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 (Angew. Chem., 2021, 60, 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. This new protocol was used to prepare a series of arginine-functionalized diblock copolymer nanoparticles of varying size via polymerization-induced self-assembly in aqueous media. Adsorption of these cationic nanoparticles onto silica was monitored using a quartz crystal microbalance. Strong electrostatic adsorption occurred at pH 7 (Γ = 14.7 mg m-2), whereas much weaker adsorption occurred at pH 3 (Γ = 1.9 mg m-2). These findings were corroborated by electron microscopy, which indicated a surface coverage of 42% at pH 7 but only 5% at pH 3.

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.

Synthesis of Autofluorescent Phenanthrene Microparticles via Emulsification: A Useful Synthetic Mimic for Polycyclic Aromatic Hydrocarbon-Based Cosmic Dust.

Phenanthrene is the simplest example of a polycyclic aromatic hydrocarbon (PAH). Herein, we exploit its relatively low melting point (101 °C) to prepare microparticles from molten phenanthrene droplets by conducting high-shear homogenization in a 3:1 water/ethylene glycol mixture at 105 °C using poly(N-vinylpyrrolidone) as a non-ionic polymeric emulsifier. Scanning electron microscopy studies confirm that this protocol produces polydisperse phenanthrene microparticles with a spherical morphology: laser diffraction studies indicate a volume-average diameter of 25 ± 21 µm. Such projectiles are fired into an aluminum foil target at 1.87 km s-1 using a two-stage light gas gun. Interestingly, the autofluorescence exhibited by phenanthrene aids analysis of the resulting impact craters. More specifically, it enables assessment of the spatial distribution of any surviving phenanthrene in the vicinity of each crater. Furthermore, these phenanthrene microparticles can be coated with an ultrathin overlayer of polypyrrole, which reduces their autofluorescence. In principle, such core-shell microparticles should be useful for assessing the extent of thermal ablation that is likely to occur when they are fired into aerogel targets. Accordingly, polypyrrole-coated microparticles were fired into an aerogel target at 2.07 km s-1. Intact microparticles were identified at the end of carrot tracks and their relatively weak autofluorescence suggests that thermal ablation during aerogel capture did not completely remove the polypyrrole overlayer. Thus, these new core-shell microparticles appear to be useful model projectiles for assessing the extent of thermal processing that can occur in such experiments, which have implications for the capture of intact PAH-based dust grains originating from cometary tails or from plumes emanating from icy satellites (e.g., Enceladus) in future space missions.

Diffusiophoresis of latex driven by anionic nanoparticles and their counterions.

HYPOTHESIS: Diffusiophoresis of colloidal latex particles has been reported for molecular anions and cations of comparable size. In the present study, this phenomenon is observed for two types of charged colloids acting as multivalent electrolyte: (i) anionic charge-stabilised silica nanoparticles or (ii) minimally-charged sterically-stabilised diblock copolymer nanoparticles. EXPERIMENTS: Using a Hele-Shaw cell, a thin layer of relatively large latex particles is established within a sharp concentration gradient of nanoparticles by sequential filling with water, latex particles and nanoparticles. Asymmetric diffusion is observed, which provides strong evidence for diffusiophoresis. Quantification involves turbidity measurements from backlit images. FINDINGS: The latex particles diffuse across a concentration gradient of charged nanoparticles and the latex concentration front scales approximately with time1/2. Moreover, the latex particle flux is inversely proportional to the concentration of background salt, confirming electrostatically-driven motion. These observations are consistent with theory recently developed to account for diffusiophoretic motion driven by multivalent ions.

Enhanced Adsorption of Epoxy-Functional Nanoparticles onto Stainless Steel Significantly Reduces Friction in Tribological Studies.

Epoxy-functional sterically-stabilized diblock copolymer nanoparticles (ca. 27 nm) are prepared via RAFT dispersion polymerization in mineral oil. Nanoparticle adsorption onto stainless steel is examined using a quartz crystal microbalance. Incorporating epoxy groups within the steric stabilizer chains results in a two-fold increase in the adsorbed amount, Γ, at 20 °C (7.6 mg m-2 ) compared to epoxy-core functional nanoparticles (3.7 mg m-2 ) or non-functional nanoparticles (3.8 mg m-2 ). A larger difference in Γ is observed at 40 °C; this suggests chemical adsorption of the nanoparticles rather than merely physical adsorption. A remarkable near five-fold increase in Γ is observed for ca. 50 nm epoxy-functional nanoparticles compared to non-functional nanoparticles (31.3 vs. 6.4 mg m-2 , respectively). Tribological studies confirm that chemical adsorption of the latter epoxy-functional nanoparticles leads to a significant reduction in friction between 60 °C and 120 °C.

Histidine-Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel.

RAFT aqueous emulsion polymerization of isopropylideneglycerol monomethacrylate (IPGMA) is used to prepare a series of PGEO5MA46 -PIPGMAy nanoparticles, where PGEO5MA is a hydrophilic methacrylic steric stabilizer block bearing pendent cis-diol groups. TEM studies confirm a spherical morphology while dynamic light scattering (DLS) analysis indicated that the z-average particle diameter can be adjusted by varying the target degree of polymerization for the core-forming PIPGMA block. Periodate oxidation is used to convert the cis-diol groups on PGEO5MA46 -PIPGMA500 and PGEO5MA46 -PIPGMA1000 nanoparticles into the analogous aldehyde-functionalized nanoparticles, which are then reacted with histidine via reductive amination. In each case, the extent of functionalization is more than 99% as determined by 1 H NMR spectroscopy. Aqueous electrophoresis studies indicate that such derivatization converts initially neutral nanoparticles into zwitterionic nanoparticles with an isoelectric point at pH 7. DLS studies confirm that such histidine-derivatized nanoparticles remain colloidally stable over a wide pH range. A quartz crystal microbalance is employed at 25°C to assess the adsorption of both the cis-diol- and histidine-functionalized nanoparticles onto planar stainless steel at pH 6. The histidine-bearing nanoparticles adsorb much more strongly than their cis-diol counterparts. For the highest adsorbed amount of 70.5 mg m-2 , SEM indicates a fractional surface coverage of 0.23 for the adsorbed nanoparticles.

