DESIGN AND DEVELOPMENT OF BODIPY-BASED FLUORESCENT PROBES FOR SENSING AND IMAGING OF CYANIDE, Zn (II) IONS, LYSOSOMAL pH AND CANCER CELLS

BODIPY (4,4-Difluoro-3a,4a-diaza-s-indacene) dyes have gained lots of attention in application of fluorescence sensing and imaging in recent years because they possess many distinctive and desirable properties such as high extinction coefficient, narrow absorption and emission bands, high quantum yield and low photobleaching effect. However, most of BODIPY-based fluorescent probes have very poor solubilities in aqueous solution, emit less than 650 nm fluorescence that can cause cell and tissue photodamages compared with bio-desirable near infrared (650-900 nm) light. These undesirable properties extremely limit the applications of BODIPY-based fluorescent probes in sensing and imaging applications. In order to overcome these drawbacks, we have developed a very effective strategy to prepare a series of neutral highly water- soluble BODIPY dyes by enhancing the water solubilities of BODIPY dyes via incorporation of tri(ethylene glycol)methyl ether (TEG) and branched oligo(ethylene glycol)methyl ether (BEG) residues onto BODIPY dyes at 1,7-, 2,6-, 3,5-, 4- and meso- positions. We also have effectively tuned absorptions and emissions of BOIDPY dyes to red, deep red and near infrared regions via significant extension of π-conjugation of BODIPY dyes by condensation reactions of aromatic aldehydes with 2,6-diformyl BODIPY dyes at 1,3,5,7-positions. Based on the foundation that we built for enhancing water solubility and tuning wavelength, we have designed and developed a series of water-soluble, BODIPY-based fluorescent probes for sensitive and selective sensing and imaging of cyanide, Zn (II) ions, lysosomal pH and cancer cells. We have developed three BODIPY-based fluorescent probes for sensing of cyanide ions by incorporating indolium moieties onto the 6-position of TEG- or BEG-modified BOIDPY dyes. Two of them are highly water-soluble. These fluorescent probes showed selective and fast ratiometric fluorescent responses to cyanide ions with a dramatic fluorescence color change from red to green accompanying a significant increase in fluorescent intensity. The detection limit was measured as 0.5 mM of cyanide ions. We also have prepared three highly water-soluble fluorescent probes for sensing of Zn (II) ions by introducing dipicoylamine (DPA, Zn ion chelator) onto 2- and/or 6-positions of BEG-modified BODIPY dyes. These probes showed selective and sensitive responses to Zn (II) ion in the range from 0.5 mM to 24 mM in aqueous solution at pH 7.0. Particularly, one of the probes displayed ratiometric responses to Zn (II) ions with fluorescence quenching at 661 nm and fluorescence enhancement at 521 nm. This probe has been successfully applied to the detection of intracellular Zn (II) ions inside the living cells. Then, we have further developed three acidotropic, near infrared emissive BODIPY- based fluorescent probes for detection of lysosomal pH by incorporating piperazine moiety at 3,5-positions of TEG- or BEG-modified BODIPY dyes as parts of conjugation. The probes have low auto-fluorescence at physiological neutral condition while their fluorescence intensities will significant increase at 715 nm when pH shift to acidic condition. These three probes have been successfully applied to the in vitro imaging of lysosomes inside two types of living cells. At the end, we have synthesized one water- soluble, near infrared emissive cancer cell targetable BODIPY-based fluorescent polymer bearing cancer homing peptide (cRGD) residues for cancer cell imaging applications. This polymer exhibited excellent water-solubility, near infrared emission (712 nm), good biocompatibility. It also showed low nonspecific interactions to normal endothelial cells and can effectively detect breast tumor cells.

TanDEM-X High Resolution DEMs and Their Applications to Flow Modeling

Lava flow modeling can be a powerful tool in hazard assessments; however, the ability to produce accurate models is usually limited by a lack of high resolution, up-to-date Digital Elevation Models (DEMs). This is especially obvious in places such as Kilauea Volcano (Hawaii), where active lava flows frequently alter the terrain. In this study, we use a new technique to create high resolution DEMs on Kilauea using synthetic aperture radar (SAR) data from the TanDEM-X (TDX) satellite. We convert raw TDX SAR data into a geocoded DEM using GAMMA software [Werner et al., 2000]. This process can be completed in several hours and permits creation of updated DEMs as soon as new TDX data are available. To test the DEMs, we use the Harris and Rowland [2001] FLOWGO lava flow model combined with the Favalli et al. [2005] DOWNFLOW model to simulate the 3-15 August 2011 eruption on Kilauea's East Rift Zone. Results were compared with simulations using the older, lower resolution 2000 SRTM DEM of Hawaii. Effusion rates used in the model are derived from MODIS thermal infrared satellite imagery. FLOWGO simulations using the TDX DEM produced a single flow line that matched the August 2011 flow almost perfectly, but could not recreate the entire flow field due to the relatively high DEM noise level. The issues with short model flow lengths can be resolved by filtering noise from the DEM. Model simulations using the outdated SRTM DEM produced a flow field that followed a different trajectory to that observed. Numerous lava flows have been emplaced at Kilauea since the creation of the SRTM DEM, leading the model to project flow lines in areas that have since been covered by fresh lava flows. These results show that DEMs can quickly become outdated on active volcanoes, but our new technique offers the potential to produce accurate, updated DEMs for modeling lava flow hazards.

