Academic literature on the topic 'Onium compounds'

Cyclic amino(ylide)carbenes (CAYCs) are the ylide-substituted analogues of N-heterocyclic Carbenes (NHCs). Due to the stronger π donation of the ylide compared to an amino moiety they are stronger donors and thus are desirable ligands for catalysis. However, no stable CAYC has been reported until today. Here, we describe experimental and computational studies on the synthesis and stability of CAYCs based on pyrroles with trialkyl onium groups. Attempts to isolate two CAYCs with trialkyl phosphonium and sulfonium ylides resulted in the deprotonation of the alkyl groups instead of the formation of the desired CAYCs. In case of the PCy3-substituted system, the corresponding ylide was isolated, while deprotonation of the SMe2-functionalized compound led to the formation of ethene and the thioether. Detailed computational studies on various trialkyl onium groups showed that both the α- and β-deprotonated compounds were energetically favored over the free carbene. The most stable candidates were revealed to be α-hydrogen-free adamantyl-substituted onium groups, for which β-deprotonation is less favorable at the bridgehead position. Overall, the calculations showed that the isolation of CAYCs should be possible, but careful design is required to exclude decomposition pathways such as deprotonations at the onium group.

Aromatic onium salts are known compounds with well understood photoactivity. Their use as acid-generating species has, in the last few years, improved the performance of photoresists, particularly for microelectronics applications. There has, however, been little research dedicated to the use of these photoinitators in aqueousrdevelopable resists. This work investigates the feasibility of employing onium salts in the formulation of resists suitable for aqueous development. The ability of the onium salts to photoinitiate the cationic polymerization or cross-linking of epoxide residues was exploited using water-soluble or water-dispersible copolymers containing glycidyl methacrylate (GMA). The comonomers included N-vinyl pyrrolidinone (NVP), NN-dimethylacrylamide (DMAc) and 2-hydroxyethyI methacrylate (HEMA). Various copolymers were prepared by radical copolymerization to low conversion, typically in chloroform. Several onium salts were prepared by literature methods and their efficiency examined using a model copolymer. The photoacid generator (PAG) that performed best was then used in the examination of the aqueous systems.

Abstract 1,3-Dioxin-4-ones from Ketones Onium salt and acid catalyzed addition of di-ketene to (-)-menthone gives improved yields of 2 and 3. Excess of diketene leads to diastereomeric mixtures of compounds 4 and 6 from menthone and menthol, respectively.

Substituted 3-furylbenzoindolizines V-X were prepared via 1,3-dipolar cycloaddition of yields generated from the furan-related N-onium salts I-IV to dimethyl butinedioate, ethyl 3-(5-nitro-2-furyl)-2-propeonate, 1-phenyl-3-(5-nitro-2-furyl)-2-propenone, and 1-phenyl-2-nitroethylene. Structure of the compounds synthesized was confirmed by spectral data.

The effect of various plant growth regulators on leaf area development of Lantana camara L. subsp. camara was investigated under three photosynthetic photon flux (PPF) conditions (100%, 72%, and 34% light transmittance). The triazole compounds paclobutrazol (0, 50, 100, 200, and 500 mg·L-1) and triapenthenol (175, 350, 700, and 1400 mg·L-1), as well as the onium-type compounds mepiquat chloride (125, 250, 500, and 1000 mg·L-1) and chlormequat chloride (750, 1500, 3000, and 6000 mg·L-1), were applied as foliar spray solutions in each PPF level after pinching the plants. Leaf area, in general, decreased logarithmically as the concentrations of paclobutrazol and triapenthenol increased at all PPF levels. On the other hand, PPF reduction was found to increase leaf area of lantana plants treated with all concentrations of each regulator. Leaf area reduction of the paclobutrazol and triapenthenol treated plants at all PPF levels exceeded 60% compared with that of nontreated plants. However, the corresponding reduction was 22%, up to 51% for the plants treated with mepiquat chloride and chlormequat chloride. These results indicate that the triazole compounds have a greater effect on the reduction of lantana leaf area than the onium-type compounds. Chemical names used: (2RS, 3RS)-1-(4-chlorophenyl)-4, 4-dimethyl-2-(1H-1, 2, 4-triazol-1-yl) pentan-3-ol (paclobutrazol); (E)-(RS)-1-cyclohexyl-4,4-dimethyl-2-(1H-1, 2, 4-triazol-1-yl) pent-1-en-1-ol (triapenthenol); 1,1-dimethyl-piperidinium chloride (mepiquat chloride); (2-chloroethyl) trimethylammonium chloride (chlormequat chloride).

