Insights into the existing form of glycolaldehyde in methanol solution: An experimental and theoretical investigation

Article abstract of DOI:10.1039/d1nj00252j

Glycolaldehyde (HOCH2CHO, GA), the simplest molecule containing both hydroxyl and aldehyde groups, is structurally the most elementary member of monosaccharide sugars, which may provide new clues for probing the origin of life on planets like the Earth. Uncovering the existing state of GA in solution systems is an important scientific issue. Generally, methanol is used as the main mobile phase in the liquid chromatography analysis of GA, but the state of GA existing in methanol solution remains unknown, thus making it difficult to analyse GA accurately. Herein, the state and dynamic equilibrium of GA in methanol solution were systematically studied by UV-visible spectroscopy, nuclear magnetic resonance (1H-NMR) spectroscopy, liquid chromatography mass spectrometry (LC-MS) and density functional theory (DFT) calculations. The results demonstrated that the equilibrium component of GA in methanol solution is different from that in aqueous solution and that glycolaldehyde hemiacetal (GAHA) is a dominant component (>90%). Laying the foundation for experimental analysis, the transformation of different components at equilibrium was studied using DFT. The results confirm that hydrogen bonding-induced proton transfer occurs between the components at equilibrium. This work provides an important reference for the analysis of sugars and related compounds in various biochemical reactions.

Full text of DOI:10.1039/d1nj00252j

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Insights into the existing form of glycolaldehyde
in methanol solution: an experimental and
theoretical investigation†
Cite this: New J. Chem., 2021,
45, 8149
Yuehui Li, Yantao Shi,
Ce Hao
Xuedan Song,
Zhengyan Zhao,
Naitian Zhang and
*
Glycolaldehyde (HOCH2CHO, GA), the simplest molecule containing both hydroxyl and aldehyde
groups, is structurally the most elementary member of monosaccharide sugars, which may provide new
clues for probing the origin of life on planets like the Earth. Uncovering the existing state of GA in
solution systems is an important scientific issue. Generally, methanol is used as the main mobile phase
in the liquid chromatography analysis of GA, but the state of GA existing in methanol solution remains
unknown, thus making it difficult to analyse GA accurately. Herein, the state and dynamic equilibrium of
GA in methanol solution were systematically studied by UV-visible spectroscopy, nuclear magnetic
resonance (1H-NMR) spectroscopy, liquid chromatography mass spectrometry (LC–MS) and density
functional theory (DFT) calculations. The results demonstrated that the equilibrium component of GA in
methanol solution is different from that in aqueous solution and that glycolaldehyde hemiacetal (GAHA)
is a dominant component (490%). Laying the foundation for experimental analysis, the transformation
of different components at equilibrium was studied using DFT. The results confirm that hydrogen
bonding-induced proton transfer occurs between the components at equilibrium. This work provides an
important reference for the analysis of sugars and related compounds in various biochemical reactions.
Received 15th January 2021,
Accepted 6th April 2021
DOI: 10.1039/d1nj00252j
rsc.li/njc
The GA molecule contains two functional groups, a hydroxyl
group and an aldehyde group. It has the dual properties of
Introduction
Glycolaldehyde (HOCH2CHO, GA), also known as hydroxyacetalde- alcohol and aldehyde. Therefore, GA is chemically active and
hyde, is regarded as the smallest sugar molecule and the first exhibits different forms in gas, solid and solution states.
monosaccharide molecule found in interstellar space.1–4 It may be Particularly in solution, there is a complex dynamic equilibrium
closely related to the origin of life, making it an important research between different forms of GA.18 In recent years, the forms of GA
topic in biochemistry and geochemistry.5,6 In particular, GA and in different states have been extensively investigated, as demon-
HCHO, small carbohydrate molecules, play an important role in strated in previous studies, by using a large number of experi-
the formation of complex biomolecules. For example, HCHO and ments and theories.19–23 For example, it has been reported that
GA are important building blocks in the construction of DNA gaseous GA exists in the form of monomer, connected by
nucleosides and DNA precursors.7–11 In terms of atmospheric intermolecular hydrogen bonds, a stable configuration in the
chemistry, GA is a volatile oxygen-containing organic compound gaseous state. In the solid state, GA exists in the form of a dimer,
and is considered to be involved in the formation of secondary and the most stable configuration of the dimer has been
aerosols.12 In addition, GA is a direct product of biomass revealed to have a P21/C crystal structure.24 Nevertheless, due
combustion (or an intermediate product in the oxidation pro- to the strong solvation effect, GA in solution exists in more
cess of organic compounds)13 and regarded as a precursor of complex forms in dynamic equilibrium (usually in the form of
photochemical smog, which in turn affects climate change and isomeric monomers and dimers) when compared to gaseous or
human health.14–17 Thus, revealing the state of GA existing in solid state.25–29 The form of GA that exists in aqueous solution
different environments (gaseous, solid, and solution) is an has been extensively studied. Schnell et al. revealed a stable
important scientific issue.
