Materials
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Bulk and transparent supramolecular glass from
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evaporation-induced noncovalent polymerization
Cite this: Mater. Horiz., 2023,
10, 5152 of nucleosides†
Received 3rd August 2023,
Accepted 4th September 2023 Shuanggen Wu,ab Changyong Cai,a Xunqiu Wang,b Qiao Zhang,a Zhijian Tan,
Fenfang Lid and Shengyi Dong *a
DOI: 10.1039/d3mh01220d
rsc.li/materials-horizons
Understanding the nature of glass is one of the most important
challenges in chemistry, physics, and materials science. In this
study, transparent bulk supramolecular glasses with excellent opti-
cal behaviors and good mechanical properties were fabricated via
the non-covalent polymerization of nucleosides. Hydrogen bond-
ing is the main driving force in the formation of bulk supramole-
cular glasses. The directional and saturated character of hydrogen
bonding enables the formation of a short-range ordered structure,
while the weak nature and reversibility of hydrogen bonds allow for
the asymmetric and random connections of the short-range
ordered structure into a long-range disordered network. Various
relaxations, including b, c, and d relaxations, are observed at
temperatures below the glass transition temperature, demonstrat-
ing the metastable nature of bulk supramolecular glasses. This
investigation offers supramolecular insights into the nature of glass
materials.
Introduction
Similar to artificial polymeric materials, glass is commonly
used in daily life and industrial production.1,2 However, glass
has a longer history, and man-made glass was first fabricated in
approximately 1500 BC in Eastern Mesopotamia and Egypt.3,4
In the past 3500 years, numerous developments have been
made in glass, which is still in great demand nowadays.5–9
Glass is recognized to be a typical isotropic material that exists
a
College of Chemistry and Chemical Engineering, Hunan University, Changsha
410082, Hunan, P. R. China. E-mail: dongsy@hnu.edu.cn
b
School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001,
P. R. China
c
Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences, Changsha
410205, Hunan, P. R. China. E-mail: tanzhijian@caas.cn
d
College of Chemistry and Chemical Engineering, Central South University,
Changsha 410083, Hunan, P. R. China
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
10.1039/d3mh01220d
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*c
New concepts
Despite the long history and wide applications of glass, the mechanism of
its formation is still controversial. Understanding the structure of glass is
one of the most critical questions in materials science, chemistry, and
physics. In this research, low-molecular-weight bulk supramolecular
glasses were prepared through the non-covalent polymerization of
nucleosides. Supramolecular glasses exhibit excellent optical and
mechanical properties comparable to those of some synthetic glasses.
In the formation of a supramolecular glass, hydrogen bonding is the
main driving force. The directional and saturated character of hydrogen
bonds results in the formation of short-range ordered structures during
supramolecular polymerization, while the weak and reversible nature of
hydrogen bonding enables asymmetric and random connection of short-
range ordered structures to a long-range disordered network. This study
highlights the importance of solvent evaporation and a rapid cooling
process in determining the amorphous and thermodynamically
metastable characteristics of supramolecular glasses. The development
of BSGs provides a supramolecular view on the nature of glass.
in a metastable state.10–12 Despite the long history and wide
applications of glass, the mechanism of its formation is still
controversial.13–15 Understanding the structure of glass is one
of the most critical questions in materials science, chemistry,
and physics.16–18
DNA behaves as an anisotropic polymorphic polymer, particu-
larly with regards its three-dimensional spatial configuration.19–21
But basically, a long DNA rod can be defined as an isotropic
homogeneous chain from the view of its average mechanical and
physicochemical properties.22–25 Inspired by the molecular struc-
ture of DNA (and RNA, in some examples), nucleosides have been
used to construct artificial isotropic assemblies at micro- and
mesoscopic scales.26–28
In this study, transparent bulk supramolecular glasses
(BSGs) were prepared via the non-covalent polymerization of
nucleosides. Isotropic, long-range disordered, and short-range
ordered structures, along with their metastable states and relaxa-
tions, were identified in BSGs. To study the formation mecha-
nism and microstructure of BSGs, a combined experimental and
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theoretical investigation was conducted. This study provides a
supramolecular perspective on understanding the nature of glass.
