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At least 145 records · Page 8

New Directions in Phthalocyanine Pigments

The objectives were the following: (1) investigation of the synthesis of new phthalocyanines; (2) characterization of the new phthalocyanines synthesized; (3) investigate the properties of the newly synthesized phthalocyanines with emphasis on UV protection of plastics and coatings; and (4) utilize quantum mechanics to evaluate the structural relationships with possible properties and synthetic approaches. The proposed research targeted the synthesis of phthalocyanines containing an aromatic bridge between two phthalocyanine rings. The goal was to synthesize pigments which would protect plastics when exposed to the photodegradation effects of the sun in space. The stability and extended conjugation of the phthalocyanines offer a unique opportunity for energy absorption and numerous radiative and non-radiative energy loss mechanisms. Although the original targeted phthalocyanines were changed early in the project, several new and unique phthalocyanine compounds were prepared. The basic goals of this work were met and some unique and unexpected outcomes of the work were the result of the integral use of quantum mechanics and molecular modeling with the synthetic effort.

Vandemark, Michael R.↗

Comparison of the seasonal and interannual variability of phytoplankton pigment concentrations in the Peru and California Current systems

Monthly composite images from the global coastal zone color scanner (CZCS) data set are used to provide an initial illustration and comparison of seasonal and interannual variability of phytoplankton pigment concentration along the western coasts of South and North America in the Peru Current system (PCS) and California Current system (CCS). The analysis utilizes the entire time series of available data (November 1978 to June 1986) to form a mean annual cycle and an index of interannual variability for a series of both latitudinal and cross-shelf regions within each current system. Within 100 km of the coast, the strongest seasonal cycles in the CCS are in two regions, one between 34 deg and 45 deg N and the second between 24 deg and 29 deg N, each with maximum concentrations (greater than 3.0 mg m(exp-3)) in May-June. Weaker seasonal variability is present north of 45 deg N and in the Southern California Bight region (32 deg N). Within the PCS, in the same 100-km-wide coastal region, highest (greater than 45 deg S) and lowest (less than 20 deg S) latitude regions have a similar seasonal cycle with maximum concentrations (greater than 1.5 mg m(exp -3)) during the austral spring, summer, and fall, matching that evident throughout the CCS. Between these regions, off northern and central Chile, the seasonal maximum occurs during July-August (austral winter), contrary to the influence of upwelling favorable winds. Within the CCS, the dominant feature of interannual variability in the 8-year time series is a strong negative concentration anomaly in 1983, an El Nino year. The relative value of this negative anomaly is strongest off central California and is followed by an even stronger negative anomaly is strongest off central California and is followed by an even stronger negative anomaly in 1984 off Baja, California. In the PCS, strong negative anomalies during the 1982-1983 El Nino period are evident only off the Peruvian coast and are evident there only in the regions 100 km or more from the coast. Although negative anomalies associated with the El Nino were not present at higher latitudes (more than approximately 20 deg S) in the PCS, the extremely sparse sampling weakens our confidence in the results of the interannual analysis in this region. An upper estimate of the systematic winter bias remaining in the global CZCS data after reprocessing with the multiple scattering algorithm is given in the appendix.

Thomas, A. C.↗

Solar radiation, phytoplankton pigments and the radiant heating of the equatorial Pacific warm pool

Recent optical, physical, and biological oceanographic observations are used to assess the magnitude and variability of the penetrating flux of solar radiation through the mixed layer of the warm water pool (WWP) of the western equatorial Pacific Ocean. Typical values for the penetrative solar flux at the climatological mean mixed layer depth for the WWP (30 m) are approx. 23 W/sq m and are a large fraction of the climatological mean net air-sea heat flux (approx. 40 W/sq m). The penetrating solar flux can vary significantly on synoptic timescales. Following a sustained westerly wind burst in situ solar fluxes were reduced in response to a near tripling of mixed layer phytoplankton pigment concentrations. This results in a reduction in the penetrative flux at depth (5.6 W/sq m at 30 m) and corresponds to a biogeochemically mediated increase in the mixed layer radiant heating rate of 0.13 C per month. These observations demonstrate a significant role of biogeochemical processes on WWP thermal climate. We speculate that this biogeochemically mediated feedback process may play an important role in enhancing the rate at which the WWP climate system returns to normal conditions following a westerly wind burst event.

