This thesis reports an experimental characterization of the ultrafast gain and refractive index dynamics of a novel InAs/InGaAsP/InP quantum-dot (QD) semiconductor optical amplifier (SOA) operating near 1.55-µm wavelengths, assessing its high-speed performance characteristics for the first time. The thesis also studies the influence of the degree of quantum confinement on the dynamics of SOAs by comparing the zero-dimensional (0-D) QD's dynamics to those in 1-D InAs/InAlGaAs/InP quantum-dash (QDash), and 2-D InGaAsP/InGaAsP/InP quantum-well (QW) SOAs, both of which also operate near 1.55-µm wavelengths, and are made with matching or similar materials and structures. The ultrafast (around 1 ps) and long-lived (up to 2 ns) amplitude and phase dynamics of the SOAs are characterized via advanced heterodyne pump-probe measurements with 150-femtosecond resolution. It is found that the QD SOA has an 80-picosecond amplitude, and 110-picosecond phase recovery lifetime in the gain regime, 4-6 times faster than the QDash and QW recovery lifetimes, as well as reduced ultrafast transients, giving it the best properties for high-speed (> 100 Gb/s) all-optical signal processing in the important telecommunications wavelength bands. An impulse response model is developed and used to analyze the dynamics, facilitating a comparison of the gain compression factors, time-resolved linewidth enhancement factors (alpha-factors), and instantaneous dynamic coefficients (two-photon absorption and nonlinear refractive-index coefficients) amongst the three structures. The quantum-dot device is found to have the lowest effective alpha-factor, 2-10, compared to 8-16 in the QW, as well as time-resolved alpha-factors lower than in the QW—promising for reduced-phase-transient operation at high bitrates. Significant differences in the alpha-factors of lasers with the same structure are found, due to the differences between gain changes that are induced optically or through the electrical bias. The relative contributions of stimulated transitions and free-carrier absorption to the total carrier heating dynamics in SOAs of varying dimensionality are also reported for the first time. Examining the QD electroluminescence and linear gain spectra in combination with the carrier dynamics also brings about conclusions on the nature of the quantum confinement, dot energy-level structure, and density of states—aspects of the material that have not been previously well understood.

This thesis reports an experimental characterization of the ultrafast gain and refractive index dynamics of a novel InAs/InGaAsP/InP quantum-dot (QD) semiconductor optical amplifier (SOA) operating near 1.55-µm wavelengths, assessing its high-speed performance characteristics for the first time. The thesis also studies the influence of the degree of quantum confinement on the dynamics of SOAs by comparing the zero-dimensional (0-D) QD's dynamics to those in 1-D InAs/InAlGaAs/InP quantum-dash (QDash), and 2-D InGaAsP/InGaAsP/InP quantum-well (QW) SOAs, both of which also operate near 1.55-µm wavelengths, and are made with matching or similar materials and structures. The ultrafast (around 1 ps) and long-lived (up to 2 ns) amplitude and phase dynamics of the SOAs are characterized via advanced heterodyne pump-probe measurements with 150-femtosecond resolution. It is found that the QD SOA has an 80-picosecond amplitude, and 110-picosecond phase recovery lifetime in the gain regime, 4-6 times faster than the QDash and QW recovery lifetimes, as well as reduced ultrafast transients, giving it the best properties for high-speed (> 100 Gb/s) all-optical signal processing in the important telecommunications wavelength bands. An impulse response model is developed and used to analyze the dynamics, facilitating a comparison of the gain compression factors, time-resolved linewidth enhancement factors (alpha-factors), and instantaneous dynamic coefficients (two-photon absorption and nonlinear refractive-index coefficients) amongst the three structures. The quantum-dot device is found to have the lowest effective alpha-factor, 2-10, compared to 8-16 in the QW, as well as time-resolved alpha-factors lower than in the QW—promising for reduced-phase-transient operation at high bitrates. Significant differences in the alpha-factors of lasers with the same structure are found, due to the differences between gain changes that are induced optically or through the electrical bias. The relative contributions of stimulated transitions and free-carrier absorption to the total carrier heating dynamics in SOAs of varying dimensionality are also reported for the first time. Examining the QD electroluminescence and linear gain spectra in combination with the carrier dynamics also brings about conclusions on the nature of the quantum confinement, dot energy-level structure, and density of states—aspects of the material that have not been previously well understood.

