Infrared study of methyl formate and formaldehyde adsorption on reduced and oxidised silica-supported copper catalysts

Infrared spectra are reported of methyl formate and formaldehyde adsorbed at 300 K on silica, Cu/SiO2 reduced in hydrogen and Cu/SiO2 which had been oxidised by exposure to nitrous oxide after reduction. Silanol groups on silica form hydrogen bonds with carbonyl groups in weakly adsorbed methyl formate molecules. Methyl formate ligates via its carbonyl groups to Cu atoms in the surface of reduced copper. A low residual concentration of surface oxygen on copper promoted the slow reaction of ligated methyl formate to give a bridging formate species on copper and adsorbed methoxy groups. Methyl formate did not ligate to an oxidised copper surface but was rapidly chemisorbed to give unidentate formate and methoxy species. Formaldehyde slowly polymerises on silica to form trioxane and other oxymethylene species. The reaction is faster over Cu/SiO2 which, in the reduced state, also catalyses the formation of bridging formate anions adsorbed on copper. The reaction between formaldehyde and oxidised Cu/SiO2 leads to both unidentate and bidentate formate and adsorbed water.

Infrared study of the adsorption of methanol on oxidised and reduced Cu/SiO2 catalysts

Infrared spectra are reported of methanol adsorbed at 295 K on reduced Cu/SiO2 and on Cu/SiO2 which had been preoxidised by exposure to excess nitrous oxide. Methanol was chemisorbed on reduced Cu/SiO2 to give methoxy species on both silica and copper, gave a trace of formate on copper via reaction with residual surface oxygen, and was weakly adsorbed at SiOH sites on the silica support. Heating the adsorbed species at 393 K led to the loss of methoxy groups on copper and the concomitant formation of a bidentate surface formate. Heating reduced Cu/SiO2 in methanol at 538 K initially gave both gaseous and adsorbed (on Cu) methyl formate which subsequently decomposed to CO and hydrogen. The reactions of methanol with oxidised Cu/SiO2 were similar to those for the reduced catalyst although surface oxygen promoted the formation of surface methoxy groups on copper. Subsequent heating at 393 K led first to unidentate formate before the appearance of bidentate formate.

In situ observation of structural changes in polycrystalline silver catalysts by environmental scanning electron microscopy

Morphology changes induced in polycrystalline silver catalysts as a result of heating in either oxygen, water or oxygen-methanol atmospheres have been investigated by environmental scanning electron microscopy (ESEM), FT-Raman spectroscopy and temperature programmed desorption (TPD). The silver catalyst of interest consisted of two distinct particle types, one of which contained a significant concentration of sub-surface hydroxy species (in addition to surface adsorbed atomic oxygen). Heating the sample to 663 K resulted in the production of 'pin-holes' in the silver structure as a consequence of near-surface explosions caused by sub-surface hydroxy recombination. Furthermore, 'pin-holes' were predominantly found in the vicinity of surface defects, such as platelets and edge structures. Reaction between methanol and oxygen also resulted in the formation of 'pin-holes' in the silver surface, which were inherently associated with the catalytic process. A reaction mechanism is suggested that involves the interaction of methanol with sub-surface oxygen species to form sub-surface hydroxy groups. The sub-surface hydroxy species subsequently erupt through the silver surface to again produce 'pin-holes'.

The molecular structure of kaolinite–potassium acetate intercalation complexes: A combined experimental and molecular dynamic simulation study

The kaolinite (Kaol) intercalated with potassium acetate (Ac) was prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry. Molecular dynamic simulation was performed to investigate the structure of Kaol–Ac intercalation complex and the hydrogen bonds between Kaol and intercalated Ac andwater using INTERFACE forcefield. The acetate anions andwater arranged in a bilayer structure in the interlayer space of Kaol. The potassium cations distributed in the interlayer space and strongly coordinated with acetate anions aswell aswater rather than keyed into the ditrigonal holes of tetrahedral surface of Kaol. Strong hydrogen bonds formed between the hydrogen atoms of hydroxyl on the octahedral surface and oxygen atoms of both acetate anions and water. The acetate anions andwater also weakly bonded hydrogen to the silica tetrahedral surface through their hydrogen atoms with the oxygen atoms of silica tetrahedral surface.

