Block Copolymers Research Articles

PH and light-triggered shape transformation of block copolymer particles in emulsion droplets

Dual-responsive shape-transformable block copolymer (BCP) particles have arisen great attentions because of their tunable physical and chemical characteristics triggered by external stimuli. Herein, we developed a simple yet effective strategy to realize pH and light dual-triggered shape-switchable BCP particles through the co-assembly of BCPs with photo-responsive additive 4-hydroxyazobenzene (Azo-OH) within the evaporation emulsion droplets. The formation of hydrogen bonding interactions between the Azo-OH and 4-vinylpyridine (4VP) unit increases the volume fraction of P4VP domain, in turn leading to a morphological transition of the particles from onions to pupas by tuning the Azo-OH content. Subsequent light-induced trans–cis transition of the Azo unit induces the enhancement of the hydrophilicity of the P4VP domains, giving rise to internal shape transitions of the BCP particles from pupas to onions with P4VP at the outmost-layer. Furtherly, since the hydrogen bonds between Azo-OH and 4VP group are sensitive to pH, the interfacial properties of the emulsion droplets and the assembled structures are tuned through adjusting the environment pH of the aqueous solution, causing the formation of various particle shape, including pupas, raspberries, and onions. This work offers a promising method to engineer the microstructures of polymeric assemblies, which may attract more attention on the applications of the stimuli-responsive particles.

Improved property of block copolymer-based anion exchange membranes by attaching multi-ion flexible strings

To meet high conductivity and sufficient anti-swelling of anion exchange membranes (AEMs), a collaborative strategy of combining multi-ion flexible string and block backbone is adopted to construct membrane’s architecture. Then a series of adamantane-contained poly(arylether ketone nitrile)s block copolymers has been synthesized and grafted with multi-ion flexible strings to form hydrophilic domains. In addition, the hydrophobic segments with nitrile groups are aimed to enhance the entanglement between chains and limit swelling degrees of membranes. Along the steps, clear phase separation morphologies are formed for creating efficient ionic channels. The resulted AEMs exhibit improved conductivity and dimensional stability at low hydration levels, e.g. conductivity of 91.7−119.4 mS cm-1, swelling ratio (SR) of 14.4%−19.5%, water uptake (WU) of 38.3%−57.9% and λ values of 13.4−15.7 at 80 °C. Furthermore, the AEMs prepared exhibit excellent mechanical properties and good thermal stability below 180 °C. However, further optimization is required for a better alkaline stability.

Efficient biotransformation of biobased raw materials into novel polyesters/polyesteramides; comparative investigation of enzymatic synthesis of block and random copolymers and terpolymers

Within the context of paving the way for a sustainable bioeconomy, there is a strong emphasis on utilizing bio-based raw materials as substitutes for fossil fuels in the production of polymers. When designing the synthesis of novel polymeric materials from bio-based building blocks, a promising green approach consists in utilizing enzymes as biocatalysts. This aspect is particularly important when aiming to obtain products from the class of polyesters and polyesteramides with biocompatible and biodegradable properties, as enzymes facilitate the synthesis of polymers that align closely with biological systems. Lipases have been proven to be very effective in the synthesis of polymers, particularly in the ring-opening polymerization of ε-caprolactone. Considering the possibility of performing the copolymerization of ε-caprolactone for obtaining random and block structures, this is the first comparative study of the enzymatic polymer synthesis utilizing an innovative approach of combining ring-opening polymerization with polycondensation. Terpolymers derived from ε-caprolactone and dimethyl itaconate or dimethyl adipate with either 1,8-octanediol or 1,8-octanediamine were obtained at 85 °C in a solventless systems, yielding products with a copolymer content of >85 % and weight-average molecular weight (Mw) up to 40,000 Da. The thermal properties and biodegradation behavior of the synthetized terpolymers were assessed.

