Rod-coil Block Copolymers Research Articles

Combining Two Powerful Living Polymerizations Using Rationally Designed Bifunctional Initiators for Versatile Synthesis of Conjugated Rod–Coil Block Copolymers

Combining Two Powerful Living Polymerizations Using Rationally Designed Bifunctional Initiators for Versatile Synthesis of Conjugated Rod–Coil Block Copolymers

Ordered Bicontinuous Network Structures Regulated by Orientational Interactions in a Rod-Coil Block Copolymer

Ordered Bicontinuous Network Structures Regulated by Orientational Interactions in a Rod-Coil Block Copolymer

Encounter between Gyroid and Lamellae in Janus Colloidal Particles Self-Assembled by a Rod-Coil Block Copolymer.

Controlling the internal structure of block copolymer (BCP) particles has a significant influence on its functionalities. Here, a structure-controlling method is proposed to regulate the internal structure of BCP Janus colloidal particles using different surfactants. Different microphase separation processes take place in two connected halves of the Janus particles. An order-order transition between gyroid and lamellar phases is observed in polymeric colloids. The epitaxial growth during the structural transformation from gyroid to lamellar phase undergoes a two-layered rearrangement to accommodate the interdomain spacing mismatch between these two phases. This self-assembly behavior can be ascribed to the preferential wetting of BCP chains at the interface, which can change the chain conformation of different blocks. The Janus colloidal particles can further experience a reversible phase transition by restructuring the polymer particles under solvent vapor. It is anticipated that the new phase behavior found in Janus particles can not only enrich the self-assembly study of BCPs but also provide opportunities for various applications based on Janus particles with ordered structures.

Tailoring Wavelength-Adaptive Visual Neuroplasticity Transitions of Synaptic Transistors Comprising Rod-Coil Block Copolymers for Dual-Mode Photoswitchable Learning/Forgetting Neural Functions.

The vision-inspired artificial neural network based on optical synapses has drawn a tremendous amount of attention for emulating biological senses. Although photoexcitation-induced synaptic functionalities have been widely studied, optical habituation via the photoinhibitory pathway is yet to be demonstrated for sophisticated biomimetic visual adaptive systems. Here, the first optical neuromorphic block copolymer (BCP) phototransistor is demonstrated as an all-optical operation responding to various wavelengths, fulfilling photoassisted dynamic learning/forgetting cycles via optical potentiation without gate bias. The polyfluorene BCPs were precisely designed to enable wavelength-adaptive responses, benefiting from interfacial semiconductor/electret morphology and the crystallinity/electron affinity of the BCPs. Notably, this is the first work to simultaneously exhibit fully light-controlled short- and long-term memory based on organic material systems. The device presents a high current contrast above 100-fold and long-term retention over 104 s. As a proof-of-concept for neural networks, a 6 × 6 array of photosynapses performed outstanding visual pattern learning/forgetting with high accuracy. This study exploits the design strategy of a conjugated BCP electret to unleash the full potential of wavelength-adaptive visual neuroplasticity transitions. It provides an effective architecture for designing high-performance and high-storage capacity required applications in next-generation neuromorphic systems.

Asymmetric Polymerization-Induced Crystallization-Driven Self-Assembly of Helical, Rod-Coil Poly(aryl isocyanide) Block Copolymers

Polymerization-induced crystallization-driven self-assembly (PI-CDSA) is combined, for the first time, with helical, rod-coil block copolymer (BCP) self-assembly to enable scalable and controllable in situ synthesis of chiral nanostructures of variable shape, size, and dimensionality. Herein, we report newly developed asymmetric PI-CDSA (A-PI-CDSA) methodologies in the synthesis and in situ self-assembly of chiral, rod-coil BCPs composed of poly(aryl isocyanide) (PAIC) rigid-rod and poly(ethylene glycol) (PEG) random-coil components. Using PEG-based nickel(II) macroinitiators, the construction of PAIC-BCP nanostructures with variable chiral morphologies is accomplished at solids contents ranging 5.0-10 wt %. At low core-to-corona ratios for PAIC-BCPs, we demonstrate the scalable formation of chiral one-dimensional (1D) nanofibers via "living" A-PI-CDSA whose contour lengths can be tuned through alterations to unimer-to-1D seed particle ratio. At high core-to-corona ratios, A-PI-CDSA was implemented for the rapid fabrication of molecularly thin, uniform hexagonal nanosheets via spontaneous nucleation and growth aided by vortex agitation. Investigations into 2D seeded, living A-PI-CDSA revealed a brand-new paradigm in the context of CDSA where hierarchically chiral, M helical spirangle morphologies (i.e., hexagonal helicoids) are size-tuned in three dimensions (i.e., heights and areas) via alterations to unimer-to-seed ratio. These unique nanostructures are formed in situ at scalable solids contents up to 10 wt % via rapid crystallization about screw dislocation defect sites in an enantioselective fashion. The liquid crystalline nature of PAIC blocks dictates the hierarchical assembly of these BCPs, with chirality translated across length scales and in multiple dimensions affording large amplifications in chiroptical activity with g-factors reaching -0.030 for spirangle nanostructures.

