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Article
Natural ultralong hemicelluloses
phosphorescence
Baozhong Lü, Qian Gao, Pengyu
Li, ..., Gegu Chen, Meizhen Yin,
Feng Peng

fengpeng@bjfu.edu.cn

Highlights
Hemicelluloses can emit
excitation-dependent and time-
dependent phosphorescence

Xylan has achieved tons of

industrial production

Oxidized xylan can be processed

into phosphorescent foams and
films

Artificial phosphors collectively suffer from complicated synthesis and purification

in small-scale laboratories, as well as poor color tunability, processability, and
sustainability. Here, Lü et al. report natural hemicelluloses, especially linear chain
and highly crystalline xylan, that serve as long-lived, color-tunable, processable,
and sustainable phosphorescence materials.

Lü et al., Cell Reports Physical Science 3, 101015

September 21, 2022 ª 2022 The Author(s).
https://doi.org/10.1016/j.xcrp.2022.101015
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Article
Natural ultralong hemicelluloses phosphorescence
Baozhong Lü,1 Qian Gao,1 Pengyu Li,2 Jun Rao,1 Ziwen Lv,1 Meichao Shi,1 Yajie Hu,1 Xiang Hao,1
Gegu Chen,1 Meizhen Yin,2 and Feng Peng1,3,*

SUMMARY
Artificial materials exhibiting ultralong organic phosphorescence
(UOP), especially those with tunable multicolor afterglow, are hin-
dered by complicated synthesis and purification, poor processabil-
ity, and issues relating to sustainability. Here, we report natural
hemicelluloses that provide excitation- and time-dependent color-
tunable afterglow. In particular, linear xylan with high crystallinity
exhibits a long lifetime of 588.8 ms under ambient conditions, not
inferior to many artificial phosphors, and has achieved industrial
production. Mechanistic study shows that the tunable UOP can be
ascribed to various clusters of oxygen groups fixed within a rigid
polysaccharide environment. The distinguishable color evolution
and duration of afterglow are useful for anticounterfeiting and
data encryption with high security levels. Furthermore, body-
shaped foams with a lifetime up to approximately 700 ms and flex-
ible, transparent, and high-strength phosphorescence film can also
be fabricated using water-soluble oxidized xylan. These results
unambiguously state that hemicellulose-based UOP materials are
convincingly promising to replace and surpass artificial phosphors.

INTRODUCTION
Persistent luminescence is an optical phenomenon in which emission can be sus-
tained for a period of time after removing the excitation source.1,2 Due to the saving
of rare elements, flexible modification, and comparable outstanding performance,
in recent years ultralong organic phosphorescence (UOP) materials have attracted
widespread interest in applications such as optoelectronics,3 high-contrast biolog-
ical imaging,4,5 information security, and anticounterfeiting.6,7 As such, there is ex-
pected to be high demand for such materials in the future considering their diverse
applications. Approaches such as crystal engineering,8 host-guest assembling,9–11
and polymer packaging12–15 have been devoted to developing UOP materials by
effective stabilization of the excited triplet state and inhibition of nonradiative
decay.5,8–29 Despite much progress, artificial phosphors face issues related to
poor processability, difficulty in large-scale preparation, and lack of renewability
and sustainability; such challenges obstruct their practical application. Furthermore, 1Beijing Key Laboratory of Lignocellulosic
the color tunability of artificial phosphors remains a challenge. Thus, developing Chemistry, MOE Engineering Research Center of
Forestry Biomass Materials and Bioenergy,
alternative versatile UOP materials that may solve the aforementioned problems College of Materials Science and Technology,
would be highly beneficial. Beijing Forestry University, Beijing 100083, China
2StateKey Laboratory of Chemical Resource
Engineering, Beijing Laboratory of Biomedical
Natural products have been widely studied and used by virtue of their sustainability, Materials, Beijing University of Chemical
natural abundance, degradability, and biocompatibility. Some biological macromol- Technology, Beijing 100029, China
ecules, such as bovine serum albumin,30 sodium alginate,31 gelatin,32 and starch,33 3Lead contact
have been found to emit phosphorescence via the synergy of the rigid environment *Correspondence: fengpeng@bjfu.edu.cn
provided by hydrogen bonds and clustering of heteroatoms and/or unsaturated https://doi.org/10.1016/j.xcrp.2022.101015

