Conformation analysis of d-glucaric acid in deuterium oxide by NMR based on its JHH and JCH coupling constants

Article abstract of DOI:10.1002/mrc.4396

d-Glucaric acid (GA) is an aldaric acid and consists of an asymmetric acyclic sugar backbone with a carboxyl group positioned at either end of its structure (i.e., the C1 and C6 positions). The purpose of this study was to conduct a conformation analysis of flexible GA as a solution in deuterium oxide by NMR spectroscopy, based on J-resolved conformation analysis using protonproton (³J_HH) and protoncarbon (²J_CH and ³J_CH) coupling constants, as well as nuclear overhauser effect spectroscopy (NOESY). The ²J_CH and ³J_CH coupling constants were measured using the J-resolved heteronuclear multiple bond correlation (HMBC) NMR technique. NOESY correlation experiments indicated that H2 and H5 were in close proximity, despite the fact that these protons were separated by too large distance in the fully extended form of the chain structure to provide a NOESY correlation. The validities of the three possible conformers along the three different bonds (i.e., C2C3, C3C4, and C4C5) were evaluated sequentially based on the J-coupling values and the NOESY correlations. The results of these analyses suggested that there were three dominant conformers of GA, including conformer 1, which was H2H3:gauche, H3H4:anti, and H4H5:gauche; conformer 2, which was H2H3:gauche, H3H4:anti, and H4H5:anti; and conformer 3, which was H2H3:gauche, H3H4: gauche, and H4H5:anti. These results also suggested that all three of these conformers exist in equilibrium with each other. Lastly, the results of the current study suggested that the conformational structures of GA in solution were bent rather than being fully extended. Copyright

Full text of DOI:10.1002/mrc.4396

Research article
Received: 14 October 2015
Revised: 10 November 2015
Accepted: 11 November 2015
Published online in Wiley Online Library: 8 January 2016
(wileyonlinelibrary.com) DOI 10.1002/mrc.4396
Conformation analysis of D-glucaric acid in
deuterium oxide by NMR based on its JHH and
JCH coupling constants
Yukiko Enomoto-Rogers,a Hisaharu Masaki,b Tetsuya Ito,b Kazuo Furihatac
and Tadahisa Iwataa*
D-Glucaric acid (GA) is an aldaric acid and consists of an asymmetric acyclic sugar backbone with a carboxyl group positioned at
either end of its structure (i.e., the C1 and C6 positions). The purpose of this study was to conduct a conformation analysis of flex-
ible GA as a solution in deuterium oxide by NMR spectroscopy, based on J-resolved conformation analysis using proton–proton
3
(3JHH) and proton–carbon (2JCH and JCH) coupling constants, as well as nuclear overhauser effect spectroscopy (NOESY). The
2JCH and 3JCH coupling constants were measured using the J-resolved heteronuclear multiple bond correlation (HMBC) NMR tech-
nique. NOESY correlation experiments indicated that H2 and H5 were in close proximity, despite the fact that these protons were
separated by too large distance in the fully extended form of the chain structure to provide a NOESY correlation. The validities of
the three possible conformers along the three different bonds (i.e., C2–C3, C3–C4, and C4–C5) were evaluated sequentially based
on the J-coupling values and the NOESY correlations. The results of these analyses suggested that there were three dominant con-
formers of GA, including conformer 1, which was H2H3:gauche, H3H4:anti, and H4H5:gauche; conformer 2, which was H2H3:
gauche, H3H4:anti, and H4H5:anti; and conformer 3, which was H2H3:gauche, H3H4: gauche, and H4H5:anti. These results also
suggested that all three of these conformers exist in equilibrium with each other. Lastly, the results of the current study suggested
that the conformational structures of GA in solution were ‘bent’ rather than being fully extended. Copyright © 2016 John Wiley &
Sons, Ltd.
