Two-dimensional assemblies from crystallizable homopolymers with charged termini

He, Xiaoming; Hsiao, Ming-Siao; Boott, Charlotte E.; Harniman, Robert L.; Nazemi, Ali; Li, Xiaoyü; Winnik, Mitchell A.; Manners, Ian

doi:10.1038/nmat4837

Cited by 184 publications

(220 citation statements)

References 42 publications

(45 reference statements)

Supporting

Mentioning

208

Contrasting

Order By: Relevance

“…Living CDSA has permitted the fabrication of monodisperse fibers that form lyotropic liquid crystalline phases, 59,60 and via the sequential addition of different BCP unimers, segmented 1D block comicelles, 54,61 including amphiphilic examples 62 and spatially distinct regions of hydrogen-bonding donors and acceptors that hierarchically self-assemble into supermicelles. 63,64 Moreover, the living CDSA, seeded growth approach has been extended beyond crystallizable BCPs 25,34,48,49,65,66 to crystallisable homopolymers with charged termini 67,68 and to molecular species [69][70][71][72][73][74][75][76] that form stacked structures by -or hydrogen bonding interactions, and also to 2 dimensions to yield platelet micelles with controlled dimensions and complexity. 32,[77][78][79] The solution self-assembly of P3AT-containing diblock copolymers (diBCPs) has attracted considerable attention as a method by which to prepare colloidally stable functional nanoparticles.…”

Section: Introductionmentioning

confidence: 99%

Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block

et al. 2018

Self Cite

View full text Add to dashboard Cite

Crystalline poly(3-alkylthiophene) (P3AT) nanofibers are promising materials for a myriad of device applications but nanofiber length control and colloidal stability are difficult to achieve. We report an in depth study of the solution self-assembly of regioregular poly(3-octylthiophene)-bpoly(dimethylsiloxane) (P3OT-b-PDMS) diblock copolymers with a crystallizable p-conjugated coreforming block. Use of "living" crystallization-driven self-assembly (CDSA) seeded-growth method in solvents selective for PDMS allowed access to relatively low length dispersity, colloidally stable P3OTb-PDMS fiber-like micelles with a crystalline, tape-like P3OT core and a PDMS corona and lengths up to ca. 600 nm under optimised conditions. Significantly, the presence of a small percentage of common solvent and the use of slightly elevated temperature (35°C) was found to enhance the length control. Analogous studies for P3OT-b-PS (PS = polystyrene) suggest that solvent composition and temperature represent key parameters for the general optimisation of fiber formation by living CDSA for P3AT block copolymers.

show abstract

Section: Introductionmentioning

confidence: 99%

Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Nevertheless, sequential or selective disassembly is still a major challenge and seldom reported . More recently, the research group of Manner reported that the self‐assembled polymer micelles can be selectively disassembled to form perforated hollow rectangular, or diamond‐shaped, platelets by selective dissolution. Herein, we reported a novel electrostatic field‐controlled disassembly of multicompartment micelles (MCPs) in spatial sequence.…”

Section: Figurementioning

confidence: 99%

Disassembly of Multicompartment Polymer Micelles in Spatial Sequence Using an Electrostatic Field and Its Application for Release in Chronological Order

Zhu

Jiang

2018

Angewandte Chemie

View full text Add to dashboard Cite

Multicompartment micelles (MCPs), comprising sequences of repeated elemental discoid parts connected by fasciculus, were formed by self‐assembly of polystyrene‐block‐poly(2‐vinyl pyridine)‐block‐poly(ethylene oxide). Using an electrostatic field, the MCPs can be disassembled through consequent release of small spherical micelles. During this disassembly process, release of loaded species can be achieved from the micelles in chronological order. Two location‐selected cargos (mitoxantrone (MTNT) and fluorescein isothiocyanate (FITC)) in the outer and inner compartments of the micelles can be released in chronological order. Under the applied electrostatic field (intensity: 16 kV cm−1), the loaded MTNT was rapidly released with more than 80 % release, whereas the loaded FITC was slowly released with less than 20 % release in 12 h. At a later stage (after more than 12 h), the loaded MTNT was slowly released with less than 20 % release, while the loaded FITC was rapidly released with more than 80 % release.

show abstract

“…Traditional atomic 2D materials are commonly isolated from layered van der Waals solids exhibiting strong in‐plane bonding and comparatively weak interactions between the layers. Assembling molecular building blocks into synthetic 2D materials offers exciting opportunities for tuning the material properties through chemical design and for discovering new behaviors . The assembly of such material, however, is a major synthetic challenge, with only a few reported examples, which include 2D covalent organic frameworks and metal–organic frameworks …”

Section: Figurementioning

confidence: 99%

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

et al. 2018

View full text Add to dashboard Cite

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties.A2D material was assembled using C 60 as ap olymerizable monomer.The C 60 building blocks are first assembled into alayered solid using am olecular cluster as structure director.T he resulting hierarchical crystal is used as atemplate to polymerizei ts C 60 monolayers,w hichc an be exfoliated down to 2D crystalline nanosheets.D erived from the parent template,t he 2D structure is composed of al ayer of inorganic cluster, sandwiched between two monolayers of polymerizedC 60 .The nanosheets can be transferred onto solid substrates and depolymerized by heating.Electronic absorption spectroscopy reveals an optical gap of 0.25 eV,narrower than that of the bulk parent crystalline solid.The discovery of graphene [1] has catalyzed acomprehensive search for two-dimensional (2D) materials,and has led to the development of 2D transition metal dichalcogenides,h exagonal boron nitride,a nd phosphorene. [2][3][4] These materials serve not only as excellent model systems for exploring 2D physics,b ut also as potential candidates for av ariety of electronic and optoelectronic devices.T raditional atomic 2D materials are commonly isolated from layered van der Waals solids exhibiting strong in-plane bonding and comparatively weak interactions between the layers.A ssembling molecular building blocks into synthetic 2D materials offers exciting opportunities for tuning the material properties through chemical design and for discovering new behaviors. [5][6][7] The assembly of such material, however, is am ajor synthetic challenge,w ith only af ew reported examples,w hich include 2D covalent organic frameworks [8][9][10][11] and metal-organic frameworks. [12,13] Herein, we describe an ew 2D material assembled from C 60 building blocks that are covalently linked. Then ano-material is formed by polymerizing al ayered van der Waals crystal assembled from C 60 and the molecular cluster Co 6 Se 8 -(PEt 2 phen) 6 (phen = 9-ethynylphenanthrene), and thereafter dissolving the supporting template (Figure 1a). Theresulting 2D structure is composed of al ayer of inorganic cluster, sandwiched between two monolayers of polymerized C 60 . Conceptually,t his structure can be visualized as as tructural analogue of 2D transition metal chalcogenides or halides in which the atomic building blocks are pseudo spherical molecular clusters rather than simply atoms. C 60 is an attractive building block for creating synthetic 2D structures owing to its remarkable physical and chemical properties.W hile crystalline C 60 has ab and gap of 2.3 eV, [14] theoretical studies on both polymeric and van der Waals C 60 monolayers predict band gaps ranging from 0.58 to 1.01 eV, [15][16][17][18] which is lower than that of any experimentally isolated monolayer semiconducting materials. [19] Additi...

show abstract

Two-dimensional assemblies from crystallizable homopolymers with charged termini

Abstract: General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above.

Cited by 184 publications

References 42 publications

Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block

Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block

Disassembly of Multicompartment Polymer Micelles in Spatial Sequence Using an Electrostatic Field and Its Application for Release in Chronological Order

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

Contact Info

Product

Resources

About