RES EARCH

◥ (10–14). Sonication of longer cylindrical mi-

REPORT celles with a crystalline PFS core yields small
seed micelles that function as initiators for
MATERIALS SCIENCE living CDSA. Colloidally dispersed seeds have
been used to prepare a variety of nanostruc-
Tailored multifunctional micellar brushes via tures, including amphiphilic triblock co-micelles
(10), concentric platelet micelles (15), and hi-
crystallization-driven growth from a surface erarchical assemblies on longer length scales
(16). In addition, hybrid assemblies have been
Jiandong Cai1,2,3,4, Chen Li2, Na Kong1, Yi Lu1, Geyu Lin2, Xinyan Wang1, Yuan Yao1, fabricated by preceding the living CDSA step
Ian Manners2,5,6*, Huibin Qiu1,2* by surface confinement of the seeds. This ap-
proach has allowed the growth of fibers on
The creation of nanostructures with precise chemistries on material surfaces is of importance in a wide seed-covered silica nanoparticles (17) and homo-
variety of areas such as lithography, superhydrophobicity, and cell adhesion. We describe a platform for polymer crystal–coated carbon nanotubes (18).
surface functionalization that involves the fabrication of cylindrical micellar brushes on a silicon wafer We extend this technique to the functionaliza-
through seeded growth of crystallizable block copolymers at the termini of immobilized, surface-confined tion of surfaces through the immobilization
crystallite seeds. The density, length, and coronal chemistry of the micellar brushes can be precisely of short cylindrical micelle seeds of PFS BCPs
tuned, and post-growth decoration with nanoparticles enables applications in catalysis and antibacterial on silicon wafers and other substrates, and
surface modification. The micellar brushes can also be grown on ultrathin two-dimensional materials the subsequent growth of cylindrical micelle
such as graphene oxide nanosheets and further assembled into a membrane for the separation of oil-in- brushes via in situ living CDSA.

Downloaded from http://science.sciencemag.org/ on November 28, 2019

water emulsions and gold nanoparticles. A silicon wafer was selected as a model
material on which to immobilize the small seeds

A
variety of conventional methods, includ-
ing physical techniques [e.g., spray-based
methods (1) and spin-coating (2)] and
chemical routes [e.g., electrochemical
deposition (3) and heat treatment (4)],
have been developed to endow material sur-
faces with a wide range of targeted proper-
ties. Surface-initiated polymer brushes (5–8),
where one of the polymer chain ends is co-
valently attached to a solid substrate, have
emerged as a powerful and versatile approach
to surface functionalization. The living charac-
teristic of the covalent polymerizations used
to create polymer brushes allows for tailoring
of the surface chemistry at the molecular level.
However, the precise fabrication of patterned
surfaces using building blocks on longer length
scales represents a key challenge.
Block copolymers (BCPs) with a short, crys-
tallizable poly(ferrocenyldimethylsilane) (PFS)
core-forming block tend to form cylindrical (or
fiber-like) micelles with a crystalline PFS core
in selective solvents for the complementary
segment (9). The cylindrical micelle termini
remain active to the addition of further added
PFS BCP in the dissolved (unimer) state through
an epitaxial growth process termed living
crystallization-driven self-assembly (CDSA)
of PFS-b-P2VP [P2VP, poly(2-vinylpyridine)]
on the basis of the high density of surface
silanol groups, which should allow tenacious
1
School of Physical Science and Technology, ShanghaiTech
University, Shanghai 201210, China. 2School of Chemistry
and Chemical Engineering, Frontiers Science Center for
Transformative Molecules, State Key Laboratory of Metal
Matrix Composites, Shanghai Jiao Tong University, Shanghai
200240, China. 3Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China.
4
University of Chinese Academy of Sciences, Beijing 100049,
China. 5School of Chemistry, University of Bristol, Bristol
BS8 1TS, UK. 6Department of Chemistry, University of
Victoria, Victoria, BC V8P 5C2, Canada.
*Corresponding author. Email: hbqiu@sjtu.edu.cn (H.Q.);
imanners@uvic.ca (I.M.)

