RAFT Dispersion Polymerization of 2-Hydroxyethyl Methacrylate in Non-polar Media.

We report the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) in -dodecane using a poly(lauryl methacrylate) (PLMA) precursor at 90 °C. This formulation is an example of polymerization-induced self-assembly (PISA), which leads to the formation of a colloidal dispersion of spherical PLMA-PHEMA nanoparticles at 10-20% w/w solids. PISA syntheses involving polar monomers in non-polar media have been previously reported but this particular system offers some unexpected and interesting challenges in terms of both synthesis and characterization.

Supra-particle formation by evaporation of aerosol droplets containing binary mixtures of colloidal particles: Controlling the final morphology.

Hypothesis: Supra-particle formation by evaporation of an aqueous aerosol droplet containing nano-colloidal particles is challenging to investigate but has significant applications. We hypothesise that the Peclet number, Pe, which compares the effectiveness of evaporation-induced advection to that of colloidal diffusion, is critical in determining supra-particle morphology and can be used to predict the dried morphology for droplet containing polydisperse nanoparticles.

Experiments: Sterically-stabilized diblock copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA).

Phage Display Against 2D Metal-Organic Nanosheets as a New Route to Highly Selective Biomolecular Recognition Surfaces.

Peptides are important biomarkers for various diseases, however distinguishing specific amino-acid sequences using artificial receptors remains a major challenge in biomedical sensing. This study introduces a new approach for creating highly selective recognition surfaces using phage display biopanning against metal-organic nanosheets (MONs). Three MONs (ZIF-7, ZIF-7-NH and Hf-BTB-NH) are added to a solution containing every possible combination of seven-residue peptides attached to bacteriophage hosts.

Effect of Added Salt on the RAFT Polymerization of 2-Hydroxyethyl Methacrylate in Aqueous Media.

We report the effect of added salt on the reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-hydroxyethyl methacrylate (HEMA) in aqueous media. More specifically, poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) was employed as a salt-tolerant water-soluble block for chain extension with HEMA targeting PHEMA DPs from 100 to 800 in the presence of NaCl. Increasing the salt concentration significantly reduces the aqueous solubility of both the HEMA monomer and the growing PHEMA chains.

Synthesis of Phenanthrene/Pyrene Hybrid Microparticles: Useful Synthetic Mimics for Polycyclic Aromatic Hydrocarbon-Based Cosmic Dust.

Polycyclic aromatic hydrocarbons (PAHs) are found throughout the interstellar medium and are important markers for the evolution of galaxies and both star and planet formation. They are also widely regarded as a major source of carbon, which has implications in the search for extraterrestrial life. Herein we construct a melting point phase diagram for a series of phenanthrene/pyrene binary mixtures to identify the eutectic composition (75 mol % phenanthrene) and its melting point (83 °C).

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment-Polymer Antenna Complexes Using a Gas Cluster Ion Source.

X-ray photoelectron spectroscopy (XPS) depth-profiling with an argon gas cluster ion source (GCIS) was used to characterize the spatial distribution of chlorophyll (Chl) within a poly(cysteine methacrylate) (PCysMA) brush grown by surface-initiated atom-transfer radical polymerization (ATRP) from a planar surface. The organization of Chl is controlled by adjusting the brush grafting density and polymerization time. For , the C, N, S elemental composition remains constant throughout the 36 nm brush layer until the underlying gold substrate is approached.

Capturing Enzyme-Loaded Diblock Copolymer Vesicles Using an Aldehyde-Functionalized Hydrophilic Polymer Brush.

Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that -diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C).

Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media.

Herein we combine the well-known processing advantages conferred by polymerization-induced self-assembly (PISA) with crystallization-driven self-assembly (CDSA) to achieve the efficient synthesis of hydrolytically degradable, highly anisotropic block copolymer nano-objects directly in aqueous solution at 30% w/w solids. This new strategy involves a so-called reverse sequence PISA protocol that employs poly(l-lactide) (PLLA) as the crystallizable core-forming block and poly(-dimethylacrylamide) (PDMAC) as the water-soluble non-ionic coronal block. Such syntheses result in PDMAC-rich anisotropic nanoparticles.

Strong coupling in molecular systems: a simple predictor employing routine optical measurements.

We provide a simple method that enables readily acquired experimental data to be used to predict whether or not a candidate molecular material may exhibit strong coupling. Specifically, we explore the relationship between the hybrid molecular/photonic (polaritonic) states and the bulk optical response of the molecular material. For a given material, this approach enables a prediction of the maximum extent of strong coupling (vacuum Rabi splitting), irrespective of the nature of the confined light field.

Arginine-Functional Methacrylic Block Copolymer Nanoparticles: Synthesis, Characterization, and Adsorption onto a Model Planar Substrate.

Recently, we reported the synthesis of a hydrophilic aldehyde-functional methacrylic polymer (, , , 12032-12037). Herein we demonstrate that such polymers can be reacted with arginine in aqueous solution to produce arginine-functional methacrylic polymers without recourse to protecting group chemistry. Careful control of the solution pH is essential to ensure regioselective imine bond formation; subsequent reductive amination leads to a hydrolytically stable amide linkage.

Low-Viscosity Route to High-Molecular-Weight Water-Soluble Polymers: Exploiting the Salt Sensitivity of Poly(-acryloylmorpholine).

We report a new one-pot low-viscosity synthetic route to high molecular weight non-ionic water-soluble polymers based on polymerization-induced self-assembly (PISA). The RAFT aqueous dispersion polymerization of -acryloylmorpholine (NAM) is conducted at 30 °C using a suitable redox initiator and a poly(2-hydroxyethyl acrylamide) (PHEAC) precursor in the presence of 0.60 M ammonium sulfate.

