Numerical characterization of the mechanical properties of metal nanowires

Nanowires (NWs) have attracted appealing and broad application owing to their remarkable mechanical, optical, electrical, thermal and other properties. To unlock the revolutionary characteristics of NWs, a considerable body of experimental and theoretical work has been conducted. However, due to the extremely small dimensions of NWs, the application and manipulation of the in situ experiments involve inherent complexities and huge challenges. For the same reason, the presence of defects appears as one of the most dominant factors in determining their properties. Hence, based on the experiments' deficiency and the necessity of investigating different defects' influence, the numerical simulation or modelling becomes increasingly important in the area of characterizing the properties of NWs. It has been noted that, despite the number of numerical studies of NWs, significant work still lies ahead in terms of problem formulation, interpretation of results, identification and delineation of deformation mechanisms, and constitutive characterization of behaviour. Therefore, the primary aim of this study was to characterize both perfect and defected metal NWs. Large-scale molecular dynamics (MD) simulations were utilized to assess the mechanical properties and deformation mechanisms of different NWs under diverse loading conditions including tension, compression, bending, vibration and torsion. The target samples include different FCC metal NWs (e.g., Cu, Ag, Au NWs), which were either in a perfect crystal structure or constructed with different defects (e.g. pre-existing surface/internal defects, grain/twin boundaries). It has been found from the tensile deformation that Young's modulus was insensitive to different styles of pre-existing defects, whereas the yield strength showed considerable reduction. The deformation mechanisms were found to be greatly influenced by the presence of defects, i.e., different defects acted in the role of dislocation sources, and many affluent deformation mechanisms had been triggered. Similar conclusions were also obtained from the compressive deformation, i.e., Young's modulus was insensitive to different defects, but the critical stress showed evident reduction. Results from the bending deformation revealed that the current modified beam models with the considerations of surface effect, or both surface effect and axial extension effect were still experiencing certain inaccuracy, especially for the NW with ultra small cross-sectional size. Additionally, the flexural rigidity of the NW was found to be insensitive to different pre-existing defects, while the yield strength showed an evident decrease. For the resonance study, the first-order natural frequency of the NW with pre-existing surface defects was almost the same as that from the perfect NW, whereas a lower first-order natural frequency and a significantly degraded quality factor was observed for NWs with grain boundaries. Most importantly, the <110> FCC NWs were found to exhibit a novel beat phenomenon driven by a single actuation, which was resulted from the asymmetry in the lattice spacing in the (110) plane of the NW cross-section, and expected to exert crucial impacts on the in situ nanomechanical measurements. In particular, <110> Ag NWs with rhombic, truncated rhombic, and triangular cross-sections were found to naturally possess two first-mode natural frequencies, which were envisioned with applications in NEMS that could operate in a non-planar regime. The torsion results revealed that the torsional rigidity of the NW was insensitive to the presence of pre-existing defects and twin boundaries, but received evident reduction due to grain boundaries. Meanwhile, the critical angle decreased considerably for defected NWs. This study has provided a comprehensive and deep investigation on the mechanical properties and deformation mechanisms of perfect and defected NWs, which will greatly extend and enhance the existing knowledge and understanding of the properties/performance of NWs, and eventually benefit the realization of their full potential applications. All delineated MD models and theoretical analysis techniques that were established for the target NWs in this research are also applicable to future studies on other kinds of NWs. It has been suggested that MD simulation is an effective and excellent tool, not only for the characterization of the properties of NWs, but also for the prediction of novel or unexpected properties.

Ownership, corporate governance and liquidity in Caribbean firms

This thesis provides the first evidence on how ownership structure and corporate governance relate to stock liquidity in the Caribbean. Based on panel data of 71 firms from three selected Caribbean markets − Barbados, Jamaica, and Trinidad & Tobago − results show that firms with concentrated ownership are associated with lower liquidity. The identity of the largest shareholder also matters: family firms and firms with foreign holding companies are more liquid than government firms. Although the second largest shareholding does not appear to matter to liquidity, there is some evidence showing that firms with foreign holding companies as the second largest shareholder are less liquid. Caribbean firms suffer from poor corporate governance but this study is unable to establish a significant relationship between corporate governance and liquidity.

