Article

Cite This: Langmuir 2019, 35, 3470−3478 pubs.acs.org/Langmuir

Design, Synthesis, and Application of a Difunctional Y‑Shaped

Surface-Tethered Photoinitiator
Shuxiang Zhang, Wenying Liu, Yishi Dong, Ting Wei, Zhaoqiang Wu,* and Hong Chen*
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical
Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
*
S Supporting Information

ABSTRACT: Mixed homopolymer brushes have unique

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interfacial properties that can be exploited for both

fundamental studies and applications in technology. Herein,
the synthesis of a new catechol-based biomimetic Y-shaped
binary photoinitiator (Y-photoinitiator) and its applications for
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surface modification with polymer brushes through both

“grafting to” and “grafting from” strategies are reported. The
“leg” of the Y consists of a catechol group as surface anchoring
moiety. The arms are photoinitiator moieties that can be
“addressed” independent of each other by radiation of different
wavelengths. Using ultraviolet and visible light successively,
each arm of the Y-photoinitiator was activated, thereby
allowing the synthesis of Y-shaped block copolymer brushes
with dissimilar polymer chains. The suitability of the Y-photoinitiator for surface modification was first investigated using N-
vinylpyrrolidone and styrene as the model monomers for successive UV-photoiniferter-mediated polymerization and visible-
light-induced polymerization, respectively. Switching of the wetting properties of the Y-shaped block copolymer brush poly(N-
vinylpyrrolidone)-block-poly(styrene) (PVP-b-PS)-grafted surfaces by contact with different solvents was also investigated. To
further exploit this novel Y-photoinitiator for the preparation of functional interfaces, Y-shaped block copolymer brushes
poly(1-(2-methacryloyloxyhexyl)-3-methylimidazolium bromide)-block-poly(N-vinylpyrrolidone-co-glycidyl methacrylate)
(PIL(Br)-b-P(NVP-co-GMA)) were also prepared and subsequently functionalized with the cell-adhesive arginine−glycine−
aspartic acid (RGD) peptides by reaction with the glycidyl groups (PILPNG-RGD). The PILPNG-RGD grafted surfaces
showed excellent cell-adhesive, bacteriostatic, and bactericidal properties. Thus, it can be concluded that further exploitation of
this novel Y-photoinitiator for graft polymerization should allow the preparation of a wide range of functional interfaces with
tailored properties.

■ INTRODUCTION
Mixed homopolymer brushes consist of two or more types of
polymer chains and can be used to prepare materials with
unique surface properties for many applications, such as
controlling adhesion (including bioadhesion), friction, and ion
transport.1−5 They can be obtained by surface-initiated
polymerization techniques using mixed monolayers of two
different initiators. For example, Vancso and co-workers
prepared mixed brushes from mixed self-assembled monolayers
(SAMs) of separate photoiniferter and atom transfer radical
polymerization initiators.6 However, mixed SAMs may not
guarantee a well-distributed layer of the two initiators if one
initiator is more preferentially adsorbed to the surface than the
other. In addition, due to differences in the attachment
processes for the different polymers, it is difficult to achieve a
uniformly distributed layer whether by grafting to or grafting
from.7,8 This may result in the formation of “islands”
containing only one of the polymers. One solution for this
problem is to use a Y-shaped polymer molecule containing two
different polymer chains linked to a single “anchor” group that
can attached to a substrate.9,10 Alternatively, a binary Y-
initiator containing two distinct initiator moieties can be
used.2,11,12 Compared with mixed initiators, in using a single
anchor site via a binary Y-initiator, the possible formation of
single brush islands is eliminated. According to theoretical
predictions, such Y-shaped initiators should lead to uniform
mixed polymer brushes.13
Although a number of Y-shaped binary initiators based on
trichlorosilane, dimethylchlorosilane, or triethoxysilane anchor
moieties have been designed and have allowed the preparation
of well-defined mixed homopolymer brush surfaces,14−22 most
of these are appropriate for modification of a single material,
such as silicon wafer or silica particles.1 In addition, the
formation of mixed homopolymer brushes based on such
binary Y-initiators typically requires different advanced and
complex polymerization techniques.2 These limitations have
Received: December 30, 2018
Revised: January 29, 2019
Published: February 6, 2019

