Zeichen Journal ISSN No: 0932-4747

Measurements of Dynamics Parameters of Low-Sensitive Nuclei through

Cross-Polarization (CP) Kinetics

Nidhi Tiwari1,2, and Neeraj Sinha1*

1
Centre of Biomedical Research
SGPGIMS Campus, Raebarelly Road
Lucknow – 226014, INDIA

2
Department of Chemistry
Institute of Sciences
Banaras Hindu University
Varanasi – 221005, INDIA

Abstract

Cross – Polarization (CP) is one of the essential experiments to observe solid-state nuclear magnetic
resonance (ssNMR) signals of low sensitive nuclei with a wide range of applications in material science.
The kinetics of CP is a reliable source of dynamics parameters (TCH and T1) for polymer and other
material science applications. For the low sensitive nuclei, the measurements of dynamics parameters are
carried out by setting up experiments on standard samples (high sensitivity) and utilizing the same
experimental setup with the test samples, which may introduce some errors in the measurements. In this
article, we systematically study the source and magnitude of these errors in the measurement of dynamic
parameters as a function of Hartmann – Hahn (HH) conditions, a crucial source of errors in the setup of
CP experiments. The results presented in the article gives insight into the CP kinetics and will serve as a
guideline for the measurements of dynamics parameters for the low-sensitive materials applications.

Keywords: Cross-polarization, magic angle spinning, Hartman-Hahn match/mismatch, kinetics

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1. Introduction

Cross polarization (CP) is building block of all solid-state NMR experiments, having wide range of
applications to low sensitive nuclei. The process is based on sensitivity enhancement through polarization
transfer from dipolar coupled high γ nuclei to low γ nuclei such as 13C, 15N at Hartmann-Hahn (HH)
match condition. During the HH match condition, a quasi-equilibrium state is established during
thermodynamic contact, and polarization transfer takes place [1]. The HH match condition is defined by,
1I=1S, where 1I= IB1I and 1s= SB1S are the amplitudes of RF field applied to I and S nuclear
spins [2]. While the 1I≠1S is the condition representing the Hartman-Hahn mismatch. Under
mismatch condition only a portion of S spin is polarized and cross-polarization process is heterogeneous
in nature [3]. Hence CP intensity behaviour is highly sensitive to HH match condition. For maximum
cross-polarization HH condition must be fulfilled, CP process relies on heteronuclear dipolar interactions,
which is sensitive to inter-nuclear distance and mobility of the molecules. CP, in combination with magic
angle spinning (MAS) [4] and high power decoupling can be used to access the structure and dynamics of
the biomolecules and complex advanced material [5].
CP has a paramount significance in sensitivity enhancement for low  nuclei having low natural
isotopic abundance. Despite this, CP Kinetics experiments had been used as reliable source for measuring
the dynamics parameters for advanced complex materials. CP build up curve at variable contact time,
enables the calculation of the CP time constants TCH, which contains the structural and dynamical
information. This parameter depends on the number of the protons attached to a given carbons atom and
the mobility of the functional groups. CP dynamics curve also provides the rates of spin diffusion and
spin-lattice relaxation in rotating frame, the profiles of distribution of dipolar coupling and other
parameters accounting the effective sizes of spin clusters [6–8]. CP kinetics parameters had been widely
studied for advanced complex material, bone mineral, and polymer system. Variable contact time 1H-15P
CP experiment revealed three sites which contain proton rich, hydroxyapatite and proton deficient
phosphate domains in bone mineral [9]. Additionally, these parameters are very useful and important in
characterizing the polymer materials, rigid and mobile part of polymer, and their crystalline and
amorphous nature [10–12]. The structural information of polymer systems is sensitive to CP kinetics
parameter. For correct interpretation of spectra, the dynamics of CP is explored by varying the contact
time over which CP is performed. Such CP kinetics experiments are essential in order to optimize the CP
experiments, to obtain complete structural information of the molecules, and to make the measurements
quantitative [13].
In routine CPMAS experiments for dynamics measurements of nuclei having low sensitivity and
abundance, CP experiment is set to standard sample prior to the investigating sample and utilizing the
same experimental conditions with the investigating samples, which may introduce some errors in the
measurements. Hence it is essential to explore the dynamics of CP by varying the contact time over which
CP is performed as a function of HH conditions, which may serve as a source of error in measured
dynamics parameters (TCH and T1Therefore, it is necessary to optimize the CP experiments at HH
match and other conditions, in order to correctly measure these parameters obtained from CP kinetics
data.
In the present Study, we performed the 13C CP-MAS experiments at variable contact time on
standard valine sample. Our aim is to explore the 1H-13C CP dynamics on standard valine sample, by
performing several experiments with increasing CP contact time at varying MAS and HH conditions. CP
kinetic data were analysed and CP constant time TCH and spin-lattice relaxation in rotating frame T1ρ
parameters were found to be sensitive to MAS and HH mismatch condition. Hence the presented study
gives insights into the CP dynamics behavior at different experimental conditions as well as sources and
magnitude of error in the dynamical parameters measurements.