La fluorescence excitée à deux photons est actuellement largement utilisée pour l’imagerie de tissus biologiques, mais la faible sensibilité des fluorophores utilisés en microscopie confocale (excitation à un photon) à une excitation à deux photons (ADP) rend nécessaire la conception et la synthèse de nouveaux fluorophores spécifiques pour la microscopie de fluorescence par excitation bi-photonique (MFEB). Mon travail de thèse a ainsi porté sur l’ingénierie moléculaire (conception, synthèse et caractérisations) de nouveaux fluorophores pour la MFEB. Nous nous sommes particulièrement intéressés à des systèmes unidimensionnels (1D) de petite taille comportant des systèmes π étendus autour d’un cœur rigide (dicétopyrrolopyrrole ou DPP) et entourés de différents systèmes électro-actifs. Nous avons modifié par la suite les fluorophores précédents de manière à pouvoir les conjuguer à des molécules d’intérêt biologique, comme des protéines. Ces fluorophores bio-conjugables ont été greffés sur un peptide du virus HIV étudié au laboratoire : TAT (Trans-Activator of Transcription). L’imagerie par microscopie biphotonique a été effectuée avec succès sur des cellules HeLa. Nous nous sommes ensuite tourné vers la mise au point de nouvelles sondes multimodales pour associer la MEBP à une autre modalité d’imagerie : la résonance magnétique nucléaire et la microscopie électronique (imagerie corrélative). Pour ce faire nous avons développé des colorants fluorescents par excitation bi-photonique comportant une entité paramagnétique ou dense aux électrons (nanoparticules de magnétite, ion gadolinium III ou atomes lourds comme le platine et l’or). / Two-photon induced fluorescence is nowadays widely used for the imaging of biological tissues. The classical fluorophores used in confocal microscopy exhibit low sensitivity to two-photon excitation for the two-photon excitation microscopy (TPEM), led the researchers towards the development of new fluorophores, specifically engineered for TPEM. This manuscript describes our work on conception, synthesis and characterizations of new one-dimensional fluorophores based on dicétopyrrolopyrrole (DPP) central core, surrounded by various electro-active systems through π conjugated systems. We also modified such fluorophores to be able to conjugate them to molecules of biological interest, such as proteins. These bio-conjugable fluorophores were grafted on a peptide of HIV virus studied in our laboratory: TAT (Trans-Activator of transcription). The imaging by TPEM was successfully performed on HeLa cells. In addition we developed new multimodal probes for the correlative light electronic microscopy and for the correlative imaging fluorescence microscopy/ Magnetic resonance imaging (MRI). Theses multimodal probes associate a fluorescent moiety based on the DPP core associated to a paramagnetic or electron dense entity (magnetite nanoparticles, gadolinium III or heavy atoms such as platinum or gold).

O poli (p-fenilenevinileno), ou PPV, é um polímero de grande relevância tecnológica devido a suas propriedades eletroluminescentes, que têm sido exploradas em diodos emissores de luz orgânicos, displays flexíveis e outros dispositivos optoeletrônicos. Embora o PPV seja um material de importância para muitas aplicações, a sua síntese na nano/microescala não pode ser obtida através do método padrão, o qual utiliza o aquecimento de um polímero precursor poli (cloreto de xileno tetrahidrotiofenio) (PTHT). Este trabalho mostra como a microestruturação com pulsos de femtosegundo pode ser empregada para a síntese de PPV em regiões pré-determinadas, empregando três diferentes abordagens, permitindo uma nova metodologia para a fabricação precisa de microcircuitos poliméricos complexos, (i) na primeira abordagem, o processo de conversão é obtido pela irradiação de filmes de PTHT com pulsos laser ultracurtos em regiões previamente determinadas, o que leva ao controle espacial da formação de PPV em microescala, (ii) na segunda abordagem, microestruturas tridimensionais dopadas com PTHT foram fotopolimerizadas por absorção de dois fótons. A conversão de PTHT para PPV nestas microestruturas dopadas foi obtida após um tratamento térmico, (iii) na terceira abordagem, a transferência direta induzida por laser (LIFT) com pulsos de femtossegundos permite a deposição controlada de PPV com alta resolução espacial, fornecendo micropadrões 2D, preservando sua estrutura e propriedades ópticas. As estruturas foram caracterizadas por microscopia eletrônica de varredura, microscopia óptica de transmissão, microscopia de fluorescência e microscopia confocal de fluorescência. Suas propriedades ópticas foram analisadas através de sistemas de micro-fotoluminescência e micro-absorção implementadas em um microscópio invertido. Medidas de espectroscopia Raman, microscopia de força atômica e medidas elétricas também foram realizadas. Este trabalho mostra como a microestruturação com laser de fs pode ser explorada para a