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Near-Infrared and Visible Photoactivation to Uncage Carbon Monoxide from an Aqueous-Soluble PhotoCORM.
Multiphoton excitation allows one to access high energy excited states and perform valuable tasks in biological systems using tissue penetrating near-infrared (NIR) light. Here, we describe new photoactive manganese tricarbonyl complexes incorporating the ligand 4'-p-N,N-bis(2-hydroxyethyl)amino-benzyl-2,2':6',2″-terpyridine (TPYOH), which can serve as an antenna for two photon NIR excitation. Solutions of Mn(CO)3(TPYOH)X (X = Br- or CF3SO3-) complexes are very photoactive toward CO release under visible light excitation (405 nm, 451 nm). The same responses were also triggered by multiphoton excitation at 750 and 800 nm. In this context, we discuss the potential applications of these complexes as visible/NIR light photoactivated carbon monoxide releasing moieties (photoCORMs). We also report the isolation and crystal structures of the TPYOH complexes Mn(TPYOH)Cl2 and [Mn(TPYOH)2](CF3SO3)2, to illustrate a possible photolysis product(s)
Photodissociation of Cl_2O at 248 and 308 nm
Molecular beam studies of Cl_2O photolysis at 248 and 308 nm have been repeated and the analysis refined. At 248 nm, three distinct dissociation pathways that led to Cl+ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic than previously reported, leaving open the possibility that Cl_2O excited at 308 nm lives longer than a rotational period
Spectroradiometric calibration of the thematic mapper and multispectral scanner system
The results obtained for the absolute calibration of TM bands 2, 3, and 4 are presented. The results are based on TM image data collected simultaneously with ground and atmospheric data at White Sands, New Mexico. Also discussed are the results of a moments analysis to determine the equivalent bandpasses, effective central wavelengths and normalized responses of the TM and MSS spectral bands; the calibration of the BaSO, plate used at White Sands; and future plans
Transit Timing Variation of Near-Resonance Planetary Pairs: Confirmation of Twelve Multiple Planet Systems
We extract Transit Timing Variation (TTV) signals for 12 pairs of transiting
planet candidates that are near first-order Mean Motion Resonances (MMR), using
publicly available Kepler light curves (Q0-Q14). These pairs show significant
sinusoidal TTVs with theoretically predicted periods, which demonstrate these
planet candidates are orbiting and interacting in the same system. Although
individual masses cannot be accurately extracted based only on TTVs because of
the well known degeneracy between mass and eccentricity, TTV phases and
amplitudes can still place upper limits on the masses of the candidates,
confirming their planetary nature. Furthermore, the mass ratios of these planet
pairs can be relatively tight constrained using these TTVs. The planetary pair
in Kepler-82 (KOI-880) seems to have a particularly high mass ratio and density
ratio, which might indicate very different internal compositions of these two
planets. Some of these newly confirmed planets are also near MMR with other
candidates in the system, forming unique resonance chains, e.g., Kepler-80
(KOI-500).Comment: Accepted to ApJS. 17 pages, 11 figures, 3 tables. KOI 869 is replaced
with KOI 2038. Kepler numbers are assigne
Correlation from undiluted vitreous cytokines of untreated central retinal vein occlusion with spectral domain optical coherence tomography
Purpose: To correlate inflammatory and proangiogenic key cytokines from undiluted vitreous of treatment-naïve central retinal vein occlusion (CRVO) patients with SD-OCT parameters.
Methods: Thirty-five patients (age 71.1 years, 24 phakic, 30 nonischemic) underwent intravitreal combination therapy, including a single-site 23-gauge core vitrectomy. Twenty-eight samples from patients with idiopathic, non-uveitis floaterectomy served as controls. Interleukin 6 (IL-6), monocyte chemoattractant protein-1 (MCP-1), and vascular endothelial growth factor (VEGF-A) levels were correlated with the visual acuity (logMar), category of CRVO (ischemic or nonischemic) and morphologic parameters, such as central macular thickness-CMT, thickness of neurosensory retina-TNeuro, extent of serous retinal detachment-SRT and disintegrity of the IS/OS and others.
Results: The mean IL-6 was 64.7pg/ml (SD ± 115.8), MCP-1 1015.7 ( ± 970.1), and VEGF-A 278.4 ( ± 512.8), which was significantly higher than the control IL-6 6.2 ± 3.4pg/ml (P=0.06), MCP-1 253.2 ± 73.5 (P<0.0000001) and VEGF-A 7.0 ± 4.9 (P<0.0006). All cytokines correlated highly with one another (correlation coefficient r=0.82 for IL-6 and MCP-1; r=0.68 for Il-6 and VEGF-A; r=0.64 for MCP-1 and VEGF-A). IL-6 correlated significantly with CMT, TRT, SRT, dIS/OS, and dELM. MCP-1 correlated significantly with SRT, dIS/OS, and dELM. VEGF-A correlated not with changes in SD-OCT, while it had a trend to be higher in the ischemic versus the nonischemic CRVO group (P=0.09).