Exploring the catalytic performance of recyclable zinc indium sulfide in polymer synthesis: Well-controlled photoATRP of acrylates

Zinc indium sulfide has been used as a heterogeneous recyclable photocatalyst in visible light-induced atom transfer radical polymerization (ATRP). The photocatalyst was found to catalyze ATRP via an oxidative quenching mechanism without any additives. Polymers in high conversion and good control can be obtained. The kinetic study, light on/off experiment and the block copolymer synthesis showed the “living”/controlled nature of the polymerization. The photocatalyst can be reused for five times without obvious loss of control in the polymerization. Metal residue was not detected in the resulting polymers. This strategy provides a noval way for well-controlled polymer synthesis using recyclable visible light photocatalysis.

Block copolymer nanoparticles doping polyacrylonitrile membranes for efficient adsorption of water-soluble dyes from water

Block copolymer nanoparticles doping polyacrylonitrile membranes for efficient adsorption of water-soluble dyes from water

Thermally Induced Gelling Systems Based on Patchy Polymeric Micelles

AbstractThermogels that exhibit a sol‐gel transition at body temperature represent a promising class of injectable biomaterials for biomedical applications. Thermogels reported thus far are generally composed of amphiphilic block copolymer micelles with an isotropic thermosensitive surface that induces intermicellar aggregation upon heating. Despite the promise, these hydrogels exhibit low mechanical strengths due to their uncontrollable aggregation resulting in void formation. To gain better control over intermicellar assembly, herein a novel thermogel design concept is presented based on patchy polymeric micelles bearing multiple thermosensitive surface domains. These domains serve as “patches” to bridge the micelles to form a percolated network structure. Patchy micelles are prepared from a binary mixture of amphiphilic block copolymers: Poly(N‐acryloylmorpholine)‐b‐poly(N‐benzylacrylamide) (PAM‐PBzAM) and poly (N‐isopropyl acrylamide)‐b‐poly(N‐benzylacrylamide) (PNIPAM‐PBzAM), where PBzAM, PAM and PNIPAM are the hydrophobic, hydrophilic and thermosensitive blocks, respectively. At 25 °C, the polymers self‐assembled into mixed shell micelles having a phase‐separated shell with PAM‐ and PNIPAM‐rich domains. At 37 °C, the PNIPAM domains undergo a hydrophilic‐to‐hydrophobic transition to induce intermicellar assembly into entangled worm‐like structures resulting in hydrogel formation. Patchy micelles form a homogeneous network structure without voids. The micelle design significantly affects the inter‐micellar assembly, the thermogelling behavior, and the mechanical properties of the hydrogels.

Precisely Prepared Hierarchical Micelles of Polyfluorene‐block‐Polythiophene‐block‐Poly(phenyl isocyanide) via Crystallization‐Driven Self‐Assembly

AbstractThe precise preparation of hierarchical micelles is a fundamental challenge in modern materials science and chemistry. Herein, poly(di‐n‐hexylfluorene)‐block‐poly(3‐tetraethylene glycol thiophene) (poly(1m‐b‐2n)) diblock copolymers and polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock copolymers were synthesized using a one‐pot process via the sequential addition of corresponding monomers using a Ni(II) complex as a single catalyst for living/controlled polymerization. The crystallization‐driven self‐assembly of amphiphilic conjugated poly(1m‐b‐2n) led to the formation of nanofibers with controlled lengths and narrow dispersity. The block copolymers exhibited white, yellow, and red emissions in different self‐assembly states. By using uniform poly(1m‐b‐2n) nanofibers as seeds, introducing the polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock polymer as a unimer in the seed growth process, and adjusting the structure of the poly(phenyl isocyanide) block and the polarity of self‐assembly solvent, A−B−A triblock micelles, multiarm branched micelles, and raft micelles were prepared.

Light-Driven Organocatalyzed Controlled Radical Copolymerization of (Perfluoroalkyl)ethylenes and Vinyl Esters/Amides.

Fluoropolymers of well-defined structures exhibit significant potential in a broad range of high-tech applications. However, the controlled synthesis of fluoropolymers from easily available monomers remains difficult. In this work, we report the development of an organocatalyzed controlled radical copolymerization of (perfluoroalkyl)ethylenes (PFAEs) and unconjugated vinyl monomers (UCMs) under light irradiation, which has enabled on-demand access toward side-chain fluorinated polymers under metal-free conditions. This method furnishes a large variety of polymers with diverse fluoroalkyl and ester/amide as pendent groups, tunable molar masses, and low dispersities (ca. Đ = 1.1-1.3), and adjustable fractions of PFAE and UCM units. Obtained fluoropolymers exhibit good chain-end fidelity and activity, allowing chain-extension polymerizations to prepare block copolymers of complicated compositions. Furthermore, the PFAE copolymers exhibit outstanding light transmission and low refractive index.

