COMMUNICATION
UV-Shielding
Cinnamate-Functionalized Cellulose Nanocrystals as
UV-Shielding Nanofillers in Sunscreen and Transparent
Polymer Films
Zhen Zhang, Boya Zhang, Nathan Grishkewich, Richard Berry, and Kam C. Tam*
Sustainable and environmentally friendly UV-shielding materials offer new
opportunities in the formulation of the next generation cosmetic products.
Cinnamate-functionalized cellulose nanocrystals (Cin-CNCs) prepared by
esterifying CNCs with cinnamoyl chloride display strong UV absorption and
high visible light transmittance. They are suitable for use as UV-shielding
nanofillers for sunscreen and transparent polymer films. The aqueous
Cin-CNC dispersion is waterborne, alcohol-free, nonwhitening, waterproof,
photo-stable, and possesses a high sun protection factor (SPF). The SPF of
Cin-CNC aqueous dispersion is more than twice that of a popular commercial
sunscreen at similar concentration. The Cin-CNCs can serve as UV-shielding
and reinforcing nanofillers in hydrophilic and hydrophobic polymer matrices.
The polyvinyl alcohol and polystyrene films incorporated with Cin-CNCs
display excellent UV-shielding capacity and their Young’s moduli are
significantly enhanced.
Sun exposure can cause severe sunburn due to the UV radiation
from the terrestrial solar radiation. Overexposure to UV radiation
can cause skin, retina, and DNA damage. This will lead to wrin-
kling and aging of skin, accelerate the deterioration of retina, and
may contribute to skin cancer.[1,2] Skin cancers are the most prev-
alent cancers, of which 90% are caused by overexposure to UV
radiation.[2,3] Therefore, UV protection is highly recommended
for beauty and health reasons. It can be achieved by using
sunscreen and UV-shielding films on windows of cars and build-
ings. The demands for UV-shielding materials are increasing
as awareness on their role in health coupled with the desire to
Dr. Z. Zhang
SCNU-TUE Joint Lab of Device Integrated Responsive Materials (DIRM)
National Center for International Research on Green Optoelectronics
South China Normal University
Guangzhou 510006, P. R. China
Dr. Z. Zhang, Dr. B. Zhang, N. Grishkewich, Prof. K. C. Tam
Department of Chemical Engineering
Waterloo Institute for Nanotechnology
University of Waterloo
Waterloo, Ontario N2L 3G1, Canada
E-mail: mkctam@uwaterloo.ca
Dr. R. Berry
CelluForce Inc.
625 Président-Kennedy Ave, Montreal, Quebec H3A 1K2, Canada
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adsu.201800156.
DOI: 10.1002/adsu.201800156
Adv. Sustainable Syst. 2019, 1800156 1800156 (1 of 5)
www.advsustainsys.com
look good fuel their demand. In general,
strong UV-shielding capability and high
visible light transmittance are fundamental
criteria for UV-shielding fillers.[4] However,
the balance and the optimal design of
products that possess the comprehensive
properties of UV-shielding fillers is still an
enormous challenge.
