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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiters Great Red Spot

The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3 ) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2 ). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

Jupiter↗
NASA NTRS1985

Chromophores with auxochrome-like function

Chromophores exist which can exert an auxochromic effect in addition to their chromophoric one. Styryl and cyan radicals are considered. Numerous chromophores were checked and those with auxochromic functions are described and tabulated.

Kauffmann, H.↗
NASA NTRS1992

Influence of the size and protonation state of acidic residue 85 on the absorption spectrum and photoreaction of the bacteriorhodopsin chromophore

The consequences of replacing Asp-85 with glutamate in bacteriorhodopsin, as expressed in Halobacterium sp. GRB, were investigated. Similarly to the in vitro mutated and in Escherichia coli expressed protein, the chromophore was found to exist as a mixture of blue (absorption maximum 615 nm) and red (532 nm) forms, depending on the pH. However, we found two widely separated pKa values (about 5.4 and 10.4 without added salt), arguing for two blue and two red forms in separate equilibria. Both blue and red forms of the protein are in the two-dimensional crystalline state. A single pKa, such as in the E. coli expressed protein, was observed only after solubilization with detergent. The photocycle of the blue forms was determined at pH 4.0 with 610 nm photoexcitation, and that of the red forms at pH 10.5 and with 520 nm photoexcitation, in the time-range of 100 ns to 1 s. The blue forms produced no M, but a K- and an L-like intermediate, whose spectra and kinetics resembled those of blue wild-type bacteriorhodopsin below pH 3. The red forms produced a K-like intermediate, as well as M and N. Only the red forms transported protons. Specific perturbation of the neighborhood of the Schiff base by the replacement of Asp-85 with glutamate was suggested by (1) the shift and splitting of the pKa for what is presumably the protonation of residue 85, (2) a 36 nm blue-shift in the absorption of the all-trans red chromophore and a 25 nm red-shift of the 13-cis N chromophore, as compared to wild-type bacteriorhodopsin and its N intermediate, and (3) significant acceleration of the deprotonation of the Schiff base at pH 7, but not of its reprotonation and the following steps in the photocycle.

Non-NASA Center↗
NASA NTRS2011

Jovian Chromophore Characteristics from Multispectral HST Images

The chromophores responsible for coloring the jovian atmosphere are embedded within Jupiter's vertical aerosol structure. Sunlight propagates through this vertical distribution of aerosol particles, whose colors are defined by omega-bar (sub 0)(lambda), and we remotely observe the culmination of the radiative transfer as I/F(lambda). In this study, we employed a radiative transfer code to retrieve omega-bar (sub 0)(lambda) for particles in Jupiter's tropospheric haze at seven wavelengths in the near-UV and visible regimes. The data consisted of images of the 2008 passage of Oval BA to the south of the Great Red Spot obtained by the Wide Field Planetary Camera 2 on-board the Hubble Space Telescope. We present derived particle colors for locations that were selected from 14 weather regions, which spanned a large range of observed colors. All omega-bar (sub 0)(lambda) curves were absorbing in the blue, and omega-bar (sub 0)(lambda) increased monotonically to approximately unity as wavelength increased. We found accurate fits to all omega-bar (sub 0)(lambda) curves using an empirically derived functional form: omega-bar (sub 0)(lambda) = 1 A exp(-B lambda). The best-fit parameters for the mean omega-bar (sub 0)(lambda) curve were A = 25.4 and B = 0.0149 for lambda in units of nm. We performed a principal component analysis (PCA) on our omega-bar (sub 0)(lambda) results and found that one or two independent chromophores were sufficient to produce the variations in omega-bar (sub 0)(lambda). A PCA of I/F(lambda) for the same jovian locations resulted in principal components (PCs) with roughly the same variances as the omega-bar (sub 0)(lambda) PCA, but they did not result in a one-to-one mapping of PC amplitudes between the omega-bar (sub 0)(lambda) PCA and I/F(lambda) PCA. We suggest that statistical analyses performed on I/ F(lambda) image cubes have limited applicability to the characterization of chromophores in the jovian atmosphere due to the sensitivity of 1/ F(lambda) to horizontal variations in the vertical aerosol distribution.

Strycker, Paul D.↗
NASA NTRS1998

Synthesis of Polymers Containing Covalently Bonded NLO Chromophores

Polymers containing covalently bonded nonlinear optical (NLO) chromophores are expected to possess special properties such as greater stability, better mechanical processing, and easier film formation than their non-polymeric equivalent. For the present work, polymethylmethacrylate (PMMA) was selected as the basic polymer unit on which to incorporate different NLO chromophores. The NLO components were variations of DIVA {[2-methoxyphenyl methylidene]-propanedinitrile} which we prepared from vanillin derivatives and malononitrile. These were esterified with methacrylic acid and polymerized either directly or with methyl methacrylate to form homopolymers or copolymers respectively. Characterization of the polymers and NLO property studies are underway.

