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Two-photon absorption in cruciform and dipolar chromophores: excitonic interactions and response to metal ionsSiegel, Nisan Naftali 04 June 2010 (has links)
Structure-property relationships for two-photon absorption (2PA) in branched organic chromophores is a topic of current interest, as is the design of chromophores with advantageous properties for two-photon laser scanning microscopy (2PLSM). The main goals of this dissertation were to study and explain the one-photon absorption (1PA) and 2PA properties of cruciform chromophores based on 1,4-distyryl-2,5-bis(phenylethynyl)benzene with varying electron donor (D) and acceptor (A) groups, and to characterize the 2PLSM-relevant response of some of these chromophores and a set of dipolar chromophores to binding with zinc ions. The compounds were studied by 1PA, fluorescence and 2PA spectroscopy. A ππ* exciton model was developed to explain the spectral properties of the 1,4-distyryl-2,5-bis(phenylethynyl)benzene cruciform with no D or A groups or with four identical D groups at the termini of the linear arms of the chromophore. This model indicated that there is some coupling and mixing of the lowest excited states e of the linear arms, leading to splitting of the 1PA spectrum of the cruciform. There was little coupling or mixing of the higher excited states e′ accessed in 2PA, leading to a two-band 2PA spectrum for the chromophore, in contrast to cruciform compounds in the literature with identical conjugated arms, which have one visible 2PA band. For cruciforms with D groups on the styryl arm and A character on the terminal phenyls of the phenylethynyl arms (D/A cruciforms), the ππ* exciton model was complemented with a charge-transfer (CT) exciton model describing interactions of charge-transfer pathways between the D and A groups. This model explained the broadness of the 1PA band of D/A cruciforms as well as the two 2PA bands observed for these chromophores.
The fluorescence and 2PA spectral responses to binding of Zn²⁺ ions to the D or A groups of some cruciform compounds were also assessed, to provide insight into the design of new analyte-sensing cruciforms for 2PLSM that take advantage of enhancement or reduction of D/A character upon analyte binding. It was found that canceling charge donation from the D groups in differing D/A cruciforms resulted in fluorescence and 2PA spectra nearly indistinguishable from each other, suggesting that turn-off of D groups is not an optimal modality of 2PLSM analyte sensing in cruciforms. Binding Zn²⁺ to A groups was shown to result in an increase in the D/A character of the cruciform, with fluorescence peak energies that changed depending on the location of the A group. It is suggested that the use of non-binding donors and analyte-binding A groups in differing patterns on the arms could be a valuable design motif to achieve 2PLSM sensor compounds based on this cruciform structure.
The 2PA spectra of a set of dipolar Zn²⁺ sensing dyes designed for ratiometric imaging in 2PLSM were also studied. These dyes had moderate 2PA strength, with redshifts of fluorescence 2PA spectra on Zn²⁺ binding. The isosbestic point of 2PA of most chromophores was within the range of 2PLSM excitation sources commonly used, rendering these dyes good candidates for use in ratiometric sensing in 2PLSM.
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Theoretical evaluation of the nonlinear optical properties of extended and π-conjugated chromophoresOhira, Shino 18 June 2009 (has links)
The nonlinear optical (NLO) properties were investigated in various extended π-conjugated chromophores: cyanine and alkyne carbocations; porphyrin dimers; and squaraine compounds that possess electronic, double resonance, and vibronic based NLO properties. In summary: (i) It was demonstrated that the alkyne carbocations have very similar optical properties to traditional cyanine dyes. Our theoretical results establish that the alkyne carbocations, in spite of their significant degree of bond-length alternation, behave in the same way as cyanine dyes. (ii) The nature of the -bridge in porphyrin dimers tunes the electronic coupling strength, which in turn determines the splitting of the energy levels and the (non)linear optical properties. (iii) We have shown that the origin of the lowest TPA-active states in squaraines is dependent on the nature of substituent donor moiety, changing from predominantly electronic to vibronic in character. For all squaraines containing indolinylidenemethyl donors, a vibronic origin for the TPA peak, and the energy and lineshape of the experimentally observed lowest TPA peak in these compounds were confirmed.
