Deviations from normal foot structure are thought to result in hyper or hypo mobility preventing the foot from providing sufficient stability or mobility at appropriate times during the stance phase of gait. Such deviations in foot structure are often suggested as a risk factor for the development of common foot and ankle injuries. Though foot structure is believed to influence function its effect on foot motion and mechanisms thought to allow stability during the end of stance phase remain poorly understood. The purpose of this study was to determine the extent to which arch height affects foot kinematics during gait using a four segment foot model. Subjects included 17 healthy individuals with a wide range of arch heights and no past history of foot pathology. A three-dimensional motion tracking system was used to determine kinematics of the hallux, first metatarsal, forefoot, calcaneus and tibia during gait while subjects ambulated at a predetermined walking velocity of 0.78 statures/s. AP and lateral radiographs were used to determine coordinate system orientation for the first metatarsal, forefoot and calcaneus. The sagittal plane angle between the first metatarsal and calcaneus was used to represent foot structure. No association was observed between foot structure, as represented by arch height, and foot kinematics as represented by excursion or coupling during the stance phase of gait. This surprising result provides no evidence to support the assertion that foot structure influences mobility during gait in individuals without foot pathology. The kinematic patterns observed were highly consistent between individuals and provide new insight into the mechanisms underlying the formation of a rigid lever for pushoff at the end of stance phase. Supination, consisting of forefoot and first metatarsal adduction and plantarflexion along with hindfoot inversion, was found to occur at approximately 76 percent stance. Kinematic coupling associated with activation of the windlass mechanism is consistent with the concept of supination and occurs shortly after forward rotation of the first metatarsal and hallux dorsiflexion. In conclusion, deviation from normal foot structure appears to have little or no influence on foot mobility or intersegmental coupling due to activation of the windlass mechanism.

Suspension-feeding bivalves produce biodeposits (faeces and pseudofaeces) that have much higher sinking velocities than their constituent particles. Consequently they cause sedimentation of material that might otherwise not be deposited. The benthic remineralisation of biodeposits increases sediment oxygen demand and nutrient regeneration, thus enhancing the benthic-pelagic coupling of nearshore ecosystems. In New Zealand the mussel Perna canaliculus has a high natural abundance and is also intensively cultured. This thesis examines the dispersal and remineralisation characteristics of mussel P. canaliculus biodeposits and the impacts of sedimentation from a mussel farm in the Firth of Thames on sediment biogeochemistry by combining laboratory, field and modelling studies. Dispersal characteristics were examined in the laboratory by measuring sinking velocities and erosion thresholds of biodeposits produced by mussels of a wide size range fed three experimental diets. The results show that biodeposit dispersal is a function of mussel diet and size and thus could differ significantly between locations and seasons. Estimates of dispersal distances based on these results demonstrated that the initial dispersal of biodeposits produced by cultured mussels is not far. Depending on the hydrodynamic conditions, secondary dispersal via resuspension potentially plays a more important role in the dispersal of biodeposits from mussel farms than initial dispersal and almost certainly serves as the major means of transport of biodeposits from natural mussel beds. Biodeposit mineralisation was studied by incubating coastal sediments with added biodeposits and measuring oxygen and nutrient fluxes as well as sediment characteristics over an 11 d period. Sediment oxygen consumption and ammonium release increased immediately after biodeposit addition and remained elevated compared to control cores without additions for the incubation period. A biodeposit decay rate (0.16 d-1) was calculated by fitting a first-order G model to the observed increase in oxygen consumption. This rate is 1 - 2 orders of magnitude higher than published decay rates of coastal sediments without organic enrichment or plant material. Nutrient fluxes during the incubation period illustrated that biodeposit remineralisation alters the stoichiometry of the nutrients released from the sediments which may potentially be more significant than the changes of the individual fluxes. To determine the impact of a mussel farm in the Firth of Thames I measured sediment oxygen and nutrient fluxes by deploying benthic chambers, sediment characteristics by collecting sediment cores and sedimentation rates by deploying sediment traps in four seasons. Oxygen consumption and sediment nutrient release rates were generally higher under the farm compared to a reference site, demonstrating the typical response to increased organic input. Unusually low nitrogen release rates measured in summer may indicate enhanced denitrification under the farm. A simple budget demonstrated the importance of benthic nutrient regeneration in maintaining primary production in this region and that mussel culture can lead to a redistribution of nutrients. This study showed that site-specific hydrodynamic and biogeochemical conditions have to be taken into account when planning new mussel farms to prevent excessive modifications of nutrient dynamics. Results of the laboratory and field studies conducted in this thesis were used to parameterise, calibrate and validate models of mussel biodeposit dispersal and remineralisation. A particle tracking model showed that the maximum initial dispersal of faecal pellets from the mussel farm is approximately 300 m and that pellets can be transported several times this distance via resuspension. The remineralisation model was able to simulate the increased nitrogen fluxes from the sediments well and highlighted the need for thorough calibration and parameterisation of the model. This thesis contributed to the current understanding of the ecosystem impacts of mussel culture and provided numerical models and model parameters that will assist in the assessment of mussel culture sustainability and the contribution of mussels to the nutrient cycling in nearshore ecosystems.