Microbial multidrug resistance presents a real problem to human health. Therefore, water-soluble polymers based on poly(aspartate-co-succinimide) were synthesized via reaction of poly(aspartate-co-succinimide) with bis-quaternary ammonium or quaternary salts. The resultant copolymers were characterized by various techniques such as FTIR, TGA, 1HNMR, 13CNMR and elemental microanalysis. Antimicrobial activities of the new onium salts were investigated against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Salmonella typhi, and the fungi; Candida albicans,Aspergillus niger, Cryptococcus neoformans and Aspergillus flavus by agar diffusion method. Antimicrobial activity was studied in terms of inhibition zone diameters, in addition to the estimation of minimal inhibitory concentration (MIC) of the prepared compounds. A. niger and E. coli were the most affected microorganisms among the tested microorganisms with an inhibition zone of 19–21 (mm) in case of biocides, (V) and (VII). The obtained results showed that the quaternary onium salts have higher activity compared to the aspartate copolymer with MIC concentrations of 25 mg/mL for (VII) and (V) and 50 mg/mL for (VI) and (IV).

The electrochemical reduction of a series of quaternary phenacyclammonium and tertiary phenacylsulphonium salts in aqueous solution at a mercury cathode has been investigated using polarography, coulometry, titrimetry and product analysis methods.

