Polymerization-Induced Polymersome Fusion

The dynamic interactions of membranes, particularly their fusion and fission, are critical for the transmission of chemical information between cells. Fusion is primarily driven by membrane tension built up through membrane deformation. For artificial polymersomes, fusion is commonly induced via the external application of a force field. Herein, fusion-promoted development of anisotropic tubular polymersomes (tubesomes) was achieved in the absence of an external force by exploiting the unique features of aqueous ring-opening metathesis polymerization-induced self-assembly (ROMPISA). The out-of-equilibrium tubesome morphology was found to arise spontaneously during polymerization, and the composition of each tubesome sample (purity and length distribution) could be manipulated simply by targeting different core-block degrees of polymerization (DPs). The evolution of tubesomes was shown to occur via fusion of “monomeric” spherical polymersomes, evidenced most notably by a step-growth-like relationship between the fraction of tubular to spherical nano-objects and the average number of fused particles per tubesome (analogous to monomer conversion and DP, respectively). Fusion was also confirmed by Förster resonance energy transfer (FRET) studies to show membrane blending and confocal microscopy imaging to show mixing of the polymersome lumens. We term this unique phenomenon polymerization-induced polymersome fusion, which operates via the buildup of membrane tension exerted by the growing polymer chains. Given the growing body of evidence demonstrating the importance of nanoparticle shape on biological activity, our methodology provides a facile route to reproducibly obtain samples containing mixtures of spherical and tubular polymersomes, or pure samples of tubesomes, of programmed length. Moreover, the capability to mix the interior aqueous compartments of polymersomes during polymerization-induced fusion also presents opportunities for its application in catalysis, small molecule trafficking, and drug delivery

Complementary Nucleobase Interactions Drive the Hierarchical Self-Assembly of Core-Shell Bottlebrush Block Copolymers toward Cylindrical Supramolecules

The self-assembly of amphiphilic block copolymers has facilitated the preparation of a wide variety of nano-objects of diverse morphology. Ready access to these nanostructures has opened up new possibilities in catalysis, sensing, and nanomedicine. In comparison, the self-assembly of large building blocks (i.e., amphiphilic bottlebrush polymers) has received less attention, owing in part to the relatively more challenging synthesis of these macromolecules. Bottlebrush amphiphiles can self-assemble into uniquely stable spherical nanostructures and can also produce dynamic cylinders with lengths modulated by environmental conditions, motivating further research in this area. Herein, we report the synthesis of core–shell bottlebrush polymers (BBPs) containing complementary nucleobase functionalities via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition–fragmentation chain transfer (RAFT) polymerization, using a “grafting-from” approach, and their hierarchical self-assembly in aqueous media. Mixtures of BBPs containing thymine or adenine units in their core blocks were found to self-assemble into higher-order cylindrical supramolecules upon heating above a critical temperature. This temperature was demonstrated to correspond to the lower critical solution temperature (LCST) of the corona-forming poly(4-acryloylmorpholine) block, providing evidence for a unique one-dimensional BBP assembly mechanism. Moreover, the formation of extended supramolecular assemblies was preferentially observed when both thymine- and adenine-functionalized BBPs were present in equimolar concentrations, pointing toward an alternating, isodesmic mechanism of organization occurring via nucleobase interactions located at their chain termini. We anticipate that these discoveries will provide the basis for future studies regarding BBP self-assembly, especially with regard to the formation of stimuli-responsive anisotropic nanostructures

Synthesis and characterization of charge-stabilized poly(4-hydroxybutyl acrylate) latex by RAFT aqueous dispersion polymerization: a new precursor for reverse sequence polymerization-induced self-assembly

The reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 4-hydroxybutyl acrylate (HBA) is conducted using a water-soluble RAFT agent bearing a carboxylic acid group. This confers charge stabilization when such syntheses are conducted at pH 8, which leads to the formation of polydisperse anionic PHBA latex particles of approximately 200 nm diameter. The weakly hydrophobic nature of the PHBA chains confers stimulus-responsive behavior on such latexes, which are characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, and 1H NMR spectroscopy. Addition of a suitable water-miscible hydrophilic monomer such as 2-(N-(acryloyloxy)ethyl pyrrolidone) (NAEP) leads to in situ molecular dissolution of the PHBA latex, with subsequent RAFT polymerization leading to the formation of sterically stabilized PHBA-PNAEP diblock copolymer nanoparticles of approximately 57 nm diameter. Such formulations constitute a new approach to reverse sequence polymerization-induced self-assembly, whereby the hydrophobic block is prepared first in aqueous media

Synthesis of crystallizable poly(behenyl methacrylate)-based block and statistical copolymers and their performance as wax crystal modifiers

Two series of behenyl methacrylate-based diblock and statistical copolymers have been prepared by reversible addition–fragmentation chain transfer (RAFT) solution polymerization in n-dodecane and evaluated as additives for the crystal habit modification of a model wax (n-octacosane). DSC studies indicated that each statistical copolymer exhibited a significantly lower crystallization temperature (Tc) and melting temperature (Tm) for the semi-crystalline behenyl methacrylate component than the corresponding diblock copolymer of almost identical overall composition. Temperature-dependent turbidimetry studies were conducted for each copolymer using a series of solutions of 5.0% w/w n-octacosane dissolved in n-dodecane to determine Tcool, which is the temperature at which zero transmittance is first observed owing to wax crystallization. At a constant molar copolymer concentration of 0.26 mM, each of the eight copolymers produced a reduction in Tcool of approximately 3–5 °C. Scanning electron microscopy (SEM) studies confirmed that the presence of such copolymers led to a reduction in the overall size and/or a higher crystal aspect ratio. The diblock and statistical copolymers were similar in their performance as potential wax crystal modifiers. However, the statistical copolymers were easier to prepare and did not suffer from any homopolymer contamination. Moreover, optical microscopy and SEM studies revealed that needle-like crystals were formed instead of platelets when employing behenyl methacrylate-rich statistical copolymers

Effect of the addition of diblock copolymer nanoparticles on the evaporation kinetics and final particle morphology for drying aqueous aerosol droplets

A deeper understanding of the key processes that determine the particle morphologies generated during aerosol droplet drying is highly desirable for spray-drying of powdered pharmaceuticals and foods, predicting the properties of atmospheric particles, and monitoring disease transmission. Particle morphologies are affected by the drying kinetics of the evaporating droplets, which are in turn influenced by the composition of the initial droplet as well as the drying conditions. Herein, we use polymerization-induced self-assembly (PISA) to prepare three types of sterically stabilized diblock copolymer nanoparticles comprising the same steric stabilizer block and differing core blocks with z-average diameters ranging from 32 to 238 nm. These well-defined nanoparticles enable a systematic investigation of the effect of the nanoparticle size and composition on the drying kinetics of aqueous aerosol droplets (20-28 μm radius) and the final morphology of the resulting microparticles. A comparative kinetics electrodynamic balance was used to obtain evaporation profiles for 10 examples of nanoparticles at a relative humidity (RH) of 0, 45, or 65%. Nanoparticles comprising the same core block with mean diameters of 32, 79, and 214 nm were used to produce microparticles, which were dried under different RH conditions in a falling droplet column. Scanning electron microscopy was used to examine how the drying kinetics influenced the final microparticle morphology. For dilute droplets, the chemical composition of the nanoparticles had no effect on the evaporation rate. However, employing smaller nanoparticles led to the formation of dried microparticles with a greater degree of buckling

Adsorption of aldehyde-functional diblock copolymer spheres onto surface-grafted polymer brushes via dynamic covalent chemistry enables friction modification

