Submitted by Luanna Matias (lua_matias@yahoo.com.br) on 2015-02-06T18:47:45Z No. of bitstreams: 2 Dissertação - Geovany Albino de Souza - 2014..pdf: 2844479 bytes, checksum: 8192fe53e727f5009913ce9db209bef1 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-02-19T14:29:50Z (GMT) No. of bitstreams: 2 Dissertação - Geovany Albino de Souza - 2014..pdf: 2844479 bytes, checksum: 8192fe53e727f5009913ce9db209bef1 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-02-19T14:29:50Z (GMT). No. of bitstreams: 2 Dissertação - Geovany Albino de Souza - 2014..pdf: 2844479 bytes, checksum: 8192fe53e727f5009913ce9db209bef1 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-10-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, we produced a fluorescent system composed of diphenylalanine (FF) nanoestructures containing the (2-benzothiazolyl)-7-dietilaminocoumarin (C6) dye as fluorescent additive. The morphological characteristics of the nanostructures and the influence of the additive on the FF self-organization were studied by scanning electron microscopy. The photophysical properties of the fluorescent system were assessed by photostationary fluorescence spectroscopy. From the morphological analysis, it was observed that the additive favors the FF self-organization, which can be attributed to the influence of the C6 aromatic rings on the π stacking interactions among the FF units. Also, it was observed that the characteristic blue fluorescence of the nanostructures at 400 nm, shifts to 408 nm in the presence of the additive. This is a result of an energy transfer complex that is formed between the FF and the C6, which promotes the fluorescence of the system from relaxed hybrid excited states. The photophysical behavior of the fluorescent system towards different concentrations of a suppressor, the molecular oxygen, was evaluated. Solutions containing the fluorescent additive alone showed poor sensitivity towards oxygen, as expected based on the properties of substituted coumarin derivatives when exposed to oxygen. However, the effect of the interaction between the FF nanostructures and the additive on the coumarin derivative sensitivity towards oxygen quenching was assessed and a remarkable increase of the dye sensitivity was observed. Therefore, we tested the applicability of this newly developed fluorescent system as a sensor for dissolved oxygen (DO) from water samples for potential application in environmental monitoring. The sensitivity and reproducibility of the fluorescent system quenching by DO were carried out in water samples from a tank containing fish specimen. In order to validate the fluorescence quenching measurements in the presence of varying DO concentration with time, the DO measurements were also simultaneously performed by the conventional electroanalytical method. We then observed that the variations in fluorescence intensities of the system agreed with the concentrations of DO measured by the conventional method. / Neste trabalho, produziu-se um sistema fluorescente de nanoestruturas de difenilalanina (FF) contendo (2-benzotiazolil)-7-dietilaminocumarina (C6) como aditivo fluorescente. As características morfológicas das nanoestruturas peptídicas e o efeito do aditivo na auto-organização da FF foram estudadas por microscopia eletrônica de varredura (MEV) e as propriedades fotofísicas do sistema fluorescente foram estudadas por espectroscopia de fluorescência fotoestacionária. Das análises morfológicas, verificou-se que o aditivo favorece a auto-organização das nanoestruturas peptídicas, o que pode ser explicado pelo efeito dos anéis aromáticos da C6 nas interações de π stacking entre as unidades de FF. Quanto às propriedades fotofísicas, observou-se que a luminescência azul característica das nanoestruturas e com máximo em 400 nm sofre um desvio batocrômico, ocorrendo em torno de 408 nm, o que é atribuído à formação de um complexo de transferência de energia entre a FF e a C6 que promove a luminescência do sistema a partir de estados híbridos relaxados. O comportamento fotofísico do sistema foi avaliado frente a concentrações distintas de um supressor, o oxigênio molecular. Soluções contendo apenas o aditivo fluorescente apresentou baixa sensibilidade ao oxigênio, o que era esperado, baseado em sua constituição e nas características de cumarinas substituídas frente a supressão. No entanto, o efeito da interação entre as nanoestruturas peptídicas com o aditivo fluorescente derivado de cumarina sobre a sensibilidade do aditivo quanto à supressão de fluorescência foi avaliada e averiguou-se que há um significativo aumento