Received: 26 November 2023 Revised: 31 January 2024 Accepted: 29 February 2024

DOI: 10.1002/pol.20230889

REVIEW

Progress in photocontrolled radical polymerization

for the synthesis of nonlinear polymer architectures

Dongjoo Lee 1 | Hanqing Wang 1 | Rafael Verduzco 1,2

1
Department of Chemical and
Biomolecular Engineering, Rice
University, Houston, Texas, USA
2
Department of Materials Science and
NanoEngineering, Rice University,
Houston, Texas, USA
Correspondence
Rafael Verduzco, Department of Chemical
and Biomolecular Engineering, Rice
University, Houston, TX, 77005, USA.
Email: rafaelv@rice.edu
Funding information
Welch Foundation, Grant/Award
Number: C-2124; Division of Chemistry,
Grant/Award Number: 2247729
Abstract
Controlled radical polymerization (CRP) techniques enable the preparation of
diverse, chemically tailored polymers with a variety of chain architectures.
Separately, light-mediated polymerization reactions offer a number of advan-
tages over thermal polymerizations in terms of energy efficiency, sustainabil-
ity, and versatility. Recent work has combined photopolymerization and CRP
techniques to advance the synthesis of polymers with nonlinear architectures,
including bottlebrush polymers, star polymers, hyperbranched polymers, and
cyclic polymers. These photoCRP methods offer novel routes to nonlinear
polymers using mild reaction conditions. In this review, we provide an over-
view of photoCRP techniques for the synthesis of nonlinear polymers. We start
with a discussion of photoCRP applied to the synthesis of linear polymers and
discuss the underlying reaction mechanisms. Then, we discuss photoCRP
applied to the synthesis of bottlebrush, star, hyperbranched, cyclic, and
surface-initiated polymer brushes. For each case, we discuss the synthetic
strategy and the unique properties and characteristics of the resulting poly-
mers, and we provide a perspective on potential future directions for research.

KEYWORDS
bottlebrush polymers, branched polymers, controlled radical polymerization, cyclic
polymers, photopolymerization, polymer brushes, star polymers

1 | INTRODUCTION interactions between the side chains, and as a result, they

The development of controlled radical polymerization (CRP)
or reversible deactivation radical polymerization (RDRP)
represents a significant breakthrough in the field of polymer
chemistry. In contrast to free radical polymerization, which
produces polymers with broad molecular weight distribu-
tions and poorly controlled molecular weights, CRP enables
control over both the molecular weights and architecture of
polymers.1,2 The ability to control polymer architecture is
critical, as polymer properties can vary significantly with the
introduction of branches, loops, and densely grafted brushes
(Figure 1).3–5 For instance, bottlebrush polymers exhibit par-
tially or fully extended backbones due to strong repulsive
have higher entanglement molecular weights and lower
Young's modulus compared to their linear counterparts.6
This control over architecture therefore enables the study
and development of polymers for unique applications.
Recent innovations have also demonstrated strategies for
achieving oxygen tolerance in CRP,7 producing graft, block,
multiblock, and stimuli-responsive polymers,8,9 and demon-
strating the depolymerization of polymers produced by
CRP.10
The development of photochemical reaction path-
ways for polymer synthesis has similarly revolutionized
the field.11–13 Various review papers on photopolymeriza-
tion have comprehensively highlighted the advantages of

J Polym Sci. 2024;1–18. wileyonlinelibrary.com/journal/pol © 2024 Wiley Periodicals LLC. 1

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2 LEE ET AL.

F I G U R E 1 Schematic for
the preparation of a variety of
polymer architectures through
photoCRP techniques.

photoCRP over thermal CRP.14–19 Some of these advan-

tages include temporal and spatial control. Temporal
control allows researchers to synthesize polymers with
accurate molecular weights by simply switching the light
source “on” and “off” over multiple cycles. The advantage
of spatial control, such as in surface-initiated polymeriza-
tion through a photomask, enables researchers to synthe-
size chemically tailored, surface-attached polymers by
selectively irradiating specific regions of the surface.
Recent work has sought to control polymer architecture
by combining the advantages of photopolymerization with
controlled radical polymerization using reversible addition-
fragmentation chain transfer (RAFT) and atom transfer
radical polymerization (ATRP). Photoinduced RAFT poly-
merization involves either direct activation of the RAFT
agent (chain transfer agent, CTA) or the utilization of an
external photoinitiator/photocatalyst to generate a radical
source, as shown in Figure 2.16,20,21 In the case of direct
activation, exposure to a light source excites the CTA which
leads to homolytic cleavage of the C-S bond. This generates
R-group-based radicals which can initiate the polymeriza-
tion. Alternatively, a radical photoinitiator can be used to F I G U R E 2 Different mechanisms for initiating photoRAFT
generate the R-group-based radicals (Figure 2B).21 A third polymerization: (A) direct activation of CTA, (B) photoinitiator,
route to photoinduced RAFT is through the use of a photo- and (C) photocatalyst approaches.
catalyst, which can participate in photoinduced electron
transfer to the CTA, generating a thiocarbonylthio anion
along with a propagating radical species (Figure 2C).16 ranges. This can be leveraged to perform multiple, sequen-
ATRP can also be activated using light. In contrast to tial polymerization reactions by activating different CTAs
conventional thermal-based ATRP, photoinduced ATRP using different wavelengths, enabling the synthesis of
involves the generation of a Cu(I) activator complex block and graft copolymers.24,25 Another advantage of
through the photochemical reduction of Cu(II) deactivator photoCRP is that, in some cases, it can also be conducted
complexes, as depicted in Figure 3A.17 Alternatively, the without initiator or catalyst. This improves the end-group
photocatalysts can directly reduce halogen-based ATRP ini- fidelity and minimizes the synthesis of dead polymer
tiators to produce active carbon-centered radical species chains. Polymerization reactions that rely on a radical ini-
which then can initiate the polymerization (Figure 3B).17,22 tiator inevitably produce some quantity of initiator-derived
PhotoCRP offers several advantages over conventional chains.26 The photoCRP method does however have disad-
thermal CRP when synthesizing polymers with nonlinear vantages relative to thermal RDRP. For example, it can be
architectures. One of the primary advantages of photoCRP more difficult to reproduce photoCRP conditions across
comes from its chemoselective reaction mechanism.23 For different laboratories due to the dependence on the config-
example, in photoinduced RAFT polymerization, CTAs uration of the photoreactor.15 Additionally, RDRP has
can undergo fragmentation over specific wavelength broader compatibility with various solvents and monomers

