Self-assembly Of Block Copolymers Research Articles

Competitive Registration Fields for The Development of Complex Block Copolymer Structures by A Layer-by-Layer Approach.

Block copolymer (BCP) self-assembly in thin films is an elegant method to generate nanometric features with tunable geometrical configurations. By combining directed assembly and hybridization methods, advances in nano-manufacturing have been attested over the past decades with flagship applications in lithography and optics. Nevertheless, the range of geometrical configurations is limited by the accessible morphologies inherent to the energy minimization process involved in BCP self-assembly. Layering of nanostructured BCP thin films has been recently proposed in order to enrich the span of nanostructures derived from BCP self-assembly with the formation of non-native heterostructures such as double-layered arrays of nanowires or dots-on-line and dots-in-hole hierarchical structures. In this work, the layer-by-layer method is further exploited for the generation of nano-mesh arrays using nanostructured BCP thin films. In particular, a subtle combination of chemical and topographical fields is leveraged in order to demonstrate design rules for the controlled registration of a BCP layer on top of an underneath immobilized one by the precise tuning of the interfacial chemical field between the two BCP layers.

Synergy of Block Copolymers and Perovskites: Template Growth through Self-Assembly.

Block copolymers (BCPs) have been widely used as templates to prepare nanostructures over the past few decades. Ordered nanostructures can be formed after microphase segregation of BCPs. In this context, the newly emerging BCP-templated perovskites, in which the perovskite crystal growth has been confined within a self-assembled BCP nanostructure due to the interaction between the polymer block and the cation of the perovskite, have shown profound optical performance and environmental stability. Considering the promising performance of BCP-templated perovskites, this Perspective comprehensively reviews recent works in which BCPs are used as templates with three-dimensional perovskites and perovskite quantum dots, and their performance and stability are thoroughly discussed. Lastly, their potential applications in optoelectronics and biology are discussed.

Dual drug delivery system of RAPTA-C and paclitaxel based on fructose coated nanoparticles for metastatic cancer treatment

Ruthenium complexes have been widely studied as potential alternatives to platinum-type anticancer drugs due to their unique medical properties such as high selectivity, strong ability to inhibit solid tumour metastasis. However, non-specific biodistribution, and weak lethality of ruthenium to cancer cells limit its use in medical application. Drug delivery systems offer the ability to integrate multiple drugs in one system, which is particularly important to enhance the chemotherapeutic efficacy and to potentially achieve a synergistic effect of both drugs. Here, we report a dual drug nanocarrier that is based on a self-assembled biodegradable block copolymer, where the ruthenium complex (RAPTA-C) is chemically attached to the polymer chain, while another drug, paclitaxel (PTX), is entrapped in the core of the micelle. The dual drug delivery system was studied via in vitro tests using MDA-MB-231 breast cancer cells and it was observed that RAPTA-C in combination with PTX significantly enhanced anti-tumour and anti-metastasis activity.

Block Copolymer Self-Assembly Directed Synthesis of Porous Materials with Ordered Bicontinuous Structures and Their Potential Applications.

Porous materials with their ordered bicontinuous structures have attracted great interest owing to ordered periodic structures as well as 3D interconnected network and pore channels. Bicontinuous structures may favor efficient mass diffusion to the interior of materials, thus increasing the utilization ratio of active sites. In addition, ordered bicontinuous structures confer materials with exceptional optical and magnetic properties, including tunable photonic bandgap, negative refraction, and multiple equivalent magnetization configurations. The attractive structural advantages and physical properties have inspired people to develop strategies for preparing bicontinuous-structured porous materials. Among a few synthetic approaches, the self-assembly of block copolymers represents a versatile strategy to prepare various bicontinuous-structured functional materials with pore sizes and lattice parameters ranging from 1 to 500nm. This article overviews progress in this appealing area, with an emphasis on the synthetic strategies, the structural control (including topologies, pore sizes, and unit cell parameters), and their potential applications in energy storage and conversion, metamaterials, photonic crystals, cargo delivery and release, nanoreactors, and biomolecule selection.