Keywords: glucaric acid; conformational analysis; carbon–proton coupling constant; NMR (J-resolved HMBC and NOESY)
to its cyclic lactone forms.[11] The results of a previous study by
Introduction
Denton et al.[12] revealed that the experimental JHH-coupling values
of GA in aqueous solution did not agree with the theoretical JHH
D-Glucaric acid (D-GA) is an aldaric acid based on an acyclic sugar
values calculated for the crystalline and lowest energy models of
backbone with a carboxyl group at either end of its structure
GA. The theoretical values for this comparison were calculated
(Fig. 1). GA occurs naturally in low concentrations in a variety of
based on the Karplus equation. Denton’s groups also suggested
different vegetables and fruits.[1] GA can be obtained by chemical
that the conformation of GA in solution was different from that of
synthesis as the corresponding monopotassium salt by the oxida-
the crystalline state, despite the fact that the conformation of GA
tion of D-glucose with nitric acid,[2] nitroxide derivatives,[3] or
in solution had not yet been determined. A unique method for
microorganisms.[4] GA has been reported to exhibit several inter-
studying the impact of solution effects on the conformational
esting biological properties, including cholesterol-lowering,[1a]
preference of acyclic compounds in solution by NMR spectroscopy
anticancer,[5] and metal chelating[6] activities. GA was recently listed
was suggested by Gerken and co-workers in 2008.[13] However, it
as one of the top 12 value-added building blocks that can be pro-
remains extremely difficult to determine the conformation or
duced from sugars via biological or chemical conversion processes
configuration of flexible and acyclic compounds in solution using
in a report published by the US Department of Energy.[7] Further-
only conventional JHH-coupling constants or NOESY correlation
more, the central theme of this list was chemicals that can be subse-
quently converted to bio-based chemicals or materials. Aldaric acids
such as GA have significant potential as building blocks for the con-
*
Correspondence to: Tadahisa Iwata, Science of Polymeric Materials, Department
of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, The
University of Tokyo. E-mail: atiwata@mail.ecc.u-tokyo.ac.jp
struction of polymers, including polyesters[8] and polyamides.[9]
D-Glucaric acid [(2R,3S,4S,5S)-tetrahydroxyhexanedioic acid] is a
flexible acyclic sugar with an asymmetric structure containing four
chiral centers. It would be useful to develop a detailed under-
standing of the stereo-chemical structure of GA in solution and
investigate the relationship between its structure and biological
properties, as well as its chelating effect. The conformation of
acyclic GA could have a significant impact on it reactivity for poly-
merization, as well as the structure of the resulting polymers, as
mentioned by Styron et al.[10] However, previous studies pertaining
to the conformational analysis of GA in solution have been limited
a Science of Polymeric Materials, Department of Biomaterial Sciences, Graduate
School of Agricultural Life Sciences, The University of Tokyo, 1-1-1 Yayoi,
Bunkyo-ku, Tokyo 113-8657, Japan
b Ensuiko Sugar Refining Co., Ltd, 1-1-1, Fukuura, Kanazawa-ku, Yokohama,
Kanagawa 236-0004, Japan
c
Department of Applied Biological Chemistry, Graduate School of Agricultural and
Life Sciences, The University of Tokyo, 1-1-1, Yayoi, Bunkyo-ku, Tokyo 113-8657,
Japan
Magn. Reson. Chem. 2016, 54, 561–567
Copyright © 2016 John Wiley & Sons, Ltd.

Y. Enomoto-Rogers et al.
D-glucaric acid
D-Glucaric acid monopotassium salt was converted to acyclic GA
using an ion exchange resin. D-Glucaric acid monopotassium salt
(50 mg) was dissolved in deuterium oxide (D2O) (1 ml), and the so-
lution was treated with an ion-exchange resin (Amberlyst H+). The
resulting slurry was stirred for about 5 min at room temperature
and turned clear. The solution was then loaded into an NMR sample
tube for NMR analysis.
Figure 1. Chemical structure of D-glucaric acid.
experiments, because acyclic compounds can exist as multiple con-
formers with flexible rotation.
It has recently been recognized that proton–proton and carbon–
proton J-coupling constants are dependent on their dihedral angles
and that J-coupling constants can be used to determine the confor-
Nuclear magnetic resonance measurements
Nuclear magnetic resonance spectra, including 1H, 13C, double-
quantum filtered correlation spectroscopy (DQF-COSY), hete-
ronuclear single-quantum coherence (HSQC), heteronuclear
multiple-bond correlation (HMBC), J-resolved HMBC1 and double-
pulsed-field-gradient-spin-echo nuclear overhauser effect spectros-
copy (DPFGSE-NOESY) (1D-selective NOESY), were recorded on a
500 MHz Varian INOVA500 NMR spectrometer (Varian, Palo Alto,
CA, USA) at 25 °C, using deuterium oxide as a solvent. Chemical
shifts (δ) and coupling constants (J) have been reported in parts
mation or configuration of acyclic compounds bearing chiral
2
centers.[14] J-coupling values (3JHH
,
3JCH, and JCH) are generally
categorized as small or large based on their magnitude in relation
to their dihedral angles, as illustrated in Fig. 2, and represent an
average of the possible conformers of a given structure.[14a] Despite
the difficulties associated with these complex measurements for
2,3
the accurate determination of small
J
CH
values, recent progress
in NMR techniques has allowed for the facile measurement of
2,3
J
CH
values using two-dimensional NMR spectroscopy, such as
per million and Hertz, respectively. The J-resolved HMBC1 was mea-
2,3
J-resolved heteronuclear multiple bond correlation (HMBC) and
heteronuclear long-range coupling (HETLOC) experiments.[14,15]
Several successful studies on J-based conformation or configura-
tion analysis have been reported.[16] However, this method has
not yet been applied to acyclic sugar compounds. It would there-
fore be valuable to use this technique to develop a deeper under-
standing of the conformations of acyclic sugars in solution from
the perspective of basic NMR analytical techniques.
