Fundamentals of electron capture dissociation fourier. Welcome to professor donald hunts tutorial on peptide sequence analysis by electron transfer dissociation etd mass spectrometry. Photoinduced electron transfer in donor acceptor complexes of. Reid, department of chemistry, marquette university, milwaukee, wisconsin 53233, united states. Unlike a monatomic ion, polyatomic ion composed of more than one atom. Rasaiah2,b 1department of chemistry, kyungsung university, pusan 608736, south korea 2department of chemistry, university of maine, orono, maine 04469, usa. Subsequently, the resulting remote carboncentered radicals formed by cc cleavage merge with the nickel catalytic cycle to create the challenging csp3csp2 bonds. Implementation of electrontransfer dissociation on a. Free web app to quickly and easily combine multiple files into one pdf online.
Proton transfer and the mobilities of the h and oh ions from. Our pdf merger allows you to quickly combine multiple pdf files into one single pdf document, in just a few clicks. Thus the overall rate constant for electron transfer in the activated case ka depends on distance between the participants. Is the system best represented by a single step transfer or a multistep transport process. Electron capture dissociation ecd and electron transfer dissociation etd in metalpeptide complexes are dependent on the metal cation in the complex. In a sense, etd is the ionion analog of electron capture dissociation the reagent anion is simply a vehicle for electron delivery. Make flashcardsnotecards for your textbooks with this free edtech tool. Proton transfer and the mobilities of the h and oh ions. Chargedependent dissociation of insulin cations via ionion.
For reagent anions in reactions with protonated peptides, proton transfer is usually significantly more exothermic than electron transfer. This paper compares the results of these microfabricated surfacesusing ultramicroelectrode arrays and steadystate currents. The objective of optimizing the fluoranthene anion is to maximize the abundance of mz 202 while maintaining adequate resolution of mz 203. Demonstrate electron transfer between atoms to form ionic bonds.
An electronrich species willing to part with an electron can give one away to an electronpoor molecule. Etd is used extensively with polymers and biological molecules such as proteins and peptides for sequence analysis. Acceptor complexes of ethylene with molecular and atomic iodine aimable kalume, lisa george, andrew d. 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. On the dissociation efficiency of charge transfer excitons. In this situation, the timedependent electron transfer rate increases in time until the wave packet reaches its thermal equilibrium on the donor potential surface. Etd is defined as electron transfer dissociation frequently. Optimization of electron transfer dissociation via. Assess the utility of different dissociation techniques for phosphorylation site analysis of human kinases. Determination of heterogeneous electron transfer rate.
Edit your pdf file online and for free with this high quality converter or compress, merge, split, rotate, sort or protect your pdf documents. The cid spectrum shows a few b and y ions, but is dominated by a peak corresponding to the loss of phosphoric acid. 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 etd user guide 3 in this guide this guide provides information about your etd source. Similar to electron capture dissociation, etd induces fragmentation of large, multiplycharged cations by transferring electrons to them. Optimization of electron transfer dissociation via informed. Photoinduced electron transfer in donor acceptor complexes. Beardsley department of chemistry, university of arizona, tucson, arizona, usa this article provides a perspective on collisions of ions with surfaces, including surface. It requires multiplycharged gasphase cations z2 and therefore it is typically limited to an electron spray ion source. For reaction centers and the bc 1 complex, a major fraction of the electron transfer distance across the insulating phase is contributed by the conjugate systems. Learn vocabulary, terms, and more with flashcards, games, and other study tools. 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. How to merge pdfs and combine pdf files adobe acrobat dc.
Transferring an electron causes peptide backbone cleavage into c and zions. Electrostatic interactions involving the extreme c. Why does n have a higher bond dissociation energy than n2. An electron rich species willing to part with an electron can give one away to an electron poor molecule. Electron transfer dissociation etd occurs only when proper formation of the fluoranthene anion reagent is achieved. Pdf merge combine pdf files free tool to merge pdf online. This introductory chapter details basic electron transfer theory and describes some. The dissociation of the bond may follow or be concerted to the et itself, as.
Electron transfer dissociation etd of peptides containing intrachain disulfide bonds article pdf available in journal of the american society for mass spectrometry 232. Pdf electron transfer dissociation etd of peptides. Data were collected with and without simultaneous ion trap collisional excitation of the first generation chargereduced product during the ionion. A free and open source software to merge, split, rotate and extract pages from pdf files. Jun 29, 2004 six years ago, mclafferty and coworkers introduced a unique method for peptideprotein ion fragmentation. The effect of charge state on the dissociation of polypeptides upon electron transfer from a radical anion was investigated by reacting azobenzene anions with different charge states of peptides including tryptic peptides of myoglobin, model peptides, and peptides of relatively large size. The purified flagppargamma2 from 293t cells and ppargamma1 protein from caco2 cells were cut from the colloidal bluestained gel, ingel digested with trypsin, and subjected to analysis by lcmsms using a combination of collisioninduced dissociation cid and. Here are links to additional resources that might be useful in interpreting etd spectra.
