Over the past several decades the phenomenon of luminescence (divided into fluorescence and phosphorescence) has received great attention in the field of biological science. This quest has motivated scientists for a variety of applications, including fluorescence imaging. Fluorescence microscopy techniques that provide unique advantages, such as high spatial resolution and superior sensitivity, have been regarded as attractive tools in biophotonics. With the progress of ultrafast laser sources, two-photon absorption (2PA), in which a molecule absorbs two photons simultaneously, has opened possibilities of using it for various applications. Two-photon fluorescence microscopy (2PFM), which affords deeper tissue penetration and excellent three-dimensional (3D) images, is now being widely employed for bioimaging. This dissertation focuses on the design, synthesis, and photophysical characterization of new fluorophores, as well as desirable applications. Chapter 1 gives an account of a brief introduction of luminescence and 2PA, as well as their utilities in biological applications. In chapter 2, a series of new BODIPY derivatives are presented along with their comprehensive linear and nonlinear characteristics. They exhibited excellent photophysical properties including large extinction coefficients, high fluorescence quantum yields, good photostability, and reasonable two-photon absorption cross sections. Two promising compounds were further evaluated as NIR fluorescent probes in one-photon and two-photon fluorescence imaging. Chapter 3 provides the design, synthesis, and photophysical characterization of two BODIPY dyes. In order to assess the potential of using the dye as a fluorescent probe, Lysotracker Red, a commercial lysosomal marker, was investigated for comparison purposes. The results indicate that figure of merit of both compounds were three orders of magnitude higher than that of Lysotracker Red. With an eye towards applications, one of the compounds was encapsulated in silica-based nanoparticles for in vitro and ex vivo one-photon and two-photon fluorescence imaging, in which the surface of the nanoparticle was modified with RGD peptides for specific targeting. The nanoprobe exhibited good biocompatibility and highly selective RGD-mediated uptake in ?V?3 integrin-overexpressing cancers, while maintaining efficient fluorescence quantum yield and high photostability. In chapter 4, the synthesis and photophysical properties of a novel photosensitizer with heavy atoms (halogen) were presented. The dye exhibited low fluorescence quantum yield, resulting in high singlet oxygen generation quantum yield. In vitro photodynamic studies demonstrated that photosensitization of the agent can induce cellular damage, subsequently leading to cell death by a necrotic cell death mechanism, supporting the therapeutic potential of using the agent for photodynamic therapy.

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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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.

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.

The technique of hyper-Rayleigh scattering is employed to measure the first molecular hyperpolarizabilities£]of nonlinear optical chromophores provided by Industrial Technology Research Institute. £]0. In the thesis, the effect of the molecular structure and the solvent on the hyperpolarizabilities will be discussed further.

Μελέτη διφωτονικά διεγερμένου φθορισμού για τον υπολογισμό των ενεργών διατομών διφωτονικής απορρόφησης οργανικών μορίων. / Study of the two photon excitation fluorescence for the estimation of two photon cross sections of organic molecules

Στην παρούσα εργασία, γίνεται αρχικά η μελέτη τριών χρωστικών ως προς την απόδοσή τους στη διφωτονική απορρόφηση. Με βάση τα αποτελέσματα της μέτρησης αυτής, επιλέχθηκαν οι δύο χρωστικές που παρουσίασαν ισχυρότερα το φαινόμενο, ώστε να μελετηθούν σχετικά με τον αποχρωματισμό τους. Για το λόγο αυτόν, τα δείγματα που παρασκευάστηκαν από τις ουσίες, δέχτηκαν ακτινοβολία μεγάλης έντασης, μέσω πολύ στενών παλμών laser. / Photobleaching of organic dyes after two photon excitation