network structure composed of GA and water molecules by
rotational spectroscopy and hydrogen bonding analysis.30 Using
experimental and theoretical methods, Kua et al. studied the
equilibrium composition and corresponding mechanism of GA
State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of
Technology, Dalian 116024, People’s Republic of China. E-mail: haoce@dlut.edu.cn
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d1nj00252j in aqueous solution, indicating that there are seven dimers and
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two monomers at the equilibrium state of GA in aqueous solution.27 of reactants, transition states and products is calculated at the level
It is well known that methanol is usually used as the mobile phase of the B3LYP-D3 (Grimme DFT-D3 corrected B3LYP) functional33,34
in the liquid chromatography analysis of GA. However, up to now, and 6-311G(d,p) basis sets.35,36 NMR calculations were performed
the existing form and equilibrium state of GA in methanol solution using the gauge invariant atomic orbital (GIAO) approach. We also
still remain unknown, which makes the accurate analysis of GA calculated the intrinsic reaction coordinates (IRCs) at the B3LYP/
difficult. Therefore, it is of great significance to study the form and 6-311G(d,p) level, from which we obtained the intermediates and
dynamic equilibrium of GA in methanol solution.
products.37 Moreover, considering the reaction of GA with metha-
Herein, the state and dynamic equilibrium of GA existing in nol solution, all calculation processes are carried out in CH3OH
methanol solution were studied by UV-visible spectroscopy, nuclear solvent, and the solvent model is SMD model; the calculated
magnetic resonance (1H-NMR) spectroscopy, liquid chromatography temperature is 298 K.30 Furthermore, noncovalent interactions
mass spectrometry (LC–MS) and density functional theory (DFT) (NCIs) were analysed using the Multiwfn software package.38
calculation. The results suggest that the existing form of GA in
methanol solution is obviously different from that in aqueous
solution. In methanol solution, the main existing form is glycolal-
dehyde hemiacetal (GAHA), accounting for more than 90%. DFT
Results and discussion
According to previously reported literature, the form of GA
existing in aqueous solution is complex; there are seven dimers
and two monomers at the equilibrium state of GA in aqueous
solution, and the main component is GA hydrate.27 Moreover,
dynamic equilibrium was also verified by the nuclear magnetic
resonance (NMR) spectra (Fig. S1, ESI†). We firstly put forward
some possible components of GA in methanol solution, as shown
in Fig. 1. Notably, a hemiacetal reaction can take place between
glycolaldehyde and methanol molecules at room temperature in
methanol solution, and the main component is conjectured to be
glycolaldehyde hemiacetal (GAHA).39 Based on the above analysis,
we could suppose that component 2 and monomer 5 react with
methanol molecules to form new components 7 and 6 in methanol
solution at room temperature (Fig. 1), which can be attributed
to the hemiacetal reaction between the aldehyde group and
hydroxyl group.
studies reveal that hydrogen bond-induced proton transfer plays an
important role in the transformation of different equilibrium
components. This study provides an important basis for the analysis
of sugars and related compounds in complex biochemical reactions.
Experimental
Materials and methods
Glycolaldehyde was purchased from Canada Toronto Research
Chemicals (TRC). Deuterium methanol (CD3OD) was purchased
from Ningbo Rotation Meditech Co., Ltd. Chromatographic
methanol was purchased from Tianjin Komeo Chemical Reagent
Co., Ltd and used without further purification. All laboratory water
was deionized water with a resistivity of 18 MO cmÀ1
.
Preparation of the standard solution of GA: A 0.5 M methanol
solution and an aqueous solution of the GA dimer were prepared,
kept stationary for 60 h, sealed and stored in a refrigerator (4 1C) to
avoid light.
For better comparisons, experimental and theoretical NMR
spectroscopy measurements were conducted to determine the
different components derived from GA in methanol solution.