síntese de PPV em regiões pré-determinadas para fabricar uma variedade de microdispositivos, abrindo novos caminhos na optoeletrônica baseada em polímeros. / Poly(p-phenylenevinylene), or PPV, is a polymer of great technological relevance due to its electroluminescent properties, which have been exploited in organic light emitting diodes, flexible displays and other optoelectronic devices. Although PPV is a material of foremost importance for many applications, its synthesis at the nano/micro scale cannot be achieved through the standard method that uses heating of a precursor polymer poly(xylene tetrahydrothiophenium chloride)(PTHT). This work demonstrates the use of direct laser writing with femtosecond pulses to obtain the synthesis of PPV in pre-determined regions, by applying three different approaches, allowing the precise fabrication of complex polymeric microcircuits, (i) in the first approach the conversion process is achieved by irradiating PTHT films with ultra-short laser pulses in previously determined regions, which leads to the spatial control of PPV formation at microscale, (ii) in the second approach, three-dimensional microstructures doped with PTHT were photopolymerized by two photons absorption. The conversion of PTHT to PPV in these doped microstructures was obtained by a subsequent thermal treatment, (iii) in the third approach, laser-induced forward transfer (LIFT) with femtosecond pulses enables the controlled deposition of PPV with high spatial resolution, providing 2D micropatterns, while preserving its structure and optical properties. The structures were characterized by scanning electron, fluorescence, transmission and confocal fluorescence microscopies. Their optical properties were analyzed by micro-photoluminescence and micro-absorption setups assembled on an inverted microscope. Raman spectroscopy, electrical measurements and atomic force microscopy were also performed. This thesis shows the use of fs-laser writing methods for the synthesis of PPV in pre-determined regions, to fabricate a variety of microdevices, thus opening new avenues in polymer-based optoelectronics.

Neste trabalho realizamos o estudo da cinética e formação de agregados em cristais iônicos halogenetos alcalinos dopados com impurezas divalentes, através da técnica de espectroscopia de absorção de dois fótons (ADF). Analisamos a formação dos agregados em cristais envelhecidos a temperaturas fixas (50 e 250&#176C), através de medidas de ADF das transições 4f7 &#8594 4f7 do Eu2+, proibidas por um fóton. A evolução do espectro de ADF em função do tempo, mostrou a existência de três fases distintas de agregação. A primeira fase consiste na formação de dímeros e é observada no espectro de ADF através de três absorções muito próximas às absorções do dipolo isolada. As outras duas fases (II e III) evoluem a partir dos dímeros, dependendo do tratamento térmico a que a amostra é submetida. Estas fases são observadas no espectro de ADF através de absorções relativamente afastadas das absorções do dipolo isolado. Todo sistema experimental foi montado em nosso laboratório, consistindo de um sistema de aquisição de dados controlado por um micro-computador; laser de corante bombeado por um YAG:Nd3+; motores de passos para a varredura do comprimento de onda do laser de corante; sistema de detecção; etc. / In this work we realize the study of the Kinetic and formation of precipitates in ionic crystals doped with divalent impurities by the TPA (two photon absorption) spectroscopy technique. We analyze the formation of the aggregates in crystals annealed at temperatures of 50 and 250&#176C. We measured the TPA of the transition 4f7 &#8594 4f7 of the Eu2+, which is forbidden by one photon. The evolution of the TPA spectra at the time showed us three phases of the precipitates. The dimmers formation was observed in the first phase, by three absorptions bands near the one of the impurity vacancy dipole. The others phases (II and III) involve from the dimmers, depending on the annealing temperature that the samples were submitted. Those phases are observed in the TPA spectra through absorptions which are relatively far from the absorptions due to the isolated (I-V) dipole. All experimental system employed is home made. It consists of a data acquisition system controlled by a micro-computer; a Dye laser pumped by a YAG:Nd3+ laser; step motors to scan the wavelength of the Dye laser; detection system and others devices.