Cell Reports Physical Science 3, 101015, September 21, 2022 ª 2022 The Author(s). 1
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
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subgroups. Excitation-dependent afterglow is ubiquitous in these nonconventional

phosphors owing to the formation of heterogeneously clustered emissive species.
This unique phenomenon is termed clustering-triggered emission (CTE).34 Nonethe-
less, at present the performances of natural phosphors are generally poor, featuring
short afterglow duration times and lifetimes, and most can only be detected by de-
tectors under ambient conditions.30–36 Consequently, the development of natural
UOP materials is still in the early stages, and the limited variety and performance of
UOP materials originating from nature hinders their development.

Lignocellulosic biomass consists of three main polymeric components: cellulose,

hemicelluloses, and lignin (Figure 1A).37 Microcrystalline cellulose has been reported
to emit phosphorescence with short lifetime of 20.4 ms;36 lignin could not emit phos-
phorescence itself until being confined in a rigid polymer network, losing the all-nat-
ural access.38 Hemicelluloses are defined as the second most abundant renewable
natural polysaccharides after cellulose, but are generally produced as by-products
of the pulp and paper-making industry.39,40 Four general classes of structurally
different hemicelluloses have been identified, i.e., xylan, mannan, b-glucan, and xy-
loglucan. Hemicelluloses extracted by dilute alkali solutions are usually diversiform
branched structures with relatively low molecular weights. In comparison, to obtain
high-quality dissolving pulp, hemicelluloses extracted using a concentrated alkali so-
lution feature linear chain structures with high crystallinity and high molecular weight,
similar to cellulose.41,42 Unfortunately, when compared with cellulose and lignin, the
photophysical properties of hemicelluloses have remained largely unexplored. It has
been noted that xylose emits better color-tunable and long-lived phosphorescence
than some other monosaccharides due to its unique molecular conformation and
stacking.43 As such, natural xylan with b-(1/4)-linked backbones of xylose, the
main type of hardwood and Gramineae hemicelluloses, can serve as more efficient
nonconventional phosphors attributed to crowded macromolecular architectures,
which favor the formation of tighter and larger clusters for restricting nonradiative
decay and boosting intersystem crossing (ISC) transitions.34,44

To elucidate this concept, we prepared several hemicelluloses and studied their

phosphorescence emission properties (Figures 1B and 1C). As expected, within
the abundant hydrogen bonds and rigid environment constructed by the polysac-
charide, linear xylan with high crystallinity reaches the highest phosphorescence
lifetime of 588.8 ms. Xylan with various oxygen clusters can also emit efficient phos-
phorescence with both excitation-dependent (color in response to excitation wave-
length) and time-dependent (color dynamically varying with time) afterglows, which
can be captured by the naked eye for several seconds in an ambient environment
(Figure 1D). These phenomena were also identified in other hemicelluloses with
different monosaccharide compositions and branched topo-structures. Moreover,
water-soluble dialdehyde xylan (DAX) was obtained by oxidation to manufacture
shaped foams and high-strength flexible and transparent films, which inherit and
even surpass the phosphorescence performance of pristine xylan owing to extra
clusters of carbonyl groups. These results will shed new light on nonconventional
natural phosphors and provide an ideal platform for the development of color-
tunable, processable, sustainable, and large-scale UOP materials.

RESULTS
Photophysical properties of xylan
Tons of water-insoluble and crystalline xylan extracted from dissolving pulp by cold
concentrated alkali solution were obtained from a viscose fiber mill (Figures 1C and

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Figure 1. Schematic illustration of ultralong phosphorescence hemicelluloses

(A) Description of the component of lignocellulosic biomass and corresponding phosphorescence performance.
(B) Structures and phosphorescence lifetimes of several hemicelluloses monitored at the peaks excited by 280 nm.
(C) Photograph of a sack of xylan.
(D) Photographs of the long-lived phosphorescence emission of xylan after turning off different UV excitations (254, 302, and 365 nm) under ambient
conditions.
See also Figures S1–S3 and Video S1.