Dynamic covalent chemistry has been exploited to prepare numerous examples of adaptable polymeric materials that exhibit unique properties. Herein, the chemical adsorption of aldehyde-functional diblock copolymer spherical nanoparticles onto amine-functionalized surface-grafted polymer brushes via dynamic Schiff base chemistry is demonstrated. Initially, a series of cis-diol-functional sterically-stabilized spheres of 30–250 nm diameter were prepared via reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization. The pendent cis-diol groups within the steric stabilizer chains of these precursor nanoparticles were then oxidized using sodium periodate to produce the corresponding aldehyde-functional spheres. Similarly, hydrophilic cis-diol-functionalized methacrylic brushes grafted from a planar silicon surface using activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) were selectively oxidized to generate the corresponding aldehyde-functional brushes. Ellipsometry and X-ray photoelectron spectroscopy were used to confirm brush oxidation, while scanning electron microscopy studies demonstrated that the nanoparticles did not adsorb onto a cis-diol-functional precursor brush. Subsequently, the aldehyde-functional brushes were treated with excess small-molecule diamine, and the resulting imine linkages were converted into secondary amine bonds via reductive amination. The resulting primary amine-functionalized brushes formed multiple dynamic imine bonds with the aldehyde-functional diblock copolymer spheres, leading to a mean surface coverage of approximately 0.33 on the upper brush layer surface, regardless of the nanoparticle size. Friction force microscopy studies of the resulting nanoparticle-decorated brushes enabled calculation of friction coefficients, which were compared to that measured for the bare aldehyde-functional brush. Friction coefficients were reasonably consistent across all surfaces except when particle size was comparable to the size of the probe tip. In this case, differences were ascribed to an increase in contact area between the tip and the brush-nanoparticle layer. This new model system enhances our understanding of nanoparticle adsorption onto hydrophilic brush layers

Structure and dynamics of Rh surfaces

Lattice relaxations, surface phonon spectra, surface energies, and work functions are calculated for Rh(100) and Rh(110) surfaces using density-functional theory and the full-potential linearized augmented plane wave method. Both, the local-density approximation and the generalized gradient approximation to the exchange-correlation functional are considered. The force constants are obtained from the directly calculated atomic forces, and the temperature dependence of the surface relaxation is evaluated by minimizing the free energy of the system. The anharmonicity of the atomic vibrations is taken into account within the quasiharmonic approximation. The importance of contributions from different phonons to the surface relaxation is analyzed.Comment: 9 pages, 7 figures, scheduled to appear in Phys. Rev. B, Feb. 15 (1998). Other related publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm

The impact of atmosphere–ocean–wave coupling on the near-surface wind speed in forecasts of extratropical cyclones

Accurate modelling of air–sea surface exchanges is crucial for reliable extreme surface windspeed forecasts. While atmosphere-only weather forecast models represent ocean and wave effects through sea-state independent parametrizations, coupled multi-model systems capture sea-state dynamics by integrating feedbacks between the atmosphere, ocean and wave model components. Here, we investigate the sensitivity of extreme surface wind speeds to air–sea exchanges at the kilometre scale using coupled and uncoupled configurations of the Met Office’s UK Regional Coupled Environmental Prediction system. The case period includes the passage of extra-tropical cyclones Helen, Ali, and Bronagh, which brought maximum gusts of 36 ms−1 over the UK. Compared with the atmosphere-only results, coupling to the ocean decreases the domain-average sea-surface temperature by up to 0.5 K. Inclusion of coupling to waves reduce the 98th percentile 10-m wind speed by up to 2 ms−1 as young, growing wind waves reduce the wind speed by increasing the sea-surface aerodynamic roughness. Impacts on gusts are more modest, with local reductions of up to 1 ms−1, due to enhanced boundary-layer turbulence which partially offsets air–sea momentum transfer. Using a new drag parametrization based on the Coupled Ocean–Atmosphere Response Experiment 4.0 parametrization, with a cap on the neutral drag coefficient and reduction for wind speeds exceeding 27 ms−1, the atmosphere-only model achieves equivalent impacts on 10-m wind speeds and gusts as from coupling to waves. Overall, the new drag parametrization achieves the same 20% improvement in forecast 10-m wind-speed skill as coupling to waves, with the advantage of saving the computational cost of the ocean and wave models