Chemiluminescence-based evaluation of styrene block copolymers' recyclability.

The study presents the chemiluminescence based (CL) evaluation of the recyclability of linear styrene block copolymers. This analysis can provide insight into the material's degradation state and predict its suitability for further recycling cycles, helping to avoid unnecessary energy consumption during processing.The thermal stability of four similar copolymer structures - styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) copolymers with different styrene/butadiene ratios, and styrene-ethylene-butadiene-styrene (SEBS) - was studied using isothermal and non-isothermal chemiluminescence (CL). The activation energies for oxidative degradation were calculated based on oxidation induction times indicated by the CL intensities evolution. The results, which highlight the influence of molecular structure on stability under aging conditions, as presented by the calculated for the activation energy (kJ mol-1), show the following sequence: SBS (styrene 30%) (117kJ mol-1) ≈ SIS 120 (kJ mol-1) < SBS (styrene 40%) (176kJ mol-1) < SEBS (180kJ mol-1). The CL data were correlated with infrared (IR) spectroscopy and differential scanning calorimetry (DSC) data, providing a comprehensive understanding of the thermal stability and degradation mechanisms during recycling proces. The sequence of the composing units determines the degradation process, with weaker points predominantly attacked in the linear moieties of isoprene, butadiene, and vinyl segments. The experimental data indicate that SIS and SBS (30% styrene) copolymers degrade the fastest likely due to the rapid accumulation of hydroperoxide radicals. The SEBS copolymer also experiences significant degradation, but this occurs at higher temperatures (above 220 ⁰C) and progresses more gradually once it begins. In contrast, the SBS copolymer with 40% styrene content degrades more slowly and exhibits minimal mass loss, primarily due to the formation of less reactive keto degradation products.

Entropically driven phase separation and effective multibody interactions in block copolymers

Entropically driven phase separation and effective multibody interactions in block copolymers

Preparation and characterization of poly(ethylene glycol)-b-poly(tert-butyl methacrylate) micelles as potential nanocarriers for donepezil

Polymeric micelles were prepared for the delivery of donepezil, a leading Alzheimer’s disease drug, to enhance its transport across the blood–brain barrier (BBB). Poly(ethylene glycol)-b-poly(tert-butyl methacrylate) amphiphilic block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by gel permeation chromatography and nuclear magnetic resonance spectroscopy. Empty and donepezil loaded polymer micelles were formed using the dialysis method and characterized by dynamic light scattering and transmission electron microscopy. Drug loading efficiency and release behavior were monitored using UV/Vis spectroscopy, and cytotoxicity was evaluated via colorimetric tests and impedance measurements. Additionally, the permeability of the nanocarriers across an in vitro BBB culture model was assessed. Drug-loaded micelles demonstrated similar permeability to free donepezil but offered sustained release and improved stability. This micellar delivery system holds significant potential for improving therapeutic outcomes in Alzheimer’s treatment by enhancing donepezil’s delivery across the BBB. Improved BBB permeability and sustained drug release could lead to more effective concentration of the drug in the brain, potentially reducing peripheral cholinergic side effects, such as nausea and vomiting, often observed with traditional donepezil administration. This could result in better patient compliance and improved cognitive outcomes, making this nanocarrier system a promising alternative for Alzheimer’s therapy.

Dual-responsive nanoparticles for enhanced drug delivery in breast Cancer chemotherapy.