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2. Experimental section.

2.1. Sample preparation

Natural abundance valine sample was purchased from Sigma-Aldrich and tightly packed inside the 3.2
mm zirconia rotor.

2.2. ssNMR spectroscopy

All ssNMR experiments were carried out on 600 MHz solid-state NMR spectrometer (Avance III, Bruker
Biospin) equipped with 3.2 mm Efree probe. 1H and 13C operating frequencies were 600.156 MHz and
150.923 MHz respectively. The spin lock power during the HH match condition was 73.53 kHz. 1H-13C
CP experiments of natural abundance valine were recorded at Hartmann-Hahn mismatch condition of 
= +11.03 kHz, +20.4 kHz, -7.12 kHz, -12.72 kHz at varying CP contact time (tcp) from 50 μs to 1.8 ms.
All ssNMR experiments were performed at room temperature under different magic angle spinning
(MAS) frequency of r = 5 kHz, 10 kHz and 15 kHz. The first /2 pulse length on 1H channel was 2.50
μs. Recycle delay was 5sec and 16 scans were acquired for experiment with valine sample. The SPINAL-
64 [14] 1H decoupling power during acquisition was 100 kHz. NMR spectra were processed using
TOPSPIN 4.01 software and Variable-contact time CP data were fitted by using Matlab 2018a software.

3. Result and discussion

1
H-13C CPMAS experiments are widely studied solid state NMR experiments [15,16]. The
efficiency of cross-polarization process depends upon the inter-nuclear distances and mobility of
functional group. Thus CP gives structural information and dynamic insights. We performed 1H-
13
C CPMAS experiment at variable contact time on valine sample to access the dynamics of
cross polarization of various 13C Nuclei in valine. The natural abundance 13C spectrum of valine
is shown in Figure 2.1. The assignment of carbonyl, C and side chain carbons are shown in the
Figure 2.1. We also performed variable contact 1H-13C CP experiments with varying MAS (5
kHz, 10 kHz and 15 kHz) and under different Hartmann-Hahn mismatch (Δ) conditions along
with HH match conditions.

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Figure 2.1. 1H-13C CPMAS spectrum of natural abundance valine.

3.1. CP dynamics under Hartmann-Hahn

Hartmann match condition

The CP profile of different carbon resonances as a function of spinlock time (tcp) at 5 kHz MAS under the
HH match condition is shown in Figure 2.2. The CP build-up up rate of carbonyl, C Cand CH3 are distinct
from each other depending upon the number of protons attached to the carbon atom, larger the number of
protons in the group, stronger
er the C-H
C H dipolar coupling network and faster the cross
cross-polarisation. That is
why, CH and CH3 carbons cross-polarises
cross faster than Carbonyl carbon. The CH3 group in valine undergo
three site-hopping
hopping and rotational motion which weakens the C-H
C dipolar coupling ing network [5], therefore
methyl carbon cross-polarises
polarises slowly. Methyl carbon and CH carbon have almost similar CP dynamics.

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Figure 2.2. shows variable contact--time CP build-up

up curve at A). 5 kHz B) 10 kHz and C) 15 kHz MAS for various
groups in valine system. D). 1H-13C CPMAS spectra of valine at 5 kHz, 15 kHz under HH match condition and their
difference spectrum. E). CP kinetic curve for carbonyl, CH and CH3 carbon at 5 kHz under HH match condition,
fitted by using equation 1.