da sensibilidade do composto fluorescente frente a presença de oxigênio molecular. Com isso, também avaliou-se a aplicabilidade do sistema desenvolvido como sensor de oxigênio dissolvido (OD) em amostras de água, como sugestão de aplicação de monitoramento ambiental. A sensibilidade e reprodutibilidade do sistema fluorescente frente a supressão pelo OD foram analisadas em amostras de água de aquário contendo peixes. Para a validação das medidas da supressão da fluorescência com relação à variação da concentração de OD com o tempo, medidas de OD foram realizadas, simultaneamente, empregando o método eletroanalítico convencional. Observou-se, com isso, que as variações de intensidades de fluorescência do sistema apresentaram uma concordância com as quantidades de OD obtidas pelo método convencional.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-01-27T13:36:30Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Diogo Lopes Dias - 2014.pdf: 5214471 bytes, checksum: 55feba00bb21a1b68af1b8e6e472f67d (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-01-28T11:15:17Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Diogo Lopes Dias - 2014.pdf: 5214471 bytes, checksum: 55feba00bb21a1b68af1b8e6e472f67d (MD5) / Made available in DSpace on 2015-01-28T11:15:17Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação - Diogo Lopes Dias - 2014.pdf: 5214471 bytes, checksum: 55feba00bb21a1b68af1b8e6e472f67d (MD5) Previous issue date: 2014-09-17 / This work aims at preparation and morphological and photophysical characterization of systems consisting of self-assembled structures based on the L-diphenylalanine dipeptide doped with magnetic and luminescent aditives. In this way, nanoparticles magnetic particles of maghemite (γ-Fe2O3) were prepared and used as magnetic additives, while Cadmium Telurium (CD and Te) - based Quantum Dots (QD) were employed as the luminescent additive. The resulting system was characterized by scanning electron microscopy and steady-state fluorescence spectroscopy techniques and their properties were compared tothose presented by the individual components and the intermediate systems. Also, a study on the interaction forces involved in the self-organization of the dipeptide was carried out by varying the method of preparation by employing in the preparation, solvents with distinct physical-chemical properties and by relating conformational differences in the nano and micro structures obtained in each preparation protocol with the balance of interactions forces that contribute to the self-assembling phenomenon. Regarding- to that, when self-assembling is promoted in solvents with distinct polarizabilities (Δf), as obtained by Lippert equation, it is possible to infer about the forces balance that are predominant. The peculiarities of each structure obtained were explored by SEM imaging and spectroscopic data. From scanning electron micrographs, it is observed that self-assembling is governed by interactions between neighboring aromatic rings, trhough π-stacking interactions and generates, in most cases, tubular structures. However, in certain protocols, lamellar structures were observed. When self-assembilng occurs in water, L-diphenylalanine (NT-F-F) nanotube growth occursfrom a starting site and develops in all directions. The use of additives with distinct properties acted in self-assebling process, favoring it when the quantum dot is additive or disfavoring it when the magnetic nanoparticles are the additives. Furthermore, it was observed that in the system containing both additives in proportions in which aggregates are not observed, nanotube´s self-asembling and their further association leaded to microtubes. Structural differences between obtained NT-F-F allow us to infer on the nature of interactions between the dopants and the NT-F-F. The photophysical behavior analysis revealed that the fluorescence emission increases due to the nature of interaction between QD and NT-F-F, to give rise to a charge transfer complex. These results indicate that there may be a conjugation xxiii effect favoring luminescent processes from relaxed energy states of the system containing the magnetic particle and QD as additives, simultaneously. / Este trabalho tem como objetivo a preparação e a caracterização morfológica e fotofísica de sistemas constituídos de estruturas auto-organizadas baseadas no dipeptídeo L-difenilalanina contendo como aditivos com propriedades magnéticas nanopartículas partículas magnéticas de maguemita (γ-Fe2O3) e como aditivo luminescente um Quantum Dot (QD) comercial a base de Cádmio e Telúrio (Cd