S1); then, pure xylan was obtained by further washing and dialysis. The structure of
xylan was fully characterized using nuclear magnetic resonance to exclude the exis-
tence of acetyl groups, neutral sugars, and impurities (Figures S2 and S3).45,46 The
photophysical properties of xylan have been largely ignored; nevertheless, under
254/302/365 nm UV irradiation, we found that xylan powders could emit blue-white

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Figure 2. Photophysical properties of xylan powders

(A) Fluorescence-excitation mapping of xylan at room temperature.
(B) Prompt and delayed phosphorescence spectra of xylan excited at 360 nm; delayed time: 1 ms.
(C) Temperature-dependent phosphorescence spectra of xylan excited at 300 nm; delayed time: 1 ms.
(D) Phosphorescence-excitation mapping of xylan at room temperature with a delay time of 1 ms.
(E) Excitation-dependent delayed phosphorescence spectra of xylan at room temperature with a delay time of 1 ms.
(F) CIE coordinate diagram of xylan with different excitation wavelengths (interval of 40 nm); delayed time: 1 ms.
(G) Trajectory of the afterglow color in the CIE coordinate diagram of xylan with varying delayed times excited by 365 nm.
(H) Time-dependent mapping of xylan at room temperature excited by 365 nm.
(I) Delayed phosphorescence spectra of xylan with varying delayed times excited by 365 nm.
(J) Phosphorescence lifetimes of xylan monitored at the peaks excited by varying excitation wavelengths.
See also Figures S4–S13.

emissions (Figure 1D). To gain a deeper insight into these emission features, the
excitation effects of xylan were investigated using photoluminescence (PL) spectros-
copy (Figure 2). Fluorescence-excitation mapping (Figure 2A) shows that the best
excitation wavelength is approximately 360 nm, and the fluorescence lifetime and
quantum yield of xylan were determined to be 4.8 ns and 3.9%, respectively
(Figures S4 and S5). When the excitation wavelength varies from 240 to 440 nm
the fluorescence emission wavelength ranges from 430 to 502 nm, revealing an
obvious excitation-dependent fluorescence behavior (Figure S6). Xylan is free of
any p-conjugated building blocks, thus its heterogeneous emissive oxygen clusters,
which originate from the overlapping of lone-paired n-electron clouds, together with

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simultaneous conformation rigidification enhanced by abundant intra- and intermo-

lecular hydrogen bonds, should be responsible for the varying emissions.34

Notably, after switching off the excitation source, e.g., the 365 nm UV lamp, xylan
powders emitted obvious afterglow under ambient conditions (Figure 1D). This
afterglow could even be observed by the naked eye for more than 4 s (Video S1),
and the corresponding phosphorescence quantum yield could reach up to 1.3%
(Figure S7). Such a process can be clearly recognized by prompt (steady-state)
and delayed (time-resolved) emission spectra (Figure 2B). When the excitation wave-
length is fixed at 360 nm, the prompt PL spectrum shows an emission peak at
440 nm, which is due to the fluorescence emission on account of its nanosecond life-
time. The delayed spectrum (td = 1 ms) shows a yellow emission peak at 560 nm. The
large Stokes shift (over 120 nm in delayed emission) confirms that the afterglow is a
characteristic phosphorescence emission. In addition, phosphorescence is sensitive
to temperature; the phosphorescence lifetime and intensity both reveal a
decreasing trend upon increasing the temperature from 77 K to 298 K (Figures 2C
and S8), excluding thermally activated delayed fluorescence (TADF). To evaluate
the phosphorescence stability of xylan, its phosphorescence emission was directly
tested under ambient conditions (Figure S9). Impressively, compared with the phos-
phorescence intensity of the initial state, phosphorescence can be sustained and
remain almost unchanged after 6 h of exposure under ambient conditions. We
also tested the phosphorescence emission of xylan soaked in water or placed in
pure oxygen environment. The phosphorescence of xylan was almost quenched
when soaked in water because xylan is hydrophilic and can absorb plenty of water,
which quenches the triplet excitons. After heating, water could be removed from
xylan and the phosphorescence restored, and xylan phosphorescence remained
almost undisturbed in a pure oxygen environment, as confirmed by the comparable
afterglow time before and after oxygen treatment.