LEE ET AL.
F I G U R E 3 Different
mechanisms for photoATRP:
(A) regeneration of active
Cu(I) species and (B) direct
reduction of halogen-based
ATRP initiators processes.
T A B L E 1 Comparison of advantages of PhotoCRP and
thermal CRP.
Thermal CRP
PhotoCRP (or RDRP)
Temporal control ✓ ✕
Spatial control ✓ ✕
Initiator/catalyst free ✓ ✕
Reproducibility ✕ ✓
Compatibility ✕ ✓
Oxygen tolerance ✓ ✓
Simplicity ✓ ✓
compared with photoCRP.14 A summary of the advantages
and disadvantages of photoCRP in comparison to
thermally-initiated-CRP or RDRP is provided in Table 1.
We note that both can be designed to be tolerant of oxygen
and both are simple approaches to polymer synthesis.
Herein, we review examples and developments in the
synthesis of polymers with nonlinear architectures using
photoCRP techniques. There have been a large number
of studies that utilize photoCRP, and a SciFinder search
using “photochemical controlled radical polymerization”
identifies over 50,000 publications in just the last 5 years.
Therefore, we do not attempt to provide a comprehensive
review of all works related to photoCRP. Rather, we focus
specifically on photoCRP methods used to prepare poly-
mers with nonlinear architectures. Specifically, we will
detail examples of photoCRP used to prepare bottle-
brushes, star, hyperbranched, cyclic, and polymer
brushes, and we note that the use of photoCRP to synthe-
size polymers with nonlinear architectures is by compari-
son much more limited. We briefly discuss the synthesis
of linear polymers using photoCRP methods, but only to
review and describe the synthetic strategies. The develop-
ment of photoCRP methods and application to linear
polymer synthesis is described in other reviews.1,2,8 We
also do not describe the role of oxygen tolerance,7 the
synthesis of block copolymers,9 or the depolymerization
of polymers prepared using CRP techniques.10 We close
by discussing future research directions in the field.
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3
F I G U R E 4 Homolytic cleavage of the C S bond in
thiocarbonate compound upon blue light (λmax = 460 nm)
irradiation. Reprinted with permission.27 Copyright 2015, American
Chemical Society.
2 | LINEAR POLYMERS
AND PHOTOCHEMICAL CRP
MECHANISM
In this section, we will describe the mechanisms for both
photoinduced RAFT and ATRP techniques using exam-
ples of linear polymer synthesis. Early advances devel-
oped photopolymerization techniques that do not rely
on catalysts. Notably, McKenzie et al. introduced a
thiocarbonate-mediated RAFT polymerization under
visible light, without the need for a catalyst or photoini-
tiator.27 Since the n ! π* electronic transition of thiocar-
bonate compound has an absorption energy that falls in
the visible light region, blue light (λmax = 460 nm) causes
homolytic cleavage of the C-S bond in thiocarbonate
compound, generating a radical, as depicted in Figure 4.
The authors used this to synthesize PMA using benzyldo-
decyl carbonotrithioate (BDTC) as a CTA with blue
LED light irradiation. The polymerized product had a
molecular weight of 8290 g/mol (Đ = 1.07) with 92%
monomer conversion after 16 h. They also compared
the polymerization of MA under visible and UV light
(λmax = 365 nm), as UV light can also initiate the photo-
polymerization through π ! π* electronic transition.
Interestingly, a significantly shorter induction period was
observed under UV light irradiation, due to the lower
absorbance energy of the n ! π* transition compared to

4 LEE ET AL.
the π ! π* transition. Despite this disparity in induction
time, the rate of polymerization under visible light was
nearly identical to that of the UV system. To validate the
end-group fidelity of the proposed approach, the authors
polymerized pseudo-diblock copolymer (PMA-b-PMA).
They successfully produced the diblock copolymer while
maintaining low molecular weight dispersity (Đ = 1.05),
indicating both successful reinitiation and high-
end-group fidelity.
In 2016, Allegrezza et al. reported that the presence of
amines accelerated the photoRAFT process.28 Specifically,
they found that dithiobenzoate-mediated RAFT photopoly-
merization was accelerated by triethylamine (TEA), which
acted as a redox-active catalyst. They first polymerized
methyl methacrylate (MMA) using 2-cyanoisopropyl
dithiobenzoate (CPDB) as the CTA with excess TEA under
blue light (λmax = 440 nm), achieving a molecular weight
of 23,000 g/mol (Đ = 1.19) with 66% monomer conversion
after 27 h of reaction. To confirm that the process was
entirely photochemically-driven, the authors monitored
the polymerization reaction with intermittent periods of
illumination and found that the polymerization only
occurred in the presence of light and that no polymeriza-
tion occurred during dark periods. Different wavelengths
of light were also tested. Since blue and green LED emis-
sion spectra overlap with the absorption spectrum of the
CTA end-group, blue and green LED irradiation produced
the highest polymerization rate (kpapp = 1.1  105 s1)
while the red LED irradiation produced the slowest
F I G U R E 5 Porphyrin-based donor-acceptor COFs. (A) Synthesis of porphyrin COFs RICE-1 and RICE-2. (B) Proposed photoRAFT
mechanism using RICE COFs as photocatalyst. Reprinted with permission.29 Copyright 2021, Royal Society of Chemistry.
26424169, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20230889 by Univ of Sao Paulo - Brazil, Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
polymerization rate (kpapp = 1.4  106 s1). Sunlight was
also proven to be capable of performing the polymeriza-
tion, with the rate of polymerization comparable to the
blue LED system (kpapp = 8.3  105 s1). CPDB itself is
photoactive in the visible light range, indicating that the
reaction can be self-initiated by direct activation of the
CTA. However, in this study, the authors showed that TEA
served as a redox catalyst which accelerated the reaction.
Under light irradiation, TEA becomes oxidized which
induces electron transfer from tertiary amines to CPDB,
generating dithiobenzoate radical anion. Subsequently, the
dithiobenzoate radical anion cleaves to generate carbon
radical which can propagate the polymerization.
Recently, heterogeneous catalysts such as covalent
organic frameworks (COFs) have been used as photocata-
lysts with several advantages over conventional small
molecule-based photocatalysts, including easy separation,
broad absorption spectra, and recyclability.30–32 In 2021,
Zhu et al. synthesized porphyrin-based COFs with strong
donor-acceptor characteristics, namely RICE-1 and RICE-2
(Figure 5A).29 In this study, the strong reduction potential
of photoexcited COF catalysts was responsible for reducing
the CTA in the system, generating radical species that could
initiate chain growth (Figure 5B). To test the catalytic ability
of the porphyrin-based COFs, the authors explored the
photopolymerization of MA using a concentration of 1 mg/
mL of the RICE COFs. When utilizing RICE-1 as a photoca-
talyst under blue light irradiation (λmax = 460 nm), they
achieved a conversion rate of 85.0% (Đ = 1.06) in 17 h.

