Arunan Nadarajah

Elastic properties and morphology of individual carbon nanofibers.

The structural complexity of vapor-grown carbon nanofibers means that they require a method that determines both their elastic properties and their corresponding morphology. A three-point bending test method was developed combining atomic force microscopy, transmission electron microscopy (TEM) and focused ion beam techniques to suspend individual nanofibers and measure their deflection coupled with accurate determinations of inner and outer diameters and morphology using high resolution TEM. This resulted in much improved accuracy and reproducibility of the measured values of the elastic modulus which ranged from 6 to 207 GPa. The data showed two distinct trends, with higher values of the modulus when the outer wall thickness of the nanofibers is larger than that of the inner wall, with the values decreasing with the overall wall thickness. These results suggest that the more ordered layers of the outer wall, closest to the inner wall, are mostly responsible for the nanofiber strength. For large nanofiber wall thicknesses of greater than 80 nm, the elastic modulus becomes independent of the thickness with a value of approximately 25 GPa. The results also demonstrate that this technique can be a standardized one for the detailed study of mechanical properties of nanofibers and their relationship to morphology.

LOCATIONS OF BROMIDE IONS IN TETRAGONAL LYSOZYME CRYSTALS

Anions have been shown to play a dominant role in the crystallization of chicken egg-white lysozyme from salt solutions. Previous studies employing X-ray crystallography have found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystals grown in bromide and chloride solutions. Five possible anion-binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four further sites were found which corresponded to the four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion-binding sites in lysozyme remain unchanged even when different anions and different crystal forms of lysozyme are employed.

Growth Mechanism of the (110) Face of Tetragonal Lysozyme Crystals

The measured macroscopic growth rates of the (110) face of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. In earlier studies it has been shown that an aggregate growth unit could account for experimental growth-rate trends. In particular molecular packing and interactions in the growth of the crystal were favored by completion of the helices along the 4(3) axes. In this study the molecular orientations of the possible growth units and the molecular growth mechanism were identified. This indicated that growth was a two-step process: aggregate growth units corresponding to the 4(3) helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds. A more comprehensive analysis of the measured (110) growth rates was also undertaken. They were compared with the predicted growth rates from several dislocation and two-dimensional nucleation growth models, employing tetramer and octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. The calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units, in agreement with the predictions from the molecular level analyses.

Growth of (101) faces of tetragonal lysozyme crystals: measured growth-rate trends.

Previous extensive measurements of the growth rates of the (110) face of tetragonal lysozyme crystals have shown unexpected dependencies on the supersaturation. In this study, similar growth-rate measurements were performed for the (101) faces of the crystals. The data show a similar dependence on the supersaturation, becoming appreciable only at high supersaturations, reaching a maximum value and then decreasing. The (101) growth rates are larger at low supersaturations than the (110) growth rates under the same conditions and are smaller at high supersaturations. These trends suggest that the growth mechanism of the (101) face is similar to that of the (110) face: both processes involve the addition of multimeric growth units formed in solution, but the average size of the units for the (101) face is likely to be smaller than for the (110) face.

Determining the molecular-growth mechanisms of protein crystal faces by atomic force microscopy

A high-resolution atomic force microscopy (AFM) study has shown that the molecular packing on the tetragonal lysozyme (110) face corresponds to only one of two possible packing arrangements, suggesting that growth layers on this face are of bimolecular height [Li et al. (1999). Acta Cryst. D55, 1023-1035]. Theoretical analyses of the packing also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size, corresponding to the 43 helices in the crystal. In this study, an AFM linescan technique was used to measure the dimensions of individual growth units on protein crystal faces as they were being incorporated into the lattice. Images of individual growth events on the (110) face of tetragonal lysozyme crystals were observed, shown by jump discontinuities in the growth step in the linescan images. The growth-unit dimension in the scanned direction was obtained from these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme growth-unit sizes were obtained. A variety of unit sizes corresponding to 43 helices were shown to participate in the growth process, with the 43 tetramer being the minimum observed size. This technique represents a new application for AFM, allowing time-resolved studies of molecular processes to be carried out.

Polyacrylamide Hydrogel Properties for Horticultural Applications

Polyacrylamide (PAAm) hydrogels are commonly employed to ensure soil hydration in horticulture, but studies have shown that they have a minimal effect on crop life and quality. The reasons for this poor performance are not understood since the commercial hydrogels have not been adequately characterized. PAAm hydrogels were synthesized and their properties were measured along with those of commercial hydrogels. Hydrogel swelling, density, and SEM analyses showed that the commercial hydrogels were most likely a derivative of PAAm with ionic groups and they were able to retain moisture for only a few hours.