Hierarchical 2D-1D micelles self-assembled from the heterogeneous seeded-growth of rod-coil block copolymers.

Precise control of size and dimension is the key to constructing complex hierarchical nanostructures, particularly multi-dimensional hybrid nanoassemblies. Herein, we conducted Brownian dynamics simulations to examine the seeded-growth of rod-coil block copolymer assemblies and discovered that 2D-1D (disk-cylinder) hybrid micelles could be formed via liquid-crystallization-driven self-assembly (LCDSA). 2D nanodisk micelles with smectic-like LC cores served as seeds. After adding rod-coil block copolymers into the seed solution, the copolymers incorporated onto the 2D seed edges to generate junction points. Several cylindrical arms were formed from the elongation of junction points, resulting in 2D-1D multi-dimensional hybrid micelles. The structural transition of the micelle core from smectic-like (disk) to cholesteric-like (cylindrical arms) LC packing manners benefit from the fluidity of LC. Such a seeded-growth behavior simultaneously exhibits the features of heterogeneous nucleation and homogenous epitaxy growth. Intriguingly, the arms generate in sequence, and its junction position is in the para-position first, followed by ortho-position or meta-position, resembling the difference in the substituent activities on the benzene ring. These theoretical findings are consistent with experimental results, and provide explanations to some unaddressed issues in experiments. The obtained results also reveal that the hybrid micelles are a good stabilizer due to their high surface area and distinctive suspension behaviors.

Fabrication of Multilayered Two-Dimensional Micelles and Fibers by Controlled Self-Assembly of Rod-Coil Block Copolymers.

Fabricating hierarchical nanomaterials by self-assembly of rod-coil block copolymers attracts great interest. However, the key factors that affect the formation of the hierarchical nanomaterials have not been thoroughly researched. Herein, we have synthesized two diblock copolymers composed of poly(3-hexylthiophene) (P3HT) and polyethylene glycol (PEG). Through a heating, cooling, and aging process, a series of multilayered hierarchical micelles and fibers were prepared in alcoholic solutions. The transition from fibers to hierarchical micelles are strictly influenced by the strength of the π-π stacking interaction, the PEG chain length, and solvent. In isopropanol, the P3HT22-b-PEG43 could self-assemble into hierarchical micelles composed of several two-dimensional (2D) laminar layers, driven by the π-π stacking interaction and van der Waals force. The P3HT22-b-PEG43 could not self-assemble into well-defined nanostructures in methanol and ethanol, but could self-assemble into fibers in isobutanol. However, the P3HT22-b-PEG113 with a longer corona block only self-assembled into fibers in four alcoholic solutions, due to the increase in dissolving capacity and steric hindrance. The sizes and the size distributions of the nanostructures both increased with the increase in polymer concentration and the decrease in solvent polarity. This study shows a method to fabricate the hierarchical micelles.

Retraction Note to: The highest power conversion efficiencies in poly(3-hexylthiophene)/fullerene photovoltaic cells modified by rod-coil block copolymers under different annealing conditions

Retraction Note to: The highest power conversion efficiencies in poly(3-hexylthiophene)/fullerene photovoltaic cells modified by rod-coil block copolymers under different annealing conditions

2D Liquid-Crystallization-Driven Self-Assembly of Rod-Coil Block Copolymers: Living Growth and Self-Similarity.

