15,845 research outputs found
Synthetic and structural investigations of some lithium thiolates and thiocarboxylates
Get PDFA series of closely related lithium aryl thiolates with pyridine as a donor ligand have been prepared. X-ray structure determination (Dr. W. Clegg) has shown that [PKSLi.(NC(_5)H(_5))] crystallises as an infinite chain polymer. Insertion of a methylene group between the phenyl ring and sulphur as in (PhCH(_2)SLi .NC(_5)H(_5). ] (_oo) produced an infinitely folded ladder polymer with Li-S rungs, while introduction of an 0-methyl group produces the monomeric complex [o-MeC(_6)H(_4)SLi .(NC(_5)H(_5))(_3)].The unusual symmetrical complex [Li(_14) (SCH(_2)Ph)(_12) S(TMEDA.)(_6)] has been prepared, in which a central sulphur atom is surrounded by a distorted cube of lithium atoms, each edge of which is bridged by a benzyl thiolate group such that the twelve S atoms form a cubo- octahedron: a further six Li atoms form a larger outer octahedron. When TMEDA is present in excess it appears that both PhSLi and PhCH(_2)SLi form dimeric compounds with a central Li(_2)S(_2) ring but structure determination of these complexes is incomplete.[PhOOSLi.TMEDA](_2)has been prepared and crystallises as a centrosymmetric dimer containing a chair shaped central eight membered (OOSLi)(_2) ring with the Li atoms out of the (COS)(-2), molecular plane. Lithiation of the related acids PhOOOH and PhCSSH has been carried out in the presence of TMEDA but crystal growth has so far been unsuccessful. Ab initio m.o. calculations on related model compounds are included. A preliminary study has been carried out on the lithiation of the thio-oxime (Ph(_2) C-NSH). Results were encouraging but detailed investigation is needed. The reaction of S(_4) N(_4) with BI(_3) produces, not the expected adduct, S(_4)N(_4) .BI(_3) , but an intractable polymer, empirical formula, S(_3)N(_3)BI. Other adducts of S(_4).N(_4) and (PhCN_2) S(_2))(_2), were prepared but were unsuitable for further reactions. The reaction of lithium borohydride and sulphur in THF to produce sulphurated lithium borohydride has been modified to give a controllable reaction. Further reaction with TMEDA gives clear orange crystals of a complex the composition of which is still unknown
Draft toxicological profile for JP-5, JP-8, and jet A fuels
Get PDFA Toxicological Profile for JP-5 and JP-8 was released in 1998. This present edition supersedes any previously released draft or final profile.Chemical manager(s)/author(s): John Risher, Obaid Faroon, ATSDR, Division of Toxicology and Human Health Sciences, Atlanta, GA; Fernando Llados, Lisa Ingerman, Mario Citra, SRC, Inc., North Syracuse, NY
Shock tube study of JP-10 ignition delay time
No full textJP-10 (exo-tetrahydrodicyclopentadiene, C10H16) ignition delay times were measured in a preheated shock tube. The vapor pressures of the JP-10 were measured directly by using a high-precision vacuum gauge, to remedy the difficulty in determining the gaseous concentrations of heavy hydrocarbon fuel arising from the adsorption on the wall in shock tube experiments. The whole variation of pressure and emission of the OH or CH radicals were observed in the ignition process by a pressure transducer and a photomultiplier with a monochromator. The emission of the OH or CH radicals was used to identify the time to ignition. Experiments were performed over the pressure range of 151-556 kPa, temperature range of 1000-2100 K, fuel concentrations of 0.1%-0.55% mole fraction, and stoichiometric ratios of 0.25, 0.5, 1.0 and 2.0. The experimental results show that for the lower and higher temperature ranges, there are different dependency relationships of the ignition time on the temperature and the concentrations of JP-10 and oxygen
Computational model of cellular metabolic dynamics in skeletal muscle fibers during moderate intensity exercise
No full textHuman skeletal muscles have different fiber types with distinct metabolic functions and physiological properties. The quantitative metabolic responses of muscle fibers to exercise provide essential information for understanding and modifying the regulatory mechanisms of skeletal muscle. Since in vivo data from skeletal muscle during exercise is limited, a computational, physiologically based model has been developed to quantify the dynamic metabolic responses of many key chemical species. This model distinguishes type I and II muscle fibers, which share the same blood supply. An underlying hypothesis is that the recruitment and metabolic activation of the two main types of muscle fibers differ depending on the pre-exercise state and exercise protocols. Here, activation measured by metabolic response (or enzymatic activation) in single fibers is considered linked but distinct from fiber recruitment characterized by the number (or mass) of each fiber type involved during a specific exercise. The model incorporates species transport processes between blood and muscle fibers and most of the important reactions/pathways in cytosol and mitochondria within each fiber type. Model simulations describe the dynamics of intracellular species concentrations and fluxes in muscle fibers during moderate intensity exercise according to various experimental protocols and conditions. This model is validated by comparing model simulations with experimental data in single muscle fibers and in whole muscle. Model simulations demonstrate that muscle-fiber recruitment and metabolic activation patterns in response to exercise produce significantly distinctive effects depending on the exercise conditions
Dynamics of Activation of Lecithin: Cholesterol Acyltransferase by Apolipoprotein A-I
