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At least 397 records · Page 22

Underlying data for characterization of phycocyanobilin (PCB) biosynthesis in Galdieria sulphuraria

This dataset contains data for studies of phycocyanobilin (PCB) synthesis in the red alga Galdieria sulphuraria. Red algae such as G. sulphuraria utilize phycobilisomes for light harvesting. The phycobilisomes of early-branching organisms such as G. sulphuraria or Cyanidioschyzon merolae contain PCB chromophores but not phycoerythrobilin (PEB), in contrast to the phycobilisomes of other red algae. The studies reported in this dataset examine biosynthesis of PCB in G. sulphuraria and C. merolae, starting from biliverdin IX-alpha (BV), the last known common precursor for PCB and PEB. In cyanobacteria, phages, green algae, and land plants, conversion of BV into PCB or PEB is carried out by a family of enzymes called ferredoxin-dependent bilin reductases (FDBRs). The current studies demonstrate that G. sulphuraria, but not C. merolae, require the action of an additional isomerase to synthesize PCB.

59 BASIC BIOLOGICAL SCIENCES↗

Photoaging of phenolic secondary organic aerosol in the aqueous phase: evolution of chemical and optical properties and effects of oxidants

Abstract. While gas-phase reactions are well established to have significant impacts on the mass concentration, chemical composition, and optical properties of secondary organic aerosol (SOA), the aqueous-phase aging of SOA remains poorly understood. In this study, we performed a series of long-duration photochemical aging experiments to investigate the evolution of the composition and light absorption of the aqueous SOA (aqSOA) from guaiacyl acetone (GA), a semivolatile phenolic carbonyl that is common in biomass burning smoke. The aqSOA was produced from reactions of GA with hydroxyl radical (•OH-aqSOA) or a triplet excited state of organic carbon (3C∗-aqSOA) and was then photoaged in water under conditions that simulate sunlight exposure in northern California for up to 48 h. The effects of increasing aqueous-phase •OH or 3C∗ concentration on the photoaging of the aqSOA were also studied. High-resolution aerosol mass spectrometry (HR-AMS) and UV–Vis spectroscopy were utilized to characterize the composition and the light absorptivity of the aqSOA and to track their changes during aging. Compared to •OH-aqSOA, the 3C∗-aqSOA is produced more rapidly and shows less oxidation, a greater abundance of oligomers, and higher light absorption. Prolonged photoaging promotes fragmentation and the formation of more volatile and less light-absorbing products. More than half of the initial aqSOA mass is lost, and substantial photobleaching occurs after 10.5 h of prolonged aging under simulated sunlight illumination for 3C∗-aqSOA and 48 h for •OH-aqSOA. By performing positive matrix factorization (PMF) analysis of the combined HR-AMS and UV–Vis spectral data, we resolved three generations of aqSOA with distinctly different chemical and optical properties. The first-generation aqSOA shows significant oligomer formation and enhanced light absorption at 340–400 nm. The second-generation aqSOA is enriched in functionalized GA species and has the highest mass absorption coefficients in 300–500 nm, while the third-generation aqSOA contains more fragmented products and is the least light absorbing. These results suggest that intermediately aged phenolic aqSOA is more light absorbing than other generations, and that the light absorptivity of phenolic aqSOA results from a competition between brown carbon (BrC) formation and photobleaching, which is dependent on aging time. Although photoaging generally increases the oxidation of aqSOA, a slightly decreased O/C of the •OH-aqSOA is observed after 48 h of prolonged photoaging with additional •OH exposure. This is likely due to greater fragmentation and evaporation of highly oxidized compounds. Increased oxidant concentration accelerates the transformation of aqSOA and promotes the decay of BrC chromophores, leading to faster mass reduction and photobleaching. In addition, compared with •OH, photoaging by 3C∗ produces more low-volatility functionalized products, which counterbalances part of the aqSOA mass loss due to fragmentation and evaporation.

54 ENVIRONMENTAL SCIENCES↗

Microchemical urinalysis. IX - Determination of hydroxyproline in urine.

A simplified procedure is described for the determination of hydroxyproline in human or monkey urine. In this procedure 1 ml of urine is subjected in succession to hydrolysis, oxidation, extraction, and color development. During these steps impurities and interfering substances are eliminated, thus resulting in a chromophore due to hydroxyproline alone.