Fig. 1. Seeded growth of hydrophobic PFS53-b-

PDMS418 micellar brushes on a silicon wafer.
(A) Schematic illustration of the process, which involves
the immobilization of PFS36-b-P2VP502 seeds
(Ln = 139 nm, Lw/Ln = 1.04) on a silicon wafer via
H-bonding (and probably also assisted by electrostatic
interactions) followed by crystallization-driven
epitaxial growth of PFS53-b-PDMS418 micellar brushes.
(B to D) AFM height images of PFS53-b-PDMS418
micellar brushes of different densities formed under a
constant unimer-to-seed mass ratio (1:1 in the feed) but
different seed concentrations: (B) 0.125 mg/ml, (C)
0.25 mg/ml, (D) 0.5 mg/ml. (E) Plot of the dependence
of contact angle (CA) value on seed concentration.
Insets are photographs of the water droplets on the
micellar brush–coated silicon wafers prepared with
seed concentrations of 0.025 mg/ml (left) and
0.5 mg/ml (right). (F to H) AFM height images of
PFS53-b-PDMS418 micellar brushes formed at a
constant seed concentration (0.5 mg/ml) but different
amounts of unimers: (F) 2 ml, (G) 4 ml, (H) 6 ml. Insets in
(B) and (H) are enlargements of the boxed areas.
(I) Plot of the dependence of CA value on unimer
amount. Error bars in (E) and (I) denote SD of the
measured CA values (≥5 locations for each sample).

Cai et al., Science 366, 1095–1098 (2019) 29 November 2019 1 of 4

RES EARCH | R E P O R T

attachment through hydrogen bonding (H-
bonding) with the P2VP corona. Low-dispersity
PFS36-b-P2VP502 (where the subscripts refer to
the number-average degree of polymerization
of each block) micelle seeds with Ln = 139 nm
[L w /L n = 1.04, where L n and L w are the
number- and weight-average lengths, respec-
tively, determined by atomic force micros-
copy (AFM)] prepared from the sonication of
preformed long polydisperse cylinders (10)
(fig. S1) were anchored to the silicon wafer
via H-bonding (Fig. 1A). An AFM height image
(fig. S1D) showed that the PFS36-b-P2VP502
crystallite seeds were relatively evenly distrib-
uted on the silicon surface. The seed-coated
silicon wafer was then immersed in a mixture
of isopropanol and hexane (1:1, v/v), and mo-
lecularly dissolved PFS53-b-PDMS418 (PDMS,
polydimethylsiloxane) in the unimer state was
added as a solution in tetrahydrofuran (THF).
addition, substantially shorter PFS36-b-P2VP502
seeds (Ln = 58 nm, Lw/Ln = 1.03) at the same
concentration (0.5 mg/ml) were immobilized
on the silicon wafer (Fig. 2C) to favor the
growth of denser micellar brush arrays. Upon
addition of the PFS20-b-P2VP140 unimers (Fig.
2A), micellar brushes with increased diame-
ter of ~25 nm grew from the seeds on the sub-
strate and formed coral-like nanoassemblies
comprising pillars (revealed by the AFM
height images both in the solution and dry
state) (Fig. 2B and fig. S5). As a result of the
hydrophilic nature of the P2VP coronas, the
hydrophilicity was increased as the CA de-
creased to 67°. Such coral-like nanoassem-
blies could be fabricated on a large scale
covering a 1 cm × 1 cm piece of silicon wafer
with relatively few defects (undergrown or
overgrown sites) (fig. S6). The micellar brushes
remained standing as the length further in-
creased by the addition of unimer, but they
eventually collapsed beyond average heights
of ~40 nm (Fig. 2D and fig. S7).
Previous studies have established that PFS
BCPs with a longer PFS core-forming block
tend to form cylindrical micelles with a larger
core diameter (20). Hence, the use of PFS30-b-
P2VP226 with a longer PFS core-forming block
and relatively larger block ratio (RP2VP/PFS =
7.5 versus 7.0 for PFS20-b-P2VP140, where R is