The experimental NMR results shown in Fig. 2 demonstrate
Characterization studies
UV-visible spectral absorption data were measured using a
Cary-300 ultraviolet/visible spectrometer. The test range was
800–200 nm. The NMR spectral data were measured using an
Avance II 500 M NMR instrument, and the peak areas were
integrated using the MestreNova fitting software. ESI-MS experi-
ments and high-resolution mass spectrometry were carried out
using a LTQ linear ion trap mass spectrometer (Thermo, San
Jose, CA, USA). An electrospray ion source (ESI+) was used to
selectively monitor the molecular ion peaks of different sub-
stances. High performance liquid chromatographic (HPLC)
separation was performed using a stainless steel column (C18,
150 mmÂ4.6 mm, 5 mm); the mobile phase was pure methanol,
and the detector was an ultraviolet detector. The flow rate was
0.6 mL minÀ1. The sample injection volume was 20 mL, and the
column temperature was 35 1C.
Computational details
All calculations in this paper were carried out using the
Gaussian 16 program package.31 All calculations are based on the
density functional theory (DFT) method.32 Geometric optimization
Fig. 1 Some possible components of GA in methanol solution.
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Table 1 1H NMR data of the different components of GA in methanol
solution (experimental and calculated values), and the content of different
components
that many peaks have been well assigned by combination with
the compounds shown in Fig. 1, among which those with low
contents and close chemical shifts are hardly determined to
originate from monomers or dimers. To analyse the contents of
different components, the chemical shifts of the characteristic
functional groups can be used to identify specific components,
and the peak area has been integrated using the Mestrenova
fitting software. The peak corresponding to the chemical shift
of 4.79 is due to the small amount of water in deuterated
methanol. Obviously, it can be concluded that the content of
GA monomer in methanol solution is lower than that in
aqueous solution (Fig. S1, ESI†), which is attributed to the
stronger affinity of the methoxy groups and higher content of
GAHA formed in the reaction with the aldehyde groups. More-
over, the content of main component 6 was B90%, which is
consistent with that reported in previous literature.39
Components
NO.
Experimental
value (ppm)
Computed
value (ppm)
Components
(%)
1
2
3
4
5
6
7
4.0, 4.7
4.1, 9.6
3.9, 5.1, 5.5
4.1, 5.2, 5.5
4.2, 9.6
3.4, 4.5
5.1
3.5, 4.9
4.0, 9.9
3.6, 5.4, 5.6
3.9, 4.2, 5.6
4.4, 9.9
3.8, 4.7
5.6
B1.23
B0.07
B2.31
B4.95
B0.54
B90.87
B0.03
can further confirm the various components of GA in methanol
solution. As displayed in Table 1, the calculated chemical shifts
are relatively consistent with the experimental observations,
suggesting the rationality of our model for calculation (Fig. 3).
Liquid chromatography–mass spectrometry (LC–MS) was
used to further determine the different components of GA in
methanol solution. During the separation process, methanol
was used as the mobile phase, but the components could not be
well separated. The retention time of different components was
kept at approximately 2.3 min, as displayed in Fig. S5 (ESI†). The
molecular ion peaks of different components were recorded by
mass spectra as shown in Table S2 (ESI†).
The components of 1, 2, 3, and 4 are isomers that cannot be
distinguished by mass spectra owing to their same molecular
weight (143.0135). The m/z values for [5 + Na]+, [6 + Na]+ and
[7 + Na]+ are 83.0102, 115.0365 and 175.0578, respectively. Here,
the difference in molecular weight between components 5 and
6 or the difference in the molecular weight of components 2 and 7
is precisely the molecular weight of methanol (M = 32), indicating
that monomer 5 and dimer 2 contain aldehyde functional groups
and react with methanol to form components 6 and 7.
To further study the equilibrium of GA in methanol solution,
1
time-resolved H-NMR was employed to analyze the content of
different components in Fig. S3 (ESI†). The first data were
recorded within 5 min of mixing, and they were recorded once
in 2 h, as the reaction proceeded. After 60 h, samples were near
equilibrium, and the final measurement was taken 65 h after
mixing. The results revealed that the equilibrium contents of
component 6 gradually increased and the concentration of
GA dimer 1 gradually decreased as the reaction proceeded.