© 2019 American Chemical Society 3470 DOI: 10.1021/acs.langmuir.8b04323

Langmuir 2019, 35, 3470−3478
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Scheme 1. Synthesis of the Binary Y-Photoinitiatora
a
The green and red colors indicate the initiation sites for photoinitiated polymerization using two different wavelengths (λ1 and λ2). The blue color
indicates the catechol moiety used to attach the initiator to the solid substrates.
hindered the development of binary Y-initiators for surface
modification.
The objective of the present study was to design a Y-shaped
binary initiator that would overcome these limitations.
Motivated by the adhesion characteristics of catechols23,24
and the advantages of photoinitiated polymerization, including
facile procedure, mild reaction conditions and spatial
control,25,26 the design is based on a catechol-type biomimetic
Y-shaped photoinitiator (Y-photoinitiator). The leg of the Y
consists of a catechol group as surface anchoring moiety. The
arms are photoinitiator moieties, which can be “addressed”
independent of each other by radiation of different wave-
lengths (Scheme 1). This strategy takes advantage of
photoinitiated polymerization and of the adhesion character-
istics of catechol-based chemistry. The advantages of this
approach are that the two polymers can be grown
independently from each arm of the Y-photoinitiator simply
by variation of the radiation wavelength and that surface
properties can thus be varied over a wide range.
■
EXPERIMENTAL SECTION
Materials. All starting chemicals and solvents used in this work
were purchased from Sigma-Aldrich unless otherwise stated. Styrene
(St, 99%) was distilled from CaH2 under reduced pressure before
polymerization. N-vinylpyrrolidone (NVP, 98%) was purified by
distillation under reduced pressure to remove inhibitors before use.
Glycidyl methacrylate (GMA, 97%) was used after removing the
inhibitor by using an inhibitor remover (Sigma-Aldrich). Arginine−
glycine−aspartic acid (RGD) peptides were purchased from GL
Biochem. Co., Ltd (Shanghai, China). Dimanganese decacarbonyl
(Mn2(CO)10, 98%), serinol (98%), N-ethylpiperidine hypophosphite
(EPHP, 95%), 2-bromoisobutyryl bromide (98%), diethylamine
(98%), carbon disulfide (99%), acrylic acid (99%), N,N′-dicyclohex-
ylcarbodiimide (DCC, 98%), 4-dimethylamino pyridine (DMAP,
99%), 3,4-dihydroxyhydrocinnamic acid (98%), and other reagents
were of analytical grade and used as received. S-(Carboxypropyl)-
N,N-diethyldithiocarbamic acid (CNDDA), 2-(2-bromoisobutyryla-
mido) propane-1,3-diol (BPDL), and 1-(2-methacryloyloxyhexyl)-3-
methylimidazolium bromide (IL(Br)) were synthesized and purified
according to published procedures.27−29 Gold-coated silicon wafers
(80 nm of gold deposited on a 10 nm chromium adhesion layer) were
cut into 0.5 cm × 0.5 cm pieces. LIVE/DEAD BacLight Bacterial
Viability Kits were purchased from Invitrogen (ThermoFisher
Scientific). L929 cells were supplied by the China Center of Type
Culture Collection (Wuhan, China). Gram-negative Escherichia coli
(ATCC-25922) was provided by the China General Microbiological
Culture Collection Center (Beijing, China).
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Instruments and Measurements. Nuclear magnetic resonance
(NMR) spectra were taken using a Varian Mercury-400 spectrometer
(Varian). Fourier transform-infrared (FT-IR) spectra were recorded
on a Nicolet 6700 FT-IR spectrometer (ThermoFisher Scientific).
Mass spectra (MS) were obtained using a micrOTOF-Q III
instrument (Bruker, Germany). The number-average molar masses
(Mn) and polydispersity indices (PDI) of the synthesized polymers
were determined using a Waters 1515 gel permeation chromatograph
(GPC, Waters) with dimethylformamide (DMF) as solvent (flow rate
1.0 mL/min) at 30 °C. An ESCALAB MK II X-ray photoelectron
spectrometer (VG Scientific Ltd., England) was used to measure the
surface chemical compositions. A fluorescence microscope (BX51,
Olympus, Japan) was used to observe bacteria and cells on the
surfaces. Sessile drop water contact angle measurements were made
using a SL200C optical contact angle meter (USA Kino Industry Co.,
Ltd.). Polymer film thicknesses on modified gold surfaces were
measured using an α-SE spectroscopic ellipsometer (J.A. Woollam
Co., Inc.). The topography of the modified gold surfaces was studied
with a multimode-8 atomic force microscope (AFM) in tapping mode
(Bruker). GY250 devices with 365 nm centered ultraviolet light were
provided by Beijing Tianmaihenghui Electric Appliance Co., Ltd.
(China). Visible light of intensity I420nm = 0.2 mW/cm2 was obtained
by filtering the shorter wavelength UV light of a 500 W mercury lamp
using JB400 filters (China).
Synthesis of the Binary Y-Photoinitiator. The binary Y-
photoinitiator was synthesized by sequential ester condensations of S-
(carboxypropyl)-N,N-diethyldithiocarbamic acid (CNDDA) and the
commercially available 3,4-dihydroxyhydrocinnamic acid with 2-(2-
bromoisobutyrylamido) propane-1,3-diol (BPDL) (Scheme S1). The
intermediate compound, 2-(2-bromo-2-methylpropanamido)-3-hy-