Liquid-crystallization-driven self-assembly (LCDSA) is an emerging methodology, which has been employed to construct controllable 1D nanostructures. However, 2D nanostructures via living LCDSA are rarely reported, and the complicated growth kinetics are not well-known. Herein, we perform Brownian dynamics (BD) simulations to investigate the 2D living growth of disklike micelles via LCDSA of rod-coil block copolymers. The 2D seeded-growth behavior is achieved by incorporating the unimers onto the edges of disklike seeds with smectic-like liquid-crystalline (LC) cores. The fluidity of such LC-like micellar cores is conducive to the chain adjustments of rod blocks during the 2D living growth process. The apparent growth rate and unique self-similarity kinetics are governed by the interplay between the variations in the growth rate coefficient and the reactive sites at the micelle edges. This work provides an in-depth understanding of the 2D living growth of micelles and guidance to construct well-defined 2D hierarchical nanostructures.

Polymer Vesicles in a Nanochannel under Flow Fields: A DPD Simulation Study

AbstractThe general lack of knowledge on the dynamics of polymer vesicles under flow field has confounded their applications in drug delivery and other fields. Therefore, dissipative particle dynamics (DPD) simulations on the dynamic behavior of diblock copolymer vesicles in a nanochannel under Poiseuille flow are conducted. The simulation results show that the block copolymer vesicles with hydrophobic blocks of different rigidities exhibit significantly different mechanical stabilities under the flow fields. With increasing the Reynolds number, the coil–coil block copolymer vesicles undergo a shape transition from spherical to bullet‐like to asymmetric and eventually split into two parts. In contrast, the rod–coil block copolymer vesicles deform from spherical to bullet‐like to parachute‐like structures and ultimately ruptured. The flow‐induced distortion and reorganization of copolymers mainly cause the deformation of vesicles. The distinguished motions of the block copolymers with different rigid blocks lead to the distinct performance of the vesicles. The findings could help understand the flow behavior of polymer vesicles in a nanochannel or a blood vessel and assist the design of bio‐functional polymersomes.

Amphiphilic PTB7-Based Rod-Coil Block Copolymer for Water-Processable Nanoparticles as an Active Layer for Sustainable Organic Photovoltaic: A Case Study.

We synthetized a new rod-coil block copolymer (BCP) based on the semiconducting polymerpoly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7) and poly-4-vinylpyridine (P4VP), tailored to produce water-processable nanoparticles (WPNPs) in blend with phenyl-C71-butyric acid methyl ester (PC71BM). The copolymer PTB7-b-P4VP was completely characterized by means of two-dimensional nuclear magnetic resonance (2D-NMR), matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS), size-exclusion chromatography (SEC), and differential scanning calorimetry (DSC) to confirm the molecular structure. The WPNPs were prepared through an adapted miniemulsion approach without any surfactants. Transmission electron microscopy (TEM) images reveal the nano-segregation of two active materials inside the WPNPs. The nanostructures appear spherical with a Janus-like inner morphology. PTB7 segregated to one side of the nanoparticle, while PC71BM segregated to the other side. This morphology was consistent with the value of the surface energy obtained for the two active materials PTB7-b-P4VP and PC71BM. The WPNPs obtained were deposited as an active layer of organic solar cells (OSCs). The films obtained were characterized by UV-Visible Spectroscopy (UV-vis), atomic force microscopy (AFM), and grazing incidence X-ray diffraction (GIXRD). J-V characteristics of the WPNP-based devices were measured by obtaining a power conversion efficiency of 0.85%. Noticeably, the efficiency of the WPNP-based devices was higher than that achieved for the devices fabricated with the PTB7-based BCP dissolved in chlorinated organic solvent.

Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers.

The combination of block copolymer (BCP) thin film self-assembly and selective infiltration synthesis of inorganic materials into one BCP block provides access to various organic-inorganic hybrids. Here, we apply sequential infiltration synthesis, a vapor-phase hybridization technique, to selectively introduce ZnO into the organic microdomains of silicon-containing rod-coil diblock copolymers and a triblock terpolymer, polydimethylsiloxane (PDMS)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS) and PDMS-b-polystyrene-b-PMPCS (PDMS-b-PS-b-PMPCS), in which the PMPCS rod block is a liquid crystalline polymer. The in-plane cylindrical PDMS-b-PMPCS and core-shell cylindrical and hexagonally perforated lamellar PDMS-b-PS-b-PMPCS films were infiltrated with ZnO with high selectivity to the PMPCS. The etching contrast between PDMS, PS and the ZnO-infused PMPCS enables the fabrication of ZnO/SiOx binary composites by plasma etching and reveals the core-shell morphology of the triblock terpolymer.

Rod-Coil Block Copolymer: Fullerene Blend Water-Processable Nanoparticles: How Molecular Structure Addresses Morphology and Efficiency in NP-OPVs.

