An electrospray ionization—flow tube study of H/D exchange in protonated serine

Ustyuzhanin, Pavel; Ustyuzhanin, Juliya; Lifshitz, Chava

doi:10.1016/s1387-3806(02)00872-2

Cited by 21 publications

(23 citation statements)

References 27 publications

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“…Although the mass spectrum of protonated YGGFL is relatively simple, much effort has been invested to understand fragmentation processes in detail (Barber et al, 1981;Katakuse & Desiderio, 1983;Gaskell, Reilly, & Porter, 1988;Alexander & Boyd, 1989;Baeten et al, 1989;Meot-Ner (Mautner) et al, 1995;Vekey, 1996;Schnier et al, 1997;Ustyuzhanin et al, 2001;Rakov, Borisov, & Whitehouse, 2004;Laskin, 2006a;Campbell et al, 2007;Allen et al, 2008). YGGFL has various protonation sites, the N-terminal amino group, the C-terminal carboxylic acid, the amide nitrogen and oxygen atoms.…”

Section: A Fragmentation Of the Protonated Molecule (Mh þmentioning

confidence: 99%

Leucine enkephalin—A mass spectrometry standard

Sztáray

Memboeuf

Drahos

et al. 2011

Mass Spectrometry Reviews

107

118

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The present article reviews the mass spectrometric fragmentation processes and fragmentation energetics of leucine enkephalin, a commonly used peptide, which has been studied in detail and has often been used as a standard or reference compound to test novel instrumentation, new methodologies, or to tune instruments. The main purpose of the article is to facilitate its use as a reference material; therefore, all available mass spectrometry-related information on leucine enkephalin has been critically reviewed and summarized. The fragmentation mechanism of leucine enkephalin is typical for a small peptide; but is understood far better than that of most other compounds. Because ion ratios in the MS/MS spectra indicate the degree of excitation, leucine enkephalin is often used as a thermometer molecule in electrospray or matrix-assisted laser desorption ionization (ESI or MALDI). Other parameters described for leucine enkephalin include collisional cross-section and energy transfer; proton affinity and gas-phase basicity; radiative cooling rate; and vibrational frequencies. The lowest-energy fragmentation channel of leucine enkephalin is the MH(+) → b(4) process. All available data for this process have been re-evaluated. It was found that, although the published E(a) values were significantly different, the corresponding Gibbs free energy change showed good agreement (1.32 ± 0.07 eV) in various studies. Temperature- and energy-dependent rate constants were re-evaluated with an Arrhenius plot. The plot showed good linear correlation among all data (R(2) = 0.97), spanned over a 9 orders of magnitude range in the rate constants and yielded 1.14 eV activation energy and 10(11.0) sec(-1) pre-exponential factor. Accuracy (including random and systematic errors, with a 95% confidence interval) is ±0.05 eV and 10(±0.5) sec(-1), respectively. The activation entropy at 470 K that corresponds to this reaction is -38.1 ± 9.6 J mol(-1) K(-1). We believe that these re-evaluated values are by far the most accurate activation parameters available at present for a protonated peptide and can be considered as "consensus" values; results on other processes might be compared to this reference value.

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Section: A Fragmentation Of the Protonated Molecule (Mh þmentioning

confidence: 99%

Leucine enkephalin—A mass spectrometry standard

Sztáray

Memboeuf

Drahos

et al. 2011

Mass Spectrometry Reviews

107

118

View full text Add to dashboard Cite

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“…H/DAustauschreaktionen wurden auch eingesetzt, um Serin und seine Cluster zu charakterisieren. [110,[132][133][134][135][136][137][138] Die ersten Versuche dieser Art ergaben, dass es mindestens zwei Isomere des protonierten Serinoctamers gibt; [134] dies wurde in späteren Untersuchungen bestätigt. [136,137] Wasserstoff/Deuterium-Austauschreaktionen von Serinoctameren wurden auch in einem Prototypen eines hochauflösenden Orbitrap-Massenspektrometers durchgeführt.…”

Section: Dissoziationunclassified

“…Der Aufbau des Orbitrap [122] ermöglicht es, H/D-Austauschreaktionen an eingefangenen Ionen in der linearen Quadrupolfalle der Ionenführung vorzunehmen. Anders als bei alternativen Methoden [132][133][134] kann die Reaktionszeit dabei präzise kontrolliert werden. Das Ausmaß des H/D-Austauschs hängt davon ab, wie oft die Serinoctamere mit dem Deuterierungsagens (in diesem Fall CH 3 OD) kollidieren.…”

Section: Dissoziationunclassified

“…[110,[132][133][134][135][136][137][138] Weitere Details kann man aus Experimenten mit Infrarot-Multiphoton-Dissoziation (IRMPD) [139,140] und quantenmechanischen Rechnungen [39,71,72] ableiten. Aus den H/D-Austauschexperimenten ist bekannt, dass es mindestens zwei isomere Octamer-Cluster gibt; [134][135][136][137] allerdings ist nur einer, nämlich das Isomer A, in Zusammenhang mit der Homochirogenese interessant, da nur dieser stereospezifische Reaktionen eingeht.…”