Grunbaum, B. W.↗

Production of organic molecules by proton irradiation

Preliminary experiments were carried out to investigate the effectiveness of proton irradiation for producing organic chromophores. The source of the 2 MeV protons used in the experiments was a model Van de Graaff accelerator. The gas cells used were hollow aluminum cylinders. The test results show that energetic protons can be an effective energy source for the formation of complex molecules from simple ones. With the exception of sulfide compounds none of the molecules that were identified are colored. However, coloring agents could be contained in unresolvable fractions.

Scattergood, T.↗

Chemical abundances in the atmospheres of the giant planets and their satellites

Recent results on the composition and structure of the atmospheres of Jupiter, Saturn, Uranus, Neptune, Pluto, and their satellites are summarized with an orientation toward topics of particular interest to the subject of exobiology. The need for an accurate Jovian temperature profile is noted, and current values are given for the known H2, NH3, and CH4 abundances of each planet as well as Titan and Triton. Trace constituents and chromophores in the Jovian atmosphere are discussed, the role of comets as a link between chemical evolution in the solar system and the chemistry of the interstellar medium is examined, and some features in the IR spectrum of Titan are interpreted. The hope is expressed that Titan will remain a useful proving ground for theories of low-temperature abiogenic organic-compound production

Owen, T.↗

Light energy transduction by the purple membrane of halophilic bacteria; Proceedings of the Symposium, San Francisco, Calif., June 6, 1976

Several aspects of bacteriorhodopsin, the retinal protein component of the purple membranes of Halobacterium halobium, are discussed. Structural studies are presented. Photochemical properties of the protein complex and of its chromophore are described. Proton translocation of bacteriorhodopsin is compared to that of a protein from a thermophilic bacterium. Ionophore activity of bacteriorhodopsin is considered with attention to conformational changes, light dependency, and electrical potential. Amino acid transport is also examined and the light-energy budget is investigated. Bacteriorhodopsin is of interest because of its similarity to rhodopsin, which plays a major role in mammalian vision, and also because its attainability and distinctive characteristics will facilitate studies of certain bacterial physiological functions, such as ion transport and membrane organization.

Source record↗

The photochemical cycle of bacteriorhodopsin

The reaction cycle of bacteriorhodopsin in the purple membrane isolated from Halobacterium halobium has been studied by optical absorption spectroscopy using low-temperature and flash kinetic techniques. After absorption of light, bacteriorhodopsin passes through at least five distinct intermediates. The temperature and pH dependence of the absorbance changes suggests that branch points and/or reversible steps exist in this cycle. Flash spectroscopy in the presence of a pH-indicating dye shows that the transient release of a proton accompanies the photoreaction cycle. The proton release occurs from the exterior and the uptake is on the cytoplasmic side of the membrane, as required by the function of bacteriorhodopsin as a light-driven proton pump. Proton translocating steps connecting release and uptake are indicated by deuterium isotope effects on the kinetics of the cycle. The rapid decay of a light-induced linear dichroism shows that a chromophore orientation change occurs during the reaction cycle.

Lozier, R. H.↗

Voyager imaging experiment

The Voyager imaging experiment, which involves two independently operated television systems (a narrow- and a wide-angle camera), is designed to conduct investigations of the atmospheres and surface properties of Jupiter, Saturn, their satellites and Saturn's rings. Objects of the investigations include the horizontal and vertical structure of visible clouds, the vertical structure of high, optically thin scattering layers on Jupiter and Saturn, the Great Red Spot, the South Equatorial Belt, chromophores on Io and Titan, the geology of several satellites, the masses, spin axes and periods of rotation of several satellites, the radial distribution of material in Saturn's rings, and the optical scattering properties of the primaries, rings, and satellites at a variety of wavelengths and phase angles.

Smith, B. A.↗

Colors on Jupiter

The colors present in the clouds of Jupiter at the time of the Voyager encounters are described as they appear in high resolution images. It is shown that latitude, altitude and dwelltime are all critical factors in determining which colors appear where, although the identities of the responsible chromophores remain unestablished. Simultaneous ground-based 5 micron observations are used to determine the relative altitudes of the cloud systems which are characterized as white clouds, tawny clouds, dark brown cloud belts, and blue-grey hot spots in equatorial regions. Correlations between cloud color and certain latitudes have been maintained for decades, which suggests the importance of the internal energy source.

Owen, T.↗

Analysis of a MIL-L-27502 lubricant from a gas-turbine engine test by size-exclusion chromatography

Size exclusion chromatography was used to determine the chemical degradation of MIL-L-27502 oil samples from a gas turbine engine test run at a bulk oil temperature of 216 C. Results revealed a progressive loss of primary ester and additive depletion and the formation of higher molecular weight products with time. The high molecular weight products absorbed strongly in the ultraviolet indicating the presence of chromophoric groups.

