Rodney D. Priestley

Core–Shell Fe3O4 Polydopamine Nanoparticles Serve Multipurpose as Drug Carrier, Catalyst Support and Carbon Adsorbent

We present the synthesis and multifunctional utilization of core-shell Fe3O4 polydopamine nanoparticles (Fe3O4@PDA NPs) to serve as the enabling platform for a range of applications including responsive drug delivery, recyclable catalyst support, and adsorbent. Magnetite Fe3O4 NPs formed in a one-pot process by the hydrothermal approach were coated with a polydopamine shell layer of ~20 nm in thickness. The as prepared Fe3O4@PDA NPs were used for the controlled drug release in a pH-sensitive manner via reversible bonding between catechol and boronic acid groups of PDA and the anticancer drug bortezomib (BTZ), respectively. The facile deposition of Au NPs atop Fe3O4@PDA NPs was achieved by utilizing PDA as both the reducing agent and the coupling agent. The nanocatalysts exhibited high catalytic performance for the reduction of o-nitrophenol. Furthermore, the recovery and reuse of the catalyst was demonstrated 10 times without any detectible loss in activity. Finally, the PDA layers were converted into carbon to obtain Fe3O4@C and used as an adsorbent for the removal of Rhodamine B from an aqueous solution. The synergistic combination of unique features of PDA and magnetic nanoparticles establishes these core-shell NPs as a versatile platform for multiple applications.

Ultrastable nanostructured polymer glasses

Owing to the kinetic nature of the glass transition, the ability to significantly alter the properties of amorphous solids by the typical routes to the vitreous state is restricted. For instance, an order of magnitude change in the cooling rate merely modifies the value of the glass transition temperature (T(g)) by a few degrees. Here we show that matrix-assisted pulsed laser evaporation (MAPLE) can be used to form ultrastable and nanostructured glassy polymer films which, relative to the standard poly(methyl methacrylate) glass formed on cooling at standard rates, are 40% less dense, have a 40 K higher T(g), and exhibit a two orders of magnitude enhancement in kinetic stability at high temperatures. The unique set of properties of MAPLE-deposited glasses may make them attractive in technologies where weight and stability are central design issues.

Flash nanoprecipitation of polystyrene nanoparticles

Aside from polymerization techniques, polymer nanoparticles can be generated through the displacement of a solvent with a nonsolvent, i.e., nanoprecipitation. In this study, we utilize a facile process termed Flash NanoPrecipitation (FNP) to generate polystyrene (PS) nanoparticles of several different molecular weights. As compared to PS nanoparticles synthesized by surfactant free emulsion polymerization, nanoparticles prepared by FNP show comparable size distributions when the diameter is less than 150 nm. Furthermore, we illustrate that the sizes of PS nanoparticles prepared by FNP can be fine-tuned by changing the polymer and/or electrolyte concentration. The stabilized nanoparticles contain only the radically polymerized polymer chains, which have sulfate anions at the chain termini and no additional external stabilizers. Calculations of the mechanism of particle formation and stabilization show that the size-dependent electrostatic repulsions between nanoparticles and single collapsed polymer chains control assembly and monodispersity. The ability to independently vary polymer molecular weight and nanoparticle size will enable fundamental studies of the effect of confinement on polymer dynamics in a way not easily achievable by other techniques.

Photoresponsive Coumarin‐Stabilized Polymeric Nanoparticles as a Detectable Drug Carrier

The ability to create aqueous suspended stable nanoparticles of the hydrophobic homopolymer poly(ϵ-caprolactone) end-functionalized with coumarin moieties (CPCL) is demonstrated. Nanoparticles of CPCL are prepared in a continuous manner using nanoprecipitation. The resulting nanoparticles are spherical in morphology, about 40 nm in diameter, and possess a narrow size distribution and excellent stability over 4 months by repulsive surface charge. Nanoparticle size can be easily controlled by manipulating the concentration of CPCL in the solution. The interparticle assembly between the nanoparticles can be reversibly adjusted with photoirradiation due to photoinduced [2 + 2] cyclodimerization and cleavage between the coumarin molecules. In addition, the CPCL nanoparticles show significant cellular uptake without cytotoxicity, and the intrinsic fluorescence of the coumarin functional group permits the direct detection of cellular internalization.

Structural relaxation of polymer nanospheres under soft and hard confinement: isobaric versus isochoric conditions.

