A Noncrystallization Approach toward Uniform Thylakoids-like 2D "Nano-coins" and Their Grana-like 3D Suprastructures.

Two-dimensional (2D) circular shape nanostructures (e.g., "nano-coins") are ubiquitously present in thylakoids and grana within chloroplasts of plant cells in nature. The design and fabrication of 2D nano-coins with controlled sizes and thicknesses yet remain challenging tasks. Herein, we present a noncrystallization approach to achieve 2D nano-coins from assemblies of a set of zwitterionic giant surfactants. Distinguished from traditional crystallization approaches where the 2D nanostructures with specific crystallographic symmetries are fabricated, the noncrystallization assembly of giant surfactants results in 2D nano-coins that are derived from the separation of assembled 3D multiple lamellar cylindrical colloids with uniform diameters. The diameters and thicknesses of these nano-coins can be readily tailored by varying the molecular length of giant surfactants' tails. The formation of 2D nano-coins or 3D cylindrical colloid suprastructures is controlled by tuning the pH value of added selective solvents. This new strategy opens a door for controlling the shape, size, and size distribution of assembled nanostructures with different hierarchies.

[1]  R. Harniman,et al.  Two-dimensional assemblies from crystallizable homopolymers with charged termini. , 2017, Nature materials.

[2]  Wen-Bin Zhang,et al.  Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants , 2016, Proceedings of the National Academy of Sciences.

[3]  Oleg Gang,et al.  Self-organized architectures from assorted DNA-framed nanoparticles. , 2016, Nature chemistry.

[4]  M. Nasilowski,et al.  Two-Dimensional Colloidal Nanocrystals. , 2016, Chemical reviews.

[5]  Chih-Hao Hsu,et al.  Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles. , 2016, ACS nano.

[6]  S. Webb,et al.  Uniform patchy and hollow rectangular platelet micelles from crystallizable polymer blends , 2016, Science.

[7]  P. Zavattieri,et al.  Self-Assembly of Coherently Dynamic, Auxetic Two-Dimensional Protein Crystals , 2016, Nature.

[8]  Ali Nazemi,et al.  Synthetic Covalent and Non-Covalent 2D Materials. , 2015, Angewandte Chemie.

[9]  Stephen Z. D. Cheng,et al.  Hydrogen-Bonding-Induced Nanophase Separation in Giant Surfactants Consisting of Hydrophilic [60]Fullerene Tethered to Block Copolymers at Different Locations , 2015 .

[10]  D. Baker,et al.  Design of ordered two-dimensional arrays mediated by noncovalent protein-protein interfaces , 2015, Science.

[11]  Chih-Hao Hsu,et al.  Selective assemblies of giant tetrahedra via precisely controlled positional interactions , 2015, Science.

[12]  Rong Wang,et al.  Self-Assembly of Polymer Tethered Molecular Nanoparticle Shape Amphiphiles in Selective Solvents , 2015 .

[13]  Chih-Hao Hsu,et al.  Pathway toward large two-dimensional hexagonally patterned colloidal nanosheets in solution. , 2015, Journal of the American Chemical Society.

[14]  Stephen Z. D. Cheng,et al.  Charge-Regulated Spontaneous, Reversible Self-Assembly of the Carboxylic Acid-Functionalized Hydrophilic Fullerene Macroanions in Dilute Solution , 2015 .

[15]  Ian Manners,et al.  Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions. , 2014, Nature chemistry.

[16]  R. Zuckermann,et al.  Assembly and molecular order of two-dimensional peptoid nanosheets through the oil–water interface , 2014, Proceedings of the National Academy of Sciences.

[17]  B. T. King,et al.  A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. , 2014, Nature chemistry.

[18]  M. Wörle,et al.  Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction. , 2014, Nature chemistry.

[19]  Stephen Z. D. Cheng,et al.  Two-dimensional nanocrystals of molecular Janus particles. , 2014, Journal of the American Chemical Society.

[20]  Debra J. Audus,et al.  A facile synthesis of dynamic, shape-changing polymer particles. , 2014, Angewandte Chemie.