Results and discussion
Preparation and optical properties of the BSGs
Two BSGs, uridine/20 -deoxyadenosine (UD) and thymidine/20 -
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deoxyadenosine (TD), were constructed according to the solution–
evaporation method.29 With the fabrication of UD as an example
(Fig. 1a), uridine (U, 0.01 mol) and 20 -deoxyadenosine (D, 0.01 mol)
were first dissolved in deionized water (10 mL). The aqueous
solution was heated in an oven at 100 1C, and then the crude
product was placed under vacuum at 25 1C to yield UD as a BSG.
UD and TD are transparent materials. As shown in Fig. 1a, a
colorful print covered by a piece of UD (0.5 cm thick) is easily
and clearly identifiable by the naked eye. Transmittance tests
confirm the good transparency of BSGs (Fig. 1b). UD and TD
exhibit the transmittance of 89.4% and 88.6%, respectively.30
No obvious changes in the transmittances of TD and UD were
observed when the measurements were carried out at low
humidity. Due to the good water solubility of nucleosides, BSGs
are not stable in water or highly humid environments.31–33
The optical properties of UD and TD were studied comprehen-
sively. The solid-state UV/Vis spectra of UD and TD show poor
Fig. 1 Preparation and properties of BSGs. (a) Preparation method of BSGs (UD). (b) Transmittance spectra of BSGs with the thickness of 2.0 mm.
(c) Solid-state UV/Vis spectra of BSGs. (d–f) Physical properties of BSGs. (g) AFM image of TD.
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absorptions in the visible region and strong absorptions in the
UV and IR regions (Fig. 1c), indicating the potential of BSGs as
anti-UV/IR glasses. These results are consistent with the macro-
scopic behavior of BSGs. In addition, the refractive indices of
UD and TD are 1.53 and 1.51, respectively (Fig. 1d). These
observations manifest that BSGs display excellent optical prop-
erties, which are comparable with those of modern inorganic
glasses.30
In addition to the optical properties, density and contact
angle are important glass parameters. UD and TD have densi-
ties of 1.47 and 1.41 g cm3, respectively, which are only 56–
59% of that of man-made glass (2.5 g cm3), showing the
potential of BSGs as light-weight optical materials (Fig. 1e).30
The contact angles of UD and TD with water are 35.5 and 32.61,
respectively, demonstrating their hydrophilic nature (Fig. 1f
and Fig. S1, ESI†). A detailed comparison of BSGs and inorganic
glass is presented in Fig. 1d–f.
Morphologies and mechanical properties of BSGs
Next, attention was focused on the surface morphology and
mechanical behavior of BSGs. No fractures or cracks are
observed in BSGs either with the naked eye or via an optical
microscope (Fig. 1a and Fig. S2, ESI†). The results of scanning
electron microscopy (SEM) and atomic force microscopy (AFM)
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reveal smooth microscopic surfaces of UD and TD (Fig. 1g and
Fig. S3, S4, ESI†). For example, the roughness of TD is approxi-
mately 1.3 nm, which is lower than that of common optical
glass (6.0 nm).