LEE ET AL.
Similarly, polymerization with RICE-2 yielded a comparable
conversion rate of 79.6% (Đ = 1.05) in 17 h. They also tested
polymerizations using different wavelengths of light. Chang-
ing the irradiation light to green (λmax = 535 nm) and red
(λmax = 635 nm) light resulted in a lower conversion of
61.8% and 50.1% while still maintaining low dispersities
(Đ = 1.10), respectively. Lastly, the recyclability of the COF
photocatalysts was tested. The authors were able to reuse
the RICE COFs for PET-RAFT polymerization of MA
monomers at least 5 times while maintaining a high conver-
sion rate ( 80%) and low dispersity (Đ < 1.15).
Konkolewicz et al. made significant contributions to
the development of photoinduced ATRP by demonstrat-
ing that it could be conducted without the use of a photo-
initiator and with ppm quantities of copper catalyst.33
They initially demonstrated the polymerization of MA
using ethyl α-bromoisobutyrate (EBiB) as an ATRP initia-
tor at room temperature with 100 ppm of CuBr2 and tri
((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine
(TPMA) ligand using three different wavelengths of light.
The fastest polymerization rate was observed under sun-
light, followed by a slower polymerization rate with violet
irradiation (λmax = 392 nm) and even slower under blue
irradiation (λmax = 450 nm). However, no polymerization
occurred under red light irradiation (λmax = 631 nm),
indicating the importance of efficient ligand-to-metal
charge transfer (LMCT) in the excited state for photoin-
duced ATRP. In addition, regardless of the polymeriza-
tion rate, the authors were able to control the molecular
weight of the polymerization which had good agreement
with the theoretical values with low dispersities
(Đ < 1.10). The proposed mechanism was remarkable, as
they proposed that halogen radicals rather than alkyl
radicals were responsible for initiating polymer chain
growth.
To avoid the incorporation of potential metal contam-
inants into polymer products and the associated purifica-
tion process, Ramsey et al. investigated organocatalyzed
photoinduced ATRP (O-ATRP) in a continuous flow sys-
tem.22 They used strong reducing organic photocatalysts,
which generated radicals under irradiation through a
photoredox reaction with alkyl halide ATRP initiators.
While batch systems can have poor light penetration
through the entire reaction medium, flow systems can
operate with narrow tubing and therefore offer higher
surface-area-to-volume ratios and more uniform irradia-
tion throughout the system. This leads to a higher con-
centration of photoexcited catalysts in the reaction and
accelerates the overall reaction kinetics. The authors first
synthesized PMMA using four different types of
photocatalysts, namely N,N-diaryl phenazines, perylene,
and N-aryl phenoxazines. Among those photocatalysts,
polymerization using N-aryl phenoxazine in a continuous
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5
flow system showed nearly 100% initiation efficiency and
produced polymers with low dispersity (Đ ≤ 1.20). To
study the effect of the photocatalyst in the continuous
flow system, the authors varied the catalyst loading from
0.1–0.005 mol%. For 0.01–0.1 mol% catalyst, the polymer-
ization reached beyond 40% conversion with relatively
low dispersity (Đ < 1.27) polymer product. However,
when the concentration of the catalyst loading decreased
to 0.005 mol%, the molecular weight distribution of the
polymer increased (Đ = 1.60), indicating the importance
of photocatalyst in the O-ATRP.
Recently, visible light-driven photoredox/copper-based
dual-catalyzed ATRP has emerged as a promising strategy
for providing well-defined polymers at low catalyst load-
ing. In 2023, Ti et al. demonstrated a photoATRP approach
to synthesize PMMA at extremely low catalyst loadings
using 5–10 ppm of CuBr2, 1 ppm organophotoredox of cat-
alysts (OPCs) relative to the monomer concentration, and
tris(2-pyridinylmethyl)amine (TPMA) as a ligand.34 Their
mechanism involved a dual-catalyzed approach, involving
both excitations of the photoredox catalyst to both generate
alkyl radicals directly and to reduce CuBr2/TPMA, as
shown in Figure 6. Ppm levels of OPCs were sufficient for
generating propagating radical species. To enhance visible
light absorption and excited state reduction capabilities,
the authors synthesized a series of donor-acceptor type
OPCs based on diarylamine-substituted terephthalate
derivatives. Even at low catalyst loading, 5 ppm CuBr2 and
1 ppm OPC, well-defined PMMA with a conversion rate of
77% (Đ = 1.17) was obtained after 24 h of reaction under
mild conditions. Interestingly, the proposed mechanism
also showed excellent oxygen tolerance. Polymerization of
PMMA in the presence of oxygen produced PMMA with
75% monomer conversion and only slightly higher in dis-
persity (Đ = 1.25).
F I G U R E 6 Proposed mechanism of dual catalyzed (OPC/Cu)
photoATRP of methacrylate monomers. Reprinted with
permission.34 Copyright 2023, American Chemical Society.
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6 LEE ET AL.

2.1 | Bottlebrush polymers study, the group developed a simplified synthetic

approach. First, the backbone of the bottlebrush polymer
Bottlebrush polymers have densely grafted side chains was synthesized through copolymerization of acrylate-
attached to a linear polymeric backbone, resulting in par- functionalized Irgacure (M2959) with AM.40 Through this
tially or fully extended backbone due to steric repulsive process, the grafting density (or density of the initiation
interactions. Due to the unique structure of the bottle- sites) was easily controlled by varying the monomer com-
brush polymers, they typically have lower entanglement position during the backbone polymerization rather than
molecular weight and lower Young's modulus compared attaching the initiating group to the bottlebrush backbone.
to linear polymers.6 Bottlebrush polymers are usually Then, using a similar approach to the previous study, AM
synthesized by either the “grafting-from” or “grafting- was grafted on the bottlebrush backbone upon UV light
through” approaches, which involve either synthesizing irradiation (λmax = 254 nm), resulting in a molecular
the bottlebrush backbone or side chains first, respec- weight of 1.36  107 g/mol with excellent water solubility.
tively.6,35–37 Each approach has specific advantages and Arrington et al. compared the thermal and photo-
disadvantages. The “grafting-from” approach can pro- chemical synthesis of bottlebrushes using both “grafting-
duce bottlebrush polymer with long backbones, but the through” and “grafting-from” approaches (Figure 7A).26
approach cannot guarantee 100% grafting density of To implement both techniques, the authors synthesized
the side chains. The “grafting-through” approach enables norbornene-functionalized trithiocarbonate-based CTA,
the synthesis of bottlebrush polymer with 100% grafting which can be used to synthesize side chains through
density of the side chains but generally cannot access photopolymerization and can undergo ring-opening
very long polymer backbones and becomes more difficult metathesis polymerization (ROMP) to produce the bottle-
with increasing molecular weight of the side chains. brush backbone. To investigate the “grafting-through”
In 2023, Sivokhin et al. developed a continuous flow
photoinduced RAFT polymerization approach for pro-
ducing high molecular weight amphiphilic polyethylene
glycol (PEG)-based bottlebrush (co)polymers under
mild reaction conditions (22–50  C).38 By using the
“grafting-through” approach, they copolymerized meth-
oxy oligo(ethylene glycol)8.5 methacrylate (MOEGMA)
and alkoxy(C12 – C14) oligo(ethylene glycol)6.2 methacry-
late (AOEGMA) under blue light (λmax = 470 nm) using
a trithiocarbonate-based CTA (CDTPA). When the (co)
polymer was synthesized at 22  C, the system reached a
conversion rate of 77% in 150 min (Đ = 1.29) at a poly-
mer production rate of 39 g per 8 h. However, when the
system temperature was increased to 50  C, the reaction
even had a higher conversion rate of 91% in 137 min
(Đ = 1.28) with a polymer production rate of 54 g in 8 h
due to the reduction in the solution viscosity. However,
regardless of the reaction temperature, both cases were
able to synthesize the (co)polymer with accurate mono-
mer compositions in a continuous flow system.
Wu et al. used a “grafting from” approach to synthe-
size water-soluble bottlebrush polymers with controllable
grafting densities. In one study, they first copolymerized
styrene and maleic anhydride to synthesize the backbone
of the bottlebrush polymer (PSM).39 Then, they attached
the initiating group (2-hydroxy-40 -(2-hydroxyethoxy)-
F I G U R E 7 (A) Two different routes to synthesizing
2-methylpropiophenone, Irgacure 2959) on the PSM bottlebrush polymers. SEC refractive index traces of bottlebrush
backbone. Next, by utilizing the “grafting-from” approach, polymers synthesized through (B) thermal and (C) light-mediated
the authors were able to polymerize the acrylamide approaches. Peaks correspond to poly(photoiniferter/CTA 2) and
(AM) under UV irradiation (λmax = 254 nm). The synthe- bottlebrush polymer are indicated in blue and orange, respectively.
sized polymer had a molecular weight of 1.54  107 g/mol Reprinted with permission.26 Copyright 2017, Royal Society of
and showed excellent water solubility. In a follow-up Chemistry.