In sunscreen, UV-shielding fillers are
expected to be biocompatible, possess strong
UV protection, nongreasy, nonwhitening,
nonirradiative, water dispersible, light-
weight, and waterproof.[5] Two types of
sunscreen ingredients are commonly
used: physical and chemical sunscreens.[2]
Physical sunscreens, such as titanium
dioxide (TiO2) and zinc oxide (ZnO), can
efficiently reflect and scatter UV irradiation
and they possess broad UV-shielding prop-
erties.[6] However, the whitening and greasy
feel of such sunscreens make them less appealing as cosmetic
products. Chemical sunscreens are usually aromatic molecules
with conjugated carbonyl groups that can absorb high-energy UV
radiation. The nonwhitening and lightweight feel of chemical
sunscreens make them appealing ingredients in sunscreen for-
mulation. However, the potential of inducing allergic reactions
limits the amounts that can be used in sunscreens.[8] Moreover,
organic solvents are necessary to disperse or dissolve the active
ingredients in physical and chemical sunscreen products,
rendering them unsuitable for water-based sunscreens. In
addition to sunscreen, UV-shielding fillers have been incorpo-
rated into transparent and robust polymer films for car and
building windows.[9]
Cinnamate groups display strong absorption for UV radia-
tion due to the conjugated structure of the benzene ring and
adjacent carbon double bonds.[2,10] Methyl cinnamate, ethyl
cinnamate, or cinnamic acid naturally found in many plants
or fruits, such as cinnamon and strawberries are nontoxic
and biocompatible.[11] Due to the balsamic and fruity odor,
cinnamate derivatives are extensively used in flavor, perfume,
and pharmaceutical industries.[2] Octyl methoxycinnamate is
one of the 17 FDA approved ingredients used in sunscreens.[2]
Most cinnamate derivatives are hydrophobic and insoluble in
water. They are photo-unstable and undergo photodimeriza-
tion upon UV irradiation (wavelength λ > 280 nm).[10,12,13]
Anchoring the cinnamate groups onto the surface of
water-dispersible nanoparticles could increase their water-
dispersibility and photo-stability.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Cellulose nanocrystals (CNCs) are biocompatible, water-
dispersible, and sustainable rod-like nanoparticles extracted
from wood pulp via acid hydrolysis.[14–17] They have attracted
increasing attention in the last two decades due to their
outstanding mechanical properties, nontoxicity, ecofriendly
with enormous potential for further functionalization.[18–22]
Poly(cinnamoyloxy ethyl methacrylate) (PCEM) was recently
grafted onto CNCs via Surface-Initiated Atom Transfer Radical
Polymerization (SI-ATRP) and the PCEM grafted CNCs
(PCEM-g-CNCs) were used to reinforce poly(vinyl chloride)
(PVC) films.[23] The PVC films containing PCEM-g-CNCs
displayed strong UV absorption, high visible light transmit-
tance, and improved UV and thermal stability. However, the
approach used to prepare PCEM-g-CNCs is costly, complicated,
and difficult to scale-up.
Recently, we used a facile method to anchor cinnamate groups
onto CNCs at room temperature via the esterification with cin-
namoyl chloride. The resulting cinnamate-functionalized CNCs
(Cin-CNCs) are efficient inverse Pickering emulsifiers.[24] In thisCNCs exhibited excellent dispersibility in DMF and THF, and
article, the dispersibility, UV–visible absorption, UV-shielding
performance, photo-stability, and miscibility of Cin-CNCs were
examined, and they were explored as UV-shielding nanofillers
for the sunscreen and polymeric films.
Figure 1 describes the synthesis of Cin-CNCs and application
as UV-shielding nanofillers. The Cin-CNCs were synthesized
by esterifying CNCs with cinnamoyl chloride at room tem-
perature, according to previous protocol with minor modifica-
tion.[16] The successful preparation of Cin-CNC was confirmed
by Fourier-transform infrared spectroscopy (FTIR) spectra
(Figure S1, Supporting Information). According to the trans-
mission electron microscopic (TEM) images of CNCs and
Cin-CNCs (Figure 2A,B), the Cin-CNCs retained their nanorod
morphology and high aspect ratio.
As elucidated earlier, nonirritating and non-oily waterborne
sunscreens are highly desirable in cosmetic formulations.
CNCs are hydrophilic and readily dispersed in water due to
Figure 1. Schematic representation of the synthesis of Cin-CNCs and application as
UV-shielding nanofillers
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their abundant hydroxyl and sulfate ester groups, and their
hydrodynamic diameter (Dh) is 84 nm (Figure S2 and Table S1,
Supporting Information). CNCs could be dispersed in DMF,
having a larger Dh (453 nm) due to the mild aggregation of
CNCs in DMF. The aqueous CNC dispersion (1 mg mL−1) was
transparent, while the CNC dispersion in DMF was translucent
(Figure S3, Supporting Information). CNCs could not be dis-
persed in THF and would precipitate in minutes (Figure S3,
Supporting Information). The water contact angle of Cin-CNCs
(75.9°) was much larger than that of CNCs (14.0°), suggesting
Cin-CNCs were less hydrophilic than pristine CNCs (Figure S4,
Supporting Informtion). The Cin-CNCs could be re-dispersed
in water via sonication; however, the Cin-CNC aqueous disper-
sion appeared opaque (Figure S3, Supporting Information).
