Resumo: Materiais híbridos orgânicos-inorgânicos são materiais bifásicos onde a interpenetração das fases em uma escala nanométrica permite preparar materiais com propriedades inéditas. Este é o caso dos eletrólitos sólidos transparentes siloxano-poli(propileno óxido) estudados neste trabalho de doutorado. Este trabalho visou estabelecer correlações entre as propriedades de condução iônica e as características estruturais destes híbridos que são preparados pelo processo sol-gel. Os objetivos específicos propostos no projeto original incluem os seguintes itens: (a) estabelecer correlações entre a estrutura e as propriedades determinantes da condutividade iônica; (b) analisar a estrutura local do dopante, sua localização no sistema, e assim determinar os sítios de adsorção bem como sua participação na formação da ligação O-Na-O ou O-K-O envolvendo oxigênios tipo éter da cadeia polimérica; (c) determinar o efeito da retração e da formação de domínios com correlação espacial em função dos diferentes sais dopantes estudados sobre as propriedades de condução iônica; (d) comparar as propriedades e estrutura dos híbridos preparados com polímeros de diferentes massas moleculares e concentrações de dopante. Para isto, estudos das propriedades microestruturais, foram realizados através das técnicas de espalhamento de raios X, e análises da estrutura local por absorção de raios X (XANES e EXAFS), e RMN 23Na e 19F, corroborados com as propriedades de condução iônica dos materiais, além de medidas de espectroscopia Raman. Foram estabelecidas diversas correlações entre a estrutura e as propriedades dos materiais. Foi verificado, para amostras dopadas com KCF3SO3, que as amostras mais condutoras são aquelas que possuem um maior número de oxigênios ao redor do potássio. Paralelo...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Siloxane-poly(oxi propylene) (PPO) or Siloxane-poly(oxi propylene) hybrid materials prepared by the sol-gel route show increasing scientific and technological interest due to its particular structure in which the polymer chains are grafted to the inorganic nanoparticules. When doped with alkaline salts these hybrids present ionic conductivity similar to that of ionic conductive polymers (10-4 S/cm), and both their mechanical and optical properties are improved. However, the nature of the mobile species, are responsible for ther conductivity (free ions, ion-pairs, aggregates) is not well established. So that the knowledge of the nature and the local structure around the mobile ions is the challenger to improve the ionic properties. The ain of this work was to establish the correlations between the local structure around the charge carriers (coordination shell, solvation sphere) and the macroscopic conductivity. To reach this objective the local structure was probed by X ray absorption (XANES and EXAFS), Raman and NMR spectroscopy and the results related to that obtained from conductivity measurements. / Orientador: Celso Valentim Santilli / Coorientador: Karim Dahmouche / Doutor

Neste trabalho investigamos o transporte eletrônico em dispositivos com estrutura ITO(óxido de estanho dopado com índio)/TiO2(dióxido de titânio)/RRP3HT(poli(3-hexiltiofeno)-regiorregular)/Al através de medidas de resposta espectral de fotocorrente, iluminando os dispositivos ora pelo eletrodo de ITO ora pelo de alumínio. O polímero RRP3HT é um politiofeno regiorregular e exibe uma atividade fotovoltaica relativamente alta. Os filmes de TiO2 e RRP3HT foram obtidos por spin-coating, sendo o óxido depositado a partir de uma dispersão coloidal de nanopartículas e o polímero a partir de uma solução de clorofórmio. O eletrodo de Al foi evaporado termicamente sobre o filme de polímero. As medidas de fotocorrente foram realizadas com o uso de uma lâmpada de Xe de 450W e de um monocromador e, depois de diversas medidas tendo a temperatura e a voltagem aplicada como parâmetros, obtivemos uma grande quantidade de importantes dados elétricos sobre os dispositivos. Dependendo das condições experimentais observamos diferentes respostas de fotocorrente: simbática ou antibática. Um modelo baseado em mecanismos de recombinação e na fotogeração de cargas, incluindo o perfil de absorção do RRP3HT, permitiu a obtenção de parâmetros elétricos importante em aplicações desse polímero a dispositivos fotodetectores e células solares. / In this work we investigated electronic transport phenomena in an ITO/TiO2/RRP3HT/Al structure using photoconductivity spectral response when devices were illuminated either by the ITO electrode or by the aluminum. RRP3HT is the regioregular poly(3-hexylthiophene), a polymer that exhibits a relatively strong photovoltaic activity. RRP3HT were dissolved in a solution of chloroform and nanoparticles of TiO2 were used in a colloidal dispersion. Both thin films of TiO2 and P3HT were deposited by spin coating technique over a commercial glass covered with ITO, and Al electrode was vacuum evaporated. Photoconductivity measurements were carried out making use of a Xenon lamp of 450 W and a monochromator to produce a single spectral line. After several measurements, having temperature and constant applied voltage as parameters, we obtained a great amount of important electrical data for the devices. Depending on the experimental conditions we obtained different photocurrent response, i. e. symbatic or antibatic. A model based on recombination mechanisms and photogenerated charges, including the absorption profile of the RRP3HT, allowed us to get some electrical parameters that are important for photovoltaic and photoconductive applications.