Evaluation of piezoelectric PVDF polymers for use in space environments. II. Effects of atomic oxygen and vacuum UV exposure

The effects of atomic oxygen (AO) and vacuum UV radiation simulating low Earth orbit conditions on two commercially available piezoelectric polymer films, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), have been studied. Surface erosion and pattern development are significant for both polymers. Erosion yields were determined as 2.8 � 10�24 cm3/atom for PVDF and 2.5 � 10�24 cm3/atom for P(VDF-TrFE). The piezoelectric properties of the residual material of both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly cross-linked network was formed in the copolymer presumably because of penetrating vacuum ultraviolet (VUV) radiation, while the homopolymer remained uncross-linked. These differences were attributed to varying degrees of crystallinity and potentially greater absorption, and hence damage, of VUV radiation in P(VDFTrFE) compared with PVDF.

In vitro cultivation of adult human chondrocytes : importance of culture system, oxygen and zonal differences

Articular cartilage exhibits limited intrinsic regenerative capacity and focal tissue defects can lead to the development of osteoarthritis (OA), a painful and debilitating loss of cartilage tissue. In Australia, 1.4 million people are affected by OA and its prevalence is increasing in line with current demographics. As treatment options are limited, new therapeutic approaches are being investigated including biological resurfacing of joints with tissue-engineered cartilage. Despite some progress in the field, major challenges remain to be addressed for large scale clinical success. For example, large numbers of chondrogenic cells are required for cartilage formation, but chondrocytes lose their chondrogenic phenotype (dedifferentiate) during in vitro propagation. Additionally, the zonal organization of articular cartilage is critical for normal cartilage function, but development of zonal structure has been largely neglected in cartilage repair strategies. Therefore, we hypothesised that culture conditions for freshly isolated human articular chondrocytes from non-OA and OA sources can be improved by employing microcarrier cultures and a reduced oxygen environment and that oxygen is a critical factor in the maintenance of the zonal chondrocyte phenotype. Microcarriers have successfully been used to cultivate bovine chondrocytes, and offer a potential alternative for clinical expansion of human chondrocytes. We hypothesised that improved yields can be achieved by propagating human chondrocytes on microcarriers. We found that cells on microcarriers acquired a flattened, polygonal morphology and initially proliferated faster than monolayercultivated cells. However, microcarrier cultivation over four weeks did not improve growth rates or the chondrogenic potential of non-OA and OA human articular chondrocytes over conventional monolayer cultivation. Based on these observations, we aimed to optimise culture conditions by modifying oxygen tension, to more closely reflect the in vivo environment. We found that propagation at 5% oxygen tension (moderate hypoxia) did not improve proliferation or redifferentiation capacity of human osteoarthritic chondrocytes. Moderate hypoxia increased the expression of chondrogenic markers during redifferentiation. However, osteoarthritic chondrocytes cultivated on microcarriers exhibited lower expression levels of chondrogenic surface marker proteins and had at best equivalent redifferentiation capacities compared to monolayer-cultured cells. This suggests that monolayer culture with multiple passaging potentially selects for a subpopulation of cells with higher differentiation capacity, which are otherwise rare in osteoarthritic, aged cartilage. However, fibroblastic proteins were found to be highly expressed in all cultures of human osteoarthritic chondrocytes indicating the presence of a high proportion of dedifferentiated, senescent cells with a chondrocytic phenotype that was not rescued by moderate hypoxia. The different zones of cartilage support chondrocyte subpopulations, which exhibit characteristic protein expression and experience varying oxygen tensions. We, therefore, hypothesised that oxygen tension affects the zonal marker expression of human articular chondrocytes isolated from the different cartilage layers. We found that zonal chondrocytes maintained these phenotypic differences during in vitro cultivation. Low oxygen environments favoured the expression of the zonal marker proteoglycan 4 in superficial cells, most likely through the promotion of chondrogenesis. The putative zonal markers clusterin and cartilage intermediate layer protein were found to be expressed by all subpopulations of human osteoarthritic chondrocytes ex vivo and, thus, may not be reliable predictors of in vitro stratification using these clinically relevant cells. The findings in this thesis underline the importance of considering low oxygen conditions and zonal stratification when creating native-like cartilaginous constructs. We have not yet found the right cues to successfully cultivate clinically-relevant human osteoarthritic chondrocytes in vitro. A more thorough understanding of chondrocyte biology and the processes of chondrogenesis are required to ensure the clinical success of cartilage tissue engineering.

