Because of its importance in the history of the verse novel and the history of women’s writing, Elizabeth Barrett Browning’s Aurora Leigh (1856) has overshadowed the works of other female verse novelists in Victorian studies scholarship. By focusing on non-canonical works by four understudied women poets writing in the late nineteenth century— Augusta Webster’s “Lota” (1867), Violet Fane’s Denzil Place: A Story in Verse (1875), Emily Pfeiffer’s The Rhyme of the Lady of the Rock, and How It Grew (1884), and Emily Hickey’s “Michael Villiers, Idealist” (1891)—this dissertation expands our understanding of both women’s poetry and the verse novel in the Victorian period. It demonstrates that the genre was taken up in multiple ways after Aurora Leigh by women poets who, like EBB, addressed urgent and controversial social and political issues—such as parliamentary enfranchisement, adultery, marital rape, political sovereignty and land use in the Scottish Highlands, as well as socialism and the Irish Question— through inventive and complex generic combinations. This dissertation does not outline a teleological development of genre but, rather, recovers works through case studies that offer microhistories of verse novels at particular historical moments in order to expand the canon and definition of the Victorian verse novel. / Graduate / 2020-04-25

Depuis leurs découvertes dans les années 60 par Dewar, les composés BN-hétérocycliques ont subi un développement croissant, s’accentuant pendant la dernière décennie. Ce travail de thèse mené en collaboration avec le Pr S-Y LIU de Boston Collège (États-Unis) et le Pr L. WEBER de l’Université de Bielefeld (Allemagne), a permis la synthèse, ainsi que la caractérisation par spectroscopie photoélectronique à rayonnement UV de nouveaux systèmes. Dans une première partie représentée par les chapitres II, III et IV, nous abordons l’étude de la structure électronique des composés suivants : 1,2-dihydro-1,2-azaborine (1), N-Me-1,2-BN-toluene (2), N-Me-1,3-BN-toluene (3), 1,2-dihydro-1-aza-2-boranaphtalene (4), 1,2-dihydro-1-aza-2-boranthracene (5), 1,2-dihydro-1-aza-2-boranthracene (6), 1,2-dihydro-1-aza-2-boraphenanthrene (7), 1,3,2-benzodiazaborole (8), 1,9,8-benzodiazaborole (9), N-tert-butyl[1,3,2]diazaborolo[1,5-a]-pyridine (10), 1,3,2-trihydro[1,3,2]diazaborolo[1,5-a]-pyridine (11). Afin de compléter les propriétés physico-chimiques de ces nouveaux systèmes et d’aider à l’interprétation des spectres photoélectroniques, l’utilisation de calculs quantiques tels que la théorie de la fonctionnelle de la densité (DFT), la théorie fonctionnelle de la densité en fonction du temps (TD-DFT), la fonction de Green (OVGF), la méthode du troisième ordre partiel (P3), ou encore l’interaction de configuration (SAC-CI) ont été utilisées. Dans le Chapitre V, nous présentons une étude comparative entre les énergies ionisations théoriques et expérimentales. / Since the Dewar’s discovering in 60 years, the BN-heterocycles has experienced an important development during the last decade. This thesis presents our work on the synthesis and on the electronic structure characterization by Ultra-Violet photoelectron spectroscopy (UV-PES), followed in collaboration with the Pr SY LIU from the Boston College (USA) and the Pr L. WEBER from the University of Bielefeld (Germany). The first part corresponding to the chapter II, III and IV, describe the electronic structure analysis of: 1,2-dihydro-1,2-azaborine (1), N-Me-1,2-BN-toluene (2), N-Me-1,3-BN-toluene (3), 1,2-dihydro-1-aza-2-boranaphtalene (4), 1,2-dihydro-1-aza-2-boranthracene (5), 1,2-dihydro-1-aza-2-boranthracene (6), 1,2-dihydro-1-aza-2-boraphenanthrene (7), 1,3,2-benzodiazaborole (8), 1,9,8-benzodiazaborole (9), N-tert-butyl[1,3,2]diazaborolo[1,5-a]-pyridine (10), 1,3,2-trihydro[1,3,2]diazaborolo[1,5-a]-pyridine (11). In order to provide more information on the physical chemistry properties and to interpret the photoelectron spectra, the quantum chemical calculations of ionization energies have been followed using the Density Functional Theory (DFT), the Time-Dependent Density Functional Theory (TD-DFT), the Outer Valence Green’s Function (OVGF), the Partial third order (P3), the Symmetry Adapted Cluster-Configuration Interaction (SAC-CI). Moreover, the comparative analysis of theoretical and the experimental ionization energies are presented.

