Merocyanine dyes exhibit interesting changes in absorption spectra with changes in solvent polarity. For example solutions of 1-methyl-4- (oxocyclohexadienylidene) ethylidene -1,4-dihydropyridine (MOED) are yellow, red, violet, or blue, in water, ethanol, acetone or pyridine respectively.1 More striking effects are observed when aqueous solutions are diluted with various proportions of the organic co-solvents such as pyridine. The color varies across the whole spectrum from golden yellow to blue.These characteristic properties of merocyanine dyes in various organic solvents have been extensively studied and correlations between [see PDF file for formula]max and solvent polarity have been determined. In this work the visible absorption have been determined. In this work the visible absorption properties of merocyanine dyes were studied in cationic and anionic surfactants in order to investigate the behaviour of these dyes in micellar system and to use their electronic spectra as probes of the micellar environment. Since the description of the literature and discussion of the experimental results will involve certain terms and concepts from surfactant chemistry, it is necessary to introduce the subject.

Nuestro modelo de negocio ofrece una propuesta innovadora y saludable que generará beneficios económicos para los accionistas en un corto plazo, ofreciendo al mercado un producto pensado en varios sectores de consumidores con una necesidad insatisfecha. Actualmente, se están generando cambios en los hábitos de consumo hacia los productos orgánicos y estilos de vida saludables. En el mercado se vienen comercializando tintes de todos los colores provenientes de una amplia oferta establecida, dado su grado de industrialización, muchos de estos tintes contienen químicos nocivos para el cuerpo humano. Existen varios segmentos de mujeres que no pueden utilizar estos productos debido a tener complicaciones para su salud. Nuestra propuesta se basa en desarrollar una marca de tintes orgánicos, con la finalidad de atender la demanda de este producto de consumo masivo, atendiendo varios segmentos de mujeres (3), en los cuales encontramos: mujeres embarazadas, con cáncer o que gusten de productos orgánicos. La entrada al mercado será mediante una estrategia de diferenciación de producto, compitiendo directamente con marcas que todavía no están posicionadas en el país, debido a que estamos entrando en un mercado de Océano azul. Nuestra propuesta de valor es ofrecer un producto 100% natural y fácil de aplicar. Generamos valor a través de las diferentes actividades (plan operacional, plan de marketing y plan financiero) que la empresa ha podido identificar asegurando el correcto desarrollo del proyecto. / Our business model offers an innovative and healthy proposal that will generate economic benefits for shareholders in the short term by offering the market a product based on many consumer segments with an unmet need. At present, there are changes that are being made in the consumption habits of organic products and healthy lifestyles. In the market, hair dyes of all colors from a wide established offer are being commercialized and due to their degree of industrialization, many of these hair dyes have harmful chemicals to the human body. These products cannot be used by many segments of women because of the complications they bring to their health. So, our proposal is based on developing a brand of organic hair dyes with the objective to satisfy the demand of this mass consumption product by meeting many segments of women (3), these are women who are pregnant, have cancer or like organic products. The market entry will be through a product differentiation strategy and due to our entry in a blue ocean market, the direct competition are brands that are not yet positioned in the country. Our value proposition is to offer a 100% natural and easy to apply product. We generate value through the different activities (operational, marketing and financial plan) that the company has identified ensuring the correct development of the project. / Trabajo de investigación

Voltage sensitive dyes are a family of chemical sensors which enable optical recording of electrical activities from large populations of neurons, but nevertheless suffer from the lack of delivery and targeting strategies in brain tissue due to their generally high lipophilicity. In this dissertation, I present a purely chemical approach to target voltage sensitive dyes to natively expressed protein targets in live brain tissue and achieve functional voltage imaging with the limited photon budget afforded by the small number of sensors targeted to endogenous molecular targets. To our knowledge, this study represents the first example of functional optical recording from specific neuronal types and their axons in live brain tissue without any genetic manipulation. Such approach is vastly significant in the long run when we ultimately need to translate findings from model animals in research laboratories to benefit real human patients in clinical settings, to which imaging and diagnostic methods requiring genetic modification are and will remain problematic in the foreseeable future. In addition, we demonstrate the high modularity and versatility of our chemical approach in targeting different voltage sensitive dyes to various molecular targets in the brain. We believe that the same concept can be applied to the targeting and delivery of other important lipophilic cargos, such as drugs and other sensors, to enable genetic modification-free, cell- or molecule-specific imaging and pharmacology in the brain.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第21190号 / エネ博第364号 / 新制||エネ||71(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 佐川 尚, 教授 森井 孝, 教授 松田 一成 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

