dissociation etd surfaceinduced dissociation sid blackbody infrared radiative dissociation bird 41 spengler b. Electron capturetransfer versus collisionally activated. Effects of cation charge state on product partitioning in ionion electron transfer to multiply protonated polypeptides. Protoncoupled electron transfer with metal complexes. Electron transfer dissociation etd utilizes radical anions produced in a chemical ionization ci source external to the trap. Peptide and protein quantification using itraq with. Electron transfer dissociation is a popular peptide fragmentation technique in mass spectrometry. Electron transfer dissociation how is electron transfer.
Etd reactions resulting from electron transfer, a type of ion chemistry. Charge transfer dissociation ctd mass spectrometry of. Analysis of intact monoclonal antibody igg1 by electron transfer. The posttranslational modifications ptms of histones play a major role in activating or silencing gene transcription. Negative electron transfer dissociation fourier transform. Burlinguette and coworkers reported a series of electronically diverse complexes and measured the turnover.
Welcome to professor donald hunts tutorial on peptide sequence analysis by electron transfer dissociation etd mass spectrometry. Electron transfer et occurs when an electron relocates from an atom or molecule to another such chemical entity. Electron transfer versus proton transfer in gasphase ion. Et is a mechanistic description of a redox reaction, wherein the oxidation state of reactant and product changes.
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. Electron capture dissociation ecd1 and electron transfer dissociation etd2. Structural and functional differences in isoforms of mouse major urinary proteins. A theory is developed for the population distribution as a function of the energy e of a dissociating model, and used to calculate the threebody low pressure recombination rate constant. The tutorial is designed to teach you how to interpret and identify etd spectra manually. Analysis of the trypanosome flagellar proteome using a. To gain better understanding of the interplay between the ptms that occur on histones, they are extensively studied using mass spectrometry techniques. With netd, we envision possibilities for direct phosphopeptide detection and characterization in the most sensitive format. Due to the abundance of lysines and arginines, the typical trypsin digestion has been found less favorable and glucdigests. Resultant data files were used to create dta files that were then separated by fragmentation method, i. The list of acronyms and abbreviations related to etd electron transfer dissociation. Activated ion electron transfer dissociation for improved. 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 mass spectrometry in proteomics.
In some cases, the site of deprotonation can be identi. Identifying drug metallation sites on peptides using. Electron transfer dissociation etd and collision induced dissociation cid have been used to locate the precise binding sites for platinum and ruthenium anticancer complexes on the peptide substance p. Electron capture and electron transfer dissociation ecd etd or exd are two alternative msms techniques that can overcome the aforementioned limitations 12. Etd capability can be added to many thermo scientific ion. Msms raw files were converted to mzxml format with msconvert, followed by spectral deconvolution with msdeconv. Ms dissociation methods, including collision induced dissociation cid, high energy collision dissociation hcd, and electron transfer dissociation etd, can each contribute distinct peptidome identifications using conventional peptide identification methods shen et al. Peptide sequence analysis by etd mass spectrometry. Demonstrate electron transfer between atoms to form ionic bonds.
The relationship between the coherent size, binding energy. In this instance, manual interpretation of the cid msms spectrum. Negative electron transfer dissociation of glycosaminoglycans. Proton transfer and electron transfer are competitive processes for any combination of anionic and cationic reactants. Difference of electron capture and transfer dissociation mass. Dissertation mechanism of electron capture dissociation and the application to protein deamidation by xiaojuan li b. Pdf the role of electron transfer dissociation in modern. Studies in recombination and dissociation reactions for. Especially when facilitated by supplementary collisional activation converting the nondissociative electron transfer products into c and ztype fragment ions, the effect of precursor ion charge states have on dissociation efficiency, which is one of the limitations imposed by the intrinsic chargereducing process in electronbased. Electron transfer from the fe protein is currently thought to be coupled to the ratelimiting step of pi release 2527 s.
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