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j.a.aguilar@durham.ac.uk
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- The definition and the reason
- One-dimensional experiments
The Zangger-Sterk pulse sequence
The ZS-BIRD-Hybrid
How to use them
- Multi-dimensional experiments
3D Variants
2D variants based on real-time compression
Constant-time versions
- Questions
j.a.aguilar@durham.ac.uk
What is it?
~ 50 Hz wide
~ 1 Hz wide
j.a.aguilar@durham.ac.uk
No, two
Pure shift
Pure shift 1H
j.a.aguilar@durham.ac.uk
128
129
Classic
Pure shift
130
131
132
7.7
7.6
7.5
H / ppm (F2)
7.7
7.6
7.5
H / ppm (F2)
j.a.aguilar@durham.ac.uk
7.6
7.6
7.8
7.8
8.0
8.0
Classic
8.4
8.2
8.0
ppm
7.8
8.2
8.2
8.4
8.4
8.4
7.6
8.2
8.0
ppm
7.8
7.6
In order to produce unambiguous data true pure shift was necessary, i.e.
both H-H and H-P splittings had to be suppressed
Br
Br
O
N
OH
P
OEt
H2SO4
(conc.)
SO3H
O
N
80 oC
OH
P
OH
+ ?
19
Pure shift 1H
Notice this is not a true
pure shift spectrum because
H-F couplings are present.
This, however, is useful.
j.a.aguilar@durham.ac.uk
Assembly
J modulation is slow, so a block of data points lasting 1/sw1 << 1/J can be measured for each value of t1
Typically 20 ms chunks
are collected
(sw1= 50 Hz)
F
CO2H
CF3
2 sw1 Hz
2 sw1 Hz
2.5
2.0
1.5
1.0
0.5
0.0
Sensitivity bw180/sw
Bo + zGz
j.a.aguilar@durham.ac.uk
Empty
space
=
wasted
sensitivity
Empty space
=
Wasted sensitivity
ZS 1H
H-X filter
BIRDd rotation
Catechol
isotopomers
BIRDd rotation
Resorcinol
isotopomers
The BIRDd rotation inverts only protons directly coupled to 13C
Isotopic dilution ensures that their coupled partners are not inverted
Mild strong
coupling
Strong coupling
Side-band?
7.8 ppm
7.4
7.0
6.6
6.2
5.8
5.4
Zangger-Sterk
Zangger-Sterk - BIRD
bw180/sw
Bottom line:
Ideal to decouple aliphatic regions
Bottom line:
Ideal to decouple aromatic regions
ZS-BIRD hybrid 1H
ZS 1H
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
ppm
j.a.aguilar@durham.ac.uk
ZS-BIRD hybrid 1H
ZS 1H
ZS snob 60 ms 5 min
PSYCHE 60 ms - 5 min
Improved sensitivity
Improved performance with strong coupling
90
t1
1
90
180
180
t2/2
t2/2
H
1
Pure shift da
Gz
G0
Pure shift 1H
with classic 2D
chemical shift sampling
-G
sl
-2G
NOESY (2D)
+
Pure shift with classic 2D
chemical shift sampling
= 3D experiment (long)
How-to: Merge the pure shift sequence with your experiment (except for COSY)
The problem: The experiment will now be 32-64 times longer
The solution: Compress the whole 2D chemical shift sampling scheme into a single acquisition
using real-time compression.
j.a.aguilar@durham.ac.uk
j.a.aguilar@durham.ac.uk
Real-time compression
How-to
Compress a full 2D sampling scheme into a single acquisition
Acquire J-refocus - acquire J-refocus - acquire - J-refocus acquire
Original fid
Shortened fid
= broadening
j.a.aguilar@durham.ac.uk
Broadening in context
Undesirable but better off with than without
Classic HSQC
122
124
126
128
130
7.8
7.6
7.5
7.3
H / ppm (F2)
7.1
6.9
7.8
7.6
7.4
H / ppm (F2)
7.2
7.0
127.6
Classic HSQC
128.0
128.4
COSY-like
anti-phase signals
128.8
129.2
7.37
7.35
7.33
7.31
H / ppm (F
7.29
7.27
7.37
7.35
7.33
7.31
H / ppm (F2)
7.29
7.27
Constant-time techniques
j.a.aguilar@durham.ac.uk
Constant-time techniques
Thanks to:
Gareth Morris (Manchester)
Mathias Nilsson (Manchester)
Alan Kenwright (Durham)
Martina Delbianco (Durham)
Julia Cassani (Mexico, Mexico DF)
ZS-1H using
a double FT
Geraniol
Camphene
ZS 1H
NO2
JHF= 4.9 Hz
JHF= 8.4 Hz
** * *
**
* *
ZS-BIRD hybrid
8.4
8.2
8.0
7.8
7.6
7.4
7.2 ppm
PSYCHE
Chunking artefacts
Chunk size= 40 ms
Chunk size= 20 ms
Chunk size= 10 ms
Chunk size= 5 ms
H