Confined Self-Assembly of Block Copolymers within Emulsion Droplets: A Perspective.

When the self-assembly of block copolymers (BCPs) occurs within organic emulsion droplets in the aqueous phase, the strong structural frustration of BCP chains causes the formation of a series of well-regulated BCP particles that cannot be obtained from the self-assembly of BCPs in the bulk state or solution. In this Perspective, we review the recent progress of the self-assembly of BCPs confined in emulsion droplets. The governing factors of the structure and morphology of the as-prepared BCP particles are summarized. In addition, the applications of the as-prepared BCP particles in photonic crystals and drug release are discussed. Finally, we also give a forward-looking perspective on future challenges in this field.

Multilevel Self-Assembly of Block Copolymers and Polymer Colloids for a Transparent and Sensitive Gas Sensor Platform.

The recent emerging significance of the Internet of Things (IoT) demands sensor devices to be integrated with many different functional structures and devices while conserving their original functionalities. To this end, optical transparency and mechanical flexibility of sensor devices are critical requirements for optimal integration as well as high sensitivity. In this work, a transparent, flexible, and sensitive gas sensor building platform is introduced by using multilevel self-assembly of block copolymers (BCPs) and polystyrene (PS) colloids. For the demonstration of an H2 gas sensor, a hierarchically porous Pd metal mesh structure is obtained by overlaying the two different patterned template structures with synergistic, distinctive characteristic length scales. The hierarchical Pd mesh shows not only high transparency over 90% but also superior sensing performance in terms of response and recovery time owing to enhanced Pd-to-hydride ratio and short H2 diffusion lengths from the enlarged active surface areas. The hierarchical morphology also endows high mechanical flexibility while securing reliable sensing performance even under severe mechanical deformation cycles. Our scalable self-assembly based multiscale nanopatterning offers an intriguing generalized platform for many different multifunctional devices requiring hidden in situ monitoring of environmental signals.

Mesogen-jacketed liquid crystal like block copolymers: synthesis and self-assembly to prepare 1D PC thin films

One dimensional photonic crystals (1D PCs) show great potential application in light control, sensors and functional displays. Self-assembly of block copolymer is a facile method to prepare 1D PCs in large area and easy processing. However, due to the low refractive index of polymer and the chain entanglement at very high molecular weight, it is difficult to prepare 1D PCs by self-assembly of linear block copolymers. In this work, mesogen-jacketed liquid crystals like block copolymers with two different lumbar connected benzene terephthalate derivatives and polynorbornene backbone are designed and synthesized. The big steric hindrance of the mesogenic benzene terephthalate derivatives extends the polymer backbone to be rigid, and the resultant block copolymers are rapidly self-assembled into lamellar structures with big domain spacing. The refractive indexes of the two blocks is differentiated by selecting the phenyl and decyl substitute group of benzene terephthalate derivatives. Hence, 1D PCs are prepared by self-assembly of mesogen-jacketed liquid crystals like block copolymers. The maximum reflectance is ranged from ultraviolet to near infrared by increasing the polymerization degree of the block copolymers from 400 to 1400 gradually. The lamellar structures are characterized by cross section scanning electron microscope and small angle X ray scattering. Mesogen-jacketed liquid crystal like block copolymer is favored in 1D PC preparation for its facile synthesis and flexible structure design.

Amphiphilic Block Copolymers: Their Structures, and Self-Assembly to Polymeric Micelles and Polymersomes as Drug Delivery Vehicles.

