Superdiffusive Thermal Transport in Polymer-Grafted Nanoparticle Melts.

In contrast to normal diffusion processes, thermal conduction in one-dimensional systems is anomalous. The thermal conductivity is found to vary with the length as κ∼L^{α}(α>0), but there is a long-standing debate on the value α. Here, we present a canonical example of this behavior in polymer-grafted spherical nanoparticle (GNP) melts at fixed grafting density and nanoparticle radius.

Enhanced efficiency of water desalination in nanostructured thin-film membranes with polymer grafted nanoparticles.

Polyamide composite (PA-TFC) membranes are the state-of-the-art ubiquitous platforms to desalinate water at scale. We have developed a novel, transformative platform where the performance of such membranes is significantly and controllably improved by depositing thin films of polymethylacrylate [PMA] grafted silica nanoparticles (PGNPs) through the venerable Langmuir-Blodgett method. Our key practically important finding is that these constructs can have unprecedented selectivity values (, ∼250-3000 bar, >99.

Polymer Molecular Weights via DOSY NMR.

Diffusion-ordered spectroscopy (DOSY) H nuclear magnetic resonance (H NMR) has become a powerful tool to characterize the molecular weights of polymers. Compared to common characterization techniques, such as size exclusion chromatography (SEC), DOSY is faster, uses less solvent, and does not require a purified polymer sample. Poly(methyl methacrylate) (PMMA), polystyrene (PS), and polybutadiene (PB) molecular weights were determined by the linear correlation between the logarithm of their diffusion coefficients (D) and the logarithm of their molecular weights based on SEC molecular weights.

Dielectric Properties of Polymer Nanocomposite Interphases Using Electrostatic Force Microscopy and Machine Learning.

Knowing the dielectric properties of the interfacial region in polymer nanocomposites is critical to predicting and controlling dielectric properties. They are, however, difficult to characterize due to their nanoscale dimensions. Electrostatic force microscopy (EFM) provides a pathway to local dielectric property measurements, but extracting local dielectric permittivity in complex interphase geometries from EFM measurements remains a challenge.

Melt State Reinforcement of Polyisoprene by Silica Nanoparticles Grafted with Polyisoprene.

We systematically vary the nanoparticle (NP) dispersion state in composites formed by mixing polyisoprene homopolymers with polyisoprene grafted silica particles, and demonstrate how creep measurements allow us to overcome the limitations of small amplitude oscillatory shear (SAOS) experiments. This allows us to access nearly 13 orders in time in the mechanical response of the resulting composites. We find that a specific NP morphology, a percolating particle network achieved at intermediate graft densities, significantly reinforces the system and has a lower NP percolation loading threshold relative to other morphologies.

Understanding Gas Transport in Polymer-Grafted Nanoparticle Assemblies.

We rationalize the unusual gas transport behavior of polymer-grafted nanoparticle (GNP) membranes. While gas permeabilities depend specifically on the chemistry of the polymers considered, we focus here on permeabilities relative to the corresponding pure polymer which show interesting, "universal" behavior. For a given NP radius, R, and for large enough areal grafting densities, σ, to be in the dense brush regime we find that gas permeability enhancements display a maximum as a function of the graft chain molecular weight, M.

Local Structure of Polymer-Grafted Nanoparticle Melts.

Polymer-grafted nanoparticle (GNP) membranes show unexpected gas transport enhancements relative to the neat polymer, with a maximum as a function of graft molecular weight (MW ≈ 100 kDa) for sufficiently high grafting densities. The structural origins of this behavior are unclear. Simulations suggest that polymer segments are stretched near the nanoparticle (NP) surface and form a dry layer, while more distal chain fragments are in their undeformed Gaussian states and interpenetrate with segments from neighboring NPs.

Unusual High-Frequency Mechanical Properties of Polymer-Grafted Nanoparticle Melts.

Brillouin light spectroscopy is used to measure the elastic moduli of spherical polymer-grafted nanoparticle (GNP) melts as a function of chain length at fixed grafting density (0.47  chains/nm^{2}) and nanoparticle radius (8 nm). While the moduli follow a rule of mixtures (Wood's law) for long chains, they display enhanced elasticity and anomalous dissipation for graft chains <100  kDa.

Universal Polymeric-to-Colloidal Transition in Melts of Hairy Nanoparticles.

