PubMed Health⌕ Search

Biomedical subjects

Jeffrey W Long

Publications and source records attributed to Jeffrey W Long.

6 recordsLinked to original sources
PubMed2006

Nanoscale conductivity mapping of hybrid nanoarchitectures: ultrathin poly(o-phenylenediamine) on mesoporous manganese oxide ambigels.

We use conductive-probe atomic force microscopy (CP-AFM) to characterize and image hybrid electrode structures comprising mesoporous manganese oxide (MnO2) ambigel nanoarchitectures coated with an ultrathin (<10 nm) electrodeposited layer of poly(o-phenylenediamine), PPD. Native MnO2 ambigel films, supported on indium tin oxide (ITO) substrates, exhibit spatially uniform conductivity that correlates well with the topography of the MnO2 film, confirming that the nanoscopic oxide network is effectively wired to the underlying ITO substrate. Following the self-limiting electrodeposition of the PPD coating onto the high-surface-area (>200 m2 g(-1)) MnO2 ambigel, the resulting hybrid structures display an approximately 20-fold reduction in conductivity, as determined from CP-AFM measurements. The CP-AFM imaging studies confirm that the ultrathin, insulating PPD layer conformally and homogeneously coats the conductive nanoarchitecture. CP-AFM imaging of PPD-MnO2 hybrid electrodes following electrochemical cycling in an aqueous acid electrolyte reveals that the ultrathin PPD coating serves as an effective barrier to the electrolyte, protecting the underlying MnO2 nanoarchitecture from electrochemical dissolution.

Journal Article↗
PubMed2005

Using an oxide nanoarchitecture to make or break a proton wire.

We report that long-range proton diffusion (>0.3 mm) is generated in monolithic ultraporous manganese oxide nanoarchitectures upon exposure to gas-phase water. The sol-gel-derived ambigel nanoarchitectures, with bicontinuous networks of covalently bonded nanoscale solid and through-connected mesopores, exhibit conductometric sensitivity to humidity as established by impedance spectroscopy. The spectra contain a Warburg feature from which the concentration and diffusion length of the protonic charge carriers are determined. Water adsorbs conformally onto the architecture's continuous solid network in equilibrium with atmospheric humidity to create a continuous water sheath that acts as a 3-D proton wire. As a result, monolithic manganese oxide ambigels exhibit an equilibrium conductometric response to humidity that is 14 times greater than that of previous reports for electrolytic manganese oxide. A packed bed of 1-10-microm ambigel particulates in physical contact with one another, each with the same nanoscale morphology as the monolithic nanoarchitecture, also support long-range proton diffusion; however, the sensitivity to humidity is four times lower than the monolithic form due to restricted proton transport between adjacent particulates. Films composed of 0.3-12-microm ambigel particulates supported on interdigitated array electrodes with 20-microm electrode spacing express finite-diffusion behavior due to the short distance between the contact electrodes and have a conductometric sensitivity to humidity comparable to electrolytic MnO2 and 17 times lower than the monolithic ambigel. These results suggest that controlling the nature of the porous and solid phases in a nanoarchitecture provides a mechanism to limit interference from condensed water in conductometric gas-phase sensors. In addition, continuous monolithic architectures should improve electrochemical performance in devices where efficient long-range transport of protons or other ions is critical.

Journal Article↗
PubMed2004

Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures.

We have developed crystalline nanoarchitectures of iron oxide that exhibit superparamagnetic behavior while still retaining the desirable bicontinuous pore-solid networks and monolithic nature of an aerogel. Iron oxide aerogels are initially produced in an X-ray-amorphous, high-surface-area form, by adapting recently established sol-gel methods using Fe(III) salts and epoxide-based proton scavengers. Controlled temperature/atmosphere treatments convert the as-prepared iron oxide aerogels into nanocrystalline forms with the inverse spinel structure. As a function of the bathing gas, treatment temperature, and treatment history, these nanocrystalline forms can be reversibly tuned to predominantly exhibit either Fe(3)O(4) (magnetite) or gamma-Fe(2)O(3) (maghemite) phases, as verified by electron microscopy, X-ray and electron diffraction, microprobe Raman spectroscopy, and magnetic analysis. Peak deconvolution of the Raman-active Fe-O bands yields valuable information on the local structure and vacancy content of the various aerogel forms, and facilitates the differentiation of Fe(3)O(4) and gamma-Fe(2)O(3) components, which are difficult to assign using only diffraction methods. These nanocrystalline, magnetic forms retain the inherent characteristics of aerogels, including high surface area (>140 m(2) g(-1)), through-connected porosity concentrated in the mesopore size range (2-50 nm), and nanoscale particle sizes (7-18 nm). On the basis of this synthetic and processing protocol, we produce multifunctional nanostructured materials with effective control of the pore-solid architecture, the nanocrystalline phase, and subsequent magnetic properties.

Journal Article↗
PubMed2004

Silver-colloid-nucleated cytochrome c superstructures encapsulated in silica nanoarchitectures.

We recently discovered that self-organized superstructures of the heme protein cytochrome c (cyt. c) are nucleated in buffer by gold nanoparticles. The protein molecules within the superstructure survive both silica sol-gel encapsulation and drying from supercritical carbon dioxide to form air-filled biocomposite aerogels that exhibit gas-phase binding activity for nitric oxide. In this investigation, we report that viable proteins are present in biocomposite aerogels when the nucleating metal nanoparticle is silver rather than gold. Silver colloids were synthesized via reduction of an aqueous solution of Ag+ using either citrate or borohydride reductants. As determined by transmission electron microscopy and UV-visible absorption spectroscopy, the silver nanoparticles vary in size and shape depending on the synthetic route, which affects the fraction of cyt. c that survives the processing necessary to form a biocomposite aerogel. Silver colloids synthesized via the citrate preparation are polydisperse, with sizes ranging from 1 to 100 nm, and lead to low cyt. c viability in the dried bioaerogels (approximately 15%). Protein superstructures nucleated at approximately 10-nm Ag colloids prepared via the borohydride route, including citrate stabilization of the borohydride-reduced metal, retain significant protein viability within the bioaerogels (approximately 45%).

Chemical Phenomena↗
PubMed2002

Transmission electron microscopy studies of the nanoscale structure and chemistry of Pt50Ru50 electrocatalysts.

The structural and chemical heterogeneity of 2.5-nm Pt50Ru50 electrocatalysts was studied by transmission electron microscopy using selected area diffraction, lattice imaging, electron-energy loss spectroscopy, and energy-dispersive X-ray spectroscopy. The catalysts with the highest methanol oxidation activities exhibit oxidation-induced phase separation on the nanoscale to from Pt-rich metal embedded in Ru-rich hydrous and anhydrous oxide. Reduction of the oxide-on metal samples produces a true bimetallic face-centered cubic Pt50Ru50 alloy, with 275 times lower oxidation activity.

Alloys↗