Self-assembly of amphiphilic block copolymers display a multiplicity of nanoscale periodic patterns proposed as a dominant tool for the 'bottom-up' fabrication of nanomaterials with different levels of ordering. The present review article focuses on the recent updates to the self-association of amphiphilic block copolymers in aqueous media into varied core-shell morphologies. We briefly describe the block copolymers, their types, microdomain formation in bulk and micellization in selective solvents. We also discuss the characteristic features of block copolymers nanoaggregates viz., polymer micelles (PMs) and polymersomes. Amphiphilic block copolymers (with a variety of hydrophobic blocks and hydrophilic blocks; often polyethylene oxide) self-assemble in water to micelles/niosomes similar to conventional nonionic surfactants with high drug loading capacity. Double hydrophilic block copolymers (DHBCs) made of neutral block-neutral block or neutral block-charged block can transform one block to become hydrophobic under the influence of a stimulus (physical/chemical/biological), and thus induced amphiphilicity and display self-assembly are discussed. Different kinds of polymer micelles (viz. shell and core-cross-linked, core-shell-corona, schizophrenic, crew cut, Janus) are presented in detail. Updates on polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are also provided. Polyion complexes (PICs) and polyion complex micelles (PICMs) are discussed. Applications of these block copolymeric micelles and polymersomes as nanocarriers in drug delivery systems are described.

Polymeric micelles in TKIs’ delivery for cancer treatment

Polymeric micelles (PMs), one of the most popular nanotechnology platforms for the delivery of various kinds of chemotherapeutics, are aggregated colloids formed through the self-assembling of amphiphilic block copolymers in an aqueous solvent. The popularity of PMs is owing to several unique physicochemical characteristics such as small size, biocompatibility, core-shell arrangement, high drug loading capacity, and favorable solubility. There is a plethora of studies on the use of these nano-delivery systems over years to overcome the issues related to drug administration, like low water solubility.Tyrosine kinase inhibitors (TKIs) are targeted therapy agents that constitute a significant part of cancer treatment modality due to targeting key biological molecules (EGFRs, PDGFR, and HER2) largely involved in the progression of cancer. However, issues associated with TKIs such as water-insolubility, short circulation time, systemic toxicity, and drug resistance pose challenges in the way of cancer therapy. In the present review, in addition to providing an introduction to micelles and different types of block copolymers, we attempt to present the latest information on clinical and preclinical research on employing PMs to deliver different TKIs to various types of tumors.

Well-Defined Nanostructures by Block Copolymers and Mass Transport Applications in Energy Conversion.

With the speedy progress in the research of nanomaterials, self-assembly technology has captured the high-profile interest of researchers because of its simplicity and ease of spontaneous formation of a stable ordered aggregation system. The self-assembly of block copolymers can be precisely regulated at the nanoscale to overcome the physical limits of conventional processing techniques. This bottom-up assembly strategy is simple, easy to control, and associated with high density and high order, which is of great significance for mass transportation through membrane materials. In this review, to investigate the regulation of block copolymer self-assembly structures, we systematically explored the factors that affect the self-assembly nanostructure. After discussing the formation of nanostructures of diverse block copolymers, this review highlights block copolymer-based mass transport membranes, which play the role of "energy enhancers" in concentration cells, fuel cells, and rechargeable batteries. We firmly believe that the introduction of block copolymers can facilitate the novel energy conversion to an entirely new plateau, and the research can inform a new generation of block copolymers for more promotion and improvement in new energy applications.

Self-Assembly of Amphiphilic Carbosilane-Based Block Copolymers in Organic Media and Structure Formation in Colloidal Confinement

Self-Assembly of Amphiphilic Carbosilane-Based Block Copolymers in Organic Media and Structure Formation in Colloidal Confinement

Control on Pt-containing ordered honeycomb mesoporous nanostructures via self-assembly of block copolymer

