Science.gov

Sample records for glycerol phase formed

  1. Treatment of glycerol phase formed by biodiesel production.

    PubMed

    Hájek, Martin; Skopal, Frantisek

    2010-05-01

    Glycerol is a by-product of biodiesel produced by transesterification and is contained in the glycerol phase together with many other materials such as soaps, remaining catalyst, water, and esters formed during the process. The content of glycerol is approximately 30-60 wt.%. In this paper, treatments of the glycerol phase to obtain glycerol with a purity of 86 wt.% (without distillation) and a mixture of fatty acids with esters (1:1) or only a mixture of fatty acids with a purity of 99 wt.% are presented. The treatment was carried out by removing of alkaline substances and esters. Fatty acids were produced by saponification of the remaining esters and subsequent neutralization of alkaline substances by phosphoric, sulfuric, hydrochloric, or acetic acids. Salts are by-products and, in the case of phosphoric acid can be used as potash-phosphate fertilizer. The process of treatment is easy and environmentally friendly, because no special chemicals or equipment are required and all products are utilizable. PMID:20074939

  2. Ethanolysis of rapeseed oil - distribution of ethyl esters, glycerides and glycerol between ester and glycerol phases.

    PubMed

    Cernoch, Michal; Hájek, Martin; Skopal, Frantisek

    2010-04-01

    The distribution of ethyl esters, triglycerides, diglycerides, monoglycerides, and glycerol between the ester and glycerol phase was investigated after the ethanolysis of rapeseed oil at various reaction conditions. The determination of these substances in the ester and glycerol phases was carried out by the GC method. The amount of ethyl esters in the glycerol phase was unexpectedly high and therefore the possibility of the reduction of this amount was investigated. The distribution coefficients and the weight distributions of each investigated substance were calculated and compared mutually. The distribution coefficients between the ester and glycerol phase increase in this sequence: glycerol, monoglycerides, diglycerides, ethyl esters, and triglycerides. Soaps and monoglycerides in the reaction mixture cause a worse separation of ethyl esters from the reaction mixture. The existence of a non-separable reaction mixture was observed also, and its composition was determined. PMID:20005094

  3. Thermodynamics of interdigitated phases of phosphatidylcholine in glycerol.

    PubMed Central

    Swamy, M J; Marsh, D

    1995-01-01

    Comparison of the electron spin resonance spectra of phosphatidylcholines spin-labeled in the sn-2 chain at a position close to the polar region and close to the methyl terminus indicate that symmetrical saturated diacyl phosphatidylcholines with odd and even chain lengths from 13 to 20 C-atoms (and probably also 12 C-atoms) have gel phases in which the chains are interdigitated when dispersed in glycerol. The chain-length dependences of the chain-melting transition enthalpies and entropies are similar for phosphatidylcholines dispersed in glycerol and in water, but the negative end contributions are smaller for phosphatidylcholines dispersed in glycerol than for those dispersed in water: d delta Ht/dCH2 = 1.48 (1.43) kcal.mol-1, d delta St/dCH2 = 3.9 (4.0) cal.mol-1K-1, and delta H o = -12.9 (-15.0) kcal.mol-1, delta S o = -29 (-40) cal.mol-1K-1, respectively, for dispersions in glycerol (water). These differences reflect the interfacial energetics in glycerol and in water, and the different structure of the interdigitated gel phase. PMID:8534810

  4. Determination of esters in glycerol phase after transesterification of vegetable oil.

    PubMed

    Hájek, Martin; Skopal, Frantisek; Kwiecien, Jirí; Cernoch, Michal

    2010-06-30

    In biodiesel production, glycerol is formed as a side product and it is contained in the glycerol phase. This phase contains (besides glycerol): water, soaps, alcohol, traces of catalyst and glycerides and the remaining esters. In this paper, a new method for the determination of esters in the glycerol phase is introduced. The determination enables the minimization of the losses of biodiesel within the production process. It is based on the gradient RP-LC method (water and acetonitrile) with refractometric detection. The analysis is easy and the samples do not need any treatment (only dilution by water) and has a low detection limit. The results of this method were compared with the results of two other published methods: isocratic HPLC and GC. The disadvantage of these two methods is that they need extensive treatment of the sample, which takes many hours, and they are able to determine only the sum of esters. The new method is reliable, much faster and able to differentiate esters of almost each higher fatty acid (e.g. linoleic, linolenic, strearic alkyl ester) in the glycerol phase. PMID:20685468

  5. Crystal structure of substrate free form of glycerol dehydratase

    SciTech Connect

    Liao, Der-Ing; Dotson, Garry; Turner, Jr., Ivan; Reiss, Lisa; Emptage, Mark

    2010-03-08

    Glycerol dehydratase (GDH) and diol dehydratase (DDH) are highly homologous isofunctional enzymes that catalyze the elimination of water from glycerol and 1,2-propanediol (1,2-PD) to the corresponding aldehyde via a coenzyme B{sub 12}-dependent radical mechanism. The crystal structure of substrate free form of GDH in complex with cobalamin and K{sup +} has been determined at 2.5 {angstrom} resolution. Its overall fold and the subunit assembly closely resemble those of DDH. Comparison of this structure and the DDH structure, available only in substrate bound form, shows the expected change of the coordination of the essential K{sup +} from hexacoordinate to heptacoordinate with the displacement of a single coordinated water by the substrate diol. In addition, there appears to be an increase in the rigidity of the K{sup +} coordination (as measured by lower B values) upon the binding of the substrate. Structural analysis of the locations of conserved residues among various GDH and DDH sequences has aided in identification of residues potentially important for substrate preference or specificity of protein-protein interactions.

  6. Excess wing in glass-forming glycerol and LiCl-glycerol mixtures detected by neutron scattering

    SciTech Connect

    Gupta, S.; Arend, N.; Lunkenheimer, P.; Loidl, A.; Stingaciu, L.; Jalarvo, N.; Mamontov, E.; Ohl, M.

    2015-01-22

    The relaxational dynamics in glass-forming glycerol and glycerol mixed with LiCl is investigated using different neutron scattering techniques. The performed neutron spin echo experiments, which extend up to relatively long relaxation time scales of the order of 10 ns, should allow for the detection of contributions from the so-called excess wing. This phenomenon, whose microscopic origin is controversially discussed, arises in a variety of glass formers and, until now, was almost exclusively investigated by dielectric spectroscopy and light scattering. In conclusion, we show here that the relaxational process causing the excess wing can also be detected by neutron scattering, which directly couples to density fluctuations.

  7. Excess wing in glass-forming glycerol and LiCl-glycerol mixtures detected by neutron scattering

    DOE PAGESBeta

    Gupta, S.; Arend, N.; Lunkenheimer, P.; Loidl, A.; Stingaciu, L.; Jalarvo, N.; Mamontov, E.; Ohl, M.

    2015-01-22

    The relaxational dynamics in glass-forming glycerol and glycerol mixed with LiCl is investigated using different neutron scattering techniques. The performed neutron spin echo experiments, which extend up to relatively long relaxation time scales of the order of 10 ns, should allow for the detection of contributions from the so-called excess wing. This phenomenon, whose microscopic origin is controversially discussed, arises in a variety of glass formers and, until now, was almost exclusively investigated by dielectric spectroscopy and light scattering. In conclusion, we show here that the relaxational process causing the excess wing can also be detected by neutron scattering, whichmore » directly couples to density fluctuations.« less

  8. Molecular dynamics simulations of liquid phase interfaces: understanding the structure of the glycerol/water-dodecane system.

    PubMed

    Beierlein, Frank R; Krause, Andreas M; Jäger, Christof M; Fita, Piotr; Vauthey, Eric; Clark, Timothy

    2013-09-24

    Modern spectroscopic techniques such as time-resolved second-harmonic-generation spectroscopy allow molecules to be examined selectively directly at phase interfaces. Two-phase systems formed by glycerol/water and alkane layers have previously been studied by time-resolved second-harmonic-generation spectroscopic measurements. In this molecular dynamics study, a triphenylmethane dye was inserted at the glycerol/water-alkane interface and was used as a probe for local properties such as viscosity. We now show how extensive simulations over a wide range of concentrations can be used to obtain a detailed view of the molecular structure at the glycerol/water-alkane interface. Glycerol is accumulated in a double layer adjacent to the alkane interface, which results in increased viscosity of the glycerol/water phase in the direct vicinity of the interface. We also show that conformational ensembles created by classical molecular-dynamics simulations can serve as input for QM/MM calculations, yielding further information such as transition dipoles, which can be compared with spectroscopic measurements. PMID:23980615

  9. Pressure and temperature dependent viscosity of two glass forming liquids: Glycerol and dibutyl phthalate

    NASA Astrophysics Data System (ADS)

    Cook, Richard L.; King, H. E., Jr.; Herbst, Chris A.; Herschbach, Dudley R.

    1994-04-01

    The pressure and temperature dependent viscosities of two glass forming liquids, glycerol and dibutyl phthalate (DBP), have been studied in the range P=0-3 GPa, T=0-125 °C, and η=101-1010 cP. These studies were made using a combination of a rolling-ball and a centrifugal-force diamond anvil cell viscometer. The majority of the results extend up to viscosities of 107 cP, with those at 22.5 °C going to 1010 cP. The overall precision of the data are approximately 10% or better throughout. This level of precision allows us to define a viscosity surface which can then be extrapolated to the glass transition along both temperature and pressure cuts. The T-dependence of viscosity is larger for glycerol than DBP but the P-dependence smaller for glycerol than for DBP, whereas the T-dependence is much more pressure sensitive for DBP. These data provide an assessment of the T-dependence of an isothermal model (free volume), the P-dependence of an isobaric model (Vogel-Tammann-Fulcher) and by extension that for isochoric conditions. Fragility parameters are evaluated for these three isometric conditions. For glycerol and (less conclusively) DBP under isobaric conditions, the fragility increases markedly at high pressure. Under isochoric conditions, the fragility for both glycerol and DBP increases with increasing density. This is dramatic for DBP, which goes from a strong to an intermediate-strength liquid. For the isothermal model, we derive a new measure of fragility. Using this, DBP shows a trend common to several liquids, a decrease in fragility with increasing temperature. Glycerol, however, becomes more fragile over the same temperature range. For glycerol, the trends towards increased fragility at elevated pressure and temperature are consistent with diminished hydrogen bonding under those conditions. The P-dependence of the glass transition is also determined over a wide range of T. The slope, dTg/dP, is positive with the pressure dependence for glycerol being

  10. Effect of the chirality of the glycerol backbone on the bilayer and nonbilayer phase transitions in the diastereomers of di-dodecyl-beta-D-glucopyranosyl glycerol.

    PubMed Central

    Mannock, D A; Lewis, R N; McElhaney, R N; Akiyama, M; Yamada, H; Turner, D C; Gruner, S M

    1992-01-01

    of annealing at 22 degrees C, the 1,2-sn glucolipid forms an Lc phase that converts to an L alpha phase at 39.5 degrees C on heating. Neither the diastereomeric mixture nor the 2,3-sn glycerol derivative shows such behavior even after extended periods of annealing. Our results suggest that the differences in the phase behavior of these glycolipid isomers may not be attributable to headgroup size per se, but rather to differences in the stereochemistry of the lipid polar/apolar interfacial region, which consequently effects hydrogen-bonding, hydration, and the hydrophilic/hydrophobic balance. Images FIGURE 5 PMID:1477284

  11. The puzzling first-order phase transition in water–glycerol mixtures

    SciTech Connect

    Popov, Ivan; Greenbaum , Anna; Sokolov, Alexei P.; Feldman, Yuri

    2015-06-05

    Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentration of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscosity and nucleation, and finally by crystallization, that might lead to significant misinterpretations.

  12. The puzzling first-order phase transition in water–glycerol mixtures

    DOE PAGESBeta

    Popov, Ivan; Greenbaum; Sokolov, Alexei P.; Feldman, Yuri

    2015-06-05

    Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentrationmore » of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscosity and nucleation, and finally by crystallization, that might lead to significant misinterpretations.« less

  13. Borrelia burgdorferi Requires Glycerol for Maximum Fitness During The Tick Phase of the Enzootic Cycle

    PubMed Central

    Pappas, Christopher J.; Iyer, Radha; Petzke, Mary M.; Caimano, Melissa J.; Radolf, Justin D.; Schwartz, Ira

    2011-01-01

    Borrelia burgdorferi, the spirochetal agent of Lyme disease, is a vector-borne pathogen that cycles between a mammalian host and tick vector. This complex life cycle requires that the spirochete modulate its gene expression program to facilitate growth and maintenance in these diverse milieus. B. burgdorferi contains an operon that is predicted to encode proteins that would mediate the uptake and conversion of glycerol to dihydroxyacetone phosphate. Previous studies indicated that expression of the operon is elevated at 23°C and is repressed in the presence of the alternative sigma factor RpoS, suggesting that glycerol utilization may play an important role during the tick phase. This possibility was further explored in the current study by expression analysis and mutagenesis of glpD, a gene predicted to encode glycerol 3-phosphate dehydrogenase. Transcript levels for glpD were significantly lower in mouse joints relative to their levels in ticks. Expression of GlpD protein was repressed in an RpoS-dependent manner during growth of spirochetes within dialysis membrane chambers implanted in rat peritoneal cavities. In medium supplemented with glycerol as the principal carbohydrate, wild-type B. burgdorferi grew to a significantly higher cell density than glpD mutant spirochetes during growth in vitro at 25°C. glpD mutant spirochetes were fully infectious in mice by either needle or tick inoculation. In contrast, glpD mutants grew to significantly lower densities than wild-type B. burgdorferi in nymphal ticks and displayed a replication defect in feeding nymphs. The findings suggest that B. burgdorferi undergoes a switch in carbohydrate utilization during the mammal to tick transition. Further, the results demonstrate that the ability to utilize glycerol as a carbohydrate source for glycolysis during the tick phase of the infectious cycle is critical for maximal B. burgdorferi fitness. PMID:21750672

  14. Vapor Phase Dehydration of Glycerol to Acrolein Over SBA-15 Supported Vanadium Substituted Phosphomolybdic Acid Catalyst.

    PubMed

    Viswanadham, Balaga; Srikanth, Amirineni; Kumar, Vanama Pavan; Chary, Komandur V R

    2015-07-01

    Vapor phase dehydration of glycerol to acrolein was investigated over heteropolyacid (HPA) catalysts containing vanadium substituted phosphomolybdic acid (H4PMo11VO40) supported on mesoporous SBA-15. A series of HPA catalysts with HPA loadings varying from 10-50 wt% were prepared by impregnation method on SBA-15 support. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, Fourier Transform infrared spectroscopy, temperature-programmed desorption of NH3, pyridine adsorbed FT-IR spectroscopy, scanning electron microscopy, pore size distribution and specific surface area measurements. The nature of acidic sites was examined by pyridine adsorbed FT-IR spectroscopy. XRD results suggest that the active phase containing HPA was highly dispersed at lower loadings on the support. FT-IR and Raman spectra results confirm that the presence of primary Keggin ion structure of HPA on the support and it was not affected during the preparation of catalysts. Pore size distribution results reveal that all the samples show unimodel pore size distribution with well depicted mesoporous structure. NH3-TPD results suggest that the acidity of catalysts increased with increase of HPA loading. The findings of acidity measurements by FT-IR spectra of pyridine adsorption reveals that the catalysts consist both the Brønsted and Lewis acidic sites and the amount of Brønsted acidic sites are increasing with HPA loading. SBA-15 supported vanadium substituted phosphomolybdic acid catalysts are found to be highly active during the dehydration reaction and exhibited 100% conversion of glycerol (10 wt% of glycerol) and the acrolein selectivity was appreciably changed with HPA active phase loading. The catalytic functionalities during glycerol dehydration are well correlated with surface acidity of the catalysts. PMID:26373149

  15. L (+)-lactic acid production by pellet-form Rhizopus oryzae NRRL 395 on biodiesel crude glycerol

    PubMed Central

    2013-01-01

    Background Given its availability and low price, glycerol derived from biodiesel industry has become an ideal feedstock for the production of fuels and chemicals. A solution to reduce the negative environmental problems and the cost of biodiesel is to use crude glycerol as carbon source for microbial growth media in order to produce valuable organic chemicals. In the present paper, crude glycerol was used as carbon substrate for production of L (+)-lactic acid using pelletized fungus R. oryzae NRRL 395 on batch fermentation. More, the experiments were conducted on media supplemented with inorganic nutrients and lucerne green juice. Results Crude and pure glycerols were first used to produce the highest biomass yield of R. oryzae NRRL 395. An enhanced lactic acid production then followed up using fed-batch fermentation with crude glycerol, inorganic nutrients and lucerne green juice. The optimal crude glycerol concentration for cultivating R. oryzae NRRL 395 was 75 g l-1, which resulted in a fungal biomass yield of 0.72 g g-1 in trial without lucerne green juice addition and 0.83 g g-1 in trial with lucerne green juice. The glycerol consumption rate was 1.04 g l-1 h-1 after 48 h in trial with crude glycerol 75 g l-1 while in trial with crude glycerol 10 g l-1 the lowest rate of 0.12 g l-1 h-1 was registered. The highest L (+)-lactic acid yield (3.72 g g-1) was obtained at the crude glycerol concentration of 75 g l-1 and LGJ 25 g l-1, and the concentration of lactic acid was approximately 48 g l-1. Conclusions This work introduced sustainable opportunities for L (+)-lactic acid production via R. oryzae NRRL 395 fermentation on biodiesel crude glycerol media. The results showed good fungal growth on crude glycerol at 75 g l-1 concentration with lucerne green juice supplementation of 25 g l-1. Lucerne green juice provided a good source of nutrients for crude glycerol fermentation, without needs for supplementation with inorganic nutrients