sured to determine the
J -coupling constants with a scaling
CH
factor of 20. The J-coupling constants were calculated as follows:
3JHH = ΔδΗ × 500, 2,3JCH = ΔδΗ × 500, or (ΔδC × 125)/20.
J-based conformation analysis
The relationships between the dihedral angles and J-coupling con-
stants (3JHH, 3JCH, and 2JCH) are shown together with a rough catego-
rization in Fig. 2. These values were determined according to the
reported method of J-based configuration analysis[14a,d] with the
In this study, we have applied J-based conformation analysis
techniques to GA. In this way, we have evaluated the possible
conformations of GA in solution and proposed three dominant
3
following characterizations: JHH = small (2–3Hz) (gauche) or large
3
conformers based on the 3JHH, JCH and 2JCH values of GA, as well
3
(9 to 11 Hz) (anti); JCH = small (1 to 3 Hz) (gauche) or large (6 to
as its NOESY correlations.
2
8 Hz) (anti); and JCH =small (0 to –2 Hz) (anti) or large (–4 to
2
–5 Hz) (gauche). The JCH value was obtained as an absolute value
Experimental
2
in this study. The JCH value can be used to provide an indication
of the angle between the H and O atoms bound to a C atom.[14d]
Experimentally determined J-coupling values that were outside of
these ranges were categorized as ‘medium’ coupling values, and
the equilibrium state of the conformers was examined.
Materials
D-Glucaric acid monopotassium salt was kindly provided by the
Ensuiko Sugar Refining Co., Ltd (Yokohama, Japan).
Results and discussion
Nuclear magnetic resonance analyses of glucaric acid
The 1H and 13C chemical shifts of GA are listed in Table 1 together
with the J-coupling constants and categorizations of the different
atoms. The peaks in the 1H and 13C NMR spectra were assigned in
accordance with those reported in a previous study using isotopi-
3
cally labeled D-GA.[12] The C–H coupling constants (2JCH and JCH
)
were determined by J-resolved HMBC-NMR analysis, as shown in
Fig. 3. A representative cross-peak for the 2JH5C6 coupling is marked
with a dotted line in Fig. 3. As shown in Fig. 4, the strong NOE
correlations between H2–H3 and H4–H5 indicated that these pro-
tons were in a gauche orientation. Furthermore, the weak NOE cor-
relation observed between H3–H4 indicated that these protons
were in an anti orientation. Surprisingly, the NOE correlation be-
tween H2 and H5 was as strong as that between H2 and H3 (gauche
conformation), as shown in Fig. 4 and d, despite the distance
between these protons in the chain structure. This observation
Figure 2. Relationships between the dihedral angles and J-coupling
constants (3JHH, 3JCH. and 2JCH).
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Magn. Reson. Chem. 2016, 54, 561–567

Conformation analyses of D-glucaric acid in deuterium oxide by NMR
Table 1. 1H and 13C chemical shifts of D-glucaric acid
Chemical shift
1
2
4.42
d
3
4
3.93
t
5
4.31
d
6
4.10
dd
1H
3JH2H3
3.1
3JH3H4
5.7
3JH4C5
4.9
small
medium
medium
176.75
72.41
72.27
73.99
72.21
176.44
2
3
3
2
3
2
2
13C JH2C1 JH3C1 JH4C2 JH3C2
3JH5C3 JH5C3 JH4C3
3JH2C4 JH3C4 2JH5C4
3JH3C5 2JH4C5
3JH4C6
3.6
small medium medium
2JH5C6
4.2
5.0 <3
<3
n.d.
<3
<3
n.d.
<3
<3
3.8
<3
3.3
large small small small
small small small
small small medium
large
Figure 3. J-resolved HMBC-NMR spectrum of D-glucaric acid.
strongly suggested that H2 and H5 were in close proximity and that
the distance between these two protons was very similar to that of
the distance between H2 and H3, which were positioned vicinal to
each other.
