Les effets de la force magnétique orthogonale (MF) sur le processus d'électropolymérisation de l'aniline dans une solution d’acide chlorhydrique ont été étudiés.La voltammétrie cyclique (CV), la chronoampérométrie et la spectroscopie d'impédance électrochimique (EIS), ont été utilisées pour examiner le processus de transfert de masse et le processus de réaction électrochimique. Différentes techniques, telles que la microscopie électronique à balayage (MEB), la microscopie à force atomique (AFM) et la diffraction à rayons X (XRD) ont été utilisées pour caractériser les revêtements préparés.Les résultats montrent que la vitesse de dépôt augmente avec la force magnétique et la concentration du monomère d’aniline en raison de la convection magnétique et les propriétés magnétiques du radical.L’imagerie MEB et l'analyse topologique ont révélé que, sous MF les films sont essentiellement composés de gonflement des nanofibres et des ilots des polymères qui sont bien répartis sur la surface. Les études de diffraction à rayons X révèlent une amélioration de la cristallinité des couches, sans orientations préférentielles.Mots clés: polymère, polyaniline, aniline, champ magnétique, électropolymerisation, impédance électrochimique, DFT, susceptibilité magnétique. / The effects of static orthogonal magnetic force (MF) on the electropolymerization process of aniline from hydrochloric bath have been investigated. Cyclic voltammetry (CV), Chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques were used to examine the mass transfer process and electrochemical reaction process. Different techniques, such as Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and X-ray Diffraction (XRD) were employed to characterize the prepared coatings. The results show that deposit rate increased with increasing MF and aniline monomer concentration due to the magneto-convection involving the mass transport and radical magnetic properties. SEM imagery and topological analysis revealed that under MF the films are essentially composed of swelling of the nanofibers and ilots of polymers that are well distributed on the surface. The XRD studies reveal an enhancement of the crystallinity of the coatings without any preferential orientations.Keywords: Polymers, Polyaniline, aniline, Magnetic fiels, Electropolymerization, electrochemical impedance, DFT, magnetic susceptibility .

Au cours de ces travaux de thèse, une voie de synthèse de différentes cyclopropylamines a été développée. Leur fonctionnalisation a ensuite été mise en œuvre à l’aide de réactions de métallation ou de couplages croisés catalysés au palladium. Les cyclopropylamines ainsi fonctionnalisées furent alors soumises à des conditions de cyclisation dans le but d’obtenir tout ou partie d’une structure 14-azastéroïde. Si notre modèle, dont la synthèse s'est construite autour d’une aniline, nous a permis d'obtenir la structure des cycles B, C et D d'un 14-azastéroïde, nous n'avons pas été en mesure d'obtenir la structure dans sa totalité en partant d'une naphtylamine. Nous avons cependant dans ce cas obtenu un arrangement original pentacyclique comportant un motif cyclobutane. Nous avons enfin réalisés des travaux sur des réactions de type condensation, principalement entre divers dérivés d'aniline et le pyruvate d'éthyle. Lors des résultats préliminaires, nous avons cette fois encore majoritairement obtenu des structures comportant un motif cyclobutane et non celles se rapprochant des azastéroïdes. / In the course of this thesis, a method to synthesize new cyclopropylamines was developed. Their functionalization was then implemented using metallation reactions or palladium catalysed cross-coupling reactions. The functionalized cyclopropylamines were then subjected to cyclization conditions in order to obtain all or part of a 14-azasteroid structure. Our synthetic model, which was built around an aniline moiety, allowed us to obtain the structure of the B, C, and D rings of a 14-azasteroid. Unfortunately, when this strategy was applied to synthesize the complete tetracyclic backbone of the 14-azasteroid from a naphthylamine, the reaction failed to give the same results. We have however in this case reached an original pentacyclic framework containing a cyclobutane motif. Finally, we studied condensation-type reactions between various derivatives of aniline and ethyl pyruvate toward synthesis of the desired structure. Preliminary results show formation of structures with a cyclobutane motif.

