Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Ultrathin Ionic Diodes with Electrostatically Heterogeneous Hybrid Interfaces of Nanoporous SiO2 Nanofilms and Polymer Layer-by-Layer Multilayers.

Nanofluidic ionic diodes have attracted much attention due to their unique functions as unidirectional ion transportation ability and promising applications from molecular sensing, and energy harvesting to emerging neuromorphic devices. However, it remains a challenge to fabricate diode-like nanofluidic systems with ultrathin film thickness <100 nm. Herein the formation of ultrathin ionic diodes from hybrid nanoassemblies of nanoporous (NP) SiO2 nanofilms and polyelectrolyte layer-by-layer (LbL) multilayers is described. Ultrathin ionic diodes are prepared by integrating polyelectrolyte multilayers onto photo-oxidized NP SiO2 nanofilms obtained from silsesquioxane-containing block copolymer thin films as a template. The obtained ultrathin ionic diodes exhibit ion current rectification (ICR) properties with high ICR factor = ≈20 under low ionic strength and asymmetric pH conditions. It is concluded that this ICR behavior arises from effective ion accumulation and depletion at the interface of NP SiO2 nanofilms and LbL multilayers attributed to high ion selectivity by combining the experimental data and theoretical calculations using finite element methods. These results demonstrate that the hybrid nano assemblies of NP SiO2 nanofilms and polyelectrolyte LbL multilayers have potential applications for (bio)sensing materials and integrated ionic circuits for seamless connection of human-machine interfaces.

Interrupting marine fouling with active buffered coatings.

Biofouling on marine surfaces causes immense material and financial harm for maritime vessels and related marine industries. Previous reports have shown the effectiveness of amphiphilic coating systems based on poly(dimethylsiloxane) (PDMS) against such marine foulers. Recent studies on biofouling mechanisms have also demonstrated acidic microenvironments in biofilms and stronger adhesion at low-pH conditions. This report presents the design and utilization of amphiphilic polymer coatings with buffer functionalities as an active disruptor against four different marine foulers. Specifically, this study explores both neutral and zwitterionic buffer systems for marine coatings, offering insights into coating design. Overall, these buffer systems were found to improve foulant removal, and unexpectedly were the most effective against the diatom Navicula incerta.

Improved camptothecin encapsulation and efficacy by environmentally sensitive block copolymer/chitosan/fucoidan nanoparticles for targeting lung cancer cells.

In this study, thermo-sensitive poly(N-isopropyl acrylamide) (PNP) was polymerized with pH-sensitive poly(acrylic acid) (PAA) to prepare a PAA-b-PNP block copolymer. Above its cloud point, the block copolymer self-assembled into nanoparticles (NPs), encapsulating the anticancer drug camptothecin (CPT) in situ. Chitosan (CS) and fucoidan (Fu) further modified these NPs, forming Fu-CPT-NPs to enhance biocompatibility, drug encapsulation efficiency (EE), and loading content (LC), crucially facilitating P-selectin targeting of lung cancer cells through a pulmonary drug delivery system. The EE and LC reached 82 % and 3.5 %, respectively. According to transmission electron microscope observation, these Fu-CPT-NPs had uniform spherical shapes with an average diameter of ca. 250 nm. They could maintain their stability in a pH range of 5.0-6.8. In vitro experimental results revealed that the Fu-CPT-NPs exhibited good biocompatibility and had anticancer activity after encapsulating CPT. It could deliver CPT to cancer cells by targeting P-selectin, effectively increasing cell uptake and inducing cell apoptosis. Animal study results showed that the Fu-CPT-NPs inhibited lung tumor growth by increasing tumor cell apoptosis without causing significant tissue damage related to generating reactive oxygen species in lung cancer cells. This system can effectively improve drug-delivery efficiency and treatment effects and has great potential for treating lung cancer.

Excellent Electroluminescent Property of Eu3+-Induced Polystyrene-co-poly(acrylic acid) Aggregates (EIPAs) in Polymeric Light-Emitting Diodes.

