Plasmoscope: Automated spectroscopy of single nanoparticles

Plasmonen sind die kollektive resonante Anregung von Leitungselektronen. Vom Licht angeregternPlasmonen in subwellenlängen-grossen Nanopartikeln heissen Partikelplasmonen und sind vielversprechende Kandidaten für zukünftige Mikrosensoren wegen der starken Abhängigkeit der Resonanz an extern steuerbaren Parametern, wie die optischen Eigenschaften des umgebenden Mediums und die elektrische Ladung der Nanopartikel. Die extrem hohe Streue_zienz von Partikelplasmonen erlaubt eine einfache Beobachtung einzelner Nanopartikel in einem Mikroskop.rnDie Anforderung, schnell eine statistisch relevante Anzahl von Datenpunkten sammeln zu können,rnund die wachsende Bedeutung von plasmonischen (vor allem Gold-) Nanopartikeln für Anwendungenrnin der Medizin, hat nach der Entwicklung von automatisierten Mikroskopen gedrängt, die im bis dahin nur teilweise abgedeckten spektralen Fenster der biologischen Gewebe (biologisches Fenster) von 650 bis 900nm messen können. Ich stelle in dieser Arbeit das Plasmoscope vor, das genau unter Beobachtung der genannten Anforderungen entworfen wurde, in dem (1) ein einstellbarer Spalt in die Eingangsö_nung des Spektrometers, die mit der Bildebene des Mikroskops zusammenfällt, gesetzt wurde, und (2) einem Piezo Scantisch, der es ermöglicht, die Probe durch diesen schmalen Spalt abzurastern. Diese Verwirklichung vermeidet optische Elemente, die im nahen Infra-Rot absorbieren.rnMit dem Plasmoscope untersuche ich die plasmonische Sensitivität von Gold- und Silbernanostrnäbchen, d.h. die Plasmon-Resonanzverschiebung in Abhängigkeit mit der Änderung des umgebendenrnMediums. Die Sensitivität ist das Mass dafür, wie gut die Nanopartikeln Materialänderungenrnin ihrer Umgebung detektieren können, und damit ist es immens wichtig zu wissen, welche Parameterrndie Sensitivität beein_ussen. Ich zeige hier, dass Silbernanostäbchen eine höhere Sensitivität alsrnGoldnanostäbchen innerhalb des biologischen Fensters besitzen, und darüberhinaus, dass die Sensitivität mit der Dicke der Stäbchen wächst. Ich stelle eine theoretische Diskussion der Sensitivitätrnvor, indenti_ziere die Materialparameter, die die Sensitivität bein_ussen und leite die entsprechendenrnFormeln her. In einer weiteren Annäherung präsentiere ich experimentelle Daten, die die theoretische Erkenntnis unterstützen, dass für Sensitivitätsmessschemata, die auch die Linienbreite mitberücksichtigen, Goldnanostäbchen mit einem Aspektverhältnis von 3 bis 4 das optimalste Ergebnis liefern. Verlässliche Sensoren müssen eine robuste Wiederholbarkeit aufweisen, die ich mit Gold- und Silbernanostäbchen untersuche.rnDie Plasmonen-resonanzwellenlänge hängt von folgenden intrinsischen Materialparametern ab:rnElektrondichte, Hintergrundpolarisierbarkeit und Relaxationszeit. Basierend auf meinen experimentellen Ergebnissen zeige ich, dass Nanostäbchen aus Kupfer-Gold-Legierung im Vergleich zu ähnlich geformten Goldnanostäbchen eine rotverschobene Resonanz haben, und in welcher Weiserndie Linienbreite mit der stochimetrischen Zusammensetzung der legierten Nanopartikeln variiert.rnDie Abhängigkeit der Linienbreite von der Materialzusammensetzung wird auch anhand von silberbeschichteten und unbeschichteten Goldnanostäbchen untersucht.rnHalbleiternanopartikeln sind Kandidaten für e_ziente photovoltaische Einrichtungen. Die Energieumwandlung erfordert eine Ladungstrennung, die mit dem Plasmoscope experimentell vermessen wird, in dem ich die lichtinduzierte Wachstumsdynamik von Goldsphären auf Halbleiternanost äbchen in einer Goldionenlösung durch die Messung der gestreuten Intensität verfolge.rn

