Digital in-line soft x-ray holography with element contrast

Digital in-line soft x-ray holography (DIXH) was used to image immobilized polystyrene and iron oxide particles and to distinguish them based on their different x-ray absorption cross sections in the vicinity of the carbon K-absorption edge. The element-specific information from the resonant DIXH images was correlated with high-resolution scanning electron microscopy (SEM) pictures. We also present DIXH images of a cell nucleus and compare the contrast obtained for nuclear components with the appearance in optical microscopy.     

Electron holography for the study of magnetic nanomaterials

Transmission electron microscopes fitted with field-emission guns (to provide coherent electron waves) can be adapted to record the magnetic fields within and surrounding nanoparticles or metal clusters, for example, the lines of force of a nanoferromagnet encapsulated within a multiwalled carbon nanotube. Whereas most chemists are aware that electron microscopy readily identifies crystallographic symmetries and phases, solves structures, and, in conjunction with electron energy-loss spectroscopy, yields valence states and electronic information of materials, relatively few know that it can also provide important quantitative information, with nanometer-scale spatial resolution, pertaining to such materials' magnetic properties. In this Account, with the aid of representative examples embracing solid-state chemistry, geochemistry, and bio-inorganic phenomena, we illustrate how off-axis electron holography affords deep insight into magnetic phenomena on the nanoscale. Specifically, we describe the unprecedented level of information available regarding the magnetic nature of magnetotactic bacteria, magnetic nanoparticle chains and chiral bracelets, and geochemically relevant phenomena involving exsolution (the un-mixing of two mineral phases, as in the magnetite-ulv?spinel system). It is, for example, possible to reveal vortices and multidomain states that have no net magnetization in minute blocks of magnetite. With the current burgeoning interest and activity in nanoscience and nanotechnology, our Account concludes with examples of some existing enigmas that electron holography, especially when augmented by the related technique of electron tomography, might play an important experimental role in resolving, such as the occurrence of ferromagnetism in nanocrystals of silver within carbon tubes and in clusters of alkali metals incarcerated within zeolites.     

Control of catalyst particle crystallographic orientation in vertically aligned carbon nanofiber synthesis

Vertically aligned carbon nanofibers (VACNF) have been synthesized where the crystallographic orientation of the initial catalyst film was preserved in the nanoparticle that remained at the nanofiber tip after growth. A substantial percentage of catalyst particles (75%), amounting to approximately 200 million nanofibers over a 100 mm Si wafer substrate, exhibited a sixfold symmetry attributed to a cubic Ni(1 1 1)∥Si(0 0 1) orientation relationship which was verified by X-ray diffraction studies. The Ni catalyst films were prepared by rf-magnetron sputtering under substrate bias conditions to yield a single (1 1 1) film texture. The total energy of the Ni thin film was estimated by calculating the sum of the surface free energy and strain energy. The total film energy was minimized by the evolution of the plane of lowest surface free energy, the (1 1 1) texture. This result was in agreement with X-ray diffraction measurements. The preferred orientation present in the Ni catalyst film prior to nanofiber growth was preserved in the Ni catalyst particles throughout the VACNF growth process. The Ni catalyst particles at the nanofiber tips were not pure single crystals but rather consisted of a mosaic structure of Ni nanocrystallites embedded within Ni catalyst nanoparticles (200-400 nm). The tip-located nanoparticles exhibited a faceted, crystal morphology with the faceting transferred to the underlying carbon nanofiber during the growth process. The possibility of precisely and accurately controlling VACNF growth velocity over macroscopic wafer dimensions with uniformly aligned catalyst particles is discussed.     