After 60 h, the contents of components 1 and 6 changed slightly,
suggesting the system achieved a dynamic equilibrium. More-
over, several concentrations of GA dimer (0.05 M, 0.1 M, 0.25 M,
and 0.5 M) in methanol solution were measured by 1H-NMR
spectra as shown Fig. S4 and Table S1 (ESI†). The NMR data
revealed that, with the increase in the concentration of the GA
dimer, the equilibrium concentration of component 6 increased
after reaching the dynamic equilibrium at about 60 h, while the
concentration of GA dimer 1 decreased significantly. The results
implied that the reactions proceed in the direction of GA
hemiacetal 6, when the concentration of reactant GA dimer
increases. Combined with the experimental results, we also
theoretically predicted 1H NMR spectrum through calculation
based on the DFT study, as shown in Table 1, using which we
From the above data, the composition and proportion of GA
in methanol solution were obtained. We could conclude that
the ring opening reaction of the GA dimer took place under the
solvent effect; components 1, 2, 3, 4, and 5 are the same as the
components in aqueous solution. However, components 6 and
7 are different. The main reason for this is that monomer 5 and
Fig. 2 1H-NMR spectra of GA in CD3OD solution. Monomer peaks (5, 6),
acyclic dimers and cyclic dimers (1, 2, 3, 4 and 7). The complete 1H-NMR
spectra are also provided in Fig. S2, ESI.†
Fig. 3 Mass spectra of different components of GA in methanol solution.
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Fig. 4 The existence state and dynamic equilibrium diagram of GA in
methanol solution at room temperature (298 K).
acyclic dimer 2 contain aldehyde functional groups and react
with methanol molecules to form GAHA 6 and acyclic dimer 7,
which is related to the hemiacetal reaction of methanol molecules.
To better comprehend the reaction process of the different
components in methanol solution, the reaction paths were
obtained, as shown in Fig. 4. At room temperature, the GA
dimer is dissolved in aqueous solution or methanol solution,
and the reaction is carried out in three steps, as discussed
above. (1) Due to the hydrogen bond effect of the methanol
solvent, the six-membered ring of the GA dimer first forms an
open ring structure, and the C–O single bond is broken to form
acyclic dimer 2, namely, the C4 compound containing a CHO
group. (2) After ring opening, component 2 continues to form GA
monomer 5 or cyclic dimers 3 and 4. (3) The GA monomer reacts
with methanol molecules to form GAHA in methanol solution.
To better explore the possibility of the conversion between
different components at room temperature, DFT calculation
was used to explain the reaction mechanism from the kinetic
point of view. Considering the effect of methanol solvation, we
considered two molecules,40 and the activation energy barriers
Fig. 5 Intrinsic reaction coordinate (IRC) path map of the reaction of GA
in methanol solution from 1 to 2, 2 to 3, 2 to 4, 2 to 5, 2 to 7, 7 to 5, and 5 to
6. The reaction was analysed using the weak interaction NCI of Multiwfn
software. Blue represents strong interactions, such as hydrogen bonds and
halogen bond, green represents van der Waals forces, and red represents
space resistance.
of different reactions were obtained. As shown in Fig. 5, initial results suggest that dimer 1 converts to 2 due to the ring opening
ring dimer 1 undergoes transformation to acyclic dimer 2, with reaction of the hydrogen bond of solvent, component 2 trans-
a barrier of 16.5 kcal molÀ1. Acyclic dimer 2 can undergo forms into 3, 4, 5, and 7 due to the solvent effect. It is obvious that
ring closure to form cyclic dimers 3 and 4, and the barriers the reaction between components 2 and 7 has a relatively low
are 14.3 kcal molÀ1 and 12.5 kcal molÀ1, respectively. Acyclic barrier of 6.1 kcal molÀ1, mainly from the reaction path of
dimer 2 can also be converted into monomer 5 with methanol components 2 to 7. Finally, acyclic dimer 7 converts to components
solvent, and the barrier is 15.5 kcal molÀ1. The hemiacetal 5 and 6, and GA monomer 5 transforms into 6 through the solvent
reaction of acyclic dimer 2 with methanol molecules leads to effect. This is consistent with the above mentioned suggesting
dimer 7, with a relatively low barrier of 6.1 kcal molÀ1. C–O that component 6 is the main equilibrium component in
fracture occurred in the conversion of the acyclic dimer 7 to methanol solution.
monomers 5 and 6 due to the effect of the methanol solvent, and
To elucidate the cause for difference in reactions, noncovalent
the barrier was 15.5 kcal molÀ1. Moreover, in the reaction of weak interaction hydrogen bonds were considered. Hydrogen
monomer GA with methanol, the barrier of the transformation of bonds are special intramolecular or intermolecular interactions
5 to 6 is 17.2 kcal molÀ1. The results confirmed that the activation that are the most common, basic, important and weak.41,42 For
energy of the conversion between different components is low example, they are an important part of carbohydrates, which
(o20 kcal molÀ1), indicating the conversion could occur between maintain their conformation through intramolecular or inter-
different components at room temperature. The calculation molecular hydrogen bond competition.39 Considering the effect
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the form of a CQO double bond, and the bond length was
1.22 Å. After the reaction, the double bond of O5–C6 was
saturated, and the bond length became 1.40 Å. The bond length
of C6–O1 changed from 2.98 Å to 1.44 Å, and the colour
between C6 and O1 changed from green to the colour of a
covalent bond. At the same time, the bond angle of H2–O3–H4
changed from 93.41 to 75.81, that of H4–O5–C6 changed from
118.81 to 107.51, that of O5–C6–O1 changed from 94.41 to
107.51, and that of C6–O1–H2 changed from 76.51 to 103.91.