LEE ET AL.
synthesis, they prepared n-butyl acrylate (nBA) side-chains
by using both thermal and photoRAFT mediated by blue
light (λmax  470 nm). Both thermal and photoinduced
approaches were able to synthesize poly(n-butyl acrylate)
(PnBA) side chains with high monomer conversions of
86% and 95%, respectively, and with low molecular weight
dispersity (Đ = 1.01). Next, these macromonomers were
polymerized through ROMP to form bottlebrush polymers.
They found that the conversion of side chains to bottle-
brush polymers was 77% for thermally-initiated and 96%
for photo-initiated side chains. The authors attributed this
to the presence of initiator-derived chains, which do not
contain the norbornene end-group, in thermally-initiated
RAFT polymerization but not the photo-initiated synthesis
of the side chains. However, this effect was more signifi-
cant in the “grafting-from” approach. Thermally synthe-
sized bottlebrush PnBA showed a significantly high
molecular weight shoulder at 40% conversion (Đ = 2.21)
due to bottlebrush oligomerization (Figure 7B). In contrast,
bottlebrush PnBA synthesized by photo irradiation showed
a symmetrical and monomodal bottlebrush peak at 50%,
indicating no bottlebrush-bottlebrush coupling occurred in
the reaction (Figure 7C). The authors hypothesized that
this was due to lower radical concentration and lower tem-
perature used in the photoinduced polymerization.
Shanmugam et al. demonstrated that bottlebrush poly-
mers could be synthesized using only photoCRP reactions,
by relying on RAFT CTAs that are active at different wave-
lengths to synthesize the bottlebrush backbone and side
chains separately (Figure 8).24 The authors first synthesized
a RAFT inibramer (initiator + branching junction +
monomer),41 2-(2-(n-butyltrithiocarbonate)propionate)ethyl
methacrylate (BTPEMA). The backbone of the bottlebrush
F I G U R E 8 Proposed two-step synthesis of branched and bottlebrush polymers via chemoselective photoRAFT polymerization.
Reprinted with permission.24 Copyright 2018, American Chemical Society.
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7
polymer was synthesized through homopolymerization of
BTPEMA mediated by CDTPA under green light irradia-
tion (λmax = 520 nm), achieving a molecular weight of
97,300 g/mol (Đ = 1.38) after 22 h of reaction. The
authors confirmed that during the homopolymerization of
the bottlebrush backbone, only the Z-group of the CDTPA
was fragmented while the Z-group of the BTPEMA
remained intact. Side chains were then polymerized using
monomer by simply switching to blue light irradiation
(λmax = 465 nm), which activated the BTPEMA units in
the backbone. After 3 h of reaction, the molecular weight
of the bottlebrush polymer reached 434,800 g/mol with
low dispersity (Đ = 1.19), indicating successful polymeri-
zation of bottlebrush polymer by using an entirely photo-
induced polymerization technique.
In addition to advancing and refining photopolymeri-
zation methods, Corrigan et al. pioneered the implemen-
tation of a flow system for the precise synthesis of
branched copolymers, eliminating the need for interme-
diate purification steps.25 Similar to the approach used by
Shanmugam et al.,24 the authors employed spatially
selective photopolymerization by using two different
RAFT agents. The backbone of the branched polymer
was synthesized through copolymerization of MMA and
BTPEMA mediated by CDTPA under green light irradia-
tion (λmax = 520 nm). After 6 h of reaction at 60  C,
poly(MMA-stat-BTPEMA) was synthesized with a molec-
ular weight of 18,300 g/mol with low dispersity
(Đ = 1.13). The authors also confirmed that the MMA
and BTPEMA monomers had a similar reactivity (conver-
sion rate of 92% after 6 h). A nonselective photoinduced
RAFT polymerization was performed to graft the side
chains to the polymeric backbone. DMA monomer was

8 LEE ET AL.
F I G U R E 9 Controlling the architecture of the polymers by
adjusting the light in each stage. (A) Provides controlled side-chain
lengths. (B) Provides branched or graft copolymer architectures.
(C) Provides controlled grafting densities and side-chain lengths.
(D) provides controlled backbone lengths, grafting densities, and
side-chain lengths. Reprinted with permission.25 Copyright 2021,
American Chemical Society.
polymerized from the poly(MMA-stat-BTPEMA) back-
bone under red light irradiation (λmax = 630 nm) acti-
vated by 5,10,15,20-tetraphenyl-21H,23H-porphine zinc
(ZnTPP) photocatalyst. Upon red light irradiation, side
chains of the branched polymer were formed, resulting in
the final molecular weight of 33,300 g/mol (Đ = 1.28)
after 4 h of reaction at room temperature. The authors
also demonstrated that they were able to control the
topology (graft, hyperbranched, etc.), grafting density,
backbone length, and side-chain length of the polymer
product by simply adjusting the light in each stage of the
polymerizations (Figure 9).
2.2 | Star polymers
Star polymers are a class of branched polymers character-
ized by linear macromolecular chains (arms) attached to
a central branching point (core).42 Star polymers are
characterized by the chemistry of the arms, which can be
homopolymer or copolymer, the number of arms (Narm),
and the degree of polymerization of the arms (DParm).
Compared to their linear counterparts, star polymers
exhibit much lower chain entanglement due to steric
interactions between arms, resulting in lower viscosity
in dilute solutions.43 Star polymers are usually prepared
by either “arm-first” or “core-first” approaches.44–46
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F I G U R E 1 0 Proposed one-pot pathway synthesis of star
polymers via “arm-first” approach. Reprinted with permission.47
Copyright 2015, American Chemical Society.
Therefore, the central core of star polymers can vary,
ranging from small molecules, crosslinked macromole-
cule cores, or nanoparticles. In the “arm-first” approach,
the linear polymeric arms are first prepared, and subse-
quent crosslinking enables the formation of star poly-
mers. On the other hand, “core-first” approaches usually
require a multifunctional core with initiating sites, from
which polymeric arms are grown.
In 2015, McKenzie et al. presented a one-pot pathway
toward controlled photoinduced RAFT polymerization of
star polymer using an “arm-first” approach.47 The authors
first synthesized the arm of the star polymers by polymer-
izing MA under blue light (λmax = 460 nm) by using
trithiocarbonate-based CTA (2-(((butylthio)-carbonothio-
lyl)thio)propanoic acid, BCTP), as shown in Figure 10.
The PMA had a molecular weight of 6000 g/mol with low
dispersity (Đ = 1.25). After reaching a high conversion of
monomer (>95%), a divinyl-based crosslinker (ethylene
glycol diacrylate, EGDA) was added to the solution to
crosslink the presynthesized arms. Interestingly, the struc-
ture of the star polymer was strongly affected by the ratio
between PMA arms and EGDA crosslinker. Lower ratios
(1:5) produced star polymer with a molecular weight of
34,430 g/mol, Narm (number of arms) = 7, and conversion
rate of 60%. However, when they increased the amount
of the EGDA crosslinker in the system (1:15), the final star
polymer had a molecular weight of 268,800 g/mol,
Narm = 56, and a conversion rate of 96%. Additionally, the
length of the polymer arm had a huge impact on the for-
mation of the star polymer. When short arms were used
(Mn = 4040 g/mol), star-star coupling occurred, leading to
the formation of high molecular weight multistars. How-
ever, when longer arms were used (Mn = 10,220 g/mol),
the conversion rate of the arm to star polymer decreased
to 89% compared to the conversion rate of 94% when the
shorter arm was used (Mn = 6000 g/mol) due to steric hin-
drance between the arms.