The use of water-processable nanoparticles (WPNPs) is an emerging strategy for the processing of organic semiconducting materials into aqueous medium, dramatically reducing the use of chlorinated solvents and enabling the control of the nanomorphology in OPV active layers. We studied amphiphilic rod-coil block copolymers (BCPs) with a different chemical structure and length of the hydrophilic coil blocks. Using the BCPs blended with a fullerene acceptor material, we fabricated NP-OPV devices with a sustainable approach. The goal of this work is to clarify how the morphology of the nanodomains of the two active materials is addressed by the hydrophilic coil molecular structures, and in turn how the design of the materials affects the device performances. Exploiting a peculiar application of TEM, EFTEM microscopy on WPNPs, with the contribution of AFM and spectroscopic techniques, we correlate the coil structure with the device performances, demonstrating the pivotal influence of the chemical design over material properties. BCP5, bearing a coil block of five repeating units of 4-vinilpyridine (4VP), leads to working devices with efficiency comparable to the solution-processed ones for the multiple PCBM-rich cores morphology displayed by the blend WPNPs. Otherwise, BCP2 and BCP15, with 2 and 15 repeating units of 4VP, respectively, show a single large PCBM-rich core; the insertion of styrene units into the coil block of BCP100 is detrimental for the device efficiency, even if it produces an intermixed structure.

Achieving Superior Energy Storage Properties of All-Organic Dielectric Polystyrene-Based Composites by Blending Rod–Coil Block Copolymers

With the excessive consumption of natural resources and the miniaturization trends of advanced electronic products and equipment, there is an urgent need to improve the energy density and efficiency of polymeric dielectrics. In this paper, we explore the effect of rod–coil block copolymer polystyrene-b-poly[bis(4-cyanophenyl) 2-vinylterephthalate] (denoted as PS-b-PBCN) on the dielectric behavior and energy storage properties of PS-based blend films. The dipolar glass rigid polymer PBCN can have a columnar nematic phase, a high glass-transition temperature of 156 °C, a high relative permittivity (εr) of 14, and a low band gap of ≈3.44 eV; however, it has poor film-forming properties. Linear dielectric PS possesses low cost, and good film-forming and insulation properties, with a low εr value of 2.5. Two types of PS-b-PBCN block copolymers (PS158-b-PBCN78 and PS158-b-PBCN16), including a coil PS block and an electronically polarized rod PBCN block, are fabricated via reversible addition–fragmentation chain transfer polymerization polymerization. The PBCN/PS- and PS-b-PBCN/PS-blended films are synthesized by solution casting. The experimental results indicate that the εr and breakdown strength of the blend films improve with an increasing mass content of homopolymer PBCN or block copolymer PS-b-PBCN. A maximum εr value of 5.8 at 1 kHz is obtained in the 30 wt % PS158-b-PBCN78/PS blend film owing to the good compatibility and high loading of the polar polymer PBCN. Moreover, a low dielectric loss of 0.018 is found. A discharged energy density of 2.16 J/cm3 with a high efficiency of 90% at 295 MV/m is achieved because PBCN can immobilize free electrons and restrict the long-distance migration of charges. This work provides an idea for the fabrication of all-organic PS-based dielectrics with a high energy storage performance by introducing rod–coil block copolymers.

Programmable Morphology Evolution of Rod-Coil-Rod Block Copolymer Assemblies Induced by Variation of Chain Ordering.

Morphology transition of block copolymer assemblies in response to external stimuli has attracted considerable attention. However, our knowledge about the mechanism of such a transition is still limited, especially for rod-coil block copolymers. Here, we report a programmable morphology evolution of assemblies induced by variation of chain ordering for rod-coil-rod triblock copolymers. A sequence of morphology transition from ellipsoids to disks, bowls, and vesicles is observed by increasing the solution temperature. At high temperatures, the mobility of the rod chain increases and the rigidity of the rod chain decreases. This gives rise to an ellipsoid-to-vesicle morphology transition. Dissipative particle dynamics theoretical simulations were performed to reveal the mechanism of this morphology transition process. It was found that the increase of rod chain mobility and the decrease of rod chain rigidity induce a decrease of chain ordering of rod blocks as temperature increases, which results in an ellipsoid-to-vesicle morphology transition. The gained information can guide the construction of nanoassemblies based on the rod-coil block copolymers.

Bending Behavior and Directed Self-Assembly of Rod-Coil Block Copolymers.