Neste trabalho são elaborados biossensores para a detecção amperométrica de glicose. Para isso, imobilizou-se a enzima glicose oxidase em matrizes de polímeros condutores. Foram construídos sensores utilizando-se poli(pirrol) e poli(N-metilpirrol). Com o objetivo de substituir o oxigênio molecular na etapa de transdução do sinal, o ferroceno foi incorporado dentro do polímero condutor. Para isso, os polímeros foram elaborados utilizando misturas água-etanol como meio de polimerização. A inclusão do ferroceno no sensor resulta em maior sensibilidad à glicose (4,33 µA Mm-1 cm-2 para o biossensor preparado a partir da mistura água-etanol contendo o ferroceno e de 0,23 µA mM-1 cm-2 para o sensor sem ferroceno ). Por outro lado, permite o funcionamento do sensor a potenciais menores que no caso do sensor sem ferroceno (0,4 V para o sensor com ferroceno vs. 0,65 V para o caso sem ferroceno). O deslocamento do potencial de detecção para valores menos positivos não foi suficiente para evitar as interferências causadas pelos íons ascorbato e ureato. Para isto, mostrou-se 100% efetivo o recobrimento dos sensores com uma película de Nafion®. A sobreoxidação do poli(pirrol) também mostrou potencialidade para a eliminação de interferentes, embora o processo resulte na perda de sensibilidade, provavelmente causada pela desnaturação da enzima. Quando usado o poli(N-metilpirrol) como suporte para a enzima, obtiveram se melhores respostas, causadas pela possibilidade de se preparar filmes mais espessos, consequentemente de imobilizar maior quantidade de enzima, sem observar perda de resposta causada por problemas difusionais. / The present work describes the elaboration of a biosensor for glucose detection. The enzyme, glucose oxidase, was immobilized in different conducting polymers. Two different polymers were used: polypyrrole and poly(N-methilpyrrole ). With the aim of replacing the molecular oxygen in the transduction step, ferrocene has been immobilized within the conducting polymer. Once the ferrocenium was insoluble in water, in order to develop a different route, the electropolymerization was carried out in a mixture of water and ethanol (1:1). This procedure leads to a polymer with a poor electroactivity, detected by Raman experiments. The ferrocene addition in the sensor increases the sensitivity to the glucose determination (4,33 µA mM-1 cm-2 for the biosensor with ferroecene and 0,23 µA mM-1 cm-2 for the sensor without ferrocene). Alternatively, the sensor containing ferrocene allows to operate at less positive potentials than that one without ferrocene (+ 0,40 V and + 0,65 V, respectively). This potential shift was not enough to inhibit the interference caused by ascorbate and ureate ions. One method to avoid the interference problem was to recover the sensor with a very thin layer of Nafion. Also poly(pyrrole) overoxidation is a very efficient method to eliminate this interference, but this process leads to a sensitivity decrease dueto enzyme denaturation. A better response was observed for sensor assembled using the poly(Nmethyl-pyrrole) as the support for enzyme immobilization. This behavior was provoked by the thicker of polymer film formed leading to higher amount of immobilized enzyme. Even though, no diminution in the response was caused by diffusion problems.

