Self-assembling of cytosine nucleoside into triply-bound dimers in acid media. A comprehensive evaluation of proton-bound pyrimidine nucleosides by electrospray tandem mass spectrometry, X-rays diffractometry, and theoretical calculations.
Electrospray tandem mass spectrometry (ESI-MS/MS) is used to evaluate the assembling of cytosine and thymine nucleosides in the gas phase, through the formation of hydrogen bonded supermolecules. Mixtures of cytidine analogues and homologues deliver in the gas phase proton-bound heterodimers stabilized by multiple interactions, as proven by the kinetics of their dissociation into the corresponding protonated monomers. Theoretical calculations, performed on initial structures of methylcytosine homodimers available in the literature, converged to a minimized structure whereby the two pyrimidine rings interact through the formation of three hydrogen bonds of similar energy. The crystallographic data here reported show the equivalency of the two interacting pyrimidines which is attributable to the presence of an inversion center. Thymine and uracil pyrimidyl nucleosides form, by ESI, gaseous proton-bound dimers. The kinetic of their dissociation into the related protonated monomers shows that the nucleobases are weekly interacting through a single hydrogen bond. The minimized structure of the protonated heterodimer formed by thymine and N-1-methylthymine confirmed the existence of mainly one hydrogen bond which links the two nucleobases through the O4 oxygens. No crystallographic data exists on thymine proton-bound species, nor have we been able to obtain these aggregates in the solid phase. The gaseous phase, under high vacuum conditions, seems therefore a suitable environment where vanishing structures produced by ESI can be studied with a good degree of approximation.
Armentano
Donatella
D
Dipartimento di Chimica, Università della Calabria, Arcavacata di Rende (CS), Italy.
De Munno
Giovanni
G
Di Donna
Leonardo
L
Sindona
Giovanni
G
Giorgi
Gianluca
G
Salvini
Laura
L
Napoli
Anna
A
D000143:Acids / Q000737:chemistry*; D003596:Cytosine / Q000737:chemistry*; D019281:Dimerization; D006860:Hydrogen Bonding; D007700:Kinetics; D008958:Models, Molecular; D011522:Protons; D011741:Pyrimidine Nucleosides / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013816:Thermodynamics; D014961:X-Ray Diffraction
D000143:Acids; D011522:Protons; D011741:Pyrimidine Nucleosides; D012996:Solutions; D003596:Cytosine