Siegel, David A.↗

Combustion of PTFE: The Effects of Gravity and Pigmentation on Ultrafine Particle Generation

Ultrafine particles generated during polymer thermodegradation are a major health hazard, owing to their unique pathway of processing in the lung. This hazard in manned spacecraft is poorly understood, because the particulate products of polymer thermodegradation are generated under low gravity conditions. Particulate generated from the degradation of PolyTetraFluoroEthylene (PTFE), insulation coating for 20 AWG copper wire (representative of spacecraft application) under intense ohmic heating were studied in terrestrial gravity and microgravity. Microgravity tests were done in a 1.2-second drop tower at the Colorado School of Mines (CSM). Thermophoretic sampling was used for particulate collection. Transmission Electron Microscopy (TEM) and Scanning Transmission Electron Microscopy (STEM) were used to examine the smoke particulates. Image software was used to calculate particle size distribution. In addition to gravity, the color of PTFE insulation has an overwhelming effect on size, shape and morphology of the particulate. Nanometer-sized primary particles were found in all cases, and aggregation and size distribution was dependent on both color and gravity; higher aggregation occurred in low gravity. Particulates from white, black, red and yellow colored PTFE insulations were studied. Elemental analysis of the particulates shows the presence of inorganic pigments.

McKinnon, J. Thomas↗

Pigment composition and concentrations within the plant (Ceratophyllum demersum L.) component of the STS-89 C.E.B.A.S. Mini-Module spaceflight experiment

The Closed Equilibrated Biological Aquatic System (C.E.B.A.S.) Mini-Module, a Space Shuttle middeck locker payload which supports a variety of aquatic inhabitants (fish, snails, plants and bacteria) in an enclosed 8.6 L chamber, was tested for its biological stability in microgravity. The aquatic plant, Ceratophyllum demersum L., was critical for the vitality and functioning of this artificial mini-ecosystem. Its photosynthetic pigment concentrations were of interest due to their light harvesting and protective functions. "Post-flight" chlorophyll and carotenoid concentrations within Ceratophyllum apical segments were directly related to the quantities of light received in the experiments, with microgravity exposure (STS-89) failing to account for any significant deviation from ground control studies. Published by Elsevier Science Ltd on behalf of COSPAR.

short duration↗

Analysis of multiple photoreceptor pigments for phototropism in a mutant of Arabidopsis thaliana

The shape of the fluence-response relationship for the phototropic response of the JK224 strain of Arabidopsis thaliana depends on the fluence rate and wavelength of the actinic light. At low fluence rate (0.1 micromole m-2 s-1), the response to 450-nm light is characterized by a single maximum at about 9 micromoles m-2. At higher fluence rate (0.4 micromole m-2 s-1), the response shows two maxima, at 4.5 and 9 micromoles m-2. The response to 510-nm light shows a single maximum at 4.5 micromoles m-2. Unilateral preirradiation with high fluence rate (25 micromoles m-2 s-1) 510-nm light eliminates the maximum at 4.5 micromoles m-2 in the fluence response curve to a subsequent unilateral 450-nm irradiation, while the second maximum at 9 micromoles m-2 is unaffected. Based on these results, it is concluded that a single photoreceptor pigment has been altered in the JK224 strain of Arabidopsis thaliana.

Non-NASA Center↗

Pigmenting agents in Martian soils: inferences from spectral, Mossbauer, and magnetic properties of nanophase and other iron oxides in Hawaiian palagonitic soil PN-9

We have examined a Hawaiian palagonitic tephra sample (PN-9) that has spectroscopic similarities to Martian bright regions using a number of analytical techniques, including Mossbauer and reflectance spectroscopy, X-ray diffraction, instrumental neutron activation analysis, electron probe microanalysis, transmission electron microscopy, and dithionite-citrate-bicarbonate extraction. Chemically, PN-9 has a Hawaiitic composition with alkali (and presumably silica) loss resulting from leaching by meteoric water during palagonitization; no Ce anomaly is present in the REE pattern. Mineralogically, our results show that nanophase ferric oxide (np-Ox) particles (either nanophase hematite (np-Hm) or a mixture of ferrihydrite and np-Hm) are responsible for the distinctive ferric doublet and visible-wavelength ferric absorption edge observed in Mossbauer and reflectivity spectra, respectively, for this and other spectrally similar palagonitic samples. The np-Ox particles appear to be imbedded in a hydrated aluminosilicate matrix material; no evidence was found for phyllosilicates. Other iron-bearing phases observed are titanomagnetite, which accounts for the magnetic nature of the sample; olivine; pyroxene; and glass. By analogy, np-Ox is likely the primary pigmenting agent of the bright soils and dust of Mars.

