The preparation and spectroscopic characterizations of size-controlled Pyridine-functionalized gold clusters formed self-assembled 2D superlattices with hexagonal packing were studied. The characterizations of pyridine-modified Au clusters using TEM, UV-vis, NMR and ESCA techniques are also reported. Pyridine-functionalized monolayer-protected Au clusters (MPCs) were prepared as illustrated in Scheme 1. The gold nanoparticles prepared by the reduction with NaBH4 have 3.2 ¡Ó 0.88 nm average core diameters established by TEM. The ~3 nm particles were used to induce size and shap evolution with heating treatment in toluene or in TOABr (tetraoctylammonium bromide). The pyridine-functionalized MPCs exhibit an identifiable plasmon resonance band at ~515 nm. The confirmation of the functionalization of pyridyl octanethiol in Au MPCs came from the downfield NMR resonances in the region of 120-150 ppm, which were established the resonances of the Py moiety.

Our group has developed a Bayesian modeling technique to determine the ages of stellar populations (in particular, open and globular clusters) using white dwarf (WD) cooling physics. As the theory of WD cooling is both simpler than, and essentially independent of, main sequence evolutionary theory, white dwarfs provide an independent measure of the ages of Galactic populations. We have developed a Bayesian technique that objectively incorporates our prior knowledge of stellar evolution, star cluster properties, and data quality estimates to derive posterior probability distributions for a cluster's age, metallicity, distance, and line-of-sight absorption, as well as the individual stellar parameters of mass, mass ratio (for unresolved binaries) and cluster membership probability. The key advantage of our Bayesian method is that we can calculate probability distributions for cluster and stellar parameters with reference only to known, quantifiable, objective, and repeatable quantities. In doing so, we also have more sensitivity to subtle changes in cluster isochrones than traditional ``chi-by-eye'' cluster fitting methods. As a critical test of our Bayesian modeling technique, we apply it to Hyades UBV photometry, with membership priors based on proper motions and radial velocities, where available. We use secular parallaxes derived from Hipparcos proper motions via the moving cluster method to put all members of the Hyades at a common distance. Under the assumption of a particular set of WD cooling and atmosphere models, we estimate the age of the Hyades based on cooling white dwarfs to be 610 +- 110 Myr, consistent with the best prior analysis of the cluster main-sequence turn-off age (Perryman, et al. 1998). Since the faintest white dwarfs have most likely evaporated from the Hyades, prior work provided only a lower limit to the cluster's white dwarf age. Our result demonstrates the power of the bright white dwarf technique for deriving ages (Jeffery, et al. 2007) and further demonstrates complete age consistency between white dwarf cooling and main-sequence turn-off ages for seven out of seven clusters analyzed to date, ranging from 150 Myr to 4 Gyr. We then turn our attention to the white dwarf luminosity function. We use Sloan Digital Sky Survey (SDSS) data to create a white dwarf luminosity function with nearly an order of magnitude (3,358) more spectroscopically confirmed white dwarfs than any previous work. We determine the completeness of the SDSS spectroscopic white dwarf sample by comparing a proper-motion selected sample of WDs from SDSS imaging data with a large catalog of spectroscopically determined WDs. We derive a selection probability as a function of a single color (g-i) and apparent magnitude (g) that covers the range -1.0 < g-i < 0.2 and 15 < g < 19.5. We address the observed upturn in log g for white dwarfs with Teff < ~12,000K and offer arguments that the problem is limited to the line profiles and is not present in the continuum. We offer an empirical method of removing the upturn, recovering a reasonable mass function for white dwarfs with Teff < 12,000K. Finally, we outline several other current and future applications of our method and our code to determine not only ages of Galactic stellar populations, but helium abundances of clusters, ages of individual field WDs, and the initial (main sequence) to final (WD) mass relation. / text

Biomolecular imaging has become one of the most exciting potential applications of the Linear Coherent Light Source (LCLS), which is a source of intense femtosecond X-rays. It has been predicted that a highly intense pulse with pulse lengths on the order of a few femtoseconds should be sufficient to capture the image of a biomolecule before it is destroyed. However, the rate at which a large biomolecule explodes during exposure is a large unknown, and will likely be one of the major factors in determining if such imaging will succeed. Clusters were chosen as a size dependant model system, ideal to study the evolution of complex systems in X-ray fields. From earlier intense near-infrared (IR) experiments, it is known that depending on size and Z constitution, clusters explode by Coulomb or hydrodynamic forces. These two limits have very different cluster explosion times and signatures. Coulomb explosion is too fast to allow imaging, whereas a hydrodynamically expanding cluster is a much slower process. The ionization process leading to cluster explosion is strongly wavelength dependent as one passes from IR through XUV to the X-ray regime because the kinetic energy of the released electrons determines the charge imbalance within the cluster, and therefore, determines the explosion dynamics. Unlike in previous experiments performed with near IR or XUV pulses, irradiation by photons at the LCLS will lead to the ejection of energetic photo- and Auger- electrons which could easily escape from the cluster, leaving behind positive ions. The buildup of this charge during exposure can lead to a Coulomb explosion of the sample. On the other hand, if the charge accumulates, the photoelectrons will be held inside the cluster, where they could contribute to the cluster temperature and form a nanoplasma and expand hydrodynamically. The main goal of the thesis was to study the explosion dynamics of clusters generated due to their interaction with intense X-rays and look at its dependencies on the X-ray energy, photon fluence, absorption cross sections, sample constituency and sample size. This thesis also compares the results from X-rays with the corresponding results obtained using ultrashort XUV and Infrared lasers. / text

Subsets of systemic lupus erythematosus (SLE) patients with distinct patterns of disease manifestations and autoantibody production have been reported, but seldom have these two phenomena been analysed together. Cluster analysis was performed on 1928 Chinese SLE patients based on autoantibody profile and the frequencies of various clinical manifestations were compared between each cluster. Separate association analyses between individual autoantibodies and clinical manifestations, as well as between clinical manifestations, were also performed. This study identifies three separate autoantibody clusters each with different clinical manifestations, and proposes that the phenomena of autoantibody clustering and clinical subsets may be inter-related. Patient clusters could also be stratified into a bipolar spectrum. On one end are patients with over-representation of anti-dsDNA and renal disorder; whilst on the other end are two distinct autoantibody clusters (anti-Sm/anti-RNP/aPL and aPL/anti-Ro/anti-La) with overlapping of other non-renal manifestations. Patient stratification could aid disease prediction and subsequent management. These findings may also elucidate disease pathogenesis and guide future study on potential common pathological processes within autoantibody clusters. / published_or_final_version / Paediatrics and Adolescent Medicine / Master / Master of Research in Medicine

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published_or_final_version / abstract / toc / Chemistry / Master / Master of Philosophy

No description available.

No description available.

No description available.