No full textThe product of transesterification of phospholipid acyl chains and unesterified cholesterol (UC) by the enzyme lecithin:cholesterol acyltransferase (LCAT) is cholesteryl ester (CE). Activation of LCAT by apolipoprotein (apo) A-I on nascent (discoidal) high-density lipoproteins (HDL) is essential for formation of mature (spheroidal) HDL during the antiatherogenic process of reverse cholesterol transport. Here we report all-atom and coarse-grained (CG) molecular dynamics (MD) simulations of HDL particles that have major implications for mechanisms of I-CAT activation. Both the all-atom and CG simulations provide support for a model in which the helix 5/5 domains or apoA-I create an amphipathic "presentation tunnel" that exposes methyl ends of acyl chains at the bilayer center to solvent. Further, CG simulations show that UC also becomes inserted with high efficiency into the amphipathic presentation tunnel with its hydroxyl moiety (UC-OH) exposed to solvent; these results are consistent with trajectory analyses of the all-atom simulations showing that UC is being concentrated in the vicinity of the presentation tunnel. Finally, consistent with known product inhibition of CE-rich HDL by CE, CG simulations of CE-rich spheroidal HDL indicate partial blockage of the amphipathic presentation tunnel by CE. These results lead us to propose the following working hypothesis. After attachment of LCAT to discoidal HDL, the helix 5/5 domains in apoA-I form amphipathic presentation tunnels for migration of hydrophobic acyl chains and amphipathic UC from the bilayer to the phospholipase A2-like and esterification active sites of LCAT, respectively. This hypothesis is currently being tested by site-directed mutagenesis
Making JP-10 Superfuel Affordable with a Lignocellulosic Platform Compound
No full textThe synthesis of renewable jet fuel from lignocellulosic platform compounds has drawn a lot of attention in recent years. So far, most work has concentrated on the production of conventional jet fuels. JP-10 is an advanced jet fuel currently obtained from fossil energy. Due to its excellent properties, JP-10 has been widely used in military aircraft. However, the high price and low availability limit its application in civil aviation. Here, we report a new strategy for the synthesis of bio-JP-10 fuel from furfuryl alcohol that is produced on an industrial scale from agricultural and forestry residues. Under the optimized conditions, bio-JP-10 fuel was produced with high overall carbon yields (approximate to 65 %). A preliminary economic analysis indicates that the price of bio-JP-10 fuel can be greatly decreased from approximate to 7091 US/ton using our new strategy. This work makes the practical application of bio-JP-10 fuel forseeable
Theory of Li in ZnO: A limitation for Li-based p-type doping
No full textp-type doping of ZnO has thus-far proved difficult. Some reports indicate that Li substituting for Zn would be a shallow acceptor, with work on ferroelectric material showing that Li can be incorporated at the atomic percent concentrations. However, Li doping typically increases the resistivity of otherwise n-type material. We report on the structure and properties of Li in ZnO as predicted by first principles calculations. We also study the diffusion of interstitial Li and show that doping may be limited by the formation of Li2O inclusions and the formation of strongly bound passive Li - H complexes
Assessment of the Validity of the Double Superhelix Model for Reconstituted High Density Lipoproteins A COMBINED COMPUTATIONAL-EXPERIMENTAL APPROACH
No full textFor several decades, the standard model for high density lipoprotein (HDL) particles reconstituted from apolipoprotein A-I (apoA-I) and phospholipid (apoA-I/HDL) has been a discoidal particle similar to 100 angstrom in diameter and the thickness of a phospholipid bilayer. Recently, Wu et al. (Wu, Z., Gogonea, V., Lee, X., Wagner, M. A., Li, X. M., Huang, Y., Undurti, A., May, R. P., Haertlein, M., Moulin, M., Gutsche, I., Zaccai, G., Didonato, J. A., and Hazen, S. L. (2009) J. Biol. Chem. 284, 3660536619) used small angle neutron scattering to develop a new model they termed double superhelix (DSH) apoA-I that is dramatically different from the standard model. Their model possesses an open helical shape that wraps around a prolate ellipsoidal type I hexagonal lyotropic liquid crystalline phase. Here, we used three independent approaches, molecular dynamics, EM tomography, and fluorescence resonance energy transfer spectroscopy (FRET) to assess the validity of the DSH model. (i) By using molecular dynamics, two different approaches, all-atom simulated annealing and coarse-grained simulation, show that initial ellipsoidal DSH particles rapidly collapse to discoidal bilayer structures. These results suggest that, compatible with current knowledge of lipid phase diagrams, apoA-I cannot stabilize hexagonal I phase particles of phospholipid. (ii) By using EM, two different approaches, negative stain and cryo-EM tomography, show that reconstituted apoA-I/HDL particles are discoidal in shape. (iii) By using FRET, reconstituted apoA-I/HDL particles show a 28 -34-angstrom intermolecular separation between terminal domain residues 40 and 240, a distance that is incompatible with the dimensions of the DSH model. Therefore, we suggest that, although novel, the DSH model is energetically unfavorable and not likely to be correct. Rather, we conclude that all evidence supports the likelihood that reconstituted apoA-I/HDL particles, in general, are discoidal in shape
Theory of Li in ZnO: A limitation for Li-based p-type doping
No full textp -type doping of ZnO has thus-far proved difficult. Some reports indicate that Li substituting for Zn would be a shallow acceptor, with work on ferroelectric material showing that Li can be incorporated at the atomic percent concentrations. However, Li doping typically increases the resistivity of otherwise n -type material. We report on the structure and properties of Li in ZnO as predicted by first principles calculations. We also study the diffusion of interstitial Li and show that doping may be limited by the formation of Li2 O inclusions and the formation of strongly bound passive Lii H complexes. \ua9 2005 The American Physical Society
Dynamics of Network Formation Processes in the Co-Author Model
Get PDFThis article studies the dynamics in the formation processes of a mutual consent network in game theory setting: the Co-Author Model. In this article, a limited observation is applied and analytical results are derived. Then, 2 parameters are varied: the number of individuals in the network and the initial probability of the links in the network in its initial state. A simulation result shows a finding that is consistent with an analytical result for a state of equilibrium while it also shows different possible equilibria.Dynamics, Network, Game Theory, Model,Simulation, Equilibrium, Complexity
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