Eu3+-induced polystyrene-co-poly(acrylic acid) aggregates (EIPAs) were synthesized using a self-assembly approach, and their structures and photophysical characteristics were examined to achieve effective monochromatic red emission in polymer light-emitting diodes (PLEDs). By adjusting the monomer ratio in RAFT polymerization, the size of Eu3+-induced block copolymer nanoaggregates can be regulated, thereby modulating the luminescence intensity. High-performance bilayer polymer light-emitting devices were fabricated using poly(9,9-dioctylfluorene) (PFO) and 2-(tert-butylphenyl)-5-biphenylyl-1,3,4-oxadiazole (PBD) as the host matrix, with EIPAs as the guest dopant. The devices exhibited narrow red emission at 615 nm with a full width at half-maximum (fwhm) of 15 nm across doping concentrations of 1, 3, 5, and 10 wt %. At a doping concentration of 3 wt %, the device achieved a maximum brightness of 1864.48 cd/m2 at 193.82 mA/cm2 and an external quantum efficiency of 3.20% at a current density of 3.5 mA/cm2. These results indicate that incorporating polystyrene-co-poly(acrylic acid) with Eu3+ complexes enhances the excitation and emission intensity, as well as the structural stability of the emitting layer in PLEDs, thereby improving the device performance.

Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing.

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor Tv and of the substrate Ts on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting Tv/Ts combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.

Block copolymer micelles as ocular drug delivery systems.

Block copolymer micelles, formed by the self-assembly of amphiphilic polymers, address formulation challenges, such as poor drug solubility and permeability. These micelles offer advantages including a smaller size, easier preparation, sterilization, and superior solubilization, compared with other nanocarriers. Preclinical studies have shown promising results, advancing them toward clinical trials. Their mucoadhesive properties enhance and prolong contact with the ocular surface, and their small size allows deeper penetration through tissues, such as the cornea. Additionally, copolymeric micelles improve the solubility and stability of hydrophobic drugs, sustain drug release, and allow for surface modifications to enhance biocompatibility. Despite these benefits, long-term stability remains a challenge. In this review, we highlight the preclinical performance, structural frameworks, preparation techniques, physicochemical properties, current developments, and prospects of block copolymer micelles as ocular drug delivery systems.

Sequential Self-Assembly of Polystyrene-block-Polydimethylsiloxane for 3D Nanopatterning via Solvent Annealing.

This study aims to develop a strategy for the fabrication of multilayer nanopatterns through sequential self-assembly of lamella-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) block copolymer (BCP) from solvent annealing. By simply tuning the solvent selectivity, a variety of self-assembled BCP thin-film morphologies, including hexagonal perforated lamellae (HPL), parallel cylinders, and spheres, can be obtained from single-composition PS-b-PDMS. By taking advantage of reactive ion etching (RIE), topographic SiO2 monoliths with well-ordered arrays of hexagonally packed holes, parallel lines, and hexagonally packed dots can be formed. Subsequently, hole-on-dot and line-on-hole hierarchical textures can be created through a layer-by-layer process with RIE treatment as evidenced experimentally and confirmed theoretically. The results demonstrated the feasibility of creating three-dimensional (3D) nanopatterning from the sequential self-assembly of single-composition PS-b-PDMS via solvent annealing, providing an appealing process for nano-MEMS manufacturing based on BCP lithography.

Fabrication of Stable Liquid-like Wetting Buckled Surfaces as Bioinspired Antibiofouling Coatings by Using Silicon-Containing Block Copolymers.

Inspired by animals with a slippery epidermis, durable slippery antibiofouling coatings with liquid-like wetting buckled surfaces are successfully constructed in this study by combining dynamic-interfacial-release-induced buckling with self-assembled silicon-containing diblock copolymer (diBCP). The core diBCP material is polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS). Because silicon-containing polymers with intrinsic characters of low surface energy, they easily flow over and cover a surface after it has undergone controlled thermal treatment, generating a slippery wetting layer on which can eliminate polar interactions with biomolecules. Additionally, microbuckled patterns result in curved surfaces, which offer fewer points at which organisms can attach to the surface. Different from traditional slippery liquid-infused porous surfaces, the proposed liquid-like PDMS wetting layer, chemically bonded with PS, is stable and slippery but does not flow away. PS-b-PDMS diBCPs with various PDMS volume fractions are studied to compare the influence of PDMS segment length on antibiofouling performance. The surface characteristics of the diBCPs─ease of processing, transparency, and antibiofouling, anti-icing, and self-cleaning abilities─are examined under various conditions. Being able to fabricate ecofriendly silicon-based lubricant layers without needing to use fluorinated compounds and costly material precursors is an advantage in industrial practice.

Antifouling Asymmetric Block Copolymer Nanofilms via Freestanding Interfacial Polymerization for Efficient and Sustainable Water Purification.