UD and TD exhibit good mechanical properties under
ambient conditions. Macroscopic weight loading tests demon-
strate the good mechanical strengths of BSGs. No deformations
or ruptures are observed, when a piece of UD is hung or covered
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temperature-resistance (Fig. 2f, g and Fig. S6, ESI†). Moreover,
the long-term structural stabilities of the BSGs were further
confirmed by time-dependent 1H NMR spectra. No obvious
changes in 1H NMR spectra of the BSGs were observed after
30 days (Fig. S7 and S8, ESI†), demonstrating that no covalent
interactions occurred in the BSGs. Meanwhile, the BSGs exhibit
good optical and mechanical stabilities in low-polarity solvents
(toluene, dichloromethane, and chloroform) (Fig. S9, S10 and

by a weight of 500 g (Fig. 2a). During the nanoindentation tests,
elastic moduli of 4.50  0.49 and 5.87  0.47 GPa are observed
for UD and TD, respectively, which are comparable with those
of some artificial tough materials (Fig. 2c and Table S1,
ESI†).34–37 Storage moduli of BSGs over 107 Pa are obtained
from the dynamic thermomechanical analysis tests (Fig. 2d and
Fig. S5, ESI†). Furthermore, UD and TD display good tensile
and compressive strengths. As shown in Fig. 2e, UD and TD
show tensile strengths of 1.24 and 1.27 MPa, respectively. The
tensile elastic moduli and compressive elastic moduli of TD are
4.94  0.32 and 58.7  3.11 MPa, respectively. The above
information indicates that UD and TD belong to stiff materials
(Table S2, ESI†). Time- and temperature-dependent tensile tests
demonstrate that UD and TD have long-term stability and low-
Tables S3, S4, ESI†). What is more, the compressive strengths of
UD and TD are 3.3 and 2.6 MPa, respectively, indicating their
good hardness (Fig. 2h). The Shore hardnesses of UD and TD
are 36 and 32 HD, respectively, which are lower than that of
polymethyl methacrylate (PMMA, 49 HD). Although UD and TD
are tough under ambient conditions, at high temperatures,
they behave as soft materials, which can be easily processed.
UD and TD of various sizes (410  10  1 or o0.1  0.1 
0.05 cm3) and shapes (cylindrical, square, and circular) can be
fabricated using the hot-forming method. Meanwhile, long and
flexible glass fibers with a diameter of 10 mm are successfully
cast from the molten BSGs, as shown in Fig. 2b. Temperature-
dependent rheological tests clearly confirm the effect of heating
on the processing of BSGs (Fig. S12, ESI†).

Fig. 2 Mechanical properties of BSGs. (a) Macroscopic stretching behavior of UD. (b) Glass fibers of UD. (c) Nanoindentation load–displacement curve
of BSGs. (d) Temperature-dependent storage modulus, loss modulus, and tan d of UD. (e) Tensile strength–displacement curve of BSGs. (f) Time-
dependent tensile stress of BSGs. (g) Temperature-dependent tensile stress of BSGs. (h) Compressive strength–strain curve of BSGs.

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Driving force of BSGs
The driving force is one of the most important intrinsic features
of supramolecular polymerization, and is closely related to the
glass-like nature of the BSGs.34,38 There is no new covalent
bond formation in the BSGs, because neither new peaks nor
obvious chemical shifts are observed in their solution-state
1
H NMR spectra (Fig. 3a and Fig. S13–S16, ESI†). This observation
indicates that the driving force of BSGs may be attributed to non-
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covalent interactions.39 Broad and intense bands (at approxi-
mately 2950 and 3104 cm1) and obvious band shifts (i.e. from
1656 to 1674 cm1, for the amide group in U) are observed in
Raman spectrum of UD, suggesting the formation of intermole-
cular hydrogen bonds therein (Fig. 3b and Fig. S17, ESI†).
Similar observations are made in the Fourier transform
infrared (FT-IR) spectra of the BSGs (Fig. S18, ESI†). Two-
dimensional infrared correction spectroscopy was used to
investigate the subtle hydrogen bonds and temperature-
dependent molecular movements in the BSGs (Fig. 3c and
Fig. S19, S20, ESI†).36,40 With UD as an example, according to
Noda’s rule, the order of the signal intensity change was
determined to be 1641 4 1679 4 1652 cm1, manifesting that
the free amide group is more sensitive to elevated temperature
than the hydrogen-bonded amide group. The hydrogen bonded
structures in the BSGs were further confirmed via density
functional theory simulations (Fig. 3d and Fig. S21, S22,
Table S7, ESI†).
