Sarah M. Hoppe

Thermally Tunable Surface Wettability of Electrospun Fiber Mats: Polystyrene/Poly(N-isopropylacrylamide) Blended versus Crosslinked Poly[(N-isopropylacrylamide)-co-(methacrylic acid)]

This work reports on thermally tunable surface wettability of electrospun fiber mats of: polystyrene (PS)/poly(N-isopropylacrylamide) (PNIPA) blended (bl-PS/PNIPA) and crosslinked poly[(N-isopropylacrylamide)-co-[methacrylic acid)] (PNIPAMAA) (xl-NIPAMAA). Both the bl-PS/PNIPA and xl-PNIPAMAA fiber mats demonstrate reversibly switchable surface wettability, with the bl-PS/PNIPA fiber mats approaching superhydrophobic ≥150° and superhydrophilic contact angle (CA) values at extreme temperatures. Weight loss studies carried out at 10 °C indicate that the crosslinked PNIPAMAA fiber mats had better structural integrity than the bl-PS/PNIPA fiber mats. PNIPA surface chemistry and the Cassie-Baxter model were used to explain the mechanism behind the observed extreme wettability.

In-situ transmission electron microscopy of liposomes in an aqueous environment.

The characterization of liposomes was undertaken using in-situ microfluidic transmission electron microscopy. Liposomes were imaged without contrast enhancement staining or cryogenic treatment, allowing for the observation of functional liposomes in an aqueous environment. The stability and quality of the liposome structures observed were found to be highly dependent on the surface and liposome chemistries within the liquid cell. The successful imaging of liposomes suggests the potential for the extension of in-situ microfluidic TEM to a wide variety of other biological and soft matter systems and processes.

Synthesis, Characterization, and Electrochemical Properties of a Series of Sterically Varied Iron(II) Alkoxide Precursors and Their Resultant Nanoparticles

A new family of iron(II) aryloxide [Fe(OAr)(2)(py)(x)] precursors was synthesized from the alcoholysis of iron(II) mesityl [Fe(Mes)(2)] in pyridine (py) using a series of sterically varied 2-alkyl phenols (alkyl = methyl (H-oMP), isopropyl (H-oPP), tert-butyl (H-oBP)) and 2,6-dialkyl phenols (alkyl = methyl (H-DMP), isopropyl (H-DIP), tert-butyl (H-DBP), phenyl (H-DPhP)). All of the products were found to be mononuclear and structurally characterized as [Fe(OAr)(2)(py)(x)] (x = 3 OAr = oMP (1), oPP (2), oBP (3), DMP (4), DIP (5); x = 2 OAr = DBP (6), DPhP (7)). The use of tris-tert-butoxysilanol (OSi(OBu(t))(3) = TOBS) led to isolation of [Fe(TOBS)(2)(py)(2)] (8). The new Fe(OAr)(2)(py)(x) (1-6) were found, under solvothermal conditions, to produce nanodots identified by PXRD as the γ-maghemite phase. The model precursor 3 and the nanoparticles 6n were evaluated using electrochemical methods. Cyclic voltammetry for 3 revealed multiple irreversible oxidation peaks, which have been tentatively attributed to the loss of alkoxide ligand coupled with the deposition of a solid Fe-containing coating on the electrode. This coating was stable out to the voltage limits for the acetonitrile solvent.

Size effects on the properties of high z scintillator materials

Particle size effects of nano- and polycrystalline metal tungstate MWO4 (M = Ca, Pb, Cd) scintillators were examined through a comparison of commercially available powders and solution precipitation prepared nanoscaled materials. The scintillation behaviors of nanoparticles and commercial powders were examined with ion beam induced luminescence (IBIL), photoluminescence (PL), and cathodoluminescence (CL) spectroscopy techniques. For commercial microns sized MWO4 powders, spectral emission differences between CL and PL were only observed for Cd and Pb tungstates when compared to reported single crystals. The IBIL wavelength emissions also differed from the commercial MWO4 CL and PL data and were red shifted by 28 and 14 nm for CaWO4 and CdWO4; respectively, while PbWO4 had no significant change. IBIL analysis on CaWO4 nanoparticles produced a 40 nm blue shift from the commercial powder emission. These preliminary results suggest that both size and cation Z may affect the emission properties of the MWO4 scintillators.

Application of in-situ ion irradiation TEM and 4D tomography toadvanced scintillator materials

Scintillating nanomaterials are being investigated as replacements for fragile, difficult to synthesize single crystal radiation detectors, but greater insight into their structural stability when exposed to extreme environments is needed to determine long-term performance. An initial study using high-Z cadmium tungstate (CdWO4) nanorods and an in-situ ion irradiation transmission electron microscope (I3TEM) was performed to determine the feasibility of these extreme environment experiments. The I3TEM presents a unique capability that permits the real time characterization of nanostructures exposed to various types of ion irradiation. In this work, we investigated the structural evolution of CdWO4 nanorods exposed to 50 nA of 3 MeV copper (3+) ions. During the first several minutes of exposure, the nanorods underwent significant structural evolution. This appears to occur in two steps where the nanorods are first segmented into smaller sections followed by the sintering of adjacent particles into larger nanostructures. An additional study combined in-situ ion irradiation with electron tomography to record tilt series after each irradiation dose; which were then processed into 3D reconstructions to show radiation damage to the material over time. Analyses to understand the mechanisms and structure-property relationships involved are ongoing.