Membrane materials that resist nonspecific or specific adsorption are urgently required in widespread applications. In water purification, inevitable membrane fouling not only limits separation performance, but also remarkably increases operation requirements, and augments extra maintenance costs and higher energy consumption. In this work, we report a freestanding interfacial polymerization (IP) fabrication strategy for in-situ creation of asymmetric block copolymer (BCP) nanofilms with antifouling properties, greatly outperforming the conventional surface post-modification approaches. The resultant asymmetric BCP nanofilms with highly-dense, highly-hydrophilic polyethylene glycol (PEG) brushes, can be readily formed via a typical IP process of a double-hydrophilic BCP composed of an antifouling PEG block and a membrane-forming multiamine block. The asymmetric BCP nanofilms have been applied for efficient and sustainable natural water purification, demonstrating extraordinary antifouling capabilities accompanied with superior separation performance far beyond commercial polyamide nanofiltration membranes. The antifouling behaviors of BCP nanofilms derived from the combined effect of the hydration layer, electrostatic repulsion and steric hindrance were further elucidated by water flux and fouling resistance in combination with all-atom molecular dynamics simulation. This work opens up a new avenue for large-scale and low-cost creation of broad-spectrum, asymmetric membrane materials with diverse functional "defect-free" surfaces in real-world applications.

Enhanced photocatalytic performance of coaxially electrospun titania nanofibers comprising yolk-shell particles.

The present paper reports the fabrication of novel types of hybrid fibrous photocatalysts by combining block copolymer (BCP) templating, sol-gel processing, and coaxial electrospinning techniques. Coaxial electrospinning produces core-shell nanofibers (NFs), which are converted into hollow porous TiO2 NFs using an oxidative calcination step. Hybrid BCP micelles comprising a single plasmonic nanoparticle (NP) in their core and thereof derived silica-coated core-shell particles are utilized as precursors to generate yolk-shell type particulate inclusions in photocatalytically active NFs. The catalytic and photocatalytic activity of calcined NFs comprising different types of yolk-shell particles is systematically investigated and compared. Interestingly, calcined NFs comprising silica-coated yolk-shells demonstrate enhanced catalytic and photocatalytic performance despite the presence of silica shell separating plasmonic NP from the TiO2 matrix. Electromagnetic simulations indicate that this enhancement is caused by a localized surface plasmon resonance and a confinement effect in silica-coated yolk-shells embedded in porous TiO2 NFs. Utilization of the coaxially electrospun TiO2 NFs in combination with yolk-shells comprising plasmonic NPs reveals to be a potent method for the photocatalytic decomposition of numerous pollutants. It is worth noting that this study stands as the first occurrence of combining yolk-shells (Au@void@SiO2) with porous electrospun NFs (TiO2) for photocatalytic purposes and gaining an understanding of plasmon and confinement effects for photocatalytic performance. This approach represents a promising route for fabricating highly active and up-scalable fibrous photocatalytic systems.

A Multifunctional Nanostructured Hydrogel as a Platform for Deciphering Niche Interactions of Hematopoietic Stem and Progenitor Cells.

For over half a century, hematopoietic stem cells (HSCs) have been used for transplantation therapy to treat severe hematologic diseases. Successful outcomes depend on collecting sufficient donor HSCs as well as ensuring efficient engraftment. These processes are influenced by dynamic interactions of HSCs with the bone marrow niche, which can be revealed by artificial niche models. Here, a multifunctional nanostructured hydrogel is presented as a 2D platform to investigate how the interdependencies of cytokine binding and nanopatterned adhesive ligands influence the behavior of human hematopoietic stem and progenitor cells (HSPCs). The results indicate that the degree of HSPC polarization and motility, observed when cultured on gels presenting the chemokine SDF-1α and a nanoscale-defined density of a cellular (IDSP) or extracellular matrix (LDV) α4ß1 integrin binding motif, are differently influenced on hydrogels functionalized with the different ligand types. Further, SDF-1α promotes cell polarization but not motility. Strikingly, the degree of differentiation correlates negatively with the nanoparticle spacing, which determines ligand density, but only for the cellular-derived IDSP motif. This mechanism potentially offers a means of predictably regulating early HSC fate decisions. Consequently, the innovative multifunctional hydrogel holds promise for deciphering dynamic HSPC-niche interactions and refining transplantation therapy protocols.

Preparation of Poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/Zinc Oxide Nanocomposite Bioplastics for Potential Use as Flexible and Antibacterial Food Packaging.

