repliement spectral de la dimention 13c. un puissant...
TRANSCRIPT
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
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
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
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+
-
16
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
18
74.37 - 40 = 34.37 ppm
Mohammadali Foroozandeh
Combining 10 ppm with 9.9 ppmAny position of CF in F1
19
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
20
Mohammadali Foroozandeh
+ ’
€
ʹ′ t 1 =t1100
DENA-HSQC
DifferentialEvolution forNon-ambiguousAliasing
Combining 10 ppm with 9.9 ppm
21
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
23