Serine Octamer Reactions: Indicators of Prebiotic Relevance

Takáts, Zoltán; Nanita, Sergio C.; Cooks, R. Graham

doi:10.1002/anie.200351210

Cited by 110 publications

(116 citation statements)

References 21 publications

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“…Briefly, these studies show that serine octamers undergo chiroselective substitution reactions in which serine molecules in the homochiral octamer are replaced by other amino acids or sugars, resulting in mixed serine/amino acid and serine/saccharide noncovalently-bound clusters. These reactions favor the enantiomers present in living systems, which supports the idea that homochiral serine octamers might have been involved in prebiotic mechanisms that led to the accumulation and transmission of homochirality [44,46,63].…”

supporting

confidence: 70%

“…Various research groups have studied clusters of this amino acid using both ESI and SSI mass spectrometry , motivated by earlier studies which showed that the formation of protonated serine octamers occurs with a remarkably strong preference for homochirality [37][38][39][40][41]. The chemistry of the ionized serine octamer in the presence of compounds of biochemical significance, such as other coding amino acids, sugars, phosphoric acid, and transition-metal cations, has also been investigated [44,46,63]. Briefly, these studies show that serine octamers undergo chiroselective substitution reactions in which serine molecules in the homochiral octamer are replaced by other amino acids or sugars, resulting in mixed serine/amino acid and serine/saccharide noncovalently-bound clusters.…”

mentioning

confidence: 99%

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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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supporting

confidence: 70%

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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“…Recently, the study of biomolecular cluster cations has become an active research field, and much work has dealt with the formation, dissociation, and charge partitioning among fragments of protein cluster cations [5][6][7][8][9][10]. Magic numbers for amino acid cationic clusters [11][12][13] and preference for homochirality [14,15] have been reported. Negatively charged clusters of amino acids have also been produced [13].…”

mentioning

confidence: 99%

Multiply-charged negative clusters of adenosine-5′-monophosphate in the gas phase

Liu

Hvelplund

Nielsen

2005

J. Am. Soc. Mass Spectrom.

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Multiply-charged noncovalent cluster anions of adenosine-5=-monophosphate (AMP) were formed by electrospray ionization (ESI). Ions in higher charge states were observed when the ions were accumulated in an ion trap with helium buffer gas before detection. We determined the smallest size (n a ) or appearance size as a function of charge state (q), i.e., n a ϭ 4 for q ϭ 2, n a ϭ 8 for q ϭ 3, and n a ϭ 13 for q ϭ 4. The relation between n a and q can be described by a charged droplet model. When the size is larger than n a for a given q, the fragmentation pathway of an anion cluster is dominated by loss of neutral fragments. In contrast, when the size approaches the appearance size, only charged fragments are formed. Cluster cations such as metal clusters have been extensively studied during the last two decades [3,4]. Recently, the study of biomolecular cluster cations has become an active research field, and much work has dealt with the formation, dissociation, and charge partitioning among fragments of protein cluster cations [5][6][7][8][9][10]. Magic numbers for amino acid cationic clusters [11][12][13] and preference for homochirality [14,15] have been reported. Negatively charged clusters of amino acids have also been produced [13].The formation and energetics of gas-phase multiplycharged anions (MCA) is a subject that has attracted much attention [16 -18]. Even though several multiplycharged molecular anions have been measured, observations of multiply-charged cluster anions are few. Multiply-charged metal cluster anions were observed by electron attachment to monoanions in a Penning trap [19 -22] . Here we report, to our knowledge, the first observation of negatively, multiply-charged noncovalent clusters made of adenosine 5=-monophosphate (AMP). The dependence of cluster size on charge state was measured, and the results, are modeled by a charged droplet model. The fragmentation pathways of multiply-charged negative clusters are also presented. ExperimentalTwo setups were applied in the experiments: an electrostatic ion storage ring (ELISA) and an accelerator mass spectrometer (AMS). In both setups, negative clusters of AMP were produced by ESI. A saturated solution of AMP in methanol was sprayed.Detailed information about the ESI source (Figure 1a) is described in reference [32]. Briefly, the source is mounted on the high-voltage platform of the accelerator. A stainless steel hypodermic needle is, via a fused silica capillary, connected to a syringe containing a solution of the analyte. A syringe pump (Harvard apparatus) delivers a constant flow through the needle. A typical flow rate is 1ϳ2 l/min. A voltage of 3 to 4 kV relative to the heated capillary is put on the needle. The capillary is normally heated for desolvation of solvent molecules from analyte molecules. At the exit of the capillary, ions emerge into the first vacuum zone where a pressure of around 1 mbar is maintained. The ions focused by a tube lens go through a skimmer into a second region. The voltage on the tube lens varies from 50 to...

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“…That it gave D-GLA dominance instead of L-GLA dominance can be characterizes by a morphological principle, which one can describe as "self-stabilizing coincidence". But once the D-GLA dominance was established the effect of chiral discrimination with the amino acids ensured a bio-organic environment of D-GLA and L-amino acids [17,18].…”

Section: Discussionmentioning

confidence: 99%

“…But L-Serine is especially interesting because it exhibits chiral discrimination in diluted aqueous solutions and forms clusters with D-GLA [17], and it exhibits corresponding chiral discrimination with other L-amino acids [18] whereby it establishes the stereospecific link between D-sugars and L-amino acids in aqueous solutions.…”

Section: Chiral Discriminationmentioning

confidence: 99%

Homochirality in Bio-Organic Systems and Glyceraldehyde in the Formose Reaction

Toxværd

2005

J Biol Phys

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Abstract. The article explores the possibility that the ordering of bio-organic molecules into a homochiral assembly at the origin of life was performed not in aqueous solutions of amino acids or related materials but in racemic glyceraldehyde in the "formose" reaction at high concentration and temperature. Based on physical chemical evidence and computer simulations of condensed fluids, it is argued that the isomerization kinetics of glyceraldehyde is responszible of the symmetry break and the ordering of molecules into homochiral domains.

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Serine Octamer Reactions: Indicators of Prebiotic Relevance

Cited by 110 publications

References 21 publications

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

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

Multiply-charged negative clusters of adenosine-5′-monophosphate in the gas phase

Homochirality in Bio-Organic Systems and Glyceraldehyde in the Formose Reaction

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