The compound p-(2-hydroxyethylsulfone) aniline was isolated from a reduced solution of a fiber-reactive azo dye. The identity and purity of this product was assessed through elemental composition analysis, high performance liquid chromatography (HPLC), gas chromatography/mass spectroscopy (GC/MS), and nuclear magnetic resonance spectroscopy (NMR). The toxicity of this purified compound was measured with Microtox and Daphnia pulex tests. Microtox tests were also performed on compounds with similar structures to p- (2-hydroxyethylsulfone) aniline. Wastewater samples containing textile dye wastes from a Publicly Owned Treatment Works (POTW) that treated textile dye wastes were monitored for the presence of p-(2-hydroxyethylsulfone) aniline using HPLC. Microtox testing was performed on these samples. Analytical tests confirmed the identity and purity of p-(2-hydroxyethylsulfone) aniline as the reduced product. Microtox tests revealed the concentration at which 50% of the light output was reduced (EC₅₀) after 5 minutes of exposure was 12.8 mg/L. Daphnia pulex testing yielded the concentration which was lethal to 50% of the tested organisms (LC₅₀) to be 113 mg/L. The 5-minute Microtox EC₅₀, values of aniline, sulfanilamide, 2-hydroxyethylsulfone, and 4-ethylaniline were 106.7, 8.15, >80, and 2.05 mg/L, respectively. The reduction product, p-(2-hydroxyethylsulfone)aniline, was not detected in textile-containing wastewater from the Martinsville POTW. The Microtox EC₅₀, for this wastewater, ranged from 6.05 to >75 mg/L. / Master of Science

It is ideal to theoretically predict the activity of a catalyst. It has been recognized that not only the type of metal, but also its atomic size plays an important role in catalysis. In the past, atomic clusters have been created by sputtering from a sacrificial metal plate and then using a mass selector to choose cluster sizes from 1-233 atoms of gold. This approach has practical limitations. In this thesis, I describe a procedure by which atomic clusters of gold containing 1-8 atoms are deposited in polyaniline as an isolation matrix. My atomic deposition follows a cyclic pathway. Atomic clusters of palladium and atomic alloys of gold and palladium are also deposited in polyaniline using the same process. It is to show that this method will also work for other metals. These composite materials are characterized, and the catalytic activity for alcohol oxidation is evaluated. This thesis is divided into seven chapters. The first chapter discusses the chemistry of polyaniline for using gold and palladium as catalysts. The technique developed to deposit the atomic clusters is discussed in the second chapter. This technique deposits one atom of metal per imine site on polyaniline, per cycle. The cycle is repeated n-times until a cluster of specified size, Mn, and composition has been synthesized. It is known that polyaniline plays an important role in stabilization of the formed clusters which prevents their aggregation. The optimization of this technique is the topic of the third chapter along with the description of how these composite films are produced. To end this chapter, the composite films are characterized by cyclic voltammetry, Kelvin probe, and X-ray photoelectron spectroscopy. In chapters 4 and 5, the catalytic activity of the polyaniline/gold composites for the oxidation of alcohols in alkaline media using cyclic voltammetry is evaluated. In chapter 4, the correlation of the electrochemical activity for the oxidation of n-PrOH with the odd-even pattern from the calculated HOMO-LUMO gap energies for the same size clusters is shown. It is shown that the infrared spectrum of polyaniline with different sizes of atomic gold clusters also follows the odd-even pattern. Chapter 5 expands on the discussion of the catalytic oxidation of alcohols. The oxidation of methanol, ethanol, propanol, and butanol is surveyed. The peak currents are again dominated by the odd-even pattern. In chapter 6, the versatility of the atomic deposition cycle is shown by depositing atomic palladium clusters. The peak currents for the oxidation of n-PrOH by these palladium composite films again follows the predicted pattern of the calculated HOMO-LUMO gap energies for atomic palladium clusters. This chapter also explores bimetallic atomic clusters of gold and palladium. The results indicate that the catalytic activity depends on the orientation of the cluster in the polyaniline matrix. Chapter 7 discusses the oxidation of methanol, ethanol, and isopropanol on AunPd1 bimetallic atomic clusters. The addition of palladium in the cluster increases the peak current densities for the oxidation of both alcohols except for the most stable of the atomic gold clusters, while it inactivated the electrodes for isopropanol. The possible future work for this project is discussed in chapter 8. Overall, this thesis has developed a novel and unique technique for depositing atomic metal clusters into a polyaniline matrix. The technique is versatile enough to deposit atomic metal clusters other than gold, as shown by creating atomic palladium clusters and atomic bimetallic clusters of gold and palladium. This is extremely useful, since this single technique can produce many different types of atomic catalysts. The composite materials have been shown to be catalytically active for the oxidation of alcohols in alkaline media. This indicates a significant improvement to conserve precious metals while still retaining a high catalytic activity.

