Crystallization-Driven Two-Dimensional Self-Assembly of Amphiphilic PCL-b-PEO Coated Gold Nanoparticles in Aqueous Solution.

This Letter reports the first formation of free-standing plasmonic monolayer nanosheets by the self-assembly of AuNPs without assistance from a planar interface. The strategy involves the coating of poly(caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) diblock copolymers on AuNPs, followed by two-dimensional (2D) self-assembly of the resultant amphiphilic AuNPs in aqueous phase. The crystallization of the PCL blocks, affected by their grafting density and radius of gyration, drives the formation of the AuNP nanosheets, which undergoes a growth process of individual micelles to small nanosheets and eventually to large sheets. Due to the plasmonic coupling of AuNPs in close proximity, the AuNP nanosheets exhibit near-infrared (NIR) absorption with the maximum at about 700 nm. This study not only brings a new approach toward polymer-AuNP hybrid superstructures in solution, but also provides a new system for fundamental study on 2D self-assembly of AuNPs.

[1]  Yi-Wei Lee,et al.  Protein delivery into cells using inorganic nanoparticle-protein supramolecular assemblies. , 2018, Chemical Society reviews.

[2]  R. O’Reilly,et al.  Precision Epitaxy for Aqueous 1D and 2D Poly(ε-caprolactone) Assemblies , 2017, Journal of the American Chemical Society.

[3]  S. Förster,et al.  Two-Dimensional Self-Assembled Structures of Highly Ordered Bioactive Crystalline-Based Block Copolymers , 2017 .

[4]  R. Selegård,et al.  Peptide Functionalized Gold Nanoparticles as a Stimuli Responsive Contrast Medium in Multiphoton Microscopy. , 2017, Nano letters.

[5]  Jun Ling,et al.  Poly(ε-caprolactone)-block-polysarcosine by Ring-Opening Polymerization of Sarcosine N-Thiocarboxyanhydride: Synthesis and Thermoresponsive Self-Assembly. , 2015, Biomacromolecules.

[6]  D. Yan,et al.  Temperature-Dependent Multidimensional Self-Assembly of Polyphenylene-Based "Rod-Coil" Graft Polymers. , 2015, Journal of the American Chemical Society.

[7]  J. Nam,et al.  Controlled Co-Assembly of Nanoparticles and Polymer into Ultralong and Continuous One-Dimensional Nanochains. , 2015, Journal of the American Chemical Society.

[8]  K. Char,et al.  Free-standing gold-nanoparticle monolayer film fabricated by protein self-assembly of α-synuclein. , 2015, Angewandte Chemie.

[9]  T. V. D. van de Ven,et al.  "Raft" formation by two-dimensional self-assembly of block copolymer rod micelles in aqueous solution. , 2014, Angewandte Chemie.

[10]  Z. Nie,et al.  Entropy-driven pattern formation of hybrid vesicular assemblies made from molecular and nanoparticle amphiphiles. , 2014, Journal of the American Chemical Society.

[11]  Chad A. Mirkin,et al.  DNA-mediated nanoparticle crystallization into Wulff polyhedra , 2013, Nature.

[12]  D. Hammer,et al.  Aqueous self-assembly of poly(ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) copolymers: disparate diblock copolymer compositions give rise to nano- and meso-scale bilayered vesicles. , 2013, Nanoscale.

[13]  Hong Liu,et al.  GALAMOST: GPU‐accelerated large‐scale molecular simulation toolkit , 2013, J. Comput. Chem..

[14]  Xinglu Huang,et al.  Self-assembly of amphiphilic plasmonic micelle-like nanoparticles in selective solvents. , 2013, Journal of the American Chemical Society.

[15]  Yiyong Mai,et al.  Morphological Control in Aggregates of Amphiphilic Cylindrical Metal–Polymer “Brushes” , 2013 .

[16]  Yiyong Mai,et al.  Self-assembly of block copolymers. , 2012, Chemical Society reviews.

[17]  Jiating He,et al.  Unconventional chain-growth mode in the assembly of colloidal gold nanoparticles. , 2012, Angewandte Chemie.

[18]  Yiyong Mai,et al.  Selective localization of preformed nanoparticles in morphologically controllable block copolymer aggregates in solution. , 2012, Accounts of chemical research.

[19]  Zhihong Nie,et al.  Self-assembly of inorganic nanoparticle vesicles and tubules driven by tethered linear block copolymers. , 2012, Journal of the American Chemical Society.

[20]  Guoying Zhang,et al.  Efficient synthesis of single gold nanoparticle hybrid amphiphilic triblock copolymers and their controlled self-assembly. , 2012, Journal of the American Chemical Society.

[21]  Jintao Zhu,et al.  Encapsulation of nanoparticles in block copolymer micellar aggregates by directed supramolecular assembly. , 2011, Angewandte Chemie.

[22]  Yiyong Mai,et al.  Controlled Incorporation of Particles into the Central Portion of Block Copolymer Rods and Micelles , 2011 .

[23]  Axel H. E. Müller,et al.  One-dimensional organic-inorganic hybrid nanomaterials , 2010 .

[24]  Liquan Wang,et al.  Ordered nanostructures self-assembled from block copolymer tethered nanoparticles. , 2010, ACS nano.

[25]  Yiyong Mai,et al.  Controlled incorporation of particles into the central portion of vesicle walls. , 2010, Journal of the American Chemical Society.

[26]  Stephen Z. D. Cheng,et al.  Solution Crystallization Behavior of Crystalline−Crystalline Diblock Copolymers of Poly(ethylene oxide)-block-poly(ε-caprolactone) , 2010 .

[27]  D. Beattie,et al.  Light-induced aggregation of colloidal gold nanoparticles capped by thymine derivatives. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[28]  Lei Zhu,et al.  Core-Shell Reversion of Hybrid Polymeric Micelles Containing Gold Nanoparticles in the Core , 2007 .

[29]  T. Azzam,et al.  Monolayer-protected gold nanoparticles by the self-assembly of micellar poly(ethylene oxide)-b-poly(epsilon-caprolactone) block copolymer. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[30]  D. Hammer,et al.  Bioresorbable Vesicles Formed through Spontaneous Self-Assembly of Amphiphilic Poly(ethylene oxide)-block-polycaprolactone. , 2006, Macromolecules.

[31]  Stephen Z. D. Cheng,et al.  Onset of tethered chain overcrowding. , 2004, Physical review letters.

[32]  Frank S. Bates,et al.  Consequences of Nonergodicity in Aqueous Binary PEO-PB Micellar Dispersions , 2004 .

[33]  Catherine J. Murphy,et al.  Seeding Growth for Size Control of 5−40 nm Diameter Gold Nanoparticles , 2001 .

[34]  P. B. Warren,et al.  DISSIPATIVE PARTICLE DYNAMICS : BRIDGING THE GAP BETWEEN ATOMISTIC AND MESOSCOPIC SIMULATION , 1997 .

[35]  Stephen Z. D. Cheng,et al.  Onsets of Tethered Chain Overcrowding and Highly Stretched Brush Regime via Crystalline-Amorphous Diblock Copolymers , 2006 .

[36]  G. Frens.  Controlled Nucleation for the Regulation of the Particle Size in Monodisperse Gold Suspensions , 1973 .