Characterizing New Fluorescent Tools for Studying 5-HT3 Receptor Pharmacology

The pharmacological characterization of ligands depends upon the ability to accurately measure their binding properties. Fluorescence provides an alternative to more traditional approaches such as radioligand binding. Here we describe the binding and spectroscopic properties of eight fluorescent 5-HT3 receptor ligands. These were tested on purified receptors, expressed receptors on live cells, or in vivo. All compounds had nanomolar affinities with fluorescent properties extending from blue to near infra-red emission. A fluorescein-derivative had the highest affinity as measured by fluorescence polarization (FP; 1.14 nM), flow cytometry (FC; 3.23 nM) and radioligand binding (RB; 1.90 nM). Competition binding with unlabeled 5-HT3 receptor agonists (5-HT, mCPBG, quipazine) and antagonists (granisetron, palonosetron, tropisetron) yielded similar affinities in all three assays. When cysteine substitutions were introduced into the 5-HT3 receptor binding site the same changes in binding affinity were seen for both granisetron and the fluorescein-derivative, suggesting that they both adopt orientations that are consistent with co-crystal structures of granisetron with a homologous protein (5HTBP). As expected, in vivo live imaging in anaesthetized mice revealed staining in the abdominal cavity in intestines, but also in salivary glands. The unexpected presence of 5-HT3 receptors in mouse salivary glands was confirmed by Western blots. Overall, these results demonstrate the wide utility of our new high-affinity fluorescently-labeled 5-HT3 receptor probes, ranging from in vitro receptor pharmacology, including FC and FP ligand competition, to live imaging of 5-HT3 expressing tissues.

Determination of chromite composition from multispectral reflectance measurements (400-1000 nm)

The relationship between the chemical composition and the multispectral reflectance values of chromite in the VNIR (Visible and Near-Infra-Red) realm is tested and mathematically analysed. Statisticaltools as Pearson's correlation coefficients, linear stepwise regression analysis and least-square adjustments are applied to two populations of data obtained from 14 selected samples 01 chromite multielemental microprobe analysis and multispectral reflectance values (400-1 000 nm). Results show that both data sets correlate, and suggest that the VNIR reflectance spectra can be used as a tool to determine the chemical composition of chromites.

Discrimination between strain and temperature effects using first and second-order diffraction from a long period grating

We study the effects of temperature and strain on the spectra of the first and second-order diffraction attenuation bands of a single long-period grating (LPG) in step-index fibre. The primary and second-order attenuation bands had comparable strength with the second-order bands appearing in the visible and near-infra red parts of the spectrum. Using first and second-order diffraction to the eighth cladding mode a sensitivity matrix was obtained with limiting accuracy given by cross-sensitivity of ~1.19% of the measurement. The sensing scheme presented as a limiting temperature and strain resolution of ±0.7 °C and ~±25 µ.

Discrimination between strain and temperature effects using first and second-order diffraction from a long-period grating

We study the effects of temperature and strain on the spectra of the first and second-order diffraction attenuation bands of a single long-period grating (LPG) in step-index fibre. The primary and second-order attenuation bands had comparable strength with the second-order bands appearing in the visible and near-infra red parts of the spectrum. Using first and second-order diffraction to the eighth cladding mode a sensitivity matrix was obtained with limiting accuracy given by cross-sensitivity of ∼ 1.19% of the measurement. The sensing scheme presented as a limiting temperature and strain resolution of ± 0.7 °C and ∼ ± 25 με. © 2002 Elsevier Science B.V. All rights reserved.

CHARACTERIZATION OF THE ATMOSPHERIC EFFECTS ON THE TRANSMISSION OF THERMAL RADIATION

Atmospheric scattering plays a crucial rule in degrading the performance of electro optical imaging systems operating in the visible and infra-red spectral bands, and hence limits the quality of the acquired images, either through reduction of contrast or increase of image blur. The exact nature of light scattering by atmospheric media is highly complex and depends on the types, orientations, sizes and distributions of particles constituting these media, as well as wavelengths, polarization states and directions of the propagating radiation. Here we follow the common approach for solving imaging and propagation problems by treating the propagating light through atmospheric media as composed of two main components: a direct (unscattered), and a scattered component. In this work we developed a detailed model of the effects of absorption and scattering by haze and fog atmospheric aerosols on the optical radiation propagating from the object plane to an imaging system, based on the classical theory of EM scattering. This detailed model is then used to compute the average point spread function (PSF) of an imaging system which properly accounts for the effects of the diffraction, scattering, and the appropriate optical power level of both the direct and the scattered radiation arriving at the pupil of the imaging system. Also, the calculated PSF, properly weighted for the energy contributions of the direct and scattered components is used, in combination with a radiometric model, to estimate the average number of the direct and scattered photons detected at the sensor plane, which are then used to calculate the image spectrum signal to- noise ratio (SNR) in the visible near infra-red (NIR) and mid infra-red (MIR) spectral wavelength bands. Reconstruction of images degraded by atmospheric scattering and measurement noise is then performed, up to the limit imposed by the noise effective cutoff spatial frequency of the image spectrum SNR. Key results of this research are as follows: A mathematical model based on Mie scattering theory for how scattering from aerosols affects the overall point spread function (PSF) of an imaging system was developed, coded in MATLAB, and demonstrated. This model along with radiometric theory was used to predict the limiting resolution of an imaging system as a function of the optics, scattering environment, and measurement noise. Finally, image reconstruction algorithms were developed and demonstrated which mitigate the effects of scattering-induced blurring to within the limits imposed by noise.

