Structural basis for carotenoid cleavage by an archaeal carotenoid dioxygenase
Abstract not provided
Daruwalla, Anahita↗
SEARCH · Engineering Papers
Results for “polyene”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Ionic and biradical mechanisms in thermal and photo cis-trans isomerizations.
Ionic and biradical mechanisms in thermal and photo cis-trans isomerizations elucidated by planar and twisted configurations of polyenes
Evleth, E. M.↗
Polymerization of perfluorobutadiene at near-ambient conditions
Peroxide catalyst under mild conditions initiates homopolymerization of perfluoro butadiene to new linear perfluoro polyenes and vulcanizable fluoro elastomers. Resulting polyperfluoro butadiene serves as hard elastomer for good chemical resistance, as intermediate in graft polymerizations, and as crosslink for high molecular weight materials.
Toy, M. S.↗
Synthesis and evaluation of polymers for use in early warning fire alarm devices
Conjugated polyacetylene polymers and one condensation polyene, all containing a high degree of conjugated unsaturation, were synthesized. These polymers were characterized by chemical analysis and by thermogravimetric analysis, as well as for their film-forming capability and gas/polymer interactions. It was found that those that had a high degree of conjugated unsaturation and had resonance - stabilizing groups were very thermally stable to 200 C, e.g., poly(dicyanoacetylene), poly(ethynylferrocene) and poly(phenylacetylene); while those with labile moieties, such as poly(p-formamidophenylacetylene), among others, suffered some degradation when heated in air. When subjected to gas/polymer interaction effects, the greatest change in electrical conductance was observed when ammonia was used as the gas and poly(p-nitrophenylacetylene) was the detector. Other polymers showed similar behavior. For example, poly(ethynylcarborane), considered to be an electron acceptor also showed a change in electrical conductance when exposed to ammonia, while poly(ethynylpyridine) and poly(ethylidenepyridazine) responded to carbon monoxide. However, for "fire gases" (gases from smoldering cotton), poly(ethynylferrocene) was the most responsive. Thus, the concept of polymers with different electronegativities forming charge-transfer complexes with different gases was found to be operable.
Byrd, N. R.↗
Semiconducting polymers for gas detection
Conjugated polyenes, and polyesters containing phthalocyanine in their backbone, were synthesized. These polymers were characterized by chemical analysis, thermogravimetric analysis, spectral analysis, and X-ray diffraction studies for crystallinity, as well as for their film-forming capability and gas/polymer interactions. Most of the polymers were relatively insensitive to water vapor up to 50 percent relative humidity, but the polyester/phthalocyanine (iron) polymer was relatively insensitive up to 100 percent RH. On the other hand, poly(p-dimethylaminophenylacetylene) was too conductive at 100 percent RH. Of the gases tested, the only ones that gave any evidence of interacting with the polymers were SO2, NOx, HCN and NH3. Poly(imidazole)/thiophene responded to each of these gases at all relative humidities, while the other polymers gave varying response, depending upon the RH. Thus, since most of these gases were electron-accepting, the electron-donating character of poly(imidazole)/thiophene substantiates the concept of electronegativity being the operating principle for interaction effects. Of the six polymers prepared, poly(imidazole)/thiophene first showed a very good response to smoldering cotton, but it later became nonresponsive; presumably due to oxidation effects.
Byrd, N. R.↗
Structure and functions of fungal cell surfaces
A review with 24 references on the biochemistry, molecular structure, and function of cell surfaces of fungi, especially dermatophytes: the chemistry and structure of the cell wall, the effect of polyene antibiotics on the morphology and function of cytoplasmic membranes, and the chemical structure and function of pigments produced by various fungi are discussed.
Nozawa, Y.↗
Optical properties and photoexcitation of a novel liquid form of soluble polyacetylene
Optical absorption, fluorescence emission, Raman scattering, and time-resolved emission experiments are reported on a new liquid form of soluble polyacetylene. This liquid consists of separate polyene chains, grown on activated sites of a polybutadiene chain. The depolarization ratios as well as the time-resolved spectrum of the secondary emission were measured. The relevant spectral features are discussed and analyzed in terms of the lack of interchain interactions which characterize the polymer in solution.