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Luminiscenční nanočástice pro 3D zobrazování / Luminescent nanoparticles for 3D imagingSmolka, Rastislav January 2021 (has links)
The aim of this diploma thesis is to study the optical properties of new -conjugated molecules based on 1,4-di(4'-N, N-diphenylaminostyryl)benzene and their potential application in advanced imaging techniques of biological specimens, the so-called multiphoton microscopy. The thesis focuses mainly on the characterization of their optical properties and the determination of their two-photon absorption cross-section using a unique laser equipment. Furthermore, a suitable methodology for the preparation of nanoparticles from these molecules, their characterization and stability are also developed. The thesis also investigates the influence of structure on the optical properties of these molecules. The relation between the length of the conjugated system and the presence of substituents on the backbone has been shown for the optical properties of the molecules in the solvent, the position and shape of the two-photon absorption spectrum and the value of two-photon absorption cross-section. It has been shown that this substance retains its unique fluorescent properties even in the form of nanoparticles and therefore appears to be a suitable candidate for the observation of biological specimens using multiphoton fluorescence microscopy. The work contributes to the knowledge base for the design of the chemical structure of molecules with desired properties.
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Structure-Property Relationship of the Two-Photon Circular Dichroism of Compounds with Axial and Helical ChiralityDiaz, Carlos 01 January 2015 (has links)
Back in 1894 Lord Kelvin coined the term "chiral" in order to refer to molecules whose mirror images were not superimposable with themselves. Over the years, research has demonstrated the important role that chiral molecules play in life, chemistry, and biology as well as their importance in the development of new drugs and technologies. The efforts to understand chiral systems have been mainly driven by spectroscopic methods that leverage on the opposite responses that enantiomers have to linear or circularly polarized light of both handedness. More specifically, Electronic Circular Dichroism (ECD) which measures the differences in linear absorption of left and right circularly polarized light has been the method par excellence for the spectroscopic characterization of chiral compounds. Unfortunately, the fact that ECD is based on linear absorption severely limits the use of this method in the near to far UV region. This is mainly due to the interferences generated by the strong linear absorption of common organic solvents and buffers in this portion of the light spectrum. Nevertheless, the fact remains that many chiral biomolecules of interest related to deceases like Alzheimer and Parkinson, exhibit most of their linear absorption in the near to far UV region where ECD cannot be employed for their study. Therefore, it has become an urgent necessity to develop spectroscopic methods to study chiral molecules that can circumvent the limitations of ECD at shorter wavelengths. In order to overcome the existent limitations in linear chiral spectroscopy, the nonlinear equivalent of ECD arises as a promising alternative, i.e. Two-Photon Circular Dichroism (TPCD). Although, this phenomenon was theoretically predicted in 1975, it was not until 2008, with the introduction of the double-L scan, that a reliable and versatile method for the measurement of TPCD was introduced. The high sensitivity of this method is based on the use of "twin" pulses that allow accounting for fluctuations in the excitation source that prevented the experimental realization of the measurement. The first measurement of a full TPCD spectrum was performed on BINOL enantiomers and the results were supported and discussed with the help of theoretical calculations. After that seminal work, we embarked in expanding the understanding of the structure-property relationship of TPCD by performing, systematically, a series of theoretical-experimental studies in chiral biaryl derivatives and compounds with helical chirality. In Chapter 2 we present the theoretical-experimental study of the effect of the π-electron delocalization curvature on the TPCD of molecules with axial chirality. The targeted molecules for this part of our investigation were S-BINOL, S-VANOL, and S-VAPOL. Our findings revealed that an increase in the TPCD signal, within this series of compounds, was related to the curvature of the π–electron delocalization. The contributions of the different transition moments to the two-photon rotatory strength support our outcomes. Then, in Chapter 3 we introduce the development of the Fragment-Recombination Approach (FRA) for the calculation of the TPCD spectra of large molecules. This simple but powerful method is based on the additivity of the TPCD signal, and is subject to a strict conditional fragmentation approach. FRA-TPCD is demonstrated, theoretically, in