Aniline Black, a polymer containing p-benzoquinodiimine groups, was synthesized chemically or electrochemically by the oxidation of aniline. The polymer salts showed the conductivity of 10⁻¹-10⁻³ ohm⁻¹cm⁻¹. Polymers containing anthroquinodiimine units were also prepared by polycondensations. The syntheses of model compounds containing p-benzoquinodiimine were attempted. Multiazobisphenol monomers were synthesized. 4,4'-(3,3'-Dimethyl-4,4'-biphenylenebisazo) bisphenol 7, 4,4'-[azobis(p-phenyleneazo)] bisphenol 8, and 4,4'-(2-methoxy-1,4-phenylenebisazo) bisphenol 10 displayed liquid crystal (l.c.) properties, while model derivatives of 7, 8, and 4,4'-(4,4'-stilbenebisazo) bisphenol 9 did likewise. Monomers and derivatives of 4-[(4-hydroxyphenyl)azo]-1-naphthol 5, and 4,4'- [oxybis(p-phenyleneazo)] bisphenol 6 showed no l.c. behavior. New thermotropic polyesters based on these multiazobisphenols were synthesized. Sebacates of 5, 6, 7, 8, and 10 showed l.c. behavior, while polymers based on isophthalic or 5-t-butylisophthalic acid did not do so. Polyformals were also synthesized from these momoners, only that of 4 showed weak l.c. behavior. The correlation between the structure of these polymers and their tractabilities, electrical properties, liquid crystal behaviors was studied. Polymers and copolymers containing p-azoarylene and p-azoxyarylene groups were synthesized by oxidative coupling of various aromatic diamines. Films were cast directly from the reaction mixtures or from the polymer solution. The films were n-doped by sodium naphthalide or p-doped by iodine. They showed electrical conductivities of 10⁻⁴ to 10⁻⁵ ohm⁻¹cm⁻¹. AB monomers containing dipolar p-phenyleneazo groups were synthesized: 4-(4-hydroxy-2-methoxyphenylazo) benzoic acid 21, 4-[4-(4-hydroxy-2-methoxyphenylazo)-2-methoxyphenylazo] benzoic acid 22, and 4-(4-hydroxy-2-methoxyphenylazo)-3-nitrobenzoic acid 23. The monomers were polymerized by direct polycondensations. The polyester synthesized from 21 formed a red, transparent film. A polymethacrylate containing dipolar p-phenyleneazo groups in the side chains was also prepared by the free radical polymerization of 1- [3-methoxy-4-(p-nitrophenylazo)-phenoxy] hexyl methacrylate 28.

De nos jours, réussir à contrôler la microstructure de la phase active des catalyseurs hétérogènes reste encore un défi d’envergure. Le présent travail s’inscrit dans cette mouvance en proposant de valoriser l’utilisation de clusters moléculaires comme précurseurs métalliques. Ces entités organométalliques comprenant au moins trois atomes métalliques (identiques ou non) en leur cœur apparaissent comme des candidats de choix pour contrôler la taille et la composition chimique des particules métalliques supportées à l’échelle nanoscopique. L’objectif de la présente thèse est de déterminer si l’utilisation de clusters moléculaires en présence d’un support carboné approprié permet d’obtenir ce contrôle. Tout d’abord, des clusters carbonylés de palladium de la littérature ont été synthétisés et une nouvelle voie de synthèse en une étape de ces entités a été découverte. Ensuite, le support carboné de départ a été dérivatisé afin d’y introduire des sites d’ancrage pour les clusters (phosphines chélatantes). Dans la troisième partie du travail, les clusters synthétisés ont été incorporés sur le support fonctionnalisé et sur celui de départ. L’obtention de nanoparticules supportées bien dispersées a démontré l’intérêt d’utiliser des clusters moléculaires comme précurseurs en présence d’un support fonctionnalisé. Les mécanismes d’ancrage ont également été étudiés et il a été prouvé que les clusters se fixent au support de manière covalent par échange de ligands. Enfin, les clusters supportés ont été activés et les catalyseurs Pd/C formés ont été testés dans l’hydrogénation du nitrobenzène en aniline. Les catalyseurs se trouvent être actifs dans cette réaction mais aucune corrélation « structure-activité » n’a pu être mise en évidence.

This research is to synthesize PANI (polyaniline) thin film for polymer organic solar cells as a hole transport layer on the top of ITO substrate by using electrochemical (cyclic voltammetry) method. The device structure is ITO (150 nm) / PANI (50 nm) / P3HT: PCBM (100 nm) / Al (200 nm). We investigated surface morphology, conductivity, and light transmission of the PANI thin film from different aniline monomer concentration and studied the factors on device efficiency, also compared with the device structured with hole transport layer PEDOT:PSS. In this study, we found PANI thin films synthesized with different aniline monomer concentration, their light transmission over 80% at the range of 450 nm ~ 650nm wavelength and the conductivity up to 0.6 S/cm. It shows that PANI thin film suitably act as hole transport layer. In addition, we found morphology of PANI thin film that varied with different aniline monomer concentration. The power conversion efficiency of the device mainly affected by morphology with different aniline monomer concentration. Comparing to other parameters of concentration, the 0.3M aniline monomer concentration polymerized PANI thin film owned the most appropriate surface morphology, and the power conversion efficiency up to 1.76%.