Στην εργασία αυτή μελετήθηκε η μεταβολή της ειδικής ηλεκτρικής αγωγιμότητας συναρτήσει της θερμοκρασίας για την πολυπυρρόλη, την πολυανιλίνη καθώς και συνθέτων αυτών εμπλουτισμένων με οξείδιο του ψευδαργύρου και ατμούς μεταλλικού ιωδίου με σκοπό την εφαρμογή των παραπάνω υλικών ως υποστρώματα σε φωτοβολταϊκές κυψελίδες (solar cells). Τα παραπάνω υλικά ανήκουν στην κατηγορία των οργανικών ημιαγωγών και αποτελούν τη λεγόμενη "τέταρτη γενιά" πολυμερών. / In this work the thermal aging of conducting polyaniline and polypyrrole and their blends with ZnO : (PPy/ZnO (x% w/w) with x =10, 20, 30, 40),PANI/ZnO (20% w/w) and iodine has been investigated for the application of these materials as substrates in photovoltaic cells. Today, research is focused on the organic solar cells, in which the electrical current flow is due to molecules, which play the role of donors or acceptors of electrical charge. Organic PV cells have the advantages of easy construction, low cost and they are friendly to the environment. Indium tin oxide is used as anode in organic PVs, which is characterized by high concentration of charge carriers and is used for the injection of positive charge carriers (holes) in the organic active layer. For all the samples conductivity followed one of the models: 1. FIT (Fluctuation Induced Tunneling), in the case that we have a granular metal structure, in which conductive grains are separated by insulating barriers. These insulating barriers are narrow enough for the carriers to tunnel through small areas where the grains are closest together and the conductivity is dominated by the thermal fluctuations of the carriers in these areas. The relationship σ=f(T) is given by σ=σ0 exp[-T1/T0+T]. From T1 and T0 the distance s between the grains can be determined. In this work the FIT model applied to the sample of pure polypyrrole throughout the duration of thermal degradation. 2. CELT (Charging Energy Limited Tunneling), in the case that we have a granular metal structure, through which the carriers move by tunneling effect. T0 is related directly to the ratio s/d, where s is the main separation and d is the mean diameter of the grains and can give informations about the shrinking of the grains during aging. The relationship between σ and T is given by: σ=σ0 exp[-(Τ0/Τ)γ] where σ0 and T0 are indepedent factors of the temperature and 0 < γ < 0,25. In this work the CELT model applied for the samples of pure polyaniline, PPy/ZnO (10% w/w), PPy/ZnO (20 %w/w), PANI/ZnO (20% w/w) and PPy/I throughout the duration of thermal degradation. 3. Mott (Variable range hopping model), in the case of heterogeneous structures of amorphous materials. The conductivity takes place by thermally activated electron hopping between localized states near Fermi energy. The localization is due to the randomly distributed atoms or molecules in the material. The relationship describing the change in conductivity with T is similar to that of the CELT model, with the exponent γ is roughly equal to 0,25. In this work the Mott model applied for the samples PPy/ZnO(40% w/w) and PPy/I (sublimation with iodine vapour for 24 h). The degreasing of conductivity σ, with thermal aging time t for a substance with a granular metal structure follows the law: σ=σαρχ exp[-(t/τ)0,5] where τ is the time which characterizes the aging. All our composites followed this relation, ensuring a granular metal structure. It also became apparent that heating greatly reduces the electrical conductivity of our composites. The thermal degradation of PANI at room temperature (300K) gives τ = (350 ± 50) h, though at 120 0C PANI gives τ = (18 ± 4) h, indicating a much faster degradation as it is expected. The characteristic parameter τ has been calculated for all the materials used in this work.