Control on the mesoporous nanostructures with uniform-sized and well-arranged mesopores can provide enhanced surface areas and mechanical properties, which are preferred for the development of energies, sensors, and electro-optical devices. Herein, Pt-containing ordered honeycomb (Pt/OHC) nanocomposites with regularly arranged mesopores were synthesized via self-assembly of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers (BCPs), following mechanism study of morphological evolution, concept of structural control, potential in catalyst application, and exploration of various metals. Particularly, it was found that the self-assembly of BCP directed the ordered arrangement of the mesopores, whereas the P4VP blocks incorporated Pt and precisely positioned it on the pore walls and on the outer surface of the honeycomb matrix. Mono- to multi-layered Pt/OHCs could be generated by controlling the thicknesses of the self-assembled pristine templates, and the average diameters of the mesopores could be varied from 12 nm to 40 nm by tuning the PS:P4VP block mass ratios. The obtained Pt/OHC demonstrated promising application as electrocatalysts in hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), for which an overpotential of 39 mV at current density of 10 mA/cm2 (η10) and a high half wave potential (E1/2) of 0.87 V (vs. RHE), respectively, were observed in acidic media. In addition, the strategy developed here could be expanded for other metals, such as Au and Ir, to be incorporated into the ordered honeycomb matrix, providing a robust method to synthesize metal-containing mesoporous nanomaterials. With this work, we aim to offer an insight of designing ordered mesoporous nanocomposites, a concept of control over the mesoporous nanostructures, and a potential for their application in electrocatalysts.

(Invited) ALD-Based Infiltration and Growth of Inorganic Materials in Polymers

Sequential infiltration synthesis (SIS) has emerged in the past decade as a powerful technique for growth of inorganic materials within polymers through atomic layer deposition (ALD) chemistry. In SIS, ALD precursors diffuse into the polymer and interact with it, leading to inorganic materials growth within the polymer’s free volume. If desired, the polymer can later be removed, yielding polymer-templated inorganic structures. Combining SIS with self-assembled block copolymer (BCP) patterns results in selective growth of inorganic materials within the polar domains of the BCP, making it an attractive method for directed templating of inorganic nanostructures. Thus, SIS opens a pathway for exploiting ALD precision and rich materials library in new 3D morphologies, defined by the polymer.To build SIS design rules and expand SIS’ possibilities, we probed SIS growth and evolution at the atomic scale and explored the role of reversible polymer-precursor interactions in SIS growth through a plethora of methods: in-situ growth analysis (microgravimetry and FTIR), ex-situ high-resolution electron microscopy and extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations. This knowledge was then applied in fabrication by design of metal oxide fibers, porous particles, and membranes.We fabricated Al2O3 and ZnO nanofibers, nanobelts, and core-shell fibers using designed growth profiles within electrospun polymer fibers. By controlling the organometallic precursors’ diffusion time, simultaneous but spatially controlled growth of Al2O3 and ZnO within the fibers was achieved, leading to the formation of metal oxide core-shell fibers. Self-assembled BCP particles were used to template porous metal oxide particles by selective growth of Al2O3 in the major block of the self-assembled structure. The uniform BCP assembly led to uniporous pores in the metal oxide particles. Finally, we utilized SIS and ALD within and onto BCP membranes for exceptional pore size control and pores’ surface engineering, yielding highly selective filtration membranes.

Nano-Pattern Oxidation of WSe2 Via Block Copolymer Self-Assembly for Highly Responsive Homojunction Phototransistors

Tungsten diselenide (WSe2), one of the two-dimensional (2D) materials, has emerged as a promising optoelectric candidate because of its thickness dependent bandgap, large optical absorption coefficient, good air stability and high carrier mobility. In addition, the electrical properties of the ambipolar WSe2 could be tuned through the electrostatic doping by the gate modulation. However, the low photo responsivity is a critical problem of WSe2-based optoelectric devices. To overcome this limitation, several approaches have been suggested such as stacking different 2D materials and coating with quantum dots. But these conventional methods were focused on the formation of heterojunctions, which requires complicated alignment process and leads to unavoidable defects and residues. Thus, the novel ways to build homojuction should be investigated for fabricating devices with a clean interface in a simple process.In this work, block copolymer (BCP) was used to prepare hexagonally packed cylinder nano-template as an oxidation mask for UV/ozone treatment, which resulted in numerous nanoscale homojunctions on WSe2. To fabricate the mask with hexagonally packed cylinders, asymmetric poly (styrene-block-methyl methacrylate) (PS-b-PMMA) was spin-coated. After thermal annealing for self-assembly, PMMA was selectively removed by reactive ion etching. UV/ozone treatment, one of the oxidation methods of the WSe2, leads to the formation of the the tungsten oxide (WOX) with high electron affinity and induces a p-doping effect. By using BCP as an oxidation mask, the only region of the WSe2 under the removed PMMA blocks could be converted into WOX.The responsivity of the nano-pattern oxidized WSe2 phototransistor manifests a dramatic change depending on the applied gate bias. The device exhibited a responsivity (532 nm, 8.515 mW/cm2) of 27.5 mA/W under applied gate bias of 0 V. However, under the gate bias of +60 V, the device showed an enhanced responsivity of 155.2 mA/W, as strong p-n junctions were induced. In conclusion, the nano-pattern oxidized WSe2 phototransistor presents increased responsivity (155.2 mA/W), external quantum efficiency (36.3%) and faster response time than the pristine WSe2.This work demonstrates that the responsivity of the WSe2 phototransistor can be improved though well-established perpendicular BCP and optimized by effective modulation of gate bias. By implementing homojunctions on the WSe2 via the nano-pattern oxidation method, this work greatly expands the potential applications of 2D TMDs materials for next-generation nanoscale optoelectronic devices.