droxypropyl 3-((diethyl-carbamothioyl)thio)propanoate (BPDL-
CNDDA), was synthesized via an etherification reaction between
BPDL and CNDDA. Briefly, BPDL (1.50 g, 6.20 mmol), DCC (1.60
g, 7.50 mmol), and DMAP (0.08 g, 0.66 mmol) were dissolved in 30
mL of dry tetrahydrofuran and a CNDDA (1.38 g, 6.20 mmol)
tetrahydrofuran solution was slowly added to the mixture. The
mixture was then stirred at room temperature for 36 h. After filtering
and removing the solvent, the product was purified using silica gel
column chromatography with ethyl acetate and hexane (1:1, v/v) to
give 1.10 g (40% yield) of a viscous white liquid. 1H NMR (CDCl3), δ
ppm: 7.10 (d, 1H, NH−), 4.29 (d, 2H, CH2−OH), 4.13 (m, 1H,
CH−), 4.01 (d, 2H, CH2−O−), 3.71 (m, 4H, (CH2)2−N−), 3.56 (t,
2H, CH2−S−), 2.84 (t, 2H, CH2−CO−), 1.94 (s, 6H, (CH3)2−C−),
1.25 (t, 6H, (CH3−CH2−)2) (Figure S1, Supporting Information).
The binary Y-photoinitiator was then conveniently prepared by
reaction of the intermediate compound with 3,4-dihydroxyhydrocin-
namic acid. In brief, BPDL-CNDDA (1.10 g, 2.50 mmol), DCC (0.61
g, 3.00 mmol), and DMAP (0.03 g, 0.25 mmol) were dissolved in 30
mL of dry tetrahydrofuran and placed in an ice bath. After adding 3,4-
dihydroxyhydrocinnamic acid (0.45 g, 2.5 mmol) in 10 mL of dry
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Figure 1. (a) 1H NMR and (b) 13C NMR spectra of Y-photoinitiator in CDCl3.
THF drop wise to the mixture, this container was transferred to a
glovebox (SG1200/750TS/F, Suzhou Weige Equipment Technology
Co., Ltd, China) and the reaction was taken to completion (36 h) at
60 °C. Finally, the mixture was filtered to remove the precipitate and
the solution was concentrated under vacuum, giving the crude
product, which was then purified by silica gel column chromatography
(ethyl acetate/hexane 1:1, v/v). The product was obtained as a white
solid (0.55 g, 36% yield). 1H NMR (CDCl3), δ ppm: 7.03 (d, 1H,
NH−), 6.79 (d, 1H, Aryl-H12), 6.71 (s, 1H, Aryl−H13), 6. 64(d, 1H,
Aryl-H11), 4.34 (m, 1H, CH−), 4.17(m, 4H, (CH2)2−O−), 3.72 (q,
2H, CH2−N−), 4.01 (q, 2H, CH2−N−), 3.56 (t, 2H, CH2−S−), 2.85
(m, 4H, (CH2)2−CO−), 2.61 (t, 2H, CH2−Ph), 1.91 (s, 6H,
(CH3)2−C−), 1.07 (t, 6H, (CH3−CH2−)2) (Figure 1a). 13C NMR
(CDCl3), δ ppm: 194.39 (CS), 172.01 (CO), 143.26 (Aryl−
C20,21), 132.46 (Aryl−C16), 120.52 (Aryl−C17), 114.95 (Aryl−
C18,19), 62.38 (C−O), 49.43 (C−Br), 48.41 (CH2−N), 46.66 (CH−
NH), 35.43 (CH2−S), 33.70 (CH2−CO), 31.95 (C−CH3), 31.23
(CH2−CH2), 29.90 (Aryl−C16−CH2−CH2) 12.35 (CH3−CH2)
(Figure 1b). FT-IR (cm−1): 1740 (s, v(O−CO)), 1640 (s,
v(NH−CO)), 1520 (s, δ(NH)) (Figure S2, Supporting Informa-
tion). ESI-MS: calculated for M+: m/z 608.10; found: m/z 609.11
(M+ + 1, M+ + H) (Figure S3, Supporting Information).
Preparation of Y-Shaped Block Copolymer Catechol-(PVP-
b-PS) Modified Surfaces (“Grafting to” Method). Synthesis of
Catechol-PVP Homopolymer. Y-photoinitiator (60.81 mg, 0.10
mmol), NVP (2.22 g, 20.0 mmol), and 3.0 mL of methanol were
placed in a 10 mL round flask, and the solution was deaerated by
bubbling with nitrogen gas for 30 min. The mixture was then
irradiated with 365 nm UV light at room temperature for 60 min.
Afterward, the dithiocarbamate end group of the resultant polymer
was removed using EPHP as a hydrogen atom donor according to
published procedures.30 The purified homopolymer catechol-PVP was
obtained after dialysis for 72 h and then vacuum freeze-dried. The 1H
NMR spectrum of the prepared catechol-PVP confirmed the efficient
photopolymerization via Y-photoinitiator. As shown in Figure S4, the
proton peaks at 1.3−.9 ppm correspond to the expected chemical
structure of PVP.31 In addition, the characteristic peaks at 6.4−6.8
ppm are attributed to protons in catechol group. Specifically, GPC
traces were unimodal and symmetrical and Mn and PDI of the
prepared catechol-PVP were 14 200 g/mol and 2.03, respectively
(Figure S5, Supporting Information).
Synthesis of Y-Shaped Block Copolymer Catechol-(PVP-b-PS).
Briefly, 0.1 g of catechol-PVP, Mn2(CO)10 (8.0 mg, 0.02 mmol), St
(0.83 g, 8.0 mmol), and 3.0 mL of DMF were placed in a 10 mL
round flask and the solution was deoxygenated by bubbling with
argon gas for 30 min. The mixture was then irradiated with visible
light at room temperature for 10 min. The purified Y-shaped catechol-
(PVP-b-PS) block copolymer was obtained by dialysis for 72 h and
then vacuum freeze-dried. The 1H NMR spectrum of the prepared
catechol-(PVP-b-PS) confirmed that photopolymerization via cat-
echol-PVP was successful. In the 1H NMR spectrum (Figure S6,
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Supporting Information), the characteristic peaks for the phenyl
protons in PS and the protons in PVP appeared at 7.2−7.6 and 1.3−
3.9 ppm, respectively. GPC traces were unimodal and symmetrical,
and the Mn and PDI of the prepared catechol-(PVP-b-PS) were 22
700 g/mol and 2.29, respectively (Figure S5, Supporting Informa-
tion).
Immobilization of Catechol-(PVP-b-PS) on Gold Surface (Au-