Fig. 3 Driving force of BSGs. (a) Solution-state 1H NMR spectra (400 MHz, D2O, room temperature) of UD, D, and U. (b) Raman spectra of UD, D, and U.
(c) Synchronous correlation spectra (left) and asynchronous correlation spectra (right) of UD from 20 to 100 1C. (d) The IGM isosurfaces for the
interaction between U and D (molar ratio 1 : 1). The color bar shows that blue, green, and red represent strong attraction interactions (hydrogen bonding),
van der Waals interactions, and strong nonbonded overlap, respectively.
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Glass nature of BSGs
The typical nature of glass that distinguishes it from other
natural or artificial materials is the inner structural character-
istics: long-range disorder, short-range order, thermodynamic
metastability, and isotropic structure.15 Thus, the investigation
was shifted to study the formation mechanism and intrinsic
nature of the BSGs. The powder X-ray diffraction data of the UD
and TD samples demonstrate that the BSGs are amorphous
(Fig. S23, ESI†). No diffraction peaks are observed in the small-
angle X-ray scattering (SAXS) spectra, indicating the lack of
an ordered periodic structure in the BSGs at the mesoscopic
scale (Fig. 4a). X-ray photoelectron spectroscopic (XPS) results
further support the isotropic nature of the BSGs (Fig. 4b and
Fig. S24, S25, ESI†). Similar binding energies and intensities
were observed at different depths in the BSGs. Simulations
of Young’s moduli of the BSGs at different directions produce
similar results (Tables S8 and S9, ESI†). For example, UD exhibits
Young’s moduli of 7.68 (X), 7.84 (Y), and 8.02 (Z) GPa, manifest-
ing its isotropic state. In addition, the refractive-index values
obtained at random positions in the BSGs are the same. UD and
TD show glass transition temperatures (Tg) of 56 and 62 1C,
respectively, which are considerably lower than that of man-
made optical glass or metal glass (Fig. 4c and d).30 The low Tg
values may be ascribed to the high fractional free volume of
BSG (8–9%) (Fig. 4e–g and Tables S10, S11, ESI†). Meanwhile,
during reversible heating–cooling cycles, the BSGs exhibit glass
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Fig. 4 Glass nature of BSGs. (a) SAXS spectra of BSGs. (b) Wide-scan XPS spectra of UD after different etching times. (c) DSC spectra of UD. (d) DSC
spectra of TD. (e) Fraction of free volume of complex containing T + D + 3 wt% water at 298.0 K. (f) Fraction of free volume of complex containing U + D
+ 3 wt% water. (g) Configuration of molecular models of a complex containing T (fuchsia) + D (purple) + 3 wt% water at 298.0 K. (h) Radial distribution
function (RDF) of the U/D/water composite at room temperature. (i) Radial distribution function (RDF) of the T/D/water composite at room temperature.

transition behavior similar to that of synthetic optical glass or
metal glass, demonstrating the structural reversibility of the
BSGs. The low Tg values of UD and TD enable an investigation
of their glass nature under mild conditions.
Coexisting long-range disorder and short-range order char-
acterize the structure of glass.15 UD and TD have this feature, as
confirmed via radial distribution function (RDF) characteriza-
tion. No prominent peaks are observed in the RDF spectra of
the BSGs when the distance is more than 4 Å (Fig. 4h and i),
indicating the absence of ordered structures at the long-range
scale. In contrast, peaks assigned to intermolecular non-
covalent bonds are found at distances less than 4 Å, suggesting
the existence of short-range ordered structures in the BSGs.15
The simultaneous appearance of isotropic, long-range dis-
order, and short-range order is directly related to the chemical
structure and rapid annealing treatment of the BSGs. In DNA,
base pairs apply self-sorted molecular recognition patterns.20
However, in the fabrication of BSGs, UD or TD is first heated to
form a liquid with low viscosity and high mobility, as shown in
Fig. 5a. Subsequently, the liquid-type BSG is rapidly cooled to
yield a compact solid, during which versatile hydrogen bonds
are formed and the dynamical recognition motifs are frozen,
yielding the thermodynamically metastable BSGs. Rheological
experiments provide detailed information (Fig. 5b).29 With a
decrease in the testing temperature from 120 to 20 1C, the
viscosities of the BSGs decrease considerably. At 20, 100,
and 120 1C, UD shows viscosities of 2.10  108, 384.27, and
8.44 Pa s, respectively, demonstrating that the viscosity of UD at
20 1C is more than 107 times its viscosity at 120 1C. Such a
significant change in viscosity results in the formation of a
metastable BSG. In a control experiment, single crystals were
obtained when a UD aqueous solution was slowly evaporated
(Fig. S26, ESI†). This result indicates that in the low tempera-
ture range, the high viscosities of the BSGs hinder the crystal-
lization abilities of the nucleosides, thus maintaining their
metastable states.
