Unveiling the Sweet Conformations of <scp>D</scp>‐Fructopyranose

Bermúdez, Celina; Peña, Isabel; Cabezas, Carlos; Daly, Adam M.; Alonso, José L.

doi:10.1002/cphc.201300057

Cited by 40 publications

(63 citation statements)

References 22 publications

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“…The low-temperature environment of a supersonic expansion provides the ideal medium for preparing individual conformers of sugars in virtual isolation conditions, ready to be interrogated by a short burst of microwave radiation. To date, rotational investigations of monosaccharides have been carried out for C 4 sugars [222], C 5 sugars [62,223,224], and C 6 sugars [225][226][227]. All factors contributing to stabilization of the observed species are given in the next sections.…”

Section: Cytosinementioning

confidence: 98%

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Microwave Spectroscopy of Biomolecular Building Blocks

Alonso

López

2014

Topics in Current Chemistry

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Microwave spectroscopy, considered as the most definitive gas phase structural probe, is able to distinguish between different conformational structures of a molecule, because they have unique spectroscopic constants and give rise to distinct individual rotational spectra.Previously, application of this technique was limited to molecular specimens possessing appreciable vapor pressures, thus discarding the possibility of studying many other molecules of biological importance, in particular those with high melting points, which had a tendency to undergo thermal reactions, and ultimately degradation, upon heating.Nowadays, the combination of laser ablation with Fourier transform microwave spectroscopy techniques, in supersonic jets, has enabled the gas-phase study of such systems. In this chapter, these techniques, including broadband spectroscopy, as well as results of their application into the study of the conformational panorama and structure of biomolecular building blocks, such as amino acids, nucleic bases, and monosaccharides, are briefly discussed, and with them, the tools for conformational assignation - rotational constants, nuclear quadrupole coupling interaction, and dipole moment.

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Section: Cytosinementioning

confidence: 98%

“…43c. The most stable structures of D-fructose in isolated conditions of gas phase have been unveiled by CP-FTMW [226] spectroscopy, bringing crystalline D-fructopyranose (m.p.120 C) into the gas phase by laser ablation. Once the lines from known photofragmentation species are removed from the broadband spectrum (see Fig.…”

Section: -Deoxy-d-ribose and Ribosementioning

confidence: 99%

Microwave Spectroscopy of Biomolecular Building Blocks

Alonso

López

2014

Topics in Current Chemistry

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“…The most stable structures of D-fructose in isolated conditions of gas phase have been unveiled by CP-FTMW [226] spectroscopy, bringing crystalline D-fructopyranose (m.p.120 C) into the gas phase by laser ablation. Once the lines from known photofragmentation species are removed from the broadband spectrum (see Fig.…”

Section: D-fructosementioning

confidence: 99%

Gas-Phase IR Spectroscopy and Structure of Biological Molecules

Rijs¹,

Oomens²

2015

Topics in Current Chemistry

104

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“…1a. Immediately significant photofragmentation effects were revealed in the congested rotational spectrum which appears to be dominated by the lines belonging to uracil[5] as well as some common decomposition lines (acetic acid, cyanoacetylene, glyoxylic acid, vinyl cyanide, glyceraldehide and water complexes) found in previous of sugars [10] and nitrogen bases studies.…”

Section: Introductionmentioning

confidence: 99%

The Nucleoside Uridine Isolated in the Gas Phase

2015

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Herein we present the first experimental observation of the isolated nucleoside uridine, placed in the gas phase by laser ablation and characterized by Fourier transform microwave techniques. Free from the bulk effects of their native environments, anti/C2'-endo-g+ conformation has been revealed as the most stable form of uridine. Intramolecular hydrogen bonds involving uracil and ribose moieties have been found to play an important role in the stabilization of the nucleoside.Keywords microwave spectroscopy; nucleoside; laser ablation; conformational analysis; hydrogen bonding Although some studies [1] have addressed the fundamental question "Why did nature choose the furanose and not the pyranose form of ribose in RNA?", the question remains open. The chemical determinants by which nature selected furanosyl oligonucleotides have been reported elsewhere, [2] but base pairing strengths were not the critical selection criterion used. In fact, all families of oligonucleotides which contain pentopyranosyl units as sugar building blocks are found to be much stronger Watson-Crick base pairing systems than RNA. Structural arguments based on the intramolecular interactions between the uracil base and ribose moieties, which may contribute to stabilize the furanose versus the pyranose form, could be invoked. One obstacle to unveiling these intramolecular interactions arises from the ability of these basic structures to form strong intermolecular hydrogen bonds with polar solvents, which normally mask their intrinsic molecular properties. To date, no experiment has yet shown a nucleotide under isolation conditions to reveal its intramolecular interactions.Fourier transform microwave spectroscopy is extremely sensitive to molecular geometry and has been proved to be a definitive tool in conformational analysis.[3] Coupled with laser ablation techniques it is being used to remove biological molecules from the solid state and to interrogate them in the cold, isolated environment of a supersonic expansion. Uridine (m.p. 165°C) is a thermally fragile molecule and cannot be transferred intact into the vapor phase by using conventional heating methods. In an attempt to provide rotational signatures of the isolated uridine structures free from environmental disturbance, we have used a recently constructed broadband chirped pulse Fourier-transform microwave (CP-FTMW) spectrometer equipped with laser ablation vaporization system. [9] In the experimental procedure, finely powdered uridine was mixed with a small amount of a commercial binder and pressed into cylindrical rods which were ablated using the third harmonic (355 nm) of a picosecond laser. The vaporized products were seeded in Ne and expanded adiabatically into the vacuum chamber of the spectrometer and then probed by broadband chirped pulsed microwave spectroscopy. A high power excitation pulse of 300 W was used to polarize the molecules from 6 to 12 GHz. Up to 120 000 individual free induction decays at a 2 Hz repetition rate were averaged in the time domain and Fo...

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Unveiling the Sweet Conformations of D‐Fructopyranose

Cited by 40 publications

References 22 publications

Microwave Spectroscopy of Biomolecular Building Blocks

Microwave Spectroscopy of Biomolecular Building Blocks

Gas-Phase IR Spectroscopy and Structure of Biological Molecules

The Nucleoside Uridine Isolated in the Gas Phase

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