Computational modelling of chemical systems is most easily carried out in the vacuum for single molecules. Accounting for environmental effects accurately in quantum chemical calculations, however, is often necessary for computational predictions of chemical systems to have any relevance to experiment. This PhD thesis focuses on accounting for environmental effects in quantum chemical calculations by quantum mechanics/ molecular mechanics (QM/MM) approaches, taking on diverse examples from the solid state, the liquid phase and the protein environment. The methods are applied to compute a variety of properties from transition metal NMR properties of molecular crystals and enzymes, via conformational properties of zwitterions in aqueous solution, to an intramolecular amidation reaction in peptides. Chapter 3 concerns QM/MM calculations of molecular properties in the solid state, both molecular crystals and metalloenzymes, with a focus on transition metal chemical shift and EFG properties. We demonstrate that solid-state effects on such properties in molecular crystals can be accounted for by a simple general black-box QM/MM approach. We also describe preliminary QM/MM calculations of 51V anisotropic NMR properties for a vanadium-dependent enzyme. In Chapter 4 the focus is on solvent effects on the conformational preference of a small zwitterionic molecule, 3F-γ-aminobutyric acid (3F-GABA), calculated using QM/MM molecular dynamics simulations. NMR spin-spin coupling constants in solution are also calculated. Our simulations highlight the difficulty of accounting for solvation effects well enough to achieve agreement with experimental observations. Chapter 5 concerns the reaction mechanism of an intramolecular amidation reaction in a bacterial peptide, predicted by QM/MM calculations. We predict a reaction mechanism that accounts well for the experimental observations both for the wild-type and mutants. We demonstrate that environmental effects can often be satisfactorily accounted for by QM/MM approaches, thus helping to bridge the gap between theory and experiment.

Critical scholars have written about the ‘squeezed middle' and the new labour process of front line and middle managers generally, but there is a gap in the literature relating to both how changes to managerial work have affected those subjected to them and how individuals and organisations have attempted to respond to, and cope with, public sector cuts and challenges. Much of contemporary HRD writing on change management suggests that leadership development has a privileged role in adjusting the ‘worker' to the situation. However, given the implicitly unitarist nature of much HRD writing, this thesis argues that insights from such literature is inadequate or incomplete because it fails to consider the interests of managers as employees. The focus of this thesis is on middle managers' (MM) ability to overcome the public sector challenges associated with work intensification; control and skills adaption via learning and development initiatives. This qualitative research comprises a data set of 17 in-depth interviews and 34 complementary semi-structured questionnaire's with middle managers in the Hong Kong Civil Service. Thematic analysis revealed that whilst managers and the organisation benefit from leadership development in terms of human capital development, power differentials and structural impediments limit the capacity to benefit from social capital and networking opportunities provided. As such LDP cannot compensate for work intensification, leading to a stressed-out, disempowered, squeezed middle management cadre, which in turn impacts on public service delivery.

Dans le monde d’aujourd’hui, il est très fréquent de vouloir modéliser la relation entre deux ou plusieurs variables. Toutefois, plusieurs expériences sont laissées à l’abandon à cause de la présence systématique de données aberrantes. Ce mémoire portera sur les estimateurs robustes permettant de modéliser des séries de données contenant des valeurs aberrantes, nous aidant ainsi à tirer un maximum d’informations de ces expériences. Dans un premier temps, nous présenterons des estimateurs robustes qui nécessitent l’imposition d’un modèle paramétrique. Ensuite, nous traiterons de l’introduction des copules à ces estimateurs robustes. Finalement, nous présenterons des simulations tirées d’une expérience réelle qui consistait à modéliser le vrai poids d’un porc selon le poids mesuré par une balance, développée au centre de recherche et développement de Sherbrooke, dans l’optique d’améliorer les techniques d’alimentation de précision.

Understanding the time evolution of the star formation in the Universe is one of the main aims of observational astronomy. Since a significant portion of the UV starlight is being absorbed by dust and re-emitted in the IR, we need to understand both of those regimes to properly describe the cosmic star formation history. In UV, the depth and the resolution of the data permits calculations of the star formation rate densities out to very high redshifts (z ∼ 8 − 9). In IR however, the large beam sizes and the relatively shallow data limits these calculations to z ∼ 2. In this thesis, I explore the SMA and PdBI high-resolution follow-up of 30 bright sources originally selected by AzTEC and LABOCA instruments at 1.1 mm and 870 μm respectively in conjunction with the SCUBA-2 Cosmology Legacy Survey (S2CLS) deep COSMOS and wide UDS maps, where 106 and 283 sources were detected, with the signal-to-noise ratio of > 5 and > 3.5 at 850 μm respectively. I find that the (sub)mm-selected galaxies reside and the mean redshifts of ¯z ≃ 2.5±0.05 with the exception of the brightest sources which seem to lie at higher redshifts (¯z ≃ 3.5 ± 0.2), most likely due to the apparent correlation of the (sub)mm flux with redshift, where brighter sources tend to lie at higher redshifts. Stellar masses, M⋆, and star formation rates, SFRs, were found (M⋆ & 1010M⊙ and SFR & 100M⊙ yr−1) and used to calculate the specific SFRs. I determine that the (sub)mm-selected sources mostly lie on the high-mass end of the star formation ‘main-sequence’ which makes them a high-mass extension of normal star forming galaxies. I also find that the specific SFR slightly evolves at redshifts 2−4, suggesting that the efficiency of the star formation seems to be increasing at these redshifts. Using the S2CLS data, the bolometric IR luminosity functions (IR LFs) were found for a range of redshifts z = 1.2 − 4.2 and the contribution of the SMGs to the total star formation rate density (SFRD) was calculated. The IR LFs were found to evolve out to redshift ∼ 2.5. The star formation activity in the Universe was found to peak at z ≃ 2 followed by a slight decline. Assuming the IR to total SFRD correction found in the literature the SFRD found in this work closely follows the best-fitting function of Madau & Dickinson (2014).

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21593号 / 理博第4500号 / 新制||理||1646(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 林 重彦, 教授 谷村 吉隆, 教授 寺嶋 正秀 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Denna uppsats undersöker fem andraspråkselevers perspektiv av modersmålsundervisningen. Forskning visar att modersmålsundervisning påverkar elevers lärande och språkutveckling positivt. Syftet med studien är att komma åt andraspråkselevers attityder till och erfarenheter av modersmålsundervisningen men även att ta reda på hur eleverna upplever modersmålsundervisningen och om de ser den som något positivt som gynnar deras lärande och språkutveckling eller inte. Utöver detta beaktar studien omkringliggande omständigheter som kan påverka elevernas attityder och erfarenheter. Detta undersöks kvalitativt genom semistrukturerade intervjuer. Analys av intervjusvaren visar att majoriteten av informanterna anser att modersmålsundervisningen är viktig, leder till bättre självförtroende och självkänsla samt att de genom den kan bevara sitt ursprung. Slutsatsen är att modersmålet till stor del ses som viktig för eleverna som individer och bevarandet av deras ursprung. Däremot påverkas deras attityder till och erfarenheter av ämnet av omständigheter såsom modersmålsundervisningens plats, tid, längd och lärare.

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