Ye Sha

Glass Transitions of Poly(methyl methacrylate) Confined in Nanopores: Conversion of Three- and Two-Layer Models

The glass transitions of poly(methyl methacrylate) (PMMA) oligomer confined in alumina nanopores with diameters much larger than the polymer chain dimension were investigated. Compared with the case of 80 nm nanopores, PMMA oligomer confined in 300 nm nanopores shows three glass transition temperatures (from from low to high, denoted as Tg,lo, Tg,inter, and Tg,hi). Such phenomenon can be interpreted by a three-layer model: there exists an interphase between the adsorbed layer and core volume called the interlayer, which has an intermediate Tg. The behavior of multi-Tg parameters is ascribed to the propagation of the interfacial interaction during vitrifaction process. Besides, because of the nonequilibrium effect in the adsorbed layer, the cooling rate plays an important role in the glass transitions: the fast cooling rate generates a single Tg; the intermediate cooling rate induces three Tg values, while the ultraslow cooling rate results in two Tg values. With decreasing the cooling rate, the thickness of interlayer would continually decrease, while those of the adsorbed layer and core volume gradually increase; meanwhile, the Tg,lo gradually increases, Tg,inter almost stays constant, and the Tg,hi value keeps decreasing. In such a process, the dynamic exchanges between the interlayer and adsorbed layer, core volume should be dominant.

Synthesis of Site‐Specific Dye‐Labeled Polymer via Atom Transfer Radical Polymerization (ATRP) for Quantitative Characterization of the Well‐Defined Interchain Distance

Novel difunctional initiators that incorporate Förster/fluorescence resonance energy transfer (FRET) pairs are generated to carry out atom transfer radical polymerization of styrene, methyl methacrylate, and n-butyl methacrylate monomers by an efficient manner. Based on the chemical structures of the initiators, the locations of the fluorophore moiety are dictated to be in the center of the chain with accurately quantified chain functionality (>90% labeling ratio). The site-specific integration of FRET dyes into separate polymer chain centers allows for characterization of the well-defined interchain distance quantitatively based on the response between these fluorescent probes. The reliability of this technique is verified in bulk state, which is in well agreement with the theoretical ones. This well-defined FRET system is expected to be a promising candidate to provide a distinct physical image at a microscopic level regarding scaling chain dimension, chain interpenetration, and polymer compatibility.

Nanoporous iron oxide@carbon composites with low carbon content as high-performance anodes for lithium-ion batteries

A composite of nanoporous iron oxide (Fe2O3) nanoparticles coated with a thin layer of carbon (designated as nanoporous Fe2O3@C) is synthesized using a convenient one-pot solvothermal method. Although the thickness of the carbon framework is only 6 nm on average, which is very small compared to the size of Fe2O3 nanoparticles, the carbon framework significantly enhances the electrochemical performance of nanoporous Fe2O3@C composites when they are used as an anode material for lithium-ion batteries. Thanks partly to the relatively low carbon content of 6.7 wt%, the nanoporous Fe2O3@C anodes exhibit a high reversible capacity of 767 mA h g−1 after 100 cycles at a current density of 500 mA g−1 and 545 mA h g−1 even at a higher current density of 2 A g−1. In comparison to commercial Fe2O3 nanoparticles and bare nanoporous Fe2O3 nanoparticles, the nanoporous Fe2O3@C anodes show superior cycle life. The nanoporous structure offers void space for volume change of Fe2O3 nanoparticles, while the thin carbon framework improves the stability of structures and SEI (solid electrolyte interphase) films during the continuous intercalation/deintercalation processes of Li ions.

Nanostructures and Dynamics of Isochorically Confined Amorphous Drug Mediated by Cooling Rate, Interfacial, and Intermolecular Interactions

The production and stabilization of amorphous drugs by the nanoconfinement effect has recently become a research hotspot in pharmaceutical sciences. Herein, two guest/host systems, indomethacin (IMC) and griseofulvin (GSF) confined in anodic aluminum oxide (AAO) templates with different pore diameters (25-250 nm) are investigated by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS). The crystallization of the confined drugs is suppressed, and their glass transition temperatures show an evident pore-size dependency. Moreover, a combination of dielectric and calorimetric results demonstrates that the significant change in the temperature dependence of the structural relaxation time during the cooling process is attributed to the vitrification of the interfacial molecules and the local density heterogeneity under isochoric confinement. Interestingly, compared with the case of IMC/AAO, which can be described by a typical two-layer model, GSF/AAO presents an rare scenario of three glass transition temperatures under fast cooling (40-10 K/min), indicating that there exists a thermodynamic nonequilibrium interlayer between the bulk-like core and interfacial layer. In contrast, the slow cooling process (0.5 K/min) would lead confined GSF into the stable core-shell nanostructure. Using surface modification, the interfacial effect is confirmed to be an important reason for the different phenomena between these two guest/host systems, and intermolecular hydrogen bonding is also suggested to be emphasized considering the long-range effect of interfacial interactions. Our results not only provide insight into the glass transition behavior of geometrically confined supercooled liquids, but also offer a means of adjusting and stabilizing the nanostructure of amorphous drugs under two-dimensional confinement.

Conformational Transitions of Polymer Chains in Solutions Characterized by Fluorescence Resonance Energy Transfer

The critical overlap concentration C* is an important concept in polymer solutions and is defined as the boundary between dilute and semidilute regimes. In this study, the chain conformational changes of polystyrene (PS) with both high (Mn = 200,000 Da) and low (Mn = 13,000 Da) molecular weights in cis-decalin were compared by intrachain fluorescence resonance energy transfer (FRET). The random labeling of donor and acceptor chromophores strategy was employed for long PS chains, whereas chain-end labeling was used for short PS chains. By monitoring the spectroscopic intensity ratio between acceptor and donor, the concentration dependence on chain conformation from dilute to semidilute solutions was determined. Both long and short chains exhibit a conformational transition concentration, above which the polymer chains begin to collapse with concentration significantly. Interestingly, for randomly labeled polymer long chains, such concentration is consistent with C* determined from the viscosity result, below which only slight conformational change of polymer chain takes place. However, for the chain-end labeled short chain, the conformational transition concentration takes place earlier than C*, below which no significant polymer conformation change is observed.