At high spinning speed, the strength of the 13C-1H and 1H-1H dipolar interactions get altered due
to which CP becomes less efficient [17,18]. Figure 2.2D shows the 1H-13C CPMAS spectra at 5 kHz and
15 kHz and their difference spectrum. At 15 kHz, intensity of 13C peaks smaller than that of intensity at 5
kHz. Figure 2.2B and 2.2C show the CP dynamics curve as a function of contact time for CH3, CH and
carbonyl carbons at 10 kHz and 15 kHz under HH match condition. CP rates for both CH3 (22.53 ppm
and 20.03 ppm) are almost similar at 10 kHz and 15 kHz MAS. CP buildbuild-up
up rate for CH (62.10 ppm and
31.69) carbons is faster than CH3’s at 10 kHz and 15 kHz MAS as compared to CP dynamics at 5 kHz,
this is due to the combined effect of the molecular motion and high MAS which make CP less efficient
for the CH3 Carbons. CH carbons are the most affected by the MAS. Distinct behaviour has been seen in
the CP kinetics of CH carbons at 61.10 ppm and 31.69 ppm at 5 kHz, 10 kHz and 15 kHz. These all
findings suggest that MAS spinning affect the dynamics of cross-polarization
cross polarization in different groups of
carbons in valine sample under HH condition. Variable contact ti time
me CP intensity for different groups of
valine molecule under match and mismatch condition at variable MAS has been shown in Figure 2.3.
From the Figure 2.3 it has been observed that at 10 kHz and 15 kHz MAS CP becomes more efficient

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under HH mismatch conditions

itions than mismatch condition. At 10 kHz CP intensity is maximum at -7.12
kHz  while at 15 kHz CP intensity is maximum at -12.72 kHz as
as shown in Figure 2.3.

Figure 2.3.. Variable contact time CP build up curve under Hartman-Hahn

Hartman Hahn match and mismatch condition for
various group in valine at 5 kHz, 10 kHz and 15 kHz MAS.

In order to get the more quantitative information, the variable contact time CP data were analysed
using the equation
( )= 1− (1)

Where I(t) is the intensity of a CP signal, Io is the amplitude of the signal, t is the contact time, TCH is the
CP time constant and T1ρ is the spin-lattice
spin lattice relaxation parameter in rotating frame [19,20]. Equation 1
describes the CP build up rate as a function of contact time t. At short contact time, that is initial part of
the curve, CP process is governed by 1H-13C dipolar interactions through 1H reservoir and dictated bby the
CP time constant TCH parameter. At long contact time, that is, the latter part of the curve follows an
exponential decay, dictated by proton spinspin-lattice
lattice relaxation time in rotating frame T1ρ. The CP time
constant parameter TCH are the characteristics
characteristics of specific functional group in a molecule since they are
governed by the heteronuclear dipolar coupling. Stronger the heteronuclear dipolar coupling, faster will

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be the cross-polarization process. The relaxation parameter T1ρ is the most suitable indicator of mobility
for rigid system.
The CP data were fitted using the equation 1, we got the two relaxation parameter TCH and T1ρ.
Figure 2.2E shows the CP data under HH match at 5 kHz MAS, fitted with equation 1 for Carbonyl
(176.4 ppm), CH (61.10 ppm) and CH3 (22.53 ppm) carbons. Similarly, fitting had been done for variable
contact time CP data under mismatch condition at 5 kHz, 10 kHz and 15 kHz MAS.

3.2. CP constant time TCH

CP constant time TCH parameter is extracted from CP kinetic data. Figure 2.4 shows the graphical
representation of TCH value for all the carbons in the valine molecule under HH match and mismatch
condition at 5 kHz (Figure 2.4A), 10 kHz (Figure 2.4B) and 15 kHz (Figure 2.4C). T1ρ values for
carbonyl, CHs and CH3s carbons are listed in Table 2A (5 kHz), 2B (10 kHz), and 2C (15 kHz). the
order of TCH value is in microsecond (s). From the Figure 2.4A, 2.4B and 2.4C it has been observed that
magic angle spinning as well as match and mismatch conditions affected the TCH parameter. At 5 kHz,
carbonyl carbon shows maximum TCH values than other groups in valine system which suggested the low
CP build up rate due to weak heteronuclear dipolar coupling with remote protons in valine molecule.
Similar trend had been at 10 kHz and 15 kHz MAS (Figure 2.4B and 2.4C). Although the values of TCH
parameter is lower at 10 kHz and 15 kHz as compared to values at 5 kHz MAS. At 5 kHz MAS TCH
values under mismatch conditions for different groups in valine shows positive as well as negative
deviation from match conditions. While at 10 kHz and 15 kHz MAS CHs and CH3s carbons shows
positive deviation from match condition except for carbonyl carbon. At different mismatch conditions the
CP dynamics is distinct at varying MAS.

