Controlled node growth on the surface of polymersomes.

Incorporating nucleobases into synthetic polymers has proven to be a versatile method for controlling self-assembly. The formation of strong directional hydrogen bonds between complementary nucleobases provides a driving force that permits access to complex particle morphologies. Here, nucleobase pairing was used to direct the formation and lengthening of nodes on the outer surface of vesicles formed from polymers (polymersomes) functionalised with adenine in their membrane-forming domains. Insertion of a self-assembling short diblock copolymer containing thymine into the polymersome membranes caused an increase in steric crowding at the hydrophilic/hydrophobic interface, which was relieved by initial node formation and subsequent growth. Nano-objects were imaged by (cryo-)TEM, which permitted quantification of node coverage and length. The ability to control node growth on the surface of polymersomes provides a new platform to develop higher-order nanomaterials with tailorable properties.

A New Architecture for DNA-Templated Synthesis in Which Abasic Sites Protect Reactants from Degradation.

The synthesis of artificial sequence-defined polymers that match and extend the functionality of proteins is an important goal in materials science. One way of achieving this is to program a sequence of chemical reactions between precursor building blocks by means of attached oligonucleotide adapters. However, hydrolysis of the reactive building blocks has so far limited the length and yield of product that can be obtained using DNA-templated reactions. Here, we report an architecture for DNA-templated synthesis in which reactants are tethered at internal abasic sites on opposite strands of a DNA duplex. We show that an abasic site within a DNA duplex can protect a nearby thioester from degradation, significantly increasing the yield of a DNA-templated reaction. This protective effect has the potential to overcome the challenges associated with programmable, sequence-controlled synthesis of long non-natural polymers by extending the lifetime of the reactive building blocks.

2D Hierarchical Microbarcodes with Expanded Storage Capacity for Optical Multiplex and Information Encryption.

The design of nanosegregated fluorescent tags/barcodes by geometrical patterning with precise dimensions and hierarchies could integrate multilevel optical information within one carrier and enhance microsized barcoding techniques for ultrahigh-density optical data storage and encryption. However, precise control of the spatial distribution in micro/nanosized matrices intrinsically limits the accessible barcoding applications in terms of material design and construction. Here, crystallization forces are leveraged to enable a rapid, programmable molecular packing and rapid epitaxial growth of fluorescent units in 2D via crystallization-driven self-assembly. The fluorescence encoding density, scalability, information storage capacity, and decoding techniques of the robust 2D polymeric barcoding platform are explored systematically. These results provide both a theoretical and an experimental foundation for expanding the fluorescence storage capacity, which is a longstanding challenge in state-of-the-art microbarcoding techniques and establish a generalized and adaptable coding platform for high-throughput analysis and optical multiplexing.

Enhancing the Scalability of Crystallization-Driven Self-Assembly Using Flow Reactors.

Anisotropic materials have garnered significant attention due to their potential applications in cargo delivery, surface modification, and composite reinforcement. Crystallization-driven self-assembly (CDSA) is a practical way to access anisotropic structures, such as 2D platelets. Living CDSA, where platelets are formed by using seed particles, allows the platelet size to be well controlled. Nonetheless, the current method of platelet preparation is restricted to low concentrations and small scales, resulting in inefficient production, which hampers its potential for commercial applications. To address this limitation, continuous flow reactors were employed to improve the production efficiency. Flow platforms ensure consistent product quality by maintaining the same parameters throughout the process, circumventing batch-to-batch variations and discrepancies observed during scale-up. In this study, we present the first demonstration of living CDSA performed within flow reactors. A continuous flow system was established, and the epitaxial growth of platelets was initially conducted to study the influence of flow parameters such as temperature, residence time, and flow rate on the morphology of platelets. Comparison of different epitaxial growth manners of seeds and platelets was made when using seeds to perform living CDSA. Size-controllable platelets from seeds can be obtained from a series flow system by easily tuning flow rates. Additionally, uniform platelets were continuously collected, exhibiting improved size and dispersity compared to those obtained in batch reactions.

Tuning the Functionality of Self-Assembled 2D Platelets in the Third Dimension.

