Dye-sensitized Solar Cells (DSSC), also known as Grätzel cells, have been identified as a cost-effective, easy-to-manufacture alternative to conventional solar cells. While mimicking natural photosynthesis, they are currently the most efficient third-generation solar technology available. Among others, their cost is dominated by the synthetic dye which consists of efficient Ruthenium based complexes due to their high and wide spectral absorbance. However, the severe toxicity, sophisticated preparation techniques as well as the elevated total cost of the sensitizing dye is of concern. Consequently, the current global trend in the field focuses on the exploitation of alternative organic dyes such as natural dyes which have been studied intensively. The main attractive features of natural dyes are their availability, environmental friendly, less toxicity, less polluting and low in cost. This contribution reports on the possibility of using sepia melanin dye for such DSSC application in replacement of standard costly ruthenium dyes. The sepia melanin polymer has interesting properties such as a considerable spectral absorbance width due to the high degree of conjugation of the molecule. This polymer is capable of absorbing light quantum, both at low and high energies ranging from the infrared to the UV region. The comprehensive literature survey on Grätzel solar cells, its operating principle, as well as its sensitization by natural dyes focusing on sepia melanin has been provided in this master’s dissertation. The obtained results in investigating the morphology, chemical composition, crystalline structure as well as optical properties of sepia melanin samples using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy x-ray diffraction, X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Raman spectroscopy, UV-VIS absorption spectroscopy as well as Photoluminescence (PL) for Grätzel solar cell application have been reported. These results represent an important step forward in defining the structure of melanin. The results clearly show that sepia melanin can be used as natural dye to DSSC sensitization. It is promising for the realization of high cell performance, low-cost production, and non-toxicity. It should be emphasized here that natural dyes from food are better for human health than synthetic dyes. / Physics / 1 online resource (xii, 101 leaves) : illustrations / M. Sc. (Physics)

A síntese de zeólitas a partir de cinzas leves e pesadas de carvão mineral foi realizada por tratamento hidrotérmico alcalino, as quais foram nomeadas ZCL e ZCP, respectivamente. As zeólitas organomodificadas ZML e ZMP foram obtidas a partir da modificação superficial de ZCL e ZCP, respectivamente, utilizando o surfactante catiônico brometo de hexadeciltrimetilamônio. A partir das soluções remanescentes geradas na síntese de ZCL e ZCP foi possível sintetizar duas novas zeólitas. As características físicoquímicas dos nanomateriais zeolíticos sintetizados, bem como de suas respectivas matérias primas, tais como: capacidade de troca catiônica, massa específica, área específica, composição química, mineralógica e morfológica, entre outras, foram determinadas. Os adsorventes ZML e ZMP foram utilizados na remoção dos corantes Azul Direto 71 (DB71) e Rodamina B (RB) de soluções aquosas em sistema de batelada. Desta forma, quatro sistemas DB71/ZML, RB/ZML, DB71/ZMP e RB/ZMP foram investigados. Os modelos de pseudoprimeira ordem e pseudo-segunda ordem foram aplicados aos dados experimentais para o estudo da cinética de adsorção. O modelo de pseudosegunda ordem foi o que melhor descreveu o processo de adsorção de todos os sistemas corante/zeólita organomodificada. O equilíbrio da adsorção foi analisado a partir de quatro modelos de isoterma, sendo eles: Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Os resultados mostram que os modelos de Freundlich e Langmuir melhor descreveram os dados experimentais dos sistemas DB71/ZML e DB71/ZMP, respectivamente. Para os sistemas com RB, o modelo de D-R foi o que melhor se ajustou para ambos adsorventes ZML e ZMP. O planejamento fatorial 24 foi aplicado para a análise dos seguintes fatores que influenciam o processo de adsorção: concentração inicial do corante (Co), pH, dose de adsorvente (M) e temperatura (T). De acordo com as condições estudadas concluiu-se, com o intervalo de confiança igual a 95%, que para o sistema DB71/ZML, os fatores e suas interações que mais influenciam foram C0, M, pH, pH*M, pH*C0, M*C0, pH*M*C0, nessa ordem. No sistema DB71/ZMP, a ordem de influência foi: M, C0, pH, pH*M, pH*C0, M*C0, pH*M*C0. Para os sistemas RB/ZML e RB/ZMP, os resultados foram: M, C0, M*C0, pH, pH*M e M, C0, M*C0, respectivamente. O equilíbrio de adsorção foi atingido em cerca de 40 min para todas as amostras. As porcentagens de remoção do DB71 estavam na faixa de 50 80% e 20 50% para ZML e ZMP, respectivamente. A faixa de porcentagens de remoção do RB variou entre 60 80% e 30 50% para ZML e ZMP, respectivamente. / The synthesis of zeolites from mineral coal fly and bottom ash was performed by alkaline hydrothermal treatment, which were named ZFA and ZBA, respectively. Organo-modified zeolites, SMZF and SMZB, were obtained from surface modification of ZFA and ZBA, respectively, using the cationic surfactant hexadecyltrimethylammonium bromide. From the remaining solutions generated in ZFA and ZBA synthesis it was possible to synthesis two new zeolites. The physicochemical characteristics of the synthesized nanomaterials zeolite as well as their respective raw materials, such as cation exchange capacity, density, specific area, chemical composition, mineralogical and morphological, among others, were determined. The adsorbents SMZF and SMZB were used to remove the dyes, Direct Blue 71 (DB71) and Rhodamine B (RB) from aqueous solutions in batch system. Thus, four systems DB71/SMZF, RB/SMZF, DB71/SMZB, RB/SMZB were investigated. The models of pseudo-first order and pseudo-second order were applied to the experimental data for the study the adsorption kinetics. The model of pseudo-second order was the one that best described the adsorption of all dye/organomodified-zeolites systems. The equilibrium adsorption was analyzed from four models isotherm, namely: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-B). The results show that the model Freundlich and Langmuir best described the experimental data systems DB71/SMZF and DB71/SMZB, respectively. For systems with RB, the model D-R was the best fit for both adsorbents (SMZF and SMZB). The factorial design 24 was applied to the analysis of the following factors influencing the adsorption process: initial concentration of dye (Co), pH, amount of adsorbent (M) and temperature (T). Under the conditions studied it concludes with the confidence interval of 95%, which for the DB71/SMZF system, the factors and their interactions that influence more were C0, M, pH, pH*M, pH*C0, M*C0, pH*M*C0, in that order. In DB71/SMZB system, the order of influence was: M, C0, pH, pH*M, pH*C0, M*C0, pH*M*C0. For RB/SMZF and RB/SMZB systems, the results were: M, C0, M*C0, pH, pH*M and M, C0, M*C0, respectively. The adsorption equilibrium was attained in about 40 min for all samples. The DB71 removal percentages were in the range of 50 80% and 20 50% for ZML and ZMP, respectively. The range of RB removal percentages varied between 60 80% and 30 50% for ZML and ZMP, respectively.