Relaxations in the BSGs
Relaxations are intrinsic and universal in natural/artificial glass
and are crucial for its glass transition behavior, mechanical
properties, and stability.14 Herein, broadband dielectric
spectroscopy was applied to study the relaxation of the BSGs,
because dielectric spectroscopy has various advantages, includ-
ing high sensitivity and a wide temperature range.39 Three

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Fig. 5 Thermodynamically metastable state of the BSGs. (a) Volume change with transforming from solution to crystal or BSGs. (b) G 0 , G00 and |Z*| value
of UD in reversible temperature-dependent rheological tests. (c) Average relaxation time as a function of temperature for relaxation processes in the
BSGs. Solid lines represent Arrhenius fitting for b-, g-, and d-relaxation. (d) Activation energies (Ea) of the BSGs for b-, g-, and d-relaxation.
distinguishable relaxation processes (b, g, and d) occur at
temperatures below Tg. To quantitatively analyze these relaxa-
tions, the dielectric loss spectra were fitted using a combi-
nation of the Havriliak–Negami function and a conductivity
term. b and g relaxations are the slowest and fastest processes
in supramolecular polymerization (for TD at 23.0 1C, the
relaxation time required for the b and g processes are 5.03
and 2.35  105 s), respectively, indicating a greater mobility of
the functional groups on the glass surface than those in the
glass interior (Fig. 5c). Relaxations in the BSGs have a promi-
nent temperature dependence, with b relaxation occurring at
higher temperatures. The activation energies (Ea) of the b, g,
and d relaxations were calculated using the Arrhenius equation
and are equal to 4.59, 3.61, and 0.84 kJ mol1, respectively,
in TD (Fig. 5d). The Ea values of the relaxation of UD and TD
(o5.0 kcal mol1) are considerably lower than those of artificial
glass materials because of the absence of covalently linked
polymeric structures.36,40 These results demonstrate that the
segmental motion occurs easily even at temperatures below Tg,
because of the metastability of the BSGs.
Discussion
The definition of glass has never been established. In fact, it
continuously changes over time. Intuitively, glass is a transpar-
ent material with desirable optical properties. In addition to
traditional inorganic glass, a variety of new glass materials,
including metal–organic framework glass and metallic glass,
have been fabricated.7,41 It has been found that glass vitrifica-
tion is a highly complex thermodynamic process involving the
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formation of ordered and disordered structures.42 In the for-
mation of common inorganic glass, the importance of metal,
covalent, and ionic bonds outweighs that of hydrogen bonds
and van der Waals forces. Therefore, the coexistence of short-
range ordered and long-range disordered structures is directly
governed by the synergistic effect of metal, covalent, and
ionic bonds.