Determining the molecular-packing arrangements on protein crystal faces by atomic force microscopy

Previous atomic force microscopy (AFM) studies and periodic bond-chain (PBC) analyses of tetragonal lysozyme crystals have suggested that the (110) face consists of chains of molecules related to one another by 43 axes parallel to the crystal face. In this study, high-resolution AFM images of the (110) face were obtained and analyzed in order to verify this prediction. A computer program was employed which constructs the theoretical AFM image corresponding to a specific crystallographic molecular-packing arrangement and AFM tip shape. The packing arrangement and tip shape were varied in order to obtain the maximum possible correlation between experimental and theoretical images. The prediction from PBC analysis of an arrangement involving 43 helices was confirmed in this manner, while the alternate arrangement, consisting of molecules related to one another by 21 axes, was not observed. However, the surface structure was found to differ significantly even from this crystallographic arrangement. The molecules were found to pack slightly closer about what will become the 43 axes within the interior of the crystal, suggesting the occurrence of surface reconstruction or rearrangement on the tetragonal lysozyme (110) face. This study represents a new approach for more precise determination of the molecular-packing arrangements on protein crystal faces employing AFM.

Growth of (101) faces of tetragonal lysozyme crystals: determination of the growth mechanism

Measurements of the macroscopic growth rates of the (101) face of tetragonal lysozyme crystals indicate an unusual dependence on the supersaturation [Forsythe et al. (1999), Acta Cryst. D55, 1005-1011] similar to that observed for the (110) face. As performed previously for the (110) face, the surface packing arrangement for the (101) face was constructed in this study based on earlier microscopic observations and theoretical analysis of the internal molecular packing. This allowed the minimum growth unit for this face to be identified as a tetramer corresponding to a single turn of helices centered about the 43 axes and the minimum growth step to be identified as of unimolecular height. A macroscopic mathematical model for the growth of the (101) face was developed based on the reversible formation of multimeric growth units in solution and the addition of a unit to the crystal face by dislocation and two-dimensional nucleation mechanisms. The calculations showed that the best fits were obtained for tetramer or octamer growth units in this model. This and other evidence suggests that while growth may proceed by a variety of growth units, the average size of these units is between that of a tetramer and an octamer.

Development and Commercialization of Vapor Grown Carbon Nanofibers: A Review

The lack of a low cost, high volume method to produce carbon nanotubes has greatly limited their commercialization. Carbon nanofibers have a similar structure and properties as nanotubes and are a commercially viable alternative to them. In recent years many of the difficulties of commercial nanofiber production have been overcome through innovations in their manufacturing process. It is now possible to produce carbon nanofibers of different grades, such as thinner and thicker walled ones, and low heat treated and high heat treated ones. Most significantly, commercial quantities can now be produced of carbon nanofibers that have been surface functionalized with carboxylic acid groups, making them suitable for further functionalization and new classes of applications, such as biomedical sensors and drug delivery. Despite their cost advantages and availability more widespread use of carbon nanofibers has been hampered by uncertainties in their molecular structure and a lack of physical property measurements. However, recent theoretical and experimental studies have addressed these deficiencies showing that these fibers have a cone-helix structure under the usual manufacturing conditions. Additionally, small amounts of a segmented carbon nanotube structure, commonly called a bamboo structure, are also present. When the conical nanofibers were heat treated they were found to transform to a stacked cone structure. Advances in surface functionalization have allowed a variety of groups to be incorporated on them, significantly enhancing their properties and potential applications. Finally, the recent development of a new method to measure the elastic properties and morphology of single nanofibers has clearly demonstrated the high strength of these fibers. These nanofibers now represent a well understood and well characterized graphitic carbon nanomaterial that can be manufactured at low cost in large quantities, and have the potential to bring widespread use of nanotechnology to a variety of fields.

Perovskite ceramics and recent experimental progress in reactor design for chemical looping combustion application

Chemical looping combustion (CLC) is a novel method of carbon capture and sequestration. It facilitates CO2 capture by lower energy penalties compared with other methods in this category. The major challenges encountered in CLC are oxygen carrier, reactor and fuel-type selection. A proper combination of these factors is required for an efficient CLC. There have been several studies with regard to oxygen carriers applicable to these processes: novel oxygen carriers, single perovskites and potential oxygen carriers, double perovskites, have been investigated for their oxygen capture and release properties in a number of studies. Different kinds of reactors have also been proposed for use in CLC processes. This paper presents information on the materials capable of oxygen storage and release and the different kinds of reactors investigated for CLC in different studies. It has been shown that, although there are several oxygen carriers and reactors with the desired function and efficiency for CLC, there remains the need for further improvement and optimisation in both areas.