High-molecular-weight poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) is a flexible and biodegradable bioplastic that has promising potential in flexible food packaging but it has no antibacterial ability. Thus, in this work, the effect of zinc oxide nanoparticles (nano-ZnOs) which have antimicrobial activity on various properties of PLLA-PEG-PLLA was determined. The addition of nano-ZnOs enhanced the crystallization, tensile, UV-barrier, and antibacterial properties of PLLA-PEG-PLLA. However, the crystallization and tensile properties of nanocomposite films decreased again as the nano-ZnO increased beyond 2 wt%. The nano-ZnO was well distributed in the PLLA-PEG-PLLA matrix when the nano-ZnO content did not exceed 2 wt% and exhibited some nano-ZnO agglomerates when the nano-ZnO content was higher than 2 wt%. The thermal stability and moisture uptake of the PLLA-PEG-PLLA matrix decreased and the film's opacity increased as the nano-ZnO content increased. The PLLA-PEG-PLLA/ZnO nanocomposite films showed good antibacterial activity against bacteria such as Escherichia coli and Staphylococcus aureus. It can be concluded that nano-ZnOs can be used as a multi-functional filler of the flexible PLLA-PEG-PLLA. As a result, the addition of nano-ZnOs as a nucleating, reinforcing, UV-screening, and antibacterial agent in the flexible PLLA-PEG-PLLA matrix may provide protection for both the food and the packaging during transportation and storage.

High χ P2PFBEMA-b-P2VP Block Copolymers Forming 6-8 nm Domains for Semiconductor Lithography.

We leveraged the potential of high χ-low N block copolymer (BCP), namely, poly[2-(perfluorobutyl) ethyl methacrylate]-block-poly(2-vinylpyridine) (P2PFBEMA-b-P2VP), and demonstrated its utility in next-generation nanomanufacturing. By combining molecular dynamics simulations with experiments, the χ value was calculated to be as high as 0.4 (at 150 °C), surpassing similar structures. Highly ordered features suitable for application were observed, ranging in periods from 19.0 nm down to 12.1 nm, with feature sizes as small as 6 nm. Transmission electron microscopy images of the BCP solutions indicated that preformed micelles in the solution facilitated the self-assembly process of the thin film. In addition, the vertical or parallel orientation of the cylindrical structure was determined by manipulating the solvent, substrate, and annealing conditions. Finally, guided by a wide topographical template, nearly defect-free directed self-assembly (DSA) lines with a resolution of 8 nm were achieved, highlighting its potential practical application in DSA lithography technology.

In situ growth of dual-responsive polymer as coating for open tubular capillary electrochromatographic separation of epimedins.

Recently, open tubular capillary electrochromatography (OT-CEC) has captured considerable interest; its efficient separation capability hinges on the interactions between analytes and polymer coatings. However, in situ growth of stimuli-responsive polymers as coatings has been rarely studied and is crucial for expanding the OT-CEC technique and its application. Herein, following poly(styrene-maleicanhydride) (PSM) chemically bonded onto the inner surface of the capillary, a dual pH/temperature stimuli-responsive block copolymer, P(SMN-COOH), was prepared by in situ polymerizing poly(N-isopropylacrylamide) carboxylic acid terminated [P(N-COOH)] in PSM. An OT-CEC protocol was first explored using the coated capillary for epimedins separation. As a proof of concept, the developed OT-CEC system facilitated hydrogen bonding and tuning the hydrophilic/hydrophobic interactions between the test analytes and the P(SMN-COOH) coating by varying buffer pH and environmental temperature. Four epimedins with similar chemical structures were baseline separated under 40 °C at pH 10.0, exhibiting dramatical improvement in separation efficiency in comparison to its performance under 25 °C at pH 4.0. In addition, the coated capillary showed good repeatability and reusability with relative standard deviations for migration time and peak area between 0.7 and 1.7% and between 2.9 and 4.6%, respectively, and no significant changes after six runs. This work introduces a paradigm for efficient OT-CEC separation of herbal medicines through adjusting the interactions between analytes and smart polymer coatings, addressing polymer coating design and OT-CEC challenges.

Biodegradation by Cancer Cells of Magnetite Nanoflowers with and without Encapsulation in PS-b-PAA Block Copolymer Micelles.