Two different classes of hairy self-suspended nanoparticles in the melt state, polymer-grafted nanoparticles (GNPs) and star polymers, are shown to display universal dynamic behavior across a broad range of parameter space. Linear viscoelastic measurements on well-characterized silica-poly(methyl acrylate) GNPs with a fixed core radius () and grafting density (or number of arms ) but varying arm degree of polymerization () show two distinctly different regimes of response. The colloidal Regime I with a small (large core volume fraction) is characterized by predominant low-frequency solidlike colloidal plateau and ultraslow relaxation, while the polymeric Regime II with a large (small core volume fractions) has a response dominated by the starlike relaxation of partially interpenetrated arms.

Nanotargeting of Resistant Infections with a Special Emphasis on the Biofilm Landscape.

Bacterial resistance to antimicrobial compounds is a growing concern in medical and public health circles. Overcoming the adaptable and duplicative resistance mechanisms of bacteria requires chemistry-based approaches. Engineered nanoparticles (NPs) now offer unique advantages toward this effort.

Tuning Selectivities in Gas Separation Membranes Based on Polymer-Grafted Nanoparticles.

Polymer membranes are critical to many sustainability applications that require the size-based separation of gas mixtures. Despite their ubiquity, there is a continuing need to selectively affect the transport of different mixture components while enhancing mechanical strength and hindering aging. Polymer-grafted nanoparticles (GNPs) have recently been explored in the context of gas separations.

Synthesis of Well-Defined Polyolefin Grafted SiO Nanoparticles with Molecular Weight and Graft Density Control.

Recent advances in surface-initiated polymerization have given rise to a range of brush nanocomposites and hybrid functional materials. However, the synthesis of pure polyolefin-grafted nanocomposites by surface-initiated ring-opening metathesis polymerization (SI-ROMP) is a significant challenge due to the particle aggregation and irreversible particle coupling. This study presents a synthetic approach toward well-defined poly(cyclooctene)- and polyethylene-grafted nanoparticles by tethering Grubbs third generation catalyst on the particle surface and initiating the polymerization in a rapid manner.

Nanoparticles as antibiotic-delivery vehicles (ADVs) overcome resistance by MRSA and other MDR bacterial pathogens: The grenade hypothesis.

Objectives: The aim of this study was to examine how the concentrated delivery of less effective antibiotics, such as the β-lactam penicillin G, by linkage to nanoparticles (NPs), could influence the killing efficiency against various pathogenic bacteria, including methicillin-resistant Staphylococcus aureus (MRSA) and other multidrug resistant (MDR) strains.

Methods: The β-lactam antibiotic penicillin G (PenG) was passively sorbed to fluorescent polystyrene NPs (20nm) that were surface-functionalized with carboxylic acid (COO-NPs) or sulfate groups (SO-NPs) to form a PenG-NP complex. Antimicrobial activities of PenG-NPs were evaluated against Gram-negative and Gram-positive bacteria, including antibiotic resistant strains.

Designing exceptional gas-separation polymer membranes using machine learning.

The field of polymer membrane design is primarily based on empirical observation, which limits discovery of new materials optimized for separating a given gas pair. Instead of relying on exhaustive experimental investigations, we trained a machine learning (ML) algorithm, using a topological, path-based hash of the polymer repeating unit. We used a limited set of experimental gas permeability data for six different gases in ~700 polymeric constructs that have been measured to date to predict the gas-separation behavior of over 11,000 homopolymers not previously tested for these properties.

Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics.

We previously showed that nanoparticles (NPs) could be ordered into structures by using the growth rate of polymer crystals as the control variable. In particular, for slow enough spherulitic growth fronts, the NPs grafted with amorphous polymer chains are selectively moved into the interlamellar, interfibrillar, and interspherulitic zones of a lamellar morphology, specifically going from interlamellar to interspherulitic with progressively decreasing crystal growth rates. Here, we examine the effect of NP polymer grafting density on crystallization kinetics.

Accelerated Local Dynamics in Matrix-Free Polymer Grafted Nanoparticles.

The tracer diffusion coefficient of six different permanent gases in polymer-grafted nanoparticle (GNP) membranes, i.e., neat GNP constructs with no solvent, show a maximum as a function of the grafted chain length at fixed grafting density.

Nanoparticle Organization by Growing Polyethylene Crystal Fronts.