Thesis advisor: John Wing / Presented here is research investigating genes that are involved in the development and maintenance of ciliated nerve endings in the nematode Caenorhabditis elegans. C. elegans utilizes a subset of neurons, referred to as ciliated sensory neurons, to sense certain changes in its environment. There are two amphid sensilla (sense organs) that mediate exposure of these ciliated endings to the animal's external environment. Those ciliated endings that penetrate the cuticle are responsible for a myriad of behaviors that range from chemotaxis to osmotic avoidance, but in general function for the reception of environmental cues and stimuli. The intraflagellar transport (IFT) process facilitates the morphogenesis of these ciliated endings, and animals lacking intact ciliated endings may not be able to detect nourishment, hazardous environments, or other worms for mating. Mutant strains used in this study were generated by EMS mutagenesis of wild-type N2 animals and a subsequent screen of those worms displaying significant cilia dysfunction as evidenced by their dye-filling defective (Dyf) phenotype. Cilia-mediated uptake of lipophilic DiI into six pairs of amphid sensory neurons and two pairs of phasmid sensory neurons is expected in wild-type (N2) animals, but in Dyf animals, this dye-filling is disrupted, either through morphological defects, or deleterious mutations in the IFT process. To investigate the morphogenesis of cilia in C. elegans, we analyzed two specific mutant strains, WX737 dyf-3(og022)IV and PK841 dyf-15(pk841)V, that are defective in the uptake of fluorescent dye DiI and abnormal in sensory cilium structure. Through a variety of genetic mapping techniques, we were able to successfully map experimental gene dyf-15(pk841) to an interval of 2.84cM on chromosome V, and identify og022 as an allele of the gene dyf-3. It has been previously shown that dyf-3 expression is detected in 26 chemosensory neurons, including six IL2 neurons, eight pairs of amphid neurons (ASE, ADF, ASG, ASH, ASI, ASJ, ASK and ADL) and two pairs of phasmid neurons (PHA and PHB). Analysis of cilium malformation and the presence of a recognition sequence for the DAF-19 transcription factor suggest that dyf-3 is involved in the intraflagellar transport system complex B. / Thesis (BS) — Boston College, 2008. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Biology. / Discipline: College Honors Program.