The decoration of 2D nanostructures using heteroepitaxial growth is of great importance to achieve functional assemblies employed in biomedical, electrical, and mechanical applications. Although the functionalization of polymers before self-assembly has been investigated, the exploration of direct surface modification in the third dimension from 2D nanostructures has, to date, been unexplored. Here, we used living crystallization-driven self-assembly to fabricate poly(ε-caprolactone)-based 2D platelets with controlled size. Importantly, surface modification of the platelets in the third dimension was achieved by using functional monomers and light-induced polymerization. This method allows us to selectively regulate the height and fluorescence properties of the nanostructures. Using this approach, we gained unprecedented spatial control over the surface functionality in the specific region of complex 2D platelets.

Understanding the Seeded Heteroepitaxial Growth of Crystallizable Polymers: The Role of Crystallization Thermodynamics.

Seeded heteroepitaxial growth is a "living" crystallization-driven self-assembly (CDSA) method that has emerged as a promising route to create uniform segmented nanoparticles with diverse core chemistries by using chemically distinct core-forming polymers. Our previous results have demonstrated that crystallization kinetics is a key factor that determines the occurrence of heteroepitaxial growth, but an in-depth understanding of controlling heteroepitaxy from the perspective of crystallization thermodynamics is yet unknown. Herein, we select crystallizable aliphatic polycarbonates (PxCs) with a different number of methylene groups (xCH2, x = 4, 6, 7, 12) in their repeating units as model polymers to explore the effect of lattice match and core compatibility on the seeded growth behavior. Seeded growth of PxCs-containing homopolymer/block copolymer blend unimers from poly(ε-caprolactone) (PCL) core-forming seed platelet micelles exhibits distinct crystal growth behavior at subambient temperatures, which is governed by the lattice match and core compatibility. A case of seeded growth with better core compatibility and a smaller lattice mismatch follows epitaxial growth, where the newly created crystal domain has the same structural orientation as the original platelet substrate. In contrast, a case of seeded growth with better core compatibility but a larger lattice mismatch shows nonepitaxial growth with less-defined crystal orientations in the platelet plane. Additionally, a case of seeded growth with poor core compatibility and larger lattice mismatch results in polydisperse platelet micelles, whereby crystal formation is not nucleated from the crystalline substrate. These findings reveal important factors that govern the specific crystal growth during a seeded growth approach by using compositionally distinct cores, which would further guide researchers in designing 2D segmented materials via polymer crystallization approaches.

Surface Hybridization Chain Reaction of Binary Mixture DNA-PEG Corona Nanostructures Produced by Low-Volume RAFT-Mediated Photopolymerization-Induced Self-Assembly.

DNA-polymer hybrids have been attracting interest as adaptable functional materials by combining the stability of polymers with DNA nanotechnology. Both research fields have in common the capacity to be precise, versatile, and tunable, a prerequisite for creating powerful tools which can be easily tailored and adapted for bio-related applications. However, the conjugation of hydrophilic DNA with hydrophobic polymers remains challenging. In recent years, polymerization-induced self-assembly (PISA) has attracted significant attention for constructing nano-objects of various morphologies owing to the one-step nature of the process, creating a beneficial method for the creation of amphiphilic DNA-polymer nanostructures. This process not only allows pure DNA-polymer-based systems to be produced but also enables the mixture of other polymeric species with DNA conjugates. Here, we present the first report of a DNA-PEG corona nano-object's synthesis without the addition of an external photoinitiator or photocatalyst via photo-PISA. Furthermore, this work shows the use of DNA-macroCTA, which was first synthesized using a solid-support method resulting in high yields, easy upscaling, and no need for HPLC purification. In addition, to the formation of DNA-polymer structures, increasing the nucleic acid loading of assemblies is of great importance. One of the most intriguing phenomena of DNA is the hybridization of single-stranded DNA with a second strand, increasing the nucleic acid content. However, hybridization of DNA in a particle corona may destabilize the nanomaterial due to the electrostatic repulsive force on the DNA corona. Here, we have investigated how changing the DNA volume fraction in hybrid DNA-polymer self-assembled material affects the morphology. Moreover, the effect of the corona composition on the stability of the system during the hybridization was studied. Additionally, the hybridization chain reaction was successfully applied as a new method to increase the amount of DNA on a DNA-based nano-object without disturbing the morphology achieving a fluorescence signal amplification.

Stereocomplex-Driven Morphological Transition of Coil-Rod-Coil Poly(lactic acid)-Based Cylindrical Nanoparticles.

