Synthesis and quantum-chemistry analysis on novel triazole compounds containing ester group

Nine novel triazole compounds containing ester group were designed and synthesized. Their structures were confirmed by elemental, H-1 NMR and IR analyses, and optimized by means of DFT (Density Functional Theory) method at the B3LYP/6-31G* level. Based on the quantum-chemical calculation results and the Pearson coefficients between FA and quantumchemical parameters, V, LogP, MR and E-HOMO are shown to be the important relative factors which affect FA of the title compounds.

Application of dynamical Lie algebraic method to atom-diatomic molecule scattering

The dynamical Lie algebraic approach developed by Alhassid and Levine combined with intermediate picture is applied to the study of translational-vibrational energy transfer in the collinear collision between an atom and an anharmonic oscillator. We find that the presence of the anharmonic terms indeed has an effect on the vibrational probabilities of the oscillator. The computed probabilities are in good agreement with those obtained using exact quantum method. It is shown that the approach of dynamical Lie algebra combining with intermediate picture is reasonable in the treating of atom-anharmonic oscillator scattering.

Control of Vibration in Mechanical Systems Using Shaped Reference Inputs

Dynamic systems which undergo rapid motion can excite natural frequencies that lead to residual vibration at the end of motion. This work presents a method to shape force profiles that reduce excitation energy at the natural frequencies in order to reduce residual vibration for fast moves. Such profiles are developed using a ramped sinusoid function and its harmonics, choosing coefficients to reduce spectral energy at the natural frequencies of the system. To improve robustness with respect to parameter uncertainty, spectral energy is reduced for a range of frequencies surrounding the nominal natural frequency. An additional set of versine profiles are also constructed to permit motion at constant speed for velocity-limited systems. These shaped force profiles are incorporated into a simple closed-loop system with position and velocity feedback. The force input is doubly integrated to generate a shaped position reference for the controller to follow. This control scheme is evaluated on the MIT Cartesian Robot. The shaped inputs generate motions with minimum residual vibration when actuator saturation is avoided. Feedback control compensates for the effect of friction Using only a knowledge of the natural frequencies of the system to shape the force inputs, vibration can also be attenuated in modes which vibrate in directions other than the motion direction. When moving several axes, the use of shaped inputs allows minimum residual vibration even when the natural frequencies are dynamically changing by a limited amount.

Quantum Monte Carlo in the Interaction Representation --- Application to a Spin-Peierls Model

A quantum Monte Carlo algorithm is constructed starting from the standard perturbation expansion in the interaction representation. The resulting configuration space is strongly related to that of the Stochastic Series Expansion (SSE) method, which is based on a direct power series expansion of exp(-beta*H). Sampling procedures previously developed for the SSE method can therefore be used also in the interaction representation formulation. The new method is first tested on the S=1/2 Heisenberg chain. Then, as an application to a model of great current interest, a Heisenberg chain including phonon degrees of freedom is studied. Einstein phonons are coupled to the spins via a linear modulation of the nearest-neighbor exchange. The simulation algorithm is implemented in the phonon occupation number basis, without Hilbert space truncations, and is exact. Results are presented for the magnetic properties of the system in a wide temperature regime, including the T-->0 limit where the chain undergoes a spin-Peierls transition. Some aspects of the phonon dynamics are also discussed. The results suggest that the effects of dynamic phonons in spin-Peierls compounds such as GeCuO3 and NaV2O5 must be included in order to obtain a correct quantitative description of their magnetic properties, both above and below the dimerization temperature.

Quantum behavior in mesoscopic systems

In this thesis I present the work done during my PhD. The Thesis is divided into two parts; in the first one I present the study of mesoscopic quantum systems whereas in the second one I address the problem of the definition of Markov regime for quantum system dynamics. The first work presented is the study of vortex patterns in (quasi) two dimensional rotating Bose Einstein condensates (BECs). I consider the case of an anisotropy trapping potential and I shall show that the ground state of the system hosts vortex patterns that are unstable. In a second work I designed an experimental scheme to transfer entanglement from two entangled photons to two BECs. This work is meant to propose a feasible experimental set up to bring entanglement from microscopic to macroscopic systems for both the study of fundamental questions (quantum to classical transition) and technological applications. In the last work of the first part another experimental scheme is presented in order to detect coherences of a mechanical oscillator which is assumed to have been previously cooled down to the quantum regime. In this regime in fact the system can rapidly undergo decoherence so that new techniques have to be employed in order to detect and manipulate their states. In the scheme I propose a micro-mechanical oscillator is coupled to a BEC and the detection is performed by monitoring the BEC with a negligible back-action on the cantilever. In the second part of the thesis I give a definition of Markov regime for open quantum dynamics. The importance of such definition comes from both the mathematical description of the system dynamics and from the understanding of the role played by the environment in the evolution of an open system. In the Markov regime the mathematical description can be simplified and the role of the environment is a passive one.