The Dh of Cin-CNCs in water was greater than 1 µm, sug-
gesting an unstable dispersion. The Cin-CNCs precipitated
from water after several hours; hence this dispersion could
not be directly employed in waterborne sunscreen. The Cin-
the Dh of Cin-CNCs in DMF and THF were 93.2 and 137.6 nm
(Figure S2 and Table S1, Supporting Information), respectively.
Solvent-exchange method was used to prepare stable aqueous
Cin-CNC dispersions. This was performed by adding deion-
ized water to the Cin-CNC dispersion in THF, followed by the
removal of THF via air purging or dialysis. The obtained Cin-
CNC aqueous dispersion (1 mg mL−1) remained transparent
(Figure S3, Supporting Information), and the Dh zeta-potential
of Cin-CNCs in aqueous solution was 150.3 nm and −35.7 mV,
respectively. The aqueous Cin-CNC dispersion obtained by
THF-exchange was stable and no precipitation was observed
over 1 year, confirming that the aqueous Cin-CNCs dispersions
are suitable for use as UV-shielding nanofillers for waterborne
sunscreen.
The durability and stability of the sunscreen should be
considered for practical applications. Cin-CNC film was spin-
coated on the surface of a quartz plate. The Cin-CNC film was
stored in dark at ambient conditions for half
a year and then immersed in water for 24 h,
and no detectable change in the UV–visible
absorbance was observed, confirming that
the Cin-CNC was waterproof and highly
stable. The cinnamate groups are known to
undergo [2π + 2π] photodimerization upon
UV irradiation (wavelength λ > 280 nm).[23]
The conjugated CC bond of the cinnamate
groups exhibited a UV absorption band due
to the π−π* electronic transition, which could
be used to monitor the photodimerization.[13]
The Cin-CNC film was irradiated at 365 nm
using a 6 W hand-held UV lamp. As shown
in Figure S5 in the Supporting Informa-
tion, the peak of Cin-CNC film at 278 nm
(At) decreased with the UV irradiation time
due to the photodimerization, which was
similar with the UV absorption of PCEM-
g-CNC.[23] Moreover, the parameter (1/At)
increased linearly with the UV irradiation
time, indicating the photodimerization pro-
cess followed the second-order kinetics. The
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Figure 2. A) TEM images of CNCs, B) Cin-CNCs, and C) sunscreen S; D) UV–visible absorbance and E) transmittance of CNCs, Cin-CNCs, and
sunscreen S aqueous dispersion at the active ingredient concentration of 0.1 mg mL−1, respectively.
Cin-CNC film retained nearly 80% of the original absorbance
after 10 h of UV irradiation, suggesting a good photo-stability
of Cin-CNCs. The photodimerization rate of Cin-CNC was
much slower than that of PCEM or other cinnamate derivatives
(from the slope of 1/At vs UV irradiation time),[10,23] which was
attributed to the increased steric hindrance.
The sun protection factor (SPF) is the fraction of sunburn-
producing UV irradiation that reaches the skin at a dosage of
2 mg sunscreen per square centimeter of skin. It is the most
popular and widely used indicator to assess the UV-shielding
performance.[12] The in-vitro methods, such as Mansur
equation (Supporting Information), are often used to calculate
the SPF due to economic and practical considerations.[25] As
UVC (below 280 nm) is blocked by the ozonosphere and UVB
(280–320 nm) is considered much more harmful than the
UVA (320–400 nm), the in vitro SPF calculated by Mansur
equation is primarily a measure of UVB protection. Here, one
of the best-selling sunscreens (denoted as “sunscreen S”) with
labeled SPF of 50 was used as a reference to compare the sun
protection performance. Sunscreen S uses the combination
of inorganic and organic compounds as the active ingredients
(27 wt%), including zinc oxide (14.5 wt%), octyl methoxycin-
namate (7.5 wt%), and octisalate (5 wt%). The sunscreen S
(1 mg mL−1) was opaque and white, suggesting strong absorp-
tion in the visible light range. Figure 2C shows the TEM image
of the sunscreen S. The black spots in the TEM image with an
average diameter of 45.4 nm are ZnO nanoparticles and the
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gray spots with an average diameter 119.0 nm may be attrib-
uted to the organic ingredients. The Dh and zeta potential of the
aqueous sunscreen S dispersion were 333.8 nm and −28.4 mV,
respectively.