In the formation of a BSG, hydrogen bonding is the main
driving force. The directional and saturated character of hydro-
gen bonds results in the formation of short-range ordered
structures during supramolecular polymerization, while the
weak and reversible nature of hydrogen bonding enables
asymmetric and random connection of short-range ordered
structures to a long-range disordered network. Compared to
silicate or metallic glass, BSGs exhibit lower annealing and
glass transition temperatures; thus, their glassy nature can be
easily studied.34,43,44 The low-molecular-weight BSGs enable
more choices for characterization. For example, solution-state
1
H NMR spectroscopy can be used to study the driving forces in
BSGs.45
Conclusions
In conclusion, BSGs were fabricated via the non-covalent poly-
merization of low-molecular-weight nucleosides. BSGs exhibit
excellent optical and mechanical properties comparable to
those of some synthetic glasses. They display distinguished
features on various scales. Macroscopically, the structures of
BSGs are random, long-range disordered, and isotropic; how-
ever, BSGs exhibit short-range order and anisotropic molecular
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Materials Horizons
organization patterns in a limited and localized scale. Solvent
evaporation and rapid cooling during the preparation process
determine the amorphous and thermodynamically metastable
characteristics of BSGs. Various relaxations in BSGs are
assigned to the local molecular motions in isolated regions of
the structures. The development of BSGs from nucleosides
provides a supramolecular view of the nature of glass.
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Experiment section
Materials and methods
All materials and reagents were commercially obtained and
used without further purification. Contact angle measurements
were determined on an XG-CAM Contact Angle Meter. Optical
microscope images were obtained on a NIKON Ti-E optical
microscope. Atomic force microscopy (AFM) images were
obtained on a Bruker Dimension Icon AFM. Nanoindentation
measurements were performed on a Hysitron TI-950 Nano
Indenter. Dynamic thermomechanical analysis (DMA) was car-
ried out on a Q800 (TA instrument) using tension mode.
Rheology measurements were performed on an Anton Paar
MCR 92. The laminator model PP15 was chosen with a dia-
meter of 15 mm with the gap at 0.5 mm. Solution-state 1H NMR
spectra were collected on a Bruker-AV400 with TMS or residual
solvent as the internal standard. Raman spectra were recorded
on a Renishaw inVia Raman Spectrometer with an excited
wavelength of 514 nm. Fourier transform infrared (FT-IR)
spectra were collected on a Bruker Vertex 70 FTIR spectro-
photometer. Temperature-dependent FTIR spectra were
recorded on a SHIMADZU IRAffinity-1S from 20 to 100 1C at
1 1C min1. The data were processed by 2DCS software and
generated the generalized 2D correlation spectra. Powder X-ray
diffraction (PXRD) data were collected on a Bruker D8
ADVANCE. X-ray photoelectron spectroscopy (XPS) analysis
was performed on Thermo escalab 250Xi X-ray photoelectron
spectrometer. Transparency and solid UV/Vis spectra were
collected on a SHIMADZU UV-3600 spectrometer. Refractive
index was recorded on Digital Gem Refractometer. Density was
determined on an AccuPyc II 1340. Tensile and compressive
strength measurements were performed on a HY-0580 Electro-
nic tensile testing machine. Small angle X-ray scattering (SAXS)
spectra were recorded on an Anton Paar SAXS mc2 using Cu Ka
radiation (l = 0.154 nm). Differential scanning calorimeter
(DSC) measurements were carried out using a TAQ200 with a
heating rate of 10 1C min1 from 80 to 120 1C, and the cooling
rate was 10 1C min1 from 120 to 80 1C in a nitrogen
atmosphere. A Shore hardness test was performed by a Shore
hardness test instrument.
Broadband dielectric measurements and analyses
Broadband dielectric measurements were performed through a
Novocontrol Concept 80 system with Alpha impedance analyzer
and Quatro Novocontrol Cryo-system temperature control. Fre-
quency sweep mode was used with a frequency range of 101 to
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106 Hz at each temperature from 40 to 80 1C with a 3 1C
interval.33
The Havriliak and Negami (H–N) function is employed to
analyze the dielectric spectra. The complex dielectric permittiv-
ity (e*) data as a function of frequency can be described by the
following equation:
De
e ¼ e1 þ
½1 þ ðiotHN Þa b
where eN is the high-frequency limit of e 0 , De is the relaxation
strength, and tHN is the characteristic relaxation time. The a
and b parameters (0 o a, ab r 1) are defined as the symme-
trical and asymmetrical broadening of the loss peak.