Evanescent field sensing: optical nanofibres, whispering-gallery-mode microspherical and microbubble resonators

In this thesis, the evanescent field sensing techniques of tapered optical nanofibres and microspherical resonators are investigated. This includes evanescent field spectroscopy of a silica nanofibre in a rubidium vapour; thermo-optical tuning of Er:Yb co-doped phosphate glass microspheres; optomechanical properties of microspherical pendulums; and the fabrication and characterisation of borosilicate microbubble resonators. Doppler-broadened and sub-Doppler absorption spectroscopic techniques are performed around the D2 transition (780.24 nm) of rubidium using the evanescent field produced at the waist of a tapered nanofibre with input probe powers as low as 55 nW. Doppler-broadened Zeeman shifts and a preliminary dichroic atomic vapour laser lock (DAVLL) line shape are also observed via the nanofibre waist with an applied magnetic field of 60 G. This device has the potential for laser frequency stabilisation while also studying the effects of atom-surface interactions. A non-invasive thermo-optical tuning technique of Er:Yb co-doped microspheres to specific arbitrary wavelengths is demonstrated particularly to 1294 nm and the 5S1/2F=3 to 5P3/2Fʹ=4 laser cooling transition of 85Rb. Reversible tuning ranges of up to 474 GHz and on resonance cavity timescales on the order of 100 s are reported. This procedure has prospective applications for sensing a variety of atomic or molecular species in a cavity quantum electrodynamics (QED) experiments. The mechanical characteristics of a silica microsphere pendulum with a relatively low spring constant of 10-4 Nm-1 are explored. A novel method of frequency sweeping the motion of the pendulum to determine its natural resonance frequencies while overriding its sensitivity to environmental noise is proposed. An estimated force of 0.25 N is required to actuate the pendulum by a displacement of (1-2) μm. It is suggested that this is of sufficient magnitude to be experienced between two evanescently coupled microspheres (photonic molecule) and enable spatial trapping of the micropendulum. Finally, single-input borosilicate microbubble resonators with diameters <100 μm are fabricated using a CO2 laser. Optical whispering gallery mode spectra are observed via evanescent coupling with a tapered fibre. A red-shift of (4-22) GHz of the resonance modes is detected when the hollow cavity was filled with nano-filtered water. A polarisation conversion effect, with an efficiency of 10%, is observed when the diameter of the coupling tapered fibre waist is varied. This effect is also achieved by simply varying the polarisation of the input light in the tapered fibre where the efficiency is optimised to 92%. Thus, the microbubble device acts as a reversible band-pass to band-stop optical filter for cavity-QED, integrated solid-state and semiconductor circuit applications.

Plate-specific gain map correction for the improvement of detective quantum efficiency in computed radiography.

PURPOSE: The purpose of this work is to improve the noise power spectrum (NPS), and thus the detective quantum efficiency (DQE), of computed radiography (CR) images by correcting for spatial gain variations specific to individual imaging plates. CR devices have not traditionally employed gain-map corrections, unlike the case with flat-panel detectors, because of the multiplicity of plates used with each reader. The lack of gain-map correction has limited the DQE(f) at higher exposures with CR. This current work describes a feasible solution to generating plate-specific gain maps. METHODS: Ten high-exposure open field images were taken with an RQA5 spectrum, using a sixth generation CR plate suspended in air without a cassette. Image values were converted to exposure, the plates registered using fiducial dots on the plate, the ten images averaged, and then high-pass filtered to remove low frequency contributions from field inhomogeneity. A gain-map was then produced by converting all pixel values in the average into fractions with mean of one. The resultant gain-map of the plate was used to normalize subsequent single images to correct for spatial gain fluctuation. To validate performance, the normalized NPS (NNPS) for all images was calculated both with and without the gain-map correction. Variations in the quality of correction due to exposure levels, beam voltage/spectrum, CR reader used, and registration were investigated. RESULTS: The NNPS with plate-specific gain-map correction showed improvement over the noncorrected case over the range of frequencies from 0.15 to 2.5 mm(-1). At high exposure (40 mR), NNPS was 50%-90% better with gain-map correction than without. A small further improvement in NNPS was seen from carefully registering the gain-map with subsequent images using small fiducial dots, because of slight misregistration during scanning. Further improvement was seen in the NNPS from scaling the gain map about the mean to account for different beam spectra. CONCLUSIONS: This study demonstrates that a simple gain-map can be used to correct for the fixed-pattern noise in a given plate and thus improve the DQE of CR imaging. Such a method could easily be implemented by manufacturers because each plate has a unique bar code and the gain-map for all plates associated with a reader could be stored for future retrieval. These experiments indicated that an improvement in NPS (and hence, DQE) is possible, depending on exposure level, over a wide range of frequencies with this technique.