Este trabalho teve por objetivo estudar as interações do corante auramina O em suspensões aquosas de argilas naturais e sintéticas, correlacionando as diferenças de comportamento do corante com as propriedades das argilas estudadas. Estes sistemas podem ser futuramente empregados no desenvolvimento de materiais híbridos corante-argila fotoativos. A Auramina O foi estudada nas argilas, utilizando-se espectroscopia de absorção molecular na região do UV - visível e técnicas de fluorescência estática e dinâmica. A fluorescência da Auramina O aumenta após a adição do corante na argila, devido à adsorção das moléculas de corante na superfície externa das argilas, que restringe o movimento de torção da Auramina. Em períodos mais longos, as moléculas do corante migram para a região interlamelar das partículas de argila. A agregação das moléculas de corante pode ocorrer na região interlamelar, conduzindo à diminuição da emissão de fluorescência. Os rendimentos quânticos de fluorescência (ΦF) da auramina O nas argilas montmorilonitas naturais SAz-1, SWy-1, e nas argilas sintéticas Syn-1 e Laponita RDS são 0,015; 0,007; 0,016 e 0,017, respectivamente. Estes valores são maiores do que o rendimento quântico de fluorescência (ΦF) da auramina em solução aquosa e são da mesma ordem de grandeza do ΦF encontrado para solventes viscosos investigados como n-hexanol e n-heptanol (0,014 e 0,015). Estudos de espectroscopia de fluorescência resolvidos no tempo da Auramina adsorvida em argilas revelaram decaimentos multiexponenciais com componentes nas faixas de 25-36 ps, 219-362 ps e 1300-1858 ps. Os componentes de vida curtos podem ser atribuídos às espécies ligadas à superfície externa e os componentes de maior tempo de vida são atribuídos a moléculas do corante nos espaços interlamelares, que interagem fortemente com a argila. Parece claro que, a adsorção da Auramina nas argilas provoca uma redução significativa da taxa de conversão interna que envolve a difusão de rotação, de modo que o corante é bloqueado em uma geometria desfavorável para a conversão conformacional interna. / This thesis aims to study the auramine dye interactions in the aqueous suspensions of natural and synthetic clays, correlating dye behavioral differences with the properties of the studied clays. The spectroscopic behavior of Auramine O in aqueous suspensions of montmorillonite clays was studied using absorption and static and dynamic fluorescence techniques. The fluorescence of Auramine O increases immediately after mixing the dye solution with the suspension of clay due to its adsorption on the external surface of the clays, which restricts the torsional molecular motion of Auramine. At longer times, the dye molecules migrate into the interlamellar region of the clay particles. Aggregation of the dye molecules can occur in the interlayer region, leading to the decrease of the fluorescence emission. The fluorescence quantum yields (ΦF) of auramine O on the natural montmorillonites SAz-1, SWy-1, Syn-1 and Laponite clays were 0.015, 0.007, 0.016 and 0.017, respectively. These values are higher than the ΦF of auramine O in aqueous solution and are of the same order of magnitude of the ΦF found for viscous solvents such as n-hexanol and n-heptanol (0.014 and 0.015). Time-resolved fluorescence spectroscopy studies of adsorbed Auramine on clays revealed multi-exponential decays with components in the 25-36 ps, 219-362 ps and 1300-1858 ps ranges. The short-lived components can be attributed to species bound to external surface and the longer lifetime is assigned to dye molecules in interlayer spaces interacting strongly with the clay. It seems clear that the binding of Auramine to clays causes a significant reduction of the rate of internal conversion that does involve rotational diffusion, so that the clay will be locked in a conformational geometry unfavorable for internal conversion.

The objective of this research was to study the adsorption and photodegradation of crystal violet (CV) dye by using poly(2-hydroxyethylmethacrylate) (PHEMA) hydrogel and nanocomposite TiO2-PHEMA hydrogel. Since the TiO2 nanoparticle has poor solubility, another goal of this study was to make a uniform TiO2 nanocomposite gel. These gels can be used in water treatment and can be easily photodegrade by exposure of sunlight which is similar to exposing to UV-vis. PHEMA was synthesized by free radical polymerization. The nanocomposite gels were characterized by FT-IR and XRD to confirm the presence of TiO2 nanoparticles and CV dye inside the PHEMA hydrogel. The XRD data showed that not only maintaining the crystallinity of the three different phases that had been used, but also the uptake of the dye inside the nanocomposite gels. Moreover, the FT-IR demonstrated the presence of the functional groups of the chemical structure of the gel as well as the nanocomposite gels with the CV dye. The adsorption of CV dye was examined through monitoring UV-Vis absorption. The kinetic study indicated the adsorption of the dye by the nanocomposite gels until reached equilibrium, which is the zero concentration. The photodegradation of CV dye was examined using a medium pressure Hg lamp. It was determined that the composite gels adsorb CV dye from the solution at the beginning while under the photochemical condition. Eventually, the dye in the gel was photodegraded, indicating that in the gel system, the photodegradation process is still effective to dyes. The composite gels containing pure anatase phase titanium are much better photocatalysts and took less time of adsorption than those containing pure rutile and anatase/rutile mixed phases of titania.