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization.

Reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to prepare well-defined ABCB tetrablock copolymer nanoparticles via sequential monomer addition at 30 °C. The A block comprises water-soluble poly(2-(-acryloyloxy)ethyl pyrrolidone) (PNAEP), while the B and C blocks comprise poly(-butyl acrylate) (PtBA) and poly(-butyl acrylate) (PnBA), respectively. High conversions are achieved at each stage, and the final sterically stabilized spherical nanoparticles can be obtained at 20% w/w solids at pH 3 and at up to 40% w/w solids at pH 7.

Controlling Adsorption of Diblock Copolymer Nanoparticles onto an Aldehyde-Functionalized Hydrophilic Polymer Brush via pH Modulation.

Sterically stabilized diblock copolymer nanoparticles with a well-defined spherical morphology and tunable diameter were prepared by RAFT aqueous emulsion polymerization of benzyl methacrylate at 70 °C. The steric stabilizer precursor used for these syntheses contained pendent -diol groups, which means that such nanoparticles can react with a suitable aldehyde-functional surface via acetal bond formation. This principle is examined herein by growing an aldehyde-functionalized polymer brush from a planar silicon wafer and studying the extent of nanoparticle adsorption onto this model substrate from aqueous solution at 25 °C using a quartz crystal microbalance (QCM).

Effect of Temperature, Oil Type, and Copolymer Concentration on the Long-Term Stability of Oil-in-Water Pickering Nanoemulsions Prepared Using Diblock Copolymer Nanoparticles.

A poly(glycerol monomethacrylate) (PGMA) precursor was chain-extended with 2,2,2-trifluoroethyl methacrylate (TFEMA) via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization. Transmission electron microscopy (TEM) studies confirmed the formation of well-defined PGMA-PTFEMA spherical nanoparticles, while dynamic light scattering (DLS) studies indicated a -average diameter of 26 ± 6 nm. These sterically stabilized diblock copolymer nanoparticles were used as emulsifiers to prepare oil-in-water Pickering nanoemulsions: either -dodecane or squalane was added to an aqueous dispersion of nanoparticles, followed by high-shear homogenization and high-pressure microfluidization.

Synthesis of Poly(propylene oxide)-Poly(-dimethylacrylamide) Diblock Copolymer Nanoparticles via Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Solution.

Sterically-stabilized diblock copolymer nanoparticles comprising poly(propylene oxide) (PPO) cores are prepared via reverse sequence polymerization-induced self-assembly (PISA) in aqueous solution. '-Dimethylacrylamide (DMAC) acts as a cosolvent for the weakly hydrophobic trithiocarbonate-capped PPO precursor. Reversible addition-fragmentation chain transfer (RAFT) polymerization of DMAC is initially conducted at 80% w/w solids with deoxygenated water.

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 -average diameters ranging from 32 to 238 nm.

Determination of Reaction Kinetics by Time-Resolved Small-Angle X-ray Scattering during Polymerization-Induced Self-Assembly: Direct Evidence for Monomer-Swollen Nanoparticles.

The kinetics of heterogeneous polymerization is determined directly using small-angle X-ray scattering (SAXS). This important advancement is exemplified for the synthesis of sterically-stabilized diblock copolymer nanoparticles by reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) in mineral oil at 90 °C. The principle of mass balance is invoked to derive a series of equations for the analysis of the resulting time-resolved SAXS patterns.

Thermoresponsive Poly(,'-dimethylacrylamide)-Based Diblock Copolymer Worm Gels via RAFT Solution Polymerization: Synthesis, Characterization, and Cell Biology Applications.

RAFT solution polymerization is used to polymerize 2-hydroxypropyl methacrylate (HPMA). The resulting PHPMA precursor is then chain-extended using ,'-dimethylacrylamide (DMAC) to produce a series of thermoresponsive PHPMA-PDMAC diblock copolymers. Such amphiphilic copolymers can be directly dispersed in ice-cold water and self-assembled at 20 °C to form spheres, worms, or vesicles depending on their copolymer composition.

Mucoadhesive pickering nanoemulsions via dynamic covalent chemistry.

Hypothesis: Submicron oil droplets stabilized using aldehyde-functionalized nanoparticles should adhere to the primary amine groups present at the surface of sheep nasal mucosal tissue via Schiff base chemistry.

Experiments: Well-defined sterically-stabilized diblock copolymer nanoparticles of 20 nm diameter were prepared in the form of concentrated aqueous dispersions via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) using a water-soluble methacrylic precursor bearing cis-diol groups. Some of these hydroxyl-functional nanoparticles were then selectively oxidized using an aqueous solution of sodium periodate to form a second batch of nanoparticles bearing pendent aldehyde groups within the steric stabilizer chains.

Efficient Synthesis of Hydrolytically Degradable Block Copolymer Nanoparticles via Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Media.

Hydrolytically degradable block copolymer nanoparticles are prepared via reverse sequence polymerization-induced self-assembly (PISA) in aqueous media. This efficient protocol involves the reversible addition-fragmentation chain transfer (RAFT) polymerization of N,N'-dimethylacrylamide (DMAC) using a monofunctional or bifunctional trithiocarbonate-capped poly(ϵ-caprolactone) (PCL) precursor. DMAC monomer is employed as a co-solvent to solubilize the hydrophobic PCL chains.

Recent Advances in Polymerization-Induced Self-Assembly (PISA) Syntheses in Non-Polar Media.

It is well-known that polymerization-induced self-assembly (PISA) is a powerful and highly versatile technique for the rational synthesis of colloidal dispersions of diblock copolymer nanoparticles, including spheres, worms or vesicles. PISA can be conducted in water, polar solvents or non-polar media. In principle, the latter formulations offer a wide range of potential commercial applications.