Conclusions: The inflammatory cytokines were more often correlated with morphologic changes assessed by SD-OCT, whereas VEGF-A did not correlate with CRVO-associated changes in SD-OCT. VEGF inhibition alone may not be sufficient in decreasing the inflammatory response in CRVO therapy
Sizing-Up Connecticut’s Public Sector
Is non-federal government in Connecticut too large? Many think so and are happy to see state and local governments scaling back to balance their budgets in the face of a major recession and a drop in tax collections. But is government here as big as the critics contend? And, if so, is this strategically the right time to rein in public spending?
Experimental study of high pressure phase equilibrium of (CO2 + NO2/N2O4) mixtures
Experimental bubble pressure, as well as liquid density of (CO2 + NO2/N2O4) mixtures are reported at temperatures ranging from (298 to 328.45) K. Experiments were carried out using a SITEC high-pressure variable volume cell. Transition pressures were obtained by the synthetic method and liquid density was deduced from measurement of the cell volume. Correlation of experimental results was carried out without considering chemical equilibrium of NO2/N2O4 system. (Liquid + vapour) equilibrium was found to be accurately modelled using the Peng–Robinson equation of state with classical quadratic mixing rules and with a binary interaction coefficient kij equal to zero. Nevertheless, modelling of liquid density values was unsatisfactory with this approach
Estimation of the vertical wavelength of atmospheric gravity waves from airglow imagery
Abstract In the summer of 2010, two imagers were installed in New Mexico with the objective of making stereoscopic observations of atmospheric gravity waves (AGWs). As AGWs propagate vertically, they spatially perturb the airglow emission layers in all three dimensions. Estimates of the vertical wavelength, horizontal wavelength, and the intrinsic frequency are needed to characterize an AGW and quantify its effects on upper atmospheric dynamics. The dispersion relation describes the relationship between vertical and horizontal wavelengths as a function of the intrinsic frequency. Thus, any two of the three aforementioned parameters can be used to determine the third. Mesospheric winds are hard to measure and consequently the intrinsic frequency is difficult to estimate. However, the horizontal wavelength can be directly measured from airglow imagery once the three-dimensional imager field of view is projected onto the two-dimensional image plane. This thesis presents a method to estimate the vertical wavelength using an airglow perturbation model proposed by Anderson et al. (2009). The model is subsequently validated using the observations from ground-based imagers installed in New Mexico.
Abstract The perturbed airglow is modeled as a quasi-monochromatic wave and thus, it can be characterized using only a few parameters, one of which is the vertical wavelength. Because the vertical wavelength is embedded in both the phase and the magnitude of this model, two values of the vertical wavelength are estimated by applying two different parameter estimation techniques on the phase and magnitude. The estimation of the vertical wavelength from the phase of the model entails solving an overdetermined system of linear equations by minimizing the sum of the squared residuals. This estimate is then compared to that obtained by iteratively finding the best approximation to the roots of a function, representing the magnitude of the perturbation model. These two techniques are applied on three nights in 2010, and the estimates for the vertical wavelength match to within a few kilometers. Thus, the perturbation model is validated using real data
Ground-State SiO Maser Emission Toward Evolved Stars
We have made the first unambiguous detection of vibrational ground-state
maser emission from SiO toward six evolved stars. Using the Very Large Array,
we simultaneously observed the v=0, J=1-0, 43.4-GHz, ground-state and the v=1,
J=1-0, 43.1-GHz, first excited-state transitions of SiO toward the oxygen-rich
evolved stars IRC+10011, o Ceti, W Hya, RX Boo, NML Cyg, and R Cas and the
S-type star chi Cyg. We detected at least one v=0 SiO maser feature from six of
the seven stars observed, with peak maser brightness temperatures ranging from
10,000 K to 108,800 K. In fact, four of the seven v=0 spectra show multiple
maser peaks, a phenomenon which has not been previously observed. Ground-state
thermal emission was detected for one of the stars, RX Boo, with a peak
brightness temperature of 200 K. Comparing the v=0 and the v=1 transitions, we
find that the ground-state masers are much weaker with spectral characteristics
different from those of the first excited-state masers. For four of the seven
stars the velocity dispersion is smaller for the v=0 emission than for the v=1
emission, for one star the dispersions are roughly equivalent, and for two
stars (one of which is RX Boo) the velocity spread of the v=0 emission is
larger. In most cases, the peak flux density in the v=0 emission spectrum does
not coincide with the v=1 maser peak. Although the angular resolution of these
VLA observations were insufficient to completely resolve the spatial structure
of the SiO emission, the SiO spot maps produced from the interferometric image
cubes suggest that the v=0 masers are more extended than their v=1
counterparts
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