  16. Green acetylation of solketal and glycerol formal by heterogeneous acid catalysts to form a biodiesel fuel additive.

    PubMed

    Dodson, Jennifer R; Leite, Thays d C M; Pontes, Nathália S; Peres Pinto, Bianca; Mota, Claudio J A

    2014-09-01

    A glut of glycerol has formed from the increased production of biodiesel, with the potential to integrate the supply chain by using glycerol additives to improve biodiesel properties. Acetylated acetals show interesting cold flow and viscosity effects. Herein, a solventless heterogeneously catalyzed process for the acetylation of both solketal and glycerol formal to new products is demonstrated. The process is optimized by studying the effect of acetylating reagent (acetic acid and acetic anhydride), reagent molar ratios, and a variety of commercial solid acid catalysts (Amberlyst-15, zeolite Beta, K-10 Montmorillonite, and niobium phosphate) on the conversion and selectivities. High conversions (72-95%) and selectivities (86-99%) to the desired products results from using acetic anhydride as the acetylation reagent and a 1:1 molar ratio with all catalysts. Overall, there is a complex interplay between the solid catalyst, reagent ratio, and acetylating agent on the conversion, selectivities, and byproducts formed. The variations are discussed and explained in terms of reactivity, thermodynamics, and reaction mechanisms. An alternative and efficient approach to the formation of 100% triacetin involves the ring-opening, acid-catalyzed acetylation from solketal or glycerol formal with excesses of acetic anhydride. PMID:25045049

  17. ROS generation and multiple forms of mammalian mitochondrial glycerol-3-phosphate dehydrogenase.

    PubMed

    Mráček, Tomáš; Holzerová, Eliška; Drahota, Zdeněk; Kovářová, Nikola; Vrbacký, Marek; Ješina, Pavel; Houštěk, Josef

    2014-01-01

    Overproduction of reactive oxygen species (ROS) has been implicated in a range of pathologies. Mitochondrial flavin dehydrogenases glycerol-3-phosphate dehydrogenase (mGPDH) and succinate dehydrogenase (SDH) represent important ROS source, but the mechanism of electron leak is still poorly understood. To investigate the ROS production by the isolated dehydrogenases, we used brown adipose tissue mitochondria solubilized by digitonin as a model. Enzyme activity measurements and hydrogen peroxide production studies by Amplex Red fluorescence, and luminol luminescence in combination with oxygraphy revealed flavin as the most likely source of electron leak in SDH under in vivo conditions, while we propose coenzyme Q as the site of ROS production in the case of mGPDH. Distinct mechanism of ROS production by the two dehydrogenases is also apparent from induction of ROS generation by ferricyanide which is unique for mGPDH. Furthermore, using native electrophoretic systems, we demonstrated that mGPDH associates into homooligomers as well as high molecular weight supercomplexes, which represent native forms of mGPDH in the membrane. By this approach, we also directly demonstrated that isolated mGPDH itself as well as its supramolecular assemblies are all capable of ROS production. PMID:23999537

  18. Characteristic length scales of the secondary relaxations in glass-forming glycerol.

    PubMed

    Gupta, S; Mamontov, E; Jalarvo, N; Stingaciu, L; Ohl, M

    2016-03-01

    We investigate the secondary relaxations and their link to the main structural relaxation in glass-forming liquids using glycerol as a model system. We analyze the incoherent neutron scattering signal dependence on the scattering momentum transfer, Q , in order to obtain the characteristic length scale for different secondary relaxations. Such a capability of neutron scattering makes it somewhat unique and highly complementary to the traditional techniques of glass physics, such as light scattering and broadband dielectric spectroscopy, which provide information on the time scale, but not the length scales, of relaxation processes. The choice of suitable neutron scattering techniques depends on the time scale of the relaxation of interest. We use neutron backscattering to identify the characteristic length scale of 0.7 Å for the faster secondary relaxation described in the framework of the mode-coupling theory (MCT). Neutron spin-echo is employed to probe the slower secondary relaxation of the excess wing type at a low temperature ( ∼ 1.13T g . The characteristic length scale for this excess wing dynamics is approximately 4.7 Å. Besides the Q -dependence, the direct coupling of neutron scattering signal to density fluctuation makes this technique indispensable for measuring the length scale of the microscopic relaxation dynamics. PMID:27021657

  19. Phase behaviour and non-monotonic film drying kinetics of aluminium chlorohydrate-glycerol-water ternary solutions.

    PubMed

    Ferretti, Giulia L; Cabral, João T

    2016-11-01

    We study the drying and film formation of a model ternary system comprising an inorganic salt (aluminium chlorohydrate, ACH), a humectant (glycerol) and water. Employing viscometric, X-ray diffraction, calorimetric, dynamic vapour sorption, spectroscopic, gravimetric and adhesion measurements, we examine the roles of humectant concentration, temperature and relative humidity (RH) in the phase behaviour and kinetics of film formation. Equilibrium film compositions are found to be non-monotonic with glycerol content. Around 15:4 ACH:glycerol mass ratio, films exhibit enhanced, albeit slower, desiccation, with water content lower than that of binary ACH-water solutions. At higher glycerol content, drying is faster, yet the resulting films have higher water content and remain tackier. Water adsorption/desorption is shown to be fully reversible, and share a similar non-monotonic kinetic dependence on glycerol composition. These findings are rationalised in terms of the competitive binding of water and glycerol to ACH, the overall miscibility and glass formation within the ternary system. Our study is relevant to a range of salt formulations, employed in a variety of commercial applications, including lyoprotectants and personal care products. PMID:27490196

  20. Biodegradable fibrous scaffolds with tunable properties formed from photo-cross-linkable poly(glycerol sebacate).

    PubMed

    Ifkovits, Jamie L; Devlin, Jeffrey J; Eng, George; Martens, Timothy P; Vunjak-Novakovic, Gordana; Burdick, Jason A

    2009-09-01

    It is becoming increasingly apparent that the architecture and mechanical properties of scaffolds, particularly with respect to mimicking features of natural tissues, are important for tissue engineering applications. Acrylated poly(glycerol sebacate) (Acr-PGS) is a material that can be cross-linked upon exposure to ultraviolet light, leading to networks with tunable mechanical and degradation properties through simple changes during Acr-PGS synthesis. For example, the number of acrylate functional groups on the macromer dictates the concentration of cross-links formed in the resulting network. Three macromers were synthesized that form networks that vary dramatically with respect to their tensile modulus ( approximately 30 kPa to 6.6 MPa) and degradation behavior ( approximately 20-100% mass loss at 12 weeks) based on the extent of acrylation ( approximately 1-24%). These macromers were processed into biodegradable fibrous scaffolds using electrospinning, with gelatin as a carrier polymer to facilitate fiber formation and cell adhesion. The resulting scaffolds were also diverse with respect to their mechanics (tensile modulus ranging from approximately 60 kPa to 1 MPa) and degradation ( approximately 45-70% mass loss by 12 weeks). Mesenchymal stem cell adhesion and proliferation on all fibrous scaffolds was indistinguishable from those of controls. The scaffolds showed similar diversity when implanted on the surface of hearts in a rat model of acute myocardial infarction and demonstrated a dependence on the scaffold thickness and chemistry in the host response. In summary, these diverse scaffolds with tailorable chemical, structural, mechanical, and degradation properties are potentially useful for the engineering of a wide range of soft tissues. PMID:20160937

  1. Biodegradable Fibrous Scaffolds with Tunable Properties Formed from Photocrosslinkable Poly(glycerol sebacate)

    PubMed Central

    Ifkovits, Jamie L.; Devlin, Jeffrey J.; Eng, George; Martens, Timothy P.; Vunjak-Novakovic, Gordana; Burdick, Jason A.

    2009-01-01

    It is becoming increasingly apparent that the architecture and mechanical properties of scaffolds, particularly with respect to mimicking features of natural tissues, are important for tissue engineering applications. Acrylated poly(glycerol sebacate) (Acr-PGS) is a material that can be crosslinked upon exposure to ultraviolet light, leading to networks with tunable mechanical and degradation properties through simple changes during Acr-PGS synthesis. For example, the number of acrylate functional groups on the macromer dictates the concentration of crosslinks formed in the resulting network. Three macromers were synthesized that form networks that vary dramatically with respect to their tensile modulus (~30 kPa to 6.6 MPa) and degradation behavior (~20 to 100% mass loss at 12 weeks) based on the extent of acrylation (~1 to 24%). These macromers were processed into biodegradable fibrous scaffolds using electrospinning, with gelatin as a carrier polymer to facilitate fiber formation and cell adhesion. The resulting scaffolds were also diverse with respect to their mechanics (tensile modulus ranging from ~60 kPa to 1 MPa) and degradation (~45 to 70% mass loss by 12 weeks). Mesenchymal stem cell adhesion and proliferation on all fibrous scaffolds was indistinguishable from controls. The scaffolds showed similar diversity when implanted on the surface of hearts in a rat model of acute myocardial infarction and demonstrated a dependence on scaffold thickness and chemistry in the host response. In summary, these diverse scaffolds with tailorable chemical, structural, mechanical and degradation properties are potentially useful for the engineering of a wide range of soft tissues. PMID:20160937

  2. Theoretical evidence of charge transfer interaction between SO₂ and deep eutectic solvents formed by choline chloride and glycerol.

    PubMed

    Li, Hongping; Chang, Yonghui; Zhu, Wenshuai; Wang, Changwei; Wang, Chao; Yin, Sheng; Zhang, Ming; Li, Huaming

    2015-11-21

    The nature of the interaction between deep eutectic solvents (DESs), formed by ChCl and glycerol, and SO2 has been systematically investigated using the M06-2X density functional combined with cluster models. Block-localized wave function energy decomposition (BLW-ED) analysis shows that the interaction between SO2 and DESs is dominated by a charge transfer interaction. After this interaction, the SO2 molecule becomes negatively charged, whereas the ChCl-glycerol molecule is positively charged, which is the result of Lewis acid-base interaction. The current result affords a theoretical proof that it is highly useful and efficient to manipulate the Lewis acidity of absorbents for SO2 capture. Moreover, hydrogen bonding as well as electrostatic interactions may also contribute to the stability of the complex. Structure analysis shows that solvent molecules will adjust their geometries to interact with SO2. In addition, the structure of SO2 is barely changed after interaction. The interaction energy between different cluster models and SO2 ranges from -6.8 to -14.4 kcal mol(-1). It is found that the interaction energy is very sensitive to the solvent structure. The moderate interaction between ChCl-glycerol and SO2 is consistent with the concept that highly efficient solvents for SO2 absorption should not only be solvable but also regenerable. PMID:26446782

  3. Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl- beta-D-glucopyranosyl)-sn-glycerol.

    PubMed Central

    Trouard, T P; Mannock, D A; Lindblom, G; Rilfors, L; Akiyama, M; McElhaney, R N

    1994-01-01

    The hydration properties and the phase structure of 1,2-di-O-tetradecyl-3-O(3-O-methyl-beta-D-glucopyranosyl)-sn-glycerol (3-O-Me-beta-D-GlcDAIG) in water have been studied via differential scanning calorimetry, 1H-NMR and 2H-NMR spectroscopy, and x-ray diffraction. Results indicate that this lipid forms a crystalline (Lc) phase up to temperatures of 60-70 degrees C, where a transition through a metastable reversed hexagonal (Hll) phase to a reversed micellar solution (L2) phase occurs. Experiments were carried out at water concentrations in a range from 0 to 35 wt%, which indicate that all phases are poorly hydrated, taking up < 5 mol water/mol lipid. The absence of a lamellar liquid crystalline (L alpha) phase and the low levels of hydration measured in the discernible phases suggest that the methylation of the saccharide moiety alters the hydrogen bonding properties of the headgroup in such a way that the 3-O-Me-beta-D-GlcDAIG headgroup cannot achieve the same level of hydration as the unmethylated form. Thus, in spite of the small increase in steric bulk resulting from methylation, there is an increase in the tendency of 3-O-Me-beta-D-GlcDAIG to form nonlamellar structures. A similar phase behavior has previously been observed for the Acholeplasma laidlawii A membrane lipid 1,2-diacyl-3-O-(6-O-acyl-alpha-D-glucopyranosyl)-sn-glycerol in water (Lindblom et al. 1993. J. Biol. Chem. 268:16198-16207). The phase behavior of the two lipids suggests that hydrophobic substitution of a hydroxyl group in the sugar ring of the glucopyranosylglycerols has a very strong effect on their physicochemical properties, i.e., headgroup hydration and the formation of different lipid aggregate structures. PMID:7811919

  4. Dynamics of glass-forming liquids. XIV. A search for ultraslow dielectric relaxation in glycerol

    NASA Astrophysics Data System (ADS)

    Richert, Ranko

    2010-08-01

    A recent dielectric study of various polyalcohols reported on the general occurrence of an ultraslow process with Debye type character in hydrogen bonded liquids [R. Bergman, H. Jansson, and J. Swenson, J. Chem. Phys. 132, 044504 (2010)], whereas previous work suggested that such behavior is specific to monoalcohols only. Clarifying this issue is highly relevant for assessing models aimed at rationalizing these modes that are slower than the primary structural relaxation and associated with a single time constant. To this end, the dielectric relaxation of glycerol is measured at different electrode distances with high accuracy. In this manner, electrode polarization can be separated from the dielectric signals intrinsic in the supercooled liquid. In the frequency range below the loss peak frequency ωmax of the α-process, only dc-conductivity is required to understand the dielectric properties of supercooled glycerol within a margin of ɛ″≈±0.1 and thus no indication of an ultraslow peak is found. More quantitatively, any dielectric Debye like mode located around 10-5ωmax would need to have an amplitude smaller than 0.4% of that of the primary dielectric process to be consistent with the present findings, in contrast to previous claims of >50%.

  5. Microemulsion formed by alkyl polyglucoside and an alkyl glycerol ether with weakly charged films.

    PubMed

    Fukuda; Olsson; Ueno

    2001-02-01

    We have studied the effects on phase equilibria of a nonionic surfactant mixture-water-oil system when replacing small amount of surfactant molecules by ionic surfactant, sodium dodecyl sulfate (SDS). The nonionic surfactant system contains dodecyl-beta-D-maltoside (C(12)AG2) and iso-octyl glyceryl ether (i-C(8)GE) as cosurfactant, water and cyclohexane at constant water to oil ratio of 60/40 (w/w). Adding a small amount of SDS has large impact on the phase behavior. Clear liquid crystalline phase and upper microemulsion phase are added to the phase sequence at high i-C(8)GE/(C(12)AG2+i-C(8)GE) ratio. We also compare the phase equilibria of pure dodecyl maltoside system with polyglucosides mixture system. PMID:11087985

  6. Glycerol production of various strains of saccharomyces

    SciTech Connect

    Radler, F.; Schuetz, H.

    1982-01-01

    The quantity of glycerol as principal by-product of the alcoholic fermentation depends to a large extent on the yeast strain. Different strains of Saccharomyces cerevisiae were found to form amounts of glycerol varying between 4.2 to 10.4 g/L. The formation of glycerol is regarded as a result of the competition between alcohol dehydrogenase and glycerol-3-phosphate dehydrogenase that compete for the reduced coenzyme NADH/sub 2/. High and low glycerol forming yeast strains showed large differences in the activity of glycerol-3-phosphate dehydrogenase and only small variation in the activity of alcohol dehydrogenase. The total amount of glycerol formed was also influenced by amino acids. In thiamine deficient media a decrease in glycerol formation was observed. Experiments indicate a correlation between the formation of acetaldehyde and glycerol and the production of cell mass that may be of practical interest. (Refs. 12).

  7. Glycerol Overproduction by Engineered Saccharomyces cerevisiae Wine Yeast Strains Leads to Substantial Changes in By-Product Formation and to a Stimulation of Fermentation Rate in Stationary Phase

    PubMed Central

    Remize, F.; Roustan, J. L.; Sablayrolles, J. M.; Barre, P.; Dequin, S.