Nonequilibrium Self-Assembly of Ultrahigh-Molecular-Weight Block Copolymers into an Asymmetric Nanostructure

Self-assembly of block copolymers (BCPs) provides a unique platform for producing periodic and orderly structured soft materials of nanometer scale. The kinetics of the assembly process defines the accessible range of morphologies and allows for the formation of asymmetric hierarchies. Here, self-assembly of ultrahigh-molecular-weight BCPs with relatively slow molecular chain dynamics is used to fabricate a metastable asymmetric structure. More specifically, a kinetically trapped solvent vapor annealing process is applied to poly(styrene-block-2-vinylpyridine) thin films, wherein the concentration ratio of trichloroethylene to tetrahydrofuran of the mixed solvent vapor gradually increases throughout the annealing process, pushing the system away from equilibrium. Under such a dynamic process, poly(styrene-block-2-vinylpyridine) micelles rearrange into vertical protuberances that mimic moth-eye structures enhancing the light transmission. Sequential infiltration synthesis is used to convert the poly-2-vinylpyridine domain into alumina in order to verify the formation mechanism of the asymmetric protuberances. It is determined that vertically packed and merged micelles are only formed under a gradually built solvent vapor environment.

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.

Well-Defined pH-Responsive Self-Assembled Block Copolymers for the Effective Codelivery of Doxorubicin and Antisense Oligonucleotide to Breast Cancer Cells.

The worldwide steady increase in the number of cancer patients motivates the development of innovative drug delivery systems for combination therapy as an effective clinical modality for cancer treatment. Here, we explored a design concept based on poly(ethylene glycol)-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate-formylbenzoic acid) [PEG-b-PDMAEMA-b-P(HEMA-FBA)] for the dual delivery of doxorubicin (DOX) and GTI2040 (an antisense oligonucleotide for ribonucleotide reductase inhibition) to MCF-7 breast cancer cells. PEG-b-PDMAEMA-b-PHEMA, the precursor copolymer, was prepared through chain extensions from a PEG-based macroinitiator via two consecutive atom transfer radical polymerization (ATRP) steps. Then, it was modified at the PHEMA block with 4-formylbenzoic acid (FBA) to install reactive aldehyde moieties. A pH-responsive polymer-drug conjugate (PDC) was obtained by conjugating DOX to the polymer structure via acid-labile imine linkages, and subsequently self-assembled in an aqueous solution to form DOX-loaded self-assembled nanoparticles (DOX-SAN) with a positively charged shell. DOX-SAN condensed readily with negatively charged GTI2040 to form GTI2040/DOX-SAN nanocomplexes. Gel-retardation assay confirmed the affinity between GTI2040 and DOX-SAN. The GTI2040/DOX-SAN nanocomplex at N/P ratio of 30 exhibited a volume-average hydrodynamic size of 136.4 nm and a zeta potential of 21.0 mV. The pH-sensitivity of DOX-SAN was confirmed by the DOX release study based on the significant cumulative DOX release at pH 5.5 relative to pH 7.4. Cellular uptake study demonstrated favorable accumulation of GTI2040/DOX-SAN inside MCF-7 cells compared with free GTI2040/DOX. In vitro cytotoxicity study indicated higher therapeutic efficacy of GTI2040/DOX-SAN relative to DOX-SAN alone because of the downregulation of the R2 protein of ribonucleotide reductase. These outcomes suggest that the self-assembled pH-responsive triblock copolymer is a promising platform for combination therapy, which may be more effective in combating cancer than individual therapies.