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work reports on the optical properties of chalcones molecules in solution, using methanol as solvent. For the characterization of the linear optical properties, were obtained absorbance spectra. While for the characterization of the nonlinear optical properties, it has been used techniques hyper-Rayleigh scattering and Z-scan. Using hyper-Rayleigh scattering technique, were determined the first hyperpolarizabilities of the molecules studied. With the Z-scan technique, we could obtain the two-photon absorption spectra at several wavelengths in the range of 480 to 790 nm. From the two-photon absorption spectra were possible to determine the coefficients of two-photon absorption and their respective cross section. The results help to understand the effects of substituents added to the basic structure of chalcones in both linear optical properties as nonlinear. / Neste trabalho, estudamos as propriedades ópticas de moléculas de chalconas em solução, usando o metanol como solvente. Para a caracterização das propriedades ópticas lineares foram determinados os espectros de absorção. Na caracterização das propriedades ópticas não lineares foram utilizadas as técnicas de espalhamento hiper-Rayleigh e de varredura-Z. Utilizando a técnica de espalhamento hiper-Rayleigh foram determinadas as primeiras hiperpolarizabilidades das moléculas estudadas. Com a técnica de varredura-Z conseguimos obter os espectros de absorção de dois fótons em vários comprimentos de onda no intervalo dos 480 aos 790 nm. A partir dos espectros de absorção de dois fótons foi possível determinar o coeficiente da absorção de dois fótons e sua respectiva seção de choque. Os resultados ajudam a compreender os efeitos de substituintes, adicionados à estrutura básica das chalconas, tanto nas propriedades ópticas lineares quanto não lineares.

Compostos orgânicos constituem uma classe interessante de materiais para aplicações em óptica por apresentarem boa processabilidade, relativa facilidade para integração em dispositivos e, principalmente, pela possibilidade de otimização de suas propriedades ópticas através da engenharia molecular. Várias estratégias têm sido empregadas para sintetizar moléculas orgânicas, que exibam singificativos efeitos ópticos não lineares. Nesta direção, nos últimos anos moléculas multi-ramificadas vêm sendo produzidas com o objetivo de intensificar efeitos não lineares, já que estas podem exibir um forte efeito cooperativo entre seus ramos. Nesta tese estudamos a relação da absorção de dois fótons (A2F) e da primeira hiperpolarizabilidade com a estrutura molecular, para um conjunto de nove derivados de trifenilamina com diferentes grupos aceitadores de elétrons arranjadas em geometrias dipolar, quadrupolar e octopolar. O processo A2F foi estudados através da técnica de Varredura-Z, enquanto que a primeira hiperpolarizabilidade foi caracterizada pela técnica de espelhamento hiper Rayleigh. Os dados experimentais para a absorção de dois fótons revelaram espectros bem definidos, com valores razoáveis de seção de choque na região do visível e infravermelho próximo. Observamos ainda um engrandecimento para a seção de choque de A2F para as moléculas quadrupolares. Os resultados obtidos para a primeira hiperpolarizabilidade (β) mostraram que moléculas quadrupolares apresentam maior β do que as dipolares e octopolares, portanto, nossos resultados permitem concluir que o acoplamento eletrônico entre os ramos contribuem fortemente para a seção de choque por A2F e β nas moléculas quadrupolares, não sendo este processo relevante nas moléculas octopolares. Todos os resultados foram interpretados por meio de estudos teóricos empregando a teoria do funcional da densidade (DFT). / Organic compounds constitute an interesting class of materials for optical applications due to their excellent processability, easy integration into devices and, mainly, the possibility of optimizing its optical properties through molecular engineering. Several strategies have been employed to synthesize organic molecules, which exhibit significant nonlinear optical effects. In this direction, in the last few years multi-branched molecules have been obtained aiming at intensifying nonlinear optical effects, since they may exhibit a strong cooperative effect among their branches. On this thesis we have studied the relationship of two-photon absorption (2PA) and first hyperpolarizability with the molecular structure of a group of nine triphenylamine derivatives attached to distinct electron acceptor groups arranged in dipole, quadrupole and octopolar geometries. The 2PA process was studied by Z-scan technique, while the first hyperpolarizability was characterized by the hyper-Rayleigh scattering technique. The experimental data for two-photon absorption revealed well-defined spectra with reasonable cross section magnitude in the visible and near infrared range. We also observed an enhancement of the 2PA cross-section for the quadrupolar molecules in comparison to the dipolar and octopolar ones. The results obtained for the first hyperpolarizability (β) shown that the quadrupolar molecules present higher β than the dipolar and octopolar, suggesting that the electronic coupling between the branches strongly contribute to the 2PA cross-section and β in quadrupolar molecules, being not relevant in the octopolar molecules. All results were interpreted through theoretical studies based on the density functional theory (DFT).