    1999-01-01

    Six commercial wine yeast strains and three nonindustrial strains (two laboratory strains and one haploid strain derived from a wine yeast strain) were engineered to produce large amounts of glycerol with a lower ethanol yield. Overexpression of the GPD1 gene, encoding a glycerol-3-phosphate dehydrogenase, resulted in a 1.5- to 2.5-fold increase in glycerol production and a slight decrease in ethanol formation under conditions simulating wine fermentation. All the strains overexpressing GPD1 produced a larger amount of succinate and acetate, with marked differences in the level of these compounds between industrial and nonindustrial engineered strains. Acetoin and 2,3-butanediol formation was enhanced with significant variation between strains and in relation to the level of glycerol produced. Wine strains overproducing glycerol at moderate levels (12 to 18 g/liter) reduced acetoin almost completely to 2,3-butanediol. A lower biomass concentration was attained by GPD1-overexpressing strains, probably due to high acetaldehyde production during the growth phase. Despite the reduction in cell numbers, complete sugar exhaustion was achieved during fermentation in a sugar-rich medium. Surprisingly, the engineered wine yeast strains exhibited a significant increase in the fermentation rate in the stationary phase, which reduced the time of fermentation. PMID:9872772

  8. Aqueous Phase Glycerol Reforming by PtMo Bimetallic Nano-Particle Catalyst: Product Selectivity and Structural Characterization

    SciTech Connect

    Stach E. A.; Dietrich, P.J.; Lobo-Lapidus, R.J.; Wu, T.; Sumer, A.; Akatay, M.C.; Fingland, B.R.; Guo, N.; Dumesic, J.A.; Marshall, C.L.; Jellinek, J.; Delgass, W.N.; Ribeiro, F.H.; Miller, J.T.

    2012-03-01

    A carbon supported PtMo aqueous phase reforming catalyst for producing hydrogen from glycerol was characterized by analysis of the reaction products and pathway, TEM, XPS and XAS spectroscopy. Operando X-ray absorption spectroscopy (XAS) indicates the catalyst consists of bimetallic nano-particles with a Pt rich core and a Mo rich surface. XAS of adsorbed CO indicates that approximately 25% of the surface atoms are Pt. X-ray photoelectron spectroscopy indicates that there is unreduced and partially reduced Mo oxide (MoO{sub 3} and MoO{sub 2}), and Pt-rich PtMo bimetallic nano-particles. The average size measured by transmission electron microscopy of the fresh PtMo nano-particles is about 2 nm, which increases in size to 5 nm after 30 days of glycerol reforming at 31 bar and 503 K. The catalyst structure differs from the most energetically stable structure predicted by density functional theory (DFT) calculations for metallic Pt and Mo atoms. However, DFT indicates that for nano-particles composed of metallic Pt and Mo oxide, the Mo oxide is at the particle surface. Subsequent reduction would lead to the experimentally observed structure. The aqueous phase reforming reaction products and intermediates are consistent with both C-C and C-OH bond cleavage to generate H{sub 2}/CO{sub 2} or the side product CH{sub 4}. While the H{sub 2} selectivity at low conversion is about 75%, cleavage of C-OH bonds leads to liquid products with saturated carbon atoms. At high conversions (to gas), these will produced additional CH{sub 4} reducing the H{sub 2} yield and selectivity.

  9. Electrochemical valorisation of glycerol.

    PubMed

    Simões, Mário; Baranton, Stève; Coutanceau, Christophe

    2012-11-01

    The worldwide glycerol stocks are increasing; to make the biodiesel industry sustainable economically, this chemical could be used as a secondary primary raw material. Electric energy or hydrogen and added-value-chemical cogeneration becomes more and more an important research topic for increasing economical and industrial interests towards electrochemical technologies. Studies on glycerol electrooxidation for fuel or electrolysis cell applications are scarce. The valorisation of glycerol is generally performed by organic chemistry reactions forming, for example, esters, glycerol carbonates, ethers, acetals or ketals. Glycerol oxidation is made up of complex pathway reactions that can produce a large number of useful intermediates or valuable fine chemicals with presently limited market impact due to expensive production processes. Many of these chemical oxidation routes lead to significant amounts of undesired by-products, and enzymatic processes are limited. Converse to classical heterogeneous processes, electrocatalytic oxidation processes can be tuned by controlling the nature, composition and structure of the electrocatalyts as well as the electrode potential. Such control may lead to very high selectivity and activity, avoiding or limiting product separation steps. The coupling of glycerol oxidation to produce chemicals with the oxygen reduction reaction in a fuel cell or water reduction reaction in an electrolysis cell on Pt-free catalysts results either in coproduction of electrical energy or hydrogen for energy storage. PMID:23112136

  10. Induced thermal dynamics in the melt of glycerol and aerosil dispersions.

    PubMed

    Sharma, Dipti; Iannacchione, Germano S

    2007-03-01

    A high-resolution calorimetric spectroscopy study has been performed on pure glycerol and colloidal dispersions of an aerosil gel in glycerol covering a wide range of temperatures from 300 to 380 K, deep in the liquid phase of glycerol. The colloidal glycerol+aerosil samples with 0.07, 0.14, and 0.32 g of silica per cm3 of glycerol reveal activated energy (thermal) dynamics at temperatures well above the Tg of the pure glycerol. The onset of these dynamics appears to be due to the frustration or pinning imposed by the silica gel on the glycerol liquid and is apparently a long-range, cooperative phenomena. Since this behavior begins to manifest itself at relatively low silica densities (large mean void length compared to the size of a glycerol molecule) and speeds up with increasing density, these induced dynamics are likely due to a coupling between the flexible aerosil gel and large groups of glycerol molecules mediated by mutual hydrogen bonding. This is supported by the lack of such thermal dynamics in pure aerosil gels, pure glycerol, or aerosil gels dispersed in a non-glass-forming, non-hydrogen-bonding, liquid crystal under nearly identical experimental conditions. The study of such frustrated colloids may provide a unique avenue for illuminating the physics of glasses. PMID:17362111

  11. Renewable hydrogen and carbon nanotubes from biodiesel waste glycerol

    PubMed Central

    Wu, Chunfei; Wang, Zichun; Williams, Paul T.; Huang, Jun

    2013-01-01

    In this report, we introduce a novel and commercially viable method to recover renewable hydrogen and carbon nanotubes from waste glycerol produced in the biodiesel process. Gas-phase catalytic reforming converts glycerol to clean hydrogen fuel and by replacing the problematical coke formed on the catalyst with high value carbon nanotubes, added value can be realised. Additional benefits of around 2.8 kg CNTs from the reforming of 1 tonne of glycerol and the production of 500 Nm3 H2 could have a considerable impact on the economics of glycerol utilization. Thereby, the contribution of this research will be a significant step forward in solving a current major technical and economic challenge faced by the biofuels industry. PMID:24067754

  12. Renewable hydrogen and carbon nanotubes from biodiesel waste glycerol.

    PubMed

    Wu, Chunfei; Wang, Zichun; Williams, Paul T; Huang, Jun

    2013-01-01

    In this report, we introduce a novel and commercially viable method to recover renewable hydrogen and carbon nanotubes from waste glycerol produced in the biodiesel process. Gas-phase catalytic reforming converts glycerol to clean hydrogen fuel and by replacing the problematical coke formed on the catalyst with high value carbon nanotubes, added value can be realised. Additional benefits of around 2.8 kg CNTs from the reforming of 1 tonne of glycerol and the production of 500 Nm(3) H2 could have a considerable impact on the economics of glycerol utilization. Thereby, the contribution of this research will be a significant step forward in solving a current major technical and economic challenge faced by the biofuels industry. PMID:24067754

  13. Outlook on the phase equilibria of the innovative system of "protected glycerol": 1,4-dioxaspiro[4.5]decane-2-methanol and alternative solvents.

    PubMed

    Melo, Catarina I; Rodrigues, Ana I; Bogel-Łukasik, Rafał; Bogel-Łukasik, Ewa

    2012-02-23

    Fundamental data on 1,4-dioxaspiro[4.5]decane-2-methanol are scarce. This work presents the foremost systematic data on the solubility of 1,4-dioxaspiro[4.5]decane-2-methanol in sustainable solvents such as water and ionic liquids accompanied by the interpretation of interactions occurring in such binary systems. 1,4-Dioxaspiro[4.5]decane-2-methanol, here called protected glycerol, has been synthesized in order to protect the two hydroxyl groups of glycerol, thus avoiding the formation of side products in a specific process. A series of imidazolium salts accompanied by pyridinium, phosphonium, and ammonium ones with various types of counterions were used in this study. The liquid-liquid and solid-liquid equilibrium measurements in binary systems were carried out by using a dynamic method at atmospheric pressure over the temperature range from 273.00 to 378.30 K or below the boiling point of the solvent. Among all tested sustainable solvents, protected glycerol exhibited limited solubility, with only a few of them in the temperature range studied. The majority of the examined ionic liquids, either hydrophilic or hydrophobic, showed complete miscibility with this monohydroxyol. The Fourier-transform infrared (FTIR) spectroscopy studies of solute and solvents showing a miscibility gap and of their mixtures were performed to obtain insight into major inter- and intramolecular interactions in the investigated systems. Furthermore, the differential scanning calorimetry was used for the first time to determine the melting point, the enthalpy of melting, and the temperature and enthalpy of the solid-solid phase transition of 1-allyl-3-methylimidazolium chloride [Amim][Cl]. The results for the solubility of protected glycerol in sustainable solvents can be used to design future alternative reactions, such as telomerization with protected glycerol in ionic liquids for more specific building blocks and extraction/or separation that involves these mixtures. PMID:22236350

  14. Spray Forming Aluminum - Final Report (Phase II)

    SciTech Connect

    D. D. Leon

    1999-07-08

    The U.S. Department of Energy - Office of Industrial Technology (DOE) has an objective to increase energy efficient and enhance competitiveness of American metals industries. To support this objective, ALCOA Inc. entered into a cooperative program to develop spray forming technology for aluminum. This Phase II of the DOE Spray Forming Program would translate bench scale spray forming technology into a cost effective world class process for commercialization. Developments under DOE Cooperative Agreement No. DE-FC07-94ID13238 occurred during two time periods due to budgetary constraints; April 1994 through September 1996 and October 1997 and December 1998. During these periods, ALCOA Inc developed a linear spray forming nozzle and specific support processes capable of scale-up for commercial production of aluminum sheet alloy products. Emphasis was given to alloys 3003 and 6111, both being commercially significant alloys used in the automotive industry. The report reviews research performed in the following areas: Nozzel Development, Fabrication, Deposition, Metal Characterization, Computer Simulation and Economics. With the formation of a Holding Company, all intellectual property developed in Phases I and II of the Project have been documented under separate cover for licensing to domestic producers.

  15. Smectic Phase Formed by DNA Dimers

    NASA Astrophysics Data System (ADS)

    Salamonczyk, Miroslaw; Gleeson, James; Jakli, Antal; Sprunt, Samuel; Dhont, Jan; Stiakakis, Emmanuel

    The rapidly expanding bio market is driving the development and characterization of new multifunctional materials. In particular, nucleic acids are under intense study for gene therapy, drug delivery and other bio-safe applications [1,2,3]. DNA is well-known to form a cholesteric nematic liquid crystal in its native form; however, much recent research has focused on self-assembly and mesomorphic behavior in concentrated solutions of short DNA helices [4]. Our work focuses on DNA dimers, consisting of 48 base-pair double-stranded helices connected by a 5 to 20 base flexible single strand, and suspended in a natural buffer. Depending on temperature, concentration and length of the flexible spacer, polarizing optical microscopy and small angle x-ray scattering reveal cholesteric nematic and, remarkably, smectic liquid crystalline phases. A model for smectic phase formation in this system will be presented. 1] J.-L. Lim et al., Int. J. of. Pharm. 490 (2015) 2652] D.-H. Kim et al., Nature Biotech. 23 (2005) 2223] K. Liu et al., Chem. Eur. J. 21 (2015) 48984] M. Nakata et al., Science 318 (2007) 1276 NSF DMR 1307674.

  16. Properties of low moisture composite materials consisting of oil droplets dispersed in a protein-carbohydrate-glycerol matrix: effect of continuous phase composition.

    PubMed

    Gu, Yeun Suk; Corradini, Maria G; McClements, D Julian; Desrochers, Julia

    2006-01-25

    The influence of continuous phase composition on the properties of low moisture (<3% water) composite materials consisting of oil droplets dispersed in a protein-carbohydrate-glycerol matrix was investigated. These composites were produced by blending canola oil (62.3%), whey protein concentrate (1.7%, WPC), and corn syrup and glycerol together (36.0% combined) using a high speed mixer equipped with a whisk. The polyol composition was varied by changing the ratio of corn syrup to glycerol in the system while keeping the total concentration of these two polyol components constant. Some composites were analyzed directly after preparation ("unbaked"), while others were analyzed after heating at 176 degrees C for 10 min to simulate baking of a food product ("baked"). The "lightness" of the composites was greater before baking (higher L value), but the color intensity of the composites was greater after baking (higher b value), which was attributed to Maillard browning reactions. The brownness of the baked composites increased with increasing corn syrup concentration, which was attributed to Maillard browning reactions. Squeezing flow viscometry indicated that the consistency and yield stress of the composites increased with baking, which was attributed to whey protein unfolding and aggregation. These rheological parameters also increased with increasing corn syrup concentration, which was attributed to its influence on the continuous phase rheology and on the interactions between the whey proteins. This study shows that the continuous phase composition and thermal history of low moisture composite materials have a large impact on their final physicochemical properties. PMID:16417299

  17. Catalytic Gas-Phase Glycerol Processing over SiO2-, Cu-, Ni- and Fe- Supported Au Nanoparticles

    PubMed Central

    Kapkowski, Maciej; Siudyga, Tomasz; Sitko, Rafal; Lelątko, Józef; Szade, Jacek; Balin, Katarzyna; Klimontko, Joanna; Bartczak, Piotr; Polanski, Jaroslaw

    2015-01-01

    In this study, we investigated different metal pairings of Au nanoparticles (NPs) as potential catalysts for glycerol dehydration for the first time. All of the systems preferred the formation of hydroxyacetone (HYNE). Although the bimetallics that were tested, i.e., Au NPs supported on Ni, Fe and Cu appeared to be more active than the Au/SiO2 system, only Cu supported Au NPs gave high conversion (ca. 63%) and selectivity (ca. 70%) to HYNE. PMID:26580400

  18. Continuous enzymatic biodiesel production from coconut oil in two-stage packed-bed reactor incorporating an extracting column to remove glycerol formed as by-product.

    PubMed

    Costa E Silva, William; Freitas, Larissa; Oliveira, Pedro C; de Castro, Heizir F

    2016-10-01

    The transesterification of coconut oil with ethanol catalyzed by Burkholderia cepacia lipase immobilized on polysiloxane-polyvinyl alcohol was performed in a continuous flow. The experimental design consisted of a two-stage packed-bed reactor incorporating a column with cationic resin (Lewatit GF 202) to remove the glycerol formed as by-product and the reactor performance was quantified for three different flow rates corresponding to space-times from 10 to 14 h. The influence of space-time on the ethyl ester (FAEE) concentrations, yields and productivities was determined. The reactor operation was demonstrated for space-time of 14 h attaining FAEE concentrations of 58.5 ± 0.87 wt%, FAEE yields of 97.3 ± 1.9 % and productivities of 41.6  ± 1.0 mgester g medium (-1)  h(-1). Biodiesel purified samples showed average kinematic viscosity values of 5.5 ± 0.3 mm(2) s(-1) that meet the criteria established by the American National Standard ASTM (D6751). The immobilized lipase was found to be stable regarding its morphological and catalytic characteristics, showing half-life time (t 1/2) around 1540 h. The continuous packed-bed reactor connected in series with simultaneous glycerol removal has a great potential to attain high level of transesterification yields, raising biodiesel productivity. PMID:27277745

  19. GPS phase scintillation correlated with auroral forms

    NASA Astrophysics Data System (ADS)

    Hampton, D. L.; Azeem, S. I.; Crowley, G.; Santana, J.; Reynolds, A.

    2013-12-01

    The disruption of radio wave propagation due to rapid changes in electron density caused by auroral precipitation has been observed for several decades. In a few cases the disruption of GPS signals has been attributed to distinct auroral arcs [Kintner, 2007; Garner, 2011], but surprisingly there has been no systematic study of the characteristics of the auroral forms that cause GPS scintillation. In the Fall of 2012 ASTRA deployed four CASES GPS receivers at UAF observatories in Alaska (Kaktovik, Fort Yukon, Poker Flat and Gakona) specifically to address the effects of auroral activity on the high latitude ionosphere. We have initiated an analysis that compares the phase scintillation, recorded at high cadence, with filtered digital all-sky camera data to determine the auroral morphology and electron precipitation parameters that cause scintillation. From correlation studies from a single site (Poker Flat), we find that scintillation is well correlated with discrete arcs that have high particle energy flux (power per unit area), and not as well correlated with pulsating forms which typically have high characteristic energy, but lower energy flux . This indicates that the scintillation is correlated with the magnitude of the change in total electron density as expected. We will also report on ongoing work where we correlate the scintillation from the Fort Yukon receiver with the all-sky images at Poker Flat to determine the altitude that produces the greatest disturbance. These studies are aimed at a model that can predict the expected local disturbance to navigation due to auroral activity.