LEE ET AL.
An alternative approach in the synthesis of star poly-
mers involves a “core-first” strategy. In 2019, Allison-
Logan et al. prepared ultra-high molecular weight star
polymer through photoinduced RAFT polymerization by
using tetrafunctional xanthate-based (4-XAN) CTA cores
to polymerize DMA arms.48 The Z-group approach was
used to polymerize the arms of the star polymers to pre-
vent any star-star coupling, a common side reaction
when using the R-group approach. Due to the highly liv-
ing property of the xanthate-based CTA, authors were
able to synthesize star polymers with an extremely long
arm degree of polymerization (DParm = 10,100). The
polymerized PDMA arms had a molecular weight of
0.96 Mg/mol with a conversion rate of 96% and a total
molecular weight of 3.8 Mg/mol for star polymer. Inter-
estingly, light had a significant impact on the polymeriza-
tion kinetics. To achieve high conversion of monomers to
star polymers ( 96%), it took 6 h of reaction time under
UV light (λmax = 365 nm) irradiation while it took 102 h
under violet light (λmax = 401 nm) irradiation. Addition-
ally, the authors prepared multifunctional xanthate-based
CTA cores by using β-cyclodextrin (21 arms). After 18 h
of reaction under UV light irradiation, the final polymer
had a DParm of 11,000 with 96% monomer conversion
(total molecular weight of 21.9 Mg/mol), confirming the
successful synthesis of star polymers with ultra-high
molecular weight.
By taking advantage of the photoinduced polymeriza-
tion, Foster et al. developed an automated photoinduced
RAFT technique to synthesize star polymer using a liquid
handling robot. In contrast to a previous study by Alli-
son-Logan et al.,48 the authors used the R-group
approach to avoid broad molecular distribution caused
by steric hindrance in the Z-group approach. However,
the R-group approach is still prone to star-star coupling
due to bimolecular radical termination. Foster et al. over-
came this problem by incorporating photocatalyst
(5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphine
zinc, ZnhTPP) in the reaction. The electron transfer from
the ZnhTPP catalyst to trithiocarbonate-based CTA leads
to the formation of trithiocarbonate anion and a radical
species that can propagate the polymerization. As these
fragments can recombine and return the electron to
ZnhTPP, it enables reversible capping of the propagating
radicals, which then reduces the probability of star-star
coupling or termination (Figure 11). The reaction was
conducted in 96-well plates to run multiple simultaneous
reactions by using trithiocarbonate-based CTA with 3 ini-
tiating sites (Narm = 3). Since the authors found that
polymerization of the first block was slow, they first syn-
thesized poly(N-acryloylmorpholine) (PACMO) with
DParm of 10 and used this as a macroCTA to synthesize
decablock star polymers. By using macroCTA, either
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9
F I G U R E 1 1 Comparison of termination routes in
conventional RAFT and PET-RAFT polymerizations. Reprinted
with permission.49 Copyright 2022, American Chemical Society.
ACMO or DMA blocks were polymerized using ZnhTPP
as a photocatalyst under green light irradiation
(λmax = 565 nm). After 4 h for each block extension, a
robot was programmed to take aliquots for analysis and
add fresh monomer solution for block extension. Interest-
ingly, the authors found that it was important to main-
tain constant catalyst concentration for each block
extension. Without the addition of fresh catalysts in each
stage, only a slight increase in the molecular weight was
observed after the 5th block. However, with the addition
of fresh catalysts in each stage, a linear increase in the
molecular weight was observed up to the ninth block
with moderate dispersity (Đ < 1.70).
Buss et al. introduced O-ATRP using multifunctional
initiators possessing 2, 3, 4, 6, and 8 alkyl bromide initiat-
ing functionalities.50 The authors polymerized star poly-
mers with MMA side chains with a target DParm of
50 catalyzed by using 3,7-di(4-biphenyl)-1-naphthalene-
10-phenoxazine as a photocatalyst. At dilute conditions
(1:2 vol. ratio of monomer to solvent), star polymers
achieved conversion rates of >50% with low dispersities
(Đ < 1.33) regardless of the Narm of the star polymer. The
authors hypothesized that the low monomer concentra-
tion of the polymer solution was the main reason for a
low conversion rate of monomer to arm of the star poly-
mer. As expected, the experiment conducted at a higher
concentration (1:1 vol. ratio of monomer to solvent)
increased the conversion rates to >84%, however, with
higher dispersities (Đ < 1.90). Significantly, regardless of
the solution concentration and Narm of the star polymer,
no star-star coupling events were observed in all cases,
indicating controllable synthesis of star polymer through
a “core-first” approach.
Cuthbert et al. demonstrated a simple approach to
synthesizing degradable star polymers using photoCRP
techniques.51 This was achieved by incorporating tannic
acid (TA), a biodegradable polyphenol-based molecule
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10 LEE ET AL.

with 25 hydroxy groups found in plants, as a core of the

star polymer. By using TA, authors were able to synthe-
size a biodegradable core with 25 ATRP initiating sites
through an esterification reaction. Both MMA and ethyl-
ene glycol (EO) were polymerized as an arm of the star
polymer under UV light (λmax = 365 nm) irradiation. All
of the resulting star polymers, regardless of arm chemis-
tries, had low molecular weight dispersities (Đ < 1.30)
except for one case when star polymer with a long arm
was synthesized (DParm = 37). Additionally, since the TA
molecule is biodegradable, TA-based star polymers were
degradable in the presence of a base (NaHCO3). After
72 h of reaction, they confirmed successful cleavage of
the polymer arms from the TA core. However, due to the
innate sterically hindered structure of TA, it was found
that grafting densities of the resulting star polymers were
low (32%–53%).
In addition to various approaches to synthesizing star
polymers, Bradford et al. developed a technique to
synthesize helical-shaped star polymer by using ortho-
phenylene hexamer (oP6(OH)6) as a core of a star poly-
mer.52 oP6(OH)6 was chosen for the core as it has a com-
pact helix structure (folded) where all dihedral angles are
55 (Figure 12A). The authors first attached the
trithiocarbonate-based CTA to the oP6(OH)6 core, as
depicted in Figure 12B. Upon blue light (λmax = 450 nm)
irradiation with tris[2-phenylpyridine]iridium(III) (Ir
(ppy)3) as a photocatalyst, various types of monomers
were successfully synthesized with target DParm of F I G U R E 1 2 (A) General structures of an ortho-phenylene
10, achieving low dispersity (Đ = 1.10–1.20). Then, the hexamer (oP6(OH)6) and its compact helix structure (folded).
(B) Attaching the trithiocarbonate-based CTA to the oP6(OH)6 core.
authors analyzed the structural conformation of
Reprinted with permission.52 Copyright 2023, Wiley-VCH.
the resulting star polymer proving that star polymers
maintained their folded structure regardless of the bulki-
ness of the monomers. To test the effect of the DParm on mass for the same hydrodynamic radius compared to its
the structure of the star polymer, oP6(MA)6 with various linear counterparts.55 Additionally, their globular struc-
DParm were synthesized (DParm = 10, 20, 40, 80). The ture endows them with abundant functional end-groups,
resulting star polymers had high conversion (>95%) with intramolecular cavities, and high solubility, which
low dispersity (Đ = 1.20–1.50). Interestingly, oP6(MA)6 enables their applications in adhesion, molecular imag-
still maintained their folded structure regardless of ing, and organic semiconductors.56–58 In photopolymeri-
DParm, indicating successful synthesis of helical-shaped zation, hyperbranched polymers are usually synthesized
star polymers with various arm chemistries. by double-monomer methodology involving copolymeri-
zation of inibramer as a comonomer with a monomer of
interest.41,59
2.3 | Hyperbranched polymers In 2013, Bektas et al. developed an approach to syn-
thesize hyperbranched polymers by using visible light-
Hyperbranched polymers are highly branched three- induced self-condensing vinyl polymerization (SCVP).61
dimensional polymers with random branch-on-branch The authors copolymerized 2-bromoethyl methacrylate
topology.53,54 Their hyperbranched structure is character- (2-BEMA) and MMA with dimanganese decacarbonyl
ized by degree of branching (DB), defined as the ratio of (Mn2(CO)10) under blue light irradiation (λ = 400–
branched and terminal units relative to that of the total 500 nm). During polymerization, 2-BEMA inibramer
possible branching sites. The morphology of the hyper- served as both a comonomer and branching site. Upon
branched polymer resembles micelles, with a high end- blue light irradiation, Mn2(CO)10 underwent irreversible
group density-to-volume ratio, leading to larger molar decomposition and abstracted a bromine atom, leading to