Minerals/analysis↗

The Climatological Annual Cycle of Satellite-derived Phytoplankton Pigments in the Alboran Sea: A Physical Interpretation

The circulation and upwelling processes (coastal and gyre-induced) that control the phytoplankton distribution in the Alboran sea are examined by analyzing monthly climatological patterns of Coastal Zone Color Scanner (CZCS) pigment concentrations, sea surface temperatures, winds, and seasonal geostrophic fields.

Alboran sea phytoplankton distribution coastal upw↗

Biomarker Pigment Divinyl Chlorophyll a as a Tracer of Water Masses?

The ecological preferences of different Phytoplankton types drive their temporal and spatial distributions, reflecting their dependence on certain temperature ranges, light levels, nutrient availability and other environmental gradients. Hence, some phytoplankton taxa can be used as water mass tracers (biotracers).

Phytoplankton↗

Expression of blue pigment synthetase a from Streptomyces lavenduale reveals insights on the effects of refactoring biosynthetic megasynthases for heterologous expression in Escherichia coli .

High GC bacteria from the genus Streptomyces harbor expansive secondary metabolism. The expression of biosynthetic proteins and the characterization and identification of biological "parts" for synthetic biology purposes from such pathways are of interest. However, the high GC content of proteins from actinomycetes in addition to the large size and multi-domain architecture of many biosynthetic proteins (such as non-ribosomal peptide synthetases; NRPSs, and polyketide synthases; PKSs often called "megasynthases") often presents issues with full-length translation and folding. Here we evaluate a non-ribosomal peptide synthetase (NRPS) from Streptomyces lavenduale, a multidomain "megasynthase" gene that comes from a high GC (72.5%) genome. While a preliminary step in revealing differences, to our knowledge this presents the first head-to-head comparison of codon-optimized sequences versus a native sequence of proteins of streptomycete origin heterologously expressed in E. coli. We found that any disruption in co-translational folding from codon mismatch that reduces the titer of indigoidine is explainable via the formation of more inclusion bodies as opposed to compromising folding or posttranslational modification in the soluble fraction. In conclusion, this result supports that one could apply any refactoring strategies that improve soluble expression in E. coli without concern that the protein that reaches the soluble fraction is differentially folded.

59 BASIC BIOLOGICAL SCIENCES↗

Interconnection of the Antenna Pigment 8-HDF and Flavin Facilitates Red-Light Reception in a Bifunctional Animal-like Cryptochrome

Cryptochromes are ubiquitous flavin-binding light sensors closely related to DNA-repairing photolyases. The animal-like cryptochrome CraCRY from the green alga Chlamydomonas reinhardtii challenges the paradigm of cryptochromes as pure blue-light receptors by acting as a (6-4) photolyase, using 8-hydroxy-5-deazaflavin (8-HDF) as a light-harvesting antenna with a 17.4 Å distance to flavin and showing spectral sensitivity up to 680 nm. The expanded action spectrum is attributed to the presence of the flavin neutral radical (FADH•) in the dark, despite a rapid FADH• decay observed in vitro in samples exclusively carrying flavin. Herein, the red-light response of CraCRY carrying flavin and 8-HDF was studied, revealing a 3-fold prolongation of the FADH• lifetime in the presence of 8-HDF. Millisecond time-resolved ultraviolet-visible spectroscopy showed the red-light-induced formation and decay of an absorbance band at 458 nm concomitant with flavin reduction. Time-resolved Fourier transform infrared (FTIR) spectroscopy and density functional theory attributed these changes to the deprotonation of 8-HDF, challenging the paradigm of 8-HDF being permanently deprotonated in photolyases. FTIR spectra showed changes in the hydrogen bonding network of asparagine 395, a residue suggested to indirectly control flavin protonation, indicating the involvement of N395 in the stabilization of FADH•. Fluorescence spectroscopy revealed a decrease in the energy transfer efficiency of 8-HDF upon flavin reduction, possibly linked to 8-HDF deprotonation. Finally, the discovery of the interdependence of flavin and 8-HDF beyond energy transfer processes highlights the essential role of the antenna, introducing a new concept enabling CraCRY and possibly other bifunctional cryptochromes to fulfill their dual function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