This study deals with medium density wood fibre (MDF) and Kraft fibre reinforced polypropylene (PP) composites produced using extrusion followed by injection moulding. Initially, composites were produced with MDF fibre using 10, 20, 30, 40, 50 and 60 wt% fibre, and 1, 2, 3 and 4 wt% maleated polypropylene (MAPP) as a coupling agent. A fibre content of 50 wt% with 3 wt% MAPP was found to be optimum. Alkali treatment of fibre was carried out to improve the interfacial bonding. After treatment, fibre surface charge was found to increase, but single fibre tensile strength (TS) and Young's modulus were (YM) decreased. Alkali treatment reduced composite TS but increased YM. The effects of hemicellulose and residual lignin content were assessed with Kraft fibre (subjected to different stages of a standard Kraft pulping process and therefore consisting of different hemicellulose and residual lignin contents). Fibre surface charge was found to increase with decreasing residual lignin content. Composites containing higher amounts of lignin lead to lower TS and lower thermal stability. Composites were subjected to accelerated weathering for 1000 hours. TS and YM were found to decrease during weathering, and the extent of reduction was found to be higher for composites with higher residual lignin. The reduction of mechanical properties was found to be due to degradation of lignin and PP chain scission as evaluated by increase in PP crystallinity after weathering. As low lignin (bleached) Kraft fibre composites were found to provide superior mechanical properties, as well as more stable during accelerated weathering, further study including optimisation of MAPP content, effects of fibre contents, fibre length, fibre beating, hygrothermal ageing and recycling were carried out with bleached Kraft fibre. MAPP contents of 1, 2, 3, 4, 5, 7 and 10 wt% were used in Kraft fibre reinforced PP composites, and 3-5 wt% was found to be most favourable. Composite fibre content was varied between 30-50 wt%, and 40 wt% found to provide the maximum TS. To investigate the effects of fibre length on composites, fibre fractions of different length distribution were separated using a pressure screen. TS, YM and impact strength were found to decrease and failure strain (FS) increased with decreasing fibre length. To improve the interfacial bonding, the fibre was treated by mechanical beater. Fibre beating increased the TS of composites up to a certain point, beyond which TS decreased. Hygothermal ageing of composites was carried out by immersing specimens in distilled water at 30, 50 and 70 C over an 8-month period. Equilibrium moisture content and diffusion coefficient increased with increased fibre content in composites as well as with increased immersion temperature. Composites without coupling agent showed higher water uptake and diffusion coefficient than that of with coupling agent. After hygrothermal ageing the TS and YM decreased but FS and impact strength were found to increase. An investigation into the effects of recycling was carried out with composites containing either 40 wt% or 50 wt% fibre (bleached Kraft) with 4 wt% MAPP, and recycled up to eight times. For composites with 40 wt% fibre, TS and YM were found to decrease with increased recycling by up to 25% for TS and 17% for YM (after being recycled 8 times). Although TS was lower for virgin composites with 50 wt% fibre than for those with 40 wt% fibre, this initially increased with recycling by up to 14% (after being recycled 2 times), which was considered to be due to improved fibre dispersion, but then decreased with further recycling, and an overall 11% reduction of TS was found after recycling 8 times compared to the virgin composites. YM was higher for virgin composites with 50 wt% fibre than those with for 40 wt% fibre, and also initially increased with recycling but decreased upon further recycling. Recycling was found to increase thermal stability. The TS of composites made by combining recycled with virgin materials was also assessed. Hygrothermal ageing behaviour of recycled composites was also investigated by immersing specimens in distilled water at 50 C over a 9 month period. It was found that the diffusion coefficient and the equilibrium moisture contents of composites decreased with increased number of times the materials were recycled. After hygrothermal ageing, TS and YM of composites were found to decrease. However, the extent of reduction was found to decrease with increased recycling.