Nesta tese, estudamos o processo de absorção multifotônica em polímeros e resinas poliméricas, abordando tanto aspectos fundamentais quanto aplicados. Com relação aos aspectos fundamentais, estudamos processos de absorção multifotônica (absorção de dois, três e quatro fótons) no polímero conjugado MEH-PPV (poly(2-methoxy-5-(2´-ethylhexyloxy)-1,4- phenylenevinylene)), utilizando a técnica de Varredura-Z com pulsos ultracurtos. Através desta técnica, determinamos o espectro da absorção de dois, três e quatro fótons do MEHPPV. As seções de choque de absorção de multi-fótons correspondentes a cada processo foram determinadas através do ajuste das curvas experimentais com um conjunto de equações desenvolvidas neste trabalho. Os resultados obtidos permitiram traçar relações entre os espectros não lineares e os níveis de energia do polímero. Na vertente mais aplicada do projeto, estudamos a fotopolimerização de resinas acrílicas através do processo de absorção de dois fótons. Devido ao confinamento espacial da polimerização, graças à absorção de dois fótons, este método permite a confecção de micro-estruturas complexas para diversas aplicações tecnológicas. Além da fabricação de microestruturas convencionais não dopadas, neste trabalho desenvolvemos uma metodologia que possibilita a fabricação de microestruturas dopadas com MEH-PPV, visando a produção de micro-elementos fluorescentes para dispositivos fotônicos, e microestruturas dopadas com quitosana, um polímero biocompatível que pode ser utilizado em aplicações médicas e biológicas. / In this thesis we have studied the multi-photon absorption process in polymers and polymeric resins, exploiting its fundamental as well as technological aspects. Regarding the fundamental aspects, we have studied the multi-photon absorption (two-, three- and four-photon absorption) in the conjugated polymer MEH-PPV (poly(2-methoxy-5-(2´-ethylhexyloxy)-1,4-phenylenevinylene)), by using the Z-scan technique with ultrashort laser pulses. Through this technique, we determined the two-, three- and four-photon absorption spectra of MEH-PPV. The multi-photon absorption cross-sections, corresponding to each specific process, have been determined by fitting the experimental data with a set of equations developed in this work. The results allowed us to correlate the nonlinear absorption spectra to the energy level of the polymer. On the technological side of this thesis, we have investigated the photopolymerization of acrylic resins by two-photon absorption. Because of the spatial confinement of the polymerization, resulting from the two-photon excitation, this method allows the fabrication of complex microstructures which can be used for several technological applications. In addition to the fabrication of undoped microstructures, in this work we have developed a methodology that allows the fabrication of microstructures doped with MEHPPV, aiming the production of fluorescent micro-elements for photonics applications, and microstructures doped with chitosan, a biocompatible polymer, that can be used for medical and biological applications.