Adsorption of sterically-stabilized diblock copolymer nanoparticles at the oil-water interface: effect of charged end-groups on interfacial rheology.

The RAFT aqueous emulsion polymerization of either methyl methacrylate (MMA) or benzyl methacrylate (BzMA) is conducted at 70 °C using poly(glycerol monomethacrylate) (PGMA) as a water-soluble precursor to produce sterically-stabilized diblock copolymer nanoparticles of approximately 30 nm diameter. Carboxylic acid- or morpholine-functional RAFT agents are employed to confer anionic or cationic functionality at the ends of the PGMA stabilizer chains, with a neutral RAFT agent being used as a control. Thus the electrophoretic footprint of such minimally-charged model nanoparticles can be adjusted simply by varying the solution pH. Giant (mm-sized) aqueous droplets containing such nanoparticles are then grown within a continuous phase of n-dodecane and a series of interfacial rheology measurements are conducted. The interfacial tension between the aqueous phase and n-dodecane is strongly dependent on the charge of the terminal group on the stabilizer chains. More specifically, neutral nanoparticles produce a significantly lower interfacial tension than either cationic or anionic nanoparticles. Moreover, adsorption of neutral nanoparticles at the n-dodecane-water interface produces higher interfacial elastic moduli than that observed for charged nanoparticles. This is because neutral nanoparticles can adsorb at much higher surface packing densities owing to the absence of electrostatic repulsive forces in this case.

Sterically Stabilized Diblock Copolymer Nanoparticles Enable Convenient Preparation of Suspension Concentrates Comprising Various Agrochemical Actives.

It is well known that sterically stabilized diblock copolymer nanoparticles can be readily prepared using polymerization-induced self-assembly. Recently, we reported that such nanoparticles can be employed as a dispersant to prepare micron-sized particles of a widely used fungicide (azoxystrobin) via ball milling. In the present study, we examine the effect of varying the nature of the steric stabilizer block, the mean nanoparticle diameter, and the glass transition temperature (Tg) of the core-forming block on the particle size and colloidal stability of such azoxystrobin microparticles. In addition, the effect of crosslinking the nanoparticle cores is also investigated. Laser diffraction studies indicated the formation of azoxystrobin microparticles of approximately 2 µm diameter after milling for between 15 and 30 min at 6000 rpm. Diblock copolymer nanoparticles comprising a non-ionic steric stabilizer, rather than a cationic or anionic steric stabilizer, were determined to be more effective dispersants. Furthermore, nanoparticles of up to 51 nm diameter enabled efficient milling and ensured overall suspension concentrate stability. Moreover, crosslinking the nanoparticle cores and adjusting the Tg of the core-forming block had little effect on the milling of azoxystrobin. Finally, we show that this versatile approach is also applicable to five other organic crystalline agrochemicals, namely pinoxaden, cyproconazole, difenoconazole, isopyrazam and tebuconazole. TEM studies confirmed the adsorption of sterically stabilized nanoparticles at the surface of such agrochemical microparticles. The nanoparticles are characterized using TEM, DLS, aqueous electrophoresis and 1H NMR spectroscopy, while the final aqueous' suspension concentrates comprising microparticles of the above six agrochemical actives are characterized using optical microscopy, laser diffraction and electron microscopy.

Block Copolymer Nanoparticles are Effective Dispersants for Micrometer-Sized Organic Crystalline Particles.

Well-defined sterically stabilized diblock copolymer nanoparticles of 29 nm diameter are prepared by RAFT aqueous emulsion polymerization of methyl methacrylate using a dithiobenzoate-capped poly(glycerol monomethacrylate) precursor. These nanoparticles are evaluated as a dispersant for the preparation of organic crystalline microparticles via ball milling. This is exemplified for azoxystrobin, which is a broad-spectrum fungicide that is widely used to protect various food crops. Laser diffraction and optical microscopy studies indicate the formation of azoxystrobin microparticles of approximately 2 µm diameter after ball milling for 10 min at 400 rpm. Nanoparticle adsorption at the surface of these azoxystrobin microparticles is confirmed by electron microscopy studies. The extent of nanoparticle adsorption on the azoxystrobin microparticles can be quantified using a supernatant assay based on solution densitometry. This technique indicates an adsorbed amount of approximately 5.5 mg m-2, which is sufficient to significantly reduce the negative zeta potential exhibited by azoxystrobin. Moreover, this adsorbed amount appears to be essentially independent of the nature of the core-forming block, with similar data being obtained for both poly(methyl methacrylate)- and poly(2,2,2-trifluoroethyl methacrylate)-based nanoparticles. Finally, X-ray photoelectron spectroscopy studies confirm attenuation of the underlying N1s signal arising from the azoxystrobin microparticles by the former adsorbed nanoparticles, suggesting a fractional surface coverage of approximately 0.24. This value is consistent with a theoretical surface coverage of 0.25 calculated from the adsorption isotherm data. Overall, this study suggests that sterically stabilized diblock copolymer nanoparticles may offer a useful alternative approach to traditional soluble copolymer dispersants for the preparation of suspension concentrates affecting the context of agrochemical applications.