Conformation along the C2–C3 bond
We initially examined the three possible staggered conformers of
the C2–C3 bond shown in Fig. 5A. The results revealed a JH2H3
3
value of 3.1 (small), which was indicative of a gauche orientation be-
tween H2 and H3, which was in agreement with the NOESY result.
3
3
We also obtained JH3C1 and JH2C4 values of less than 3 (small),
which were indicative of gauche orientations between H3 and C1,
and H2 and C4, respectively. The 2JH3C2 and 2JH2C3 values were both
less than 3 (small) and, therefore, indicative of anti orientations be-
tween H3 and O2, and H2 and O3, respectively. It is noteworthy that
the measured J-coupling values were in agreement with all of the
theoretical values for conformer 5a. With regard to conformers 5b
and 5c, we observed several differences between the theoretical
Conformation analysis of GA
The conformation of GA was investigated based on its J-coupling
constants. The NOESY data collected for this compound were ex-
amined with high priority to reduce the number of possible
conformations. The configurations of the four stereocenters were
fixed to C2(R), C3(S), C4(S), and C5(R), according to the original
stereochemical structure of D-GA.
Magn. Reson. Chem. 2016, 54, 561–567
Copyright © 2016 John Wiley & Sons, Ltd.
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Y. Enomoto-Rogers et al.
Figure 4. Nuclear overhauser effect spectroscopy NMR spectra of D-glucaric acid. Excited at (a) H2, (b) H3, (c) H4, and (d) H5.
and experimental J-coupling and NOE values. Based on these
results, conformer 5a was determined to be the dominant
conformer for the C2–C3 bond.
Based on these results, conformer 5d was considered to be
impossible.
We then proceeded to investigate conformer 5e, where H3–H4
existed in the anti conformation. Notably, this conformer also
allowed for H2 and H5 to be placed close enough to each other to
give a strong NOE, as shown in Fig. 6, whilst the H4–H5 conforma-
tions were gauche and anti. The H5 proton could rotate along the
C4–C5 axis within the same range; maintaining its close proximity
to H2. This conformation agreed well with the NOESY results. Taken
together, these results suggested that conformer 5e was possible.
Lastly, we investigated conformer 5f. None of the J-coupling or
NOE values for this conformer completely satisfied the measured
values. However, this conformer did allow for the H2 and H5 pro-
tons to be held in close proximity to each other, as shown in Fig. 6c,
although the H5 position had to be strongly restricted to maintain
its close proximity with H2. Conformer 5f was therefore considered
to be less possible than conformer 5e.
Conformation along the C3–C4 bond
The conformation of the C3–C4 bond was also investigated based
on the three possible conformers shown in Fig. 5B. However, the
measured J-coupling values did not completely satisfy any of these
three conformers. This result suggested that there was an equilib-
rium between the three different conformers and that the mea-
sured coupling constant therefore represents an average value for
the three possible conformers.[14a] The eclipsed conformation for
this bond was considered to be impossible.
For conformer 5d, H5 extended away from C5 in the opposite di-
rection to H2, which was in agreement with the molecular model.
The distance between H2–H5 was not small enough to allow for a
strong NOE correlation between these protons. Furthermore, the
weak NOE correlation observed experimentally between H3 and
H4 was inconsistent a gauche conformation for these two protons.
With regard to the 2JCH values, the measured values (small) were
contrary to the theoretical values (large) for conformers 5e and 5f.
However, there have been very few studies concerning acyclic
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Conformation analyses of D-glucaric acid in deuterium oxide by NMR
Figure 5. Conformation analysis of D-glucaric acid based on its NOESY and J-coupling constants. Bold (blue): reasonable, plain (red): unreasonable.
Magn. Reson. Chem. 2016, 54, 561–567
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Y. Enomoto-Rogers et al.
Figure 6. Dominant conformers of D-glucaric acid.
sugars or polyols, and it is therefore difficult to interpret these
results in a meaningful way. For example, it is not clear from previ-
ous results whether conformational analysis based on 2JCH can be
applied to GA or any other sugar, such as glucose, galactose, or
mannose.[16c] Furthermore, the effects of neighboring O atoms or
NOE effects on the J-coupling values of O–H moieties have not
been thoroughly investigated. For this reason, we did not investi-
gate the differences observed in the 2JCH values in this study any
further.
Having conducted a comprehensive evaluation of the J-value
and NOE results, it was concluded that conformer 5e was the dom-
inant conformer and that 5f was only present as a small component
of the mixture. Conformer 5f may have contributed to the medium
3JHH value of 5.7, but would not have made a significant enough
contribution to effect the 3JCH value.