Interocular corneal symmetry in refractive error groups

Purpose: To examine between eye differences in corneal higher order aberrations and topographical characteristics in a range of refractive error groups. Methods: One hundred and seventy subjects were recruited including; 50 emmetropic isometropes, 48 myopic isometropes (spherical equivalent anisometropia ≤ 0.75 D), 50 myopic anisometropes (spherical equivalent anisometropia ≥ 1.00 D) and 22 keratoconics. The corneal topography of each eye was captured using the E300 videokeratoscope (Medmont, Victoria, Australia) and analyzed using custom written software. All left eye data were rotated about the vertical midline to account for enantiomorphism. Corneal height data were used to calculate the corneal wavefront error using a ray tracing procedure and fit with Zernike polynomials (up to and including the eighth radial order). The wavefront was centred on the line of sight by using the pupil offset value from the pupil detection function in the videokeratoscope. Refractive power maps were analysed to assess corneal sphero-cylindrical power vectors. Differences between the more myopic (or more advanced eye for keratoconics) and the less myopic (advanced) eye were examined. Results: Over a 6 mm diameter, the cornea of the more myopic eye was significantly steeper (refractive power vector M) compared to the fellow eye in both anisometropes (0.10 ± 0.27 D steeper, p = 0.01) and keratoconics (2.54 ± 2.32 D steeper, p < 0.001) while no significant interocular difference was observed for isometropic emmetropes (-0.03 ± 0.32 D) or isometropic myopes (0.02 ± 0.30 D) (both p > 0.05). In keratoconic eyes, the between eye difference in corneal refractive power was greatest inferiorly (associated with cone location). Similarly, in myopic anisometropes, the more myopic eye displayed a central region of significant inferior corneal steepening (0.15 ± 0.42 D steeper) relative to the fellow eye (p = 0.01). Significant interocular differences in higher order aberrations were only observed in the keratoconic group for; vertical trefoil C(3,-3), horizontal coma C(3,1) secondary astigmatism along 45 C(4, -2) (p < 0.05) and vertical coma C(3,-1) (p < 0.001). The interocular difference in vertical pupil decentration (relative to the corneal vertex normal) increased with between eye asymmetry in refraction (isometropia 0.00 ± 0.09, anisometropia 0.03 ± 0.15 and keratoconus 0.08 ± 0.16 mm) as did the interocular difference in corneal vertical coma C (3,-1) (isometropia -0.006 ± 0.142, anisometropia -0.037 ± 0.195 and keratoconus -1.243 ± 0.936 μm) but only reached statistical significance for pair-wise comparisons between the isometropic and keratoconic groups. Conclusions: There is a high degree of corneal symmetry between the fellow eyes of myopic and emmetropic isometropes. Interocular differences in corneal topography and higher order aberrations are more apparent in myopic anisometropes and keratoconics due to regional (primarily inferior) differences in topography and between eye differences in vertical pupil decentration relative to the corneal vertex normal. Interocular asymmetries in corneal optics appear to be associated with anisometropic refractive development.

The acetal concept : regioselective access toortho,ortho-diphenols via dibenzo-1,3-dioxepines

Traditional methods are ill-suited for the synthesis of ortho,ortho-biphenols, a structural motif found in many polyphenolic natural products, as well as synthetically useful compounds such as the chiral ligands binol, vapol, and vanol. The new route consists of a radical-based reaction of an acetal-tethered biphenyl ether substrate and subsequent hydrolytic cleavage of the dibenzo-1,3-dioxepine intermediate.

The impact of corporate governance on private placements in Australia

In private placement transactions, issuing firms sell a block of securities to just a small group of investors at a discounted price. Non-participating shareholders suffer from ownership dilution and lose the opportunity to receive the discount. This thesis provides the first evidence on whether and how corporate governance can protect non-participating shareholders' interests. Results from an examination of 329 private placements issued by the top 250 Australian firms between 2002 and 2009 demonstrate that firms with higher governance quality are more likely to issue a share purchase plan (SPP) along with the private placement, thus providing greater protection to non-participating shareholders' interests.

Preparative deracemization of unnatural amino acids

Unnatural amino acids are a growing class of intermediates required for pharmaceuticals, agrochemicals and other industrial products. However, no single method has proven sufficiently versatile to prepare these compounds broadly at scale. To address this need, we have developed a general chemoenzymatic process to prepare enantiomerically pure L- and D-amino acids in high yield by deracemization of racemic starting materials. This method involves the concerted action of an enantioselective oxidase biocatalyst and a non-selective chemical reducing agent to effect the stereoinversion of one enantiomer and can result in an enantiomeric excess of >99% from the starting racemate, and product yields of over 90%. This approach compares very favourably with resolution processes, which have a maximum single-pass yield of 50%. We have developed efficient methods to adapt the process towards new target compounds and to optimize key factors that influence process efficiency and offer competitive economics at scale.