As técnicas de Espectroscopia de Alta Resolução em Sólidos e Relaxação por RMN são largamente utilizadas no estudo da estrutura e dinâmica de polímeros. Neste trabalho estudamos, utilizando estas técnicas, duas classes distintas de polímeros: os condutores iônicos e os condutores eletrônicos. O polímero condutor iônico estudado foi o Diesterato de Polietileno Glicol (PEGD) complexado com sais de metais alcalinos, LiClO4 ou NaClO4. A metodologia básica que empregamos para o estudo destes materiais foi a análise da forma de linha e do tempo de relaxação longitudinal para os núcleos associados tanto aos portadores de carga, 7Li e 23Na, quanto à cadeia polimérica, 1H e 13C. Todas estas medidas foram realizadas em função da temperatura e da concentração de sal de metal alcalino presente na amostra. Estudos adicionais, por condutividade elétrica, análise térmica e viscosidade foram realizados para complementar o conhecimento obtido por RMN sobre a mobilidade e estrutura das cadeias poliméricas e dos portadores de carga. Os polímeros com ligações de elétrons-\'pi\' conjugados apresentam propriedades eletrônicas especiais, particularmente a condutividade elétrica, e formam uma classe de polímeros condutores eletrônicos que podem ser facilmente oxidados ou reduzidos através de um agente dopante. Estudamos dois polímeros deste tipo: As polianilinas dopadas com 1H ou 7Li. A metodologia básica que empregamos para o estudo destes polímeros foi a análise das formas de linhas espectrais de um dos núcleos que compõem a cadeia polimérica, 13C, e de um dos agentes dopantes, 7Li, em função do método de preparação e da condutividade elétrica, de forma a poder elucidar características estruturais e dinâmicas deste grupo de polímeros. A partir do estudo destas duas classes de polímeros, conseguimos coletar uma quantidade muito grande de resultados experimentais por RMN, a partir de diferentes núcleos atômicos, que contribuíram para elucidar várias de suas características estruturais e dinâmicas / High resolution solid-state NMR spectroscopic techniques are widely used in the study of polymer structure and dynamics. In the present work we are studying, with the employment of these techniques, two distinct kinds of polymers: the ionic conductors and the electronic conductors. The ionic conductor polymer considered was the Poliethyleneglycol Distereate - 400)/MclO4, (M=Li,Na), DPEG/MclO4. The basic methodology employed for the study of these materials were the line shape analysis of the resonance lines and the longitudinal relaxation time, for the nuclei associated with the charge carriers, 7Li and 23Na, and with the polymeric chain, 1H and 13C. The measurements were related to temperature and to the alkali metal salt concentration in the sample. Additional studies, of electrical conductivity, thermal analysis and viscosity were also conducted for the complementation of the information obtained by NMR about the mobility and structure of polymeric chains and the charge carriers. The polymers with conjugated n-electron bounds present special electronic properties, particularly related to the electrical conductivity, and are easily oxidized or reduced by the action of a doping agent. We studied two of these kind of polymers: the 1H and 7Li doped Polyaniline. The basic methodology employed for the study of these polymers was the line shape analysis of the resonance lines related to one of the component nuclei of the polymeric chain, 13C , and the lines related to one of doping agents, 7Li, as a function of the preparation method and the electrical conductivity, as a way of elucidate structural and dynamic characteristics of this class of polymers. From the study of these two classes of polymers we could collect a huge quantity of NMR data from different atomic nuclei, and it led to the elucidation of important structural and dynamic characteristics of the polymers