Drug delivery efficiency often affects chemotherapy outcome due to dense collagen barrier in tumor environment. Here, we report a nanoparticle capable of pH and glutathione dual-responsive drug delivery to enhance the efficacy of breast cancer chemotherapy. Maleiminated polyethylene glycol and polylactide block copolymer were synthesized as a core material, doxorubicin was encapsulated into the nanoparticle by self-assembly. Thiocollagenase and maleimide were connected on the nanoparticle surface by click chemistry, and further coated with chondroitin sulfate as a protective layer to form dual-responsive doxorubicin nanoparticle. The results showed that the nanoparticle had the ability to penetrate deep tumor tissue, to target on CD44 of cancer cell, and to release doxorubicin in cancer cell in response to pH and glutathione signals, demonstrating superior anticancer efficacy in breast cancer-bearing mice. In conclusion, the dual-responsive nanoparticle could be used as a drug carrier to enhance drug delivery in breast cancer chemotherapy.

Neuro-Actuating Photonic Skin Enabled by Ion-Gel Transistor with Thermo-Adaptive Block Copolymer.

Despite significant progress in developing artificial synapses to emulate the human nervous system for bio-signal transmission, synapses with thermo-adaptive coloration and soft actuators driven by temperature change have seldom been reported. Herein, a photonic neuro-actuating synaptic skin is presented enabling thermoresponsive synaptic signal transmission, color variation, and actuation. First, a thermoresponsive display synapse is developed based on a 3-terminal ion-gel transistor with a poly (3,4-ethylene dioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) semiconducting channel mixed with 2D titanium carbide (Ti3C2Tx) MXene and a thermo-adaptive 1D block copolymer (BCP) photonic crystal (PC) gate insulator. Temperature-dependent synaptic behavior is successfully observed in the ion-gel transistor with the corresponding structural colors, leading to a thermo-adaptive display synapse. The 3 × 3 arrays of thermo-adaptive display synapses with Joule heaters show that each pixel is controlled by the thermoresponsive structural color and synaptic output. The synaptic output current from the MXene ion-gel transistor can be converted and amplified to a voltage signal, which powers a soft actuator connected to the ion-gel display synapse and triggers temperature-dependent actuation related to the thermoresponsive synaptic performance. This study showcases a thermo-adaptive photonic neuro-actuating artificial skin that emulates muscle-combined neuronal human skin with visualization capability.

Computational Phase Discovery in Block Polymers.

Self-consistent field theory (SCFT), the mean-field theory of polymer thermodynamics, is a powerful tool for understanding ordered state selection in block copolymer melts and blends. However, the nonlinear governing equations pose a significant challenge when SCFT is used for phase discovery because converging an SCFT solution typically requires an initial guess close to the self-consistent solution. This Viewpoint provides a concise overview of recent efforts where machine learning methods (particle swarm optimization, Bayesian optimization, and generative adversarial networks) have been used to make the first strides toward converting SCFT from a primarily explanatory tool into one that can be readily deployed for phase discovery.

The Role of Interfacial Effects in the Impedance of Nanostructured Solid Polymer Electrolytes

The role of interfacial effects on an ion-conducting poly(styrene-b-ethylene oxide) (PS-b-PEO or SEO) diblock copolymer doped with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was investigated by electrochemical impedance spectroscopy (EIS). Coating the surface of commonly used stainless steel electrodes with a specific random copolymer brush increases the measured ionic conductivity by more than an order of magnitude compared to the uncoated electrodes. The increase in ionic conductivity is related to the interfacial structure of the block copolymer domain morphology on the electrode surface. We show that the impedance associated with the electrode–electrolyte interface can be detected using nonmetallic electrodes, allowing us to distinguish the ionic conductivity behaviors of the bulk electrolyte and the interfacial layers for both as-prepared and annealed samples.

Propagator-Biased Chain Generation: Accurately Reverse Mapping Microphase-Separated Block Copolymers

Propagator-Biased Chain Generation: Accurately Reverse Mapping Microphase-Separated Block Copolymers

Preparation of Lipid–Polymer Conjugates by Photoiniferter Polymerization and Application to Cell Surface Modification