Color-tunable phosphorescence of xylan

After switching off the excitation source of 254/302/365 nm, xylan powders were
observed to emit different afterglow colors, ranging from green/dark green to
deep yellow under ambient conditions (Figure 1D). In phosphorescence-excitation
mapping (Figure 2D), the phosphorescence emission is dominated by the excitation
wavelength, further verifying excitation-dependent emission behavior. With excita-
tion wavelength varying from 240 to 420 nm, the delayed spectra (td = 1 ms) of xylan
show gradually bathochromic-shifted maxima ranging from 526 to 598 nm (Fig-
ure 2E). The Commission Internationale del’Eclairage (CIE) coordinate of the after-
glow variation is shown in Figure 2F, where the marked colors are consistent with
naked-eye observations. Differing from traditional UOP molecules, whose phospho-
rescence originates from typical chromophores, the phosphorescence of xylan is
derived from generally statistically distributed emission species offered by clusters
of different scales, as presented in its extensive emission mapping and broad emis-
sion peaks (full width at half maxima [FWHM] at a fixed lex is greater than 140 nm)
without obvious shoulders (Figures 2B, 2C, and 2E).43 The excitation-dependent
phosphorescence of xylan became more obvious when cooled to 77 K, extending
to the blue area. As revealed by excitation-phosphorescence mapping spectra
and the CIE coordinates at 77 K (Figures S10–S12), this could be ascribed to the
further rigidification of the oxygen clusters and emission enhancement induced by
low temperatures.

Further identification of the emission color after ceasing varying excitation sources
revealed that afterglow colors could evolve with time (Figures 1D and 2G). For

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example, the afterglow changed from deep yellow (observed immediately after UV
off) to yellow (toff = 0.1 s), yellowish green (0.3 s), and then to green (toff = 0.5 s) after
removing the 365 nm UV irradiation. To gain a deeper insight into such an intriguing
time-dependent afterglow phenomenon, we mapped the transient PL decay image
(Figure 2H). With increasing time, the emission profiles show a hypochromatic shift
trend with a decreasing FWHM (Figure 2I). Further time-resolved measurements
demonstrate that the long lifetime values of xylan decrease with increasing excita-
tion wavelength (250 to 420 nm) and emission wavelength (526 to 598 nm), ranging
from 588.8 to 294.2 ms (Figure 2J and Table S1). Lifetimes of xylan with varying de-
layed times were also tested (Figure S13), whereby time-resolved measurements
demonstrated that the long lifetime values of xylan vary with delayed times. These
results again confirm the existence of various emissive clusters with different life-
times. Upon UV irradiation, multiple phosphorescence clusters are simultaneously
activated and generate fast-decaying bathochromic phosphorescence and slow-de-
caying hypochromatic phosphorescence, which merge first into a yellow afterglow
before evolving to a green afterglow, thus displaying time-dependent afterglow.
Similarly, afterglows of xylan after removing 302 and 254 nm UV irradiation also
show time-dependent features, but their color changes are relatively mild in the
green region (Figure 1D). This is because different scale clusters individually feature
optimal excitation wavelengths while larger clusters with redder emission are not
activated under shorter excitation wavelengths.25,47 Previous research has shown
that time-dependent afterglows originate from the same emission species with the
synergy of TADF and phosphorescence.48,49 In this case, it is highly significant
that the time-dependent afterglow of xylan was realized solely through pure n-elec-
tron phosphorescence clusters. Such time-dependent afterglows from non-
conventional UOP systems at room temperature without doping have rarely been
reported.50 Compared with previous studies in which tunable multicolor phospho-
rescence was achieved by tedious synthesis processes, natural xylan shows the
same effect with an even longer lifetime (Table S2).