A STUDY OF SO2 EMISSIONS AND GROUND SURFACE DISPLACEMENTS AT LASTARRIA VOLCANO, ANTOFAGASTA REGION, NORTHERN CHILE

Lastarria volcano (Chile) is located at the North-West margin of the `Lazufre' ground inflation signal (37x45 km²), constantly uplifting at a rate of ~2.5 cm/year since 1996 (Pritchard and Simons 2002; Froger et al. 2007). The Lastarria volcano has the double interest to be superimposed on a second, smaller-scale inflation signal and to be the only degassing area of the Lazufre signal. In this project, we compared daily SO2 burdens recorded by AURA's OMI mission for 2005-2010 with Ground Surface Displacements (GSD) calculated from the Advanced Synthetic Aperture Radar (ASAR) images for 2003-2010. We found a constant maximum displacement rate of 2.44 cm/year for the period 2003-2007 and 0.80- 0.95 cm/year for the period 2007-2010. Total SO2 emitted is 67.0 kT for the period 2005-2010, but detection of weak SO2 degassing signals in the Andes remains challenging owing to increased noise in the South Atlantic radiation Anomaly region.

MAGNETO-PHOTONIC CRYSTALS FOR OPTICAL SENSING APPLICATIONS

Among the optical structures investigated for optical sensing purpose, a significant amount of research has been conducted on photonic crystal based sensors. A particular advantage of photonic crystal based sensors is that they show superior sensitivity for ultra-small volume sensing. In this study we investigate polarization changes in response to the changes in the cover index of magneto-optic active photonic band gap structures. One-dimensional photonic-band gap structures fabricated on iron garnet materials yield large polarization rotations at the band gap edges. The enhanced polarization effects serve as an excellent tool for chemical sensing showing high degree of sensitivity for photonic crystal cover refractive index changes. The one dimensional waveguide photonic crystals are fabricated on single-layer bismuth-substituted rare earth iron garnet films ((Bi, Y, Lu)3(Fe, Ga)5O12 ) grown by liquid phase epitaxy on gadolinium gallium garnet substrates. Band gaps have been observed where Bragg scattering conditions links forward-going fundamental waveguide modes to backscattered high-order waveguide modes. Large near-band-edge polarization rotations which increase progressively with backscattered-mode order have been experimentally demonstrated for multiple samples with different composition, film thickness and fabrication parameters. Experimental findings are supported by theoretical analysis of Bloch modes polarization states showing that large near stop-band edge rotations are induced by the magneto-photonic crystal. Theoretical and experimental analysis conducted on polarization rotation sensitivity to waveguide photonic crystal cover refractive index changes shows a monotonic enhancement of the rotation with cover index. The sensor is further developed for selective chemical sensing by employing Polypyrrole as the photonic crystal cover layer. Polypyrrole is one of the extensively studied conducting polymers for selective analyte detection. Successful detection of aqueous ammonia and methanol has been achieved with Polypyrrole deposited magneto-photonic crystals.

GROUND-BASED AND SATELLITE REMOTE SENSING OF PAROXYSMAL ERUPTIONS AT ETNA VOLCANO, 2011-2012.

Mt Etna's activity has increased during the last decade with a tendency towards more explosive eruptions that produce paroxysmal lava fountains. From January 2011 to April 2012, 25 lava fountaining episodes took place at Etna's New South-East Crater (NSEC). Improved understanding of the mechanism driving these explosive basaltic eruptions is needed to reduce volcanic hazards. This type of activity produces high sulfur dioxide (SO2) emissions, associated with lava flows and ash fall-out, but to date the SO2 emissions associated with Etna's lava fountains have been poorly constrained. The Ultraviolet (UV) Ozone Monitoring Instrument (OMI) on NASA's Aura satellite and the Atmospheric Infrared Sounder (AIRS) on Aqua were used to measure the SO2 loadings. Ground-based data from the Observatoire de Physique du Globe de Clermont-Ferrand (OPGC) L-band Doppler radar, VOLDORAD 2B, used in collaboration with the Italian National Institute of Geophysics and Volcanology in Catania (INGV-CT), also detected the associated ash plumes, giving precise timing and duration for the lava fountains. This study resulted in the first detailed analysis of the OMI and AIRS SO2 data for Etna's lava fountains during the 2011-2012 eruptive cycle. The HYSPLIT trajectory model is used to constrain the altitude of the observed SO2 clouds, and results show that the SO2 emission usually coincided with the lava fountain peak intensity as detected by VOLDORAD. The UV OMI and IR AIRS SO2 retrievals permit quantification of the SO2 loss rate in the volcanic SO2 clouds, many of which were tracked for several days after emission. A first attempt to quantitatively validate AIRS SO2 retrievals with OMI data revealed a good correlation for high altitude SO2 clouds. Using estimates of the emitted SO2 at the time each paroxysm, we observe a correlation with the inter-paroxysm repose time. We therefore suggest that our data set supports the collapsing foam (CF) model [1] as driving mechanism for the paroxysmal events at the NSEC. Using VOLDORAD-based estimates of the erupted magma mass, we observe a large excess of SO2 in the eruption clouds. Satellite measurements indicate that SO2 emissions from Etnean lava fountains can reach the lower stratosphere and hence could pose a hazard to aviation. [1] Parfitt E.A (2004). A discussion of the mechanisms of explosive basaltic eruptions. J. Volcanol. Geotherm. Res. 134, 77-107.