Nonequilibrium photoinduced electron transfer minhaeng cho and robert j. Chapter 1 basic operation and maintenance this chapter describes basic operation and maintenance of the etd source. Many of the ions that form have eight electrons in their valence shell. Terms in this set 2 how do polyatomic ions differ from monatomic ions. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. Structural characterization of proteins in the gas phase is becoming increasingly popular, highlighting the need for a greater understanding of how proteins behave in the absence of solvent. If both molecules begin with an even number of electrons, the transfer of one electron makes both. The negative mode proteome with activated ion negative. The benefits of the born effect and of participation of large conjugate ring structures in electron transfer are dependent on the quantummechanical properties of the electron. The negative mode proteome with activated ion negative electron transfer dissociation nicholas m. All reactions that involve molecular oxygen, such as combustion and. Chapter 11 electron transfer reactions and electrochemistry introduction redox, or electron transfer, reactions constitute one of the broadest and most important classes of reactions in chemistry. Yet the bulk of industry consolidation still lies ahead.
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 transfer dissociation etd is a method of fragmenting multiplycharged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry msms. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evaporated or dc magnetron sputtered surface, have not previously been performed. Electron transfer dissociation how is electron transfer. Bond dissociation energy is directly proportional to bond order of a. Difference of electron capture and transfer dissociation. Much of this information, along with more details, additional rate constant expressions, and full references to the original papers, is available in the following jpc feature article. 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. Electrontransfer dissociation is a method of fragmenting multiplycharged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry. Start studying group 1a ions, group 2a ions, group 3a ions, group 4a ions, group 5a ions, group 6a ions, group 7a ions. Lecture 19, factors determining rates of electron transfer.
Chapter 1 introduction to charge transfer and charge transport. A common use of tandemms is the analysis of biomolecules, such as proteins and peptides the molecules of a given sample are ionized and the first. If br is small for a given rda, then the interaction is large and electron transfer occurs effectively. Electron transfer dissociation is a popular peptide fragmentation technique in mass spectrometry.
Mass spectrometry has rapidly evolved to become the platform of choice for proteomic analysis. Introduction electron transfer reactions are of fundanental importance to both chemistry and bioloby. Electron transfer dissociation of peptide anions sciencedirect. In the nearly 15 years since electron transfer dissociation etd was introduced, bioanalytical mass spectrometry ms and msdriven proteomics have continued to develop as the premier tools for characterizing proteome composition, structure, and function. L motif, where l is an electronegative ligand f, oh, och 3, cch, etc. Reid, department of chemistry, marquette university, milwaukee, wisconsin 53233, united states department of chemistry, missouri university of science and technology, rolla, missouri 65409. In this method, multiply protonated peptides or proteins are confined in the penning trap of a fourier transform ion cyclotron resonance fticr mass spectrometer and exposed to electrons with nearthermal energies. Optimization of electron transfer dissociation via informed selection of reagents and operating parameters philip d. The germanyus megadeal between zf group and trw automotive announced in september will likely usher in more mergers between large automotive suppliers.
The sample, usually in solution, is first ionized by electrospray. Peptide and protein sequence analysis by electron transfer. In simple terms, an electron transfer reaction involves the transfer of an clcctron from a donor to an acceptor. The dissociation reactions of various charge states of insulin cations obtained directly from nanoelectrospray were investigated as a result of ionion electron transfer from azobenzene anions. To study proton transfer reactions of peptide anions, we introduced another cationprotonated fluoranthene. One can calculate the energy needed to assemble an electron due, essentially, to the interaction of the electron with its own field. Hornshaw1 and nick morrice2 1thermo fisher scientific, hemel hempstead, uk and 2mrc protein phosphorylation unit, dundee, uk overview purpose. Electrostatic interactions involving the extreme c terminus of nuclear export factor. All the files you upload as well as merged pdf will be deleted permanently within a few minutes. If both molecules begin with an even number of electrons, the transfer of one electron makes both products odd electron species radicals. Surfaceinduced dissociation of small molecules, peptides. Electrontransfer dissociation etd is a method of fragmenting multiplycharged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry msms.