La caractérisation des ions multichargés dans le plasma d'une source ECR utilise comme moyen de diagnostic non perturbatif la spectroscopie dans le domaine de l'ultraviolet sous vide. Dans ce type de source, les électrons sont chauffés par interaction avec une onde HF et confinés magnétiquement par effet miroir. Les électrons interagissent avec l'onde HF à la résonance cyclotronique au cours de leurs allers et retours successifs dans le miroir magnétique. Ils acquièrent ainsi l'énergie nécessaire pour dépasser les potentiels d'ionisation de chacun des états de charge de l'élément injecté dans la source. L'amélioration des performances d'une source ECR en courant d'ions extraits et en états de charge obtenus passe par la connaissance des grandeurs physiques fondamentales des espèces présentes dans le plasma. Le but de la spectroscopie V.U.V. est de déterminer la densité et la température électronique d'une part et la densité et le temps de confinement des ions d'autre part. Nous avons utilisé des galettes de micro canaux comme détecteurs de position sur un spectromètre à incidence rasante muni d'un réseau de 3 mètres de rayon de courbure comportant 600 traits/mm. On effectue l'étalonnage en intensité de l'ensemble réseau-détecteur par 2 méthodes. Ce sont les méthodes des rapports de branchement et d'échanges de charge. L'identification des raies émises par le plasma qui regroupe l'ensemble des états de charge possibles de l'élément étudié est nécessaire pour faire une étude exhaustive de l'état du plasma. Finalement, la détermination des paramètres du plasma sur la base théorique de 2 sources ECR disponibles au laboratoire a été réalisée pour la première fois.

<p>Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals.</p><p>In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases.</p><p>The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.</p>

Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals. In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases. The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques persistants potentiellement mutagènes et cancérigènes. Leur transfert de l'atmosphère vers les écosystèmes, notamment vers les plantes, conditionne leur entrée dans les chaines alimentaires mais les modalités de ce transfert restent encore mal connues. L'objectif de ce travail était donc de caractériser le transfert et d'identifier les effets biologiques des HAP atmosphériques sur un système sol-plante-microorganismes symbiotiques.Un dispositif expérimental a été conçu afin de recréer en laboratoire une pollution atmosphérique par les HAP avec comme HAP modèle le phénanthrène (PHE). Le dispositif a fait l'objet d'une validation et d'une calibration élaborée de manière originale par une double approche mêlant l'expérimental à la simulation mathématique. Les niveaux d'exposition en polluant (150 µg m-3), contrôlés par des échantillonneurs passifs, se sont avérés pertinents par rapport aux conditions in situ. Ce dispositif a donc été utilisé pour exposer durant un mois des microsystèmes sol-plante-microorganismes au PHE par voie atmosphérique.Les différentes études ont mis en évidence un transfert du PHE depuis l'atmosphère vers tous les compartiments du microsystème, avec une accumulation majeure vers les feuilles de trèfle ou de ray-grass (respectivement 170 et 70 µg g־ ¹MS) et un transfert phloémien vers les racines est suggéré. Chez le trèfle, la mycorhization n'a pas été affectée, tandis que le nombre de nodules actifs a diminué de manière significative. Contrairement aux racines, la biomasse aérienne du trèfle a été significativement affectée (environ - 25%) par l'exposition au PHE atmosphérique, suggérant un impact sur le métabolisme carboné de la plante. Une expérience de marquage des trèfles au ¹³C-CO2 a effectivement montré un impact négatif du PHE atmosphérique sur la croissance, l'allocation de biomasse et l'allocation carbonée. Pour conclure, ces études ont permis non seulement de caractériser les effets biologiques et physiologiques des HAP atmosphériques sur les végétaux mais également de proposer l'utilisation du potentiel mycorhizien comme indicateur de pollution atmosphérique par les HAP.

