PS1D – 1H Spectra with

Broadband Proton Decoupling

Application Note

Authors Abstract
Péter Sándor VnmrJ 3 Software provides easy-to-use, interactive tools for setting up advanced
Applications Chemist experiments. This allows even novice users to get critical information about their
Agilent Technologies
research samples using the most advanced NMR experiments available. This
Waldbronn, Germany
applications note is just one of a series designed to provide step-by-step guidance
for setting up sophisticated experiments to collect exactly the data you need for
your analyses.

Introduction
One of the attractive features of broadband 1H decoupled 13C NMR spectra is
that signals appear as single lines, facilitating the extraction of chemical shifts
from a simple line listing. Ordinary 1H NMR spectra, however, are typically much
more complicated due to homonuclear coupling which can create a number of
multiplet components for each proton resonance. Broad or strongly coupled proton
multiplets often overlap, seriously compromising the resolution power of proton
spectra and making analysis difficult.

Zangger and Sterk published the concept of pure-shift (PS) spectroscopy in 1997
using a 180° pulse that is simultaneously chemical shift and spatially selective1.
This allows the construction of a synthetic PS1D (Pure Shift 1D) FID piece by piece
from the interferograms of a pseudo-2D acquisition. The result is suppression
of the multiplet structure, yielding almost an order of magnitude gain in proton
spectral resolution. This sequence was rediscovered and modified by Morris
and Nilsson 2,3, in 2010. The second generation PS1D experiment, which is
implemented in VnmrJ 3.2, produces cleaner spectra and is approximately 16 times
faster than the original version.
A PS1D Example N
18 20
17
Strychnine was used as a test case 1 16
2 6 7 15
to demonstrate the utility of the PS1D 3 H
14 21
4 5 8
experiment. Data were collected at N 13 22
500 MHz on an Agilent DD2 NMR 10
H
12
H
23
11
instrument. The 1H proton spectrum O O
H
together with the structure and
numbering scheme of strychnine is
displayed in figure 1.

The PS1D experiment has only two

pulse sequence specific parameters 8 7 6 5 4 3 2 ppm
that require consideration. The first
Figure 1. The 500 MHz proton spectrum and the structure of strychnine.
is the Slice Selection Bandwidth
which determines the size of the RF
bandwidth of the selective refocusing
pulses. The default value of 100 Hz
corresponds to 2 % of a 10 ppm wide
spectral region at 500 MHz. For the
optimal decoupling results, the actual C.
bandwidth should not exceed the
smallest chemical shift difference
expected between any coupled proton
pairs. This parameter has a strong
inverse relationship to the overall
sensitivity of the PS1D spectrum and,
in the same time, defines the minimum B.
chemical shift difference where
decoupling is still complete.

The second important parameter

is the Pure Shift tau delay. This
parameter has an inverse relationship
to the biggest coupling constant to A.
be suppressed; it determines the
number of data points used from each
acquired element of the pseudo-2D
data set to synthesize the final PS1D 8 7 6 5 4 3 2 ppm
free induction decay. Larger coupling
constants correspond to smaller Figure 2. The 500 MHz proton spectrum of strychnine (A), with PS1D spectra acquired with 100 Hz (B)
and 30 Hz (C) slice selection bandwidth.
FID sizes to be concatenated, and
will therefore lengthen the overall
experimental time to achieve the same
line width (2 Hz by default) in the final
PS1D spectrum.

The ordinary 1D proton spectrum of

strychnine together with two pure-
shift proton spectra, collected using
100 Hz and 30 Hz slice selection, is
displayed in figure 2. Apart from two
regions (indicated by red arrows in
figure 2B), most of the signals are

2
completely decoupled even with C.
the default (100 Hz) selectivity. The H14 H11α
H18α
maximum resolution achievable
by the method is clearly illustrated
by the expansions in figure 3. In
the displayed regions, both PS1D
spectra show complete decoupling. B.
The strychnine spectrum between
3.1-3.2 ppm contains three heavily
overlapping proton multiplets (H18α,
H14, and H11α). The chemical shift
difference between H14 and H11α,
A. water trace
protons that are not coupled to each
other, is only 3.8 Hz, while the width
of the two multiplets is about 35 Hz.
To achieve the same signal separation
between these two protons with the 3.24 3.18 3.12 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 ppm
homonuclear couplings retained, one
Figure 3. Expanded regions of the 500 MHz proton spectrum of strychnine (A), with PS1D spectra
would need a 5 GHz spectrometer. acquired with 100 Hz (B) and 30 Hz (C) slice selection bandwidths.