Rapid identification of cytochrome P450cam variants by in vivo screening of active site libraries

The selection of cytochrome P450 enzymes from large variant libraries, and the subsequent use of these enzymes in preparative scale biotransformations, remains a formidable challenge due to the complexities of the associated electron transport systems. Here, a powerful approach for the generation and screening of P450cam libraries for new function is presented that is both flexible and robust. A targeted library was generated wherein only the P450cam active-site amino acids Y96 and F98 were fully randomized and biotransformations, using a novel P450cam whole-cell system, were screened by GC–MS for the hydroxylation of diphenylmethane. One in 50 of the reactions screened, including 16 different variants, produced 4-hydroxydiphenylmethane with up to 92% conversion observed in the case of the Y96A variant. These results demonstrate a primary example of the screening of P450cam libraries in a format that is compatible with extension to preparative scale reactions.

Electromagnetic propulsion and separation by chirality of nanoparticles in liquids

We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope. © 2012 American Physical Society.

Assessing the bilateral geometrical differences of the tibia : are they the same?

Contralateral bones are often used in many medical applications but it is assumed that their bilateral differences are insignificant. Previous studies used a limited number of distance measurements in quantifying the corresponding differences; therefore, little is known about their bilateral 3D surface asymmetries. The aim of the study is to develop a comprehensive method to quantify geometrical asymmetries between the left and right tibia in order to provide first results on whether the contralateral tibia can be used as an equivalent reference. In this study, 3D bone models were reconstructed from CT scans of seven tibiae pairs, and 34 variables consisting of 2D and 3D measurements were measured from various anatomical regions. All 2D measurements, and lateral plateau and distal subchondral bone surface measurements showed insignificant differences (p > 0.05), but the rest of the surfaces showed significant differences (p < 0.05). Our results suggest that the contralateral tibia can be used as a reference especially in surgical applications such as articular reconstructions since the bilateral differences in the subchondral bone surfaces were less than 0.3 mm. The method can also be potentially transferable to other relevant studies that require the accurate quantification of bone bilateral asymmetries.

Mismatch negativity in recent-onset and chronic schizophrenia : a current source density analysis

Mismatch negativity (MMN) is a component of the event-related potential elicited by deviant auditory stimuli. It is presumed to index pre-attentive monitoring of changes in the auditory environment. MMN amplitude is smaller in groups of individuals with schizophrenia compared to healthy controls. We compared duration-deviant MMN in 16 recent-onset and 19 chronic schizophrenia patients versus age- and sex-matched controls. Reduced frontal MMN was found in both patient groups, involved reduced hemispheric asymmetry, and was correlated with Global Assessment of Functioning (GAF) and negative symptom ratings. A cortically-constrained LORETA analysis, incorporating anatomical data from each individual's MRI, was performed to generate a current source density model of the MMN response over time. This model suggested MMN generation within a temporal, parietal and frontal network, which was right hemisphere dominant only in controls. An exploratory analysis revealed reduced CSD in patients in superior and middle temporal cortex, inferior and superior parietal cortex, precuneus, anterior cingulate, and superior and middle frontal cortex. A region of interest (ROI) analysis was performed. For the early phase of the MMN, patients had reduced bilateral temporal and parietal response and no lateralisation in frontal ROIs. For late MMN, patients had reduced bilateral parietal response and no lateralisation in temporal ROIs. In patients, correlations revealed a link between GAF and the MMN response in parietal cortex. In controls, the frontal response onset was 17 ms later than the temporal and parietal response. In patients, onset latency of the MMN response was delayed in secondary, but not primary, auditory cortex. However amplitude reductions were observed in both primary and secondary auditory cortex. These latency delays may indicate relatively intact information processing upstream of the primary auditory cortex, but impaired primary auditory cortex or cortico-cortical or thalamo-cortical communication with higher auditory cortices as a core deficit in schizophrenia.