Because of the hydrogen bond effect between the methanol
molecule and GA monomer, the bond length and the bond
angle changed obviously, and a new substance (GAHA) was
formed. Overall, glycolaldehyde hemiacetal is the main compo-
nent of GA in methanol solution at room temperature (298 K),
while in aqueous solution it is mainly glycolaldehyde hydrate.
Hydrogen bond induced proton transfer occurs between differ-
ent equilibrium components.
Fig. 6 The reaction path for
5 - 6 of GA in methanol solution,
(a) reactant and (b) product. The reaction was analysed by using the weak
interaction NCI of Multiwfn software. Blue represents strong interactions,
that is, hydrogen bonds, green represents van der Waals forces, and red
represents space resistance.
of the hydrogen bonds (HÁÁÁO–H) on different components, the
mechanism of hydrogen bond induced proton transfer was
studied, as shown in the ESI† Fig. S6–S11. Additionally, we used
Multiwfn software to analyse the noncovalent weak interaction
(NCI) of the different reactions, as illustrated in Fig. 5. Blue
represents strong interactions (hydrogen bonds and halogen
bonds), green represents weak interactions (van der Waals
forces), and red represents space resistance.43–46 At the same
time, the bond length and bond angle of reactants and products
have changed and are shown in the ESI† Tables S3–S8.
Considering the difference between the components of GA
in methanol and aqueous solutions, component 6 is the main
component in methanol solution. We focus on the chemical
reaction energy barriers of monomer 5 transforming into
component 6. As discussed above, the activation energy barrier
is 17.2 kcal molÀ1. As displayed in Fig. 6 and Table 2, the bond
length of H2–O3 changed from 1.82 Å to 0.97 Å, and the acting
force changed from blue to green, indicating that the acting
force changed from hydrogen bonds to covalent bonds. The
bond length of H4–O5 changed from 1.92 Å to 0.98 Å, and
the acting force changed from blue to green, indicating that the
acting force changed from hydrogen bonds to covalent bonds.
However, after the reaction occurred for 52 h, the bond length
of O1–H2 changed from 0.98 Å to 1.89 Å, and the colour of the
bond changed to blue, suggesting that the covalent bond
changed to a hydrogen bond. The bond length of O3–H4
changed from 0.97 Å to 1.93 Å, and the colour of the bond
changed to blue, indicating that the chemical bond broke and
formed a hydrogen bond. Before the reaction, O5–C6 existed in
Conclusions
In this paper, the state and dynamic equilibrium of GA existing
in methanol solution was studied by UV-visible spectroscopy,
1H-NMR spectroscopy, LC–MS and DFT calculations. The results
show that the equilibrium composition of GA in methanol solution
is different from that in aqueous solution. GA exists in the form
of five dimers and two monomers at equilibrium in methanol
solution, while previous reports suggest that GA exists as seven
dimers and two monomers in aqueous solution. The main differ-
ence is that GAHA is a dominant component in methanol solution
(490%); however, GA hydrate is the main component (470%) in
aqueous solution. At the same time, we used DFT calculations to
study hydrogen bond-induced proton transfer between different
equilibrium components. The combination of experiments and
theory provides the basis for the analysis of sugars and related
compounds in complex biochemical reactions.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Grant No. 21677029 and 21606040).
Table 2 The bond length and angle of the 5 - 6 reactant and product of
GA in methanol solution
Notes and references
Parameters
Reactant
Product
`
1 M. T. Beltran, C. Codella, S. Viti, R. Neri and R. Cesaroni,
Bond length (Å)
H2–O3
O3–H4
H4–O5
O5–C6
C6–O1
O1–H2
H2–O3–H4
H4–O5–C6
O5–C6–O1
C6–O1–H2
1.82
0.97
1.92
1.22
2.98
0.98
93.4
118.8
94.4
76.5
0.97
1.93
0.98
1.40
1.44
1.89
75.8
107.5
107.5
103.9
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