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Unimers grew at the termini of the immobi-
lized seeds and eventually formed a layer of
nanoscopic brushes on the surface, as revealed
by AFM (Fig. 1, B to D and F to H, and fig. S2).
AFM analysis indicated that the micellar brushes
were ~20 nm in diameter (Fig. 1B, inset) and
had an extended fiber-like morphology with
lengths of ~1 mm. This indicated that the crys-
talline seeds immobilized on the silicon wafer
remained active and enabled the living growth.
Control experiments demonstrated that the
micellar brushes were almost entirely formed
by seeded growth that initiated on the surface
(figs. S2 and S3). The density of the micellar
brushes could be varied by the feed concen-
tration of seeds (Fig. 1, B to D, and fig. S1, D
and E). As a result of the presence of a PDMS
corona, the formation of a series of surfaces
with tunable hydrophobicity was revealed by
contact angle (CA) values ranging from 81° to
109° (Fig. 1E). Furthermore, on the basis of
the characteristics of living CDSA processes
performed in homogeneous solution, the
length of these brushes should be adjusta-
ble through the addition of further unimer
(Fig. 1, F to H). With an increase in the amount
of unimeric PFS53-b-PDMS418, the CA increased
steadily from 109° to 119° (Fig. 1I); this can be
attributed to the elongation of the hydrophobic
fibers forming a brush layer.
Further utility of the PFS-b-PDMS micellar
brushes was restricted by their collapse after
drying (fig. S4), probably as a consequence of Fig. 2. Seeded growth of hydrophilic PFS-b-P2VP and segmented micellar brushes on a silicon wafer.
the thin, high–aspect ratio cylindrical struc- (A) Schematic illustration of the growth process for PFS20-b-P2VP140 micellar brushes. (B to D) AFM
tures, as well as the very soft, low-Tg (glass height images of (C) PFS36-b-P2VP502 seed-coated silicon wafer (for seeds, Ln = 58 nm, Lw/Ln = 1.03,
transition temperature, ~ –123°C) PDMS co- concentration = 0.5 mg/ml in isopropanol) and PFS20-b-P2VP140 micellar brushes formed by the addition
rona, and also by the lack of facile coronal of (B) 4 ml and (D) 10 ml of solution of PFS20-b-P2VP140 unimers, respectively. (E) Schematic illustration of
functionalization chemistries. We therefore the growth process for PFS30-b-P2VP226 micellar brushes and segmented micellar brushes. (F to H) AFM
used PFS-b-P2VP BCPs for the seeded growth, height images of (G) short PFS30-b-P2VP226 micellar brushes formed by the addition of 3 ml of PFS30-b-
taking advantage of the higher Tg (~104°C, P2VP226 unimer solution, (F) elongated micellar brushes formed by further addition of 3 ml of PFS30-b-
which may provide additional rigidity after P2VP226 unimer solution to the short micellar brushes shown in (G), and (H) segmented micellar brushes
drying in addition to that provided by the formed by further addition of 3 ml of PFS32-b-PDMS385 unimer solution to the short micellar brushes shown
crystalline PFS core) (19) and the more readily in (G). Insets at lower left are enlargements of the respective boxed areas; insets at upper right are
functionalized corona-forming P2VP block. In photographs of water droplets on the surfaces, showing the corresponding CA results.