Tubino, R.↗
Nonlinear susceptibilities of finite conjugated organic polymers
Tight-binding calculations of the length dependence of the third-order molecular hyperpolarizability for polyenes and polyynes are reported. The pi-electron wave functions were determined by exploiting the limited translational symmetry of the molecules. Perturbation theory was used to calculate the longitudinal component of the electronic nonresonant hyperpolarizability. This is the first two-'band' calculation of third-order hyperpolarizabilities on finite pi-electron systems of varying length. In contrast to the results of the one-'band' models, the hyperpolarizability densities increase rapidly and then, after about 10-15 repeating units, approach an asymptotic value.
Beratan, David N.↗
In Site Analysis of a High Temperature Cure Reaction in Real Time Using Modulated Fiber-Optic FT-Raman Spectroscopy
The vibrational spectrum of a high temperature (330 C) polymerization reaction was successfully monitored in real time using a modulated fiber-optic FT-Raman spectrometer. A phenylethynyl terminated monomer was cured, and spectral evidence for two different reaction products was acquired. The products are a conjugated polyene chain and a cyclized trimer. This is the first report describing the use of FT-Raman spectroscopy to monitor a high temperature (greater than 250 C) reaction in real time.
Cooper, John↗
In Situ Analysis of a High-Temperature Cure Reaction in Real Time Using Modulated Fiber-Optic FT-Raman Spectroscopy
The vibrational spectrum of a high-temperature (330 C) polymerization reaction was successfully monitored in real time with the use of a modulated fiber-optic Fourier transform (FT)-Raman spectrometer. A phenylethynyl-terminated monomer was cured, and spectral evidence for two different reaction products was acquired. The products are a conjugated polyene chain and a cyclized trimer. This is the first report describing the use of FT-Raman spectroscopy to monitor a high temperature (greater than 250 C) reaction in real time.
Aust, Jeffrey F.↗
Deriving the intermediate spectra and photocycle kinetics from time-resolved difference spectra of bacteriorhodopsin. The simpler case of the recombinant D96N protein
The bacteriorhodopsin photocycle contains more than five spectrally distinct intermediates, and the complexity of their interconversions has precluded a rigorous solution of the kinetics. A representation of the photocycle of mutated D96N bacteriorhodopsin near neutral pH was given earlier (Varo, G., and J. K. Lanyi. 1991. Biochemistry. 30:5008-5015) as BRhv-->K<==>L<==>M1-->M2--> BR. Here we have reduced a set of time-resolved difference spectra for this simpler system to three base spectra, each assumed to consist of an unknown mixture of the pure K, L, and M difference spectra represented by a 3 x 3 matrix of concentration values between 0 and 1. After generating all allowed sets of spectra for K, L, and M (i.e., M1 + M2) at a 1:50 resolution of the matrix elements, invalid solutions were eliminated progressively in a search based on what is expected, empirically and from the theory of polyene excited states, for rhodopsin spectra. Significantly, the average matrix values changed little after the first and simplest of the search criteria that disallowed negative absorptions and more than one maximum for the M intermediate. We conclude from the statistics that during the search the solutions strongly converged into a narrow region of the multidimensional space of the concentration matrix. The data at three temperatures between 5 and 25 degrees C yielded a single set of spectra for K, L, and M; their fits are consistent with the earlier derived photocycle model for the D96N protein.
NASA Program Exobiology↗
The Relationship Between Second-Order Nonlinear Optical Properties and Ground-State Polarization
A review is presented describing our recent work to correlate the first hyperpolarizability, of organic materials with the molecular parameter bond length alternation (BLA). Donor-acceptor polyenes displaying a wide BLA range were synthesized.