Phosphorescence of other hemicelluloses

Based on the promising performance of xylan, five other hemicelluloses with
different monosaccharides and branches, namely arabinoxylan (AX), galactogluco-
mannan (GGM), glucomannan (GM), glucuronoxylan (GX), and arabinoglucuronoxy-
lan (AGX), were selected to develop potential hemicellulose UOP materials (Fig-
ure 1B and Table S1). It remains challenging to obtain conspicuous UOP under
ambient conditions; however, with the exception of short-lived AGX, the natural
hemicelluloses studied here show obvious phosphorescence emission (Figure S14).
Their levels of excitation-dependent and time-dependent afterglows differ
(Figures S15–S19) because distinguishing monosaccharides and branched struc-
tures lead to different aggregation conformations, stacking of clusters, and active
excited-state molecular motion in the solid state, resulting in distinct emission per-
formance. Xylan without any branches shows the highest degree of crystallinity (Fig-
ure S20), which is in favor of highly rigidified conformations and can significantly frus-
trate intramolecular motions toward the best performance.51 It should be noted that
the studied hemicelluloses showed distinct lifetimes and afterglow durations
compared with previous work in which a wide-ranging lifetime was achieved by a
multi-host/guest doping strategy.52 The adjustable lifetime can be determined by
simply modulating the structures of the hemicelluloses.

Mechanism insights of xylan phosphorescence

Structure-defined xylan was chosen to obtain a closer look at the emission mecha-
nism. Xylose, the constituent unit of xylan, emits more obvious tunable multicolor

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Figure 3. Mechanism study

(A) UV-visible absorption of xylose and xylan.
(B) Number of hydrogen bonds in optimized unit cell model calculated by molecular dynamics simulations. Inset shows an optimized unit cell model of
xylan.
(C) Independent gradient model scatterplots of xylan. Inset shows the independent gradient model of three xylan chains. Strong noncovalent
interactions such as hydrogen bonds (blue), weak noncovalent interactions such as van der Waals forces (green), and repulsive effects (red or orange).
(D) HOMO and LUMO electron densities of three xylan chains.
(E) XRD pattern of xylan with labeled crystal indices.
(F) Left: schematic illustration of oxygen clusters and hydrogen bonds in xylan. Right: proposed mechanism for ultralong and color-tunable
phosphorescence of xylan under ambient conditions.
See also Figures S20–S25.

phosphorescence than some other monosaccharides.43 However, we found that

xylose can emit only very weak phosphorescence with negligible afterglow under
ambient conditions (Figure S21), although the phosphorescence lifetime values of
xylose were measured to be 679.8/224.5/246.6 ms under excitation wavelengths
of 250/280/320 nm, respectively (Table S1). UV-visible absorption spectra of xylose
and xylan were carried out in order to comprehensively characterize this phenome-
non (Figure 3A). It has been found that both exhibit absorption peaks in the short
wavelength region of 200–250 nm, which should be assigned to the absorption of
C–O and O–H. Apparent shoulder peaks beyond 250 nm could also be found,
and can be ascribed to the formation of clusters with complex electronic vibrations;
however, xylan and other hemicelluloses give more intense and bathochromic

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absorption peaks with a striking absorption tail extending to the visible region of ca.
600 nm (Figure S22), indicating the formation of larger and tighter clusters.47 In com-
parison, xylose exhibits insufficient absorption with weak absorbing ability of excita-
tion light, resulting in inferior phosphorescence performance. Thus, when excited by
lower-energy UV excitation (such as 365 nm), the afterglow emission of xylose van-
ished (Figures S21 and S23). Although time-dependent afterglow changes of xylose
can also be detected in delayed emission spectra (Figure S24), the afterglow varia-
tion was ignored and difficult to capture due to the insufficient formation of clusters
and faint afterglow emission. In sharp contrast, amplified afterglow emission and co-
lor tunability was achieved for xylan in its macromolecular state, due to enhanced
clustering.