During transport of hand-held objects, the grip force is modulated in parallel with the load force changes. The control scheme underlying this grip-load force coupling involves subtle interplay between feedforward and feedback mechanisms. Based on internal models of the motor system and object properties, the load force can be predicted and the GF motor command can be specified in a feedforward manner. Moreover, during the course of arm movement, the CNS is informed by sensory feedback about mechanical events such as the lift-off of the object, slippage or excessive grip force. This information is used to correct the motor commands and to update the internal model of the motor apparatus and object. In this thesis, three experiments were conducted to examine the relative contributions of sensory-driven and anticipatory control of GF adjustments during cyclic vertical movement with a hand-held load. The main point was to assess whether internal models underlying the grip-load force coupling are robust when the environmental context was changed or when the sensory feedback was suppressed. Two experiments in parabolic flight were conducted to study the effects of a change in gravity on the dynamics of prehension. The main perturbation was that the novice subjects applied unnecessarily high safety margins during their first trial at 0 and 1.8 g in order to secure the grasp insofar as the gravitational component of the load force was unpredictable. By contrast, the temporal coupling between GF and LF was maintained regardless of the gravity conditions because the inertial component of the load could be still predicted from the arm motor command (efference copy). In the second study performed during parabolic flight, we have observed that the subjects were able to exert the same grip force for equivalent load generated either by a change of mass, gravity or acceleration despite the fact that it requires different arm motor commands. These two experiments brought further evidence that the predictive mechanisms largely contribute to the GF adjustment. Static forces such gravity are taken into account in the motor plan allowing adequate motor command and precise prediction of the incoming load force change. The GF output would depend on the precision of this prediction that can be evaluatedonly after the movement onset through sensory information about the actual state of the system. The third experiment performed in this thesis studied the role of cutaneous afferents in object manipulation by anesthetizing the thumb and index finger. In addition to their phasic slip-detection function, the cutaneous afferents are required for setting the background level of the grip force. Actually, in absence of tactile feedback, the temporal coupling between the grip and load forces is maintained but the mean magnitude of GF progressively decreases leading to object slipping. It is hypothesized that accumulating error occurred in the LF prediction leading to inadequate level of GF. Cutaneous afferents are thus required to correct and maintain the internal model of the arm-hand object system.