Wavelength-tuneable liquid crystal lasers from the visible to the near-infrared

The study of band-edge lasing from dye-doped chiral nematic liquid crystals has thus far been largely restricted to visible wavelengths. In this paper, a wide range of commercially available laser dyes are examined for their suitability as infrared emitters within a chiral nematic host. Problems such as poor solubility and reduced quantum efficiencies are overcome, and successful band-edge lasing is demonstrated within the range of 735-850 nm, using the dyes LD800, HITC-P and DOTC-P. This paper also reports on progress towards widely tuneable liquid crystal lasers, capable of emission in the region 460- 850 nm. Key to this is the use of common pump source, capable of simultaneously exciting all of the dyes (both infrared and visible) that are present within the system. Towards this aim, we successfully demonstrate near-infrared lasing (800 nm) facilitated by Förster energy transfer between the visible dye DCM, and the infra-red dye LD800, enabling pump wavelengths anywhere between 420 and 532 nm to be used. These results demonstrate that small and low-cost tuneable visible to near-infrared laser sources are achievable, using a single common pump source. Such devices are envisaged to have wide-ranging applications including medical imaging (including optical coherence tomography), point-of-care optical medical diagnostics (such as flow cytometry), telecommunications, and optical signatures for security coatings. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).

Wavelength-tuneable liquid crystal lasers from the visible to the near-infrared

The study of band-edge lasing from dye-doped chiral nematic liquid crystals has thus far been largely restricted to visible wavelengths. In this paper, a wide range of commercially available laser dyes are examined for their suitability as infrared emitters within a chiral nematic host. Problems such as poor solubility and reduced quantum efficiencies are overcome, and successful band-edge lasing is demonstrated within the range of 735-850 nm, using the dyes LD800, HITC-P and DOTC-P. This paper also reports on progress towards widely tuneable liquid crystal lasers, capable of emission in the region 460- 850 nm. Key to this is the use of common pump source, capable of simultaneously exciting all of the dyes (both infrared and visible) that are present within the system. Towards this aim, we successfully demonstrate near-infrared lasing (800 nm) facilitated by Förster energy transfer between the visible dye DCM, and the infra-red dye LD800, enabling pump wavelengths anywhere between 420 and 532 nm to be used. These results demonstrate that small and low-cost tuneable visible to near-infrared laser sources are achievable, using a single common pump source. Such devices are envisaged to have wide-ranging applications including medical imaging (including optical coherence tomography), point-of-care optical medical diagnostics (such as flow cytometry), telecommunications, and optical signatures for security coatings. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).

SiC-like phase and room-temperature photoluminescence of low-k SiOCH films

Carbon-doped hydrogenated silicon oxide (SiOCH) low-k films have been prepared using 13.56 MHz discharge in trimethylsilane (3MS) - oxygen gas mixtures at 3, 4, and 5 Torr sustained with RF power densities 1.3 - 2.6 W/cm2. The atomic structure of the SiOCH films appears to be a mixture the amorphous SiO2-like and the partially polycrystalline SiC-like phases. Results of the infra-red spectroscopy reflect the increment in the volume fraction of the SiC-like phase from 0.22 - 0.28 to 0.36 - 0.39 as the RF power increment. Steady-state near-UV laser-excited (364 nm wavelength, 40±2 mW) photoluminescence (PL) has been studied at room temperatures in the visible (1.8 eV - 3.1 eV) subrange of photon spectrum. Two main bands of the PL signal (at the photon energies of 2.5 - 2.6 eV and 2.8 - 2.9 eV) are observed. Intensities of the both bands are changed monotonically with RF power, whereas the bandwidth of ∼0.1 eV remains almost invariable. It is likely that the above lines are dumped by the non-radiative recombination involving E1-like centres in the amorphous-nanocrystalline SiC-like phases. Such explanation of the PL intensity dependences on the RF power density is supported by results of experimental studies of defect states spectrum in bandgap of the SiOCH films.