We investigate the crystallization-induced ordering of C grafted 14 nm diameter spherical silica nanoparticles (NPs) in a short chain ( = 4 kDa, ≈ 2.3) polyethylene and a commercial high-density polyethylene ( = 152 kDa, ≈ 3.2) matrix.

High-Capacity Poly(4-vinylpyridine) Grafted PolyHIPE Foams for Efficient Plutonium Separation and Purification.

The use of anion-exchange resins to separate and purify plutonium from various sources represents a major bottleneck in the throughput that can be achieved when this step is part of a larger separation scheme. Slow sorption kinetics and broad elution profiles necessitate long contact times with the resin, and the recovered Pu is relatively dilute, requiring the handling of large volumes of hazardous material. In this work, high internal-phase emulsion (HIPE) foams were prepared with a comonomer containing a dormant nitroxide.

High-Frequency Mechanical Behavior of Pure Polymer-Grafted Nanoparticle Constructs.

Polymer-grafted nanoparticle (GNP) membranes show increased gas permeability relative to pure polymer analogs, with this effect evidently tunable through systematic variations in the grafted polymer chain length and grafting density. Additionally, these materials show less deleterious aging effects relative to the pure polymer. To better understand these issues, we explore the solid-state mechanical properties of GNP layers using quartz crystal microbalance (QCM) spectroscopy, which operates under conditions (≈5 MHz) that we believe are relevant to gas transport.

Polyethylene Grafted Silica Nanoparticles Prepared via Surface-Initiated ROMP.

Polyethylene and nanosilica represent the most ubiquitous commodity plastic and nanocomposite filler, respectively. Despite their potential utility, few examples exist in the literature of successfully combining these two materials to form polyethylene nanocomposites. Synthesizing well-defined polyethylene grafted to a surface is a significant challenge in the nanocomposites community.

Location of Imbibed Solvent in Polymer-Grafted Nanoparticle Membranes.

Membranes made purely from nanoparticles (NPs) grafted with polymer chains show increased gas permeability relative to the analogous neat polymer films, with this effect apparently being tunable with systematic variations in polymer graft density and molecular weight. To explore the structural origins of these unusual transport results, we use small angle scattering (neutron, X-ray) on the dry nanocomposite film and to critically examine in situ the structural effects of absorbed solvent. The relatively low diffusion coefficients of typical solvents (∼10 m/s) restricts us to thin films (≈1 μm in thickness) if solute concentration profiles are to equilibrate on the 1 s time scale.

pH and Thermal Dual-Responsive Nanoparticles for Controlled Drug Delivery with High Loading Content.

A pH and thermal dual-responsive nanocarrier with silica as the core and block copolymer composed of poly(methacrylic acid) (PMAA) and poly(-isopropylacrylamide) (PNIPAM) as the shell was prepared by surface-initiated reversible addition-fragmentation chain-transfer (SI-RAFT) polymerization. The resulting SiO-PMAA--PNIPAM particles dispersed individually in an aqueous solution at a high pH and a low temperature but reversibly agglomerated under acidic conditions or at elevated temperatures. These dual-responsive nanoparticles were used as carriers to deliver the model drug doxorubicin (DOX) with unusually high entrapment efficiency and loading content, which is due to the small size (15 nm), light weight of the cores, and high graft density (0.

Charged Metallopolymer-Grafted Silica Nanoparticles for Antimicrobial Applications.

Inappropriate and frequent use of antibiotics has led to the development of antibiotic-resistant bacteria, which cause infectious diseases that are difficult to treat. With the rising threat of antibiotic resistance, the need to develop effective new antimicrobial agents is prominent. We report antimicrobial metallopolymer nanoparticles, which were prepared by surface-initiated reversible addition-fragmentation chain transfer polymerization of a cobaltocenium-containing methacrylate monomer from silica nanoparticles.

A Useful Method for Preparing Mixed Brush Polymer Grafted Nanoparticles by Polymerizing Block Copolymers from Surfaces with Reversed Monomer Addition Sequence.

The preparation of well-defined block copolymers using controlled radical polymerization depends on the proper order of monomer addition. The reversed order of monomer addition results in a mixture of block copolymer and homopolymer and thus has typically been avoided. In this paper, the low blocking efficiency of reversed monomer addition order is utilized in combination with surface initiated reversible addition-fragmentation chain-transfer polymerization to establish a facile procedure toward mixed polymer brush grafted nanoparticles SiO -g-(PS (polystyrene), PS-b-PMAA (polymethacrylic acid)).