Catechol-(PVP-b-PS)). Gold-coated wafers were cleaned by a 30 min
ozone plasma treatment, washed with water and pure ethanol and
dried with nitrogen. The cleaned gold surfaces were then immersed in
a 30 mg/mL catechol-(PVP-b-PS) DMF solution mixed with 10 μL of
periodate (1.0 mg/mL) at room temperature,32 in which periodate
acted as an oxidant to activate the adhesion. After incubation for 24 h,
the gold surfaces were removed from the solution and washed with
DMF. Finally, they were dried with nitrogen, to give the Y-shaped
catechol-(PVP-b-PS) block copolymer-modified gold surfaces.
Preparation of Surfaces Modified with Mixed Homopol-
ymer Brushes Au-g-(PVP-b-PS) (“Grafting from” Method). Y-
Photoinitiator Immobilization on Gold Surface (Au-Y-Photo-
initiator). Briefly, cleaned gold surfaces were immersed in a 0.05
mol/L Y-photoinitiator DMF solution and mixed with 10 μL of
periodate (1.0 mg/mL) at room temperature. After incubation for 24
h, the gold surfaces were removed and washed with DMF and
methanol. Finally, they were dried with nitrogen to afford the required
Y-photoinitiator immobilized gold slides (Au-Y-photoinitiator).
UV-Photoiniferter-Mediated Graft NVP Polymerization. NVP
(2.22 g, 20.0 mmol) and 3.0 mL of methanol were placed in a 10
mL round flask, and the prepared Au-Y-photoinitiator slides were
immersed in the mixture. The solution was deoxygenated by bubbling
with argon for 30 min and then irradiated with a 365 nm UV light at
room temperature for 60 min. At the end of the irradiation, the PVP-
grafted gold substrates (Au-g-PVP) were treated with EPHP and
rinsed with methanol and dried in a nitrogen stream.
Successive Visible-Light-Induced Graft St Polymerization. Pre-
pared Au-g-PVP slides were placed in a 10 mL round flask containing
Mn2(CO)10 (8.0 mg, 0.02 mmol), styrene (0.83 g, 8.0 mmol), and 3.0
mL DMF. The flask was deoxygenated by bubbling with argon for 30
min and then irradiated with visible light at room temperature for 10
min. Finally, the product gold surfaces modified with mixed
homopolymer brushes (Au-g-(PVP-b-PS)) were rinsed with DMF
and methanol and dried in a nitrogen stream.
Water Contact Angles of Au-Catechol-(PVP-b-PS) and Au-g-
(PVP-b-PS) Samples. To investigate the changes in contact angle of
the grafted layers after treatment with different solvents, samples were
immersed, respectively, in toluene (good solvent for PS), water (good
solvent for PVP), or chloroform (nonselective good solvent for both
PS and PVP) for 24 h. Contact angles were measured within 10 min
after the solvent treatment.
Preparation of a Cell-Adhesive, Bacteriostatic, and Bacter-
icidal Coating (Grafting from Method). Preparation of PIL(Br)-
Grafted Surfaces. IL(Br) (2.5 g, 10.0 mmol), 3.0 mL of methanol,
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Scheme 2. Strategies of Grafting to and Grafting from for the Preparation of Mixed Homopolymer Brushes through Successive
Photoiniferter-Mediated Polymerization at 365 nm (λ1) and Visible-Light-Induced Polymerization at 420 nm (λ2) Steps Using
the Binary Y-Photoinitiator
and the prepared Au-Y-photoinitiator slides were placed in a 10 mL
round flask. The flask was deoxygenated with argon and then
irradiated with 365 nm UV light at room temperature for 60 min. At
the end of the irradiation, the PIL(Br)-grafted gold substrates (Au-g-
PIL(Br)) were treated with EPHP and rinsed with methanol and
dried with nitrogen.
Preparation of PIL(Br)-b-P(NVP-co-GMA)-Modified Surfaces.
Prepared Au-g-PIL(Br) slides were placed in a 10 mL round flask
containing Mn2(CO)10 (8.0 mg, 0.02 mmol), NVP (2.22 g, 20.0
mmol), GMA (0.29 g, 2.0 mmol), and 3.0 mL of CH3OH/DMF (1:1,
v/v). The flask was then deoxygenated by bubbling with argon for 30
min. After irradiation with visible light, it was kept at room
temperature for 30 min; the slides modified with mixed PIL(Br)-b-
P(NVP-co-GMA) brushes (Au-g-PILPNG) were rinsed with DMF
and methanol and dried under a nitrogen flow.
RGD Immobilization. The RGD peptides were immobilized onto
the Au-g-PILPNG substrates by nucleophilic ring-opening reaction
between amino groups of peptides and epoxy groups. Briefly, prepared
Au-g-PILPNG slides were immersed in a phosphate buffered saline
(PBS, pH 7.4) solution containing 2.0 mg/mL RGD at 55 °C for 12 h
under gentle shaking. The obtained surfaces (Au-g-PILPNG-RGD)
were removed from the reaction solution, rinsed with PBS buffer, and
dried with a stream of nitrogen.
Bacterial Attachment. Gram-negative E. coli was used as a modal
bacterium and cultured as previously reported.33 After sterilization
with 75% alcohol and washing twice with PBS, the sample surfaces
were incubated in 250 μL of E. coli suspension (1 × 107 CFU/mL) at
37 °C for 2 h to attach the bacteria. Afterward, the viability of the
attached bacteria on sample surfaces was measured using a LIVE/
DEAD BacLight Bacterial Viability Kits. Briefly, the staining solution
was first prepared by mixing 3 μL of SYTO 9 and 3 μL of propidium
iodide in 2 mL of PBS buffer. Then, 20 μL of a staining solution was
dropped onto the surfaces and incubated at room temperature in the