Theoretical calculations were conducted to further elucidate the CTE of xylan. Mo-
lecular dynamics (MD) simulations show that there are plentiful hydrogen bonds in
xylan (Figure 3B).53 In the independent gradient model, strong and abundant inter-
molecular attractive and repulsive interactions with dense interaction isosurfaces
were discovered (Figure 3C), which can significantly suppress the nonradiative decay
of excitons. Effective intramolecular and intermolecular O$$$O electronic interac-
tions (distances shorter than the sum of the van der Waals radii) can be found in xylan
(Figure S25), leading to effective through-space conjugation of the lone pairs and
formation of oxygen clusters, as verified by theoretical calculations of the highest
occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital
(LUMO) electron densities of certain xylan chains (Figure 3D). Consequently, the
aggregated clusters in xylan from different chromophoric centers, which are syn-
chronously restricted by the rigid environment constructed by hydrogen bonds in
a crystalline polysaccharide matrix (Figure 3E), thereby restricting molecular mo-
tions, further promote spin-orbit coupling and subsequent ISC transitions (Fig-
ure 3F). Taken together, the chromophoric centers can be effectively stabilized to
generate phosphorescence emission through the suppression of nonradiative
decay. Based on the energy-tunable intermediate platform featured as different ef-
ficiency of ISC transitions and various energy gaps between the lowest singlet state
and the lowest triplet state of various clusters, phosphorescence colors and lifetimes
could be effectively manipulated over a wide range, resulting in both excitation-
dependent and time-dependent phosphorescence (Figure 3F).

Applications of hemicellulose phosphorescence

Color changes with time can lead to additional encryption modes, namely 4D cod-
ing, to improve security levels. Thus, time-dependent afterglows of xylan are useful
in anticounterfeiting and data encryption applications. The numbers are hidden
behind a blue matrix pattern of ‘‘8,’’ ‘‘8,’’ ‘‘8,’’ and ‘‘8’’ under 365 nm UV excitation;
once the excitation is switched off, a matrix pattern of numbers ‘‘1,’’ ‘‘9,’’ ‘‘5,’’ and ‘‘2’’
becomes visible, and their colors evolve from yellow to green with time (Figure 4A
and Video S2). In the dual-coded setup, codes ‘‘1 in yellow’’ at 0.0 s, ‘‘9 in yellow’’
at 0.1 s, ‘‘5 in yellowish green’’ at 0.3 s, and ‘‘2 in green’’ at 0.5 s arise, i.e., the correct
information is concealed until reading out all four pattern-, time-, and color-depen-
dent codes. Taking advantage of the distinguishable afterglow duration time of
various hemicelluloses, large amounts of digital information can also be stored in
a time carrier (Figure 4B and Video S3). The number ‘‘78’’ can evolve into ‘‘70,’’
‘‘7,’’ and ‘‘1’’ within 2 s. Previously, UOP materials with poor processability and me-
chanical properties have critically hampered practical applications. Here, we also
demonstrated the eco-friendly aqueous processability of oxidized dialdehyde xylan
(denoted as DAX t, with t representing the oxidation time in hours) (Figures 4C and
S26–S29). Aldehyde contents could be adjusted by controlling the reaction time,

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Figure 4. Applications of hemicellulose UOP materials

(A) Dual-coded anticounterfeiting setup for data encryption using time-dependent afterglow color changes of xylan excited by 365 nm.
(B) UOP images of number made up of different hemicelluloses along with duration time after turning off the UV 365 nm excitation.
(C) Structure transformation of xylan into water-soluble DAX by oxidation treatment with sodium periodate.
(D) Photograph of lightweight DAX foam on the pine needle.
(E) Photographs of DAX foams upon turning different UV lamps on and off under ambient conditions.
(F) Transmission of a pure DAX film. Upper photographs are DAX film before and after turning off the 365 nm UV excitation with an interval of 0.5 s. Inset
shows photograph of transparent film.
(G) Photograph of DAX film, which can lift a 100 g weight (left) and can be tied into a knot (right).
(H) Tensile strength of DAX films with different oxidation reaction times. Error bars denote mean G SD (two-tailed Student’s t test).
See also Figures S26–S37 and Videos S2, S3, S4, S5, and S6.