Iron burning in pressurised oxygen under microgravity conditions

An investigation of cylindrical iron rods burning in pressurised oxygen under microgravity conditions is presented. It has been shown that, under similar experimental conditions, the melting rate of a burning, cylindrical iron rod is higher in microgravity than in normal gravity by a factor of 1.8 ± 0.3. This paper presents microanalysis of quenched samples obtained in a microgravity environment in a 2.0 s duration drop tower facility in Brisbane, Australia. These images indicate that the solid/liquid interface is highly convex in reduced gravity, compared to the planar geometry typically observed in normal gravity, which increases the contact area between liquid and solid phases by a factor of 1.7 ± 0.1. Thus, there is good agreement between the proportional increase in solid/liquid interface surface area and melting rate in microgravity. This indicates that the cause of the increased melting rates for cylindrical iron rods burning in microgravity is altered interfacial geometry at the solid/liquid interface.

Influencing factors on kaolinite-potassium acetate intercalation complexes

This paper presents an immersion method for preparing the kaolinite-potassium acetate intercalation complexes. The effectiveness of intercalation and influencing factors were analysed and evaluated. The results show that the intercalation of kaolinite by potassium acetate is strongly related to crystallinity of kaolinite, concentration of intercalating agent solution, aging time and pH. The well-crystallized kaolinite is conducive to intercalation by potassium acetate. A higher concentration of intercalating agent (≥30%) can complete the intercalation in a short time (<12h), but at lower concentrations intercalation took significantly longer (≥144h). The weak alkaline condition of pH=10 proved to be the most suitable environment for the formation of intercalation complex. A good intercalated complex can be obtained at room temperature.

Application of hyperbaric oxygen in bone tissue engineering : effect of hyperbaric oxygen treatment on bone marrow stem cells

and non-union of bony fractures has been proposed since 1966, little has been known about the effect of HBOT on bone marrow stem cells (BMSC). The aim of this study is to investigate the effect of HBO treatment on osteogenetic differentiation of BMSC and potential application in bone tissue engineering. Adhesive stromal cells harvested from bone marrow were characterized by mesenchymal differentiation potential, cell surface markers and their proliferation capacity. Mesenchymal stem cells, which demonstrated osteogenic, chondrogenic and adipogenic differentiation potential and expressed positively for CD 29, CD 44, CD 73, CD 90, CD 105, CD 166 and negatively for CD34 and CD 45, were selected and treated in a laboratory-scale HBO chamber using different oxygen pressures and exposure times. No obvious effect of HBO treatment on BMSC proliferation was noticed. However, cytotoxic effects of HBO were considerably less pronounced when cells were cultured in medium supplemented with 10% FBS in comparison to medium supplemented with 2% FCS, as was evaluated by WST-1 assay. Under HBO treatment, bone nodules were formed in three days, which was clearly revealed by Von Kossa staining. In contrasts, without HBO treatment, bone nodules were not detected until 9-12 days using the same inducing culture media. Calcium deposition was also significantly increased after three days of HBO treatments compared to no HBO treatment. In addition it was also found that oxygen played a direct role in the enhancement of BMSC osteogenic differentiation, which was independent of the effect of air pressure.

Oxygen transport in soil and the vertical distribution of roots

An analytical solution for steady-state oxygen transport in soils including 2 sink terms, viz roots and microbes with the corresponding vertical distribution scaling lengths forming a ratio p, showed p governed the critical air-filled porosity, θ_c, needed by most plants. For low temperature and p, θ_c was <0.1 but at higher temperatures and p = 1, θ_c was >0.15 m³/m³. When root length density at the surface was 10⁴ m/m³ and p > 3, θ_c was 0.25 m³/m³, more than half the pore space. Few combinations of soil and climate regularly meet this condition. However, for sandy soils and seasonally warm, arid regions, the theory is consistent with observation, in that plants may have some deep roots. Critical θ_c values are used to formulate theoretical solutions in a forward mode, so different levels of oxygen uptake by roots may be compared to microbial activity. The proportion of respiration by plant roots increases rapidly with p up to p ≈2.

Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]

Hyaluronic acid : evaluation as a potential delivery vehicle for vitronectin:growth factor complexes in wound healing applications

We have previously reported that novel vitronectin:growth factor (VN:GF) complexes significantly increase re-epithelialization in a porcine deep dermal partial-thickness burn model. However, the potential exists to further enhance the healing response through combination with an appropriate delivery vehicle which facilitates sustained local release and reduced doses of VN:GF complexes. Hyaluronic acid (HA), an abundant constituent of the interstitium, is known to function as a reservoir for growth factors and other bioactive species. The physicochemical properties of HA confer it with an ability to sustain elevated pericellular concentrations of these species. This has been proposed to arise via HA prolonging interactions of the bioactive species with cell surface receptors and/or protecting them from degradation. In view of this, the potential of HA to facilitate the topical delivery of VN:GF complexes was evaluated. Two-dimensional (2D) monolayer cell cultures and 3D de-epidermised dermis (DED) human skin equivalent (HSE) models were used to test skin cell responses to HA and VN:GF complexes. Our 2D studies revealed that VN:GF complexes and HA stimulate the proliferation of human fibroblasts but not keratinocytes. Experiments in our 3D DED-HSE models showed that VN:GF complexes, both alone and in conjunction with HA, led to enhanced development of both the proliferative and differentiating layers in the DED-HSE models. However, there was no significant difference between the thicknesses of the epidermis treated with VN:GF complexes alone and VN:GF complexes together with HA. While the addition of HA did not enhance all the cellular responses to VN:GF complexes examined, it was not inhibitory, and may confer other advantages related to enhanced absorption and transport that could be beneficial in delivery of the VN:GF complexes to wounds.

Effect of geometry on the melting rates of iron rods burning in high pressure oxygen

The effect of sample geometry on the melting rates of burning iron rods was assessed. Promoted-ignition tests were conducted with rods having cylindrical, rectangular, and triangular cross-sectional shapes over a range of cross-sectional areas. The regression rate of the melting interface (RRMI) was assessed using a statistical approach which enabled the quantification of confidence levels for the observed differences in RRMI. Statistically significant differences in RRMI were observed for rods with the same cross-sectional area but different cross-sectional shape. The magnitude of the proportional difference in RRMI increased with the cross-sectional area. Triangular rods had the highest RRMI, followed by rectangular rods, and then cylindrical rods. The dependence of RRMI on rod shape is shown to relate to the action of molten metal at corners. The corners of the rectangular and triangular rods melted faster than the faces due to their locally higher surface area to volume ratios. This phenomenon altered the attachment geometry between liquid and solid phases, increasing the surface area available for heat transfer, causing faster melting. Findings relating to the application of standard flammability test results in industrial situations are also presented.