  20. Ammonia control in children with urea cycle disorders (UCDs); Phase 2 comparison of sodium phenylbutyrate and glycerol phenylbutyrate☆

    PubMed Central

    Lichter-Konecki, Uta; Diaz, G.A.; Merritt, J.L.; Feigenbaum, A.; Jomphe, C.; Marier, J.F.; Beliveau, M.; Mauney, J.; Dickinson, K.; Martinez, A.; Mokhtarani, M.; Scharschmidt, B.; Rhead, W.

    2016-01-01

    Twenty four hour ammonia profiles and correlates of drug effect were examined in a phase 2 comparison of sodium phenylbutyrate (NaPBA) and glycerol phenylbutyrate (GPB or HPN-100), an investigational drug being developed for urea cycle disorders (UCDs). Study Design Protocol HPN-100-005 involved open label fixed-sequence switch-over from the prescribed NaPBA dose to a PBA-equimolar GPB dose with controlled diet. After 7 days on NaPBA or GPB, subjects underwent 24-hour blood sampling for ammonia and drug metabolite levels as well as measurement of 24-hour urinary phenyacetylglutamine (PAGN). Adverse events (AEs), safety labs and triplicate ECGs were monitored. Results Eleven subjects (9 OTC, 1 ASS, 1 ASL) enrolled and completed the switch-over from NaPBA (mean dose=12.4 g/d or 322 mg/kg/d; range=198–476 mg/kg/d) to GPB (mean dose=10.8 mL or 0.284 mL/kg/d or 313 mg/kg/d; range = 192–449 mg/kg/d). Possibly-related AEs were reported in 2 subjects on NaPBA and 4 subjects on GPB. All were mild, except for one moderate AE of vomiting on GPB related to an intercurrent illness. No clinically significant laboratory or ECG changes were observed. Ammonia was lowest after overnight fast, peaked postprandially in the afternoon to early evening and varied widely over 24 h with occasional values >100 μmol/L without symptoms. Ammonia values were ~25% lower on GPB vs. NaPBA (p ≥ 0.1 for ITT and p<0.05 for per protocol population). The upper 95% confidence interval for the difference between ammonia on GPB vs. NaPBA in the ITT population (95% CI 0.575, 1.061; p = 0.102) was less than the predefined non-inferiority margin of 1.25 and less than 1.0 in the pre-defined per-protocol population (95% CI 0.516, 0.958; p<0.05). No statistically significant differences were observed in plasma phenylacetic acid and PAGN exposure during dosing with GPB vs. NaPBA, and the percentage of orally administered PBA excreted as PAGN (66% for GPB vs. 69% for NaPBA) was very similar. GPB and Na

  1. Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent.

    PubMed

    Lee, Kyung Hwa; Park, Chang-Ho; Lee, Eun Yeol

    2010-11-01

    Glycerol carbonate was synthesized from renewable glycerol and dimethyl carbonate using lipase in solvent-free reaction system in which excess dimethyl carbonate played as the reaction medium. A variety of lipases have been tested for their abilities to catalyze transesterification reaction, and Candida antartica lipase B and Novozyme 435 exhibited higher catalytic activities. The silica-coated glycerol with a 1:1 ratio was supplied to prevent two-phase formation between hydrophobic dimethyl carbonate and hydrophilic glycerol. Glycerol carbonate was successfully synthesized with more than 90% conversion from dimethyl carbonate and glycerol with a molar ratio of 10 using Novozyme 435-catalyzed transesterification at 70 °C. The Novozyme 435 [5% (w/w) and 20% (w/w)] and silica gel were more than four times recycled with good stability in a repeated batch operation for the solvent-free synthesis of glycerol carbonate. PMID:20502921

  2. Glycerol citrate polyesters produced through microwave heating

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The influence of various heating methods without catalysis to prepare copolyesters from citric acid:glycerol blends were studied. In the presence of short term microwave treatments, i.e., 60 sec at 1200 W, blends of glycerol and citric acid invariably formed solid amorphous copolyesters. Fourier tra...

  3. Dielectric and specific heat relaxations in vapor deposited glycerol.

    PubMed

    Kasina, A; Putzeys, T; Wübbenhorst, M

    2015-12-28

    Recently [S. Capponi, S. Napolitano, and M. Wübbenhorst, Nat. Commun. 3, 1233 (2012)], vapor deposited glasses of glycerol have been found to recover their super-cooled liquid state via a metastable, ordered liquid (MROL) state characterized by a tremendously enhanced dielectric strength along with a slow-down of the relaxation rate of the structural relaxation. To study the calorimetric signature of this phenomenon, we have implemented a chip-based, differential AC calorimeter in an organic molecular beam deposition setup, which allows the simultaneous measurement of dielectric relaxations via interdigitated comb electrodes and specific heat relaxation spectra during deposition and as function of the temperature. Heating of the as-deposited glass just above the bulk Tg and subsequent cooling/reheating revealed a step-wise increase in cp by in total 9%, indicating unambiguously that glycerol, through slow vapour deposition, forms a thermodynamically stable glass, which has a specific heat as low as that of crystalline glycerol. Moreover, these glasses were found to show excellent kinetic stability as well as evidenced by both a high onset-temperature and quasi-isothermal recovery measurements at -75 °C. The second goal of the study was to elucidate the impact of the MROL state on the specific heat and its relaxation to the super-cooled state. Conversion of "MROL glycerol" to its "normal" (ordinary liquid, OL) state revealed a second, small (∼2%) increase of the glassy cp, a little gain (<10%) in the relaxed specific heat, and no signs of deviations of τcal from that of normal "bulk" glycerol. These findings altogether suggest that the MROL state in glycerol comprises largely bulk-type glycerol that coexist with a minor volume fraction (<10%) of PVD-induced structural anomalies with a crystal-like calorimetric signature. Based on the new calorimetric findings, we have proposed a new physical picture that assumes the existence of rigid polar clusters (RPCs

  4. Ferroelectric Smectic Phase Formed by Achiral Straight Core Mesogens

    NASA Astrophysics Data System (ADS)

    Stannarius, Ralf; Li, Jianjun; Weissflog, Wolfgang

    2003-01-01

    We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (CSPF) high temperature phase and an anticlinic, probably antiferroelectric (CAPA) low temperature phase.

  5. Production of polyhydroxybutyrate and alginate from glycerol by Azotobacter vinelandii under nitrogen-free conditions

    PubMed Central

    Yoneyama, Fuminori; Yamamoto, Mayumi; Hashimoto, Wataru; Murata, Kousaku

    2015-01-01

    Glycerol is an interesting feedstock for biomaterials such as biofuels and bioplastics because of its abundance as a by-product during biodiesel production. Here we demonstrate glycerol metabolism in the nitrogen-fixing species Azotobacter vinelandii through metabolomics and nitrogen-free bacterial production of biopolymers, such as poly-d-3-hydroxybutyrate (PHB) and alginate, from glycerol. Glycerol-3-phosphate was accumulated in A. vinelandii cells grown on glycerol to the exponential phase, and its level drastically decreased in the cells grown to the stationary growth phase. A. vinelandii also overexpressed the glycerol-3-phosphate dehydrogenase gene when it was grown on glycerol. These results indicate that glycerol was first converted to glycerol-3-phosphate by glycerol kinase. Other molecules with industrial interests, such as lactic acid and amino acids including γ-aminobutyric acid, have also been accumulated in the bacterial cells grown on glycerol. Transmission electron microscopy revealed that glycerol-grown A. vinelandii stored PHB within the cells. The PHB production level reached 33% per dry cell weight in nitrogen-free glycerol medium. When grown on glycerol, alginate-overproducing mutants generated through chemical mutagenesis produced 2-fold the amount of alginate from glycerol than the parental wild-type strain. To the best of our knowledge, this is the first report on bacterial production of biopolymers from glycerol without addition of any nitrogen source. PMID:25880041

  6. Glycerol combustion and emissions

    EPA Science Inventory

    With the growing capacity in biodiesel production and the resulting glut of the glycerol by-product, there is increasing interest in finding alternative uses for crude glycerol. One option may be to burn it locally for combined process heat and power, replacing fossil fuels and i...

  7. Preparation of Glycerol Cinnamate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glycerol was combined with cinnamic acid to prepare the corresponding ester, glycerol cinnamate. Conversions of 81% were achieved after 16 hr in toluene at reflux conditions. The product was recovered by extraction with distilled water and diethyl ether. The isolated product displayed strong abso...

  8. Mathematical modeling of glycerol biotransformation

    NASA Astrophysics Data System (ADS)

    Popova-Krumova, Petya; Yankova, Sofia; Ilieva, Biliana

    2013-12-01

    A method for mathematical modeling of glycerol biotransformation by Klebsiella oxytoca is presented. Glycerol is a renewable resource for it is formed as a by-product during biodiesel production. Because of its large volume production, it seems to be a good idea to develop a technology that converts this waste into products of high value (1, 3-Propanediol; 2, 3-Butanediol). The kinetic model of this process consists of many equations and parameters. The minimization of the least square function will be used for model parameters identification. In cases of parameters identification in multiparameter models the minimization of the least square function is very difficult because it is multiextremal. This is the main problem in the multiextremal function minimization which will be solved on the base a hierarchical approach, using a polynomial approximation of the experimental data.

  9. Assemblages: Functional units formed by cellular phase separation

    PubMed Central

    Wright, Peter E.

    2014-01-01

    The partitioning of intracellular space beyond membrane-bound organelles can be achieved with collections of proteins that are multivalent or contain low-complexity, intrinsically disordered regions. These proteins can undergo a physical phase change to form functional granules or other entities within the cytoplasm or nucleoplasm that collectively we term “assemblage.” Intrinsically disordered proteins (IDPs) play an important role in forming a subset of cellular assemblages by promoting phase separation. Recent work points to an involvement of assemblages in disease states, indicating that intrinsic disorder and phase transitions should be considered in the development of therapeutics. PMID:25179628

  10. Naturally occurring crystalline phases: analogues for radioactive waste forms

    SciTech Connect

    Haaker, R.F.; Ewing, R.C.

    1981-01-01

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included.

  11. Mechanical spectra of glass-forming liquids. II. Gigahertz-frequency longitudinal and shear acoustic dynamics in glycerol and DC704 studied by time-domain Brillouin scattering.

    PubMed

    Klieber, Christoph; Hecksher, Tina; Pezeril, Thomas; Torchinsky, Darius H; Dyre, Jeppe C; Nelson, Keith A

    2013-03-28

    This paper presents and discusses the temperature and frequency dependence of the longitudinal and shear viscoelastic response at MHz and GHz frequencies of the intermediate glass former glycerol and the fragile glass former tetramethyl-tetraphenyl-trisiloxane (DC704). Measurements were performed using the recently developed time-domain Brillouin scattering technique, in which acoustic waves are generated optically, propagated through nm thin liquid layers of different thicknesses, and detected optically after transmission into a transparent detection substrate. This allows for a determination of the frequency dependence of the speed of sound and the sound-wave attenuation. When the data are converted into mechanical moduli, a linear relationship between longitudinal and shear acoustic moduli is revealed, which is consistent with the generalized Cauchy relation. In glycerol, the temperature dependence of the shear acoustic relaxation time agrees well with literature data for dielectric measurements. In DC704, combining the new data with data from measurements obtained previously by piezo-ceramic transducers yields figures showing the longitudinal and shear sound velocities at frequencies from mHz to GHz over an extended range of temperatures. The shoving model's prediction for the relaxation time's temperature dependence is fairly well obeyed for both liquids as demonstrated from a plot with no adjustable parameters. Finally, we show that for both liquids the instantaneous shear modulus follows an exponential temperature dependence to a good approximation, as predicted by Granato's interstitialcy model. PMID:23556795

  12. Optical beam forming techniques for phased array antennas

    NASA Technical Reports Server (NTRS)

    Wu, Te-Kao; Chandler, C.

    1993-01-01

    Conventional phased array antennas using waveguide or coax for signal distribution are impractical for large scale implementation on satellites or spacecraft because they exhibit prohibitively large system size, heavy weight, high attenuation loss, limited bandwidth, sensitivity to electromagnetic interference (EMI) temperature drifts and phase instability. However, optical beam forming systems are smaller, lighter, and more flexible. Three optical beam forming techniques are identified as applicable to large spaceborne phased array antennas. They are (1) the optical fiber replacement of conventional RF phased array distribution and control components, (2) spatial beam forming, and (3) optical beam splitting with integrated quasi-optical components. The optical fiber replacement and the spatial beam forming approaches were pursued by many organizations. Two new optical beam forming architectures are presented. Both architectures involve monolithic integration of the antenna radiating elements with quasi-optical grid detector arrays. The advantages of the grid detector array in the optical process are the higher power handling capability and the dynamic range. One architecture involves a modified version of the original spatial beam forming approach. The basic difference is the spatial light modulator (SLM) device for controlling the aperture field distribution. The original liquid crystal light valve SLM is replaced by an optical shuffling SLM, which was demonstrated for the 'smart pixel' technology. The advantages are the capability of generating the agile beams of a phased array antenna and to provide simultaneous transmit and receive functions. The second architecture considered is the optical beam splitting approach. This architecture involves an alternative amplitude control for each antenna element with an optical beam power divider comprised of mirrors and beam splitters. It also implements the quasi-optical grid phase shifter for phase control and grid

  13. Glycerol monooleate-blood interactions.

    PubMed

    Ericsson, Emma M; Faxälv, Lars; Weissenrieder, Anna; Askendal, Agneta; Lindahl, Tomas L; Tengvall, Pentti

    2009-01-01

    In the present study the initial blood compatibility of glycerol monooleate (GMO)-coated surfaces was evaluated after deposition to surfaces and in bulk. The model surface was silica onto which multiple layers of fibrinogen or human serum albumin (HSA) was immobilized. The protein-coated surfaces were subsequently dip-coated in GMO in ethanol and used for blood plasma and whole blood experiments. The characterization methods included null ellipsometry, scanning electron microscopy, imaging of coagulation, hemolysis test and whole blood coagulation time by free oscillation rheometry. The results showed a GMO film thickness of approximately 350 A (approximately 4 microg/cm(2)) upon dip-coating in ethanolic solution. A major part of the deposited layer detached in aqueous solutions, especially during shear conditions. The coagulation time on GMO was significantly prolonged compared to that on HSA coated silica. Whole blood tests showed that GMO is a very weak hemolytic agent. Deposited GMO detached easily from surfaces upon rinsing or shearing, although a stable layer with undefined phase structure and a thickness of 50-70 A remained on HSA and fibrinogen precoated surfaces. This indicates that GMO has stronger adhesive forces to its substrate compared to the cohesive forces acting within the bulk GMO. The ability of GMO to detach from itself and tentatively form micelles or lipid bilayers when subjected to flowing blood may be of use in extravascular applications. It is concluded that GMO results in weak blood activation, and the material may in spite of this be suitable in selected biomaterial applications, especially as a biosealant and in colloidal dispersions. PMID:18996684

  14. Glycerol uptake is by passive diffusion in the heart but by facilitated transport in RBCs at high glycerol levels in cold acclimated rainbow smelt (Osmerus mordax).

    PubMed

    Clow, Kathy A; Driedzic, William R

    2012-04-15

    Rainbow smelt (Osmerus mordax) is a small fish that accumulates glycerol at low winter seawater temperatures. In laboratory-held fish, glycerol concentration typically reaches 225 mM in plasma and in all cells. Glycerol uptake by the heart and red blood cells (RBCs) was assessed by tracking [(14)C(U)]glycerol into the acid-soluble pool. In fish acclimated to 9-10°C a decrease in perfusion/incubation temperature from 8 to 1°C resulted in a decrease in glycerol uptake with a Q(10) of 3.2 in heart and 2.4 in RBCs. Acclimation to ∼1.5°C did not result in an adaptive enhancement of glycerol uptake as rates were unchanged in heart and RBCs. Glycerol uptake at 1°C was by passive diffusion in heart as evidenced by a linear relationship between glycerol uptake and extracellular glycerol concentration and a lack of inhibition by phloretin. In contrast, in RBCs, glycerol uptake with respect to glycerol concentration showed two linear relationships with a transition point around 50 mM extracellular glycerol. The slope of the second phase was much steeper and eliminated with the inclusion of phloretin. In RBCs from Atlantic salmon (Salmo salar), a related species that does not accumulate glycerol, glycerol uptake showed only a single linear curve and was not inhibited by phloretin. The data imply a strong facilitated component to glycerol uptake in rainbow smelt RBCs at high glycerol concentrations. We propose this is related to cyclic changes in RBC glycerol content involving a loss of glycerol at the gill and a reaccumulation during passage through the liver. PMID:22319051

  15. Studies of phase transitions in the aripiprazole solid dosage form.

    PubMed

    Łaszcz, Marta; Witkowska, Anna

    2016-01-01

    Studies of the phase transitions in an active substance contained in a solid dosage form are very complicated but essential, especially if an active substance is classified as a BCS Class IV drug. The purpose of this work was the development of sensitive methods for the detection of the phase transitions in the aripiprazole tablets containing initially its form III. Aripiprazole exhibits polymorphism and pseudopolymorphism. Powder diffraction, Raman spectroscopy and differential scanning calorimetry methods were developed for the detection of the polymorphic transition between forms III and I as well as the phase transition of form III into aripiprazole monohydrate in tablets. The study involved the initial 10 mg and 30 mg tablets, as well as those stored in Al/Al blisters, a triplex blister pack and HDPE bottles (with and without desiccant) under accelerated and long term conditions. The polymorphic transition was not observed in the initial and stored tablets but it was visible on the DSC curve of the Abilify(®) 10 mg reference tablets. The formation of the monohydrate was observed in the diffractograms and Raman spectra in the tablets stored under accelerated conditions. The monohydrate phase was not detected in the tablets stored in the Al/Al blisters under long term conditions. The results showed that the Al/Al blisters can be recommended as the packaging of the aripiprazole tablets containing form III. PMID:26397209

  16. Diamond-like phases formed from fullerene-like clusters

    NASA Astrophysics Data System (ADS)

    Belenkov, E. A.; Greshnyakov, V. A.