Interações do estado fundamental e espécies transientes, formadas após fotólise e fotossensibilização de 2-ethylaminodiphenylborinate (2APB) e diphenylboronic anhydride (TPhB), foram estudadas por várias técnicas. Os espectros UV mostram uma grande banda de absorção na região do Ultra-violeta. Os espectros de fluorescência mostram o aumento da intensidade de emissão, em 300 nm, que se desloca para o vermelho até 10-3 M. Em concentrações mais elevadas, a intensidade de emissão diminui, provavelmente devido à formação de agregados. Excitação dos organoboranos no UV, em soluções livre de oxigênio, mostram a formação de dois transientes em 300 e 360 nm. Este último, atribuído a espécie triplete, tem uma vida útil de 5 ms em etanol e é totalmente suprimida na presença de oxigênio. A banda em 300 nm não é afetada por oxigênio, tem uma vida útil da ordem de milisegundos e corresponde a uma espécie com radical centrado no boro. O radical também pode ser obtido por transferência eletrônica do estado triplete da Safranina ao organoborano, formando a forma semioxidada do corante. Experimentos EPR, usando DMPO, mostram que a fotólise direta no UV de 2ABP forma o radical arilborano, seguido pela clivagem de uma ligação B-C e formação de radicais fenil. Radicais de boro são formados quando organoboranos são fotossensíveis por Safranina. Na tentativa de se estender o uso de organoboranos em sistemas de poliméricos, sais ônium foi usado para produzir mais iniciadores e melhorar a velocidade de polimerização. Na excitação visível, induzida a produzir iniciadores, o sentitizador (corante *) é oxidado pelo organoborano para formar o cátion radical correspondente (coranteo+) e R3Bo -. Este ânion radical pode iniciar a polimerização ou interagir com sal de ônio, resultando na liberação de uma grande quantidade de radicais que inicia a polimerização mais eficiente. / Ground state interactions and excited states and transients formed after photolysis and photosensitization of 2-ethylaminodiphenylborinate (2APB) and diphenylboronic anhydride (TPhB) were studied by various techniques. The UV spectra show a large absorption band at UV-spectra. The fluorescence spectra show increasing emission intensity with maximum at 300 nm, which shifts to the red up to 10-3 M concentrations. At higher concentrations, the emission intensity decreases, probably due to the formation of aggregates. UV excitation in deareated solutions shows the formation of two transients at 300 and 360 nm. The latter has a lifetime of 5 ms in ethanol and is totally quenched in the presence of oxygen and assigned to the triplet state of organoborane. The 300 nm peak is not affected by oxygen, has a lifetime in the order of milliseconds, and corresponds to a boron-centered radical species originated from the triplet state. The radical can also be obtained by electron transfer from triplet Safranine to the borane forming the semioxidized form of the dye. EPR experiments using DMPO show that the UV-direct photolysis of 2ABP renders initially arylboroncentered radicals followed by the cleavage of a B-C bond and formation of phenyl radicals. Similar boron radicals are formed when 2APB is photosensitized by Safranine. To extend the use of organoboranes in polymeric system, ônium salts was used to produce more initiators and improve the polymerization velocity. In the visible-induced excitation to produce initiators, the sentitizer (dye*) is oxidized by trivalent and neutral organoborane compound to form the corresponding radical cation (dyeo+) and R3Bo-. This radical anion may itself initiate the polymerization or may interact with onium salt, resulting in the release of a lot of radical that can initiate the polymerization more efficiently.