dark for 15 min. The surfaces were finally gently rinsed with sterile
water and dried under a nitrogen stream. The fluorescence images of
the stained bacteria on the surfaces were taken in a fluorescence
microscope, and Image Pro Plus analysis software was used to
determine the bacterial surface density.
Cell Adhesion. L929 cells were cultured in RPMI medium 1640
(Gibco), supplemented with 10% fetal bovine serum, 2 mmol/L
glutamine, 100 U/mL penicillin, and 10 mg/mL streptomycin. The
cultures were maintained at 37 °C in a humidified atmosphere
containing 5% CO2. The cells were seeded on gold substrates in a cell
culture plate at a density of 1.0 × 104 cells/cm3 and allowed to attach
for 6 h. The cytoplasm of live cells was stained with 4 μmol/L
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Calcein-AM (Dojindo Inc., Shanghai, China) for 10 min and then
washed thrice with PBS buffer for 2 min each. Images of cells were
recorded under a fluorescence microscope. The cell number was
obtained by analyzing the images of cells using the Image Pro Plus
analysis software.
■
RESULTS AND DISCUSSION
Synthesis of the Binary Y-Photoinitiator. The binary Y-
photoinitiator is synthesized in two steps (Scheme 1): first,
ester condensation of S-(carboxypropyl)-N,N-diethyldithiocar-
bamic acid (CNDDA) with 2-(2-bromoisobutyrylamido)
propane-1,3-diol (BPDL); second, condensation of 3,4-
dihydroxyhydrocinnamic acid with the product of step 1. In
Scheme 1, the green color highlights the visible-light initiator
moiety,4,34 the red, the photoiniferter moiety,35,36 and the blue,
the catechol moiety used to attach the initiator to the solid
substrate. The molecular structure of Y-photoinitiator was
confirmed using 1H and 13C NMR spectra, MS, and FT-IR
spectrum. The characteristic chemical shifts at 6.64−6.79, 1.91,
and 1.07 ppm (Figure 1a) are assigned to phenyl, CH3 groups
of 2-bromoisobutyrylamido fragment, and CH3 groups of
diethylcarbamodithioate fragment, respectively. The 13C NMR
spectrum showed chemical shifts at 194.4 and 172.0 ppm
assigned to the CS group in the diethylcarbamodithioate
fragment and carbonyl groups, respectively (Figure 1b). In
addition, the infrared peaks at 1740 and 1640 cm−1 are
attributed to O−CO, and NH−CO groups, respectively
(Figure S2, Supporting Information). These data indicate the
successful synthesis of the binary Y-photoinitiator.
Preparation of Au-Catechol-(PVP-b-PS) (Grafting to
Method). The suitability of the Y-photoinitiator for surface
modification through both grafting to and grafting from
strategies37 was first investigated using N-vinylpyrrolidone
(NVP) and styrene (St) as the model monomers for successive
UV-photoiniferter-mediated polymerization and visible-light-
induced polymerization, respectively (Scheme 2). For the
grafting to strategy, a Y-shaped catechol-(PVP-b-PS) block
copolymer was first prepared. From 1H NMR spectra showing
the characteristic chemical shifts for poly(N-vinylpyrrolidone),
polystyrene (PS), and catechol units (Figures S4 and S6,
Supporting Information), it may be concluded that the binary
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Y-photoinitiator is effective for the polymerization of both
monomers. Gel permeation chromatography (GPC) data
(Figure S5, Supporting Information) show that the number-
average molecular weight (Mn) of the initially obtained
Catechol-PVP was 14 200 g/mol and that of the Catechol-
(PVP-b-PS) block copolymer was 22 700 g/mol, again
indicating the successful polymerization of both monomers.
The catechol-(PVP-b-PS) with relatively high PDI values may
have resulted from bimolecular recombination between two
propagating radicals and disproportional reactions in the
photopolymerization process.35 It has been reported that a
unimolecular activation mechanism was preferred for the
grafting of the second brush component due to the steric
hindrance induced by the existing polymer chains.6 In this
work, the photoiniferter-mediated polymerization of NVP at
365 nm (λ1) was performed first since visible-light-induced
polymerization does not proceed in the absence of the catalyst
Mn2(CO)10.34 To avoid chain extension via the dithiocarba-
mate end group in the photoiniferter-mediated system during
the subsequent visible-light-induced polymerization of styrene,
the photoiniferter agent was removed using N-ethylpiperidine
hypophosphite (EPHP) as a hydrogen atom donor after the
photoiniferter-mediated polymerization step.30
Successful immobilization of the synthesized catechol-(PVP-
b-PS) polymer on gold, used here as a model surface but often
used in biosensors,38,39 was confirmed by X-ray photoelectron
spectroscopy (XPS) and ellipsometry. XPS spectra (Figure S7,
Supporting Information) showed that the unmodified gold
surface was composed mainly of Au, C, and O. After
immobilization of catechol-(PVP-b-PS), a substantial decrease
in Au from 63 to 29% and increases in C and O from 32 to
47% and 6−15%, respectively, were observed (Table 1). A
Table 1. Surface Analysis Data for Polymer-Modified Gold