LEE ET AL.
the formation of initiating radicals in the 2-BEMA end-
group. Increasing the amount of 2-BEMA monomer,
Mn2(CO)10, and irradiation time increased both monomer
conversion rates and molecular weight of the resulting
hyperbranched polymer with the highest molecular
weight of 596,500 g/mol. Interestingly, increasing the
2-BEMA amount to 10 mol% resulted in gelation and
the formation of partially cross-linked polymers due to the
dual functionality of the 2-BEMA monomer. However, the
synthetic approach involved conventional free radical
polymerization, resulting in hyperbranched polymers with
uncontrolled structures. Therefore, in 2017, the same
group reported an O-ATRP technique to synthesize hyper-
branched polymers with controlled structures.60 They
used a similar approach, except 2-(2-bromo-isobutryloxy)
ethyl methacrylate (BIBEM) was used as an inibramer
instead of 2-BEMA. BIBEM was copolymerized with
MMA to form hyperbranched polymers (Figure 13). As
expected, increasing the amount of inibramer (BIBEM)
and light irradiation time resulted in an increase in mono-
mer conversion and polymer molecular weight, with the
highest molecular weight achieved of 604,000 g/mol
(Đ = 6.2 with degree of branching of 0.39). Additionally,
increasing the inibramer amount to 40 mol% and 12 h of
light irradiation resulted in gelation of the product, sug-
gesting the importance of the reaction conditions in con-
trolling the structure of the hyperbranched polymers.
Rong et al. demonstrated photoinduced RAFT poly-
merization of hyperbranched polymers in a flow reactor
system.62 The authors first synthesized the RAFT inibra-
mers, BTPEMA, and 2-(2-(n-butyltrithiocarbonate)propio-
nate)ethyl acrylate (BTPEA). Under green light irradiation
with Eosin Y as a photocatalyst, hyperbranched polymer
F I G U R E 1 3 o-ATRP
synthetic approach to
hyperbranched polymer by
copolymerizing BIBEM with
MMA under light irradiation.
Reprinted with permission.60
Copyright 2017, American
Chemical Society.
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11
was synthesized by copolymerizing RAFT inibramer with
poly(ethylene glycol) methyl ether acrylate (PEGMEA) as
a monomer. Reactions were conducted in both batch and
flow reactor systems. Interestingly, monomer conversions
were low (<5%) for the batch reactor system, regardless of
the RAFT inibramer. The highest conversion, 77%, was
achieved using flow and a total of 20 h of reaction time,
resulting in a product with molecular weight dispersity
Đ < 1.6. The authors concluded that higher conversion
was achieved in the flow system due to more uniform
light irradiation compared to the batch system. This
enhanced the reaction rate in the flow system. Addition-
ally, the versatility of the approach was tested by chain
extension polymerization of ethylene glycol methyl ether
acrylate (EGMEA) monomer achieving a molecular
weight of 19,500 g/mol with dispersity Đ = 1.58.
While previous examples were limited to photoin-
duced controlled radical polymerization, either thiol-ene
or thiol-yne reactions are also common alternative
approaches to synthesizing hyperbranched polymers. In
2016, Cook et al. presented an approach to synthesize
hyperbranched polymers with well-controlled architec-
tures.63 The approach involved photopolymerization of
the thiol-yne reaction of bifunctional (thiol/yne) mono-
mer (prop-2-ynyl 3-mercaptopropanoate) with trialkyne
core (tri(prop-2-yn-1-yl) 1,3,5-benzene-tricarboxylate)
under UV light (λmax = 365 nm) irradiation (Figure 14).
The authors found that using a trialkyne core was impor-
tant for synthesizing hyperbranched polymers with low
molecular weight dispersities. Without the trialkyne core,
the synthesized hyperbranched polymers had a molecular
weight of 16,100 g/mol with a degree of branching
(DB) of 0.84 and high molecular weight dispersity

12
F I G U R E 1 4 Synthesis of hyperbranched polymers via
thiol-yne reactions. Reprinted with permission.63 Copyright 2016,
American Chemical Society.
(Đ = 2.88). However, the addition of trialkyne core in the
system (1.1 M) significantly decreased the molecular
weight dispersity (Đ = 1.44) of the hyperbranched poly-
mers with similar molecular weight (19,600 g/mol) and
degree of branching (DB = 0.82).
The solution concentration was also found to impact
the molecular weight and dispersity of the hyperbranched
polymers. As the solution concentration increased, the
molecular weight and dispersity of the product increased
from 13,300 g/mol (Đ = 1.38) to 77,700 g/mol (Đ = 4.44)
for 0.5 M and 2.0 M, respectively.
In 2023, Kapil et al. presented an open-air photoinduced
ATRP technique under biologically relevant conditions to
synthesize hyperbranched polymers.64 The authors chose
2-bromoacrylic acid (BAA) as a starting material. BAA forms
sodium 2-bromoacrylate (SBA), which acts as an inibramer,
when dissolved in an aqueous solution of Na2CO3. After the
in situ formation of SBA in aqueous solution, oligo(ethylene
oxide) methyl ether methacrylate (OEOMA) was copolymer-
ized with SBA using Eosin Y as a photocatalyst and CuBr2/
TPMA as a deactivator under green light (λmax = 520 nm)
irradiation. After 30 min of reaction, OEOMA-based hyper-
branched polymer was synthesized with a molecular weight
of 81,000 g/mol and low molecular weight dispersity
(Đ = 1.19). The authors were able to control the molecular
weight of the hyperbranched polymer by simply lowering
the initiator concentration in the solution. Due to the mild
reaction conditions, they were able to graft hyperbranched
polymers directly from biomacromolecules. Hyperbranched
protein-polymer conjugates were synthesized by copolymer-
izing SBA inibramer with 3-[[2-(methacryloyloxy)ethyl]-
dimethylammonium] propionate (CBMA) using chymotryp-
sin with α-bromoisobutyrate groups as a macroinitiator.
The synthesized bioconjugate had a molecular weight
of 480,000 g/mol with low molecular weight dispersity
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LEE ET AL.
(Đ = 1.38), indicating uniform grafting of hyperbranched
polymers.
2.4 | Cyclic polymers
Cyclic polymers, distinguished by their ring-like architec-
ture without chain ends, exhibit unique characteristics
that set them apart from other polymer architectures.65,66
Their closed-loop architecture leads to higher effective
intramolecular repulsion between polymer segments,
leading to improved mechanical properties and potential
usage in biomaterial applications. While some cyclic
photopolymerization techniques involve step-growth
polymerization,67,68 there are a handful of studies on
photoinduced CRP of cyclic polymers. In 2021, Hakobyan
et al. demonstrated an approach to synthesize a cyclic
polymer through intermolecular cyclization of homo-tele-
chelics.69 They first synthesized the homo-telechelic by
using photoinduced RAFT polymerization using either
xanthate-based or trithiocarbonate-based CTA with bis-
muth oxide (Bi2O3) as a catalyst under irradiation with
compact fluorescent lamp (CFL). Regardless of CTA type,
the synthesized polymers had controllable molecular
weight with moderate dispersity (Đ < 1.70). Through
aminolysis of synthesized polymers, the CTA end-groups
were removed, resulting in polymer chains with thiol
( SH) end-groups. Interestingly, the CTA was completely
removed in xanthate-based polymers while dimers were
formed in trithiocarbonate-based polymers. Upon addi-
tion of iron trichloride to the polymer solution with thiol
end-group, the telechelics underwent intermolecular
cyclization at a dilute concentration (0.05 mg/mL) to
form cyclic polymers (Figure 15).
2.5 | Surface-initiated polymer brushes
The physical and chemical properties of surfaces can be
modified by tethering polymers, resulting in robust chemi-
cal functionality.70,71 Photopolymerization methods for
surface grafting generally involve a “grafting-from”
approach from surface-bound initiators, enabling precise
control of the functionality, density, and thickness of poly-
mer brushes. There are broad applications of polymer
brush coatings, including antibacterial coatings and bio-
sensing platforms.72,73
In 2013, Poelma et al. demonstrated a method to con-
trol the brush formation on the silicon oxide surface
through visible light-mediated radical polymerization.74
First, the authors functionalized silicon oxide with
trichlorosilane-substituted α-bromoisobutyrate-based initia-
tors, achieving grafting density of 0.27 ± 0.02 chains/nm2.