ABSTRACTThe growing demand for lipid–polymer conjugates (LPCs) in biomedicine highlights the need for efficient synthesis methods. This study presents a novel Y‐type photoiniferter reagent (Lipid‐PIT) with a diethyldithiocarbamate group and a diacylglycerol group. Lipid‐PIT efficiently initiated the polymerization of vinyl monomers such as oligo(ethylene glycol) methacrylate (OEGMA), N,N‐dimethylacrylamide (DMA), tert‐butyl acrylate (tBA), and n‐butyl acrylate (nBA) under UV irradiation at room temperature, yielding LPCs. Proton NMR confirmed the presence of diethyldithiocarbamate and diacylglycerol moieties at the chain ends. The polymerization kinetics of DMA showed a linear increase in molecular weight (Mn) with time, with a polydispersity (Đ) below 1.50, demonstrating high controllability. Moreover, Lipid‐PIT allows for the creation of block copolymers via secondary chain extension. In vitro assays revealed that LPCs synthesized from OEGMA monomers successfully modified L929 and HeLa cell surfaces and exhibited good biocompatibility. This study offers a rapid, efficient method for LPC synthesis with promising biomedical applications.

Research Trends in the Development of Block Copolymer-Based Biosensing Platforms

Biosensing technology, which aims to measure and control the signals of biological substances, has recently been developed rapidly due to increasing concerns about health and the environment. Top–down technologies have been used mainly with a focus on reducing the size of biomaterials to the nano-level. However, bottom–up technologies such as self-assembly can provide more opportunities to molecular-level arrangements such as directionality and the shape of biomaterials. In particular, block copolymers (BCPs) and their self-assembly have been significantly explored as an effective means of bottom–up technologies to achieve recent advances in molecular-level fine control and imaging technology. BCPs have been widely used in various biosensing research fields because they can artificially control highly complex nano-scale structures in a directionally controlled manner, and future application research based on interactions with biomolecules according to the development and synthesis of new BCP structures is greatly anticipated. Here, we comprehensively discuss the basic principles of BCPs technology, the current status of their applications in biosensing technology, and their limitations and future prospects. Rather than discussing a specific field in depth, this study comprehensively covers the overall content of BCPs as a biosensing platform, and through this, we hope to increase researchers’ understanding of adjacent research fields and provide research inspiration, thereby bringing about great advances in the relevant research fields.

Engineering an Ultrasound-Responsive Glycopolymersome for Hepatocyte-Specific Gene Delivery.

The ability to design liver-targeted gene delivery vectors is plagued with difficulties ranging from carrier-mediated cellular toxicity to challenges in encapsulating sensitive nucleic acids. Herein, we present an ultrasound-responsive glycopolymersome strategy for in situ loading of nucleic acids and achieving hepatocyte-specific gene delivery. This glycopolymersome is self-assembled from a block copolymer, N-acetylgalactosamine-grafted poly(glutamic acid)-block-poly(ε-caprolactone) (PGAGalNAc-b-PCL). GalNAc is introduced to afford liver targeting through the selective binding to the asialoglycoprotein receptor overexpressed on hepatocytes. External ultrasound is utilized to assist in encapsulating nucleic acids within the hydrophilic lumen of glycopolymersomes by exploiting their ultrasound responsiveness nature. Biological studies confirmed the successful encapsulation of plasmid DNA (pDNA) and small interfering RNA (siRNA), rapid nuclear internalization, and efficient gene transfection. These findings collectively demonstrated that this ultrasound-responsive glycopolymersome could be exploited as a novel safe and efficient gene vector targeting hepatocytes.

Understanding Separation of Oil-Water Emulsions by High Surface Area Polymer Gels Using Experimental and Simulation Techniques.

This work examines the functional dependence of the efficiency of separation of oil-water emulsions on surfactant adsorption abilities of high surface area polymer gels. The work also develops an understanding of the factors and steps that are involved in emulsion separation processes using polymer gels. The work considers four polymer gels offering different surface energy values, namely, syndiotactic polystyrene (sPS), polyimide (PI), polyurea (PUA), and silica. The data reveal that surfactant adsorption abilities directly control the emulsion separation performance. The gels of sPS and PI destabilize the emulsions due to significant surfactant adsorption. The surfactant-lean oil droplets are then absorbed in the pores of sPS and PI gels due to the preferential wettability of the oil phase. The PUA and silica gels are more hydrophilic and show a lower surfactant adsorption ability. These gels cannot effectively remove the surfactant molecules from the emulsions, leading to a poor emulsion separation performance. The study uses simulation data to understand the adsorption characteristics of two poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer surfactants. The simulation results are used for the interpretation of emulsion separation performance by the gels.