The stereocomplexation of poly(lactic acid) (PLA) enantiomers opens up an avenue for the formation of new materials with enhanced performance, specifically regarding their mechanical and thermal resistance and resistance to hydrolysis. Despite these useful features, the study of the stereocomplexation between block copolymers based on PLA in solution is limited, and a comprehensive understanding of this phenomenon is urgently needed. Herein, triblock copolymers of poly(N-hydroxyethyl acrylamide) and PL(or D)LA in which PLA was midblock (PHEAAmy-b-PL(D)LAx-b-PHEAAmy) were synthesized and assembled into cylindrical micelles via crystallization-driven self-assembly . The stereocomplexation between enantiomeric micelles facilitates the morphological transition, and the transformation process was investigated in detail by varying the aging temperature, block composition, and solvent. It was found that the solubility of the copolymers played a vital role in determining the occurrence and the speed of the chain exchange between the micelles and the unimers, which thereafter has a significant impact on the shape transition. These results lead to a deeper understanding of the stereocomplex-driven morphological transition process and provide valuable guidance for further optimization of the transition under physiological conditions as a new category of stimuli-responsive systems for biomedical applications.

Correction to Crystal Structure of Poly(7-heptalactone).

[This corrects the article DOI: 10.1021/acs.macromol.3c00710.].

Synthesis, Morphology, and Crystallization Kinetics of Polyheptalactone (PHL).

Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer-Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.

Uniform segmented platelet micelles with compositionally distinct and selectively degradable cores.

The creation of nanoparticles with controlled and uniform dimensions and spatially defined functionality is a key challenge. The recently developed living crystallization-driven self-assembly (CDSA) method has emerged as a promising route to one-dimensional (1D) and 2D core-shell micellar assemblies by seeded growth of polymeric and molecular amphiphiles. However, the general limitation of the epitaxial growth process to a single core-forming chemistry is an important obstacle to the creation of complex nanoparticles with segmented cores of spatially varied composition that can be subsequently exploited in selective transformations or responses to external stimuli. Here we report the successful use of a seeded growth approach that operates for a variety of different crystallizable polylactone homopolymer/block copolymer blend combinations to access 2D platelet micelles with compositionally distinct segmented cores. To illustrate the utility of controlling internal core chemistry, we demonstrate spatially selective hydrolytic degradation of the 2D platelets-a result that may be of interest for the design of complex stimuli-responsive particles for programmed-release and cargo-delivery applications.

Correction: Elucidating the role of multivalency, shape, size and functional group density on antibacterial activity of diversified supramolecular nanostructures enabled by templated assembly.

Correction for 'Elucidating the role of multivalency, shape, size and functional group density on antibacterial activity of diversified supramolecular nanostructures enabled by templated assembly' by Amrita Sikder et al., Mater. Horiz., 2023, 10, 171-178, https://doi.org/10.1039/D2MH01117D.

Triggered Polymersome Fusion.

The contents of biological cells are retained within compartments formed of phospholipid membranes. The movement of material within and between cells is often mediated by the fusion of phospholipid membranes, which allows mixing of contents or excretion of material into the surrounding environment. Biological membrane fusion is a highly regulated process that is catalyzed by proteins and often triggered by cellular signaling. In contrast, the controlled fusion of polymer-based membranes is largely unexplored, despite the potential application of this process in nanomedicine, smart materials, and reagent trafficking. Here, we demonstrate triggered polymersome fusion. Out-of-equilibrium polymersomes were formed by ring-opening metathesis polymerization-induced self-assembly and persist until a specific chemical signal (pH change) triggers their fusion. Characterization of polymersomes was performed by a variety of techniques, including dynamic light scattering, dry-state/cryogenic-transmission electron microscopy, and small-angle X-ray scattering (SAXS). The fusion process was followed by time-resolved SAXS analysis. Developing elementary methods of communication between polymersomes, such as fusion, will prove essential for emulating life-like behaviors in synthetic nanotechnology.

Elucidating the role of multivalency, shape, size and functional group density on antibacterial activity of diversified supramolecular nanostructures enabled by templated assembly.

With the increased prevalence of antibiotic-resistant infections, there is an urgent need to develop novel antibacterial materials. In addition, gaining a complete understanding of the structural features that impart activity toward target microorganisms is essential to enable materials optimisation. Here we have reported a rational design to fabricate antibacterial supramolecular nanoparticles with variable shape, size and cationic group density, by exploiting noncovalent interactions between a shape determining template amphiphile and a cationic amphiphile to introduce charge on the nanoparticle surface. We have shown that the monomeric cationic amphiphile alone showed poor antibacterial activity, whereas nanostructures formed by co-assembling the complementary units showed significantly enhanced antibacterial efficiency. Further, the systematic variation of several structural parameters such as shape, spacing between the cationic groups and size of these nanostructures allowed us to elicit the role of each parameter on the overall antibacterial properties. Finally, we investigated the origin of the differing antibacterial activity of these nanoparticles having different shape and size but with the same molecular composition, by comparing the thermodynamic parameters of their binding interactions with a bacterial membrane mimic.

