Furanosic forms of sugars: conformational equilibrium of methyl β-<scp>d</scp>-ribofuranoside

Écija, Patricia; Uriarte, Iciar; Spada, Lorenzo; Davis, Benjamin G.; Camináti, Walther; Basterretxea, Francisco J.; Lesarri, Alberto; Cocinero, Emilio J.

doi:10.1039/c6cc01180b

Cited by 20 publications

(21 citation statements)

References 33 publications

(27 reference statements)

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“… Cremer–Pople sphere with the observed conformers of levoglucosan (this work, red dots), β‐glucose (ref. , green) and β‐ribose (ref. , orange).…”

Section: Resultsmentioning

confidence: 99%

“…Even enantiomers have been identified using rotational spectroscopy with the recent advances in three‐wave mixing techniques . Microwave spectroscopy has been successfully used in the past to evaluate the gas phase conformations of several monosaccharides, which are structurally similar to levoglucosan. In particular, up to seven conformations of glucose were detected in the gas phase .…”

Section: Introductionmentioning

confidence: 99%

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Investigating the Conformation of the Bridged Monosaccharide Levoglucosan

et al. 2018

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Levoglucosan is one of the main products of the thermal degradation of glucose and cellulose and is commonly used as a tracer for biomass burning. Herein we report a conformational analysis of levoglucosan under isolation conditions, by means of microwave spectroscopy coupled with ultrafast laser vaporization in supersonic expansions. We observed three different conformations of levoglucosan in the gas phase. They all share a common heavy atom rigid bicyclic structure. The difference between the three of them lies in the network of intramolecular hydrogen bonds that arises from the OH groups at positions 2, 3 and 4. The different combinations of H-bonds give richness to the conformational landscape of levoglucosan. The gas phase conformers obtained in this work are compared to the crystal structure of levoglucosan previously reported. Although the heavy atom frame remains unchanged, there are significant differences in the positions of the H-atoms. In addition, the levoglucosan structure can be compared to the related glucose, for which gas phase conformational studies exist in the literature. In this case, in going from glucose to levoglucosan, there is an inversion in the chair conformation of the pyranose ring. This forces the OH groups to adopt axial positions (instead of the more favorable equatorial positions in glucose) and completely changes the pattern of intramolecular H-bonds.

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“… Cremer–Pople sphere with the observed conformers of levoglucosan (this work, red dots), β‐glucose (ref. , green) and β‐ribose (ref. , orange).…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Investigating the Conformation of the Bridged Monosaccharide Levoglucosan

et al. 2018

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“…We note that besides CHOCHOHCH 2 OH and DHA, other interesting sugars are ribose, ribofuranoside, or deoxyribose, for which their rotational spectra have been recently measured and characterized in the laboratory (Cocinero et al, 2012;Peña et al, 2013;É cija et al, 2016). Toward astronomical sources with low excitation temperatures of the gas such as the quiescent GMC G + 0.693-0.027, the peak of the spectra of these prebiotic COMs shifts to frequencies between 30 and 80 GHz.…”

Section: Evolution Of Astrochemistry and Prebiotic Chemistry: Toward mentioning

confidence: 93%

Toward the RNA-World in the Interstellar Medium—Detection of Urea and Search of 2-Amino-oxazole and Simple Sugars

et al. 2020

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In the past decade, astrochemistry has witnessed an impressive increase in the number of detections of complex organic molecules. Some of these species are of prebiotic interest such as glycolaldehyde, the simplest sugar, or aminoacetonitrile, a possible precursor of glycine. Recently, we have reported the detection of two new nitrogen-bearing complex organics, glycolonitrile and Z-cyanomethanimine, known to be intermediate species in the formation process of ribonucleotides within theories of a primordial RNA-world for the origin of life. In this study, we present deep and high-sensitivity observations toward two of the most chemically rich sources in the galaxy: a giant molecular cloud in the center of the Milky Way (G 1 0.693-0.027) and a proto-Sun (IRAS16293-2422 B). Our aim is to explore whether the key precursors considered to drive the primordial RNA-world chemistry are also found in space. Our high-sensitivity observations reveal that urea is present in G + 0.693-0.027 with an abundance of *5 • 10-11. This is the first detection of this prebiotic species outside a star-forming region. Urea remains undetected toward the proto-Sun IRAS16293-2422 B (upper limit to its abundance of £2 • 10-11). Other precursors of the RNA-world chemical scheme such as glycolaldehyde or cyanamide are abundant in space, but key prebiotic species such as 2-amino-oxazole, glyceraldehyde, or dihydroxyacetone are not detected in either source. Future more sensitive observations targeting the brightest transitions of these species will be needed to disentangle whether these large prebiotic organics are certainly present in space.

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“…This type of hydrogen bonding is associated with enhanced hydrogen bond cooperativity, as polarization of the chains strengthens hydrogen bonds and increases the hydrogen bond energy. In comparison with five‐ and six‐membered cyclic ribose, the longer chains of hydrogen bonds of ribitol and the lack of a hemiacetal oxygen acting as a chain stopper are likely to result in stronger hydrogen bond cooperativity. In fact, ribitol has generally shorter O−H⋅⋅⋅O hydrogen bonds, ranging 1.8–2.6 Å if the theoretical bond lengths of ribitol conformers are taken as good descriptions of the actual ones (which is granted by the small differences between theoretical and experimental rotational constants, lower than 1 % on average).…”

Section: Methodsmentioning

confidence: 99%

The Multiple Hydrogen‐Bonding Networks of Polyol Ribitol

Peña

Sanz

Alonso

et al. 2018

Chemistry A European J

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Conformational flexibility and non-covalent interactions determine the structure and activity of molecules in biological processes. In this work, the hydrogen bonding networks of the polyol ribitol have been determined for the first time using a combination of laser ablation and broadband rotational spectroscopy. Five conformations of ribitol have been identified, two with extended carbon chains and three with bent chains. All conformations are stabilized by sequential hydrogen bonding networks of either four or five intramolecular O-H⋅⋅⋅O bonds in a clockwise or counter-clockwise arrangement. The hydrogen bonding patterns are related to the extended or bent-chain conformations of ribitol, and involve 2OH-4OH or 2OH-5OH linkages, respectively. Interestingly, all hydrogen bonds wrap round the carbon backbone of ribitol rather than being located above or below it as it happens for other polyols and cyclic sugars.

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Furanosic forms of sugars: conformational equilibrium of methyl β-d-ribofuranoside

Cited by 20 publications

References 33 publications

Investigating the Conformation of the Bridged Monosaccharide Levoglucosan

Investigating the Conformation of the Bridged Monosaccharide Levoglucosan

Toward the RNA-World in the Interstellar Medium—Detection of Urea and Search of 2-Amino-oxazole and Simple Sugars

The Multiple Hydrogen‐Bonding Networks of Polyol Ribitol

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