Publications

Functional polyethylenes possess valuable bulk and surface properties, but the limits of current synthetic methods narrow the range of accessible materials and prevent many envisioned applications. Instead, these materials are often used in composite films that are challenging to recycle. We report a Cu-catalyzed amination of polyethylenes to form mono- and bifunctional materials containing a series of polar groups and substituents. Designed catalysts with hydrophobic moieties enable the amination of linear and branched polyethylenes without chain scission or cross-linking, leading to polyethylenes with otherwise inaccessible combinations of functional groups and architectures. The resulting materials possess tunable bulk and surface properties, including toughness, adhesion to metal, paintability, and water solubility, which could unlock applications for functional polyethylenes and reduce the need for complex composites.

From 1996 June 10 to July 29, the International Ultraviolet Explorer monitored the Seyfert 1 galaxy NGC 7469 continuously in an attempt to measure time delays between the continuum and emission-line fluxes. From the time delays, one can estimate the size of the region dominating the production of the UV emission lines in this source. We find the strong UV emission lines to respond to continuum variations with time delays of about 2.d3-3.d1 for Lyα, 2.d7 for C IV λ1549, 1.d9-2.d4 for N IV λ 1240, 1.d7-1.d8 for Si IV λ 1400, and 0.d7-1.d0 for He II λ1640. The most remarkable result, however, is the detection of apparent time delays between the different UV continuum bands. With respect to the UV continuum flux at 1315 Å, the flux at 1485 Å, 1740 Å, and 1825 Å lags with time delays of 0.d21, 0.d35, and 0.d28, respectively. Determination of the significance of this detection is somewhat problematic since it depends on accurate estimation of the uncertainties in the lag measurements, which are difficult to assess. We attempt to estimate the uncertainties in the time delays through Monte Carlo simulations, and these yield estimates of ~0.d07 for the 1 σ uncertainties in the interband continuum time delays. Possible explanations for the delays include the existence of a continuum-flux reprocessing region close to the central source and/or a contamination of the continuum flux with a very broad time-delayed emission feature such as the Balmer continuum or merged Fe II multiplets.

Inorganic nanotubes were successfully integrated with microfluidic systems to create nanofluidic devices for single DNA molecule sensing. Inorganic nanotubes are unique in their high aspect ratio and exhibit translocation characteristics in which the DNA is fully stretched. Transient changes of ionic current indicate DNA translocation events. A transition from current decrease to current enhancement during translocation was observed on changing the buffer concentration, suggesting interplay between electrostatic charge and geometric blockage effects. These inorganic nanotube nanofluidic devices represent a new platform for the study of single biomolecule translocation with the potential for integration into nanofluidic circuits.

The effects of interface defects on the sharpness of the conductance switch can be seen both in the intrinsic band tail steepness (for shallow defects) observed at all temperatures, as well as in a subthreshold regime clearly dominated by thermal activation (for deep defects). To realize a steep turn-on, reduced dimensionality on both sides of the junction is needed [1]. However, increasing the tunneling probability of the device will increase not only the band-to-band current in the on-state but also leakage into the band tail. In order to achieve a turn-on steepness better than 60 mV/dec over at least six decades of current, a very high quality tunneling interface is needed, comparable to the best achieved interface trap densities in semiconductor systems. This suggests future investigation into the engineering of pristine material interfaces, possibly at atomic levels of control, with high yield.

We describe observational evidence for a new kind of interacting-binary-star outburst that involves both an accretion instability and an increase in thermonuclear shell burning on the surface of an accreting white dwarf. We refer to this new type of eruption as a combination nova. In late 2000, the prototypical symbiotic star Z Andromedae brightened by roughly two magnitudes in the optical. We observed the outburst in the radio with the VLA and MERLIN, in the optical both photometrically and spectroscopically, in the far ultraviolet with FUSE, and in the X-rays with both Chandra and XMM. The two-year-long event had three distinct stages. During the first stage, the optical rise closely resembled an earlier, small outburst that was caused by an accretion-disk instability. In the second stage, the hot component ejected an optically thick shell of material. In the third stage, the shell cleared to reveal a white dwarf whose luminosity remained on the order of 10^4 Lsun for approximately one year. The eruption was thus too energetic to have been powered by accretion alone. We propose that the initial burst of accretion was large enough to trigger enhanced nuclear burning on the surface of the white dwarf and the ejection of an optically thick shell of material. This outburst therefore combined elements of both a dwarf nova and a classical nova. Our results have implications for the long-standing problem of producing shell flashes with short recurrence times on low-mass white dwarfs in symbiotic stars.

The Lorenz number (L) of a conductor is the ratio between its electronic thermal conductivity and electrical conductivity. It takes the Sommerfeld value of L0=π2/3kB/e2 in simple, metallically electronic systems where charge and heat are both carried by the same group of quasi-particles that experience elastic scattering. Higher values of L than L0 are possible in semiconductors where both electrons and holes co-exist at high densities, that is, in bipolar conduction. As a narrow-bandgap semiconductor, Bi2Te3 exhibits L > L0 which has been generally attributed to such bipolar conduction mechanisms. However, in this work, we report that L > L0 is still observed in individual, single-crystal Bi2Te3 nanoribbons even at low temperatures and when degenerately doped, that is, far from the bipolar conduction condition. This discovery calls for different mechanisms to explain the unconventional electronic thermal transport behavior in Bi2Te3.

Iron is essential for sustaining life, as its ability to cycle between multiple oxidation states is critical for catalyzing chemical transformations in biological systems. However, without proper regulation, this same redox capacity can trigger oxidative stress events that contribute to aging along with diseases ranging from cancer to cardiovascular and neurodegenerative disorders. Despite its importance, methods for monitoring biological iron bound weakly to cellular ligands-the labile iron pool-to generate a response that preserves spatial and temporal information remain limited, owing to the potent fluorescence quenching ability of iron. We report the design, synthesis, and biological evaluation of FRET Iron Probe 1 (FIP-1), a reactivity-based probe that enables ratiometric fluorescence imaging of labile iron pools in living systems. Inspired by antimalarial natural products and related therapeutics, FIP-1 links two fluorophores (fluorescein and Cy3) through an Fe(II)-cleavable endoperoxide bridge, where Fe(II)-triggered peroxide cleavage leads to a decrease in fluorescence resonance energy transfer (FRET) from the fluorescein donor to Cy3 acceptor by splitting these two dyes into separate fragments. FIP-1 responds to Fe(II) in aqueous buffer with selectivity over competing metal ions and is capable of detecting changes in labile iron pools within living cells with iron supplementation and/or depletion. Moreover, application of FIP-1 to a model of ferroptosis reveals a change in labile iron pools during this form of cell death, providing a starting point to study iron signaling in living systems.

<p>PDF file - 61K, Relative Abundance of Phyla of CM and RM Mice by Genotype and Intestinal Region.</p>