    2015-11-01

    The geometrically optimized structure and properties of thirteen diamond-like carbon phases formed by linking or combining fullerene-like clusters (C4, C6, C8, C12, C16, C24, or C48) have been investigated. Atoms in the structures of these phases are located in crystallographically equivalent positions. The calculations have been performed using the density functional theory in the generalized gradient approximation. The calculated values of the structural characteristics and properties (sublimation energies, bulk moduli, band gaps, X-ray diffraction patterns) of the studied diamond-like phases differ significantly from the corresponding values for cubic diamond.

  17. Glycerol-induced hyperhydration

    NASA Technical Reports Server (NTRS)

    Riedesel, Marvin L.; Lyons, Timothy P.; Mcnamara, M. Colleen

    1991-01-01

    Maintenance of euhydration is essential for maximum work performance. Environments which induce hypohydration reduce plasma volume and cardiovascular performance progressively declines as does work capacity. Hyperhydration prior to exposure to dehydrating environments appears to be a potential countermeasure to the debilitating effects of hypohydration. The extravascular fluid space, being the largest fluid compartment in the body, is the most logical space by which significant hyperhydration can be accomplished. Volume and osmotic receptors in the vascular space result in physiological responses which counteract hyperhydration. Our hypothesis is that glycerol-induced hyperhydration (GIH) can accomplish extravascular fluid expansion because of the high solubility of glycerol in lipid and aqueous media. A hypertonic solution of glycerol is rapidly absorbed from the gastrointestinal tract, results in mild increases in plasma osmolality and is distributed to 65 percent of the body mass. A large volume of water ingested within minutes after glycerol intake results in increased total body water because of the osmotic action and distribution of glycerol. The resulting expanded extravascular fluid space can act as a reservoir to maintain plasma volume during exposure to dehydrating environments. The fluid shifts associated with exposure to microgravity result in increased urine production and is another example of an environment which induces hypohydration. Our goal is to demonstrate that GIH will facilitate maintenance of euhydration and cardiovascular performance during space flight and upon return to a 1 g environment.

  18. Formed platelet combustor liner construction feasibility, phase A

    NASA Technical Reports Server (NTRS)

    Hayes, W. A.; Janke, D. E.

    1992-01-01

    Environments generated in high pressure liquid rocket engines impose severe requirements on regeneratively cooled combustor liners. Liners fabricated for use in high chamber pressures using conventional processes suffer from limitations that can impair operational cycle life and can adversely affect wall compatibility. Chamber liners fabricated using formed platelet technology provide an alternative to conventional regeneratively cooled liners (an alternative that has many attractive benefits). A formed platelet liner is made from a stacked assembly of platelets with channel features. The assembly is diffusion bonded into a flat panel and then three-dimensionally formed into a section of a chamber. Platelet technology permits the liner to have very precisely controlled and thin hot gas walls and therefore increased heat transfer efficiency. Further cooling efficiencies can be obtained through enhanced design flexibility. These advantages translate into increased cycle life and enhanced wall compatibility. The increased heat transfer efficiency can alternately be used to increase engine performance or turbopump life as a result of pressure drop reductions within the regeneratively cooled liner. Other benefits can be obtained by varying the materials of construction within the platelet liner to enhance material compatibility with operating environment or with adjoining components. Manufacturing cost savings are an additional benefit of a formed platelet liner. This is because of reduced touch labor and reduced schedule when compared to conventional methods of manufacture. The formed platelet technology is not only compatible with current state-of-the art combustion chamber structural support and manifolding schemes, it is also an enabling technology that allows the use of other high performance and potentially low cost methods of construction for the entire combustion chamber assembly. The contract under which this report is submitted contains three phases: (1) phase

  19. Massive 2-form field and holographic ferromagnetic phase transition

    NASA Astrophysics Data System (ADS)

    Cai, Rong-Gen; Yang, Run-Qiu; Wu, Ya-Bo; Zhang, Cheng-Yuan

    2015-11-01

    In this paper we investigate in some detail the holographic ferromagnetic phase transition in an AdS4 black brane background by introducing a massive 2-form field coupled to the Maxwell field strength in the bulk. In two probe limits, one is to neglect the back reaction of the 2-form field to the background geometry and to the Maxwell field, and the other to neglect the back reaction of both the Maxwell field and the 2-form field, we find that the spontaneous magnetization and the ferromagnetic phase transition always happen when the temperature gets low enough with similar critical behavior. We calculate the DC resistivity in a semi-analytical method in the second probe limit and find it behaves as the colossal magnetic resistance effect in some materials. In the case with the first probe limit, we obtain the off-shell free energy of the holographic model near the critical temperature and compare with the Ising-like model. We also study the back reaction effect and find that the phase transition is always second order. In addition, we find an analytical Reissner-Norström-like black brane solution in the Einstein-Maxwell-2-form field theory with a negative cosmological constant.

  20. Synthesis of glycerol carbonate from glycerol and urea with gold-based catalysts.

    PubMed

    Hammond, Ceri; Lopez-Sanchez, Jose A; Ab Rahim, Mohd Hasbi; Dimitratos, Nikolaos; Jenkins, Robert L; Carley, Albert F; He, Qian; Kiely, Christopher J; Knight, David W; Hutchings, Graham J

    2011-04-21

    The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed. PMID:21258674

  1. Hydrophobic Surfactant Proteins Induce a Phosphatidylethanolamine to Form Cubic Phases

    PubMed Central

    Chavarha, Mariya; Khoojinian, Hamed; Schulwitz, Leonard E.; Biswas, Samares C.; Rananavare, Shankar B.; Hall, Stephen B.

    2010-01-01

    Abstract The hydrophobic surfactant proteins SP-B and SP-C promote rapid adsorption of pulmonary surfactant to an air/water interface. Previous evidence suggests that they achieve this effect by facilitating the formation of a rate-limiting negatively curved stalk between the vesicular bilayer and the interface. To determine whether the proteins can alter the curvature of lipid leaflets, we used x-ray diffraction to investigate how the physiological mixture of these proteins affects structures formed by 1-palmitoyl-2-oleoyl phosphatidylethanolamine, which by itself undergoes the lamellar-to-inverse hexagonal phase transition at 71°C. In amounts as low as 0.03% (w:w) and at temperatures as low as 57°C, the proteins induce formation of bicontinuous inverse cubic phases. The proteins produce a dose-related shift of diffracted intensity to the cubic phases, with minimal evidence of other structures above 0.1% and 62°C, but no change in the lattice-constants of the lamellar or cubic phases. The induction of the bicontinuous cubic phases, in which the individual lipid leaflets have the same saddle-shaped curvature as the hypothetical stalk-intermediate, supports the proposed model of how the surfactant proteins promote adsorption. PMID:20409474

  2. Dietary effects in the early recovery phase of kwashiorkor. Plasma levels of triglycerides, FFA, D-beta-hydroxybutyrate, glycerol, postheparin lipoprotein lipase (LPL), glucose and insulin.

    PubMed

    Persson, B; Habte, D; Sterky, G

    1976-05-01

    The fatty liver often found in untreated kwashiorkor has been associated with highly variable concentration of circulating lipids. The effect on lipid metabolism of two isocaloric diets--one synthetic monomolecular (Vivonex) and one standard (Casilan)--which both initiated satisfactory clinical improvement was studied in 21 Ethiopian children with kwashiorkor during the first weeks of rehabilitation. Before treatment mean fasting values of all biochemical parameters were within normal ranges except for moderately elevated triglycerides--an unexpected finding-and low insulin. Individual values varied greatly; triglyceride between 0.39 and 3.49 mmol/1. FFA correlated both to glycerol, D-beta-hydroxybutyrate and triglyceride values. During treatment insulin, glucose and glycerol remained essentially unchanged and were similar in both dietary groups. In the Vivonex group only there was an initial marked, parallel fall of FFA and D-beta-hydroxybutyrate suggesting greater availability of carbohydrate and enhanced glucose utilization. This pattern of response seemed to occur without comparable inhibition of lipolysis. Triglycerides--like serum albumin--increased faster in the Casilan group. The highest mean triglyceride value was reached by day 8 in the Casilan group and by day 15 in the Vivonex group. Ten minutes following heparin injection triglycerides declined, FFA and glycerol increased indicating release of in vivo active lipase. LPL activity assayed in vitro was similar and unaffected by 2 weeks of dietary treatment in both groups. LPL activity was inversely correlated to triglycerides providing--beside the type of diet--another possible explanation for the wide variations seen in circulatory triglycerides. PMID:1274567

  3. High consistency forming process for papermaking. Phase II. Final report

    SciTech Connect

    Kranz, W.T.; Judd, M.; Rotherham, J.

    1980-09-01

    The demonstration program for saving energy that can be obtained by forming paper and paperboard products at initial high fiber concentration is discussed. Under Phase II, a limited number of design modifications were made to the low speed high consistency headbox. These resulted in improved sheet formation for samples used in subsequent press studies. Comparisons of sheet physical and drainage properties were made between low and high consistency sheets. Equipment for these tests was designed and fabricated during Phase II, including a laboratory scale dynamic roll nip press with single felt. The high consistency sheet had significantly higher permeability and compressive modulus than the low consistency sheet. In simulated three nip press studies the high consistency sheet demonstrated a 1.5 to 2.5% higher solids content than the low consistency sheet under the same operating parameters. The effect of variables such as machine speed, sheet basis weight, nip loading and entering sheet consistency were investigated. Rules for scaling between laboratory and full size press nips have been established. The energy saving potential for the paper industry through the use of high consistency forming was estimated as 6 to 7% of current total consumption.

  4. Transketolase activity modulates glycerol-3-phosphate levels in Escherichia coli.

    PubMed

    Vimala, A; Harinarayanan, R

    2016-04-01

    Transketolase activity provides an important link between the metabolic pathways of glycolysis and pentose phosphate shunt and catalyzes inter-conversions between pentose phosphates and glycolytic intermediates. It is widely conserved in life forms. A genetic screen for suppression of the growth defect of Escherichia coli tktA tktB mutant in LB medium revealed two mutations, one that rendered the glpK expression constitutive and another that inactivated deoB. Characterizing these mutations aided in uncovering the role of ribose-5-P (a transketolase substrate) as an inhibitor of glycerol assimilation and de novo glycerol-3-P synthesis. Using lacZ fusions, we show that ribose-5-P enhances GlpR-mediated repression of the glpFKX operon and inhibits glycerol assimilation. Electrophoretic Mobility Shift Assay (EMSA) showed ribose-5-P made the DNA-GlpR complex less sensitive to the inducer glycerol-3-P. In addition to inhibition of glycerol assimilation, obstruction of ribose-5-P metabolism retards growth from glycerol-3-P limitation. Glucose helps to overcome this limitation through a mechanism involving catabolite repression. To our knowledge, this report is the first to show ribose-5-P can modulate glycerol-3-P concentration in the cell by regulation of glycerol assimilation as well as its de novo synthesis. This regulation could be prevalent in other organisms. PMID:26691989

  5. Impact of impurities in biodiesel-derived crude glycerol on the fermentation by Clostridium pasteurianum ATCC 6013.

    PubMed

    Venkataramanan, Keerthi P; Boatman, Judy J; Kurniawan, Yogi; Taconi, Katherine A; Bothun, Geoffrey D; Scholz, Carmen

    2012-02-01

    During the production of biodiesel, crude glycerol is produced as a byproduct at 10% (w/w). Clostridium pasteurianum has the inherent potential to grow on glycerol and produce 1,3-propanediol and butanol as the major products. Growth and product yields on crude glycerol were reported to be slower and lower, respectively, in comparison to the results obtained from pure glycerol. In this study, we analyzed the effect of each impurity present in the biodiesel-derived crude glycerol on the growth and metabolism of glycerol by C. pasteurianum. The crude glycerol contains methanol, salts (in the form of potassium chloride or sulfate), and fatty acids that were not transesterified. Salt and methanol were found to have no negative effects on the growth and metabolism of the bacteria on glycerol. The fatty acid with a higher degree of unsaturation, linoleic acid, was found to have strong inhibitory effect on the utilization of glycerol by the bacteria. The fatty acid with lower or no degrees of unsaturation such as stearic and oleic acid were found to be less detrimental to substrate utilization. The removal of fatty acids from crude glycerol by acid precipitation resulted in a fermentation behavior that is comparable to the one on pure glycerol. These results show that the fatty acids in the crude glycerol have a negative effect by directly affecting the utilization of glycerol as the carbon source, and hence their removal from crude glycerol is an essential step towards the utilization of crude glycerol. PMID:22202963

  6. Preparation of glycerol dimethacrylate-based polymer monolith with unusual porous properties achieved via viscoelastic phase separation induced by monodisperse ultra high molecular weight poly(styrene) as a porogen.

    PubMed

    Aoki, Hiroshi; Kubo, Takuya; Ikegami, Tohru; Tanaka, Nobuo; Hosoya, Ken; Tokuda, Daisuke; Ishizuka, Norio

    2006-06-30

    The preparation of polymer-based monolith capillary was examined by the use of glycerol dimethacrylate (GDMA) as monomer and monodisperse standard polystyrene (PS) solution in chlorobenzene as porogen. Poly-GDMA monoliths were prepared in situ in test tubes with standard PS having the variety of molecular weight (defined as Mw hereafter) from 50,000 to 3,840,000, and their morphology was compared to that of poly-GDMA monolith prepared in situ with a poor porogenic solvent of GDMA. According to scanning electron micrograph (SEM) observation, the structure of poly-GDMA monolith prepared in situ with toluene as a poor porogenic solvent showed a typical agglomerated globular structure, whereas the morphology of poly-GDMA monolith prepared in situ with the polymer (PS) porogenic solution was transformed from the aggregated globule form to three dimensionally (3D) continuous skeletal structure with the increase of Mw of standard PS utilized. Along with this morphological transformation or change, in the case of poly-GDMA monolith prepared in situ with ultra high Mw standard PS porogenic solution, the pore size distribution showed a sharp bimodal distribution, with one peak being located around 4 nm in the mesopore range (2-50 nm) and the other peak located around 1-2 microm in the macropore range (>50 nm), respectively. The poly-GDMA capillaries were prepared in situ with toluene, low Mw (50,000, 600,000) PS solution in chlorobenzene and the above mentioned ultra high Mw PS solution in chlorobenzene as a porogen, respectively, and measured by mu-HPLC with benzene and n-alkyl phenyl ketone as solutes for the evaluation in aqueous methanol (MeOH/H(2)O = 50/50-80/20, v/v). The permeability of capillaries prepared in situ with ultra high Mw standard PS polymer porogenic solution was much larger, compared to those of the capillaries prepared in situ with low Mw standard PS polymer porogenic solution or with toluene as porogen. On the other hand, the column efficiency was

  7. Coproduction of ethanol and glycerol.

    PubMed

    Gong, C S; Du, J X; Cao, N J; Tsao, G T

    2000-01-01

    Ethanol and glycerol are both metabolic products of yeasts. There are occasions when coproduction of both is considered desirable in industrial operations. In this article, we describe the potential of integrating the two processes. A LORRE Y8 yeast culture isolated from molasses is capable of efficient glycerol production from glucose, and a yeast Culture 1400 is an excellent producer of ethanol. By controlling the process conditions, the ratio of ethanol and glycerol production can be varied. PMID:10849818

  8. Method for forming single phase, single crystalline 2122 BCSCO superconductor thin films by liquid phase epitaxy

    NASA Technical Reports Server (NTRS)

    Pandey, Raghvendra K. (Inventor); Raina, Kanwal (Inventor); Solayappan, Narayanan (Inventor)

    1994-01-01

    A substantially single phase, single crystalline, highly epitaxial film of Bi.sub.2 CaSr.sub.2 Cu.sub.2 O.sub.8 superconductor which has a T.sub.c (zero resistance) of 83 K is provided on a lattice-matched substrate with no intergrowth. This film is produced by a Liquid Phase Epitaxy method which includes the steps of forming a dilute supercooled molten solution of a single phase superconducting mixture of oxides of Bi, Ca, Sr, and Cu having an atomic ratio of about 2:1:2:2 in a nonreactive flux such as KCl, introducing the substrate, e.g., NdGaO.sub.3, into the molten solution at 850.degree. C., cooling the solution from 850.degree. C. to 830.degree. C. to grow the film and rapidly cooling the substrate to room temperature to maintain the desired single phase, single crystalline film structure.