e Te). O sistema resultante foi caracterizado morfológica e fotofisicamente e suas propriedades foram comparadas às apresentadas pelos componentes isolados e pelos sistemas intermediários. Observou-se que quando a auto-organização é promovida em solventes com polarizabilidades (Δf) distintas, é possível inferir sobre o balanço de forças que, predominantemente, atuam sobre a auto-organização. Por meio de imagens de microscopia eletrônica de varredura, observou-se que, quando auto-organizadas em água, nanotubos de Ldifenilalanina (NT-F-F) se auto-organizam, partindo de uma região e se desenvolvendo em todas as direções. A adição de compostos com propriedades distintas influenciou distintamente o processo de auto-organização, favorecendo-o com o uso do quantum dot como aditivo, ou desfavorecendo-o, com a adição das nanopartículas magnéticas. No entanto, no sistema contendo ambos aditivos em proporções em que não são observados agregados, a auto-organização de nanotubos é favorecida. Ainda, a análise do comportamento fotofísico revelou que a emissão de fluorescência pode ter sua intensidade aumentada em decorrência da natureza da interação entre os QD e os NT-F-F, por dar origem a um complexo de transferência de carga. Estes resultados indicam que pode haver um efeito de conjugação que favorece os processos luminescentes que partem de estados relaxados de menor energia nos sistemas contendo a partícula magnética e o QD como aditivos, simultaneamente.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2017-10-25T13:48:38Z No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-10-25T13:49:10Z (GMT) No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-10-25T13:49:10Z (GMT). No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-07-31 / Nanostructures of diphenylalanine (FF) have been extensively studied and are quite varied. This work aims to obtain self-assembled structures of diphenylalanine, containing electroluminescent compounds, with distinct morphological and photophysical characteristics from those of the starting materials. This work also intent to describe the photophysical properties of the structures obtained, integrating the experimental information to the theoretical predictions of computational simulations. For this, FF were self-assembled having chromophores as additives and its photophysical properties determined by steady state fluorescence spectroscopy, time-resolved fluorescence spectroscopy and its morphology was studied by scanning electron microscopy. Experimental data were compared to the results of semi-empiric theoretical calculation performed by AM1 and ZINDO/S approaches. The resulting materials exhibit different time resolved and steady state fluorescence response from the starting materials and it is related to charge transfer complexes formation. On theoretical approach, dimers and trimers can be part of the early stages of self-assembling. This find is important because this type of arrangement can lead to more conductive materials, of industrial interest, when combined with luminescent materials, especially if considered for energy conversion devices. / Nanoestruturas de difenilalanina (FF) vêm sendo extensivamente estudadas e são bastante variadas. Este trabalho busca obter estruturas auto-organizadas de difenilalanina, contendo compostos eletroluminescentes, que apresentem características morfológicas e fotofísicas distintas daquelas apresentadas pelos materiais de partida. Busca também descrever as propriedades fotofísicas das estruturas obtidas, integrando informações experimentais a previsões teóricas obtidas por simulações computacionais. Amostras de FF foram autoorganizadas na presença de aditivos cromóforos e suas propriedades fotofísicas determinadas por espectroscopia de fluorescência fotoestacionária, espectroscopia com resolução temporal e morfologia caracterizada por microscopia eletrônica de varredura. Os dados experimentais foram comparados aos resultados obtidos por métodos computacionais semi-empíricos, em nível AM1 e ZINDO/S para validar as previsões. Os materiais combinados exibem espectros de fluorescência fotoestacionária e resolvida no tempo diferentes dos materiais de partida e é possível identificar a presença de transferentes de carga. Sob o aspecto teórico, dímeros e trímeros podem fazer parte dos estágios iniciais de auto-organização da FF. Esta constatação é importante pois este tipo de arranjo pode levar a materiais mais condutores, de interesse industrial, quando combinados com materiais luminescentes, principalmente se considerados para dispositivos de conversão energética.

