A NMR crystallography study shows how intermolecular NH...O, NH...N, OH...N, OH...O and CH–π interactions stabilize the ribbon-like supramolecular structures of three different guanosine derivatives; guanosine dihydrate (G), 3/, 5/–O– dipropanolyl deoxyguanosine (dGC(3)2) and 3/, 5/ –O– isopropylideneguanosine hemihydrate (Gace). Experimental solid-state 1H NMR spectra obtained at 20 T using fast Magic-Angle Spinning (MAS), here at 75 kHz, are presented for a dihydrate of G. For each guanosine derivative, the role of specific interactions is probed by means of NMR chemical shifts calculated using the Density Functional Theory (DFT) Gauge-Including Projector-Augmented Wave (GIPAW) approach for the full crystal and extracted isolated single molecules. Specifically, the isolated molecule to full crystal transformations result in net changes in the GIPAW calculated 1H NMR chemical shifts of up to 8 ppm for OH...O, up to 6.5 ppm for NH...N and up to 4.6 ppm for NH...O hydrogen bonds; notably, the presence of water molecules in G and Gace reinforces the molecular stacking through strong OH...O hydrogen bonds. The sugar conformations are markedly different in G, dG(C3)2 and Gace, and it is shown that the experimental 13C solid-state NMR chemical shift at the C8 position is a reliable indicator of a ‘syn’ (> 135 ppm) or ‘anti’ (< 135 ppm) conformer

Brown, Steven P.

Davis, Jeffery T.

Marsh, Andrew

Masiero, Stefano

Reddy, G. N. Manjunatha

Crystal Growth & Design

An NMR crystallography study shows
how intermolecular N–H···O,
N–H···N, O–H···N, O–H···O,
and CH−π interactions stabilize the ribbon-like supramolecular
structures of three different guanosine derivatives: guanosine dihydrate
(G), 3′,5′-O-dipropanolyl
deoxyguanosine (dG­(C3)2), and
3′,5′-O-isopropylideneguanosine hemihydrate
(Gace). Experimental solid-state 1H NMR spectra
obtained at 20 T using fast magic-angle spinning (MAS), here at 75
kHz, are presented for a dihydrate of G. For each guanosine
derivative, the role of specific interactions is probed by means of
NMR chemical shifts calculated using the density functional theory
(DFT) gauge-including projector-augmented wave (GIPAW) approach for
the full crystal and extracted isolated single molecules. Specifically,
the isolated molecule to full crystal transformations result in net
changes in the GIPAW calculated 1H NMR chemical shifts
of up to 8 ppm for O–H···O, up to 6.5 ppm for
N–H···N and up to 4.6 ppm for N–H···O
hydrogen bonds; notably, the presence of water molecules in G and Gace reinforces the molecular stacking
through strong O–H···O hydrogen bonds. The sugar
conformations are markedly different in G, dG­(C3)2, and Gace, and it is shown
that the experimental 13C solid-state NMR chemical shift
at the C8 position is a reliable indicator of a “syn” (>135 ppm) or “anti” (<135
ppm) conformer

G. N.
Manjunatha Reddy (1390156)

Andrew Marsh (1334043)

Jeffery T. Davis (547862)

Stefano Masiero (1390155)

Steven P. Brown (1296819)

FigShare

Interplay of Noncovalent Interactions in Ribbon-like
Guanosine Self-Assembly: An NMR Crystallography Study

An NMR crystallography study shows how intermolecular N−H···
O, N−H···N, O−H···N, O−H···O, and CH−π interactions stabilize the ribbonlike
supramolecular structures of three different guanosine derivatives: guanosine
dihydrate (G), 3′,5′-O-dipropanolyl deoxyguanosine (dG(C3)2), and 3′,5′-Oisopropylideneguanosine
hemihydrate (Gace). Experimental solid-state 1H NMR
spectra obtained at 20 T using fast magic-angle spinning (MAS), here at 75 kHz,
are presented for a dihydrate of G. For each guanosine derivative, the role of
specific interactions is probed by means of NMR chemical shifts calculated using
the density functional theory (DFT) gauge-including projector-augmented wave
(GIPAW) approach for the full crystal and extracted isolated single molecules.
Specifically, the isolated molecule to full crystal transformations result in net
changes in the GIPAW calculated 1H NMR chemical shifts of up to 8 ppm for O−
H···O, up to 6.5 ppm for N−H···N and up to 4.6 ppm for N−H···O hydrogen
bonds; notably, the presence of water molecules in G and Gace reinforces the molecular stacking through strong O−H···O
hydrogen bonds. The sugar conformations are markedly different in G, dG(C3)2, and Gace, and it is shown that the
experimental 13C solid-state NMR chemical shift at the C8 position is a reliable indicator of a “syn” (&gt;135 ppm) or “anti” (&lt;135
ppm) conformer

MASIERO, STEFANO

Archivio istituzionale della ricerca - Alma Mater Studiorum Università di Bologna

English

Interplay of Noncovalent Interactions in Ribbon-like Guanosine Self-Assembly: An NMR Crystallography Study

G. N. Manjunatha Reddy

Andrew Marsh

Jeffery T. Davis

Stefano Masiero

Steven P. Brown

Crossref

Warwick Research Archives Portal Repository