Section: Rechnungenunclassified

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Serinoctamere: Clusterbildung, Reaktionen und Auswirkungen auf die Homochiralität von Biomolekülen

Nanita

Cooks

2006

Angewandte Chemie

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Noch immer ist die Entwicklung der Homochiralität eines der spannendsten Rätsel im Zusammenhang mit der Entstehung des Lebens. Ein mögliches Szenario geht davon aus, dass Aminosäure‐Aggregate an einer Folge chemischer Ereignisse beteiligt waren, die zu chiralen Biomolekülen in sich selbst replizierenden Systemen und damit zur Homochirogenese führten. Serin steht als Aminosäure im Zentrum des Interesses, weil es ionische Cluster bildet, die sich aus der “magischen” Zahl von acht Aminosäureeinheiten zusammensetzen; diese Cluster zeigen eine auffällige Präferenz für Homochiralität. Die Serinoctamer‐Cluster (Ser8) können unter simulierten präbiotischen Bedingungen erzeugt werden, und sie reagieren enantioselektiv mit anderen Biomolekülen. Diese Beobachtungen führten zu der Hypothese, dass die Chiralität in der Natur ursprünglich auf Serin zurückgeht und durch chemische Reaktionen auf andere Aminosäuren, Saccharide und Peptide übertragen wurde. Der vorliegende Aufsatz bewertet kritisch die Chemie von Ser8‐Clustern und die Experimente, die ihre mögliche Rolle bei der Homochirogenese stützen.

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“…Tandem mass spectrometry [38,41,56], ion mobility cross section measurements [36,40,41], theoretical calculations [38 -41, 45], and hydrogen/deuterium exchange reactions [47][48][49][57][58][59][60][61] have all been used to gain information about the structure(s) of serine clusters. These studies have demonstrated that there are two structural types of protonated serine octamers and that at least one is composed of zwitterionic monomers.…”

mentioning

confidence: 99%

Alkali metal-cationized serine clusters studied by sonic spray ionization tandem mass spectrometry

Nanita

Sokol

Cooks

2007

J. Am. Soc. Mass Spectrom.

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, or Cs ϩ therefore represent a new type of cluster ion that is homochiral in its internal subunits, which then assemble in a random fashion to form octamers. We tentatively interpret the homochirality of these tetramers as a consequence of assembly of the serine molecules around a central metal ion. The data provide additional evidence that the neutral serine octamer is homochiral and is readily cationized by smaller ions. (J Am Soc Mass Spectrom 2007, 18, 856 -868) © 2007 American Society for Mass Spectrometry C ations of the alkali metals, especially Na ϩ and K ϩ , are involved in a wide variety of biological processes. To take just one example, they participate in the stabilization of noncovalently bound complexes of biological macromolecules in living organisms. In particular, telomeric DNA found at the ends of chromosomes is stabilized by forming multistrand complexes, known as G-quadruplexes, which are held together by hydrogen bonds and further stabilized by the incorporation of alkali metal cations into cavities in their structures [1][2][3]. Mass spectrometry [1], nuclear magnetic resonance, X-ray crystallography and other spectroscopic techniques have shown that small biomolecules can also form relatively stable clusters with alkali metal cations. Examples include nucleobases [4 -6] and nucleosides (as well as their derivatives) [7][8][9], and amino acids [10,11]. A particular feature of alkali metal adducts of small molecular clusters is that they often have a net positive charge and can be characterized by mass spectrometry, a technology that has proven to be key in many studies of clusters [11][12][13][14][15][16][17][18][19].Electrospray ionization (ESI) [20,21] is a versatile ionization technique, which allows biological macromolecules, fragile noncovalently bound complexes [22][23][24][25][26], and other fragile nonvolatile species to be easily transferred from solution into the gas-phase, where mass spectral data can be obtained on the resulting ions. Although the possibility exists of conformational rearrangement [27,28] and other structural changes during the ESI process, there is overwhelming evidence that electrospray ionization is successful in the characterization of solution-phase species via a study of the corresponding gas-phase ions [24,26]. Spray ionization methods derived from the original ESI method include sonic spray ionization (SSI) [29,30] and cold spray ionization (CSI) [31,32]. Recently, electrosonic spray ionization (ESSI) [33,34], a combination of ESI and SSI, was introduced. This particular spray ionization method is very gentle, yet readily yields fully desolvated ions [33,34]. The variant methods SSI, CSI, and ESSI are all believed to provide gentler ionization than normal electrospray, allowing labile species that exist in solution to survive the ionization process as well as being applicable to nonvolatile analytes.The droplet evaporation process in the gentle variant methods on ESI can lead to even more aggregation than occurs in ESI itself. This tendency has been fo...

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An electrospray ionization—flow tube study of H/D exchange in protonated serine

Cited by 21 publications

References 27 publications

Leucine enkephalin—A mass spectrometry standard

Leucine enkephalin—A mass spectrometry standard

Serinoctamere: Clusterbildung, Reaktionen und Auswirkungen auf die Homochiralität von Biomolekülen

Alkali metal-cationized serine clusters studied by sonic spray ionization tandem mass spectrometry

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