Preparing Reagents: Time Dependence of HCl(v =1, J) Alignment Following Pulsed Infrared Excitation

We discuss the use of photon absorption as a means of aligning reagents for studies of dynamical stereochemistry. A linearly polarized infrared beam from an optical parametric oscillator prepares HCl(v = 1, J = 1), and the alignment is monitored at subsequent times by (2+1) resonance-enhanced multiphoton ionization. The degree of alignment oscillates in time caused by hyperfine quantum beats. Experimental observations are well matched by calculations that account for the presence of unresolved hyperfine structure. Following reagent preparation by optical pumping, a cumulative hyperfine-depolarization coefficient can be used to describe the effective reagent alignment in a subsequent chemical reaction.     

Enhancing phosphorus removal in constructed wetlands with ochre from mine drainage treatment.

No single end-use has yet been identified that is capable of consuming the projected production of ochre (mainly iron (III) oxides) from mine drainage treatment. However, the high sorption capacity of ochre for phosphorus (up to 26 mg kg(-1)) means that it could be used in constructed wetlands to enhance phosphorus removal. Laboratory batch experiments showed that coarse-grained ochre removes 90% of all phosphorus forms from sewage effluent after 15 minutes of shaking. From a larger-scale experiment, it is estimated that constructed wetlands with an ochre substrate should remove phosphorus from sewage effluent for up to 200-300 years. The suitability of ochre for phosphorus removal is being investigated at the field scale in a wastewater constructed wetland (175 m2 area) in Berwickshire, UK. The hydraulic and treatment performance of the wetland were monitored for 15 months prior to installation at the inlet in November 2003 of a tank containing approximately 1200 kg ochre. Results so far show that improved hydraulic design is required for ochre to increase the mean phosphorus removal efficiency of the system (27 +/- 28%), but potentially toxic metals (Al, Cd, Cr, Cu, Fe, Ni, Pb, Zn) have not been released from the ochre into the wetland outflow.     

The NavChair Assistive Wheelchair Navigation System.

The NavChair Assistive Wheelchair Navigation System [19] is being developed to reduce the cognitive and physical requirements of operating a power wheelchair for people with wide ranging impairments that limit their access to powered mobility. The NavChair is based on a commercial wheelchair system with the addition of a DOS-based computer system, ultrasonic sensors, and an interface module interposed between the joystick and power module of the wheelchair. The obstacle avoidance routines used by the NavChair in conjunction with the ultrasonic sensors are modifications of methods originally used in mobile robotics research. The NavChair currently employs three operating modes: general obstacle avoidance, door passage, and automatic wall following. Results from performance testing of these three operating modes demonstrate their functionality. In additional to advancing the technology of smart wheelchairs, the NavChair has application to the development and testing of "shared control" systems where a human and machine share control of a system and the machine can automatically adapt to human behaviors.     

Considerations for capping metal-contaminated sediments in dynamic estuarine environments

The effects of tides, bioturbating organisms, and periods of anoxia on metal fluxes from contaminated harbor sediments in a shallow tidal estuarine bay were studied, together with capping technology options for the containment of metal contaminants. Zinc fluxes from the sediments were high, ranging from 10 to 89 mg of Zn m(-2) day(-1). In the absence of capping, experiments in corer-reactors showed that simulated tidal processes increased zinc fluxes 5-fold. Fluxes were also greater in the presence of sediment-dwelling organisms. If organisms were removed, and recolonizing organisms later added, their bioturbation activities initially lowered zinc fluxes, but fluxes gradually reached steady state at the higher levels seen previously. Capping materials physically isolate contaminated sediments, provide a binding substrate for metals released from the sediment and importantly create an anoxic environment below the cap, which stimulates the formation of insoluble metal sulfides. Clean sediment (5 mm) was the most effective capping material in reducing zinc fluxes. Zeolite/sand mixtures (10 mm) also greatly reduced these fluxes, but significant breakthrough of zinc occurred after 2 weeks. Sand (20 mm) was not effective. The presence of organisms disturbed capping materials and increased zinc fluxes. Installed capping materials should have depths of >30 cm to minimize organisms burrowing to contaminated sediments beneath.