Orientador: Giselle Maria Marchi Baron
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba
Made available in DSpace on 2018-08-22T19:05:45Z (GMT). No. of bitstreams: 1 Palialol_AlanRodrigoMuniz_M.pdf: 12504444 bytes, checksum: a578af5941e733ad7dd18243b934355c (MD5) Previous issue date: 2013
Resumo: O objetivo desse estudo foi avaliar a resistência de união de cimentos resinosos experimentais contendo diferentes concentrações do sal de hexafluorfosfato de difeniliodônio (DPIHFP) à cerâmica reforçada por dissilicato de lítio, com ou sem aplicação do adesivo após o uso do silano. Para isso, cinco diferentes formulações de cimento foram confeccionadas utilizando como base os monômeros Bis-GMA e TEGDMA (na proporção 1:1 em massa) e 60% em peso de partículas silanizadas de vidro de bárioalumínio- silicato. O sistema fotoiniciador foi composto por 1 mol% de canforoquinona (CQ), 2 mol% de metacrilato de dimetilaminoetil (DMAEMA) e diferentes concentrações de DPIHFP: 0; 0,25; 0,5; 1 e 2 mol%, definindo assim, cinco formulações de cimentos resinosos experimentais. Como inibidor foi acrescido à mistura uma quantidade de 0,1 mol% de hidroxitolueno butilado e 60% em peso de partículas silanizadas de vidro de bário-alumínio-silicato foram incorporadas como carga inorgânica. Diante disso, a cimentação foi realizada com ou sem a aplicação do adesivo (Adper Scotchbond Multi- Purpose - Bond) estabelecendo assim, 12 grupos (n=7), sendo avaliados os cinco cimentos experimentais formulados e um cimento comercial (RelyX ARC). Foram confeccionados 84 espécimes de cerâmica IPS e.max (10 mm de comprimento x 10 mm de largura x 3 mm de espessura) e divididos, aleatoriamente, entre os 12 grupos previamente estabelecidos. Para todos os grupos foi realizado o condicionamento ácido da cerâmica (ácido hidrofluorídrico a 10%, 20 s) e aplicação de silano (RelyX Ceramic Primer). Logo após, os espécimes foram cimentados a blocos de resina fotopolimerizável Filtek Z250 (10 mm de comprimento x 10 mm de largura x 5 mm de espessura), utilizando os diferentes cimentos de acordo com o respectivo grupo, sob carga estática de 500 g, por 1 minuto. Para os grupos com utilização de adesivo, este foi aplicado 1 minuto após a aplicação do silano, sendo fotoativado através da cerâmica com LED 3a geração (Bluephase G2) a 1200 mW/cm2 juntamente com o cimento resinoso por 60 segundos. Após armazenamento (sob umidade relativa) em estufa por 24 horas a 37oC, as amostras foram seccionadas perpendicularmente à interface de união, gerando palitos de 1 mm2 (30 palitos por bloco) que foram submetidos ao ensaio de microtração em máquina de ensaio universal EMIC com velocidade de 0,5 mm/min. Foi realizado análise do padrão de fratura em lupa estereoscópica (Leica MZ75) com aumento de 40x e uma imagem representativa de cada padrão foi realizada em microscopia eletrônica de varredura. Os dados foram analisados através de Análise de Variância a dois critérios e teste Tukey, a um nível de significância de 5%. O cimento resinoso dual RelyX ARC apresentou os maiores valores de união, para os grupos com ou sem aplicação de sistema adesivo. Nos grupos com aplicação do sistema adesivo, os cimentos experimentais não diferiram estatisticamente entre si quanto à resistência de união. Nos grupos sem aplicação de adesivo, o cimento contendo 2mol% de DPIHFP obteve os menores valores de união. A aplicação do adesivo propiciou maiores valores de união somente para os cimentos RelyX ARC e DPIHFP 2mol%. De acordo com os resultados, pode-se concluir que a adição do sal de DPIHFP não foi capaz de aumentar os valores de união dos cimentos experimentais. O sistema de dupla ativação apresentou resistência de união à cerâmica superior aos cimentos experimentais fotoativados e a aplicação do adesivo promoveu o aumento dos valores de união apenas para os cimentos RelyX ARC e DPIHFP 2mol%
Abstract: The aim of this study was to evaluate the bond strength of experimental resin cements (ERCs) containing different concentrations of Diphenyliodonium Hexafluorphosphate (DPIHFP) salt to a lithium disilicate ceramic with or without the adhesive application after silane treatment. For this purpose, five ERCs were prepared using a Bis-GMA/TEGDMA (1:1 molar ratio) base compound with a 60% mass fraction of silanated Barium-Aluminum-Silicate glass fillers. The photoinitiator system was composed by 1 mol% of camphorquinone (CQ) 2 mol% of dimethylaminoethil methacrylate (DMAEMA) and different DPIHFP concentrations of 0, 0.25, 0.5, 1 or 2 mol%, resulting in five ERCs. As an inhibitor, 0.1mol% of hydroxyl butyl toluene was used. Therefore, the fixing protocol was performed with or without the application of adhesive (Scotchbond Multi-Purpose Adper - Bond) thereby establishing, 12 groups (n = 7), evaluating the five experimental resin cements and a commercial cement (RelyX ARC). Eighty four IPS e.max Press ceramic specimens (10 mm lenght x 10 mm width x 3 mm thickness) were fabricated and randomly divided among the 12 groups previously established. All the groups were etched with 10% hydrofluoric acid for 20 seconds and silane couple agent applied on the bond