Denga, Xiao-Hua↗
NASA NTRS2021

Photochemical and Microbial Degradation of Chromophoric Dissolved Organic Matter Exported from Tidal Marshes

Wetlands export chromophoric dissolved organic matter (CDOM) to estuaries, where CDOM is removed and transformed through biotic and abiotic process, subsequently impacting nutrient cycling, light availability, ecosystem metabolism, and phytoplankton activity. We examined the bioavailability and photoreactivity of CDOM exported from four Chesapeake Bay tidal marshes across three seasons and along an estuarine salinity gradient using three incubation treatments: 14-day microbial (MD), 7-day combined photochemical/microbial (PB+MD), and 7-day microbial incubation after photobleaching (MD after PB). CDOM absorption at 300 nm (aCDOM300) and dissolved organic carbon (DOC) concentrations showed strong seasonality, with minima in winter, but CDOM quality (absorption spectral slopes, fluorescence component ratios) was less variable seasonally. PB+MD over 7 days decreased aCDOM300 (–56.0%), humic-like fluorescence (–67.6%), and DOC (–17.8%), but increased the spectral slope ratio SR (=S275-295/S300-350) (+94.8%), suggesting a decrease in CDOM molecular weight. Photochemistry dominated the PB+MD treatment. Photoreactivity was greater during the winter and in marsh/watershed versus down-estuary sites, likely due to less previous light exposure. Prior photobleaching increased the bioavailability of marsh-exported CDOM, resulting in a greater loss of aCDOM300 and DOC, and a greater increase in humic-like fluorescence (–6.0%, –5.9%, and +18.4% change, respectively, over 7-day MD after PB incubations, versus –2.8%, –5.5%, and +2.6% change, respectively, over 14-day MD incubations). CDOM exported from a marsh downstream of a major wastewater treatment plant showed the greatest photoreactivity and bioavailability. This highlights the significance of human activity on estuarine CDOM quality and biogeochemical cycles.

Dissolved organic matter↗
NASA NTRS1987

HCN and chromophore formation on Jupiter

Reaction paths for the formation of HCN and chromophores on Jupiter are suggested. The reactions involve photolysis of ammonia/acetylene mixtures. Experimental data supporting these pathways are reported.

Ferris, James P.↗
NASA NTRS1996

Impact of Chromophoric Dissolved Organic Matter on UV Inhibition of Primary Productivity in the Sea

A model was developed to assess the impact of chromophoric dissolved organic matter (CDOM) on phytoplankton production within the euphotic zone. The rate of depth-integrated daily gross primary productivity within the euphotic zone was evaluated as a function of date, latitude, CDONI absorption characteristics, chlorophyll a (chl a) concentration, vertical stratification, and phytoplankton sensitivity to UV radiation (UVR). Results demonstrated that primary production was enhanced in the upper 30 m of the water column by the presence of CDOM, where predicted increases in production due to the removal of damaging UVR more than offset its reduction resulting from the absorption of photosynthetically usable radiation. At greater depths, where little UVR remained, primary production was always reduced due to removal by CDOM of photosynthetically usable radiation. When CDOM was distributed homogeneously within the euphotic zone, the integral over z [(GPP)(sub ez)], was reduced under most bio-optical (i.e. solar zenith angle, and CDOM absorption, and ozone concentration) and photophysiological production at depth was greater than the enhancement of production at the surface.

Arrigo, Kevin R.↗
NASA NTRS1975

Cyclic octatomic sulfur - A possible infrared and visible chromophore in the clouds of Jupiter

Near-ultraviolet light is known to be an effective agent for the photoproduction of a variety of organic molecules from simulated primitive Earth and contemporary Jovian environments. The study discusses the infrared spectrum of a brown polymeric material produced under simulated Jovian conditions and its comparison with recent high-altitude infrared spectra of Jupiter. It is shown that this polymeric material is composed mainly of cyclic octatomic sulfur, even though a range of complex organic compounds is also present. The polymeric sulfur, produced from the ultraviolet photolysis of hydrogen sulfide, displays its strongest band at 465 reciprocal centimeters. This is in fair agreement with the frequency of the unidentified Jovian absorber recently reported by Houck et al. (1975). Polymeric octatomic sulfur may thus be an important constituent of Jovian clouds.