Cai et al., Science 366, 1095–1098 (2019) 29 November 2019 2 of 4

RES EARCH | R E P O R T

the block ratio) favored the formation of
thicker and presumably more rigid micellar
brushes (cylinder diameter of ~35 nm and
average brush height of ~125 nm by AFM;
Fig. 2G and fig. S8). The coral-like nanoassem-
blies thus can be further elongated by sub-
sequent addition of PFS30-b-P2VP226 unimers
(Fig. 2, E and F, and fig. S8). Moreover, seg-
mented micellar brushes can be generated by
sequential addition of PFS30-b-P2VP226 and
PFS32-b-PDMS385 unimers (Fig. 2H and fig.
S9), as evidenced by the transformation of
wettability (CA of 67° for the PFS30-b-P2VP226
micellar brushes compared to a value of 107°
for the segmented brushes).
We attempted post-assembly functionaliza-
tion of the PFS-b-P2VP micellar brushes based
on the functional P2VP corona and the redox-
active PFS core (Fig. 3A). First, protonation of
the P2VP corona was conducted by immersing
the micellar brushes in a solution of CF3COOH
(Fig. 3A, i) (21). This led to the yield of posi-
tively charged micellar brushes with structur-
ally retained integrity and a highly hydrophilic
surface (CA = 26° versus 67° for the neutral
micellar brush precursor) (Fig. 3B, inset). The
P2VP corona was also manipulated to provide
a viable platform for functionalization with
inorganic nanoparticles (Fig. 3A, ii) (15, 22).
For example, the brushes were selectively dec-
orated by gold nanoparticles (AuNPs; diame-
ter ~15 nm) via coordination interactions
(Fig. 3C), allowing the fabrication of a func-
tional hybrid surface. This was confirmed by
scanning electron microscopy (SEM) and
selected-area energy-dispersive x-ray (EDX)
spectroscopy mapping (fig. S10A). The AuNP-
decorated micellar brushes were found to possess
useful catalytic activity toward the borohydride-
mediated reduction of 4-nitrophenol (Nip) to
4-aminophenol (Amp) (23) (Fig. 3E); they also
appeared to be durable and recyclable, as the
catalytic performance was retained with sim-
ilar activity over 15 cycles (Fig. 3, E to G). Fur-

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thermore, the redox-active PFS core provides
another route to generate nanoparticle arrays
(Fig. 3A, iii) (9, 24). In situ reduction of AgNO3
by the Fe(II) sites in the core gave rise to a
highly dense array of silver nanoparticles
(AgNPs; diameter ~35 nm) (Fig. 3D and fig.
S10B). We found that the antibactericidal
activity of AgNPs (25) readily renders the silicon
wafer resistant to the growth of Gram-negative
Escherichia coli (fig. S11).
To expand our approach to other material
surfaces, we also explored the formation of
micellar brushes on graphene oxide (GO) sheets
(26) [Fig. 4A; additional anchoring tech-
niques and substrates were also explored,
such as coordination interactions for metallic
substrates and covalent immobilization for
hydroxylated surfaces (figs. S20 and S21)].
Seed-coated GO sheets were prepared by
addition of the PFS30-b-P2VP226 seeds (Ln =
46 nm, Lw/Ln = 1.04) to a suspension of GO in
isopropanol, followed by a sedimentation/
redispersal process (fig. S12, A to C). Trans-
mission electron microscopy (TEM) and AFM
height images (Fig. 4, B and C) showed that
the PFS30-b-P2VP226 seeds were densely im-
mobilized on the GO sheets, presumably as
a result of the H-bonding and electrostatic
interactions between the pyridyl groups in
the P2VP corona and the carboxyl and hy-
droxyl groups of GO. The sheets retained the
Fig. 3. Functionalization and application of PFS-b-P2VP micellar brushes. (A) Schematic illustration of unilaminar structure and no obvious aggre-
the pathways for the functionalization of PFS20-b-P2VP140 micellar brushes: (i) protonation, (ii) coordination gation was observed. Upon addition of the
interaction, and (iii) in situ redox chemistry. (B to D) AFM height images of micellar brushes bearing (B) PFS30-b-P2VP226 unimers, fiber-like micelles
positive charges (the inset photograph shows a water droplet on the surface), (C) AuNPs, and (D) AgNPs. grew from the GO surface and eventually
Insets in (C) and (D) are SEM-assisted EDX mapping images, where the yellow features represent N existing in formed a compact hairy brush layer (Fig. 4,
the P2VP coronas of the micellar brushes, the red features identify Au, and the pink features identify Ag. D and E, and figs. S12D and S13). These hairy
Scale bars, 200 nm [inset in (C)], 2 mm [inset in (D)]. (E) Schematic illustration of the borohydride-mediated GO sheets were found to be colloidally stable
reduction of 4-nitrophenol (Nip) to 4-aminophenol (Amp) catalyzed by AuNP-decorated micellar brushes over several months, probably as a result of
in aqueous solution at room temperature. (F) Ultraviolet-visible (UV-vis) spectrum monitoring the reduction the solubility arising from the voluminous
process of Nip in aqueous solution with an interval of 10 min. The reduction was accomplished in micellar brushes. In a similar manner to the
~100 min; the solution color changed from yellow to colorless (inset photographs). (G) Recyclability test for silicon wafer system, elongated or segmented
AuNP-decorated micellar brushes for the reduction of Nip. The data variability over the 15 cycles is attributed micellar brushes could be constructed by
to the absence of stirring, as the reaction was run in a cuvette within a UV-vis spectrophotometer. subsequent addition of PFS30-b-P2VP226 or