Squaraine dyes have been the subject of intensive studies due their unusual electronic properties that make them good candidates for a wide range of applications in various technological fields. They are particularly promising in nonlinear optics, bioimaging for labeling and sensing of biomolecules, as sensitizers for solar energy harvesting in solar cells and organic photovoltaics, two-photon absorbing materials, near-infrared (NIR) emitting fluorescent probes, second harmonic generation organic dyes, and sensitizers for photodynamic therapy among others. In this dissertation, the aggregation behaviors and features of several squaraine dye derivatives in solid state thin films were studied and reported. In the first chapter of the dissertation, three squaraine dye derivatives with two and four hydroxy groups and with different N-alkyl amino donor substituents were synthesized and used as models to study aggregation behavior. Their UV-vis absorption, thermal properties, and photoluminescence properties were determined. The models with four hydroxy substituents exhibited higher thermal stability and melt at higher temperature compared to the dye with only two hydroxy substituents due to increased hydrogen bonding. The UV-vis absorption and photoluminescence properties in liquid solution at room temperature were found to be similar. In the second chapter, the squaraine dyes, 2,4-bis [4-(N,N-di-n-pentylamino)-2-hydroxyphenyl] squaraine [SQC5(OH)2], 2,4-bis [4-(N,N-di-n-pentylamino)-2,4-hydroxyphenyl] squaraine [SQC5(OH)4 n], and 2,4-bis [4-(N,N-di-isopentylamino)-2,4-hydroxyphenyl] squaraine [SQC5(OH)4 b], where "n" and "b" stand for normal or linear and branched alkyl groups, respectively, were investigated to study their aggregation in solid state thin film form using UV-vis absorption spectroscopy. The investigation revealed significant differences in aggregation behaviors and features. The dye SQC5(OH)2 mainly exhibited J-type aggregation with an intense absorption band in the NIR region. In contrast, the SQC5(OH)4 n and SQC5(OH)4 b compounds mainly exhibited H-type aggregation, characterized by less intense and blue shifted absorption bands. The third chapter presents the kinetic study conducted on the squaraine dye derivative 2,4-bis [4-(N,N-di-n-pentylamino)-2-hydroxyphenyl] squaraine [SQC5(OH)2] in solid state spin-coated thin films. The study revealed the formation of J-aggregates with bands at 767 nm at room temperature. This aggregate was temperature dependent. It was transformed into H-aggregates as the temperature increased. The activation energy of the decay (transformation) process was found to be 91.2 kJ. The values of ΔH and ΔS are 88.4 kJ/mol and 48.2 J/K.mol, respectively, indicating the J-aggregate of SQC5(OH)2 was a kinetic product while the H-aggregate was thermondynamically more stable.

Organic open-shell materials, which are responsive to external stimuli; such as light, electronic field, magnetic field, etc., are subject to intensive studies in recent years for their potential application in the field of organic solar cells, semiconductors, supercapacitors, singletission, non-linear optical (NLO), spintronics, and magnetic materials. As the materials with an open-shell diradical (two unpaired electrons) or polyradical (multiple unpaired electrons) character have a significant promise for next-generation optoelectronics, magnetic, and spintronic devices, it is of paramount importance to design suitable materials with tunable electronic properties. Also, a proper understanding of the molecular topology with electro-magnetic properties and correlate with quantum functionalities can move forward the field of organic photovoltaics and optoelectronics. Here, we show that controlling the radical character based on the different molecular scaffolds can lead to materials from closed-shell (all electrons are paired) low-spin (singlet state) to intermediate open-shell (multi)radical state to high-spin (triplet state) ground-state in the pristine form. In this regard, several organic donoreptor (D-A) polymeric and small molecular systems are designed and characterized. We find that the diradical character is ubiquitous in the narrow bandgap organic materials. Based on this design rule, we have reported open-shell dyes for dye-sensitized solar cells (DSCs), which show significantly red-shifted absorption in the NIR than the closed-shell counterpart dyes. Our work on the alternating D-A polymers indicate stabilization of the high-spin triplet ground-state in the neutral form, not reported for D-A type polymers. A significant delocalization of the unpaired electrons provides thermodynamic stability of the polymer, which when used in supercapacitors, a best-in-class energy density, and a long cycle life are observed. Also, we find that the spin topology can be modulated by careful selection of molecular scaffold in the extended pi-conjugated D-A polymers. Furthermore, our study on D-A macrocycles indicates that the antiferromagnetic (AFM) couplings between the unpaired electrons can be tuned by thiophene pi-spacer, developing a record polyradical character in the macromolecular systems.

This research investigated the efficacy of chlorine dioxide (ClO₂), ultraviolet (UV) irradiation, UV in combination with chlorine dioxide (UV/ClO₂), and UV in combination with hydrogen peroxide (UV/H₂O₂) for decolorizing three reactive azo dyes (sultan red, indigo blue and cypress green) and treated textile-manufacturing wastewater. The objective was to determine the best treatment for reducing color to the Virginia Pollutant Discharge Elimination System (VPDES) permit level of 300 American Dye Manufacturers Institute (ADMI) units. The effects of the three chemical oxidation treatments provided color reduction for all three dyes. The results suggested UV/H₂O₂ and UV/ClO₂2 treatments provided maximum color reduction of the red and blue dyes, and UV/H₂O₂ was the most effective for maximum reduction of the green dye. A research goal was to provide predictive models of the wastewater effluent for the treatment processes, including the UV exposure time required to reach the 300 ADMI permit value and the effective ClO₂ dose necessary to achieve the 300 units. The results of the investigations regarding the effluent indicated that UV/H₂O₂ and UV/ClO₂ (5 mg/L) provided reduction to 300 units in less than 10 minutes UV exposure when the initial effluent color was less than 500 ADMI units. Without the addition of oxidant, contact times longer than 10 minutes were required for UV to decolorize these effluents to 300 ADMI units. Chlorine dioxide dosages between 10 and 30 mg/L both with and without UV irradiation achieved the same results. / Master of Science