In this study, silver nanorods and nanospheroids were prepared both in aqueous solution and on the surface of glass slides through seed-mediated growth approach at room temperature and used as a surface enhanced Raman scattering (SERS) substrate. The synthesis of metallic nanorods was started with the production of silver nanospheres as seed utilizing sodium borohydride and trisodium citrate as reducing and capping agents, respectively. These seeds were then added to a growth solution containing additional silver salt, ascorbic acid and cetyltrimethylammonium bromide (CTAB.) Nanorod preparation conditions were first optimized in solution phase. The plasmon absorption of the formed nanocrystals was monitored by UV-Visible spectrometry. The largest red shift in the longitudinal plasmon resonance absorption of silver nanostructures was tried to be achieved in order to realize the highest electromagnetic enhancement in Raman measurements. The images of the formed nanorods were recorded using field emission scanning electron microscopy (FE-SEM). The optimized colloidal growth conditions were adopted for the growth of nanorods on the surface of the glass substrate. Sol-gel coated glass slides were used in order to increase the porosity on the surface for an effective seeding process. We reported the development of a novel SERS substrate prepared by growing silver nanorods directly on the surface of glass surface without using any linker molecule. The SERS performances of the nanorod growth surfaces were evaluated with crystal violet (CV), brilliant cresyl blue (BCB) and benzoic acid (BA). Some modifications such as the increase in the AgNO3 concentration in the growth solution and the addition of hydrocarbons to the growth solution were investigated for the enhancement of the SERS signal. The intense spectra obtained for the model compounds demonstrated the efficiency of the prepared substrate for the SERS enhancement and its potential as a SERS detection probe for chemical and biological analysis.

A dynamic mathematical model was developed to simulate the response of polyacrylamide gel (PAG) dosimeters to a single spherical radioactive brachytherapy seed. Simulations were conducted for a high dose-rate (HDR) seed using 192Ir and a low dose-rate (LDR) seed using 125I. The model is able to predict the amount of polymer formed, the crosslink density, and the volume fraction of aqueous phase as a function of radial distance and time. Results show that PAG dosimeters can provide accurate HDR brachytherapy dosimetry at distances larger than 4 mm from the centre of the seed but will give poor results for LDR due to monomer diffusion. Experiments were conducted to evaluate the potential for using pentacosa-10,12-diynoic acid (PCDA) as the reporter molecule in micelle gel dosimeters for optical computed tomography (CT) readout. Several gels containing PCDA that was solubilized using sodium dodecyl sulfate (SDS) responded to radiation by changing from colourless to blue. Unfortunately, all phantoms that showed colour changes were turbid, making them unsuitable for optical CT scanning. Several techniques were used to produce transparent gels containing PCDA but none of these gels responded noticeably to radiation. Only turbid gels with precipitated PCDA responded, indicating that the colour change was due to oligomerization within PCDA crystals and that PCDA molecules solubilized in micelles did not undergo oligomerization. As a result, PCDA is not suitable for use in radiochromic micelle gel dosimeters. A new recipe for a radiochromic leuco crystal violet (LCV) micelle gel dosimeters with enhanced dose sensitivity was developed for optical CT readout. The recipe contains LCV, trichloro acetic acid (TCAA), Cetyl Trimethyl Ammonium Bromide (CTAB), 2,2,2-Trichloroethanol (TCE), and gelatin. Experiments were conducted to improve understanding about interactions between the different components of LCV micelle gel, highlighting the importance of pH on dose sensitivity and transparency. Results also showed the effectiveness of chlorinated compounds in improving dose sensitivity. Statistical techniques were used to build empirical models that were used to optimize the gel recipe. Additional testing in larger phantoms will be required to assess the effectiveness of the proposed gel for clinical dosimetry. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2014-03-27 11:11:47.655

Le sujet de la thèse initié dans le cadre de l'ANR UV-Borate s'inclut dans le projet UV-Conversion labellisée par 2 pôles de compétitivité (Matériala - Lorraine - et Route des lasers - Aquitaine -) soumis à l'ANR en 2011. Les études se portent particulièrement sur les borates YxLaySc4-(x+y)(BO3)4 (LYSB) et YAl3(BO3)4 (YAB), cristaux Optiques Non Linéaires (ONL) possédant la même structure cristallographique (R32). La croissance de ces cristaux est effectuée par les collaborateurs industriels et universitaires de l'ANR. Ces deux matériaux présentent en effet des possibilités de conversion de fréquence jusqu'à des longueurs d'onde λ < 300 nm, de plus une non hygroscopicité procure une plus grande durée de vie des échantillons et par conséquent un net intérêt pour les applications industrielles. L'endommagement laser étant lié à l'absorption et ainsi, en partie, aux impuretés, une étude de la qualité cristalline et de l'homogénéité de nos cristaux a été effectuée. Les résultats ont permis de relier des défauts de structure (dislocations et etch pits) à la croissance de la maille rhomboédrique via des caractérisations par ombre portée (Photography Schlieren) et par attaque chimique suivi d'une observation par microscopie optique, MEB et MFA. Par ailleurs, des études théoriques et expérimentales d'accord de phase (détermination de θ et φ) lors de conversions de type I principalement ont été réalisées sur les cristaux de YAB, LYSB ainsi que sur des cristaux de référence tel que β-BaB2O4 (β-BBO). L'aspect de l'endommagement laser dans les matériaux ONL a été abordé dans les locaux de l'Institut Fresnel de Marseille au sein de l'équipe Interaction Laser Matière (ILM) sur des échantillons de Li2B4O7 (LTB). L'équipe a effectivement développé un dispositif de mesure de la probabilité d'endommagement laser et de mesure de tenue du seuil d'endommagement laser des matériaux optiques. Par ailleurs, un effort a été mené dans la conception d'un dispositif de mesure de la transmission optique et absorption à température ambiante et aux basses températures afin de révéler des défauts absorbants. Des premiers résultats ont été obtenus et discutés sur des échantillons de β-BBO et LYSB.