The formation of zigzags, chevrons, Y-junctions, and line segments is demonstrated in thin films formed from cylindrical morphology silicon-containing conformationally asymmetric rod-coil diblock copolymers and triblock terpolymers under solvent annealing. Directed self-assembly of the block copolymers within trenches yields well-ordered cylindrical microdomains oriented either parallel or transverse to the sidewalls depending on the chemical functionalization of the sidewalls, and the location and structure of concentric bends in the cylinders is determined by the shape of the trenches. The innate etching contrast, the spontaneous sharp bends and junctions, and the range of demonstrated periodicity and line/space ratios make these conformationally asymmetric rod-coil polymers attractive for nanoscale pattern generation.

Annealing Process Dependence of the Self-Assembly of Rod–Coil Block Copolymer Thin Films

Thermal annealing, solvent vapor annealing, and a two-step solvent plus thermal annealing are applied to a series of silicon-containing rod–coil thermotropic liquid crystalline (LC) block copolymer thin films with LC volume fractions of 0.42–0.85. Solvent vapor annealing using selective solvents of acetone and heptane produced a wide range of ordered nanostructures with small feature sizes, such as sub-10 nm cylinders, gyroids, and spheres. Subsequent thermal annealing yields final morphologies that depend on the initial morphology and the thermotropic LC phase transition. Combined thermal and solvent annealing as well as design of the rod and coil volume fractions provides an effective way to control the morphologies of rod–coil block copolymers.

Hierarchical nanochannels based on rod-coil block copolymer for ion transport and energy conversion

Designable block copolymer (BCP) membranes are emerging for reverse electrodialysis to capture the salinity gradient energy between seawater and river water. However, present BCP based nanochannels are usually prepared from flexible blocks. Flexible blocks adopt random coil in phase-separated nanostructure that cage charge carriers, increasing the counterions transport resistance. To free the charge carriers, this work engineers a hierarchical ordered hybrid membrane composed of a rod-coil BCP containing positively charged ionic groups and a porous polymeric membrane with negatively charged groups. The rod-coil BCP can self-assembly into hierarchical ordered nanochannels. The rod block adopts rigid rod-like structure inside the channels which improves the orderliness of channels and effectively avoids embedding of ionic groups, dominating the ion transport. The porous polymeric membrane functioning as a supporting layer also participates in the ion transport. This hierarchical ordered device with asymmetric geometry and charge polarity achieves high performance in ion rectification and energy conversion. This strategy highlights the promise in BCP for salinity gradient energy conversion due to its designability and controllability.

Spiral- and meridian-patterned spheres self-assembled from block copolymer/homopolymer binary systems.

Spiral nanostructures, mainly in the 2D form, have been observed in polymer self-assembly, while well-defined 3D spirals are rarely reported. Here we report that a binary system containing polypeptide-based block copolymers and homopolymers can self-assemble into well-defined spiral spheres (3D spirals), in which the homopolymers form the core and the copolymers form the spirals. Upon increasing the preparation temperature, meridian spheres were obtained. Mixing polypeptide block copolymers with opposite backbone chirality also leads to the formation of meridian spheres. In the meridian patterns, a tighter packing manner of the phenyl groups appended to the polypeptide blocks was observed, which is responsible for the spiral-to-meridian transitions. This work enriches the research of spiral assemblies and provides a facile route to switch chiral/achiral nanostructures by regulating the packing manner of the pendant groups.

Tailored Polymer Particles with Ordered Network Structures in Emulsion Droplets.

The structural control of block copolymer (BCP) particles, which determines their properties and utilities, is quite important. Understanding the structural relationship between solution-cast samples and polymer particles in a confined space is necessary to precisely regulate the internal structure of polymer particles. Therefore, a facile method by choosing an appropriate selective solvent is reported to prepare spherical polymer particles with ordered network structures. The rod-coil BCP, poly(dimethylsiloxane)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS), was chosen as a model polymer because of its strong phase segregation ability. First, the structures of the BCP with a thermodynamically stable lamellar structure cast from different selective solvents were systematically studied. Then, a polymer particle with the same internal structure as that of the solution-cast sample can be easily prepared by self-assembling in an emulsion confined space. The relatively large particle size is of importance in this process because the large value of the particle size to periodicity ratio can provide a weak confined environment. This method helps us understand the inherent self-assembling mechanism of polymer particles in an emulsion confined space and accurately control the internal structure of the polymer particle obtained.