Surfaces
XPS atomic concentration (%)
sample [Au] [C] [N] [O]
Au 62.70 31.70 5.60
Au-catechol-(PVP-b-PS) 28.65 46.89 6.14 14.85
Au-Y-photoinitiator 42.43 37.70 4.75 9.07
Au-g-PVP 15.37 54.49 9.52 16.40
Au-g-(PVP-b-PS) 17.84 59.19 5.48 14.88
nitrogen signal originating from the pyrrolidone ring was also
observed. From ellipsometry measurements, the thickness of
the immobilized catechol-(PVP-b-PS) polymer layer was found
to be ∼4.4 nm and using densities of 1.04 g/cm3 for PVP and
1.05 g/cm3 for PS,40,41 the graft density of catechol-(PVP-b-
PS) may be estimated from the following: δ = hρNA/Mn as
0.12 chains/nm,2,41 similar to values previously reported for
surface-bound Y-shaped amphiphilic brushes.10
Preparation of Au-g-(PVP-b-PS) (Grafting from
Method). For the grafting from strategy (Scheme 2), three
steps were required: (1) attachment of the binary Y-
photoinitiator to the substrate, (2) UV-photoiniferter-medi-
ated graft polymerization of NVP monomer, and (3) visible-
light-induced graft polymerization of styrene monomer. The
brush thickness and surface elemental composition were
determined after each step. As shown in Table 1 and in the
XPS spectra (Figure S7, Supporting Information), N and S
signals (5 and 6%, respectively) appeared in the XPS of the Y-
photoinitiator layer (Au-Y-photoinitiator) and the Au content,
Article
relative to gold, decreased from 63 to 42%. After UV-
photoiniferter-mediated graft polymerization of NVP at 365
nm (λ1) for 60 min (Au-g-PVP), a further decrease in Au
content and a substantial increase in N and O indicated the
successful grafting of PVP. Finally, visible-light-induced styrene
graft polymerization at 420 nm (λ2) (10 min) on the Au-g-PVP
surface (to give Au-g-(PVP-b-PS)) was confirmed by an
increase in C and decreases in N and O contents. Ellipsometry
measurements showed that after photoiniferter-mediated PVP
grafting and subsequent visible-light-induced PS grafting on
gold, the polymer thicknesses were ∼4.5 and ∼5.8 nm,
respectively, again confirming the successful formation of the
mixed homopolymer brush.
Stimuli-Responsive Behavior of Au-Catechol-(PVP-b-
PS) and Au-g-(PVP-b-PS) Brush Samples. The effects of
solvents on the microstructure and morphologies of Au-
catechol-(PVP-b-PS) and Au-g-(PVP-b-PS) layers were also
investigated using atomic force microscopy (AFM). In this
regard, it has been shown that the properties of conventional
mixed brush layers can change significantly under the influence
of selective solvents.42 In the dry state in air (a bad “solvent”),
both the PVP and PS arms collapsed, forming a relatively
homogenous dry layer with root-mean-square (RMS) surface
roughness of 0.46 and 1.69 nm for Au-catechol-(PVP-b-PS)
and Au-g-(PVP-b-PS), respectively (Figure 2a,a′). After
toluene treatment (good for PS, bad for PVP), the brushes
showed heterogeneous segregated surface morphologies
(Figure 2b,b′) and increased RMS roughness, possibly because
the topmost surface layer is composed mainly of low-surface-
energy PS. Compared with the dry state, the contact angle
increased by ∼5° after toluene treatment (Table 2), addition-
ally indicating the presence of a small amount of the
hydrophobic PS component in the copolymer brushes. In
contrast, after water treatment (good for PVP, bad for PS),
stratification of the polymer film was observed with PVP in the
topmost layer and PS underneath in contact with the gold
(Figure 2c,c′),43 in agreement with the water contact angles of
[S] 39 and 49° for Au-catechol-(PVP-b-PS) and Au-g-(PVP-b-PS)
surfaces, respectively (Table 2). In the case of chloroform, a
3.47 nonselective solvent good for both PVP and PS, the
6.05 confinement of dissimilar (hydrophobic and hydrophilic)
4.22 arms caused by covalent attachment to the same grafting
2.61 point leads to the suppression of microphase separation.10
AFM images of Au-catechol-(PVP-b-PS) and Au-g-(PVP-b-PS)
revealed that the grafted layers were of high quality with fairly
smooth surfaces (Figure 2d,d′).
Preparation of Au-g-PILPNG-RGD (Grafting from
Method). To further exploit this novel Y-photoinitiator for
the preparation of functional interfaces, a trifunctional coating
that repels contaminating bacteria, kills those that adhere, and
promotes cells adhesion was designed. Scheme 3 shows the
synthesis of the mixed PIL(Br)-b-P(NVP-co-GMA) brushes
with conjugated RGD peptides. PIL(Br) brushes were first
prepared through UV-photoiniferter-mediated graft polymer-
ization (Au-g-PIL(Br)). Due to their strong bactericidal
activity,44 this imidazolium-type ionic liquids brushes are
expected to kill the bacteria that adhere on the surfaces.
Afterward, P(NVP-co-GMA) brushes were fabricated on the
Au-g-PIL(Br) surfaces through visible-light-induced graft
copolymerization of NVP and GMA (Au-g-PILPNG). Each
GMA bears an epoxy group that can react with an amino group
in RGD, whereas the PVP provides the repelling property.45
Therefore, these copolymer brushes are expected to repel the
3474 DOI: 10.1021/acs.langmuir.8b04323
Langmuir 2019, 35, 3470−3478
Langmuir Article