We have measured the glassy-state structural relaxation of aqueous suspended polystyrene (PS) nanoparticles (the case of soft confinement) and the corresponding silica-capped PS nanoparticles (the case of hard confinement) via differential scanning calorimetry. Suspended and capped PS nanoparticles undergo physical aging under isobaric and isochoric conditions, respectively. With decreasing diameter, suspended and capped PS nanoparticles exhibited reduced and bulk glass transition temperatures (T(g)), respectively. To account for T(g) changes with confinement, all physical aging measurements were performed at a constant value of T(g) - T(a), where T(a) is the aging temperature. With decreasing diameter, aqueous suspended PS nanoparticles exhibited enhanced physical aging rates in comparison to bulk PS. Due to differences in thermodynamic conditions during aging and interfacial effects from nanoconfinement, at all values of T(g) - T(a) investigated, capped PS nanoparticles aged at reduced rates compared to the corresponding aqueous suspended PS nanoparticles. We captured the physical aging behavior of all nanoparticles via the Tool, Narayanaswamy, and Moynihan model of structural relaxation.

Fragility of an Isochorically Confined Polymer Glass.

We report the effect of isochoric confinement on the dynamic fragility of a polymeric glass-former, that is, polystyrene (PS). Utilizing silica-capped PS nanospheres as a model system, the fictive temperature (Tf) and the isochoric heat capacity (Cv) are measured as a function of diameter via differential scanning calorimetry. By examining Tf as a function of cooling rate for each sample, the isochoric fragility (mv) is obtained, which decreases significantly as the diameter of the nanospheres is reduced from 260 to 129 nm. Hence, the temperature dependence of structural relaxation near the glass transition is weakened with isochoric confinement.

Rational design and fabrication of core–shell nanoparticles through a one-step/pot strategy

Core–shell nanoparticles (NPs) have emerged as a type of important nanomaterial for various applications. The challenge in the preparation of core–shell NPs is to find a simple, cost-effective and less time-consuming strategy with minimum environmental impact. The consolidation of multiple preparation steps into one step represents a new green synthesis pathway in chemistry and materials science. In this review, we provide an overview of the recent developments in the fabrication of core–shell NPs through one-step/pot methodologies. A variety of one-step/pot preparation methods are presented, discussed and compared, followed by the summary and outlook of this emerging area.

Thermomechanical behavior of hydrogen-bond based supramolecular poly(ε-caprolactone)-silica nanocomposites

Supramolecular polymer nanocomposites represent an attractive alternative to traditional polymers for advanced materials that exhibit stimuli-responsive and self-healing properties. Here, we investigate the effects of specific hydrogen bonding interactions between surface functionalized silica nanoparticles and ureidopyrimidinone (UPy) based hydrogen bonded supramolecular poly(e-caprolactone) in a supramolecular polymer nanocomposite. The effect of varying levels of nanoparticle UPy surface functionalization is considered. In addition to the anticipated improvements in Youngs modulus (∼50%) and storage modulus (∼2×) with silica loading, increases in strain at breaking point (∼25%) with silica loading were observed and attributed to particle–matrix hydrogen bonding. However, increasing the extent of UPy surface functionality at a constant nanoparticle loading level led to a marked decrease in storage modulus relative to nanocomposites prepared with as-received silica nanoparticles. TEM investigation of these nanocomposites show an increase in nanoparticle aggregation. Nanoparticle aggregation provides both an explanation for the observed storage modulus reduction and evidence of particle–particle interactions. These results give interesting insight into the competing effects of specific supramolecular interactions in supramolecular polymer nanocomposite materials.

Directed Assembly of Soft Colloids through Rapid Solvent Exchange

We studied the directed assembly of soft nanoparticles through rapid micromixing of polymers in solution with a nonsolvent. Both experiments and computer simulations were performed to elucidate the underlying physics and to investigate the role of various process parameters. In particular, we discovered that no external stabilizing agents or charged end groups are required to keep the colloids separated from each other when water is used as the nonsolvent. Furthermore, the size of the nanoparticles can be reliably tuned through the mixing rate and the ratio between polymer solution and nonsolvent. Our results demonstrate that this mechanism is highly promising for the mass fabrication of uniformly sized colloidal particles, using a wide variety of polymeric feed materials.

Origins of nanostructure in amorphous polymer coatings via matrix assisted pulsed laser evaporation

We investigate the nanostructure of sub-monolayer and monolayer amorphous polymer films deposited via Matrix Assisted Pulsed Laser Evaporation (MAPLE). The structure is quantified by analyzing the size distribution of polymer nanoglobules as a function of deposition parameters: time and polymer concentration. Two deposition regimes are observed in the early stages of MAPLE deposition, with a transition at a critical time. The observed distribution of nanoglobule sizes that is present after the critical time agrees well with prior molecular dynamics simulations of the MAPLE process. We discuss the mechanism of nanostructured coatings within the framework of the Zhigilei model.