Jones, W. R., Jr.↗

Photooxidative degradation of clear ultraviolet absorbing acrylic copolymer surfaces

Photodegradation of copolymer of methyl methacrylate and 2(2'-hydroxy 5'vinyl-phenyl) 2H-benzotriazole has been investigated in order to determine the changes in the chemical composition of the surface of the copolymer on photooxidation. An electronic energy transfer mechanism has been postulated in order to interpret the observed photochemical changes in the polymer. Preliminary examination of the photophysical properties of the chromophore provides support for such a mechanism.

Gupta, A.↗

Albedo asymmetry of Iapetus

Observational data for Iapetus and other Saturn moons are used to show that the dark areas on Iapetus feature organic chromophores caused by UV irradiation of CH4-rich ice. The Iapetus albedo pattern, brighter at the poles and in the trailing hemisphere, is suggested to originate from ballistic impact redistribution of surface material in terms of an impact flux gradient. The orange/violet color ratios from Voyager imagery were measured as 1.46 for the leading hemisphere and 1.24 for the trailing hemisphere. The evolution of the Iapetus regolith during processes of ice evaporation, impact ablation, material transport, and chemical alteration is discussed for factors causing the albedo asymmetry. Comparisons of surface features of Titan, Oberon,, and Hyperion with those of Iapetus indicate a balance may exist between UV photochemistry and ablation on Iapetus, with the impact gradient having been determined by the tidally locked revolution of the moon. Voyager 2 data on the uranian moons are expected to offer confirmation or denial of the model.

Squyres, S. W.↗

Phosphine photochemistry in Saturn's atmosphere

The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

Kaye, J. A.↗

Liquid chromatographic analysis of a formulated ester from a gas-turbine engine test

Size exclusion chromatography (SEC) utilizing mu-Bondagel and mu-Styragel columns with a tetrahydrofuran mobile phase was used to determine the chemical degradation of lubricant samples from a gas-turbine engine test. A MIL-L-27502 candidate, ester-based lubricant was run in a J57-29 engine at a bulk oil temperature of 216 C. In general, the analyses indicated a progressive loss of primary ester, additive depletion, and formation of higher molecular weight material. An oil sample taken at the conclusion of the test showed a reversal of this trend because of large additions of new oil. The high-molecular-weight product from the degraded ester absorbed strongly in the ultraviolet region at 254 nanometers. This would indicate the presence of chromophoric groups. An analysis of a similar ester lubricant from a separate high-temperature bearing test yielded qualitatively similar results.

Jones, W. R., Jr.↗

The Jovian atmospheric window at 2.7 microns: A search for H2S

The atmospheric transmission window at 2.7 microns in Jupiter's atmosphere was observed at a spectral resolution of 0.1/cm from the Kuiiper Airborne Observatory. From an analysis of the CH4 abundance (80 m-am) and the H2O abundance ( 0.0125 cm-am) it was determined that the penetration depth of solar flux at 2.7 microns is near the base of the NH3 cloud layer. The upper limit to H2O at 2.7 microns and other results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. A search for H2S in Jupiter's atmosphere yielded an upper limit of 0.1 cm-am. The corresponding limit to the element abundance ratio S/H was approx. 1.7x10(-8), about 10(-3) times the solar value. Upon modeling the abundance and distribution of H2S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH4SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.

Larson, H. P.↗

Evaluation of colorless polyimide film for thermal control coating applications

A series of essentially colorless aromatic polyimide films was synthesized and characterized with the objective of obtaining maximum optical transparency for applications in space. Optical transparency is a requirement for high performance polymeric films used in second surface mirror coatings on thermal control systems. The intensity in color of aromatic polyimide films was lowered by reducing the electronic interaction between chromophoric centers in the polymer molecular structure and by using highly purified monomers. The resulting lightly colored to colorless polyimide films were characterized by UV-visible and infrared spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. After irradiation, the films were found to be 2 to 2.5 times more transparent than commercial polyimide film of the same thickness.

St.clair, A. K.↗

Mechanism of colour discrimination by a bacterial sensory rhodopsin

A photosensitive protein resembling the visual pigments of invertebrates enables phototactic archaebacteria to distinguish color. This protein exists in two spectrally-distinct forms, one of which is a transient photoproduct of the other and each of which undergoes photochemical reactions controlling the cell's swimming behaviour. Activation of a single pigment molecule in the cell is sufficient to signal the flagellar motor. This signal-transduction mechanism makes evident a color-sensing capability inherent in the retinal/protein chromophore.

Spudich, J. L.↗