Khare, B. N.↗
NASA NTRS1998

Singlet Excited States of Cl and Br Molecules: New Theories Applied to the -XO and -XO2 (X=C1 and Br) Chromophores

Electronic excitation energies are determined using single-reference based theories derived from response equations involving perturbation theory and coupled-cluster theory. These methods are applied to the singlet manifold of excited electronic states of the HClO, HBrO, HOClO, HOBrO, HClO2, and HBrO2 molecules. The reliability of the various perturbation theory approaches is assessed by comparison to the linear-response singles and doubles coupled-cluster (LRCCSD) method. The excitation energies for the Y-XO compounds are compared and contrasted for Y=H and HO, and X=Cl and Br. A similar comparison is performed for the H-XO2 compounds.

Lee, Timothy J.↗
NASA NTRS1998

Development of Polyimides-Based NLO Materials for Electrooptical Applications

Development of thermally stable optical materials for nonlinear optics have recently focused on the covalent incorporation of NLO chromophores into high performance polymers, especially thermally stable and processable polyamides. One key aspect for the incorporation of robust NLO chromophores into high Tg polymers is to sustain poling induced order. Other advantages include high loading level of chromophores, and elimination of possible phase separation as well as chromophore sublimation at processing or working temperature. We have prepared several polyimide based polymers which are covalently linked with thermally stable chromophores that we have developed, since polyamides generally exhibit high Tg and good film transparency. Here, we report the development and subsequent incorporation of indoline based chromophores into polyamides, leading to thermally stable NLO polymers.

Rutherford, Jacqueline↗
NASA NTRS1976

Particles, environments and possible ecologies in the Jovian atmosphere

The eddy diffusion coefficient is estimated as a function of altitude, separately for the Jovian troposphere and mesosphere. Complex organic molecules produced by the Ly alpha photolysis of methane may possibly be the absorbers in the lower mesosphere which account for the low reflectivity of Jupiter in the near ultraviolet. The optical frequency chromophores are localized at or just below the Jovian tropopause. Candidate chromophore molecules must satisfy the condition that they are produced sufficiently rapidly that convective pyrolysis maintains the observed chromophore optical depth. The condition is satisfied if complex organic chromophores are produced with high quantum yield by NH3 photolysis at less than 2,300 A. Jovian photoautotrophs in the upper troposphere satisfy this condition well, even with fast circulation, assuming only biochemical properties of comparable terrestrial organisms. An organism in the form of a thin, gas filled balloon can grow fast enough to replicate if (1) it can survive at the low mesospheric temperatures, or if (2) photosynthesis occurs in the troposphere.

Sagan, C.↗
NASA NTRS1976

Equilibrium and disequilibrium chemistry of adiabatic, solar-composition planetary atmospheres

The impact of atmospheric and cloud-structure models on the nonequilibrium chemical behavior of the atmospheres of the Jovian planets is discussed. Quantitative constraints on photochemical, lightning, and charged-particle production of organic matter and chromophores are emphasized whenever available. These considerations imply that inorganic chromophore production is far more important than that of organic chromophores, and that lightning is probably a negligibly significant process relative to photochemistry on Jupiter. Production of complex molecules by gas-phase disequilibrium processes on Saturn, Uranus, and Neptune is severely limited by condensation of even simple intermediates.

Lewis, J. S.↗
NASA NTRS2023

Quantification of Discharge-Specific Effects on Dissolved Organic Matter Export From Major Arctic Rivers From 1982 Through 2019

Long-term increases in Arctic river discharge have been well documented, and observations in the six largest Arctic rivers show strong positive correlations between dissolved organic carbon (DOC) concentration, river discharge, and chromophoric dissolved organic matter (CDOM) content. Here, observations of DOC and CDOM collected from 2009-2019 by the Arctic Great Rivers Observatory were used to estimate chromophoric DOC (CDOC) concentrations in the Kolyma, Lena, Mackenzie, Ob’, Yenisey, and Yukon Rivers. All rivers but the Mackenzie showed significant positive correlations between annual watershed runoff and the proportion of the DOC that is chromophoric. Historical estimates of DOC and CDOC export were calculated for 1982-2019 by extrapolating the DOC and CDOC concentration – discharge relationships from 2009-2019 as a hindcast modeled estimate. For the six rivers combined, modeled DOC and CDOC export increased, but CDOC increased faster than total DOC. The Lena and Ob’ Rivers showed significant increases in DOC export individually, with annual trends of 39.1 and 20.4 Gg C yr -1 respectively. November-April (winter) DOC and CDOC export increased in all rivers but the Yenisey, with the hindcast winter Kolyma export increasing by more than 20% per decade. There were no significant trends in discharge or associated DOC and CDOC fluxes during the observational period from 2009-2019; only when hindcasted values driven by changes in river discharge were analyzed did trends in DOC and CDOC emerge. This demonstrates how shifting seasonal distributions and increases in discharge can drive changes in DOC and CDOC concentrations and export, independent of other environmental factors.

carbon cycle↗