by Lam King Shun. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves [40-41]). / by Lam King Shun. / Acknowledgement --- p.i / Biographical Sketch --- p.ii / Abstract --- p.iii / Table of Contents --- p.iv / Chapter Chapter One --- Introduction --- p.1 / Chapter Chapter Two --- The Sol-Gel Derived Silica / Chapter 2.1 --- Introduction to the so-gel science --- p.3 / Chapter 2.2 --- The procedure of the silica formation --- p.5 / Chapter 2.3 --- During the sol-gel process --- p.7 / Chapter 2.4 --- The silica characterization --- p.12 / Chapter 2.4.1 --- Physical properties --- p.12 / Chapter 2.4.2 --- Optical properties --- p.13 / Chapter 2.5 --- Sample preparation --- p.15 / Chapter Chapter Three --- Laser Experiments / Chapter 3.1 --- Basic principle of dye laser --- p.16 / Chapter 3.2 --- Experimental procedure --- p.20 / Chapter 3.3 --- Data and discussion --- p.23 / Chapter 3.3.1 --- Spectral and temporal behaviour --- p.2 3 / Chapter 3.3.2 --- The performance of the sol-gel silica laser --- p.37 / Chapter Chapter Four --- Conclusions and Suggestions for Further Work --- p.39 / References

Models for electron transport and back reaction in dye-sensitized nanocrystalline solar cells were investigated by developing novel measurement techniques and the results were used to test two complementary models; diffusive electron transport within the TiO2 medium and the quasi-static approximation to deal with non steady-state conditions where trapping plays a role. These will be shown to be partly correct and the shortfalls highlighted and discussed. In the end it was found that more knowledge of the parameters governing the behaviour of electrons is required to further test and develop the models. The incorporation of a secondary sensing electrode allowed the internal quasi-Fermi level (QFL) within the TiO2 to be probed. The behaviour of the voltage measured by the secondary sensing electrode was in accordance with diffusive electron transport in the TiO2. This was confirmed by measuring the QFL along the current-voltage curve of the cell, and by the temperature dependence of the measured QFL. Discrepancies concerning the behaviour of the ideality of the open-circuit voltage (and hence the electron lifetime) between experiment and modelling are highlighted and discussed throughout. Assuming an Arrhenius relationship simple expressions for the temperature dependence of the open-circuit voltage were derived and experimentally tested. The trapped electron density was measured along the current-voltage curve. With the inclusion of the secondary sensing electrode and measuring the trap distribution, the way the trapped charge varied could be modelled and compared to experiment. This provided an important link between the free and trapped electron density profiles but again highlighted shortcomings of the applied models. The quasi-static approximation was tested against a full numerical solution (continuum model) to determine the phase space in which it is applicable. Knowing this, an almost ideally behaving cell was used to test the quasi-static approximation. Having shown that it was valid for the given cell, the quasi-static approximation was used to determine how the conduction band electron lifetime varied with temperature, resulting in an Arrhenius dependence of the back reaction rate of electrons. A strong temperature dependence of the electron lifetime, and hence a strong temperature dependence of the electron diffusion length was demonstrated.

Electrochemical and spectroelectrochemical techniques were employed to investigate the redox characteristics of dyes for dye sensitized solar cells (DSCs) adsorbed at the surface of fluorine-doped tin oxide (FTO) and FTO TiO2 electrodes. In this work are studied Ru-based dyes such as cis-bis(isothiocyanato)-bis(2,2’-bipyridyl- 4,4’dicarboxylato)-ruthenium(II) (N719) and (cis-RuLL'(SCN)2 with L=4,4'- dicarboxylic acid-2,2'-bipyridine and L'=4,4'-dinonyl-2,2'-bipyridine) known as Z907, and indoline organic dyes coded as D102, D131, D149, and D205. The adsorption, diffusion and stability of adsorbed dyes were studied using cyclic voltammetry in acetonitrile and 0.1 M NBu4PF6. The adsorption technique at FTO electrodes was optimized in order to be reproducible so that electrochemical studies as a function of dye coverage were carried out. Langmuirian binding constants were approximately estimated for all dyes adsorbed at FTO electrodes. Rate constants for the chemical degradation of the oxidized dye were also obtained. Is shown that degradation of the dyes mainly occurs at the surface of FTO and only insignificant degradation is evident once the dyes are adsorbed on TiO2. The degradation of dye adsorbed on FTO is shown to affect charge transport from the nonporous TiO2 via electron hopping. Spectroelectrochemical studies of indoline dyes adsorbed on FTO/TiO2 electrodes revealed a red shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near IR that suggest delocalization of holes in the dye layer. This is consistent with observation that the diffusion coefficient for hole conduction in the adsorbed dye layer is several orders of magnitude higher for the organic dyes compared to the Ru-based dyes. DSCs fabricated using indoline dyes showed good performance. Incident photon-tocurrent conversion efficiency (IPCE) spectra and I-V characteristics are presented.

No description available.