Optical Properties Polarization↗
Cumulene Wires Display Increasing Conductance with Increasing Length
One-dimensional sp-hybridized carbon wires, including cumulenes and polyynes, can be regarded as finite versions of carbynes. They are likely to be good candidates for molecular-scale conducting wires as they are predicted to have a high-conductance. In this study, we first characterize the single-molecule conductance of a series of cumulenes and polyynes with a backbone ranging in length from 4 to 8 carbon atoms, including [7]cumulene, the longest cumulenic carbon wire studied to date for molecular electronics. We observe different length dependence of conductance when comparing these two forms of carbon wires. Polyynes exhibit conductance decays with increasing molecular length, while cumulenes show a conductance increase with increasing molecular length. Their distinct conducting behaviors are attributed to their different bond length alternation, which is supported by theoretical calculations. Furthermore, this study confirms the long-standing theoretical predictions on sp-hybridized carbon wires and demonstrates that cumulenes can form highly conducting molecular wires.
36 MATERIALS SCIENCE↗
A Visual Understanding of Circular Dichroism Spectroscopy
Mapping chemical and structural properties to electronic and magnetic responses is critical to many applications such as quantum information science, where the precise storage and transmission of unique information is paramount. Specifically, constructing molecules and materials that provide strong polarized responses at tunable frequencies and with large anisotropies is key to optical processing of quantum information. Chiral molecules provide chiroptical response to circularly polarized light, making them attractive for quantum information science and other applications related to sensing, polarized photodetectors, and spintronics. Predicting a molecular design, a priori, with large anisotropies to circularly polarized light is challenging due to the complex interplay between electric and magnetic components of the optical response. In this work, we explore a visual representation of the electronic chiroptical response by decomposing the rotary strength into its constituent components. Here, we make use of the intuitive electronic oscillator framework to develop classical intuition regarding the rotary strength and its constituents. We explore three model chemical systems that exhibit local and global chirality. Our analysis reveals that local chirality necessarily exhibits competition between the local chiral center and chirality induced in other fragments of the molecule, resulting in both unexpected nonmonotonic trends and sign flips in chemically adjacent geometries. Furthermore, we can visually distinguish between local and global chirality via examination of the transition chiral tensor. Interestingly, we make strong connections to ferromagnetic and antiferromagnetic spin systems in that chiroptically inactive transitions exhibit antiferromagnetic-like alternating orbital patterns while active transitions show domain formation in an ferromagnetic-like alignment that produces a net chiroptical response.
36 MATERIALS SCIENCE↗
Human mononuclear cell function after 4 degrees C storage during 1-G and microgravity conditions of spaceflight
Future space missions of long duration may require that autologous leukocytes be stored in flight for infusion to restore normal immune competence in crewmembers. Peripheral blood mononuclear cells (PBMNCs), as leukocyte concentrates in autologous plasma and 2% dextrose, were stored in the microgravity conditions provided by the U.S. Space Shuttle Columbia (Mission 61-C). Activity of PBMNC after space flight was compared with that from a series of preflight ground control experiments, which demonstrated in culture a progressive daily loss in mitogen-stimulated protein synthesis at 24 h and thymidine uptake at 72 h after storage for 7 d at 4 degrees C. Post-storage viabilities were at least 90% as determined by trypan dye exclusion. A progressive reduction in the percentage of PBMNC expressing cell-surface phenotype markers, which was similar for monocytes, B cells, and T-cell subsets, also occurred after storage. The ability of PBMNC, stored for 8 d in Columbia's middeck, to become activated and proliferate in vitro was similar to that of cells that remained in identical flight lockers on the ground as 1-G controls, thus indicating that PBMNCs were not adversely affected by storage under microgravity conditions.
NASA Discipline Number 00-00↗
An Investigation of the Interrelationships Between Linear and NonLinear Polarizabilities and Bond Length Alternation on Connugated Organic Molecules
A computational method was devised to explore the relationship between charge separation, geometry, molecular dipole moment, polarizability, and hyperpolarizabilities in comjugated organic molecules. It is shown that bond length alternation (the average difference in length between single and double bonds in the molecule) is a key structurally observable parameter that can be correlated with hyperpolarizabilities and is thus relevant to the optimizaton of molecules and materials.
nonlinear optics computation electric field cyanin↗