O presente trabalho tem como objetivo o estudo e o desenvolvimento de dispositivos eletrônicos, para o monitoramento de gás de amônia, confeccionados com filmes ultrafinos de polianilina e ftalocianinas metálicas. Foram fabricados três diferentes tipos de sistemas: polianilina/PVS, polianilina/ftalocianina de níquel e polianilina/ftalocianina de cobre, sendo a espessura dos filmes o parâmetro de análise. Foram preparadas amostras com 10, 20 e 40 bicamadas. Os filmes foram caracterizados por profilometria e espectroscopia de absorção na faixa da radiação do UV - visível. Observou-se um aumento linear da espessura dos filmes com o aumento do número de bicamadas depositadas. Os dispositivos foram preparados a partir da deposição dos filmes ultrafinos de polianilina e ftalocianinas sobre substratos de vidro com eletrodos interdigitados de ouro evaporados termicamente. Os dispositivos foram caracterizados eletricamente por medidas de variação da resistência elétrica, em regime de corrente contínua e alternada, para diferentes concentrações de amônia. Também foi analisado o efeito da temperatura e da umidade relativa do ar na sensibilidade dos dispositivos. Todas as estruturas apresentaram uma dependência direta do valor da resistência elétrica com a concentração de amônia. Os dispositivos baseados em filmes de polianilina e ftalocianina de níquel apresentaram a menor variação do valor de resistência elétrica com a umidade relativa do ar. Esta característica é bastante desejável já que os ambientes nos quais se pretende utilizar este tipo de dispositivo para de monitoramento do gás de amônia, pode sofrer grandes variações no valor da umidade relativa do ar, como é o caso de granjas em geral. / The aim of this work is the study and development of electronic devices for ammonia gas monitoring based on polyaniline and metal phthalocyanines ultrathin films. It was produced three different systems: polyaniline/PVS, polyaniline/nickel phthalocyanine of and polyaniline/copper phthalocyanine and the analysis parameter of the films is the thickness. Samples were prepared with 10, 20 and 40 bilayers. The films were characterized by profilometry and spectroscopy of absorption of radiation in the range of UV-visible. There was a linear increase the thickness of the films with the increase in the number of deposited bilayers. The devices were prepared from the deposition of polyaniline and ftalocianines ultrathin films on glass substrates with interdigited electrodes of gold evaporated thermally. The devices were prepared from the polyaniline and phthalocyanine deposition of ultrathin films over glass substrates with gold interdigited electrodes. The devices were characterized electrically by measures of variation of electrical resistance, under the direct current and alternating, for different concentrations of ammonia. It was also examined the effect of temperature and relative humidity of the air in the sensitivity of the devices. All structures had a direct dependence of the value of the electrical resistance with the ammonia concentration. Devices based on films of polyaniline and nickel phthalocyanine of had the slightest variation in the amount of electrical resistance with the relative humidity. This feature is desirable because the environments in which it intends to use this type of device for tracking of ammonia gas, may undergo major changes in the value of the relative humidity of the air, such as poultry houses in general.

Polyelectrolytes are conductive polymers because of their ionic side group and PEDOT-S is one of those conductive polyelectrolytes. Previously, recombinant silk fibre has been dyed with PEDOT-S. PEDOT-S showed that it can be dyed with recombinant silk fibre over a very wide range of pH from 11 to 1.7. Previous experiments of dyeing recombinant silk fibre with PEDOT-S has shown that it is a very versatile process and can also be applied on other types of protein-based fibres, and that prompted me to dye wool and silk fibre from Bombyx Mori and make these fibres functionalized. So in this thesis dyeing of wool and silk fibres with PEDOT-S has been carried out. By this bottom-up approach of making an organic polymer electrically conductive and utilising the flexibility of organic polymer, one can integrate it in OLEDs and in smart textiles. In this thesis dyeing of silk and wool fibres with different dyeing pH has been carried out to maximise the exhaustion of dyes on to the fibres to acquire maximum conductance. Then the wool and silk fibres’ conductance and mechanical properties after dyeing were compared. Wool showed better conductance and mechanical properties as compare to silk after being dyed with PEDOT-S. These results helped to propose a model that tells about the interaction between protein-based fibres and polyelectrolytes and gives us better understanding of how these protein-based fibres show certain conductivity at different pH. Results also showed that these conductive fibres can be used further in special purposes and applications. / Program: Magisterutbildning i textilteknologi

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.