Figure 2D,E compares the UV–visible absorbance and
transmittance of CNC, Cin-CNC, and aqueous sunscreen S
dispersion at the active ingredient concentration of 0.1 mg mL−1.
The sunscreen S exhibited a broad UV spectrum protection
for both UVA and UVB. The SPF of sunscreen S calculated
according to the Mansur equation was 54.0 at the concentration
of 27 wt%, which was consistent with the labeled SPF value.
However, the sunscreen S also displayed a broad visible light
absorption, leading to the observed whitening appearance. The
CNC aqueous dispersion displayed negligible absorption over
the whole UV and visible ranges, indicating that CNCs by them-
selves do not possess UV-shielding capability. The Cin-CNCs
dispersion exhibited a slightly weaker absorption in the UVA
range but a much stronger absorption in the UVB range than
sunscreen S. According to the Mansur equation, the SPF of
CNC, Cin-CNC, and sunscreen S at the concentration of 5 wt%
were 0.1, 20.3, and 10.0, respectively. The SPF of Cin-CNC was
more than two times higher than the SPF of sunscreen S at
the same active ingredient concentration. Another prominent
advantage of the Cin-CNC was the high transmittance for
visible light. As shown in Figure 2E, the Cin-CNC dispersion
exhibited a much higher transmittance than sunscreen S in the
visible region, indicating it is a nonwhitening sunscreen.
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 www.advancedsciencenews.com
Another promising application of Cin-CNCs is in the prepa-
ration of UV-shielding polymer films for windows. Cin-CNCs
were used as both UV-shielding and reinforcing nanofillers in
polymeric substrates, such as films. CNCs have been exten-
sively employed as reinforcing agents in polymer matrices due
to their outstanding mechanical properties.[16,18,21] The inter-
facial area between the reinforcing nanofillers and polymer
matrices is critical for the mechanical performance of the
nanocomposites.[27] CNCs could be directly used as reinforcing
fillers in hydrophilic polymer matrices due to their hydro-
philic surface, while hydrophobic modification of CNCs could
be readily performed for their incorporation into hydrophobic
poly­mer matrices.[23,26,27] Herein, polyvinyl alcohol (PVA) and
polystyrene (PS) were selected as representative hydrophilic
and hydrophobic polymer matrices, respectively. PVA films
were prepared by solution casting the aqueous mixture of
PVA and Cin-CNCs in Petri dishes under ambient conditions,
while PS films were prepared by solution-casting the DMF
mixture of PS and Cin-CNCs in a glass mold at 60 °C.
Both the PVA and PS films with 6 wt% of Cin-CNCs were
highly transparent (Figure 3A,E), suggesting good miscibility
between Cin-CNCs and PVA or PS matrices. The PVA films
were flexible and could be folded (inset of Figure 3A), while the
PS films were fragile and would break when folded. However,
this could be overcome by introducing plasticizer to the nano-
composite films. The UV–vis absorbance and transmittance of
PVA and PS films are shown in Figure 3. Both the neat PVA
and PS films exhibited negligible absorption in the UVA and
UVB range. The PVA film incorporated with 1 wt% Cin-CNCs
shielded almost all the UV below 310 nm while maintaining a
high transmittance in visible light. The Cin-CNCs showed
a much better UV-shielding capability than p-aminobenzoic
acid modified CNCs (PABA-CNCs) reported previously.[9] With
increasing Cin-CNC contents in the PVA, the UV-shielding
capability of PVA films increased gradually with a slight reduc-
tion of transmittance in the visible light range. The PS films
displayed strong absorption for UVB after the incorporation
Figure 3. Optical images of (A) PVA and (E) PS films with 6 wt% of Cin-CNCs; absorbance and transmittance of (B,C) PVA films and (F,G) PS film
with different content of Cin-CNCs; and EY of (D) PVA and (H) PS films as a function of Cin-CNC content, respectively.