Similar to electroncapture dissociation, etd induces fragmentation of large, multiplycharged cations by transferring electrons to them. Online pdf converter edit, rotate and compress pdf files. Group 1a ions, group 2a ions, group 3a ions, group. Over what molecular distance is transport feasible. Chargedependent dissociation of insulin cations via ion. Etd capability can be added to many thermo scientific ion. Electron transfer dissociation mass spectrometry in proteomics.
In this work we study the important contribution to this field dependence due to the dissociation efficiency of the weakly bound interfacial charge transfer ct state, crucial for organic bulk heterojunction solar cells. Singly charged anthracene anions transfer an electron to multiply protonated peptides in a radio frequency quadrupole linear ion trap qlt and induce fragmentation of the peptide backbone along pathways that are analogous to those observed in electron capture dissociation. Aug 28, 2015 electron transfer dissociation is a popular peptide fragmentation technique in mass spectrometry. Dectris, and the sample to the detector distance was 2. In particular, in part ii we presented selfconsistent solutions of the transfer equation for the radiation intensity zn and the kinetic equation for the distribution function of excited atoms fv. Protoncoupled electron transfer sharon hammesschiffer pennsylvania state university note. Electron self energy corrections if one calculates the energy of a point charge using classical electromagnetism, the result is infinite, yet as far as we know, the electron is point charge. Easily combine multiple files into one pdf document. Electron capturetransfer versus collisionally activated. Hammesschiffer and soudackov, jpc b 112, 14108 2008. Silbey department of chemistry, massachusetts institute of technology, cambridge, massachusetts 029 received 15 november 1994.
Switching between cation and reagent anion injection schemes is automated and accomplished within. 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. We consider photoinduced electron transfer, which is intrinsically a threestate system consisting of. Electrontransfer dissociation an overview sciencedirect. We describe the adaptation of a hybrid quadrupole linear ion trap. The method utilizes pulsed, dual electrospray ion sources and requires minimal instrument modification. Photoelectron transfer dissociation reveals surprising. Electron transfer dissociation and multistage activation analysis of human kinase sites of phosphorylation martin p.
Chapter 1 introduction to charge transfer and charge. Electron transfer dissociation is a supremely useful tool for the analysis of posttranslationally modified proteins. Etd capability can be added to many thermo scientific ion trap and orbitrap mass spectrometers. All reactions that involve molecular oxygen, such as combustion and corrosion, are electron transfer reactions.
View enhanced pdf access article on wiley online library html view download pdf for offline viewing. It is clear that charged residues exert significant influence over structures in the gas phase due to strong coulombic and hydrogenbonding interactions. Electron transfer versus proton transfer in gasphase ion. Peptide sequence analysis by etd mass spectrometry. Electron transfer reactions can occur both tliennally and pliotochcnically. Hornshaw1 and nick morrice2 1thermo fisher scientific, hemel hempstead, uk and 2mrc protein phosphorylation unit, dundee, uk. 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 coulombic energy transfer no electrons change molecules, but rather two transitions occur simultaneously in a process that could be described as the transfer of a virtual photon. The role of electron transfer dissociation in modern. Surfaceinduced dissociation of small molecules, peptides, and noncovalent protein complexes vicki h.
Recently our laboratory described electron transfer reactions of multiply protonated peptide cations with singly charged polynuclear aromatic anions to induce extensive peptide backbone fragmentation, electron transfer dissociation etd 1, 2. Soda pdf is the solution for users looking to merge multiple files into a single pdf document. Chapter 11 electron transfer reactions and electrochemistry. The tutorial is designed to teach you how to interpret and identify etd spectra manually. Comprehensive comparison of collision induced dissociation.
The solvation coordinate u is defined as ll e \i 1 \i x. Topdown charge transfer dissociation ctd of gasphase. The proton transfer reaction mainly reduced the charge of the peptide eq 1, with only a small amount of fragmentation, co 2 loss. Proton transfer and electron transfer are competitive processes for any combination of anionic and cationic reactants. The stacking of these reactants and the intervening base pairs, both statically and dynamically. Since no electrons are actually transferred in the coulombic mechanism, it is clear that this process cannot have an analogy in the case of electron transfer. Browse or search notecards flashcards easy notecards. In contrast, the etd spectrum displays a rich fragmentation pattern of c and z ions that reveals the exact location of the phosphorylation t. The new era of proteomics has focused on throughput, sampling depth, and reproducibility, often relying on traditional collisionbased. 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. Hunt lab, department of chemistry, university of virginia. The current crosscoupling proceeds with the generation of an alkoxy radical utilizing bond dissociation free energy bdfe as the thermodynamic driving force. Nov 22, 2010 the field dependence of photocurrent found in many organic solar cells is a significant and detrimental setback for internal quantum efficiency. Electron transfer dissociation and multistage activation.
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