We will briefly outline a computational theory of the first stages of human vision according to which (a) the retinal image is filtered by a set of centre-surround receptive fields (of about 5 different spatial sizes) which are approximately bandpass in spatial frequency and (b) zero-crossings are detected independently in the output of each of these channels. Zero-crossings in each channel are then a set of discrete symbols which may be used for later processing such as contour extraction and stereopsis. A formulation of Logan's zero-crossing results is proved for the case of Fourier polynomials and an extension of Logan's theorem to 2-dimentsional functions is also approved. Within this framework, we shall describe an experimental and theoretical approach (developed by one of us with M. Fahle) to the problem of visual acuity and hyperacuity of human vision. The positional accuracy achieved, for instance, in reading a vernier is astonishingly high, corresponding to a fraction of the spacing between adjacent photoreceptors in the fovea. Stroboscopic presentation of a moving object can be interpolated by our visual system into the perception of continuous motion; and this "spatio-temporal" interpolation also can be very accurate. It is suggested that the known spatiotemporal properties of the channels envisaged by the theory of visual processing outlined above implement an interpolation scheme which can explain human vernier acuity for moving targets.

During transport of hand-held objects, the grip force is modulated in parallel with the load force changes. The control scheme underlying this grip-load force coupling involves subtle interplay between feedforward and feedback mechanisms. Based on internal models of the motor system and object properties, the load force can be predicted and the GF motor command can be specified in a feedforward manner. Moreover, during the course of arm movement, the CNS is informed by sensory feedback about mechanical events such as the lift-off of the object, slippage or excessive grip force. This information is used to correct the motor commands and to update the internal model of the motor apparatus and object. In this thesis, three experiments were conducted to examine the relative contributions of sensory-driven and anticipatory control of GF adjustments during cyclic vertical movement with a hand-held load. The main point was to assess whether internal models underlying the grip-load force coupling are robust when the environmental context was changed or when the sensory feedback was suppressed. Two experiments in parabolic flight were conducted to study the effects of a change in gravity on the dynamics of prehension. The main perturbation was that the novice subjects applied unnecessarily high safety margins during their first trial at 0 and 1.8 g in order to secure the grasp insofar as the gravitational component of the load force was unpredictable. By contrast, the temporal coupling between GF and LF was maintained regardless of the gravity conditions because the inertial component of the load could be still predicted from the arm motor command (efference copy). In the second study performed during parabolic flight, we have observed that the subjects were able to exert the same grip force for equivalent load generated either by a change of mass, gravity or acceleration despite the fact that it requires different arm motor commands. These two experiments brought further evidence that the predictive mechanisms largely contribute to the GF adjustment. Static forces such gravity are taken into account in the motor plan allowing adequate motor command and precise prediction of the incoming load force change. The GF output would depend on the precision of this prediction that can be evaluatedonly after the movement onset through sensory information about the actual state of the system. The third experiment performed in this thesis studied the role of cutaneous afferents in object manipulation by anesthetizing the thumb and index finger. In addition to their phasic slip-detection function, the cutaneous afferents are required for setting the background level of the grip force. Actually, in absence of tactile feedback, the temporal coupling between the grip and load forces is maintained but the mean magnitude of GF progressively decreases leading to object slipping. It is hypothesized that accumulating error occurred in the LF prediction leading to inadequate level of GF. Cutaneous afferents are thus required to correct and maintain the internal model of the arm-hand object system.

To address the issue of unnecessary functional group transformations in synthesis, the direct functionalization of carbon-hydrogen (C―H) bonds presents itself as an efficient and atom economical process. In particular, palladium(II)-catalyzed oxidative functionalization of arene C–H bonds were investigated to yield intermolecular and intramolecular arylations. Kinetic studies and characterization of bimetallic palladium(II) complexes led to the discovery of two other palladium(II)-catalyzed processes: arene hydroxylation and selective chlorination of anilides. Realizing the potential of biocatalysis and of transition-metal catalysis, we marriaged these two fundamentally different methods to access complex molecules in rapid and step economical ways and chose popular synthetic target, 6-deoxyerythronolide B to showcase the efficiency of these stereoselective reactions. To form the 14-membered lactone, we employed a transition-metal catalyzed ring-closing metathesis. Two different fragments were assembled via traditional and reliable aldols, oxidations and reductions, crotylations and protective group chemistry.