L’utilisation de chromophores absorbant à deux photons (ADP) pour des applications en photothérapie dynamique (PDT) et en imagerie de fluorescence présente de nombreux avantages. Les propriétés non-linéaires de ces chromophores permettent notamment d’améliorer la longueur de pénétration dans les organismes vivants ainsi que la résolution. Pour des applications in-vivo la biocompatibilité de ces chromophores lipophiles doit aussi se poser. Une étude d’ingénierie pour le développement de chromophores pour la PDT-ADP en utilisant des atomes de brome comme groupe générateur d’oxygène singulet est décrite. Différents paramètres dont le nombre et la position des atomes de brome sur la chaîne carbonée, la longueur de conjugaison, la géométrie des chromophores ont été étudiés. Cette étude permet de mettre en évidence l’importance de la position des substituants bromes et de la symétrie sur le rendement de croisement inter-système.Les observations spectroscopiques faites lors de l’étude d’ingénierie ont permis de développer des chromophores pour la microscopie de fluorescence à deux photons. La biocompatibilité est apportée grâce à un polymère d’(hydroxyethyl)acrylate. Ce polymère permet de créer une coquille hydrosolubilisante covalente. Ces chromophores ont été utilisés pour faire de l’imagerie de vascularisation cérébrale de haute résolution. Une observation particulière sur un chromophore, marquage des cellules endothéliales des parois des vaisseaux sanguins intravitaux ainsi que les applications en résultant sont présentées. Des stratégies visant l’amélioration de la sélectivité des systèmes polymères/chromophores pour des applications intravitales, comme le traitement des tumeurs cancéreuses sont décrites. Une stratégie de modification des fonctions hydroxy des chaînes polymères par des groupements imidazoliums est présentée. L’étude de complexation des polymères avec l’ADN et les études spectroscopiques in-cellulo ont été réalisées. / The use of two-photon absorbing (TPA) chromophore for applications in photodynamic therapy (PDT) and fluorescence imaging provides many advantages. The non-linear properties make it possible to increase both observation depth in animals and 3D resolution. Nevertheless, for in-vivo applications, improving bio-compatibility of these inherently lipophilic chromophore is a challenge. The development of new chromophores for PDT-TPA using a molecular engineering approach using bromide substituents as singlet oxygen generators is described. Parameters like position and number of bromide, the conjugated length and chromophore symmetry are studied. The study shows the importance of bromide atom position and of the symmetry on the inter system crossing efficiency. During the engineering study, spectroscopic observation and rationalization permit to envision the design of new chromophores for two photon laser scanning fluorescent microscopy. Bio-compatibility of these chromophores is provided by (hydroxyethyl)acrylate polymer, which provides a covalent water-soluble shell. These chromophores are used to make high resolution image of cerebral vascularization. One of these chromophores shows intravital specific interaction with endothelial cells in blood vessels. Some applications of the chromophore are described. Strategies to increase the intravital selectivity of polymer/chromophores units towards cancer cells and tumor are presented. A modification of hydroxyl function by imidazolium group is described. This new chromophore is evaluated towards its complexation properties with DNA and in cellulo spectroscopic studies.

This thesis explores and expands upon theoretical means of quantifying a number of nonlinear spectroscopies, including two-photon absorption, resonant-inelastic x-ray scattering, Jones birefringence, and magnetic circular dichroism. On top of that, detailed information is given for the derivation and program implementation of damped cubic response functions. Complex-valued cubic response functions have been implemented in the quantum chemistry package DALTON, based on working equations formulated for an approximate-state wave function. An assessment of the implementation, such that for small frequencies the second-order hyperpolarizability should behave according to an analytic function that depends quadratically on the optical frequencies. It is demonstrated how two-photon absorption (TPA) can be described either through second-order transition moments or via the damped cubic response function. A few calculated TPA profiles are produced for a set of smaller molecules, in order to display the capability of the cubic response function in the x-ray frequency region. Resonance-inelastic x-ray scattering (RIXS) is explored in a similar manner as two-photon absorption. It is shown how the second-order hyperpolarizability can represent RIXS in the limit of intermediate-state and final-state resonances. Complications emerging from the complex dispersion of the hyperpolarizability are discussed. Moreover, linear birefringences, with focus on the Jones birefringence, are investigated for noble gases, monosubstituted benzenes, furan homologues, and a pure acetonitrile liquid. A linear relation between the Jones birefringence and the empirical para-Hammett constant as well as the permanent electric dipole moment is presented. Estimations of three linear birefringences --- Kerr, Cotton--Mouton, and Jones ---are obtained by averaging over a set of liquid snapshots. The Jones effect for acetonitrile turns out to be unusually large inmparison to the other two investigated linear birefringences. The final chapter of the thesis investigates magnetically induced circular dichroism (MCD). A question regarding relative stability of the first set of excited states for DNA-related molecular systems is resolved through MCD by exploiting the signed nature of circular dichroisms. Furthermore, to what extent solvent contributions affect MCD spectra is explored. The effect on uracil MCD spectrum due to thionation is studied, for which the degree of redshifting for systems 2-thiouracil and 4-thiouracil can be seen to be addative as compared to the 2,4-dithiouracil system. / <p>QC 20171129</p>