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硅片和GO上PFS BCP
硅片和GO上PFS BCP
A
of PFS-b-P2VP [P2VP, poly(2-vinylpyridine)]
variety of conventional methods, includ- of the surface chemistry at the molecular level. on the basis of the high density of surface
ing physical techniques [e.g., spray-based However, the precise fabrication of patterned silanol groups, which should allow tenacious
methods (1) and spin-coating (2)] and surfaces using building blocks on longer length
chemical routes [e.g., electrochemical scales represents a key challenge.
1
deposition (3) and heat treatment (4)], Block copolymers (BCPs) with a short, crys- School of Physical Science and Technology, ShanghaiTech
University, Shanghai 201210, China. 2School of Chemistry
have been developed to endow material sur- tallizable poly(ferrocenyldimethylsilane) (PFS) and Chemical Engineering, Frontiers Science Center for
faces with a wide range of targeted proper- core-forming block tend to form cylindrical (or Transformative Molecules, State Key Laboratory of Metal
ties. Surface-initiated polymer brushes (5–8), fiber-like) micelles with a crystalline PFS core Matrix Composites, Shanghai Jiao Tong University, Shanghai
200240, China. 3Shanghai Institute of Organic Chemistry,
where one of the polymer chain ends is co- in selective solvents for the complementary
Chinese Academy of Sciences, Shanghai 200032, China.
valently attached to a solid substrate, have segment (9). The cylindrical micelle termini 4
University of Chinese Academy of Sciences, Beijing 100049,
emerged as a powerful and versatile approach remain active to the addition of further added China. 5School of Chemistry, University of Bristol, Bristol
to surface functionalization. The living charac- PFS BCP in the dissolved (unimer) state through BS8 1TS, UK. 6Department of Chemistry, University of
Victoria, Victoria, BC V8P 5C2, Canada.
teristic of the covalent polymerizations used an epitaxial growth process termed living *Corresponding author. Email: hbqiu@sjtu.edu.cn (H.Q.);
to create polymer brushes allows for tailoring crystallization-driven self-assembly (CDSA) imanners@uvic.ca (I.M.)
attachment through hydrogen bonding (H- addition, substantially shorter PFS36-b-P2VP502 blies could be fabricated on a large scale
bonding) with the P2VP corona. Low-dispersity seeds (Ln = 58 nm, Lw/Ln = 1.03) at the same covering a 1 cm × 1 cm piece of silicon wafer
PFS36-b-P2VP502 (where the subscripts refer to concentration (0.5 mg/ml) were immobilized with relatively few defects (undergrown or
the number-average degree of polymerization on the silicon wafer (Fig. 2C) to favor the overgrown sites) (fig. S6). The micellar brushes
of each block) micelle seeds with Ln = 139 nm growth of denser micellar brush arrays. Upon remained standing as the length further in-
[L w /L n = 1.04, where L n and L w are the addition of the PFS20-b-P2VP140 unimers (Fig. creased by the addition of unimer, but they
number- and weight-average lengths, respec- 2A), micellar brushes with increased diame- eventually collapsed beyond average heights
tively, determined by atomic force micros- ter of ~25 nm grew from the seeds on the sub- of ~40 nm (Fig. 2D and fig. S7).
copy (AFM)] prepared from the sonication of strate and formed coral-like nanoassemblies Previous studies have established that PFS
preformed long polydisperse cylinders (10) comprising pillars (revealed by the AFM BCPs with a longer PFS core-forming block
(fig. S1) were anchored to the silicon wafer height images both in the solution and dry tend to form cylindrical micelles with a larger
via H-bonding (Fig. 1A). An AFM height image state) (Fig. 2B and fig. S5). As a result of the core diameter (20). Hence, the use of PFS30-b-
(fig. S1D) showed that the PFS36-b-P2VP502 hydrophilic nature of the P2VP coronas, the P2VP226 with a longer PFS core-forming block
crystallite seeds were relatively evenly distrib- hydrophilicity was increased as the CA de- and relatively larger block ratio (RP2VP/PFS =
uted on the silicon surface. The seed-coated creased to 67°. Such coral-like nanoassem- 7.5 versus 7.0 for PFS20-b-P2VP140, where R is
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).
the block ratio) favored the formation of wettability (CA of 67° for the PFS30-b-P2VP226 surface (CA = 26° versus 67° for the neutral
thicker and presumably more rigid micellar micellar brushes compared to a value of 107° micellar brush precursor) (Fig. 3B, inset). The
brushes (cylinder diameter of ~35 nm and for the segmented brushes). P2VP corona was also manipulated to provide
average brush height of ~125 nm by AFM; We attempted post-assembly functionaliza- a viable platform for functionalization with
Fig. 2G and fig. S8). The coral-like nanoassem- tion of the PFS-b-P2VP micellar brushes based inorganic nanoparticles (Fig. 3A, ii) (15, 22).
blies thus can be further elongated by sub- on the functional P2VP corona and the redox- For example, the brushes were selectively dec-
sequent addition of PFS30-b-P2VP226 unimers active PFS core (Fig. 3A). First, protonation of orated by gold nanoparticles (AuNPs; diame-
(Fig. 2, E and F, and fig. S8). Moreover, seg- the P2VP corona was conducted by immersing ter ~15 nm) via coordination interactions
mented micellar brushes can be generated by the micellar brushes in a solution of CF3COOH (Fig. 3C), allowing the fabrication of a func-
sequential addition of PFS30-b-P2VP226 and (Fig. 3A, i) (21). This led to the yield of posi- tional hybrid surface. This was confirmed by
PFS32-b-PDMS385 unimers (Fig. 2H and fig. tively charged micellar brushes with structur- scanning electron microscopy (SEM) and
S9), as evidenced by the transformation of ally retained integrity and a highly hydrophilic 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-
microscopy (fig. S12, E to G). In addition, facile We have demonstrated a versatile bottom- science.sciencemag.org/content/366/6469/1095/suppl/DC1
Materials and Methods
decoration by nanoparticles is possible using up strategy that represents a platform for the Figs. S1 to S21
noncovalent interactions, such as coordination controlled functionalization of surfaces, using References (29–35)
(e.g., for AuNPs; fig. S16) and H-bonding (e.g., the crystallization-driven growth of BCP mi- 3 May 2019; accepted 17 October 2019
for silica nanoparticles; fig. S17). For demon- cellar brushes with precisely controlled chem- 10.1126/science.aax9075
SUPPLEMENTARY http://science.sciencemag.org/content/suppl/2019/11/25/366.6469.1095.DC1
MATERIALS
RELATED http://science.sciencemag.org/content/sci/366/6469/1078.full
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