  9. O/W nano-emulsion formation using an isothermal low-energy emulsification method in a mixture of polyglycerol polyricinoleate and hexaglycerol monolaurate with glycerol system.

    PubMed

    Wakisaka, Satoshi; Nishimura, Takahisa; Gohtani, Shoichi

    2015-01-01

    We investigated how phase behavior changes by replacing water with glycerol in water/mixture of polyglycerol polyricinoleate (PGPR) and hexaglycerol monolaurate (HGML) /vegetable oil system, and studied the effect of glycerol on o/w nano-emulsion formation using an isothermal low-energy method. In the phase behavior study, the liquid crystalline phase (Lc) + the sponge phase (L3) expanded toward lower surfactant concentration when water was replaced with glycerol in a system containing surfactant HLP (a mixture of PGPR and HGML). O/W nano-emulsions were formed by emulsification of samples in a region of Lc + L3. In the glycerol/surfactant HLP/vegetable oil system, replacing water with glycerol was responsible for the expansion of a region containing Lc + L3 toward lower surfactant concentration, and as a result, in the glycerol/surfactant HLP/vegetable oil system, the region where o/w nano-emulsions or o/w emulsions could be prepared using an isothermal low-energy emulsification method was wide, and the droplet diameter of the prepared o/w emulsions was also smaller than that in the water/surfactant HLP/vegetable oil system. Therefore, glycerol was confirmed to facilitate the preparation of nano-emulsions from a system of surfactant HLP. Moreover, in this study, we could prepare o/w nano-emulsions with a simple one-step addition of water at room temperature without using a stirrer. Thus, the present technique is highly valuable for applications in several industries. PMID:25766932

  10. In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol

    SciTech Connect

    Karim, Ayman M.; Howard, Christopher J.; Roberts, Benjamin Q.; Kovarik, Libor; Zhang, Liang; King, David L.; Wang, Yong

    2012-10-30

    In situ x-ray absorption spectroscopy (XAS) results on correlating the Pt local coordination and electronic structure with the Pt/C catalyst activity and selectivity during aqueous reforming of glycerol at different pH are reported. The results show that both low and high pH favor C-O cleavage over that of C-C. However, the selectivity towards C-O bond cleavage was higher under the acidic conditions. XANES measurements under reaction conditions showed that low pH increased the Pt electron density while the effect of basic conditions was minimal. ΔXANES was used to estimate the coverage of adsorbates under reaction conditions and the results suggest a change in the adsorbates coverage by the acidic conditions, resulting in higher electron density on Pt

  11. Phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs).

    PubMed

    Zhang, Tao; Xu, Zhiguang; Cai, Zengxiao; Guo, Qipeng

    2015-06-28

    Herein, we report the phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs) induced by salt concentration and pH changes. The ionomers are sulfonated polystyrenes (SPSs) with different sulfonation degrees. The emulsion types were determined by conductivity measurements, confocal microscopy and optical microscopy, and the formation of HIPE organogels was verified by the tube-inversion method and rheological measurements. SPSs with high sulfonation degrees (water-soluble) and low sulfonation degrees (water-insoluble) can stabilize oil-in-water emulsions; these emulsions were transformed into water-in-oil HIPEs by varying salt concentrations and/or changing the pH. SPS, with a sulfonation degree of 11.6%, is the most efficient, and as low as 0.2 (w/v)% of the organic phase is enough to stabilize the HIPEs. Phase inversion of the oil-in-water emulsions occurred to form water-in-oil HIPEs by increasing the salt concentration in the aqueous phase. Two phase inversion points from oil-in-water emulsions to water-in-oil HIPEs were observed at pH 1 and 13. Moreover, synergetic effects between the salt concentration and pH changes occurred upon the inversion of the emulsion type. The organic phase can be a variety of organic solvents, including toluene, xylene, chloroform, dichloroethane, dichloromethane and anisole, as well as monomers such as styrene, butyl acrylate, methyl methacrylate and ethylene glycol dimethacrylate. Poly(HIPEs) were successfully prepared by the polymerization of monomers as the continuous phase in the ionomer-stabilized HIPEs. PMID:26028420

  12. Dynamical and orientational structural crossovers in low-temperature glycerol.

    PubMed

    Seyedi, Salman; Martin, Daniel R; Matyushov, Dmitry V

    2016-07-01

    Mean-square displacements of hydrogen atoms in glass-forming materials and proteins, as reported by incoherent elastic neutron scattering, show kinks in their temperature dependence. This crossover, known as the dynamical transition, connects two approximately linear regimes. It is often assigned to the dynamical freezing of subsets of molecular modes at the point of equality between their corresponding relaxation times and the instrumental observation window. The origin of the dynamical transition in glass-forming glycerol is studied here by extensive molecular dynamics simulations. We find the dynamical transition to occur for both the center-of-mass translations and the molecular rotations at the same temperature, insensitive to changes of the observation window. Both the translational and rotational dynamics of glycerol show a dynamic crossover from the structural to a secondary relaxation at the temperature of the dynamical transition. A significant and discontinuous increase in the orientational Kirkwood factor and in the dielectric constant is observed in the same range of temperatures. No indication is found of a true thermodynamic transition to an ordered low-temperature phase. We therefore suggest that all observed crossovers are dynamic in character. The increase in the dielectric constant is related to the dynamic freezing of dipolar domains on the time scale of simulations. PMID:27575188

  13. Dynamical and orientational structural crossovers in low-temperature glycerol

    NASA Astrophysics Data System (ADS)

    Seyedi, Salman; Martin, Daniel R.; Matyushov, Dmitry V.

    2016-07-01

    Mean-square displacements of hydrogen atoms in glass-forming materials and proteins, as reported by incoherent elastic neutron scattering, show kinks in their temperature dependence. This crossover, known as the dynamical transition, connects two approximately linear regimes. It is often assigned to the dynamical freezing of subsets of molecular modes at the point of equality between their corresponding relaxation times and the instrumental observation window. The origin of the dynamical transition in glass-forming glycerol is studied here by extensive molecular dynamics simulations. We find the dynamical transition to occur for both the center-of-mass translations and the molecular rotations at the same temperature, insensitive to changes of the observation window. Both the translational and rotational dynamics of glycerol show a dynamic crossover from the structural to a secondary relaxation at the temperature of the dynamical transition. A significant and discontinuous increase in the orientational Kirkwood factor and in the dielectric constant is observed in the same range of temperatures. No indication is found of a true thermodynamic transition to an ordered low-temperature phase. We therefore suggest that all observed crossovers are dynamic in character. The increase in the dielectric constant is related to the dynamic freezing of dipolar domains on the time scale of simulations.

  14. Toxic and osmotic effects of glycerol on human granulocytes

    SciTech Connect

    Armitage, W.J.; Mazur, P.

    1984-11-01

    Human granulocytes are damaged by exposure to concentrations of glycerol as low as 0.5 M. We therefore investigated the addition of glycerol to granulocytes and its subsequent dilution under various conditions to try to distinguish between toxic and harmful osmotic effects of glycerol. The lesion caused by glycerol at 0/sup 0/C was expressed as a loss of plasma membrane integrity (as visualized by fluorescein diacetate) only after incubation (greater than or equal to1 h) at 37/sup 0/C. This damage was not ameliorated when osmotic stress was lessened by reducing the rates of addition and dilution of glycerol to keep the computed cell volume within 80-170% of isotonic cell volume. However, when osmotic stress was reduced further by increasing the temperature of addition and dilution of glycerol from 0/sup 0/ to 22/sup 0/C, the tolerance of the cells to 1 M glycerol increased somewhat. Reducing exposure to glycerol to 3 min or less at 0/sup 0/C greatly increased survival, but this time was too short to allow glycerol to equilibrate intracellularly. Finally, the presence of extra impermeant solute (NaCl or sucrose) in the medium to reduce the equilibrium cell volume to 60% of isotonic cell volume enabled granulocytes to survive 30-min exposure to 1 M glycerol at 0/sup 0/C, but cells had to remain shrunken during the 37/sup 0/C incubation to prevent the loss of membrane integrity. Suspensions that contained damaged granulocytes formed aggregates when incubated at 37/sup 0/C, and these aggregates were responsible for a major fraction of the observed loss in viability.

  15. Dielectric and specific heat relaxations in vapor deposited glycerol

    SciTech Connect

    Kasina, A. E-mail: wubbenhorst@fys.kuleuven.be; Putzeys, T.; Wübbenhorst, M. E-mail: wubbenhorst@fys.kuleuven.be

    2015-12-28

    Recently [S. Capponi, S. Napolitano, and M. Wübbenhorst, Nat. Commun. 3, 1233 (2012)], vapor deposited glasses of glycerol have been found to recover their super-cooled liquid state via a metastable, ordered liquid (MROL) state characterized by a tremendously enhanced dielectric strength along with a slow-down of the relaxation rate of the structural relaxation. To study the calorimetric signature of this phenomenon, we have implemented a chip-based, differential AC calorimeter in an organic molecular beam deposition setup, which allows the simultaneous measurement of dielectric relaxations via interdigitated comb electrodes and specific heat relaxation spectra during deposition and as function of the temperature. Heating of the as-deposited glass just above the bulk T{sub g} and subsequent cooling/reheating revealed a step-wise increase in c{sub p} by in total 9%, indicating unambiguously that glycerol, through slow vapour deposition, forms a thermodynamically stable glass, which has a specific heat as low as that of crystalline glycerol. Moreover, these glasses were found to show excellent kinetic stability as well as evidenced by both a high onset-temperature and quasi-isothermal recovery measurements at −75 °C. The second goal of the study was to elucidate the impact of the MROL state on the specific heat and its relaxation to the super-cooled state. Conversion of “MROL glycerol” to its “normal” (ordinary liquid, OL) state revealed a second, small (∼2%) increase of the glassy c{sub p}, a little gain (<10%) in the relaxed specific heat, and no signs of deviations of τ{sub cal} from that of normal “bulk” glycerol. These findings altogether suggest that the MROL state in glycerol comprises largely bulk-type glycerol that coexist with a minor volume fraction (<10%) of PVD-induced structural anomalies with a crystal-like calorimetric signature. Based on the new calorimetric findings, we have proposed a new physical picture that assumes the

  16. Dehydration of glycerol over niobia-supported silicotungstic acid catalysts.

    PubMed

    Lee, Young Yi; Ok, Hye Jeong; Moon, Dong Ju; Kim, Jong Ho; Park, Nam Cook; Kim, Young Chul

    2013-01-01

    Liquid-phase dehydration of glycerol to acrolein over nanosized niobia-supported silicotungstic acid catalysts was performed to investigate the effect of the silicotungstic acid loading on the catalytic performance of the catalysts. The catalysts were prepared by following an impregnation method with different HSiW loadings in the range of 10-50 wt%. The prepared catalysts were characterized by N2 physisorption, XRD, FT-IR, TPD of ammonia, and TGA. Dehydration of glycerol was conducted in an autoclave reactor under the conditions of controlled reaction temperatures under corresponding pressure. Increasing HSiW loading rapidly increased the acidity of HSiW/Nb205 catalyst and rate of glycerol conversion, but acrolein selectivity decreased due to enhanced deactivation of the catalyst by carbon deposit. Consequently, it was confirmed that catalytic activity for the dehydration of glycerol to acrolein was dependant on the acidity of catalyst and can be controlled by HSiW loading. PMID:23646735

  17. On the phase form of a deformation quantization with separation of variables

    NASA Astrophysics Data System (ADS)

    Karabegov, Alexander

    2016-06-01

    Given a star product with separation of variables on a pseudo-Kähler manifold, we obtain a new formal (1, 1)-form from its classifying form and call it the phase form of the star product. The cohomology class of a star product with separation of variables equals the class of its phase form. We show that the phase forms can be arbitrary and they bijectively parametrize the star products with separation of variables. We also describe the action of a change of the formal parameter on a star product with separation of variables, its formal Berezin transform, classifying form, phase form, and canonical trace density.

  18. Glass polymorphism in glycerol-water mixtures: II. Experimental studies.

    PubMed

    Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A; Wong, Jessina; Giovambattista, Nicolas; Loerting, Thomas

    2016-04-20

    We report a detailed experimental study of (i) pressure-induced transformations in glycerol-water mixtures at T = 77 K and P = 0-1.8 GPa, and (ii) heating-induced transformations of glycerol-water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s(-1)-10 K h(-1)) and for the whole range of glycerol mole fractions, χg. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χg ≥ 0.20), ice (χg ≤ 0.32), and/or "distorted ice" (0 < χg ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χg ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol-water mixtures is shown to be possible only up to χg ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χg < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χg ≈ 0.38. Accordingly, in the range 0.32 < χg < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χg ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 < χg ≤ 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (χg ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol-water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex "phase" behavior of glassy binary

  19. On the Propensity of Phosphatidylglycerols to Form Interdigitated Phases

    PubMed Central

    Pabst, Georg; Danner, Sabine; Karmakar, Sanat; Deutsch, Günter; Raghunathan, Velayudhan A.

    2007-01-01

    We have determined the phase behavior of disaturated phosphatidylglycerols (PGs) of chain lengths nCH2 = 14–18 at high pH and ionic strength using calorimetry, dilatometry, as well as x-ray diffraction. PGs with nCH2 = 14 and 16 show thermotropic behavior similar to that of phosphatidylcholines (PCs). The area/lipid obtained in the gel phase is smaller than that reported for PCs despite the expected larger effective headgroup size. This can be explained by the tilting of the PG headgroup out of the bilayer plane, and we provide experimental evidence for a headgroup tilt transition. For distearoyl PG, we further find that the “usual” gel phase coexists with an interdigitated phase, which exhibits a transition from an orthorhombic into a hexagonal chain packing. The total amount of the interdigitated phase depends significantly on the temperature but is found to be largely independent of temperature equilibration time and different sample preparation protocols. Thus, the development of the interdigitated phase appears to be kinetically trapped. The formation of interdigitated phases in PGs at much smaller chain lengths than in PCs is of high relevance to interaction studies with antimicrobial peptides, as it provides a mechanism for the discrimination of membranes composed of different lipid species. PMID:17449673

  20. Scaling of the hysteresis in the glass transition of glycerol with the temperature scanning rate

    NASA Astrophysics Data System (ADS)

    Wang, Yi-Zhen; Li, Ying; Zhang, Jin-Xiu

    2011-03-01

    By measuring the dependences of the temperature-dependent primary ("alpha") dielectric relaxation time behavior on the temperature scanning rate for the glass-forming glycerol, we study the scaling of hysteresis at the glass transition in glycerol. Based on the Vogel-Fulcher-Tammann (VFT) expression and the Angell's fragility concept, notable correlations of the systematic kinetic fragility, and of the hysteresis effect in the vitrification/fusion "alpha"-relaxation process of glycerol, with the temperature scanning rate, were reasonably analyzed and discussed. It was observed that the kinetic fragility m and the apparent glass-transition temperature hysteresis width Δ T_g^a, respectively, scaled the temperature scanning rate q as m ≈ αmq-γ and Δ T_g^a ≈ A0 + αqβ, at which the exponents, γ and β, were suggested to be characteristic of the resistance to the structure change or fragility change of the system during the glass transition. The observed scaling laws are quite similar to the scaling power law for the thermal hysteresis in the first-order phase transition (FOPT) of solids, providing a significant insight into the hysteresis effect in the glass transition of the glass-forming liquids.

  1. Optimizing aerobic conversion of glycerol to 3-hydroxypropionaldehyde

    SciTech Connect

    Slininger, P.J.; Bothast, R.J.