The relationship between tmax and temperature can be
described by Arrhenius functions:
 
Ea
tmax ¼ t0 exp
RT
where Ea is the activation energy and t0 is a constant.
Density functional theory (DFT) calculation
To study the intermolecular interaction, 200 sets of configura-
tions were generated using a random method, and then these
configurations were optimized by using the PM6-DH+ method.
Finally, the optimal configuration was obtained through using
MOPAC 2016 software and used for DFT calculation.46
All calculations were performed by using the Gaussian16
software with the M06-2X functional. Crimme’s D3 dispersion
correction was used for improving the calculation accuracy. The
6-311g(d) basis set was used to optimize the geometry. The
nature of noncovalent interaction was investigated by using the
IGM (Independent Gradient Model) method through Multiwfn
software. The IGM diagram was rendered by VMD (Visual
Molecular Dynamics).29
The binding energy between compound A and compound B
was calculated by the following formula:
Ebinding = Etotal  (EpartA + EpartB)
Ebinding represents the binding energy between compound A
and compound B; Etotal represents the total energy of the
system containing compound A and compound B; EpartA repre-
sents the energy of compound A; EpartB represents the energy of
compound B.
Molecular dynamic (MS) calculation
To further explore the formation of BSGs, molecular dynamics
simulations at an atomic level were carried out in the commer-
cial platform Materials Studio (V.8.0, Accerlys, San Diego,
USA).47 Firstly, the molecular model was created by using an
amorphous cell construction module, and its configuration was
optimized by using the COMPASS force field to find the mini-
mum global energy configuration. An energy convergence
criterion of 105 kcal mol1 and force convergence criterion
of 104 kcal mol1 Å1 were used in this process. Secondly, the
molecular model was annealed for 5-cycles under constant
temperature and constant volume (NVT ensemble) from 200
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to 500 K for 150 ps to relax it in a wide range to obtain an energy
minimum of the resultant trajectories. Thirdly, the optimized
model was further treated under constant pressure (101 kPa)
and constant temperature (298 K) (NPT ensemble) with 1 ps
time step to obtain density and free volume. During this
process, a Nose thermostat and Berendsen barostat algorithm
were used in the pressure and temperature control.
Fraction of free volume (FFV) of BSGs
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FFV = Vf/Vsp = (Vsp  1.3Vw)/Vsp
where Vsp is the cell volume. Vw is the van der Waals volume
obtained from the van der Waals surface. Vf is free volume.
Preparation of BSGs
The detailed procedure is as follows: taking UD as an example,
0.01 mol of U and 0.01 mol of D were added into 10 mL of
deionized water. The aqueous solution was placed in an oven at
100 1C to yield a viscous material. Then the crude product was
dried under vacuum for 24 h at room temperature to obtain UD.
To yield uniform BSGs, hot-pressing is applied in the molding
process.
Author contributions
Conceptualization: Z. Tan, F. Li, and S. Dong. Methodology:
S. Wu, X. Wang, Z. Tan, and S. Dong. Investigation: S. Wu,
C. Cai, and Q. Zhang. Supervision: Z. Tan and S. Dong. Statistical
and other formal analysis: S. Wu, C. Cai, Q. Zhang, and S. Dong.
Writing—original draft: S. Wu, X. Wang, and C. Cai. Writing—
review & editing: X. Wang, Z. Tan, F. Li, and S. Dong.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors gratefully acknowledge the National Natural
Science Foundation of China (22271087 and 21704024), the
Outstanding Youth Scientist Foundation of Hunan Province
(2021JJ10010 and 2021JJ10014), the Huxiang Young Talent Pro-
gram from Hunan Province (2021RC3116 and 2018RS3036), the
Agricultural Science and Technology Innovation Program
(ASTIP-IBFC08), and the Earmarked fund for the China Agricul-
ture Research System (CARS-16-E24).
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