Orientador: Prof. Dr. Wendel Andrade Alves / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / O consumo de produtos eletrônicos pela sociedade provoca forte impacto ambiental no momento de descartar tais eletrônicos. Neste contexto, a busca por materiais ambientalmente amigáveis está alinhada às necessidades de nosso tempo. Nanoestruturas peptídicas derivadas de aminoácidos naturais possuem grande potencial para a fabricação de uma nova geração de dispositivos biodegradáveis, utilizando a rota de síntese de baixo para cima, sem a necessidade de caros processos litográficos. Neste trabalho, nanomateriais peptídicos foram utilizados tanto em sua forma pura quanto modificados com polímeros para a criação de dispositivos eletrônicos. Os efeitos da auto-organização das nanoestruturas sobre o desempenho e eficiência desses dispositivos foram investigados. Transistores orgânicos de efeito de campo (OFETs) baseados no dipeptídeo L,L-difenilalanina foram desenvolvidos pela primeira vez, tendo apresentado razões on/off e mobilidades da ordem de 103 e de 10-3 cm2 Vs-1. Esses valores são bastante promissores na busca de componentes eletrônicos que atendam às necessidades de desempenho atuais. Um diodo orgânico emissor de luz (OLED) também foi fabricado utilizando as nanoestruturas peptídicas de L,L-difenilalanina modificadas com o polímero emissor poli[2,7-(9,9-dioctilfluoreno)]. Embora o dispositivo tenha apresentado eficiência cerca seis vezes menor comparado ao sistema produzidos com o polímero puro, a introdução de peptídeos permitiu o uso de uma quantidade menor de polímero, além de exibir taxas de biodegradabilidade cerca de 85% maiores. A integração de nanoestruturas de peptídeos com dispositivos de eletrônica orgânica pode significar o início do desenvolvimento de materiais biodegradáveis para aplicação em dispositivos com alta demanda de consumo, tendo como consequência a diminuição do impacto ambiental proveniente da utilização destes dispositivos. / The consumption of electronic products in our society leads to strong environmental impact when such devices need to be discarded. In this sense, research on environmental friendly materials is aligned with the needs of our time. Peptide nanostructures derived from natural amino acids have great potential for producing a new generation of biodegradable devices using the "bottom-up" synthesis route without need for expensive lithographic processes. In this work, peptide nanomaterials were used either in pure form or modified with polymers for designing organic electronic devices and the effects of self-organization on performance and efficiency of these devices were investigated. Organic field effect transistors (OFETs) based on the dipeptide L-L-diphenylalanine were developed for the first time, exhibiting on/off and mobility values of the order of 103 and of 10-3 cm2 Vs-1. These values are very promising and meet the current performance needs in organic devices. An organic light emitting diode (OLED) was fabricated using a combination of peptide nanostructures and 9,9-dioctylfluorene emitting polymer. Although this device shows efficiency six times lower than those build up from pure polymer, they required a lower amount of polymer in the hybrid material and exhibited biodegradability rates ~ 85% higher than architectures exclusively based on pristine polymer. Integration of peptide nanostructures with organic electronic devices represent a milestone on developing biodegradable materials for use in devices with high demand in our society, resulting in reduced environmental impact.