Figure 2. AFM images (1.0 × 1.0 μm2 overview height scans) of Au-catechol-(PVP-b-PS) (a−d) and Au-g-(PVP-b-PS) (a′−d′) brush samples.
Scans are: a, a′ in air; b, b′ after toluene treatment; c, c′ after water treatment; d, d′ after chloroform treatment.

Table 2. Water Contact Angles (Degrees) of Au-Catechol- substrate, the static contact angle decreased by ∼23° after
(PVP-b-PS) and Au-g-(PVP-b-PS) Brush Samples after PIL(Br) grafting (Figure S8, Supporting Information), also
Different Solvent Treatments confirming the formation of a hydrophilic PIL(Br) layer. In
after after after
contrast, the water contact angle increased a little after the
toluene water chloroform subsequent P(NVP-co-GMA) grafting and RGD immobiliza-
sample in air treatment treatment treatment tion (Au-g-PILPNG-RGD). However, all conditions rendered
Au-catechol-(PVP-b-PS) 46 ± 2 51 ± 2 39 ± 2 38 ± 2 contact angle values lower (more hydrophilic) than the
Au-g-(PVP-b-PS) 55 ± 2 61 ± 2 49 ± 2 46 ± 2 unmodified gold substrate. It should be mentioned that the
nucleophilic ring-opening reaction between −NH2 in RGD
adhesion of contaminating bacteria and provide multiple peptides and epoxy groups was carried out in PBS solution
reactive sites for covalent immobilization of cell-adherent RGD (pH 7.4) at 55 °C for 12 h. Therefore, the amount of
peptides. unreacted epoxy groups should be very small and thereby
The brush thickness and static water contact angle were would not affect cell adhesion and other properties
determined after each step. Ellipsometry measurements significantly.46
showed that after photoiniferter-mediated PIL(Br) grafting Antibacterial Properties of the Au-g-PILPNG-RGD
and subsequent visible-light-induced P(NVP-co-GMA) grafting Surfaces. After confirming the successful preparation of the
on gold, the dry polymer thicknesses were ∼3.2 and ∼11.6 nm, PILPNG-RGD coating, a common clinically relevant Gram-
respectively, indicating the successful formation of the mixed negative bacterium E. coli was used as a model bacterium to
polymer brush. In addition, compared to the unmodified gold evaluate the antibacterial efficacy of the Au-g-PILPNG-RGD