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of Cin-CNCs, and the UV-shielding capability of PS films was
enhanced with increasing Cin-CNC contents. It is worthwhile
to note that the transmittance of PS films in the visible light
range did not change after the addition of Cin-CNC, which is
attributed to the excellent miscibility between Cin-CNCs and
PS matrices. Figure 3D,H shows the Young’s modulus (EY) of
the PVA and PS films with varying amounts of Cin-CNCs. The
EY of PVA films were significantly enhanced after the addition
of Cin-CNCs. When 2 wt% of Cin-CNCs were added, the EY of
PVA film increased by more than three times (from 148.5 to
477.7 MPa); however, a much higher amount of PABA-CNCs
(>10 wt%) were required to achieve a doubling of the mod-
ulus.[9] However, a further increase of Cin-CNCs in PVA led to
a reduction in EY, which may be attributed to the slight aggrega-
tion of Cin-CNCs. The EY of PS films gradually increased with
the content of Cin-CNCs (0–6 wt%). However, no reduction of
EY was observed when Cin-CNC content exceeded 2 wt%, which
also indicated the excellent miscibility between Cin-CNCs and
PS matrices.
In summary, UV-shielding cinnamate groups were
grafted to the surface of CNCs via the esterification of surfi-
cial hydroxyl groups with cinnamoyl chloride. The resulting
Cin-CNCs retained the rod-like shape character of pristine
CNCs. Cin-CNCs were less hydrophilic than pristine CNCs
and could be re-dispersed directly in DMF and THF instead of
water. Stable Cin-CNC aqueous dispersion could be obtained
by a THF-exchange process. Cin-CNCs exhibited outstanding
UV-shielding capability and transmittance in visible light.
Therefore, Cin-CNCs could be employed as UV-shielding
nanofillers in both sunscreen and transparent polymer films.
The aqueous Cin-CNC dispersion in sunscreen is waterborne,
alcohol-free, nongreasy, nonwhitening, photo-stable, high SPF,
waterproof, and lightweight. The SPF of Cin-CNC dispersion
was two times higher than a popular commercial Sunscreen S
at the same active ingredient concentration. When Cin-CNCs
were incorporated into PVA and PS matrices as reinforcing
and UV-shielding nanofillers, the PVA and PS films displayed
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 www.advancedsciencenews.com
excellent UV-shielding capability and high visible transmit-
tance, and the Young’s moduli of PVA and PS films were
significantly enhanced. Therefore, Cin-CNCs are promising
sustainable nanomaterials for use as UV-shielding nanofillers
for sunscreen and polymer films.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors wish to acknowledge Celluforce Inc. for providing
the cellulose nanocrystals. The research funding from CelluForce,
AboraNano, and FP Innovations facilitated the research on CNCs. K.C.T.
wishes to acknowledge funding from CFI and NSERC. Z.Z. wishes to
acknowledge the funding support from Natural Science Foundation
of China under Grant (No. 51561135014, U1501244); Guangdong
Innovative Research Team Program under Grant (No. 2013C102); Science
and technology project of Guangdong Province (No. 2017B090903008);
Guangdong Provincial Key Laboratory of Optical Information Materials
and Technology under Grant (No. 2017B030301007); MOE International
Laboratory for Optical Information Technologies and The 111 Project.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
cellulose nanocrystals, cinnamate, polymer films, sunscreen, UV-shielding
Received: November 30, 2018
Revised: January 1, 2019
Published online:
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