    1985-12-01

    Chemical oxidation of 3-hydroxypropionaldehyde (3-HPA) leads to acrylic acid, an industrially important polymerizable monomer currently derived from petroleum. As the availability of petroleum declines, 3-HPA may become attractive as a product to be obtained through fermentation of glycerol, a renewable resource. When cells of Klebsiella pneumoniae NRRL B-199 (ATCC 8724) were grown aerobically on a rich glycerol medium and then suspended in buffer supplemented with semicarbazide and glycerol, aerobic conversion of glycerol to 3-hydroxypropionaldehyde (3-HPA) ensued. Depending on conditions, 0.38 to 0.67 g of 3-HPA were formed per gram of glycerol consumed. This means that up to 83.8% of the carbon invested as glycerol could potentially be recovered as the target product, 3-HPA. Production of 3-HPA was sensitive to the age of cells harvested for resuspension and was nonexistent if cells were cultivated on glucose instead of glycerol as the sole carbon source. Compared with 24- and 72-h cells, 48-h cells produced 3-HPA at the highest rate and with the greatest yield. The cell biomass concentration present during the fermentation was never particularly critical to the 3-HPA yield, but initial fermentation rates and 3-HPA accumulation displayed a linear dependence on biomass concentration that faded when biomass exceeded 3 g/liter. Fermentation performance was a function of temperature, and an optimum initial specific 3-HPA productivity occurred at 32/sup 0/C, although the overall 3-HPA yield increased continuously within the 25 to 37/sup 0/C range studied. The pH optimum based on fermentation rate was different from that based on overall yield; 8 versus 7, respectively. Initial glycerol concentrations in the 20 to 50 g/liter range optimized initial 3-HPA productivity and yield.

  2. Characterization of crude glycerol from biodiesel plants.

    PubMed

    Hu, Shengjun; Luo, Xiaolan; Wan, Caixia; Li, Yebo

    2012-06-13

    Characterization of crude glycerol is very important to its value-added conversion. In this study, the physical and chemical properties of five biodiesel-derived crude glycerol samples were determined. Three methods, including iodometric-periodic acid method, high performance liquid chromatography (HPLC), and gas chromatography (GC), were shown to be suitable for the determination of glycerol content in crude glycerol. The compositional analysis of crude glycerol was successfully achieved by crude glycerol fractionation and characterization of the obtained fractions (aqueous and organic) using titrimetric, HPLC, and GC analyses. The aqueous fraction consisted mainly of glycerol, methanol, and water, while the organic fraction contained fatty acid methyl esters (FAMEs), free fatty acids (FFAs), and glycerides. Despite the wide variations in the proportion of their components, all raw crude glycerol samples were shown to contain glycerol, soap, methanol, FAMEs, water, glycerides, FFAs, and ash. PMID:22612334

  3. Electron beam irradiation of maltodextrin and cinnamyl alcohol mixtures: influence of glycerol on cross-linking.

    PubMed

    Khandal, Dhriti; Aggarwal, Manjeet; Suri, Gunjan; Coqueret, Xavier

    2015-03-01

    The influence of glycerol on the electron beam-induced changes in maltodextrins-cinnamyl alcohol (CA) blends is examined with respect to its influence on the degree of chain scission, grafting, and cross-linking. The study is relevant to radiation-induced polysaccharide modification, specifically in the perspective of using blended starch as a thermoplastic material, where glycerol is commonly used as a plasticizer. In the absence of CA, glycerol protects maltodextrin from chromophore formation onto the main chain, but also induces more chain scission. The presence of CA provides efficient radiation-protection against scission. Glycerol is shown to affect the interaction between maltodextrin and CA, most likely in the form of an inclusion complex when glycerol is absent. The global behavior under radiation is therefore governed by the physical interactions between the blend constituents rather than on the role of glycerol role as a plasticizer, or as an OH˙ radical scavenger. PMID:25498620

  4. Electrohydraulic forming of dual phase steels; numerical and experimental work

    NASA Astrophysics Data System (ADS)

    Hassannejadasl, Amir; Green, Daniel E.; Golovashchenko, Sergey F.

    2013-12-01

    Electrohydraulic Forming (EHF) is a high velocity forming process, in which the strain-rate in the sheet metal can reach very high values depending on the prescribed input energy, the chamber geometry, the die geometry, instrumentation efficiency and the mechanical properties of the sheet material. In EHF, a high voltage discharge between electrodes that are submerged in a water-filled chamber generates a plasma channel that leads to propagation of a shockwave through the water that forms the sheet, with or without a die, in less than a millisecond. EHF generates a complex pressure pulse history that is extremely challenging to simulate. In this work, three-dimensional finite element simulations of DP590 sheet were completed in free-forming (EHFF) and die-forming (EHDF) conditions using ABAQUS/Explicit and a combination of Eulerian and Lagrangian elements. The Johnson-Cook constitutive plasticity model was selected and the parameters were calibrated based on uniaxial tensile test data at different strain-rates. A comprehensive numerical study was carried out with a view to understanding the differences between EHFF and EHDF in terms of the history of the deformation profile of the specimen, the strain-rate history, the loading path and through-thickness stresses. Higher strain-rates and more complex strain-paths were predicted in EHDF compared to EHFF due to dynamic sheet/die interaction. Good correlation between the experimental and numerical results demonstrated the ability of numerical models to accurately predict the history of the deformation profile in both EHDF and EHFF conditions.

  5. Phase Diagram of α-Helical and β-Sheet Forming Peptides

    NASA Astrophysics Data System (ADS)

    Auer, Stefan; Kashchiev, Dimo

    2010-04-01

    The intrinsic property of proteins to form structural motifs such as α helices and β sheets leads to a complex phase behavior in which proteins can assemble into various types of aggregates including crystals, liquidlike phases of unfolded or natively folded proteins, and amyloid fibrils. Here we use a coarse-grained protein model that enables us to perform Monte Carlo simulations for determining the phase diagram of natively folded α-helical and unfolded β-sheet forming peptides. The simulations reveal the existence of various metastable peptide phases. The liquidlike phases are metastable with respect to the fibrillar phases, and there is a hierarchy of metastability.

  6. Identifying plasma glycerol concentration associated with urinary glycerol excretion in trained humans.

    PubMed

    Nelson, Jeff L; Harmon, Molly E; Robergs, Robert A

    2011-11-01

    Glycerol has been used as a means to legitimately hyperhydrate the body in an attempt to offset the deleterious effects of dehydration. It has the potential to mask blood doping practices and as a result has been added to the WADA prohibited substance list. The purpose of this study was to identify the plasma glycerol concentration coinciding with urinary glycerol excretion. Twelve healthy, trained male subjects completed five separate trials under resting conditions. For each trial, subjects consumed a different glycerol dose (0.025, 0.05, 0.10, 0.15, or 0.20 g glycerol/kg LBM) of a 5% glycerol solution in order to determine at what plasma glycerol concentration an increase in urine glycerol concentration becomes apparent. Based on regression analysis, plasma glycerol concentrations > 0.327 ± 0.190 mmol/L and a glycerol dose > 0.032 ± 0.010 g glycerol/kg LBM would be associated with urinary glycerol excretion. There were significant linear relationships between peak plasma glycerol concentration and time to reach peak plasma glycerol concentration to the ingested glycerol doses. Our findings illustrate the importance of considering the effect of urinary glycerol excretion on legitimate hyperhydration regimens as well as suggesting that it is possible to detect surreptitious use of glycerol as a masking agent through urinary analysis. PMID:22080901

  7. Growth and form of spherulites: A phase field study.

    NASA Astrophysics Data System (ADS)

    Granasy, Laszlo

    2006-03-01

    Polycrystalline patterns termed spherulites are present in a broad variety of systems including metal alloys, polymers, minerals, and have biological relevance as well (see e.g. semi-crystalline amyloid spherulites and spherultic kidney stones). The fact that similar polycrystalline patterns are observed in systems of very different nature suggests that a minimal model based on coarse-grained fields, which neglects the details of molecular interactions, might be appropriate. Although such a field-theoretic approach disregards most of the molecular scale details of formation, some features such as crystal symmetries can be incorporated via the anisotropies of the model parameters. The rationale for developing such coarse-grained models is the current inability of fully molecular models to address the formation of large scale morphologies. A phase field theory of polycrystalline growth, we developed recently, is applied for describing spherulitic solidification in two and three dimensions. Our model consists of several mechanisms for nucleating new grains at the perimeter of the crystallites, including homogeneous (trapping of orientational disorder and branching in certain crystallographic directions) and heterogeneous (particle-induced nucleation) processes. It will be shown that the diversity of spherulitic growth morphologies arises from a competition between the ordering effect of discrete local crystallographic symmetries and the randomization of the local crystallographic orientation that accompanies crystal grain nucleation at the growth front. This randomization in the crystal orientation accounts for the isotropy of spherulitic growth at large length-scales and long times. We find the entire range of observed spherulite morphologies can be reproduced by this generalized phase field model of polycrystalline growth.

  8. Alumina-Forming MAX Phases in Turbine Material Systems

    NASA Technical Reports Server (NTRS)

    Smialek, James L.; Harder, Bryan J.; Garg, Arnita; Nesbitt, James A.

    2015-01-01

    Coatings for high temperature turbine components are based on low conductivity YSZ thermal barriers and protective NiAl, NiCoCrAlY bond coats. Good oxidation hot corrosion resistance, intermediate CTE, and strain tolerance of Ti2AlC and Cr2AlC MAX phases are thus of special interest. Their alumina scale growth follows a cubic law in accord with FeCrAlY alloys, with oxygen grain boundary diffusivity: Dgb 1.8 x 10-10 exp(-375 kJmole) m3s. Protective cubic kinetics are also found in high pressure burner rig (6 atm., 25 ms) and TGA tests of MAXthal 211Ti2AlC. The initial portion (0.1 hr) is dominated by fast TiO2 growth (with little evidence of scale volatility in high pressure water vapor, as found for SiO2 scales). Bulk Ti2AlC and Cr2AlC substrates show promise as potential bond coats for YSZ TBCs in 1000-1200 C furnace life (500 h) tests. Cr2AlC is proving to be very resistant to 700-900 C Na2SO4 hot corrosion and is of interest for disk alloys. Preliminary diffusion bonded Cr2AlC-superalloy hybrid couples have survived 1000 hr interrupted furnace tests at 800C with no indication of cracking or debonding. Diffusion zones of -NiAl+Cr7C3 were produced in these above 1000 C, but did not grow to any great extent after 1000 hr at 800 C. Processing as coatings presents challenges, however the basic properties of MAX phases provide novel opportunities for high temperature turbine components.

  9. Kinetics of phase transformation in glass forming systems

    NASA Technical Reports Server (NTRS)

    Ray, Chandra S.

    1994-01-01

    The objectives of this research were to (1) develop computer models for realistic simulations of nucleation and crystal growth in glasses, which would also have the flexibility to accomodate the different variables related to sample characteristics and experimental conditions, and (2) design and perform nucleation and crystallization experiments using calorimetric measurements, such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA) to verify these models. The variables related to sample characteristics mentioned in (1) above include size of the glass particles, nucleating agents, and the relative concentration of the surface and internal nuclei. A change in any of these variables changes the mode of the transformation (crystallization) kinetics. A variation in experimental conditions includes isothermal and nonisothermal DSC/DTA measurements. This research would lead to develop improved, more realistic methods for analysis of the DSC/DTA peak profiles to determine the kinetic parameters for nucleation and crystal growth as well as to assess the relative merits and demerits of the thermoanalytical models presently used to study the phase transformation in glasses.

  10. Glycerol clearance in alcoholic liver disease.

    PubMed Central

    Johnston, D G; Alberti, K G; Wright, R; Blain, P G

    1982-01-01

    Glycerol clearance was studied by a primed dose-constant infusion technique in 14 patients with alcoholic liver disease and six normal control subjects. Fasting blood glycerol concentrations were raised in the alcoholic subjects (0.09 +/- 0.01 vs 0.06 +/- 0.01 mumol/l, p less than 0.05) and glycerol clearance was impaired (24.5 +/- 1.9 vs 37.5 +/- 3.2 ml/kg/min, p less than 0.005). Endogenous production rate of glycerol and distribution space at steady state were similar in alcoholic and control subjects. The metabolic clearance rate of glycerol correlated negatively with basal glycerol concentrations. Thus tissue uptake of glycerol is impaired in liver disease. As glycerol is metabolised primarily in the liver by conversion to glucose, these data suggest a defect of gluconeogenesis in alcoholic liver disease. PMID:7076002

  11. Glycerol inhibition of ruminal lipolysis in vitro

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Supplemental glycerol inhibits rumen lipolysis, a prerequisite for rumen biohydrogenation, which is responsible for the saturation of dietary fatty acids consumed by ruminant animals. Feeding excess glycerol, however, adversely affects dry matter digestibility. To more clearly define the effect of...

  12. An experimental verification of a criterion for forming metastable phases in containerless solidification

    NASA Astrophysics Data System (ADS)

    Kuribayashi, K.; Kato, H.; Nagayama, K.; Inatomi, Y.; Kumar, M. S. Vijaya

    2015-04-01

    On the thermodynamic condition for forming a metastable phase from undercooled melt in a containerless state, we had proposed a criterion that crystals will preferentially form if they have a smaller entropy of fusion than the entropy of fusion of equilibrium crystals (Kuribayashi et al., Mater. Sci. Eng., A 449-451, 675 (2007)). This criterion is proposed for being applied to materials that exhibit a faceted interface, such as semiconductors and oxides. However, no experimental data that support this criterion have been obtained. From this point, we used an aerodynamic levitator as a tool for forming metastable phases from undercooled melt and verified the above-mentioned criterion using LnFeO3 (Ln: lanthanide and Y) as the model material. In addition, the condition for double recalescence, which corresponds to forming metastable phases and stable phases, was discussed in terms of competitive 2D isomorphic nucleation of the metastable phase and 3D polymorphic nucleation of the stable phase.

  13. An experimental verification of a criterion for forming metastable phases in containerless solidification

    SciTech Connect

    Kuribayashi, K.; Inatomi, Y.; Kumar, M. S. Vijaya

    2015-04-21

    On the thermodynamic condition for forming a metastable phase from undercooled melt in a containerless state, we had proposed a criterion that crystals will preferentially form if they have a smaller entropy of fusion than the entropy of fusion of equilibrium crystals (Kuribayashi et al., Mater. Sci. Eng., A 449–451, 675 (2007)). This criterion is proposed for being applied to materials that exhibit a faceted interface, such as semiconductors and oxides. However, no experimental data that support this criterion have been obtained. From this point, we used an aerodynamic levitator as a tool for forming metastable phases from undercooled melt and verified the above-mentioned criterion using LnFeO{sub 3} (Ln: lanthanide and Y) as the model material. In addition, the condition for double recalescence, which corresponds to forming metastable phases and stable phases, was discussed in terms of competitive 2D isomorphic nucleation of the metastable phase and 3D polymorphic nucleation of the stable phase.

  14. Effects of Forming Induced Phase Transformation on Crushing Behavior of TRIP Steel

    SciTech Connect

    Liu, Wenning N.; Choi, Kyoo Sil; Soulami, Ayoub; Sun, Xin; Khaleel, Mohammad A.

    2010-04-15

    In this paper, results of finite element crash simulation are presented for a TRIP steel side rail with and without considering the phase transformation during forming operations. A homogeneous phase transformation model is adapted to model the mechanical behavior of the austenite-to-martensite phase. The forming process of TRIP steels is simulated with the implementation of the material model. The distribution and volume fraction of the martensite in TRIP steels may be greatly influenced by various factors during forming process and subsequently contribute to the behavior of the formed TRIP steels during the crushing process. The results indicate that, with the forming induced phase transformation, higher energy absorption of the side rail can be achieved. The phase transformation enhances the strength of the side rail

  15. Antioxidant properties of feruloyl glycerol derivatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The natural plant components, 1-feruloyl-sn-glycerol (FG) and 1,3-diferuloyl-sn-glycerol (F2G), were synthesized by the enzymatic esterification of glycerol and soybean oil mono- and diacylglycerols, respectively, with ethyl ferulate. The isolated FG and F2G were examined for their antioxidant acti...

  16. Kinetics of cinnamoyl glycerol formation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The esterifications of glycerol with cinnamic acid, 2-methoxy cinnamic acid, and 4-methoxy cinnamic acid were investigated in batch reactions. Conversions of over 50% were achieved for cinnamic acid and 4-methoxy cinnamic acid within 8 hours. After 24 hours conversions of over 80% were obtained fo...

  17. Esterification of glycerol from biodiesel production to glycerol carbonate in non-catalytic supercritical dimethyl carbonate.