To address the issue of unnecessary functional group transformations in synthesis, the direct functionalization of carbon-hydrogen (C―H) bonds presents itself as an efficient and atom economical process. In particular, palladium(II)-catalyzed oxidative functionalization of arene C–H bonds were investigated to yield intermolecular and intramolecular arylations. Kinetic studies and characterization of bimetallic palladium(II) complexes led to the discovery of two other palladium(II)-catalyzed processes: arene hydroxylation and selective chlorination of anilides. Realizing the potential of biocatalysis and of transition-metal catalysis, we marriaged these two fundamentally different methods to access complex molecules in rapid and step economical ways and chose popular synthetic target, 6-deoxyerythronolide B to showcase the efficiency of these stereoselective reactions. To form the 14-membered lactone, we employed a transition-metal catalyzed ring-closing metathesis. Two different fragments were assembled via traditional and reliable aldols, oxidations and reductions, crotylations and protective group chemistry.

<i>N</i>-heterocyclic carbenes (NHC) have widely been used as spectator ligands in organometallic chemistry. Chelating bidentate di-<i>N-</i>heterocyclic carbenes (diNHC) provide additional entropic stability to their complexes relative to monodentate analogues. The steric and electronic environment around the metal centre can be fine-tuned by varying the substituents on the nitrogen atoms of the diNHC ligand. Synthesis and characterization of air and moisture stable bis(diimidazolylidene)nickel(II) complexes, [(diNHC)2Ni]2+, and their corresponding silver(I) and palladium(II) analogues are described.<p> Investigations into the catalytic potential of diNHC complexes of nickel as an alternative to palladium systems in carbon-carbon coupling reactions are discussed. In the Suzuki-Miyaura coupling reaction, the [(diNHC)2Ni]2+ complex was active for the coupling of aryl chlorides as well as aryl fluorides. The analogously synthesized Pd(II) complexes resulted in formation of (diNHC)PdCl2 species which were not active for the coupling of aryl fluorides. Transition-metal free coupling reactions were investigated and the results indicated that in the Mizoroki-Heck reaction, aryl iodides could be activated in the absence of nickel or palladium precatalysts when using Na2CO3 or NEt3 as base, while in the Suzuki-Miyaura reaction, aryl iodides and aryl bromides could be activated without any precatalyst when K3PO4 was used as base.<p> A general route into the synthesis of non-symmetrically substituted ligand precursors has been developed. Synthesis and characterization of non-symmetrically substituted ligand precursors, and their corresponding silver(I), palladium(II) and nickel(II) complexes are described. The activity of one of the non-symmetrically substituted (diNHC)Pd(II) complexes in the Suzuki-Miyaura coupling reaction of bulky substrates has been investigated. Non-symmetrically substituted diNHC ligand precursors with a hemi-labile pyridine arm have been synthesized and their corresponding Ni(II) and Pd(II) complexes are described.<p> Attempts to synthesize three-coordinate Pd(II) complexes using bulky â-diketiminato ligands are also discussed.

The synthesis of the nitrogen containing heterocyclic compounds is one of the leading research areas throughout the organic chemistry due to their significant activities in biological systems. Among the various biologically active molecules, pyridine-fused ring systems are of prime importance on the grounds of their proven clinical roles. The coupling reactions with 6-membered heterocyclic compounds and diazepines gave rise to new pharmalogical compounds in recent years. Therefore, our object was the synthesis of pyridine-fused 6- and 7-membered heterocycles. Starting from bromopyridine, two different methods were applied for the synthesis of target compounds. In the first part of the this thesis, coupling products were synthesized using Sonogashira coupling reaction. After synthesis of the coupling derivatives, ring-closure under the basic conditions generated the heterocyclic units without using any catalyzer. In the second part of study, nicotinic acid and pyridopyranone derivatives were synthesized by using intramolecular cyclization reactions. The formed products were conscientiously purified and characterized by means of spectroscopics method.