Ce travail est consacré à l'étude du dopage de la polyaniline et de ses dérivés substitutés (polyanisidine, poly(2-ethylaniline)) avec d'une part le chlorure d'aluminium AlCl3 ou le chlorure ferrique FeCl3, d'autre part avec leurs dérivés contenant les ligands mixtes chlorure-acétylacétonate (AlCl2(acac) ou (FeCl(acac)2). Les polymères dopés avec AlCl3 ou FeCl3 sont conducteurs, et leur conductivité électronique est de l'ordre de 10-3 S/cm. Des études spectroscopiques complémentaires (UV-VIS-Proche IR, IRTF, RPE, RMN du noyau 27Al (dans le cas du dopage avec AlCl3) et spectroscopie Mössbauer sur le noyau 57Fe (dans le cas du dopage avec FeCl3)), combinées avec l'analyse élémentaire, permettent de comprendre et d'identifier un même mécanisme de dopage. Celui-ci correspond en un premier temps à une dissociation de la molécule du dopant. La partie cationique résultant de cette dissociation est complexée sur les sites azote de type imine de la chaîne du polymère, tandis que la partie anionique s'incorpore à la matrice polymère afin de neutraliser la charge positive imposée à la chaîne du polymère. La sphère de coordination du complexe cationique est complétée par solvatation avec une molécule de nitrométhane. Le réarrangement des charges accompagnant le processus de dopage entraîne la création de radicaux cationiques mobiles sur la chaîne du polymère, donnant ainsi au polymère dopé des propriétés de conduction électronique. Ce mécanisme rend parfaitement compte de la présence de porteurs de charge et de la structure cationique des radicaux de la chaîne polymérique dopée mises en évidence par les expériences de spectroscopie RPE et d'absorption UV-VIS-Proche IR. La polyaniline dopée avec FeCl3 présente de faibles propriétés mécaniques, qui peuvent cependant être améliorées par un traitement ultérieur avec l'hexafluoroacetylacetone (HFAA). Ce traitement conduit à la transformation de la polyaniline dopée avec FeCl3 (acide de Lewis) en un polymère dopé avec HFeCl4 (acide de Brönsted), simultanément plastifié par HFAA. Le dopage avec les ligands mixtes (AlCl2(acac) ou (FeCl(acac)2), bien qu'inopérant en ce qui concerne la polyaniline, conduit clairement au dopage de la polyanisidine et de la poly(2-éthylaniline). Les chaînes de ces polymères dopés présentent une structure radicalaire cationique mise en évidence par les expériences d'absorption UV-VIS-Proche IR ; mais le mécanisme de dopage reste plus complexe à définir que dans le cas du dopage avec AlCl3 ou FeCl3. Le dopage avec AlCl2(acac) conduit à un polymère dopé avec AlCl3 avec Al(acac)3 incorporé à la matrice du polymère comme sous-produit. Le dopage avec FeCl(acac)2 donne un composé présentant davantage de sites de fer non équivalents qu'il en est attendu ; leur nature reste difficile à identifier par spectrométrie Mössbauer.

The goal of the thesis is to incorporate materials with either fluorescent or conductive properties in silk fibers, by feeding silkworms with a diet containing these materials. To achieve this, one would have to breed (rear) silkworm from eggs into larvaes, then to feed the silkworms with this special diet containing fluorescent or conductive materials. Samples of silk were then collected either from spun cocoons or via removing the silk producing organs (silk glands) from the silkworms via dissection. The samples were then analyzed with absorbance spectrometer, spectrofluorometer or via photoluminesecent measurement to determine if any materials had been incorporated into the silk fibers.   Silkworms were successfully reared from eggs up to moths, once the silkworm larvae had grown enough in size their diet were switches from their regular food (silkworm chow) to food containing conjugated molecules or polymers with fluorescent or conductive properties. A total of 14 materials were tested. One material gave a clear positive result and that was from the fluorescent compound Rhodamine B. Other fluorescent materials, Nile red and POWT yielded some results indicating their presence in the silk but the results were not conclusive. The rest of the materials all failed with being incorporated within the silk fibers; this was due to their lethality, size, lack of zwitterionic properties and such.  The properties of the materials are of great importance for the uptake process, where a small zwitterionic molecule has a great change of being taken up and incorporated in the silk fibers. Whereas a big materials such as a polymer without any zwitterionic will in most cases just follow through the food in the digestive track without any uptake.