Deep near-infrared spectroscopy of high-redshift galaxies: the physical growth of passive systems

The assembly history of massive galaxies is one of the most important aspects of galaxy formation and evolution. Although we have a broad idea of what physical processes govern the early phases of galaxy evolution, there are still many open questions. In this thesis I demonstrate the crucial role that spectroscopy can play in a physical understanding of galaxy evolution. I present deep near-infrared spectroscopy for a sample of high-redshift galaxies, from which I derive important physical properties and their evolution with cosmic time. I take advantage of the recent arrival of efficient near-infrared detectors to target the rest-frame optical spectra of z > 1 galaxies, from which many physical quantities can be derived. After illustrating the applications of near-infrared deep spectroscopy with a study of star-forming galaxies, I focus on the evolution of massive quiescent systems.

Most of this thesis is based on two samples collected at the W. M. Keck Observatory that represent a significant step forward in the spectroscopic study of z > 1 quiescent galaxies. All previous spectroscopic samples at this redshift were either limited to a few objects, or much shallower in terms of depth. Our first sample is composed of 56 quiescent galaxies at 1 < z < 1.6 collected using the upgraded red arm of the Low Resolution Imaging Spectrometer (LRIS). The second consists of 24 deep spectra of 1.5 < z < 2.5 quiescent objects observed with the Multi-Object Spectrometer For Infra-Red Exploration (MOSFIRE). Together, these spectra span the critical epoch 1 < z < 2.5, where most of the red sequence is formed, and where the sizes of quiescent systems are observed to increase significantly.

We measure stellar velocity dispersions and dynamical masses for the largest number of z > 1 quiescent galaxies to date. By assuming that the velocity dispersion of a massive galaxy does not change throughout its lifetime, as suggested by theoretical studies, we match galaxies in the local universe with their high-redshift progenitors. This allows us to derive the physical growth in mass and size experienced by individual systems, which represents a substantial advance over photometric inferences based on the overall galaxy population. We find a significant physical growth among quiescent galaxies over 0 < z < 2.5 and, by comparing the slope of growth in the mass-size plane dlogR_e/dlogM_∗ with the results of numerical simulations, we can constrain the physical process responsible for the evolution. Our results show that the slope of growth becomes steeper at higher redshifts, yet is broadly consistent with minor mergers being the main process by which individual objects evolve in mass and size.

By fitting stellar population models to the observed spectroscopy and photometry we derive reliable ages and other stellar population properties. We show that the addition of the spectroscopic data helps break the degeneracy between age and dust extinction, and yields significantly more robust results compared to fitting models to the photometry alone. We detect a clear relation between size and age, where larger galaxies are younger. Therefore, over time the average size of the quiescent population will increase because of the contribution of large galaxies recently arrived to the red sequence. This effect, called progenitor bias, is different from the physical size growth discussed above, but represents another contribution to the observed difference between the typical sizes of low- and high-redshift quiescent galaxies. By reconstructing the evolution of the red sequence starting at z ∼ 1.25 and using our stellar population histories to infer the past behavior to z ∼ 2, we demonstrate that progenitor bias accounts for only half of the observed growth of the population. The remaining size evolution must be due to physical growth of individual systems, in agreement with our dynamical study.

Finally, we use the stellar population properties to explore the earliest periods which led to the formation of massive quiescent galaxies. We find tentative evidence for two channels of star formation quenching, which suggests the existence of two independent physical mechanisms. We also detect a mass downsizing, where more massive galaxies form at higher redshift, and then evolve passively. By analyzing in depth the star formation history of the brightest object at z > 2 in our sample, we are able to put constraints on the quenching timescale and on the properties of its progenitor.

A consistent picture emerges from our analyses: massive galaxies form at very early epochs, are quenched on short timescales, and then evolve passively. The evolution is passive in the sense that no new stars are formed, but significant mass and size growth is achieved by accreting smaller, gas-poor systems. At the same time the population of quiescent galaxies grows in number due to the quenching of larger star-forming galaxies. This picture is in agreement with other observational studies, such as measurements of the merger rate and analyses of galaxy evolution at fixed number density.