two hypothetical molecular systems from the biaryl derivatives family. Afterward, in Chapter 4 we show the first experimental demonstration of FRA-TPCD through the conformational analysis of an axially-chiral Salen ligand in solution (AXF-155). The FRA-TPCD spectra calculated for the different isomers of AXF-155 allowed narrowing the number of possible isomers of this complex molecule in THF solution to only two. This represents a significant improvement from previously reported results using ECD. Subsequently, in Chapter 5 we present the study of the effect of intramolecular charge transfer (ICT) in S-BINAP, an axially dissymmetric diphosphine ligand with strong ICT. The evaluation of the performance of two different exchange-correlation functional (XCF) confirmed that in order to properly predict the theoretical TPCD spectrum of a molecule exhibiting strong ICT, it is required to use an XCF such as CAM-B3LYP. In addition, our findings revealed the importance of considering an adequate number of excited states in order to be able to fully reproduce the experimental TPCD spectrum, thus avoiding wrong assignments of theoretical transitions to experimental spectral features. Finally, and expanding on our previous study, in Chapter 6 we investigated the effect of the nature of ICT on two hexahelicene derivatives. Our investigation demonstrated that the TPCD signal of chiral molecules with strong ICT does not only depend on the strength of this effect but on its nature, i.e. extension of the π–electronic delocalization increasing beyond (EXO-ICT) or within (ENDO-ICT) the helicene core. In summary, with the results presented in this thesis we closed a first loop in the understanding of the structure-property relationship of TPCD. In the future, we expect to deepen in our knowledge of the structure-property relationship of this phenomenon by studying further helicene derivatives with donor-acceptor motif, and through the application of FRA-TPCD to the conformational analysis of amino acids in peptides. We foresee numerous applications of TPCD for the study of optically active molecules with implications in biology, medicine, and the drug and food industry, and applications in nanotechnology, asymmetric catalysis and photonics.
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Squaraine dyes for two-photon fluorescence bioimaging applicationsColon Gomez, Maria 01 May 2013 (has links)
No description available.
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Development of Photoreactive Organic Compounds with Large Two-Photon Absorption Cross SectionsUrdabayev, Nurtay 01 June 2006 (has links)
No description available.
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IR Sensitive Photorefractive Polymers, The First Updateable Holographic 3D DisplayTay, Savas January 2007 (has links)
This work presents recent advances in the development of infra-red sensitive photorefractive polymers, and updateable near real-time holographic 3D displays based on photorefractive polymers. Theoretical and experimental techniques used for design, fabrication and characterization of photorefractive polymers are outlined. Materials development and technical advances that made possible the use of photorefractive polymers for infra-red free-space optical communications, and 3D holographic displays are presented.Photorefractive polymers are dynamic holographic materials that allow recording of highly efficient reversible holograms. The longest operation wavelength for a photorefractive polymer before this study has been 950nm, far shorter than 1550nm, the wavelength of choice for optical communications and medical imaging. The polymers shown here were sensitized using two-photon absorption, a third order nonlinear effect, beyond the linear absorption spectrum of organic dyes, and reach 40% diffraction efficiency with a 35ms response time at this wavelength. As a consequence of two-photon absorption sensitization they exhibit non-destructive readout, which is an important advantage for applications that require high signal-to-noise ratios.Holographic 3D displays provide highly realistic images without the need for special eyewear, making them valuable tools for applications that require "situational awareness" such as medical, industrial and military imaging. Current commercially available holographic 3D displays employ photopolymers that lack image updating capability, resulting in their restricted use and high cost per 3D image. The holographic 3D display shown here employs photorefractive polymers with nearly 100% diffraction efficiency and fast writing time, hours of image persistence, rapid erasure and large area, a combination of properties that has not been shown before. The 3D display is based on stereography and utilizes world's largest photorefractive devices (4x4 inch in size). It can be recorded within a few minutes, viewed for several hours without the need for refreshing and can be completely erased and updated with new images when desired, thusly comprising the first updateable holographic 3D display with memory, suitable for practical use.