Thermoresponsive Block Copolymer Core-Shell Nanoparticles with Tunable Flow Behavior in Porous Media.

With the purpose of investigating new polymeric materials as potential flow modifiers for their future application in enhanced oil recovery (EOR), a series of amphiphilic poly(di(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate) [P(DEGMA-co-OEGMA)]-based core-shell nanoparticles were prepared by aqueous reversible addition-fragmentation chain transfer-mediated polymerization-induced self-assembly. The developed nano-objects were shown to be thermoresponsive, demonstrating a reversible lower-critical solution temperature (LCST)-type phase transition with increasing solution temperature. Characterization of their thermoresponsive nature by variable-temperature UV-vis and dynamic light scattering analyses revealed that these particles reversibly aggregate when heated above their LCST and that the critical transition temperature could be accurately tuned by simply altering the molar ratio of core-forming monomers. Sandpack experiments were conducted to evaluate their pore-blocking performance at low flow rates in a porous medium heated at temperatures above their LCST. This analysis revealed that particles aggregated in the sandpack column and caused pore blockage with a significant reduction in the porous medium permeability. The developed aggregates and the increased pressure generated by the blockage were found to remain stable under the injection of brine and were observed to rapidly dissipate upon reducing the temperature below the LCST of each formulation. Further investigation by double-column sandpack analysis showed that the blockage was able to reform when re-heated and tracked the thermal front. Moreover, the rate of blockage formation was observed to be slower when the LCST of the injected particles was higher. Our investigation is expected to pave the way for the design of "smart" and versatile polymer technologies for EOR applications in future studies.

Polymer nanoparticles pass the plant interface.

As agriculture strives to feed an ever-increasing number of people, it must also adapt to increasing exposure to minute plastic particles. To learn about the accumulation of nanoplastics by plants, we prepared well-defined block copolymer nanoparticles by aqueous dispersion polymerisation. A fluorophore was incorporated via hydrazone formation and uptake into roots and protoplasts of Arabidopsis thaliana was investigated using confocal microscopy. Here we show that uptake is inversely proportional to nanoparticle size. Positively charged particles accumulate around root surfaces and are not taken up by roots or protoplasts, whereas negatively charged nanoparticles accumulate slowly and become prominent over time in the xylem of intact roots. Neutral nanoparticles penetrate rapidly into intact cells at the surfaces of plant roots and into protoplasts, but xylem loading is lower than for negative nanoparticles. These behaviours differ from those of animal cells and our results show that despite the protection of rigid cell walls, plants are accessible to nanoplastics in soil and water.

Stimuli-responsive and core cross-linked micelles developed by NiCCo-PISA of helical poly(aryl isocyanide)s.

We report the synthesis of redox- and pH-sensitive block copolymer micelles that contain chiral cores composed of helical poly(aryl isocyanide)s. Pentafluorophenyl (PFP) ester-containing micelles synthesised via nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers are modified post-polymerisation with various diamines to introduce cross-links and/or achieve stimulus-sensitive nanostructures. The successful introduction of the diamines is confirmed by Fourier-transform infrared spectroscopy (FT-IR), while the stabilisation effect of the cross-linking is explored by dynamic light scattering (DLS). The retention of the helicity of the core-forming polymer block is verified by circular dichroism (CD) spectroscopy and the stimuli-responsiveness of the nanoparticles towards a reducing agent (l-glutathione, GSH) and pH is evaluated by following the change in the size of the nanoparticles by DLS. These stimuli-responsive nanoparticles could find use in applications such as drug delivery, nanosensors or biological imaging.

Enhancing Dual-State Emission in Maleimide Fluorophores through Fluorocarbon Functionalisation.