Conductance of quantum impurity models from quantum monte carlo

The conductance of two Anderson impurity models, one with twofold and another with fourfold degeneracy, representing two types of quantum dots, is calculated using a world-line quantum Monte Carlo (QMC) method. Extrapolation of the imaginary time QMC data to zero frequency yields the linear conductance, which is then compared to numerical renormalization-group results in order to assess its accuracy. We find that the method gives excellent results at low temperature (T TK) throughout the mixed-valence and Kondo regimes but it is unreliable for higher temperature. © 2010 The American Physical Society.

An online daily diary study of alcohol use using Amazon's mechanical turk

Introduction and Aims: In recent years, unprecedented levels of Internet access and the widespread growth of emergent communication technologies have resulted in significantly greater population access for substance use researchers. Despite the research potential of such technologies, the use of the Internet to recruit individuals for participation in event-level research has been limited. The purpose of this paper is to provide a brief account of the methods and results from an online daily diary study of alcohol use. Design and Methods: Participants were recruited using Amazon's Mechanical Turk. Eligible participants completed a brief screener assessing demographics and health behaviours, with a subset of individuals subsequently recruited to participate in a 2 week daily diary study of alcohol use. Results: Multilevel models of the daily alcohol data derived from the Mechanical Turk sample (n=369) replicated several findings commonly reported in daily diary studies of alcohol use. Discussion and Conclusions: Results demonstrate that online participant recruitment and survey administration can be a fruitful method for conducting daily diary alcohol research. © 2014 Australasian Professional Society on Alcohol and other Drugs.

Combined vertex-based - cell-centred finite volume method for flows in complex geometries

CFD modelling of 'real-life' processes often requires solutions in complex three dimensional geometries, which can often result in meshes where aspects of it are badly distorted. Cell-centred finite volume methods, typical of most commercial CFD tools, are computationally efficient, but can lead to convergence problems on meshes which feature cells with high non-orthogonal shapes. The vertex-based finite volume method handles distorted meshes with relative ease, but is computationally expensive. A combined vertex-based - cell-centred (VB-CC) technique, detailed in this paper, allows solutions on distorted meshes that defeat purely cell-centred physical models to be employed in the solution of other transported quantities. The VB-CC method is validated with benchmark solutions for thermally driven flow and turbulent flow. An early application of this hybrid technique is to three-dimensional flow over an aircraft wing, although it is planned to use it in a wide variety of processing applications in the future.

An integrated approach to flow, thermal and mechanical modeling of electronics devices

The future success of many electronics companies will depend to a large extent on their ability to initiate techniques that bring schedules, performance, tests, support, production, life-cycle-costs, reliability prediction and quality control into the earliest stages of the product creation process. Earlier papers have discussed the benefits of an integrated analysis environment for system-level thermal, stress and EMC prediction. This paper focuses on developments made to the stress analysis module and presents results obtained for an SMT resistor. Lifetime predictions are made using the Coffin-Manson equation. Comparison with the creep strain energy based models of Darveaux (1997) shows the shear strain based method to underestimate the solder joint life. Conclusions are also made about the capabilities of both approaches to predict the qualitative and quantitative impact of design changes.