J
HH-coupling constants for GA in solution represent the averaged
values of these three different conformers based on an equilibrium
between the three states. The conformational structures of GA in
solution were ‘bent’ rather than being fully extended. Similar con-
formational structures have been reported for GA following crystal
analysis and computer modeling studies.[10b,12]
All four of the hydroxyl groups extending away from the main
carbon chain in conformers 1, 2, and 3. Interestingly, conformer 1
had the same conformational structure as crystalline GA and the
lowest energy conformer determined by computer modeling.[12]
This result suggested that conformer 1 was also the most stable
structure in solution. However, in solution, the free rotation of the
C2–C3 or C4–C5 axis in conformer 1 would provide access to sev-
eral other conformations. However, the rotation around this bond
would be restricted because of electronic repulsion and steric hin-
drance, meaning that the GA would most likely adopt conformers
2 and 3. These results suggest that intermolecular electronic repul-
sion and steric hindrance effects between the hydroxyl and car-
boxyl groups could control the changes in the conformations of
GA. Although it has been reported that the nature of the solvent
can have a significant impact on the conformational preferences
of a molecule,[13] water molecules had no significant effect on the
conformation of GA in this study compared with these other
factors. The C4–C6 bond appeared to be more flexible than the
C1–C3 bond, most likely because the configuration of the OH group
at C5 was different from that of the OH group at C2, resulting in the
asymmetric conformation.
Conformation along the C4–C5 bond
Lastly, we investigated the conformation along the C4–C5 bond
based on the three possible conformers shown in Fig. 5C. The mea-
sured J-coupling values for the C4–C5 bond were 3JH5C3 < 3 (small),
3JH4C6 = 3.6 (medium), 3JH4H5 = 4.9 (medium), 2JH4C5 < 3.3 (medium),
2
and JH5C4 = 3.8 (medium), which suggested that there was an
equilibrium between the three possible conformers. The eclipses
conformations were all considered to be impossible.
We initially investigated conformer 5g. A molecular model of this
conformer suggested that it would not allow for the experimentally
observed NOE between H2 and H5 based on the distance between
these two protons in the model. This conformer was therefore
considered to be impossible. We subsequently evaluated con-
formers 5h and 5i. The molecular models of these two conformers
allowed for H2 and H5 to be placed close enough to other to ex-
hibit a strong NOE correlation. Taken together with the medium
J-coupling values observed along the C4–C5 bonds of 5h and 5i,
these results indicated that the medium J-values represented
the averaged theoretical values of the different conformers, with
5h and 5i existing as the dominant species.
The conformation of GA disclosed in this study could have a
significant impact on its biological activity, chelating ability, struc-
ture and reactivity toward polymerization, and the structure of
the resulting polymers.
Conclusion
We have conducted a conformational analysis of GA in D2O by
NOESY and J-resolved HMBC-NMR. We have evaluated the con-
formation of GA based on its JHH-coupling and
3
2,3
J -coupling
CH
constants, which were measured by 1H NMR and J-resolved
HMBC-NMR, respectively, as well as its NOESY correlations. We iden-
tified three dominant conformers of GA, including 1 (H2H3:gauche,
H3H4:anti, and H4H5:gauche), 2 (H2H3:gauche, H3H4:anti, and
H4H5:anti), and 3 (H2H3:gauche, H3H4: gauche, and H4H5:anti),
which existed in an equilibrium state. The results of this study also
suggested that GA exists in a ‘bent’ form in solution rather than its
fully extended form. The results of the J-based conformational
analysis method proved to be effective for determining the confor-
mation of GA and could be used to determine the conformations of
other acyclic sugars and their derivatives. The results of this study
could also be used as a platform to investigate the biological
Dominant conformers of glucaric acid
Following our analysis of the C2–C3, C3–C4, and C4–C5 bonds, we
proposed three dominant conformers, including 1 (H2H3:gauche,
H3H4:anti, H4H5:gauche), 2 (H2H3:gauche, H3H4:anti, H4H5:anti)
and 3 (H2H3:gauche, H3H4:gauche, H4H5:anti), which most likely
existed in equilibrium with each other, as shown in Fig. 6. The dom-
inant conformers 1 and 2 appeared to be preferred to conformer 3,
which was less dominant. The results of this study have successfully
shown that there are three dominant conformers of GA (i.e., 1, 2,
and 3) and that these are preferred over one statistical conforma-
tion. Furthermore, the results have shown that the measured
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Conformation analyses of D-glucaric acid in deuterium oxide by NMR
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This study was supported by a Grant-in-Aid for Scientific Research
(A) (No.22245026 and 26248044) (to T.I.) from the Japan Society
for the Promotion of Science (JSPS).
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