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and the highest aldehyde content and longest phosphorescence lifetime were real-
ized in DAX 6 (Figure S30 and Table S3). Due to the extra clusters of unsaturated
carbonyl groups which would further provide n-p* transition and facilitate the gen-
eration of triplet excitons (Figures S31 and S32),34 DAX 6 exhibited an enhanced
phosphorescence lifetime of up to approximately 700 ms and a phosphorescence
quantum yield of up to 5.8% (Table S3 and Figure S33). Ultralong phosphorescence
foams with different bodies and a duration of afterglow even more than 5 s under
ambient conditions could be shaped (Figures 4D and S34). The time-dependent
afterglow was also preserved (Figure 4E; Videos S4 and S5). Additionally, flexible,
transparent, and high-strength UOP film can also be fabricated by water-casting
(Figures 4F and S35; Video S6). The film could be easily tied into a knot and be
made to lift 100 g of weight (Figure 4G), with tensile strength up to 70 MPa in
DAX 6 (Figure 4H), higher than in some other films (Figure S36), which should be
highly promising for flexible electronics and information storage applications. More-
over, a large-area phosphorescent DAX film can be obtained easily (Figure S37).
These results indicate that DAX provides color-tunable, processable, sustainable,
and large-scale UOP materials, showing advantages among various reported UOP
systems (Table S2). Furthermore, processable hemicellulose UOP materials are
composed of only a single component without doping, which can avoid many prob-
lems related to poly(vinyl alcohol) or other polymer-based phosphorescence com-
posite systems, such as migration, leaching, and poor stability.

DISCUSSION
In summary, we reported a series of natural hemicellulose UOP materials with
tunable afterglow, which can be used for anticounterfeiting and data encryption.
The phosphorescence lifetime of linear chain xylan with high crystallinity can reach
up to 588.8 ms under ambient conditions. Water-soluble DAX with a phosphores-
cence lifetime of up to approximately 700 ms was obtained successfully to manu-
facture shaped foams and large-area, flexible, transparent, and high-strength films,
demonstrating the possibility to produce processable emitting materials and de-
vices. More importantly, hemicelluloses are sustainable natural resources, tradi-
tionally considered by-products and limited to low value-added applications in
the pulp and paper-making industry. Thus, to broaden the high values of the hemi-
celluloses, we have herein described a new class of high-performance UOP mate-
rials from sustainable, abundant, and low-cost natural lignocellulosic biomass. We
consider this work to mark an important beginning for natural hemicellulose-based
UOP materials, and further works related to processing and modification are under
way.

EXPERIMENTAL PROCEDURES
Resource availability
Lead contact
Further information and requests for resources and reagents should be directed to
and will be fulfilled by the lead contact, Feng Peng (fengpeng@bjfu.edu.cn).

Materials availability
This study did not generate new unique materials.

Data and code availability

Data supporting the findings of this paper are available as supplemental informa-
tion, and any additional information required to reanalyze the data reported in
this paper is available from the lead contact upon request.

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General procedure for xylan preparation

Xylan was received from a viscose fiber mill. Dissolving pulp was firstly extracted by
cold concentrated alkali solution. The alkali-extracted solution was then neutralized,
filtrated by membrane, and dried by spraying to obtain the xylan. Pure xylan powder
was obtained by further dialysis for 7 days and freeze-drying.

Oxidation of xylan
Freeze-dried xylan powder (26.4 g) was dissolved in 400 mL of deionized water in a
round-bottom flask covered with aluminum foil under vigorous magnetic stirring for
0.5 h. Next, 400 mL of sodium periodate solution (75.28 g) was added dropwise to
the xylan mixture under magnetic stirring at 40 C for different reaction times, such as
2, 4, 6, 8, 10, and 12 h (product denoted as DAX t, with t representing reaction time
in hours), and the mixture was quenched by ethylene glycol (30 mL) under stirring for
20 min. The mixture solution was then dialyzed for 7 days to remove oligomers and
impurities, and the DAX powder was obtained by freeze-drying. The reaction time
was used to control the aldehyde content of xylan.