Orientador: Prof. Dr. Herculano da Silva Martinho / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / Espectroscopia vibracional é uma ferramenta poderosa para investigar um grande número de sistemas, permitindo uma melhor compreensão de suas estruturas, composição química e propriedades físicas e químicas. Neste trabalho, nós aplicamos espectroscopia no infravermelho e Raman (espontâneo e anti-Stokes coerente, CARS) para estudar 2 sistemas: micro/nanotubos de difenilalanina (MNTFF) e água confinada em nanoporos presentes em fibras de ácido polilático (PLA). MNTFF é uma das nanoestruturas de peptídeos que tem ganhado grande atenção nos últimos tempos devido a suas interessantes propriedades químicas e físicas e, também, devido a sua correlação com a formação de fibrilas amilóides que são associadas com a doença de Alzheimer. Portanto, é de grande importância entender como o processo de automontagem ocorre, pelas seguintes razões: i) para obter, de forma controlada e reprodutiva, estruturas com determinada morfologia e tamanho para aplicações tecnológicas, ii) para desenvolver drogas terapêuticas capazes de prevenir ou controlar a formação das fibrilas amilóides e iii) é um tópico muito interessante do ponto de vista científico. Portanto, nós focamos na detecção de espectros vibracionais durante a formação dos MNTFF. Algumas características específicas dos espectros Raman sugerem, claramente, que as moléculas de FF formam espécies intermediárias antes da formação dos MNTFF, seguindo uma cinética de 2-etapas. Cálculos computacionais baseados na Teoria do Funcional Densidade (DFT) permitiram a atribuição dos modos vibracionais da espécie intermediária. Nós também investigamos a homogeneidade estrutural dos MNTFF analisando a distribuição da frequência e largura de linha de algumas bandas selecionadas. Nossos resultados indicaram que as regiões mais externas dos MNTFF contém quantidade diferente de moléculas de água nos canais hidrofílicos em relação às regiões mais internas. Já o estudo das propriedades físicas da água confinada em nanoporos de fibras de PLA foi motivado pelas propriedades anômalas da água. Entretanto, o método utilizado para confinar água não garantiu o confinamento das moléculas de água no interior dos poros. / Vibrational spectroscopy is a powerful tool to invetigate a wide range of systems to gain a deeper understanding of their structures, chemical composition, molecular dynamics, physical properties and so on. In this work, we applied Raman and infrared spectroscopy in order to study 2 different systems: micro/nanotube of diphenylalanine (FF-MNT) and confined water in nanoporous of polylactic acid (PLA) fibers. FF-MNT is one of peptides nanostructures that has gained great attention due to its interesting properties and its correlation to the formation of -amyloids fibrils which is associated to Alzheimer¿s disease. Therefore, it is of extremely importance to understand how the self-assembly process takes place due to the following reasons: i) to obtain, in a controlled and reproductive way, structures with determined morphology and size to use them in technological applications, ii) to develop therapeutic drugs capable of preventing or controlling the amyloid formation, and iii) it is an interesting topic from scientific point of view. We focused on the detection of vibrational spectra during the formation of supramolecular structures after triggering the process with water injection. Specific features in the Raman spectra clearly suggest that FF-molecules after water injection form an intermediate species before forming the FF-MNT, following a 2-step kinetics. Density Functional Theory (DFT) computational simulations results enabled us assign the vibrational modes of the intermediate species and stablish an mechanism selfassembling mechanism based on electric-dipole interactions among the FF-monomers. We also investigated the structural homogeneity of FF-MNT by checking the distribution of frequency and linewidth of some selected bands. Our results indicated the outer and inner regions of MNT present different number of water molecules in the hydrophilic channel. The study of physical properties of confined water in nanoporous of PLA fibers was motivated by anomalous properties of water. However, unfortunately, it was found the method we used to confine water did not guarantee the confinement of water molecules in PLA fibers.