Nonlinear optics has had extensive application into a vast array of scientific fields. One such nonlinear process, two-photon absorption (TPA), has had a wildly successful adoption into the field of biological imaging and microscopy. As far and as fast as this field is progressing, limitations stemming from the use of ultrafast lasers are starting to appear. In this work, an alternative nonclassical light source will be motivated for the application of low photon-flux two-photon microscopy. The origin and properties of the chosen nonclassical source, spontaneous parametric downconversion (SPDC), will be discussed along with the spatial and spectral properties modelled. Nonlinear processes such as TPA and sum frequency generation (SFG) will be viewed as "ultrafast coincidence measurements" of two photons arriving at a molecule within the time window of excitation. These ultrafast coincidence measurements will be viewed in an alternative manner: in terms of the second-order coherence from a light source. This degree of second-order coherence can be subdivided into two categories arising from different combinations of correlations within and between entangled photon pairs. Of interest, the energy-time correlations within the photon pair allow for enhancements in ultrafast coincidence rates over coherent light sources. The makings of an experimental setup to demonstrate enhanced rates from ultrafast two-photon coincidences taking place in SFG in a nonlinear crystal will be discussed.

Quantum information science has shown that computers which exploit the quantum nature of particles, namely quantum computers, can outperform contemporary computers in some computational tasks. The fundamental building blocks of a quantum computer are quantum logical gates and quantum bits (qubits). Previous research has shown that the optical approach to quantum computing is promising. However, linear optical quantum computing (LOQC) schemes require a huge amount of resource, which makes large scale LOQC impractical, and hence there have been renewed interests in nonlinear optical quantum computing schemes, where less resource is required. The performance of these quantum gates depends on the properties of the nonlinear media. However, requirements on some of the properties for high performance quantum gates are not fully known. This thesis intends to bridge this gap of knowledge and examines the necessary conditions on several types optical nonlinearities that are common in two-qubit quantum gates schemes. These types of nonlinearities are, namely two-photon absorption, $\chi^{(2)}$ nonlinearity and $\chi^{(3)}$ cross-Kerr nonlinearity. The two-photon absorption based quantum Zeno gate is modeled in this thesis. It is shown that for practical absorbers, the photon loss significantly lowers the quantum fidelity of the Zeno gate. Nevertheless, this thesis proposes to use the Zeno gate for fusing optical cluster states. With the best theoretical estimate of single photon loss in the absorbers, the Zeno gate can outperform linear optical schemes. This thesis also proposes to embed the Zeno gate in the teleportation-type of two-qubit gate, namely GC-Zeno gate, such that the success rate of the gate can be traded off for higher gate fidelity. The effect of some mode matching error and detector inefficiency on the GC-Zeno gate are also considered here. It is shown that the photon loss requirement as well as the mode matching requirement are both stringent for having a fault tolerant GC-Zeno gate. This thesis models some of the properties of a $\chi^{(3)}$ optical medium and explores how they affect the fidelity of the cross-Kerr nonlinearity based quantum gate. This thesis shows that for a cross-Kerr medium with fast time response but negligible wave dispersion, the medium would induce spectral entanglement between the input photons and this significantly lowers the fidelity of the quantum gate. Nevertheless, when the dispersion has a stronger effect than the time response, and if phase noise is negligible, it is possible to achieve a quantum gate with high fidelity. However, the noise is actually significant, and this thesis suggests that spectral filtering can be applied to prohibit the occurrence of the noise. The requirements on employing optical $\chi^{(2)}$ nonlinearity for quantum computing are also examined. This study models the spectral effects of a $\chi^{(2)}$ medium on its efficiency. It is shown in this thesis that since the Hamiltonian of the medium does not commute at different times, the unitary operation should be modeled by a Dyson series, which leads to undesired spectral entanglement that lowers the efficiency of the medium. However, in the case of periodical poling, the unitary operation can be modeled by a Taylor series, where under some phase matching conditions, the medium can have a high efficiency. Furthermore, this thesis proposes a Bell measurement scheme and a quantum gate scheme based on $\chi^{(2)}$ nonlinearity that can always outperform linear optics even when the nonlinearity strength is weak. In the case of sufficiently strong nonlinearity, a quantum gate with high success rate can be achieved. In summary, this thesis models some of the properties of two-photon absorbers, $\chi^{(2)}$ nonlinearity and $\chi^{(3)}$ nonlinearity, and shows that it is possible to achieve the conditions required for high performance quantum gates, however these conditions are experimentally challenging to meet.