Cai et al., Science 366, 1095–1098 (2019) 29 November 2019 3 of 4

RES EARCH | R E P O R T

istry. In principle, this approach should be

suitable for any arbitrary material surface
given the existence of an effective anchoring
technique for the micelle seeds, thereby en-
abling a range of applications.
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process, which involves the immobilization of PFS30-b-P2VP226 seeds on GO via H-bonding and electrostatic 13645–13649 (2017).
23. B. Baruah, G. J. Gabriel, M. J. Akbashev, M. E. Booher,
interactions followed by living growth of PFS30-b-P2VP226 micellar brushes. (B and C) TEM (B) and AFM Langmuir 29, 4225–4234 (2013).
(C) height images of PFS30-b-P2VP226 seed-coated GO sheets (Ln = 46 nm, Lw/Ln = 1.04) after removal of the 24. H. Wang, X. Wang, M. A. Winnik, I. Manners, J. Am. Chem. Soc.
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illustration describing the vacuum filtration process, which rejects specific objects by means of a laminated
membrane assembled from the hairy GO sheets. (G and H) Optical microscopy images and photographs AC KNOWLED GME NTS
(insets) of a heptane-in-water emulsion before (G) and after (H) filtration by the membrane. The absence We thank P. Choi, V. A. Du, and Y. Gao (University of Bristol) for
of heptane droplets in (H) compared with the feed emulsion shown in (G) indicates that heptane was rejected providing some of the block copolymer samples; the Analytical
Instrumentation Center and Center for High-Resolution Electron
by the membrane, presumably as a result of the hydrophilic corona of the micellar brush layer. (I) UV-vis
Microscopy (School of Physical Science and Technology,
spectra and photographs of a AuNP solution before and after filtration by the membrane. The AuNPs ShanghaiTech University) for AFM and TEM; and the Instrumental
were removed, as evidenced by the absence of the peak at 523 nm and the transparent filtrate compared Analysis Center (Shanghai Jiao Tong University) for SEM, confocal
laser scanning microscopy (CLSM), and STED. Funding: H.Q.
with the original purple solution.
thanks the National Natural Science Foundation of China
(21674062, U1632117), the Science and Technology Commission
PFS32-b-PDMS385 unimers (fig. S14). Analo- stration of potential utility, a thin laminated of Shanghai Municipality (16ZR1422600, 17JC1400700,
18JC1415500), and the Shanghai Education Development
gous to the “grafting-from” method applied membrane (thickness of ~60 nm) was further Foundation and the Shanghai Municipal Education Commission
in the synthesis of polymer brushes (8), this assembled from the hairy GO sheets (fig. S18). (16SG54) for financial support. I.M. thanks the University of Bristol,
seeded growth approach provided a facile This membrane exhibited higher water perme- the Canadian Government for a Canada 150 Research Chair, and
the Chinese Government for a Thousand Talents Distinguished
bottom-up approach to fabricate GO-based ance upon subsequent protonation with trifluo- Visiting Professor position at Shanghai Jiao Tong University.
hybrid assemblies with controllable brush roacetic acid, with substantially higher flux Author contributions: J.C. and H.Q. conceived the project;
layer functionalization. The method also has (4520 liters hour–1 m–2 bar–1) compared to the polymer samples were prepared in I.M.’s group; J.C. performed the
advantages over conventional approaches in- original membrane (226 liters hour–1 m–2 bar–1) experiments with assistance from C.L. and N.K.; J.C. and C.L.
prepared the hairy GO sheets and performed the filtration
volving direct anchoring of long fibers on GO (see supplementary materials for details) and experiments; J.C., N.K., Y.L., and Y.Y. conducted the antibacterial
sheets (fig. S15) in terms of uniformity and similar to the fluxes of recently reported GO- experiments; J.C., C.L., and G.L. performed the EDX imaging;
grafting density (27). based membranes (27, 28). Because of the nano- J.C. and X.W. performed the fluid AFM analysis; and J.C., I.M., and
H.Q. analyzed the data and prepared the manuscript with input
The hairy GO sheets can be functionalized porosity and hydrophilicity of the protonated from all the other authors. The project was supervised by I.M. and
using various post-assembly chemistries. For P2VP corona of the constitutive micellar brushes, H.Q. Competing interests: A relevant patent application has
example, fluorescent dyes can be covalently the membrane efficiently separated heptane from been submitted to the State Intellectual Property Office of China.
Data and materials availability: All data are available in the
anchored onto the P2VP corona via quater- a heptane-in-water emulsion (Fig. 4, F to H, and manuscript or the supplementary materials.
nization, making them observable in solution fig. S19) and filtered AuNPs (diameter ~15 nm)
through stimulated emission depletion (STED) from an aqueous solution (Fig. 4I and fig. S19). SUPPLEMENTARY MATERIALS