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Photochemical kinetics and fluorescence spectroscopy in photonic crystal fibresWilliams, Gareth Owen Scott January 2013 (has links)
This thesis describes work carried out to demonstrate the use of photonic crystal fibres for the study of photochemistry reaction kinetics and fluorescence spectroscopy. Photonic crystal fibre allows the guidance of light, in a well-defined mode, over long path lengths. When the fibre’s microstructure is filled with a sample solution this, therefore, provides a greatly increased measurement path length and greater light-sample interaction than is possible in conventional spectroscopic systems, leading to enhanced sensitivity whilst greatly reducing the required sample volumes. The use of photonic crystal fibre as a micro reaction chamber for carrying out photochemical reactions and the study of their kinetics was achieved through monitoring the photoisomerisation of two azobenzene-based dyes, Disperse Red 1 and Disperse Orange 1, using real-time UV/Vis absorption spectroscopy. Both the 488 nm excitation laser and the broadband light source for the measurements were co-coupled through the fibre, giving perfect overlap of both with the sample. The fibre used for the measurements was a hollow core kagomé-type fibre with a core diameter of 19μm, giving a sample volume of 2.8 nL cm-1. The 30 cm path-length of the fibre allowed the use of sample concentrations down to 5×10-6 M, over an order of magnitude lower than in a conventional 1cm cuvette, with a sample volume of 90 nl in the core, a reduction of five orders of magnitude over conventional measurements. The kinetics of the photoisomerisation from the trans to the cis isomers of the dyes and the thermally driven cis-to-trans isomerisation could be tracked on the ms timescale, using a grating spectrometer which recorded the entire absorption spectrum of the dye. The data were numerically fitted using a custom model to take into account the properties of the fibre system. This led to the calculation of rate constants for the isomerisation processes in good agreement with those previously measured for these dye systems in bulk solution. Furthermore, the measurement of the dyes in pentane, in which they are highly insoluble, could be achieved due to the low concentrations that could be used; such measurements have not previously been reported. For the study of photonic crystal fibre as a system for the excitation and collection of fluorescence, two types of fibre were used; the same kagomé hollow-core fibre used for the photochemistry absorption measurements and a suspended-core “Mercedes” fibre. This allowed for the excitation of fluorophores in two contrasting environments. In the kagomé fibre fluorophores in bulk solution are excited whilst, in the Mercedes fibre, only fluorophores either on or in close proximity to the silica core interact with the evanescent field of the excitation light. The Fluorescein fluorophore was used initially to measure the detection limits in both fibre types and limits of 2x10-11 M in the kagomé and 10-9 M in the Mercedes fibre were obtained. This equates to 106 molecules in the kagomé fibre, which displays the lower detection limit due to greater light-sample interaction. Two-photon excitation of the Fluorescein fluorophore was then carried out using a mode-locked Ti-Sapphire laser as an excitation source, demonstrating the ability of the fibre system to sustain two-photon excitation of a long (30 cm) path length. The two-photon measurements showed remarkable detection sensitivity allowing detection of fluorescence from 10-9 M solutions of Fluorescein, showing the potential of using PCF for two-photon based experiments which are of particular interest in fields such as photodynamic therapy. A further study was carried out, using the two fibre types, for measurement of the fluorescence lifetime of the Rhodamine B fluorophore. Unperturbed lifetimes could be measured in the fibres showing no interference from the fibre. The measurements confirmed, in reference to known lifetime values, that in the kagomé fibre the excited fluorophores are in the bulk solution with only a minor influence from surface effects, whilst in the Mercedes fibre all of the excited molecules experience interaction with the surface of the silica core. This, therefore, gives a method of locating the fluorophores with respect to the fibre surface and the ability to choose between measurement of bulk solution and long path-length evanescent field-induced fluorescence.