Ocular surface changes with short-term contact lens wear

Contact lenses are a common method for the correction of refractive errors of the eye. While there have been significant advancements in contact lens designs and materials over the past few decades, the lenses still represent a foreign object in the ocular environment and may lead to physiological as well as mechanical effects on the eye. When contact lenses are placed in the eye, the ocular anatomical structures behind and in front of the lenses are directly affected. This thesis presents a series of experiments that investigate the mechanical and physiological effects of the short-term use of contact lenses on anterior and posterior corneal topography, corneal thickness, the eyelids, tarsal conjunctiva and tear film surface quality. The experimental paradigm used in these studies was a repeated measures, cross-over study design where subjects wore various types of contact lenses on different days and the lenses were varied in one or more key parameters (e.g. material or design). Both, old and newer lens materials were investigated, soft and rigid lenses were used, high and low oxygen permeability materials were tested, toric and spherical lens designs were examined, high and low powers and small and large diameter lenses were used in the studies. To establish the natural variability in the ocular measurements used in the studies, each experiment also contained at least one “baseline” day where an identical measurement protocol was followed, with no contact lenses worn. In this way, changes associated with contact lens wear were considered in relation to those changes that occurred naturally during the 8 hour period of the experiment. In the first study, the regional distribution and magnitude of change in corneal thickness and topography was investigated in the anterior and posterior cornea after short-term use of soft contact lenses in 12 young adults using the Pentacam. Four different types of contact lenses (Silicone hydrogel/ Spherical/–3D, Silicone Hydrogel/Spherical/–7D, Silicone Hydrogel/Toric/–3D and HEMA/Toric/–3D) of different materials, designs and powers were worn for 8 hours each, on 4 different days. The natural diurnal changes in corneal thickness and curvature were measured on two separate days before any contact lens wear. Significant diurnal changes in corneal thickness and curvature within the duration of the study were observed and these were taken into consideration for calculating the contact lens induced corneal changes. Corneal thickness changed significantly with lens wear and the greatest corneal swelling was seen with the hydrogel (HEMA) toric lens with a noticeable regional swelling of the cornea beneath the stabilization zones, the thickest regions of the lenses. The anterior corneal surface generally showed a slight flattening with lens wear. All contact lenses resulted in central posterior corneal steepening, which correlated with the relative degree of corneal swelling. The corneal swelling induced by the silicone hydrogel contact lenses was typically less than the natural diurnal thinning of the cornea over this same period (i.e. net thinning). This highlights why it is important to consider the natural diurnal variations in corneal thickness observed from morning to afternoon to accurately interpret contact lens induced corneal swelling. In the second experiment, the relative influence of lenses of different rigidity (polymethyl methacrylate – PMMA, rigid gas permeable – RGP and silicone hydrogel – SiHy) and diameters (9.5, 10.5 and 14.0) on corneal thickness, topography, refractive power and wavefront error were investigated. Four different types of contact lenses (PMMA/9.5, RGP/9.5, RGP/10.5, SiHy/14.0), were worn by 14 young healthy adults for a period of 8 hours on 4 different days. There was a clear association between fluorescein fitting pattern characteristics (i.e. regions of minimum clearance in the fluorescein pattern) and the resulting corneal shape changes. PMMA lenses resulted in significant corneal swelling (more in the centre than periphery) along with anterior corneal steepening and posterior flattening. RGP lenses, on the other hand, caused less corneal swelling (more in the periphery than centre) along with opposite effects on corneal curvature, anterior corneal flattening and posterior steepening. RGP lenses also resulted in a clinically and statistically significant decrease in corneal refractive power (ranging from 0.99 to 0.01 D), large enough to affect vision and require adjustment in the lens power. Wavefront analysis also showed a significant increase in higher order aberrations after PMMA lens wear, which may partly explain previous reports of "spectacle blur" following PMMA lens wear. We further explored corneal curvature, thickness and refractive changes with back surface toric and spherical RGP lenses in a group of 6 subjects with toric corneas. The lenses were worn for 8 hours and measurements were taken before and after lens wear, as in previous experiments. Both lens types caused anterior corneal flattening and a decrease in corneal refractive power but the changes were greater with the spherical lens. The spherical lens also caused a significant decrease in WTR astigmatism (WRT astigmatism defined as major axis within 30 degrees of horizontal). Both the lenses caused slight posterior corneal steepening and corneal swelling, with a greater effect in the periphery compared to the central cornea. Eyelid position, lid-wiper and tarsal conjunctival staining were also measured in Experiment 2 after short-term use of the rigid and SiHy contact lenses. Digital photos of the external eyes were captured for lid position analysis. The lid-wiper region of the marginal conjunctiva was stained using fluorescein and lissamine green dyes and digital photos were graded by an independent masked observer. A grading scale was developed in order to describe the tarsal conjunctival staining. A significant decrease in the palpebral aperture height (blepharoptosis) was found after wearing of PMMA/9.5 and RGP/10.5 lenses. All three rigid contact lenses caused a significant increase in lid-wiper and tarsal staining after 8 hours of lens wear. There was also a significant diurnal increase in tarsal staining, even without contact lens wear. These findings highlight the need for better contact lens edge design to minimise the interactions between the lid and contact lens edge during blinking and more lubricious contact lens surfaces to reduce ocular surface micro-trauma due to friction and for. Tear film surface quality (TFSQ) was measured using a high-speed videokeratoscopy technique in Experiment 2. TFSQ was worse with all the lenses compared to baseline (PMMA/9.5, RGP/9.5, RGP/10.5, and SiHy/14) in the afternoon (after 8 hours) during normal and suppressed blinking conditions. The reduction in TFSQ was similar with all the contact lenses used, irrespective of their material and diameter. An unusual pattern of change in TFSQ in suppressed blinking conditions was also found. The TFSQ with contact lens was found to decrease until a certain time after which it improved to a value even better than the bare eye. This is likely to be due to the tear film drying completely over the surface of the contact lenses. The findings of this study also show that there is still a scope for improvement in contact lens materials in terms of better wettability and hydrophilicity in order to improve TFSQ and patient comfort. These experiments showed that a variety of changes can occur in the anterior eye as a result of the short-term use of a range of commonly used contact lens types. The greatest corneal changes occurred with lenses manufactured from older HEMA and PMMA lens materials, whereas modern SiHy and rigid gas permeable materials caused more subtle changes in corneal shape and thickness. All lenses caused signs of micro-trauma to the eyelid wiper and palpebral conjunctiva, although rigid lenses appeared to cause more significant changes. Tear film surface quality was also significantly reduced with all types of contact lenses. These short-term changes in the anterior eye are potential markers for further long term changes and the relative differences between lens types that we have identified provide an indication of areas of contact lens design and manufacture that warrant further development.