Magnetomicelles were produced by the self-assembly of magnetite iron oxide nanoflowers and the amphiphilic poly(styrene)-b-poly(acrylic acid) block copolymer to deliver a multifunctional theranostic agent. Their bioprocessing by cancer cells was investigated in a three-dimensional spheroid model over a 13-day period and compared with nonencapsulated magnetic nanoflowers. A degradation process was identified and monitored at various scales, exploiting different physicochemical fingerprints. At a collective level, measurements were conducted using magnetic, photothermal, and magnetic resonance imaging techniques. At the nanoscale, transmission electron microscopy was employed to identify the morphological integrity of the structures, and X-ray absorption spectroscopy was used to analyze the degradation at the crystalline phase and chemical levels. All of these measurements converge to demonstrate that the encapsulation of magnetic nanoparticles in micelles effectively mitigates their degradation compared to individual nonencapsulated magnetic nanoflowers. This protective effect consequently resulted in better maintenance of their therapeutic photothermal potential. The structural degradation of magnetomicelles occurred through the formation of an oxidized iron phase in ferritin from the magnetic nanoparticles, leaving behind empty spherical polymeric ghost shells. These results underscore the significance of encapsulation of iron oxides in micelles in preserving nanomaterial integrity and regulating degradation, even under challenging physicochemical conditions within cancer cells.

Substrate Neutrality for Obtaining Block Copolymer Vertical Orientation.

Nanopatterning methods utilizing block copolymer (BCP) self-assembly are attractive for semiconductor fabrication due to their molecular precision and high resolution. Grafted polymer brushes play a crucial role in providing a neutral surface conducive for the orientational control of BCPs. These brushes create a non-preferential substrate, allowing wetting of the distinct chemistries from each block of the BCP. This vertically aligns the BCP self-assembled lattice to create patterns that are useful for semiconductor nanofabrication. In this review, we aim to explore various methods used to tune the substrate and BCP interface toward a neutral template. This review takes a historical perspective on the polymer brush methods developed to achieve substrate neutrality. We divide the approaches into copolymer and blended homopolymer methods. Early attempts to obtain neutral substrates utilized end-grafted random copolymers that consisted of monomers from each block. This evolved into side-group-grafted chains, cross-linked mats, and block cooligomer brushes. Amidst the augmentation of the chain architecture, homopolymer blends were developed as a facile method where polymer chains with each chemistry were mixed and grafted onto the substrate. This was largely believed to be challenging due to the macrophase separation of the chemically incompatible chains. However, innovative methods such as sequential grafting and BCP compatibilizers were utilized to circumvent this problem. The advantages and challenges of each method are discussed in the context of neutrality and feasibility.

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates.

Utilizing the self-assembly of block copolymers with large Flory-Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air-polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. We further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

Streamlined Formation and Manipulation of Charged Polymersomes.

Charged polymersomes are attractive for advanced material applications due to their versatile encapsulation capabilities and charge-induced functionality. Although desirable, the pH-sensitivity of charged block copolymers adds complexity to its self-assembly process, making it challenging to produce charged polymersomes in a reliable manner. In this work, a flow approach to control and strike a delicate balance between solvent composition and pH for self-assembly is used. This allows for the identification of a phase window to reliably produce of charged polymersomes. The utility of this approach to streamline downstream processes, such as morphological transformation or in-line purification is further demonstrated. As proof-of-concept, it is shown that the processed polymersomes can be used for surface modifications facilitated by charge complexation.

Block Copolymer Self-assembly: Exploitation of Hydrogen Bonding for Nanoparticle Morphology Control via Incorporation of Triazine Based Comonomers by RAFT Polymerization.

Synthesis of polymeric nanoparticles of controlled non-spherical morphology is of profound interest for a wide variety of potential applications. Self-assembly of amphiphilic diblock copolymers is an attractive bottom-up approach to prepare such nanoparticles. In the present work, RAFT polymerization is employed to synthesize a variety of poly(N,N-dimethylacrylamide)-b-poly[butyl acrylate-stat-GCB] copolymers, where GCB represents vinyl monomer containing triazine based Janus guanine-cytosine nucleobase motifs featuring multiple hydrogen bonding arrays. Hydrogen bonding between the hydrophobic blocks exert significant influence on the morphology of the resulting nanoparticles self-assembled in water. The Janus feature of the GCB moieties makes it possible to use a single polymer type in self-assembly, unlike previous work exploiting, e.g., thymine-containing polymer and adenine-containing polymer. Moreover, the strength of the hydrogen bonding interactions enables use of a low molar fraction of GCB units, thereby rendering it possible to use the present approach for copolymers based on common vinyl monomers for the development of advanced nanomaterials.