Design and test of a custom instrumented leg press for injury and recovery intervention

There is an increasing desire and emphasis to integrate assessment tools into the everyday training environment of athletes. These tools are intended to fine-tune athlete development, enhance performance and aid in the development of individualised programmes for athletes. The areas of workload monitoring, skill development and injury assessment are expected to benefit from such tools. This paper describes the development of an instrumented leg press and its application to testing leg dominance with a cohort of athletes. The developed instrumented leg press is a 45° reclining sled-type leg press with dual force plates, a displacement sensor and a CCD camera. A custom software client was developed using C#. The software client enabled near-real-time display of forces beneath each limb together with displacement of the quad track roller system and video feedback of the exercise. In recording mode, the collection of athlete particulars is prompted at the start of the exercise, and pre-set thresholds are used subsequently to separate the data into epochs from each exercise repetition. The leg press was evaluated in a controlled study of a cohort of physically active adults who performed a series of leg press exercises. The leg press exercises were undertaken at a set cadence with nominal applied loads of 50%, 100% and 150% of body weight without feedback. A significant asymmetry in loading of the limbs was observed in healthy adults during both the eccentric and concentric phases of the leg press exercise (P < .05). Mean forces were significantly higher beneath the non-dominant limb (4–10%) and during the concentric phase of the muscle action (5%). Given that symmetrical loading is often emphasized during strength training and remains a common goal in sports rehabilitation, these findings highlight the clinical potential for this instrumented leg press system to monitor symmetry in lower-limb loading during progressive strength training and sports rehabilitation protocols.

Three essays on banks trading activities

With a fair share of the blame for the subprime crisis pointing to banks' extensive involvement in trading, this thesis examines three closely related issues. The first essay shows that regulatory capital arbitrage, insolvency risk, and non-interest income are all important motivations for banks to become involved in trading. The second essay support the widely held perception that trading activities such as off-balance sheet derivatives, securitization, and assets sales all are making banks more opaque. With banks' business model changing from ''originate and hold'' to ''originate, repackage, and sell'', the last essay show that trading channel exist and it has weakened the effectiveness of monetary policy transmission through banks' capital and lending channel.

Theory and practice of automotive modal lock-in – an Indonesian case

This thesis examines the question why the automotive mode and the large technological system it creates, continues to dominate urban transport systems despite the availability of more cost-efficient alternatives. A number of theoretical insights are developed into the way these losses evolve from path dependent growth, and lead to market failure and lock-in. The important role of asymmetries of influence is highlighted. A survey of commuters in Jakarta Indonesia is used to provide a measure of transport modal lock-in (TML) in a developing country conurbation. A discrete choice experiment is used to provide evidence for the thesis central hypothesis that in such conurbations there is a high level of commuter awareness of the negative externalities generated by TML which can produce a strong level of support for its reversal. Why TML nevertheless remains a strong and durable feature of the transport system is examined with reference to the role of asymmetries of influence.

Visual field coordinates of pupillary circular axis and optical axis

Purpose: We term the visual field position from which the pupil appears most nearly circular as the pupillary circular axis (PCAx). The aim was to determine and compare the horizontal and vertical co-ordinates of the PCAx and optical axis from pupil shape and refraction information for only the horizontal meridian of the visual field. Method: The PCAx was determined from the changes with visual field angle in the ellipticity and orientation of pupil images out to ±90° from fixation along the horizontal meridian for the right eyes of 30 people. This axis was compared with the optical axis determined from the changes in the astigmatic components of the refractions for field angles out to ±35° in the same meridian. Results: The mean estimated horizontal and vertical field coordinates of the PCAx were (‒5.3±1.9°, ‒3.2±1.5°) compared with (‒4.8±5.1°, ‒1.5±3.4°) for the optical axis. The vertical co-ordinates of the two axes were just significantly different (p =0.03) but there was no significant correlation between them. Only the horizontal coordinate of the PCAx was significantly related to the refraction in the group. Conclusion: On average, the PCAx is displaced from the line-of-sight by about the same angle as the optical axis but there is more inter-subject variation in the position of the optical axis. When modelling the optical performance of the eye, it appears reasonable to assume that the pupil is circular when viewed along the line-of-sight.

A generalised deficit can account for problems in facial emotion recognition in schizophrenia

Neuroimaging research has shown localised brain activation to different facial expressions. This, along with the finding that schizophrenia patients perform poorly in their recognition of negative emotions, has raised the suggestion that patients display an emotion specific impairment. We propose that this asymmetry in performance reflects task difficulty gradations, rather than aberrant processing in neural pathways subserving recognition of specific emotions. A neural network model is presented, which classifies facial expressions on the basis of measurements derived from human faces. After training, the network showed an accuracy pattern closely resembling that of healthy subjects. Lesioning of the network led to an overall decrease in the network’s discriminant capacity, with the greatest accuracy decrease to fear, disgust and anger stimuli. This implies that the differential pattern of impairment in schizophrenia patients can be explained without having to postulate impairment of specific processing modules for negative emotion recognition.