LEE ET AL.
F I G U R E 1 5 Intermolecular cyclization of homo-telechelics.
Reprinted with permission.69 Copyright 2021, American Chemical
Society.
F I G U R E 1 6 (A) Patterning of polymer brushes on the surface
of silicon oxide with trichlorosilane-substituted
α-bromoisobutyrate-based initiators with (B) spatial control and
(C) gradient control. Reprinted with permission.74 Copyright 2013,
Wiley-VCH.
Then, MMA was polymerized using fac-tris(2-phenylpyri-
dine)iridium(III) (fac-[Ir(ppy)3]) as a photocatalyst under
visible light irradiation (CFL) (Figure 16A). Three factors
were varied to control the architecture of the brush layer
on the surface: light exposure time, photomasking, and
optical density. It was found that the brush height was line-
arly dependent on the light exposure time. The produced
brushes with a height of 25 nm after 10 min for light expo-
sure and 115 nm after 60 min of light exposure. They also
demonstrated spatial control over brush growth using pat-
terning (Figure 16B). Using light irradiation through a pho-
tomask, MMA was polymerized only in the unmasked
regions. They achieved a high resolution of the patterned
structure due to the short excited state lifetime ( 50 ns) of
the fac-[Ir(ppy)3] photocatalyst. Lastly, it was found that
brush height was inversely proportional to optical density
of the photomask. In order to test this relationship, the sur-
face was covered by a grayscale photomask with gradient
optical density (0.2–0.9) (Figure 16C). Brush heights of 42
and  16 nm were produced using photomasks with opti-
cal densities of 0.2 and 0.9, respectively. This study shows
the advantages of the photopolymerization technique to
precisely control the architecture of the brush on a surface.
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13
In 2023, Rong et al. developed an approach to synthesize
hyperbranched polymer films using oxygen-tolerant SI-
RAFT polymerization.75 Their approach could produce poly-
mer brushes with linear, branched, linear-block-branched,
and branched-block-linear polymers tethered to a surface.
The authors first attached the carbazole-functionalized
BTPA (Cbz-BTPA) and hydroxyl-terminated carbazole
(Cbz-OH) on the gold-coated glass substrate by electrodepo-
sition. Cbz-OH was used to provide additional space on the
surface for the hyperbranched polymers to grow. To synthe-
size the linear brush, PEGMEA was polymerized by using
Eosin Y as a photocatalyst and triethanolamine (TEOA) as
an electron donor under green light (λmax = 506 nm) irradi-
ation, achieving a brush height of 10 nm after 2 h of irradia-
tion. When acrylate-functionalized BTPA inibramer (2-(n-
butyltrithiocarbonate)propionate acrylate), which acted as
both CTA monomer and branching point, was copolymer-
ized with PEGMEA, the branched structure was formed
with the height of 17 nm after 2 h of green light irradiation.
By sequential addition or alternating the order of the desired
monomers, more complex structures such as linear-block-
branched and branched-block-linear structures were formed
with brush heights of 21.8 and 33.8 nm, respectively.
Seo et al. further developed an open-air SI-RAFT
polymerization by using glucose oxidase (GOx) for in situ
oxygen removal.76 The incorporation of GOx in the pres-
ence of glucose (reducing agent) resulted in the reduction
of molecular oxygen. By using this method, a PDMA
brush was synthesized on the BTPA-grafted silicon sur-
face under ambient conditions. Upon green light
(λmax = 530 nm) irradiation, the brush height reached
30 nm after 15 min and reached 100 nm after 2 h of light
irradiation. They found that the stability of the GOx was
crucial to the open-air photopolymerization. When DI
water was used as a reaction solvent, a brush height of
50 nm was observed after 2 h of light irradiation. How-
ever, when nanopore water (MilliQ) was used as a sol-
vent, a brush height of 100 nm was achieved after the
same irradiation time. The authors concluded that
the difference in the brush heights was due to the resid-
ual minerals and salts in the DI water which affected
GOx stability and as a result decreased the reaction kinet-
ics. Lastly, to test the importance of the GOx in the poly-
merization, the reaction was conducted in the absence of
GOx. As expected, little to no polymer brush growth was
observed ( 10 nm) demonstrating the GOx for enabling
polymerization.
Binary polymer brushes, which include two different
polymer brushes grafted on the surface, have gained great
interest for functional coatings and micro-electromechanical
materials.78–80 However, current methods to fabricate sur-
faces with binary polymer brushes are often limited to
surface-initiated photopolymerization from the surface with
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14 LEE ET AL.

F I G U R E 1 7 (A) Schematic illustration of negative-type patterning of polymer brushes on the surface of silicon oxide with alkyl iodide
(R-I) initiator. (B) Comparison between brush height in masked and unmasked regions. (C) Preparation of binary polymer brushes using
sequential polymerization reactions along with partial masking of the surface. (D) contact angle measurements reflecting the hydrophobicity
or hydrophilicity of the brush grafted on the surface. Reprinted with permission.77 Copyright 2018, Wiley-VCH.

pre-patterned initiators. To overcome this limitation, Wang
et al. demonstrated a simple approach to synthesizing
binary polymer brushes using an alkyl iodide (R-I) initiator,
which can be degraded under UV light (λmax = 250–
385 nm) irradiation, as shown in Figure 17A.77 The authors
demonstrated both positive-type and negative-type pattern-
ing using this initiator. To demonstrate, positive-type
patterning, they grafted the R-I initiator (6-(2-iodo-2-isobu-
tyloxy) hexyltriethoxysilane, IHE) on the silicon wafer.
Next, they polymerized benzyl methacrylate (BzMA)
through a glass photomask using 10 ,30 -dihydro-8-methoxy-
10 ,30 ,30 -trimethyl-6-nitrospiro[2H-1-benzopyran-2,20 -(2H)
indole] (DHMI) as a photocatalyst under visible light irradi-
ation (λmax = 550 nm). This produced a brush height of
64 nm only for the exposed portions of the surface. They
could also produce negative patterns by exposing the
surface to UV light to degrade the initiator. By selectively
degrading unmasked regions of the surface, a brush
height remained constant only in masked regions
(Figure 17B). Finally, they combined positive and
negative-type approaches to produce surfaces selectively
patterned with different types of brushes. As shown in
Figure 17C, employing photomask allows the sequential
polymerization of the hydrophobic 1H,1H,2H,2H-tride-
cafluoro-n-octyl methacrylate (PRfMA) and hydrophilic
poly(poly(ethylene glycol) methyl ether methacrylate)
(PPEGMA) polymer brushes as well as removal of the
R-I initiator to deactivate the polymerization in specific
regions. Contact angle measurements supported the suc-
cessful fabrication of the binary polymer brushes with
water contact angle measurements of 113 and 51 for
hydrophobic and hydrophilic regions, respectively
(Figure 17D).
While previous papers focused on the synthesis of
polymer brushes on glass or silicon substrate, Hou et al.
prepared homogenous polymer brushes on the surface of
the metal–organic framework (MOF) nanoparticles and
membranes without immobilization of external initia-
tors.81 MOFs are usually comprised of various functional-
ities including amino or phenol groups. Due to the low
bond dissociation energies of these R-H bonds, hydrogen
atoms from these functional groups can be abstracted to
form radicals on the MOF surface, which will serve as
initiating sites for the photoinduced free radical polymer-
ization. MOF (UiO-66-NH2) nanoparticle was grafted
with PMMA upon UV light (λmax = 300 nm) irradiation,
achieving a molecular weight of 470,000 g/mol with high
dispersity (Đ = 2.80). The authors showed that grafting
with PMMA on the surface of MOF significantly
increased the chemical and thermal stability of the mate-
rial. They showed that the porous structure of the
IRMOF-3 was preserved even after grafting with PMMA.
Additionally, unmodified MOF decomposed and porous
architecture was lost after 3 days of air exposure while
PMMA-modified MOF maintained its crystallinity and
porous structure.
2.6 | Future directions
1. Photoinduced Depolymerization of Polymers with
Nonlinear Architectures
Recent studies have shown that linear polymers syn-
thesized through controlled radical polymerization tech-
niques, such as ATRP and RAFT, can be depolymerized