surface. After that, the specimens were fixed to photoactivated composite resin Filtek Z250 blocks (10 mm lenght x 10 mm width x 5 mm thickness), using different cements according to the respective group under static load of 500 g per one minute. For groups with adhesive application, this was applied 1 minute after applying the silane being cured by a third generation LED (Bluephase G2) together with the resin cement for 60 seconds. After storage for 24 hours at 37oC, the samples were sectioned perpendicular to the bond interface to obtain 1 mm2 sectional area beams (30 beams per sample) and submitted to a microtensile bond strength test in a universal testing machine EMIC, at a crosshead speed of 0.5 mm/min. The failure mode was analyzed by a stereomicroscope (Leica MZ75) at 40x magnification and one example of each type of failure mode was analyzed in scanning electron microscopy. Data were analyzed using ANOVA two criteria (ANOVA two-way) and Tukey test at a significance level of 5%. The dual resin cement RelyX ARC showed the highest bond strength values using or not the adhesive system. In groups with adhesive system, the ERCs were not statistically different from each other on the bond strength values to ceramics. In groups without adhesive system, the 2mol% of DPIHFP resin cement obtained the lowest bond strength values. The adhesive application led to higher bond strength values only for RelyX ARC and 2mol % DPIHFP resin cements. According to results, it can be concluded that the addition of DPIHFP salt was not able to increase the bond strength values of the experimental cements. The dual activation system showed higher values of bond strength when compared to photoactivated ERCs and adhesive system protocol increased the bond strength values only for the RelyX ARC and 2mol% DPIHFP resin cements
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The discovery of M (II)-α-diimine (M = Ni, Pd) catalysts has been promoting a revolution in industrial production of polyolefins, once these can produce polymers with different topologies only varying the reaction conditions, using only ethylene as monomer. This ability has been explored by many researchers in recent decades, experimental and theoretical levels. In this study, we developed theoretical calculations on the behavior of different catalytic systems in ethylene polymerization and dimerization reactions. In the first study, we employ the Hartree-Fock (HF) Method to evaluate energies and structures involved in steps representing the ethylene dimerization by Ni (II)-bis [(pyrazolyl) ethyl] amine cationic bulky complex, discussing the behavior of complex through the dimerization steps, π-complex formation, isomerization and low probability for trimerization during dimerization process. In the last two papers we describe a theoretical investigation of ethylene polymerization reaction catalyzed by cationic complexes bulky Ni (II)-α-diimine. We employ a combination of Density Functional Theory (DFT) and molecular mechanics (MM) contained in the ONIOM approach to evaluate structures and energies of representing steps of ethylene polymerization mechanism catalyzed by Brookhart and Guan systems, discussing electronic influences and stereo environment imposed by ligands around the active site in each stage of the process, highlighting the olefin coordination angles and isomerization process of growing polymer chain.
Conselho Nacional de Desenvolvimento Científico e Tecnológico
A descoberta de catalisadores do tipo M(II)-α-diimina (M=Ni, Pd) vem promovendo uma revolução na produção industrial de poliolefinas, pois estes podem produzir polímeros com diferentes topologias variando apenas as condições reacionais, usando apenas o eteno como monômero. Esta habilidade foi explorada por diversos pesquisadores nas últimas décadas, em nível experimental e teórico. Neste estudo, desenvolvemos cálculos teóricos sobre o comportamento de diferentes sistemas catalíticos nas reações de polimerização e dimerização do eteno. No primeiro estudo, empregamos o Método Hartree-Fock (HF) para avaliar energias e estruturas envolvidas nos passos representativos da dimerização do eteno via complexo catiônico volumoso do tipo Ni(II)-bis[(pirazolil)etil]amina, discutindo o comportamento do complexo ao longo dos passos da dimerização, formação de complexos-π, isomerização da cadeia e baixa probabilidade para trimerização durante o processo de imerização.Nos dois últimos trabalhos descrevemos uma investigação teórica da reação de polimerização do eteno catalisada por complexos catiônicos volumosos Ni(II)-α-diimina. Empregamos a combinação da Teoria do Funcional de Densidade (DFT) e Mecânica Molecular (MM), contida na aproximação ONIOM, para avaliar estruturas e energias dos passos representativos do mecanismo de polimerização do eteno catalisado pelos sistemas de Brookhart e Guan discutindo as influências eletrônicas e do ambiente estéreo imposto pelos ligantes em torno do sítio ativo em cada estágio do processo, enfatizando principalmente ângulos de coordenação da olefina e processo de isomerização da cadeia polimérica em crescimento.