Table- 2A. Values of T1 and TCH parameters extracted from CP kinetic data at 5 kHz MAS are listed.

Peak/ -12.7 kHz -7.1 kHz 0 kHz +11.03 kHz +20.3 kHz

T1 TCH T1 TCH T1 TCH T1 TCH T1 TCH
(ms) (s) (ms) (s) (ms) (s) (ms) (s) (ms) (s)
Carbonyl 408.8 274.9 3.6 374.8 2.4 478.1 15.9 210.5
- -
(176.4 ppm) ± 77.9 ± 35.7 ± 0.5 ± 39.3 ± 0.3 ± 46.3 ± 3.0 ± 14.1
CH 5.7 136.1 4.8 24.9 2.3 63.5 2.3 61.2 4.5 72.5
(62.1 ppm) ± 0.8 ± 14.9 ± 0.6 ± 3.3 ± 0.1 ± 4.6 ± 0.1 ± 3.9 ± 0.3 ± 4.4
CH 6.9 204.7 5.1 43.4 2.9 87.6 2.8 88 13.9 81.1
(31.6 ppm) ± 1.0 ± 30.7 ± 0.8 ± 5.3 ± 0.2 ± 7.2 ± 0.3 ± 8.1 ± 3.3 ± 10.1
CH3 7.7 305.1 11.9 81.6 3.8 117.1 3.2 127.4 13.2 85.3
(22.5 ppm) ± 1.1 ± 21.9 ± 2.2 ± 8.7 ± 0.3 ± 7.4 ± 0.2 ± 7.0 ± 2.7 ± 10.0
CH3 7.1 299.5 8.6 81.2 3.9 106.6 3.1 117.5 14.5 78.6
(20.0 ppm) ± 0.8 ± 23.9 ± 1.2 ± 9.3 ± 0.4 ± 6.6 ± 0.2 ± 6.1 ± 3.4 ± 9.5

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Table- 2B. Values of T1 and TCH parameters extracted from CP kinetic data at 10 kHz MAS are listed.

Peak/ -12.7 kHz -7.1 kHz 0 kHz +11.03 kHz +20.3 kHz

T1 TCH T1 TCH T1 TCH T1 TCH T1 TCH
(ms) (s) (ms) (s) (ms) (s) (ms) (s) (ms) (s)

Carbonyl 12 76.8 5.4 237.3 153.02 19.7 289.9 3.3 397.7

-
(176.4 ppm) ± 1.5 ± 9.2 ± 0.8 ± 28.5 ± 13.0 ± 2.0 ± 32.7 ± 0.3 ± 5.1

CH 6.1 17.6 4.1 19.1 8.4 21.1 5.2 24.3 4.08 26.6
(62.1 ppm) ± 0.6 ± 3.1 ± 0.4 ± 2.6 ± 1.2 ± 2.3 ± 0.8 ± 2.9 ± 0.3 ± 2.7

CH 12.9 28.7 10.7 31 34.2 18.9 17.9 38.2 7.9 36.7

(31.6 ppm) ± 1.2 ± 3.2 ± 1.8 ± 3.5 ± 5.5 ± 2.2 ± 2.1 ± 3.0 ± 0.8 ± 3.6

CH3 58.6 10.2 88.5 48.9 30 80.9 9.9 88.8

- -
(22.5 ppm) ± 6.2 ± 2.1 ± 6.9 ± 4.4 ± 3.8 ± 7.0 ± 1.1 ± 7.9

CH3 53.5 9.3 72.6 42.03 61.5 69.7 12 ± 76.8

- -
(20.0 ppm) ± 5.1 ± 1.2 ± 8.2 ± 3.4 ± 11.6 ± 8.2 1.4 ± 8.1

Table- 2C. Values of T1 and TCH parameters extracted from CP kinetic data at 15 kHz MAS are listed.