LEE ET AL.
primarily at high temperatures (100–170  C) under
dilute reaction conditions (approximately 5–750 mM)
(Figure 18A,B).10,83,84 Moreover, these polymers can be
depolymerized in solvent-free condition at 150–230  C
with spontaneous removal of the depolymerized mono-
mers from the system.85–87 In 2023, Bellotti et al. demon-
strated that the rate of depolymerization could be
accelerated under visible light irradiation by using Eosin
Y as a photocatalyst.82 Eosin Y enhanced the activation
of the CTA group in the polymer chain, which led to fas-
ter macroradical generation and subsequent depolymeri-
zation. Compared to the depolymerization experiment
conducted without light and Eosin Y, the rate of the
monomer regeneration increased from 12 to 50% within
1 h of the reaction and from 40% to 70% within 8 h of the
reaction (Figure 18B).
F I G U R E 1 8 (A) Simplified comparison of ATRP mechanism
favoring polymerization and depolymerization. Reprinted with
permission.10 Copyright 2023, American Chemical Society.
(B) Comparison between kinetics of depolymerization with and
without the presence of Eosin Y photocatalyst. Reprinted with
permission.82 Copyright 2023, Royal Society of Chemistry.
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15
This work demonstrates that light accelerated the
average rate of depolymerization and the maximum
depolymerization rate in the system, and similar
approaches could potentially be applied to polymers with
nonlinear architectures that are synthesized by using
either photo or thermal CRP. Previous studies on the deg-
radation of polymers with nonlinear architectures have
generally been limited to degrading them to form macro-
monomers instead of the original monomers or the start-
ing reagents.88,89 This may be architecture-independent
and could provide a simpler and more energy-efficient
strategy for polymer degradation.
2. Heterogeneous photocatalysts
Various types of organic photocatalysts have been
developed to conduct light-mediated reactions.91,92 These
organic catalysts have advantages over inorganic catalysts
in terms of sustainability, cost, and safety, but they cannot
be easily recycled or separated from the final product.
Therefore, developing organic photocatalysts that can be
recycled multiple times should be a priority for future
work. Photoactive covalent organic frameworks (COFs)
provide a potential approach to recyclable and reusable
catalysts.30–32 COFs have high surface areas and can be
designed to have broad absorption spectra and highly
reductive conduction bands, favorable for their use as a
photocatalyst. Also, pore size and functionality can be
F I G U R E 1 9 (A) PhotoRAFT polymerization of methyl
methacrylate using FPB@SiO2. (B) Recycle of FPB@SiO2
photocatalyst for multiple photoRAFT polymerization. Reprinted
with permission.90 Copyright 2022, Royal Society of Chemistry.

16
molecularly tuned based on the desired reaction. Since
most COFs are completely insoluble in any solvent, they
can easily be separated and recovered through filtration
or centrifugation.29 Another example was reported in
2022 by Bell et al., in which they demonstrated an
approach to synthesize a reusable photocatalyst based on
polymerizing a fluorescein o-acrylate chain on the
surface of glass beads (≤106 μm).90 As shown in
Figure 19A, these polymer-grafted macroparticles
(FPB@SiO2) were used as a catalyst for photoRAFT of
MMA. In addition, FPB@SiO2 photocatalysts were
reused for up to eight subsequent reactions while achiev-
ing high monomer conversions (65.4 ± 4.9%) throughout
the test (Figure 19B). While immobilizing catalysts on a
surface introduces additional steps, developing recyclable
catalysts can enable large-scale and flow-based produc-
tion of polymers with nonlinear architectures and reduce
the costs associated with the purification and separation
of the final product.
3 | C ON C L U S I ON
PhotoCRP is a powerful method to produce well-defined
polymeric materials through spatially and temporally
controlled techniques and with nonlinear architectures.
The examples reviewed in this article demonstrate the
remarkable progress made in photoCRP techniques,
which can now be used to produce linear and nonlinear
architectures with a wide variety of chemistries. How-
ever, compared with thermally-activated CRP or RDRP,
photoCRP for the synthesis of nonlinear polymers
remains limited. The technique is still not widely used
in polymer engineering labs due to the need for specific
initiators or catalysts that are not commercially avail-
able. Consistency of the photoCRP technique can also be
a challenge, especially across different labs that rely on
different photoreactors or configurations. We hope this
review will help more polymer scientists and engineers
to use photoCRP techniques in their work or advance
photoCRP and related techniques. Future areas of inter-
est include photoinduced depolymerization and the
development of robust and versatile heterogeneous cata-
lysts to perform photoCRP.
A C K N O WL E D G M E N T S
The authors acknowledge support from the Welch Foun-
dation for Chemical Research (C-2124) and the National
Science Foundation CHE-2247729.
ORCID
Dongjoo Lee https://orcid.org/0000-0002-8319-7878
Rafael Verduzco https://orcid.org/0000-0002-3649-3455
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LEE ET AL.
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18 LEE ET AL.

AUTHOR BIOGRAPHIES
B.S. in chemical engineering from Rice University in
2001. Rafael then went on to a postdoctoral position
Dongjoo Lee received his B.S. in the Center for Nanophase Materials Sciences at the
degree in Chemical Engineering Oak Ridge National Laboratory in Tennessee, where
from Pennsylvania State Univer- he studied bent-core liquid crystals and conjugated
sity in 2019. He is currently pur- polymeric materials for organic electronics. The Ver-
suing a Ph.D. degree in Chemical duzco laboratory uses a combination of polymer
and Biomolecular Engineering at chemistry and multiscale characterization tools to
Rice University, working under broadly address challenges in polymer science, and
the supervision of Prof. Rafael current areas of research include polymers for micro-
Verduzco. His research focuses on bial bioelectronics, polymeric membranes for water
understanding the properties of bottlebrush polymer treatment, and bottlebrush polymer additives for sur-
additives and innovative chemistries for synthesizing face modification.
bottlebrush polymers.
Hanqing Wang is an undergrad-
uate student at Rice University,
majoring in Chemical and Biomo- How to cite this article: D. Lee, H. Wang,
lecular Engineering. Starting in R. Verduzco, J. Polym. Sci. 2024, 1. https://doi.org/
2022, she started to work as an 10.1002/pol.20230889
undergraduate researcher under
the guidance of Prof. Rafael Ver-
duzco. Her current research inter-
est includes the synthesis of
degradable bottlebrush polymers under mild reaction
conditions.
Rafael Verduzco is a Professor
of Chemical and Biomolecular
Engineering and Materials Sci-
ences and NanoEngineering at
Rice University. He received his
Ph.D. in chemical engineering
from the California Institute of
Technology in 2007 studying liq-
uid crystal polymer gels and his