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Microfabricação por fotopolimerização via absorção de dois fótons / Two-photon absorption photopolymerization microfabricationGomes, Vinicius Tribuzi Rodrigues Pinheiro 10 February 2009 (has links)
Neste trabalho usamos pulsos de femtossegundos na fabricação de estruturas poliméricas em escala microscópica, através da técnica de fotopolimerização via absorção de dois fótons. Graças ao confinamento espacial da polimerização, resultante do processo de absorção de dois fótons, este método permite a fabricação de microestruturas tridimensionais complexas, com alta resolução, visando diversas aplicações tecnológicas, de fotônica até biologia. Inicialmente, desenvolvemos a técnica de fotopolimerização via absorção de dois fótons, desde a implantação da montagem óptica até a confecção dos sistemas de movimentação e controle do posicionamento do feixe laser. Através da fabricação e caracterização de microestruturas, produzidas em resinas acrílicas, o sistema foi aperfeiçoado permitindo a produção de microestruturas da pordem de 30um com razoável resolução espacial. Uma vez que a maior parte as microestruturas reportadas na literatura são elementos passivos, ou seja, suas propriedades ópticas não podem ser controladas por meios externos, numa segunda etapa deste projeto produzimos microestruturas opticamente ativas. Neste caso, a microfabricação foi feita em resinas acrílicas dopadas Rodamina B, exibindo, portanto, fluorescência quando excitadas com luz de comprimento de onda em torno de 540nm. Finalmente, visando a produção eficiente de estruturas em escala milimétrica para aplicações biológicas, implementamos também um sistema de fotopolomerização via absorção de um fóton. / In this work we used femtosecond pulses to fabricate polymeric structures at microscopic scale, by using the two-photon photopolymerization technique. Due to the spatial confinement of the polymerization, provided by the two-photon absorption, this method allows for the fabrication of complex three-dimensional microstructures, with high resolution, aiming to several technological applications, from photonics to biology. Initially, we developed the two-photon polimerization technique, from the optical setup to the mechanical systems to control the movement and the positioning of the laser beam. Through the fabrication and characterization os microestrutures, produced in acrylic resin, the apparatus was improved, allowing the fabriation of 30-um microstructures with reasonable spatial resolution. Since most the report in the literature are passive elements that is, their optical properties cannot be altered by any external means, in a second stage of this project we fabricated optical active microstructures. In this case, the microfabrication was carried out in acrylic resins doped with Rodamine B, exhibiting, consenquently, fluorescence when excited with light at 540nm. Finally, in order to eficiently produce milimetric structures for biological applications, we also implemented a one-photon polimerization setup.
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Espectroscopia de dois fotons do ion Gd+3 em estruturas perovskitas / Two photon spectroscopy in perovskite crystalNunes, Luiz Antonio de Oliveira 15 April 1988 (has links)
Através da absorção de um e de dois fótons estudamos as diferentes transições do íon \'Gd POT.+3\' e GGG. Utilizando técnicas espectroscópicas com laser pulsado e laser contínuo, analisamos a influência do campo cristalino sobre o íon. Estes resultados estão em concordância com as previsões advindas da teoria de grupo. A partir da análise dos espectros de luminescência das amostras de GdAl\'O IND.3\', conseguimos detectar pequenos traços de impurezas nas mesmas. Não conseguimos detectar nenhuma anomalia nos espectros obtidos, de modo a não acreditarmos na existência de alguma interação Gadolínio - Galdoíno, acima da temperatura de transição de fase. Laser de corante contínuo de alta resolução, laser de corante pulsado foram construídos para a realização dos experimentos. Também desenvolvemos os equipamentos eletrônicos envolvidos. / The different transitions of \'Gd POT.3+\' ion in samples of GdAl\'O IND.3\' and GGG were studied by means of the absorption of one and two photons. The crystalline field influence an the ion was studied by using spectroscopic techniques with pulsed laser as well as continuous laser. These results are in agreement with the group theory prediction. From the luminescence spectrum of this sample little impurities aspects in the GdA1\'O IND.3\' sample were detected. No anomaly was detected in the spectra obtained so that we believed there is no \'Gd POT.3+\'-\'Gd POT.3+\' interaction above the phase transition temperature. High resolution continuous dye laser and pulsed die laser were built up to carry out the experiments. The electronic equipment used in the experiment was developed by us.
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