Une série d'anils originaux, de groupe d'espace non centrosymétrique actifs en génération de second harmonique (GSH) et photochromes à l'état cristallin, a été obtenue. Un des composés présente une GSH de 11 (vs urée), un deuxième une photo conversion de 16% sous irradiation UV et un troisième une quasi bistabilité (durée de vie de 460 j pour la forme métastable). La photo commutation réversible de la GSH peut aller jusqu'à 50%. Des études sur monocristaux orientés sous microscope confocal ont permis de corréler anisotropie de GSH et structure déterminée par diffraction de rayons X, via des calculs ZINDO. Elles ont aussi montré que la réaction photo induite créait un désordre dans le cristal, entraînant la commutation de GSH, mais que l'ordre initial était recréé après réaction retour. La spectroscopie a mis en évidence le mécanisme du photochromisme et un temps de commutation de 250 ps à l'état solide, montrant ainsi le potentiel de ces matériaux comme interrupteurs optiques rapides.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

A series of 31 sulfur-nitrogen donor ligands and 64 metal(II) complexes have been investigated. The thiomethylated aniline ligands 2–(methylthiomethyl)aniline 2MT and 2–(methylthio)aniline 2MA were synthesized with their substituted derivatives (-Me, -MeO, -Cl, -Br, -NO2) to serve as chelating agents. These ligands behave as bidentate ligands with SN donor group with Co(II), Ni(II) and Cu(II). The Co(II) and Ni(II) complexes have the ML2Cl2 molecular formula while the Cu(II) complexes formed with MLCl2 stoichiometry where L is the bidentate ligand. The ligands and their metal(II) complexes have been characterized by elemental analysis and with spectroscopic techniques. The trend observed in the NMR spectra and IR frequencies of the thiomethylated compounds shows there is a significant difference between the 2MT and 2MA series as a result of sulfur lone pairs extending the conjugation of the aromatic ring in the case of the latter. The effect of the position and electronic nature of ring substituent on the NMR shifts of the amine protons is discussed. The 6- and 5-membered chelate complexes formed by the 2MT and 2MA ligands respectively do not show significant diversity in their spectroscopic properties. From the elemental analysis for the Co(II) and Ni(II) complexes, their compositions reveal 1:2 M:L stoichiometry with 2 chlorine atoms from the respective metal salts. In addition, the spectroscopic data are largely indicative of tetragonally distorted structures for these solid complexes. The X-ray crystallography data reveal the Cu(II) complexes exist as square pyramidal dimers and with long Cu–Cl equitorial bonds fit into the tetragonally distorted octahedral structure. The electrolytic nature of Co(II) and Cu(II) complexes in DMF were found to be similar, they behave as non electrolytes in contrast to Ni(II) complexes which are 1:1 electrolytes. The electronic spectra of these metal(II) complexes were found to be different for both their solid forms and in solutions of DMF and DMSO and this has been discussed. The thiomethylated aniline ligands possess the amine and thioether groups which are present in many known biologically active compounds, hence the biological activity of the ligands and their metal complexes were tested against three strains of bacteria and one fungus. The methoxy-substituted derivatives were found to possess better inhibitory activity and this was similarly reflected in the metal(II) complexes. The activity of the complexes can be said to be in the order, Cu(II) > Co(II) > Ni(II). The Schiff-base derivatives were prepared from the ligands and para-methoxysalicylaldehyde and their Cu(II) complexes were synthesized in order to determine their biological activity. The Schiff-base ligands were found to be less active than their parent ligands. The Cu(II) complexes are not soluble in water, DMSO or DMF, as a result and could not be evaluated for their biological activity. Based on the good results from the antimicrobial evaluation, the antiplasmodial activity of some of the Co(II), Ni(II) and Cu(II) complexes of the thiomethylated ligands against Plasmodium falciparum (FCR-3) was determined. At 50 μM concentration level, the Cu(II) complexes show activity equal or better than the prophylactic chloroquine. The Cu(II) complexes with the methoxy-substituted demonstrated exceptional activity but their Co(II) and Ni(II) analogues did not show any activity. The cytotoxicity of the active Cu(II) complexes at 50 μM concentration was determined against the breast cancer cell line (MDA-MB-231). The compounds destroyed the cancer cell in the range of 28–40%, thus showing their preferred activity against the parasitic cell instead of the cancer cell. The selectivity demonstrated by these compounds have shown them to be potential antimalarial agents and this could be further investigated.