[21]  Stephen Z. D. Cheng,et al.  Molecular Nanoparticles Are Unique Elements for Macromolecular Science: From “Nanoatoms” to Giant Molecules , 2014 .

[22]  Ke Zhang,et al.  Disk-cylinder and disk-sphere nanoparticles via a block copolymer blend solution construction , 2013, Nature Communications.

[23]  Stephen Z. D. Cheng,et al.  Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering , 2013, Proceedings of the National Academy of Sciences.

[24]  Stephen Z. D. Cheng,et al.  Giant molecular shape amphiphiles based on polystyrene-hydrophilic [60]fullerene conjugates: click synthesis, solution self-assembly, and phase behavior. , 2012, Journal of the American Chemical Society.

[25]  B. T. King,et al.  A two-dimensional polymer prepared by organic synthesis. , 2012, Nature chemistry.

[26]  B. Lotz Frustration and Frustrated Crystal Structures of Polymers and Biopolymers , 2012 .

[27]  William R. Dichtel,et al.  Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene , 2011, Science.

[28]  M. Nothisen,et al.  Gene delivery with polycationic fullerene hexakis-adducts. , 2011, Chemical communications.

[29]  K. Müllen,et al.  Two-dimensional nanostructures from positively charged polycyclic aromatic hydrocarbons. , 2011, Angewandte Chemie.

[30]  L. Staehelin,et al.  Three-Dimensional Architecture of Grana and Stroma Thylakoids of Higher Plants as Determined by Electron Tomography1[W][OA] , 2011, Plant Physiology.

[31]  Wen-Bin Zhang,et al.  A giant surfactant of polystyrene-(carboxylic Acid-functionalized polyhedral oligomeric silsesquioxane) amphiphile with highly stretched polystyrene tails in micellar assemblies. , 2010, Journal of the American Chemical Society.

[32]  Ryan A. Mesch,et al.  Free-floating ultrathin two-dimensional crystals from sequence-specific peptoid polymers. , 2010, Nature materials.

[33]  H. Yabu,et al.  Suprapolymer structures from nanostructured polymer particles. , 2009, Angewandte Chemie.

[34]  Seung‐Man Yang,et al.  Cooperative Assembly of Block Copolymers with Deformable Interfaces: Toward Nanostructured Particles , 2008 .

[35]  K. Buttle,et al.  The Three-Dimensional Network of the Thylakoid Membranes in Plants: Quasihelical Model of the Granum-Stroma Assembly[W] , 2008, The Plant Cell Online.

[36]  Sheng Zhong,et al.  Block Copolymer Assembly via Kinetic Control , 2007, Science.

[37]  D. Pochan,et al.  Controlled stacking of charged block copolymer micelles. , 2007, Langmuir.

[38]  I. Ohad,et al.  Three-Dimensional Organization of Higher-Plant Chloroplast Thylakoid Membranes Revealed by Electron Tomographyw⃞ , 2005, The Plant Cell Online.

[39]  Kai Qi,et al.  Disk morphology and disk-to-cylinder tunability of poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene triblock copolymer solution-state assemblies. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[40]  B. Schade,et al.  Switchable supramolecular organization of structurally defined micelles based on an amphiphilic fullerene. , 2005, Angewandte Chemie.

[41]  Hee‐Tae Jung,et al.  Supramolecular crystalline sheets with ordered nanopore arrays from self-assembly of rigid-rod building blocks. , 2004, Angewandte Chemie.

[42]  Zhibo Li,et al.  Multicompartment Micelles from ABC Miktoarm Stars in Water , 2004, Science.

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

[44]  V. Seredyuk,et al.  Micellization and adsorption properties of novel Zwitterionic surfactants , 2001 .

[45]  Schuster,et al.  Synthesis and characterization of water-soluble amino fullerene derivatives , 2000, Organic letters.

[46]  N. Seeman,et al.  Design and self-assembly of two-dimensional DNA crystals , 1998, Nature.

[47]  Xiaodong Zhuang,et al.  Two‐Dimensional Soft Nanomaterials: A Fascinating World of Materials , 2015, Advanced materials.

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