The expansions in figure 4 are focused

on the more challenging regions
of the spectra. The chemical shift
H3
difference between the aromatic
H23αβ
protons H3, H1, and H2 (7.1-7.3 ppm), H1 H2
as well as between the H23 αβ geminal CHCI3
proton pair (~4.1 ppm), is well below
the 100 Hz bandwidth. As shown
in figure 4B, these protons show
a complicated, partially decoupled C.
multiplet structure. Reducing the slice
selection to 30 Hz (Figure 4C) results
in optimal decoupling in the aromatic
region, while the H23 αβ pair, with a
17 Hz geminal coupling, still exhibits
some strong coupling effects. Figures
4B and 4C also demonstrate the
sensitivity loss when higher selectivity B.
is required.

A.

7.28 7.18 7.08 4.30 4.10 3.90 ppm

Figure 4. Expanded regions of the 500 MHz proton spectrum of strychnine (A), with PS1D spectra
acquired with 100 Hz (B) and 30 Hz (C) slice selection bandwidths.

3
Experimental Method
The 1D homonuclear broadband-
decoupled proton spectrum originates
from a pseudo-2D acquisition. While
this might sound like a complicated
task, in practice it is a simple operation
as the necessary tools are either
provided in the experiment panels or
are executed automatically:

1. Collect a PROTON spectrum as a

study in the Study Queue.

2. Load the PROTON spectrum into

the current workspace, select
Continue Study, and then select
Pure Shift 1D from the Experiment
Selector (Figure 5).

3. Set the common acquisition

parameters and adjust the two
Figure 5. Setting up the PS1D pulse sequence requires customization of only two pulse sequence
sequence specific parameters,
specific parameters, the Slice Selection Bandwidth and the Pure Shift tau delay.
if necessary:

a. Slice Selection Bandwidth is

set to 100 Hz by default. For
optimal decoupling, the actual
value should not exceed the
smallest expected chemical shift
difference between any coupled
proton pairs. This parameter has
a strong inverse relationship to
the overall sensitivity of the
PS1D spectrum.
b. Pure Shift tau delay: this
parameter has an inverse
relationship to the largest
coupling constant to be
suppressed (8 ms by default,
corresponding to a 12.5 Hz
coupling constant). Larger
coupling constants require
shorter tau delays and therefore
lengthen the overall experimental
time of the PS1D experiment.
4. The experiment is now ready to
acquire PS1D data. Use the Submit
button in the Study Queue to
initiate data collection. When the
acquisition is complete, the data are
automatically processed and saved.
Conclusions
The PS1D is a very powerful tool for
structure elucidation. While it does
suffer from limited sensitivity due to
slice selective excitation, it provides
multiplet-free, or in other words,
pure-shift proton spectra. Using PS1D,
1 NMR: a resolution of the resolution
H chemical shifts can be directly
extracted, even in crowded spectra,
with very high accuracy. The pure-
shift concept can be extended to any
homonuclear 2D experiments (e.g.,
NOESY, TOCSY, and more).
References
1. Zangger, K., and Sterk, H.
Homonuclear broadband-decoupled
NMR spectra. J. Magn. Reson.,
1997, 124:486-489.
2. Aguliar, A. et al. Pure shift 1H
problem? Angew. Chem. Int. Ed.,
2010, 49:3901-3903.
3. Morris, G.A., et al. True chemical
shift correlation maps: a TOCSY
experiment with pure shifts in both
dimensions. J. Am. Chem. Soc.,
2010, 132:12770-12772.
www.agilent.com/chem/nmr
Information, descriptions, and specifi cations in this
publication are subject to change without notice.
© Agilent Technologies Inc., 2011
Published in the USA, September 16, 2011
5990-9084EN