Diphenylalanine peptide (Phe-Phe or FF) is a very promising bio-material in the future wearable electronics application due to its self-assembly into nanotubes and nanoribbons with high shear piezoelectric coefficient which is comparable to traditional inorganic piezoelectric materials. In order to efficiently harvest piezoelectric response, alignment and unidirectional polarization of FF nanotubes are required. Most prior works show that there mainly two methods to achieve the alignment and unidirectional polarization. They are epitaxial growth and meniscus-driven dip-coating. However, they still have some disadvantages like low productivity or harsh conditions. In this work, we use inkjet printing technology to develop a scalable, programmable and patterns designable process for the fabrication of FF nanotubes. Most prior works use toxic solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) to dissolve FF peptide. In our work, the ink only contains sustainable and ecofriendly solvent like acetic acid and ethylene glycol. In the inkjet printing process, patterns can be perfectly printed on the substrate of graphene and ethyl cellulose. The direction and length of FF nanoribbons are controllable. Aligned FF nanoribbons can be observed in the printed devices. Orthorhombic crystal structure is characterized by SEM and XRD. The piezoelectric performance of the device with aligned FF nanoribbons is much higher than the random FF based devices. The FF piezoelectric nanogenerator generates voltage, current, and power density of up to 1.49 V, 10.5 nA, and 4.4 nW/cm2, respectively, under a force of 50 N. Our results show the promising future of FF-based piezoelectric devices in self-powered and wearable electronics application. / Diphenylalanine peptide (Phe-Phe eller FF) är ett mycket lovande biomaterial i den framtida bärbara elektronikapplikationen pågrund av dess självmontering till nanorör och nanorband med hög piezoelektrisk koefficient som är jämförbar med traditionella oorganiska piezoelektriska material. För att effektivt skörda piezoelektrisk respons krävs inriktning och enkelriktad polarisering av FF-nanorör. De flesta tidigare arbeten visar att det huvudsakligen finns tvåmetoder för att uppnå inriktning och enkelriktad polarisering. De är epitaxiell tillväxt och menisk-driven dopp-beläggning. Men de har fortfarande vissa nackdelar som låg produktivitet eller svåra förhållanden. I detta arbete använder vi bläckstråleutskriftsteknik för att utveckla en skalbar, programmerbar och mönsterdesignbar process för tillverkning av FF-nanorör. De flesta tidigare verk använder giftigt lösningsmedel 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) för att lösa upp FF-peptid. I vårt arbete innehåller bläcket endast hållbara och miljövänliga lösningsmedel som ättiksyra och etylenglykol. I bläckstråleutskriftsprocessen kan mönster tryckas perfekt på substratet av grafen och etylcellulosa. Riktningen och längden på FF nanoband är kontrollerbara. Justerade FF-nanoband kan observeras i de utskrivna enheterna. Ortorhombisk kristallstruktur kännetecknas av SEM och XRD. Den piezoelektriska prestandan hos enheten med justerade FF-nanoband är mycket högre än de slumpmässiga FF-baserade enheterna. FF piezoelektriska nanogeneratorn genererar spänning, ström och effekttäthet på upp till 1,49 V, 10,5 nA respektive 4,4 nW/cm2 med en kraft på 50 N. Våra resultat visar den lovande framtiden för FF-baserade piezoelektriska enheter i sig själv -driven och bärbar elektronikapplikation.

Diphenylalanine peptide (Phe-Phe or FF) is a very promising bio-material in the future wearable electronics application due to its self-assembly into nanotubes and nanoribbons with high shear piezoelectric coefficient which is comparable to traditional inorganic piezoelectric materials. In order to efficiently harvest piezoelectric response, alignment and unidirectional polarization of FF nanotubes are required. Most prior works show that there mainly two methods to achieve the alignment and unidirectional polarization. They are epitaxial growth and meniscus-driven dipcoating. However, they still have some disadvantages like low productivity or harsh conditions. In this work, we use inkjet printing technology to develop a scalable, programmable and patterns designable process for the fabrication of FF nanotubes. Most prior works use toxic solvent 1,1,1,3,3,3-hexafluoro2-propanol (HFIP) to dissolve FF peptide. In our work, the ink only contains sustainable and ecofriendly solvent like acetic acid and ethylene glycol. In the inkjet printing process, patterns can be perfectly printed on the substrate of graphene and ethyl cellulose. The direction and length of FF nanoribbons are controllable. Aligned FF nanoribbons can be observed in the printed devices. Orthorhombic crystal structure is characterized by SEM and XRD. The piezoelectric performance of the device with