microscopy (fig. S12, E to G). In addition, facile
decoration by nanoparticles is possible using
noncovalent interactions, such as coordination
(e.g., for AuNPs; fig. S16) and H-bonding (e.g.,
for silica nanoparticles; fig. S17). For demon-
We have demonstrated a versatile bottom- science.sciencemag.org/content/366/6469/1095/suppl/DC1
Materials and Methods
up strategy that represents a platform for the Figs. S1 to S21
controlled functionalization of surfaces, using References (29–35)
the crystallization-driven growth of BCP mi- 3 May 2019; accepted 17 October 2019
cellar brushes with precisely controlled chem- 10.1126/science.aax9075

Cai et al., Science 366, 1095–1098 (2019) 29 November 2019 4 of 4

Tailored multifunctional micellar brushes via crystallization-driven growth from a surface
Jiandong Cai, Chen Li, Na Kong, Yi Lu, Geyu Lin, Xinyan Wang, Yuan Yao, Ian Manners and Huibin Qiu

Science 366 (6469), 1095-1098.

DOI: 10.1126/science.aax9075

Growing polymer brushes from surfaces

Surface functionalization is important in a broad range of fields. One approach involves polymer brushes, where
polymer chains are grafted onto a surface. Cai et al. describe the nanoscale functionalization of surfaces by exploiting
the living crystallization-driven self-assembly of polyferrocenyl-based block copolymers (see the Perspective by Presa

Downloaded from http://science.sciencemag.org/ on November 28, 2019

Soto). Small crystalline cylindrical micelle seeds were attached using noncovalent bonds to a variety of surfaces,
including silicon wafers, graphene oxide nanosheets, and gold. Addition of dissolved unimers over the seed-coated
surfaces allowed micellar brushes to grow. Protonation and postdecoration with gold and silver nanoparticles
demonstrated the applicability of such modified surfaces in catalysis, as antibacterial agents, and in separation
processes.
Science, this issue p. 1095; see also p. 1078

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