Peak/ -12.7 kHz -7.1 kHz 0 kHz +11.03 kHz +20.3 kHz

T1 TCH T1 TCH T1 TCH T1 TCH T1 TCH
(ms) (s) (ms) (s) (ms) (s) (ms) (s) (ms) (s)

Carbonyl 15.02 205.6 23.96 135.5 15.9 105.7 77.7 124.3 124.3
-
(176.4 ppm) ± 2.5 ± 2.7 ± 4.8 ± 15.3 ± 2.8 ± 14.4 ± 16.3 ± 29.8 ± 14.5

CH 7.5 62.9 7.8 71.7 34.01 16.2 71.3 58.8 58.8

-
(62.1 ppm) ± 1.5 ± 1.1 ± 1.4 ± 10.1 ± 5.7 ± 4.3 ± 8.5 ± 10.5 ± 11.2

CH 68.4 75.6 23.9 95.2 3.2 73.5 68.8 68.8

- -
(31.6 ppm) ± 10.8 ± 8.9 ± 4.5 ± 1.1 ± 0.5 ± 8.6 ± 12.3 ± 9.5

CH3 55.5 55.04 49.2 50.3 35.3 136.2 53.7 53.7

- -
(22.5 ppm) ± 5.7 ± 8.2 ± 5.8 ± 4.8 ± 4.9 ± 17.4 ± 12.2 ± 4.4

CH3 51.5 43.8 45.2 33.3 84.4 188.8 46.5 46.5

- -
(20.0 ppm) ± 5.5 ± 7.8 ± 5.7 ± 2.5 ± 13.5 ± 24.1 ± 8.2 ± 4.4

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3.3 Spin-lattice
lattice relaxation in rotating frame T1ρ

T1ρ parameter is the characteristic of final decay of the CP kinetic curve, is a good indicator of mobility
of the H atom in a molecular frame. T1ρ describes the relaxation time of 1H nuclei. Figure 2.5 shows the
graphical representation of T1ρ value for aallll the carbons in the valine molecule under HH match and
mismatch condition at 5 kHz (Figure 2.5A), 10 kHz (Figure 2.5B) and 15 kHz (Figure 2.5C). the order of
T1ρ value is in millisecond (ms). Values of T1ρ extracted from CP kinetics data for different gr groups in
valine molecules are listed in Table 2A (5 kHz), 2B (10 kHz), and 2C (15 kHz). From the Figure 2.5 it
has been observed that on increasing the spinning speed the values of T1ρ get increased, indicating the
slower decay rate. The decay rate of carbonyl
carbonyl carbons, CHs and CH3s carbons are distinct from each
other depending upon the heteronuclear dipolar coupling network and mobility present in the group. the
T1ρ value under match and mismatch conditions also varied with increasing the MAS from 5 kHz to 10
kHz and 15 kHz MAS. From the above observations, it has been found that change in the CP dynamics
under HH match and mismatch condition at varying MAS reflected into change in the CP kinetic
parameters TCH and T1ρ values.

Figure 2.4. Graphical representation of CP constant time TCH extracted from CP kinetic curve under HH match and
mismatch conditions for various groups in valine system at A) 5 kHz, B) 10 kHz and 15 kHz MAS.

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Figure 2.5. Graphical representation of spin-lattice

spin relaxation time in rotating frame T1ρ extracted from CP kinetic
curve under HH match and mismatch conditions for various groups in valine system at A) 5 kHz, B) 10 kHz and 15
kHz MAS.

4. Conclusion

The dynamics of cross-polarization

polarization play an essential role in defining the structure and dynamics of the
molecule. The parameters TCH and T1ρ obtained from the fitting the CP kinetic data contains structural
and dynamical information, which span a different time scale, TCH in microsecond and T1ρ in
millisecond. We have studied the 1H-13C1H 13C CP kinetics under HH match and mismatch conditions at
varying magic angle spinning. The extracted parameter TCH and T1ρ from CP kinetic data found to be
sensitive to HH match/mismatch condi condition
tion as well as variation in MAS. At high spinning speed CP is
more efficient at Hartmann-Hahn Hahn mismatch condition. The study of CP kinetic data is helpful in
optimization of CP experiments. Since CP kinetics parameters are crucial for the structural inform
information of
polymer system and advanced complex material therefore it is necessary to optimize the CP for correct
interpretation of spectra to obtain complete structural information of the molecule.

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