Repliement spectral de la dimention 13C.Un puissant outil d’étude de mélanges
complexes de petites molécules utilisants des expériences basées sur l’HSQC
Spectral Aliasing of the 13C dimension. A powerful tool to Study Mixtures of Small Molecules Using HSQC-Based experiments
Damien Jeannerat, University of Geneva, Switzerland
Do not hesitate to contact: [email protected]
1
High resolution in indirect dimensions
2
SW0
SWa
νa = mod(ν0 + SWa/2 − CF, SWa) − SWa/2 + CF ν0 = νa ± n SWa
Spectral aliasing
3
Spectral aliasing
4
Computer-optimized spectral aliasing1D carbon or DEPTspectrum
13 48.468 6.4 ...
...
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
C# !(13C) LW 1H dispersion
...
...
...
...
13 48.468 6.4 5.8-5.7
2D Full-width heteronuclear spectrum
Optimization
2D aliased heteronuclear spectrum
Optimization
Series of2D aliased heteronuclear spectrum
5
Computer-optimized spectral aliasing1D carbon or DEPTspectrum
13 48.468 6.4 ...
...
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
C# !(13C) LW 1H dispersion
...
...
...
...
13 48.468 6.4 5.8-5.7
2D Full-width heteronuclear spectrum
Optimization
2D aliased heteronuclear spectrum
Optimization
Series of2D aliased heteronuclear spectrum
6
Computer-optimized spectral aliasing1D carbon or DEPTspectrum
13 48.468 6.4 ...
...
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
C# !(13C) LW 1H dispersion
...
...
...
...
13 48.468 6.4 5.8-5.7
2D Full-width heteronuclear spectrum
Optimization
2D aliased heteronuclear spectrum
Optimization
Series of2D aliased heteronuclear spectrum
7
Computer-optimized spectral aliasing1D carbon or DEPTspectrum
13 48.468 6.4 ...
...
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
C# !(13C) LW 1H dispersion
...
...
...
...
13 48.468 6.4 5.8-5.7
2D Full-width heteronuclear spectrum
Optimization
2D aliased heteronuclear spectrum
Optimization
Series of2D aliased heteronuclear spectrum
D. Jeannerat, J.Magn. Reson. 186, p112,
8
Computer-optimized spectral aliasing1D carbon or DEPTspectrum
13 48.468 6.4 ...
...
13 48.468 6.4 5.8-5.7 5.1-5.0 4.7-4.6
C# !(13C) LW 1H dispersion
...
...
...
...
13 48.468 6.4 5.8-5.7
2D Full-width heteronuclear spectrum
Optimization
2D aliased heteronuclear spectrum
Optimization
Series of2D aliased heteronuclear spectrum
D. Jeannerat, J.Magn. Reson. 186, p112,
9
α-Cubebin
β-Cubebin
Combining full and 10-ppm spectra
10
52.0?
?2.04
52.04
α-Cubebin
β-Cubebin
Combining full and 10-ppm spectra
11
Combining full and 10-ppm spectra
Bruno Vitorge
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Applications
Combinations2D HSQC-TOCSY2D HSQC-NOESY
Seriesselective-TOCSY-HSQC
2D-aliasing 3D HSQC-TOCSY3D HSQC-COSY
D. Mury, et al. Magn. Reson. in Chem. (2009), 47, 909
13
CT-HSQC-IDOSY
Vitorge et al. Anal. Chem. 2006, 78, 5601-5606
Diffusion measurements
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NMR titrations
titrant
Mixture of compounds
Rupali Shivapurkar
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NMR titrations
Rupali Shivapurkar
--O OH
OH
HO
caffeic acid
O OH
2,3 dimethyl benzoic acid
O
O
O OH
cinnamic acid
O OH
OHcoumaric acid
O
O
OOH
camphanic acid
O OH
OH
HO
caffeic acid
O OH
2,3 dimethyl benzoic acid
O
O
O OH
cinnamic acid
O OH
OHcoumaric acid
O
O
OOH
camphanic acid
H H
+ H+
-
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NMR titrations
Rupali Shivapurkar
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Acetic ac / coumaric ac. Δ pKa = 0.025Normalization of the 13C chemical shifts
5.26
O OH
OH
HO
caffeic acid
O OH
2,3 dimethyl benzoic acid
O
O
O OH
cinnamic acid
O OH
OHcoumaric acid
O
O
OOH
camphanic acid
5.794.804.77 6.60
NMR titrations
Rupali Shivapurkar
4.24 4.72 4.70 3.71 2.9
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74.37 - 40 = 34.37 ppm
Mohammadali Foroozandeh
Combining 10 ppm with 9.9 ppmAny position of CF in F1
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74.37 - 40 = 34.37 ppm
Mohammadali Foroozandeh
Combining 10 ppm with 9.9 ppmCarrier at -5 ppm scaled to +5 ppm in F1
Multiplicity edition
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Mohammadali Foroozandeh
+ ’
€
ʹ′ t 1 =t1100
DENA-HSQC
DifferentialEvolution forNon-ambiguousAliasing
Combining 10 ppm with 9.9 ppm
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DENA-HSQC spectra
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Département de Chimie OrganiqueQuai E. Ansermet, CH-1211 Geneva 4Switzerland
Acknowledgments
former PhD Students Bruno Vitorge, HSQC-IDOSY, HMBC, 10 ppm experiments PhD Students Rupali Shivapurkar, Titration experiments
Mohammadali Foroozandeh, Q3 sign alternation and 10.1 ppm Technicians André Pinto Stéphane Grass Patrick Romanens Collaborations
Jean-Marc Nuzillard, Univ. Champagne-Ardenne, Reim, FrancePhilippe Christen, Phytochemistry, Univ. Geneva, Switzerland
FundingSNF, Etat de Genève
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