Efficient excitations of radially and azimuthally polarized Nd 3+:YAG ceramic microchip laser by use of subwavelength multilayer concentric gratings composed of Nb2O5/SiO2

Cylindrical vector beams were produced from laser diode end-pumped Nd:YAG ceramic microchip laser by use of two types of subwavelength multilayer gratings as the axisymmetric-polarization output couplers respectively. The grating mirrors are composed of high- and low-refractive-index (Nb2O5/SiO2) layers alternately while each layer is shaped into triangle and concentric corrugations. For radially polarized laser output, the beam power reached 610mW with a polarization extinction ratio ( PER) of 61: 1 and a slope efficiency of 68.2%; for azimuthally polarized laser output, the beam power reached 626mW with a PER of 58: 1 and a slope efficiency of 47.6%. In both cases, the laser beams had near-diffraction limited quality. Small differences of beam power, PER and slope efficiency between radially and azimuthally polarized laser outputs were not critical, and could be minimized by further optimized adjustment to laser cavity and the reflectances of respective grating mirrors. The results manifested, by use of the photonic crystal gratings mirrors and end-pumped microchip laser configuration, CVBs can be generated efficiently with high modal symmetry and polarization purity. (C) 2008 Optical Society of America.

Design of spectrometer based on volume phase grating for near infrared range

In order to design and fabricate a spectrometer for the infrared range widely used in the different applications, Volume Phase Grating (VPG) with. low Polarization Dependence Loss (PDL) and high efficiency has been adopted as the dispersion element. VPG is constructed by coating an optical substrate with a thin film of dichromated. gelatin and exposing the film to two mutually coherent laser beams to form index modulation. The diffraction efficiency for a VPG is governed by Bragg effects. The depth (d) and index modulation contrast of the grating structure control the efficiency at which the light is diffracted when the Bragg condition is satisfied. Gradient index lens with high performance and low aberration are used as collimating system instead of standard lens. The spot diagrams and MTF curve of the collimating lens are shown in the paper. The receive system is InCaAs photodiode (PD) array including 512 pixels with 25 mum pitch. The spectrum resolution of the spectrometer reaches to 0.2nm and wavelength accuracy is 40pm.

Evolution of elastic x-ray scattering in laser-shocked warm dense lithium

We have studied the dynamics of warm dense Li with near-elastic x-ray scattering. Li foils were heated and compressed using shock waves driven by 4-ns-long laser pulses. Separate 1-ns-long laser pulses were used to generate a bright source of 2.96 keV Cl Ly-alpha photons for x-ray scattering, and the spectrum of scattered photons was recorded at a scattering angle of 120 degrees using a highly oriented pyrolytic graphite crystal operated in the von Hamos geometry. A variable delay between the heater and backlighter laser beams measured the scattering time evolution. Comparison with radiation-hydrodynamics simulations shows that the plasma is highly coupled during the first several nanoseconds, then relaxes to a moderate coupling state at later times. Near-elastic scattering amplitudes have been successfully simulated using the screened one-component plasma model. Our main finding is that the near-elastic scattering amplitudes are quite sensitive to the mean ionization state Z and by extension to the choice of ionization model in the radiation-hydrodynamics simulations used to predict plasma properties within the shocked Li.

Plume characteristics and dynamics of UV and IR laser-desorbed oligonucleotides

Laser desorption of dye-tagged oligonucleotides was studied using laser-induced fluorescence imaging. Desorption with ultra violet (UV) and infra-red (IR) lasers resulted in forward directed plumes of molecules. In the case of UV desorption, the initial shot desorbed approximately seven-fold more material than subsequent shots. In contrast, the initial shot in IR desorption resulted in the ejection of less material compared to subsequent shots and these plumes had a component directed along the path of the laser. Thermal equilibrium of the molecules in the plume was achieved after approximately 25 µs with a spread in molecular temperature which was described by a modified Maxwell-Boltzmann equation.

High-order-harmonic generation in benzene with linearly and circularly polarised laser pulses

High-order-harmonic generation in benzene is studied using a mixed quantum-classical approach in which the electrons are described using time-dependent density functional theory while the ions move classically. The interaction with both linearly and circularly polarised infra-red ($\lambda = 800$ nm) laser pulses of duration 10 cycles (26.7 fs) is considered. The effect of allowing the ions to move is investigated as is the effect of including self-interaction corrections to the exchange-correlation functional. Our results for circularly polarised pulses are compared with previous calculations in which the ions were kept fixed and self-interaction corrections were not included while our results for linearly polarised pulses are compared with both previous calculations and experiment. We find that even for the short duration pulses considered here, the ionic motion greatly influences the harmonic spectra. While ionization and ionic displacements are greatest when linearly polarised pulses are used, the response to circularly polarised pulses is almost comparable, in agreement with previous experimental results.