The persistence of biofilms in hospital settings are associated with Healthcare Associated Infections (HCAI), causing increased morbidity, mortality and healthcare costs. The resistance of biofilms against commonly used hospital disinfectants has been well reported. Metal and metal oxide nanoparticles (NP) such as silver (Ag), copper (Cu), zinc oxide (ZnO) and copper oxide (CuO) exhibit antimicrobial properties against various pathogens. Methods: Biofilm formation of Pseudomonas aeruginosa and Staphylococcus aureus in a Centre for Disease Control (CDC) biofilm reactor and a 96 well plate was compared. A three stage approach including Minimum Biofilm Reduction Concentration (MBRC), R2 values and log(10) reductions was used to assess the efficacy of Ag and ZnO NPs both alone and in combination against P. aeruginosa and S. aureus biofilms. Atomic Absorption Spectroscopy (AAS), Scanning Electron Microscopy (SEM) and Confocal Laser Scanning Microscopy (CLSM) was used to further assess the antimicrobial ability of the metal and metal oxide NPs. The prevention of P. aeruginosa and S. aureus adherence on Ag and ZnO thin film coating on silicon (Si) surfaces was also investigated, as well as icaC, ebpS and fnbB gene expression in S. aureus biofilms. Results: The CDC biofilm reactor demonstrated to be the most effective method for P. aeruginosa and S. aureus biofilm production in comparison to 96 well plates, with lower standard errors of the mean (SE) and higher replicability. Individual MBRC of ZnO and Ag NPs in suspension were 256 and 50 µg/ml for P. aeruginosa and 16 and 50 µg/ml for S. aureus respectively. The concentrations in combination were reduced by at least a half, with concentrations of 32/25 µg/ml of ZnO/Ag NPs in suspension resulting in a significant (p ≤0.05) reduction of 3.77 log(10) against P. aeruginosa biofilms and 8/12 µg/ml of ZnO/Ag NPs in suspension resulted in a 3.91 log(10) (p ≤0.05) against S. aureus biofilms. Both combinations showed an additive effect. Time point analysis confirmed that a 24 hour treatment is vital for any significant (p ≤0.05) antimicrobial activity. AAS data suggested that the Ag+ ions quenched Zn2+ ions, therefore the antimicrobial efficacy of the combination is mainly due to Ag+ ions. Damage of the biofilms from Ag and ZnO NPs was observed in the SEM imaging and energy dispersive X-ray (EDX) analysis confirmed the adherence of Zn and Ag within the biofilms. CLSM imaging showed dead (red) cells of P. aeruginosa and S. aureus biofilms throughout the depth of the biofilm. P. aeruginosa formation was reduced by 1.41 log(10) and 1.43 log(10) on Ag and ZnO thin film coatings respectively. For S. aureus, a reduction of 1.82 log(10) and 1.65 log(10) was obtained for Ag and ZnO coating respectively. Only low levels of ribonucleic acid (RNA) were achieved so no further gene analysis could occur. Conclusion: Reductions of ≥3 log(10) were observed for P. aeruginosa and S. aureus biofilm treatment with ZnO/Ag NP suspensions. It can be concluded that the ZnO/Ag NP suspensions had greater antimicrobial activity than Ag and ZnO coated surfaces owing to large concentrations of Ag+ and Zn2+ ions acting upon the biofilms. The slower release of ions from coated surfaces suggest an inadequate concentration of ions in the media, which are therefore unable to prevent biofilm formation as rapidly as NP suspensions, however provide a sustained release of ions over time. The results from this investigation propose that Ag and ZnO NPs in suspension could be a potential alternative to disinfectants for use in nosocomial environments against P. aeruginosa and S. aureus biofilms.