Thermal-mechanical modelling of power electronic module packaging

In this paper the reliability of the isolation substrate and chip mountdown solder interconnect of power modules under thermal-mechanical loading has been analysed using a numerical modelling approach. The damage indicators such as the peel stress and the accumulated plastic work density in solder interconnect are calculated for a range of geometrical design parameters, and the effects of these parameters on the reliability are studied by using a combination of the finite element analysis (FEA) method and optimisation techniques. The sensitivities of the reliability of the isolation substrate and solder interconnect to the changes of the design parameters are obtained and optimal designs are studied using response surface approximation and gradient optimization method

Development and mechanical characterization of solvent-cast polymeric films as potential drug delivery systems to mucosal surfaces

Solvent-cast films from three polymers, carboxymethylcellulose (CMC), sodium alginate (SA), and xanthan gum, were prepared by drying the polymeric gels in air. Three methods, (a) passive hydration, (b) vortex hydration with heating, and (c) cold hydration, were investigated to determine the most effective means of preparing gels for each of the three polymers. Different drying conditions [relative humidity - RH (6-52%) and temperature (3-45 degrees C)] were investigated to determine the effect of drying rate on the films prepared by drying the polymeric gels. The tensile properties of the CMC films were determined by stretching dumbbell-shaped films to breaking point, using a Texture Analyser. Glycerol was used as a plasticizer, and its effects on the drying rate, physical appearance, and tensile properties of the resulting films were investigated. Vortex hydration with heating was the method of choice for preparing gels of SA and CMC, and cold hydration for xanthan gels. Drying rates increased with low glycerol content, high temperature, and low relative humidity. The residual water content of the films increased with increasing glycerol content and high relative humidity and decreased at higher temperatures. Generally, temperature affected the drying rate to a greater extent than relative humidity. Glycerol significantly affected the toughness (increased) and rigidity (decreased) of CMC films. CMC films prepared at 45 degrees C and 6% RH produced suitable films at the fastest rate while films containing equal quantities of glycerol and CMC possessed an ideal balance between flexibility and rigidity.

The impact of nurse-directed protocolised-weaning from mechanical ventilation on nursing practice: A quasi-experimental study

Background:
Internationally, nurse-directed protocolised-weaning has been evaluated by measuring its impact on patient outcomes. The impact on nurses’ views and perceptions has been largely ignored.

Aim:
To determine the change in intensive care nurses’ perceptions, satisfaction, knowledge and attitudes following the introduction of nurse-directed weaning. Additionally, views were obtained on how useful protocolised-weaning was to practice.

Methods:
The sample comprised nurses working in general intensive care units in three university-affiliated hospitals. Nurse-directed protocolised-weaning was implemented in one unit (intervention group); two ICUs continued with usual doctor-led practice (control group). Nurses’ perceptions, satisfaction, knowledge and attitudes were measured by self-completed questionnaires before (Phase I) and after the implementation of nurse-directed weaning (Phase II) in all units.

Results:
Response rates were 79% (n=140n=140) for Phase 1 and 62% (n=132n=132) for Phase II. Regression-based analyses showed that changes from Phase I to Phase II were not significantly different between the intervention and control groups. Sixty-nine nurses responded to both Phase I and II questionnaires. In the intervention group, these nurses scored their mean perceived level of knowledge higher in Phase II (6.39 vs 7.17, p=0.01p=0.01). In the control group, role perception (4.41 vs 4.22, p=0.01p=0.01) was lower and, perceived knowledge (6.03 vs 6.63, p=0.04p=0.04), awareness of weaning plans (6.09 vs 7.06, p=0.01p=0.01) and satisfaction with communication (5.28 vs 6.19, p=0.01p=0.01) were higher in Phase II. The intervention group found protocolised weaning useful in their practice (75%): this was scored significantly higher by junior and senior nurses than middle grade nurses (p=0.02p=0.02).

Conclusion

We conclude that nurse-directed protocolised-weaning had no effect on nurses’ views and perceptions due to the high level of satisfaction which encouraged nurses’ participation in weaning throughout. Control group changes are attributed to a ‘reactive effect’ from being study participants. Weaning protocols provide a uniform method of weaning practice and are particularly beneficial in providing safe guidance for junior staff.

Microabrasion : A novel method to assess surface degradation of UHMWPE following sterilisation and ageing

The ageing behaviour of ultra-high molecular weight polyethylene (UHMWPE) has been studied following gamma irradiation (25 or 40 kGy) in air. Accelerated ageing procedures used elevated temperature (70°C) and/or pressurised oxygen (5 bar). Shelf-aged UHMWPE was also studied. The variation in surface density and mechanical properties were determined following the various sterilisation and ageing treatments. Microabrasive wear testing was also performed. Wear rates were found to correlate well with stress at break for sterilised and aged UHMWPE but not with elongation to failure. It is proposed that the wear mechanism is fracture dominated and occurs following some disentanglement of the polymer chains. Wear also depends upon embrittlement of the surface layer due to its processing and ageing. Elongation to failure in a tensile test is not a good measure of this embrittlement whereas the microabrasion test provides more surface sensitive information concerning this property.