Herein, a library of trifluoroethyl substituted aminomaleimide derivatives are reported with small size and enhanced emissions in both solution and solid-state. A diCH2 CF3 substituted aminochloromaleimide exhibits the most efficient dual-state emission (Φf >50 % in solution and solid-state), with reduced quenching from protic solvents. This is attributed to the reduction of electron density on the maleimide ring and suppressed π-π stacking in the solid-state. This mechanism was explored in-depth by crystallographic analysis, and modelling of the electronic distribution of HOMO-LUMO isosurfaces and NCI plots. Hence, these dual-state dyes overcome the limitations of single-state luminescence and will serve as an important step forward for this rapidly developing nascent field.

Nucleobase-Interaction-Directed Biomimetic Supramolecular Self-Assembly.

The design and fabrication of synthetic self-assembled systems that can mimic some biological features require exquisitely sophisticated components that make use of supramolecular interactions to attain enhanced structural and functional complexity. In nature, nucleobase interactions play a key role in biological functions in living organisms, including transcription and translation processes. Inspired by nature, scientists are progressively exploring nucleobase synthons to create a diverse range of functional systems with a plethora of nanostructures by virtue of molecular-recognition-directed assembly and flexible programmability of the base-pairing interactions. To that end, nucleobase-functionalized molecules and macromolecules are attracting great attention because of their versatile structures with smart and adaptive material properties such as stimuli responsiveness, interaction with external agents, and ability to repair structural defects. In this regard, a range of nucleobase-interaction-mediated hierarchical self-assembled systems have been developed to obtain biomimetic materials with unique properties. For example, a new "grafting to" strategy utilizing complementary nucleobase interactions has been demonstrated to temporarily control the functional group display on micellar surfaces. In a different approach, complementary nucleobase interactions have been explored to enable morphological transitions in functionalized diblock copolymer assembly. It has been demonstrated that complementary nucleobase interactions can drive the morphological transformation to produce highly anisotropic nanoparticles by controlling the assembly processes at multiple length scales. Furthermore, nucleobase-functionalized bottle brush polymers have been employed to generate stimuli-responsive hierarchical assembly. Finally, such interactions have been exploited to induce biomimetic segregation in polymer self-assembly, which has been employed as a template to synthesize polymers with narrow polydispersity. It is evident from these examples that the optimal design of molecular building blocks and precise positioning of the nucleobase functionality are essential for fabrication of complex supramolecular assemblies. While a considerable amount of research remains to be explored, our studies have demonstrated the potential of nucleobase-interaction-mediated supramolecular assembly to be a promising field of research enabling the development of biomimetic materials.This Account summarizes recent examples that employ nucleobase interactions to generate functional biomaterials by judicious design of the building blocks. We begin by discussing the molecular recognition properties of different nucleobases, followed by different strategies to employ nucleobase interactions in polymeric systems in order to achieve self-assembled nanomaterials with versatile properties. Moreover, some of their prospective biological/material applications such as enhanced drug encapsulation, superior adhesion, and fast self-healing properties facilitated by complementary nucleobase interactions are emphasized. Finally, we identify issues and challenges that are faced by this class of materials and propose future directions for the exploration of functional materials with the aim of promoting the development of nucleobase-functionalized systems to design the next generation of biomaterials.

Log Poct/SA Predicts the Thermoresponsive Behavior of P(DMA-co-RA) Statistical Copolymers.

Polymers that exhibit a lower critical solution temperature (LCST) have been of great interest for various biological applications such as drug or gene delivery, controlled release systems, and biosensing. Tuning the LCST behavior through control over polymer composition (e.g., upon copolymerization of monomers with different hydrophobicity) is a widely used method, as the phase transition is greatly affected by the hydrophilic/hydrophobic balance of the copolymers. However, the lack of a general method that relates copolymer hydrophobicity to their temperature response leads to exhaustive experiments when seeking to obtain polymers with desired properties. This is particularly challenging when the target copolymers are comprised of monomers that individually form nonresponsive homopolymers, that is, only when copolymerized do they display thermoresponsive behavior. In this study, we sought to develop a predictive relationship between polymer hydrophobicity and cloud point temperature (TCP). A series of statistical copolymers were synthesized based on hydrophilic N,N-dimethyl acrylamide (DMA) and hydrophobic alkyl acrylate monomers, and their hydrophobicity was compared using surface area-normalized octanol/water partition coefficients (Log Poct/SA). Interestingly, a correlation between the Log Poct/SA of the copolymers and their TCPs was observed for the P(DMA-co-RA) copolymers, which allowed TCP prediction of a demonstrative copolymer P(DMA-co-MMA). These results highlight the strong potential of this computational tool to improve the rational design of copolymers with desired temperature responses prior to synthesis.