The removal of color and organic matter contributed by the azo dye, 'Reactive Black 5,’ and Navy 106 wash water from a textile mill were studied in sludges under aerobic and anaerobic conditions. The potential of the dyes to leach from landfills was also investigated using Toxicity Characteristic Leaching Procedure (TCLP) analysis. The vinyl sulfone group of the Reactive Black 5 dye appeared to enable the dye to sorb to biomass better than the hydrolyzed form of the dye. Sorption and aerobic color degradation of the hydrolyzed Reactive Black 5 dye and the Navy 106 wash water appeared to be related to biomass concentration. Little, if any, sorption or degradation of the dyes was observed with Blacksburg municipal treatment plant sludge which contained a biomass concentration of 3500 mg/L. However, sorption and degradation of wash water was observed with Peppers Ferry treatment plant sludge at a biomass level of 7000 mg/L. An inhibition to aerobic color removal of dye wash water was found at a higher color to biomass ratio. The inhibition to color degradation was accompanied by a lower rate of nitrate and sulfate release. TOC and COD of the dyes decreased under aerobic conditions. Under anaerobic conditions the color was degraded within a day. But the TOC and COD of the dye did not decrease. The TCLP extracts indicated the presence of little or no dye added to the reactors. / M.S.

The effect of process conditions, temperature, time and rate of temperature rise, on the exhaustion of disperse dye on polyester yarn under High-Temperature dyeing conditions was investigated. Two ply spun type Dacron 54 polyester yarn was dyed with Disperse Red 60 in 0.5 g/l dye bath concentration using an Ahiba Texomat Dyeing Apparatus under High-Temperature Dyeing conditions. The dyeing process design used, consists of three levels of dyeing temperature (105°C, 120°C, 135°C), four levels of holding time (0 min, 15 min, 30 min, 60 min) and two levels of rate of temperature rise (1ºC/min, 3°C/min). After the dyeing process, the dye concentration in the yarn was obtained through extraction and measured spectrophotometrically. A factorial analysis of variance (ANOVA) test was used to determine whether or not significant differences existed among dyeing process conditions in regard to the dye uptake of the yarn. If significant differences existed, which parameter of process conditions (temperature, time, rate of temperature rise or their interactions) was responsible. The results of this study indicated that a three-way interaction of temperature, time, and rate of temperature rise was responsible for the differences in dye uptake of the yarn. The dye uptake of the yarn increased by increasing dyeing temperature from 105°C to 120°C for all levels of holding time and rate of temperature rise. However, increasing dyeing temperature from 120°C to 135°C, did not increase dye uptake of the yarn. The dye uptake of the yarn increased by increasing holding time from zero to 15 minutes for dyeing temperature of 120°C. However, increasing holding time from 15 to 60 minutes, did not increase dye uptake of the yarn. At the dyeing temperature of 120°C, a slower rate of temperature rise resulted in greater dye uptake of the yarn. It can be concluded that high temperature dyeing of polyester yarn at 120°C for 15 minutes with a rate of temperature rise of 1°C/min was the optimum dyeing process in achieving full exhaustion. / Master of Science

The effects of fiber reactive and direct dyes on certain physical properties (tenacity, elongation, and initial modulus) of cotton fibers were investigated. Raw cotton fiber and raw yarn spun from the same batch of fiber were obtained. Fiber and yarn were processed by scouring, bleaching, and dyeing with both dyes, using an Ahiba Texomat Dyeing Apparatus, and the appropriate chemical systems. Fibers from treated fiber and fibers removed from treated yarns were tested after each treatment step, using an Instron Tensile Tester. The Wilks multivariate F test was used to determine whether or not significant differences existed between sequential treatments, and between fibers treated as fiber or as yarn. When significant differences were indicated, univariate analysis of variance was computed to identify the property(s) responsible. The results of this study indicated that the physical properties of both fiber reactive dyed and direct dyed fibers were not significantly different from each other or from the bleached fiber from which they were dyed. The properties of bleached (and dyed) fibers were significantly different (lower tenacity and elongation, higher initial modulus) from untreated or scoured fibers, indicating that the bleaching step was responsible for most of the changes noted. The properties of fibers treated as fiber were generally different (lower tenacity, higher elongation, lower initial modulus) than those of fibers removed from yarn. / M.S.