aligned FF nanoribbons is much higher than the random FF based devices. The FF piezoelectric nanogenerator generates voltage, current, and power density of up to 1.49 V, 10.5 nA, and 4.4 nW/cm2, respectively, under a force of 50 N. Our results show the promising future of FFbased piezoelectric devices in self-powered and wearable electronics application. / Diphenylalanine peptide (Phe-Phe eller FF) är ett mycket lovande biomaterial i den framtida bärbara elektronikapplikationen på grund av dess självmontering till nanorör och nanorband med hög piezoelektrisk koefficient som är jämförbar med traditionella oorganiska piezoelektriska material. För att effektivt skörda piezoelektrisk respons krävs inriktning och enkelriktad polarisering av FFnanorör. De flesta tidigare arbeten visar att det huvudsakligen finns två metoder för att uppnå inriktning och enkelriktad polarisering. De är epitaxiell tillväxt och menisk-driven dopp-beläggning. Men de har fortfarande vissa nackdelar som låg produktivitet eller svåra förhållanden. I detta arbete använder vi bläckstråleutskriftsteknik för att utveckla en skalbar, programmerbar och mönsterdesignbar process för tillverkning av FF-nanorör. De flesta tidigare verk använder giftigt lösningsmedel 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) för att lösa upp FF-peptid. I vårt arbete innehåller bläcket endast hållbara och miljövänliga lösningsmedel som ättiksyra och etylenglykol. I bläckstråleutskriftsprocessen kan mönster tryckas perfekt på substratet av grafen och etylcellulosa. Riktningen och längden på FF nanoband är kontrollerbara. Justerade FF-nanoband kan observeras i de utskrivna enheterna. Ortorhombisk kristallstruktur kännetecknas av SEM och XRD. Den piezoelektriska prestandan hos enheten med justerade FF-nanoband är mycket högre än de slumpmässiga FF-baserade enheterna. FF piezoelektriska nanogeneratorn genererar spänning, ström och effekttäthet på upp till 1,49 V, 10,5 nA respektive 4,4 nW/cm2 med en kraft på 50 N. Våra resultat visar den lovande framtiden för FF-baserade piezoelektriska enheter i sig själv -driven och bärbar elektronikapplikation.

Le marquage isotopique par le deutérium et le tritium est largement utilisé en chimie, en biologie ainsi qu’en recherche pharmaceutique.De nombreuses méthodes de marquage par échange isotopique permettent d’atteindre des enrichissements isotopiques élevés, mais elles requièrent généralement l’utilisation de conditions drastiques (température élevée, acidité). Ainsi, une méthode générale de marquage, régiosélective et douce, applicable à une grande variété de substrats, reste encore à développer. Dans le premier volet de cette thèse, nous avons montré que des nanoparticules de ruthénium (RuNP@PVP), synthétisées par l’équipe du Pr. Bruno Chaudret (INSA Toulouse), catalysaient avec une grande efficacité la réaction d’échange H/D sur des amines, des pyridines et des indoles par C‒H activation, sous 2 bars de D2 à 55 °C. L’application à la deutération de huit molécules azotées d'intérêt biologique a montré que la réaction était efficace sans pour autant altérer l’intégrité chimique ou stéréochimique des composés. Cependant, le respect de la stéréochimie originelle d’un centre chiral C‒H activé demeurait un problème majeur. Nous avons donc entrepris l’étude de la réactivité des RuNP@PVP sur différentes classes de substrats azotés chiraux (amines, aminoacides et peptides) dans l’eau ou dans des solvants organiques. Nos résultats ont montré sans ambiguïté que la C-H activation des carbones C(sp3) chiraux s’effectuait efficacement, sélectivement et dans tous les cas avec une rétention totale de configuration. La large gamme d’application de cette procédure a été démontrée par le marquage de 3 amines chirales, 14 aminoacides naturels, 3 aminoesters aromatiques et 4 peptides. D’autre part, notre collaboration avec l’équipe du Pr. Romuald Poteau (INSA Toulouse) a permis d’identifier deux mécanismes réactionnels par simulation ab initio en parfait accord avec nos résultats expérimentaux : le mécanisme par métathèse de liaison σ et le mécanisme d’addition oxydante. Ces deux mécanismes impliquent deux atomes de ruthénium voisins agissant ensemble pour conduire à la formation d’un intermédiaire-clé original dimétallacycle à quatre centres.Le second volet de cette thèse est consacré au développement d’une nouvelle méthode de détermination de la conformation et de l’arrangement relatif de petites molécules auto-assemblées. Elle repose sur la synergie entre chimie de marquage, RMN du tritium à l’état solide et modélisation moléculaire. Nous nous sommes plus particulièrement intéressés au dipeptide diphénylalanine (Phe-Phe) qui, selon le solvant utilisé, peut former des cristaux (structure résolue) ou s’auto-assembler en nanotubes dont la structure atomique reste inconnue. Trois dipeptides Phe-Phe ditritiés sur des positions aromatiques, définies à l’aide de la modélisation moléculaire par le Dr. Yves Boulard (CEA Saclay), ont été synthétisés. La RMN du tritium à l’état solide a permis au Dr. Thibault Charpentier (CEA Saclay) de mesurer, sur des échantillons cristallisés, trois distances inter-tritiums très proches des distances de référence. Cette technique a également mis en évidence un éventuel désordre d’orientation d’un cycle aromatique de Phe-Phe cristallisé. Une modélisation ab initio nous a également incités à entreprendre un double marquage Caryl et Cα de Phe-Phe, ce dernier utilisant les nanoparticules de ruthénium. Les essais de marquage au deutérium avec RuNP@PVP sont très encourageants et des études complémentaires sont en cours dans notre laboratoire pour parvenir au marquage au tritium. Ainsi, nous espérons mettre au point un nouvel outil d’étude structurale permettant d’accéder à la structure atomique de petites molécules intégrées dans des ensembles supramoléculaires complexes (nanotubes, peptides amyloïdes ou membranaires). / Isotopic labeling with deuterium and tritium is extensively used in chemistry, biology and pharmaceutical research.Numerous methods of labeling by isotopic exchange allow high isotopic enrichments but generally require harsh conditions (high temperatures, acidity). As a consequence, a general, regioselective and smooth labeling method that might be applicable to a wide diversity of substrates remains to develop. In the first part of this thesis, we demonstrated that the use of ruthenium nanoparticles, synthesized by Pr. Bruno Chaudret’s team (INSA Toulouse), allowed the mild (2 bar of deuterium gas at 55°C), effective and selective H/D exchange reaction of a large variety of nitrogen-containing compounds, such as pyridines, indoles and primary, secondary and tertiary alkyl amines. The usefulness and the efficiency of this novel methodology was demonstrated by the deuteration of eight nitrogen-containing molecules of biological interest without altering their chemical and stereochemical properties. However, the conservation of the original stereochemistry of an activated chiral C-H center remains a major issue. We studied the reactivity of RuNP@PVP on different categories of nitrogen-containing substrates (amines, aminoacids and peptides) in water or in organic solvents. Our results showed that C-H activation of chiral carbons C(sp3) took place efficiently, selectively and, in all cases, with total retention of configuration. The wide range of applications of this procedure was demonstrated by the labeling of three chiral amines, fourteen aminoacids, three aromatic aminoesters and four peptides. Moreover, our collaboration with Pr. Romuald Poteau’s team (INSA Toulouse) led to the identification of two mechanisms by ab initio simulation in agreement with our experimental results: the σ-bond metathesis mechanism and the oxidative addition mechanism. These two mechanisms imply two vicinal ruthenium atoms leading to the formation an original dimetallacycle key-intermediate with four centers.The second part of this thesis deals with the development of a new method for the determination of the conformation and the relative arrangement of auto-assembled small molecules. It is based on the synergy between labeling chemistry, tritium solid-state NMR and molecular modeling. We focused on the diphenylalanine dipeptide (Phe-Phe) which forms either crystals or self-assembled nanotubes depending on the solvent. If the crystalline atomic structure of Phe-Phe has been solved, the structure of the self-assembled nanotubes of Phe-Phe is still unknown. Three Phe-Phe dipeptides ditritiated on aromatic positions, determined with the help of molecular modeling by Dr. Yves Boulard (CEA Saclay), were synthesized. Tritium solid-state NMR allowed Dr. Thibault Charpentier (CEA Saclay) to measure, on crystallized samples, three inter-tritiums distances very close to the reference distances. This technique also revealed a possible orientational disorder on an aromatic cycle of crystallized Phe-Phe. Ab initio modeling led us to set a double labeling Caryl and Cα on Phe-Phe with ruthenium nanoparticles. Deuteration with RuNP@PVP are very promising and supplementary studies are in progress to perform tritium labeling. We expect to set a new tool of structural study to determine atomic structures of small molecules integrated in supramolecular complexes (nanotubes, amyloid peptides or membranes).