Scheme 3. Strategies of Grafting from for the Preparation of Mixed PIL(Br)-b-P(NVP-co-GMA) Brushes through Successive
Photoiniferter-Mediated Polymerization at 365 nm (λ1) and Visible-Light-Induced Polymerization at 420 nm (λ2) Steps Using
the Binary Y-Photoinitiator and the Covalent Immobilization of RGD Peptides by Reaction with Epoxy Groups

3475 DOI: 10.1021/acs.langmuir.8b04323

Langmuir 2019, 35, 3470−3478
Langmuir Article

Figure 3. Fluorescent images of attached E. coli bacteria exposed to live/dead stains on Au (a), Au-g-PIL(Br) (b), Au-g-PILPNG (c), and Au-g-
PILPNG-RGD (d) after incubation at 37 °C for 2 h. The scale bar represents 100 μm. (e) Density of E. coli on the Au, Au-g-PIL(Br), Au-g-
PILPNG, and Au-g-PILPNG-RGD surfaces. Error bars represent the standard deviation of the mean (n = 3).

Figure 4. Fluorescent Calcein-AM staining images of L929 cells adhered on Au (a), Au-g-PIL(Br) (b), Au-g-PILPNG (c), and Au-g-PILPNG-RGD
(d) after being cultured for 6 h. The scale bar represents 100 μm. (e) Density of L929 cells on the Au, Au-g-PIL(Br), Au-g-PILPNG, and Au-g-
PILPNG-RGD surfaces. Error bars represent the standard deviation of the mean (n = 3).

surfaces. As shown in Figure 3a, the attached E. coli bacteria on
the unmodified gold surface were stained by a green stain,
which means they were alive with an intact membrane. In
contrast, most of the attached bacteria (∼86%) to the Au-g-
PIL(Br), Au-g-PILPNG, and Au-g-PILPNG-RGD surfaces
were dead (red stain), indicating that the surfaces containing
PIL(Br) brushes have excellent bactericidal properties (Figure
3b−d). Furthermore, due to the low fouling properties of PVP,
the adherent bacterial density was drastically reduced on the
PILPNG and PILPNG-RGD brush-modified surfaces (Figure
3e). Especially, compared with the unmodified gold surfaces,
the Au-g-PILPNG-RGD surfaces reduced the levels of bacterial
density by ∼96%. These results indicated that the PILPNG-
RGD brush-modified surfaces have excellent bacteriostatic and
bactericidal properties. This may attribute to the antifouling
character of PVP45 and the bactericidal properties of PIL(Br)
brushes,44 which repel bacteria adhesion and kill those that
adhere, respectively.
Cell Adhesion on the Au-g-PILPNG-RGD Surfaces. It is
well known that cell adhesion is the very initial interactions of
cells to substrates.46 Therefore, the effects of the modified gold
surfaces on cell adhesion were investigated by using
fluorescence microscopy after 6 h of incubation. As shown in
Figure 4a, only a few cells were observed on the unmodified
3476
gold surface, whereas on the Au-g-PIL(Br) and Au-g-PILPNG
surfaces, two contrast results were observed: a larger number of
cells adhered on the Au-g-PIL(Br) surfaces, whereas a fewer
number of cells attached to the Au-g-PILPNG surface (Figure
4b,c). This phenomenon can be explained by the antifouling
character of PVP and the electrostatic interaction between
PIL(Br) brushes and cells,47 which may resist and enhance cell
adhesion, respectively. In contrast to the Au-g-PILPNG
surface, the cells adhered on the Au-g-PILPNG-RGD surfaces
very well (Figure 4d). Compared to those on the Au-g-
PILPNG surfaces, the density of adhered cells cultured on the
Au-g-PILPNG-RGD surfaces was improved by nearly 3.4-folds
(Figure 4e), indicating that covalent immobilization of RGD
peptides on Au-g-PILPNG surfaces is an effective way to
enhance the cell-adhesive capacity but not bacterial adhesion.
This result can be explained by the fact that the RGD motif is
known to interact specifically with cell surface integrin
receptors, but is not recognized by bacteria.48 Taking these
results of cellular and bacterial behavior together, the methods
established in this study shed light on the design of other types
of multifunctional interfaces for diverse applications.
DOI: 10.1021/acs.langmuir.8b04323
Langmuir 2019, 35, 3470−3478
Langmuir
■ CONCLUSIONS
In conclusion, a new catechol-based biomimetic Y-shaped
photoinitiator was designed and used for surface modification
through both grafting to and grafting from strategies. For
grafting to, a Y-shaped catechol-(PVP-b-PS) block copolymer
was first prepared via successive UV-photoiniferter-mediated
polymerization and visible-light-induced polymerization and
subsequently immobilized directly on gold surface. For grafting
from, the Y-shaped photoinitiator was first immobilized on the
gold substrate; Y-shaped block copolymer brushes PVP-b-PS
with dissimilar polymer chains were then obtained by
successive surface-initiated photoiniferter-mediated graft poly-
merization of NVP and visible-light-induced graft polymer-
ization of styrene. Switching of the surface wetting properties
by treatment with selective solvents was also investigated.
Finally, to further exploit this novel Y-photoinitiator for the
preparation of functional interfaces, Y-shaped block copolymer
brush PILPNG-RGD-grafted surfaces were also prepared
through the grafting from approach and showed excellent
cell-adhesive, bacteriostatic, and bactericidal properties. In
principle, the method is feasible for any monomer amenable to
photoinitiated polymerization and can be used on different
substrates. This general approach should allow the preparation
of a wide range of functional surfaces with tailored properties.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.8b04323.
(i) General procedure for the synthesis of the binary Y-
photoinitiator; (ii) 1H NMR spectrum of BPDL-
CNDDA, catechol-PVP catechol-(PVP-b-PS); (iii) FT-
IR and MS spectrum of Y-photoinitiator; (iv) GPC
traces of the catechol-PVP and catechol-(PVP-b-PS)
block copolymer; (v) XPS survey spectra of modified
gold surfaces; (vi) water contact angles (degrees) of
modified gold surfaces (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: wzqwhu@suda.edu.cn (Z.W.).
*E-mail: chenh@suda.edu.cn (H.C.)
ORCID
Zhaoqiang Wu: 0000-0002-9921-4871
Hong Chen: 0000-0001-7799-4961
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grant no. 21774087).
■
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3478 DOI: 10.1021/acs.langmuir.8b04323

Langmuir 2019, 35, 3470−3478