Reorientation of Crystalline Block Copolymer Membranes by Phospholipid Hybridization

Block copolymer (BCP) self-assembly and crystallization determine their fundamental mechanical, optical, and transport properties. Multiple physical and chemical routes to control BCP self-assembly have been developed over the years. In contrast, modulating the crystallization behavior, particularly crystallite size and orientation, has received considerably less attention. This paper underpins that 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) phospholipid additives enable precise control of BCP crystallization via a combination of interfacial and confinement effects. The assembly and crystallization behavior of methoxy-poly(ethylene glycol)-b-poly(ε-caprolactone) (mPEG-b-PCL) hybridized with DPPC was elucidated in solid-supported dry-film forms. mPEG-b-PCL/DPPC hybrid films coassemble into multilamellar structures with BCP and lipid domains stacked in registry across the film thickness. With small amounts of DPPC (3 wt %), mPEG-b-PCL/DPPC hybrid films unexpectedly exhibit nonadditive thermal conductivity, reaching ∼0.1 W m–1 K–1, a value considerably lower than pure BCP or DPPC films. Hybridization alters DPPC chain packing and induces specific PCL crystallite orientation at the nanoscale. PCL chains on the folding plane of an orthorhombic lattice optimize molecular interactions with vertically aligned DPPC alkyl chains by orienting PCL crystallites at a 20° tilt. These results enable new applications of polymeric systems in which switchable crystallization routes are used to tune heat transport.

Self-assembly of POSS-Polystyrene Bottlebrush Block Copolymers on an Angle-Robust Selective Absorber for Enhancing the Purity of Reflective Structural Color.

A facile approach for improving color purity is explored by the introduction of an angle-robust selective absorber (ARSA) into bottlebrush block copolymer (BBCP)-based one-dimensional (1D) photonic crystals (PCs). The BBCPs of poly[(3-(12-(cis-5-norbornene-exo-2,3-dicarboximido)dodecanoylamino)propyl POSS)-block-(norbornene-graft-styrene)], Px (x = 1-4), with ultrahigh molecular weights (Mn ∼ 2260 kDa) and low dispersities (D̵ ∼ 1.07) are synthesized by ring-opening metathesis polymerization. The 1D PCs of the lamellar structure are fabricated by self-assembly of the BBCP with different periodicities for full color-generation (blue, green, and red). The optically tailored substrate (i.e., ARSA) is used to modulate the spectral line shape with selective absorption in the near-infrared range. Optical simulation proposes the optimized 1D PC structures on the ARSA, and it provides the reproducibility of the predictable color. The simulated structures are well matched with the experimental results, verifying the enhancement of color saturation even at various incident angles (0-70°).

The Effect of Topology on Block Copolymer Nanoparticles: Linear versus Star Block Copolymers in Toluene.

Linear and star block copolymer (BCP) nanoparticles of (polystyrene-block-poly(4-vinylpyridine))n (PS-b-P4VP)n with arm numbers of 1, 2, 3, and 4 were prepared by two methods of polymerization-induced self-assembly (PISA) and general self-assembly of block copolymers in the low-polar organic solvent, toluene. The effect of the arm number on the size and/or morphology of the (PS-b-P4VP)n nanoassemblies synthesized by the two methods in toluene and on the polymerization kinetics was investigated in detail. Our results show that in toluene, a low-polar solvent, the topology not only affected the morphology of the BCP nanoparticles prepared by PISA, but also influenced the BCP nanoparticles synthesized through general self-assembly.