Determination of aldehyde content

The aldehyde content of dialdehyde xylan was determined according to the previous
method with a slight modification.54 DAX (0.2 g) was dissolved in deionized water
(15 mL) followed by adding aqueous hydroxylamine hydrochloride (15 mL), after which
the pH of the mixed solution was adjusted to 5 using aqueous NaOH (0.1 M). The mixture
was heated to 70 C for 2 h under stirring. Finally, the released hydrochloric acid was
titrated up to pH 5.0 by aqueous NaOH (0.1 M), and the consumption was recorded
as Vsample. Xylan of the same concentration was titrated with the same method, and
the consumption was recorded as Vcontrol. The aldehyde content was calculated by
the followed formula: aldehyde content (mmol/g) = CNaOHVsample Vcontrol)/0.2.

Preparation of xylan-based films

The aqueous suspension of DAX (2% w/v, 20 mL) was transferred into polytetra-
fluoroethylene molds and slowly dried at a constant temperature and humidity
(30 C, 50% relative humidity) for 7 days.

Calculation details
The initial structure of xylan linked by b-1,4 glycosidic bonds was built from carbo-
hydrate builder on the GLYCAM website (http://glycam.org) and was then per-
formed on the basis of B3LYP/6-31G(d) geometry optimizations using the Gaussian
16.55 All the all-atom MD simulations were based on a general AMBER force field
with the RESP charges and were carried out using the GROMACS 2019 software
package.56–58 A standard MD procedure of 1 ns was run to equilibrate the geometry
structure. Initial simulation systems were built, including 50 optimized six unit-con-
tained xylan chains in a cubic box with a length of 6.0 nm. The 50 ns MD procedures
were performed under NPT ensemble, using the V-rescale thermostat to control the
temperature at 298.15 K and the Berendsen barostat to control pressure at 1 bar.
Prior to the MD simulation, energy minimization was carried out according to a pro-
tocol of conjugate gradient, using termination gradients of 100 kJ/mol$nm. The
leap-frog Verlet integration algorithm with a time step of 1 fs was used for the MD
simulation.59 Systems were simulated with periodic boundary conditions in three di-
mensions. The LINCS algorithm was performed for constrained bond lengths of
hydrogen atoms.60 The long-range electrostatics interactions were computed by
particle mesh-Ewald module,61 whereas short-range van der Waals interactions cut-
off was kept at 0.9 nm. The hydrogen-bond interactions were analyzed from the tra-
jectory data by GROMACS tool suites in the MD model of coiled xylan chains.

Cell Reports Physical Science 3, 101015, September 21, 2022 11

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OPEN ACCESS
Article

The ground-state geometry of xylan was optimized using MOPAC software at PM6-
D3H4 level.62 Density functional theory (DFT) computations were carried out using
Gaussian 16 software, and singlet point energy calculations were performed with
the B3LYP functional and 6-31G(d) basis set. DFT-D3 dispersion correction with
BJ-damping was applied to improve the calculation accuracy.63 Independent
gradient model (IGM) analysis was used to study the weak interaction between xylan
chains based on the B3LYP/6-31G(d) optimized molecular structures.53 IGM analysis
was conducted with the Multiwfn program.64 The graphics analyzed by IGM were
obtained through VMD rendering.65

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.xcrp.
2022.101015.

ACKNOWLEDGMENTS
This work was supported by the National Key Research and Development Project of
China (2019YFB1503803), National Science Fund for Distinguished Young Scholars
(32225034), National Natural Science Foundation of China (31971611), Beijing
Forestry University Outstanding Young Talent Cultivation Project (2019JQ03017),
and China-111 Project (BP0820033).

AUTHOR CONTRIBUTIONS
B.L. and F.P. conceived the overall project and designed the experiments. B.L., Q.G.,
J.R., Z.L., M.S., and Y.H. contributed to experimental work. P.L. and M.Y. contributed
to theoretical calculation. X.H. and G.C. contributed to analysis of the data and discus-
sion. All authors contributed to the writing and commented on the manuscript.

DECLARATION OF INTERESTS
The authors declare no competing interests.

Received: June 1, 2022

Revised: July 4, 2022
Accepted: July 27, 2022
Published: August 18, 2022

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