    PubMed

    Ilham, Zul; Saka, Shiro

    2016-01-01

    Conversion of glycerol from biodiesel production to glycerol carbonate was studied by esterification with dimethyl carbonate in a non-catalytic supercritical condition. It was found that in a non-catalytic supercritical condition, glycerol at higher purity gave higher yield of glycerol carbonate at 98 wt% after reaction at 300 °C/20-40 MPa/15 min. The yield of glycerol carbonate was observed to increase with molar ratio, temperature, pressure and time until a certain equilibrium limit. The existence of impurities such as water and remnants of alkaline catalyst in crude glycerol will direct the reaction to produce glycidol. Although impurities might not be desirable, the non-catalytic supercritical dimethyl carbonate could be an alternative method for conversion of glycerol from biodiesel production to value-added glycerol carbonate.Graphical abstractPlausible reaction scheme for conversion of glycerol to glycerol carbonate in non-catalytic supercritical dimethyl carbonate. PMID:27386367

  18. Characterization of the CDP-2-Glycerol Biosynthetic Pathway in Streptococcus pneumoniae▿ †

    PubMed Central

    Wang, Quan; Xu, Yanli; Perepelov, Andrei V.; Xiong, Wei; Wei, Dongmei; Shashkov, Alexander S.; Knirel, Yuriy A.; Feng, Lu; Wang, Lei

    2010-01-01

    Capsule polysaccharide (CPS) plays an important role in the virulence of Streptococcus pneumoniae and is usually used as the pneumococcal vaccine target. Glycerol-2-phosphate is found in the CPS of S. pneumoniae types 15A and 23F and is rarely found in the polysaccharides of other bacteria. The biosynthetic pathway of the nucleotide-activated form of glycerol-2-phosphate (NDP-2-glycerol) has never been identified. In this study, three genes (gtp1, gtp2, and gtp3) from S. pneumoniae 23F that have been proposed to be involved in the synthesis of NDP-2-glycerol were cloned and the enzyme products were expressed, purified, and assayed for their respective activities. Capillary electrophoresis was used to detect novel products from the enzyme-substrate reactions, and the structure of the product was elucidated using electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy. Gtp1 was identified as a reductase that catalyzes the conversion of 1,3-dihydroxyacetone to glycerol, Gtp3 was identified as a glycerol-2-phosphotransferase that catalyzes the conversion of glycerol to glycerol-2-phosphate, and Gtp2 was identified as a cytidylyltransferase that transfers CTP to glycerol-2-phosphate to form CDP-2-glycerol as the final product. The kinetic parameters of Gtp1 and Gtp2 were characterized in depth, and the effects of temperature, pH, and cations on these two enzymes were analyzed. This is the first time that the biosynthetic pathway of CDP-2-glycerol has been identified biochemically; this pathway provides a method to enzymatically synthesize this compound. PMID:20729354

  19. Accelerated dynamics of supercooled glycerol in soft confinement

    NASA Astrophysics Data System (ADS)

    Blochowicz, T.; Gouirand, E.; Fricke, A.; Spehr, T.; Stühn, B.; Frick, B.

    2009-06-01

    We investigate the dynamics of supercooled glycerol in a soft confinement within microemulsion droplets. The structure of the system is characterized by small-angle neutron scattering. We show that temperature-stable droplets establish a confinement, which may be varied in size from about 1 to 10 nm. Subsequently we focus on the dynamics of glass-forming glycerol confined within nanodroplets of different sizes. By combining neutron backscattering and time-of-flight for a broad dynamic range we obtain the incoherent intermediate scattering function S(q,t), which reveals increasingly accelerated dynamics as glycerol is confined to smaller droplets and for the relaxation times a crossover from Vogel-Fulcher behavior in the bulk to an Arrhenius law in confinement.

  20. 77 FR 38061 - Mobility Fund Phase I Auction Supplemental Short-Form Instructions and Other Information

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-26

    ... Notice, 77 FR 32092, May 31, 2012, the Bureaus provided general instructions for completing FCC Form 180... COMMISSION Mobility Fund Phase I Auction Supplemental Short-Form Instructions and Other Information AGENCY... provide other information regarding Auction 901. DATES: Short-Form applications are due prior to 6 p.m....

  1. Interfacial reaction using particle-immobilized reagents in a fluidized reactor. Determination of glycerol in biodiesel.

    PubMed

    Shishov, Andrey; Zabrodin, Andrey; Moskvin, Leonid; Andruch, Vasil; Bulatov, Andrey

    2016-03-31

    A novel fluidized beads strategy for utilization of particle-immobilized reagents in flow analysis was developed in this study. The performance of the suggested strategy was demonstrated by the determination of glycerol in biodiesel. This analytical task was used as a proof-of-concept example. The method is based on on-line extraction of glycerol from biodiesel into aqueous stationary phase of extraction-chromatographic column, followed by elution and spectrophotometric determination in the form of copper glycerate formed in a fluidized reactor of stepwise injection system. The floating of cation exchange resin Dowex(®) 50WX4, saturated with Cu(II) ions in liquid phase, was accomplished by air-bubbling. The linear range was from 100 to 1000 mg kg(-1), and the limit of detection, calculated as 3s of a blank test (n = 5), was found to be 30 mg kg(-1). The method was successfully applied to the analysis of biodiesel and biodiesel-blend (B 20) samples. PMID:26965329

  2. Ruminal fermentation of propylene glycol and glycerol.

    PubMed

    Trabue, Steven; Scoggin, Kenwood; Tjandrakusuma, Siska; Rasmussen, Mark A; Reilly, Peter J

    2007-08-22

    Bovine rumen fluid was fermented anaerobically with 25 mM R-propylene glycol, S-propylene glycol, or glycerol added. After 24 h, all of the propylene glycol enantiomers and approximately 80% of the glycerol were metabolized. Acetate, propionate, butyrate, valerate, and caproate concentrations, in decreasing order, all increased with incubation time. Addition of any of the three substrates somewhat decreased acetate formation, while addition of either propylene glycol increased propionate formation but decreased that of butyrate. R- and S-propylene glycol did not differ significantly in either their rates of disappearance or the products formed when they were added to the fermentation medium. Fermentations of rumen fluid containing propylene glycol emitted the sulfur-containing gases 1-propanethiol, 1-(methylthio)propane, methylthiirane, 2,4-dimethylthiophene, 1-(methylthio)-1-propanethiol, dipropyl disulfide, 1-(propylthio)-1-propanethiol, dipropyl trisulfide, 3,5-diethyl-1,2,4-trithiolane, 2-ethyl-1,3-dithiane, and 2,4,6-triethyl-1,3,5-trithiane. Metabolic pathways that yield each of these gases are proposed. The sulfur-containing gases produced during propylene glycol fermentation in the rumen may contribute to the toxic effects seen in cattle when high doses are administered for therapeutic purposes. PMID:17655323

  3. Secondary phases formed during nuclear waste glass-water interactions: Thermodynamic and derived properties

    SciTech Connect

    McKenzie, W.F.

    1992-08-01

    The thermodynamic properties of secondary phases observed to form during nuclear waste glass-water interactions are of particular interest as it is with the application of these properties together with the thermodynamic properties of other solid phases, fluid phases, and aqueous species that one may predict the environmental consequences of introducing radionuclides contained in the glass into groundwater at a high-level nuclear waste repository. The validation of these predicted consequences can be obtained from laboratory experiments and field observations at natural analogue sites. The purpose of this report is to update and expand the previous compilation (McKenzie, 1991) of thermodynamic data retrieved from the literature and/or estimated for secondary phases observed to form (and candidate phases from observed chemical compositions) during nuclear waste glass-water interactions. In addition, this report includes provisionally recommended thermodynamic data of secondary phases.

  4. Polyurethane foams based on crude glycerol-derived biopolyols: One-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties

    SciTech Connect

    Li, Cong; Luo, Xiaolan; Li, Tao; Tong, Xinjie; Li, Yebo

    2014-01-01

    Environmentally friendly biopolyols have been produced with crude glycerol as the sole feedstock using a one-pot thermochemical conversion process without the addition of extra catalysts and reagents. Structural features of these biopolyols were characterized by rheology analysis. Rigid polyurethane (PU) foams were obtained from these crude glycerol-based biopolyols and the foaming mechanism was explored. Investigations revealed that partial carbonyl groups hydrogen-bonded with NeH were replaced by aromatic rings after the introduction of branched fatty acid ester chains in the “urea rich” phase, and that distinct microphases had formed in the foams. Studies showed that branched fatty acid ester chains in the biopolyols played an important role in reducing the degree of microphase separation and stabilizing bubbles during foaming processes. PU foams with thermal conductivity comparable to commercial products made from petroleum-based polyols were obtained. These studies show the potential for development of PU foams based on crude glycerol, a renewable resource.

  5. Phase demodulation method from a single fringe pattern based on correlation with a polynomial form.

    PubMed

    Robin, Eric; Valle, Valéry; Brémand, Fabrice

    2005-12-01

    The method presented extracts the demodulated phase from only one fringe pattern. Locally, this method approaches the fringe pattern morphology with the help of a mathematical model. The degree of similarity between the mathematical model and the real fringe is estimated by minimizing a correlation function. To use an optimization process, we have chosen a polynomial form such as a mathematical model. However, the use of a polynomial form induces an identification procedure with the purpose of retrieving the demodulated phase. This method, polynomial modulated phase correlation, is tested on several examples. Its performance, in terms of speed and precision, is presented on very noised fringe patterns. PMID:16353793

  6. Phase demodulation method from a single fringe pattern based on correlation with a polynomial form

    SciTech Connect

    Robin, Eric; Valle, Valery; Bremand, Fabrice

    2005-12-01

    The method presented extracts the demodulated phase from only one fringe pattern. Locally, this method approaches the fringe pattern morphology with the help of a mathematical model. The degree of similarity between the mathematical model and the real fringe is estimated by minimizing a correlation function. To use an optimization process, we have chosen a polynomial form such as a mathematical model. However, the use of a polynomial form induces an identification procedure with the purpose of retrieving the demodulated phase. This method, polynomial modulated phase correlation, is tested on several examples. Its performance, in terms of speed and precision, is presented on very noised fringe patterns.

  7. Structural-phase states and wear resistance of surface formed on steel by surfacing

    SciTech Connect

    Kapralov, Evgenie V.; Raykov, Sergey V.; Vaschuk, Ekaterina S.; Budovskikh, Evgenie A. Gromov, Victor E.; Ivanov, Yuri F.

    2014-11-14

    Investigations of elementary and phase structure, state of defect structure and tribological characteristics of a surfacing, formed on a low carbon low-alloy steel by a welding method were carried out. It was revealed that a surfacing, formed on a steel surface is accompanied by the multilayer formation, and increases the wear resistance of the layer surfacing as determined.

  8. The role of energetic processing on solid-phase chemistry in star forming regions

    NASA Astrophysics Data System (ADS)

    Palumbo, M. E.; Urso, R. G.; Kaňuchová, Z.; Scirè, C.; Accolla, M.; Baratta, G. A.; Strazzulla, G.

    2016-05-01

    It is generally accepted that complex molecules observed in star forming regions are formed in the solid phase on icy grain mantles and are released to the gas-phase after desorption of icy mantles. Most of our knowledge on the physical and chemical properties of ices in star forming regions is based on the comparison between observations and laboratory experiments performed at low temperature (10-100 K). Here we present some recent laboratory experiments which show the formation of (complex) molecular species after ion bombardment of simple ices.

  9. Evolution of Secondary Phases Formed upon Solidification of a Ni-Based Alloy

    NASA Astrophysics Data System (ADS)

    Zuo, Qiang; Liu, Feng; Wang, Lei; Chen, Changfeng

    2013-07-01

    The solidification of UNS N08028 alloy subjected to different cooling rates was studied, where primary austenite dendrites occur predominantly and different amounts of sigma phase form in the interdendritic regions. The solidification path and elemental segregation upon solidification were simulated using the CALPHAD method, where THERMO-CALC software packages and two classical segregation models were employed to predict the real process. It is thus revealed that the interdendritic sigma phase is formed via eutectic reaction at the last stage of solidification. On this basis, an analytical model was developed to predict the evolution of nonequilibrium eutectic phase, while the isolated morphology of sigma phase can be described using divorced eutectic theory. Size, fraction, and morphology of the sigma phase were quantitatively studied by a series of experiments; the results are in good agreement with the model prediction.

  10. Selective glycerol oxidation by electrocatalytic dehydrogenation.

    PubMed

    Kim, Hyung Ju; Lee, Jechan; Green, Sara K; Huber, George W; Kim, Won Bae

    2014-04-01

    This study demonstrates that an electrochemical dehydrogenation process can be used to oxidize glycerol to glyceraldehyde and glyceric acid even without using stoichiometric chemical oxidants. A glyceric acid selectivity of 87.0 % at 91.8 % glycerol conversion was obtained in an electrocatalytic batch reactor. A continuous-flow electrocatalytic reactor had over an 80 % high glyceric acid selectivity at 10 % glycerol conversion, as well as greater reaction rates than either an electrocatalytic or a conventional catalytic batch reactor. PMID:24664518

  11. The role of micronutrients and strategies for optimized continual glycerol production from carbon dioxide by Dunaliella tertiolecta.

    PubMed

    Chow, Yvonne; Tu, Wang Yung; Wang, David; Ng, Daphne H P; Lee, Yuan Kun

    2015-10-01

    The microalga Dunaliella tertiolecta synthesizes intracellular glycerol as an osmoticum to counteract external osmotic pressure in high saline environments. The species has recently been found to release and accumulate extracellular glycerol, making it a suitable candidate for sustainable industrial glycerol production if a sufficiently high product titre yield can be achieved. While macronutrients such as nitrogen and phosphorus are essential and well understood, this study seeks to understand the influence of the micronutrient profile on glycerol production. The effects of metallic elements calcium, magnesium, manganese, zinc, cobalt, copper, and iron, as well as boron, on glycerol production as well as cell growth were quantified. The relationship between cell density and glycerol productivity was also determined. Statistically, manganese recorded the highest improvement in glycerol production as well as cell growth. Further experiments showed that manganese availability was associated with higher superoxide dismutase formation, thus suggesting that glycerol production is negatively affected by oxidative stress and the manganese bound form of this enzyme is required in order to counteract reactive oxygen species in the cells. A minimum concentration of 8.25 × 10(-5)  g L(-1) manganese was sufficient to overcome this problem and achieve 10 g L(-1) extracellular glycerol, compared to 4 g L(-1) without the addition of manganese. Unlike cell growth, extracellular glycerol production was found to be negatively affected by the amount of calcium present in the normal growth medium, most likely due to the lower cell permeability at high calcium concentrations. The inhibitory effects of iron also affected extracellular glycerol production more significantly than cell growth and several antagonistic interaction effects between various micronutrients were observed. This study indicates how the optimization of these small amounts of nutrients in a two

  12. Glycerol-3-phosphatase of Corynebacterium glutamicum.

    PubMed

    Lindner, Steffen N; Meiswinkel, Tobias M; Panhorst, Maren; Youn, Jung-Won; Wiefel, Lars; Wendisch, Volker F

    2012-06-15

    Formation of glycerol as by-product of amino acid production by Corynebacterium glutamicum has been observed under certain conditions, but the enzyme(s) involved in its synthesis from glycerol-3-phosphate were not known. It was shown here that cg1700 encodes an enzyme active as a glycerol-3-phosphatase (GPP) hydrolyzing glycerol-3-phosphate to inorganic phosphate and glycerol. GPP was found to be active as a homodimer. The enzyme preferred conditions of neutral pH and requires Mg²⁺ or Mn²⁺ for its activity. GPP dephosphorylated both L- and D-glycerol-3-phosphate with a preference for the D-enantiomer. The maximal activity of GPP was estimated to be 31.1 and 1.7 U mg⁻¹ with K(M) values of 3.8 and 2.9 mM for DL- and L-glycerol-3-phosphate, respectively. For physiological analysis a gpp deletion mutant was constructed and shown to lack the ability to produce detectable glycerol concentrations. Vice versa, gpp overexpression increased glycerol accumulation during growth in fructose minimal medium. It has been demonstrated previously that intracellular accumulation of glycerol-3-phosphate is growth inhibitory as shown for a recombinant C. glutamicum strain overproducing glycerokinase and glycerol facilitator genes from E. coli in media containing glycerol. In this strain, overexpression of gpp restored growth in the presence of glycerol as intracellular glycerol-3-phosphate concentrations were reduced to wild-type levels. In C. glutamicum wild type, GPP was shown to be involved in utilization of DL-glycerol-3-phosphate as source of phosphorus, since growth with DL-glycerol-3-phosphate as sole phosphorus source was reduced in the gpp deletion strain whereas it was accelerated upon gpp overexpression. As GPP homologues were found to be encoded in the genomes of many other bacteria, the gpp homologues of Escherichia coli (b2293) and Bacillus subtilis (BSU09240, BSU34970) as well as gpp1 from the plant Arabidosis thaliana were overexpressed in E. coli MG1655 and

  13. Glycerol inhibition of ruminal lipolysis in vitro.

    PubMed

    Edwards, H D; Anderson, R C; Miller, R K; Taylor, T M; Hardin, M D; Smith, S B; Krueger, N A; Nisbet, D J

    2012-09-01

    Supplemental glycerol inhibits rumen lipolysis, a prerequisite for rumen biohydrogenation, which is responsible for the saturation of dietary fatty acids consumed by ruminant animals. Feeding excess glycerol, however, adversely affects dry matter digestibility. To more clearly define the effect of supplemental glycerol on rumen lipolysis, mixed populations of ruminal bacteria were incubated with 6 or 20% glycerol (vol/vol). After 48-h anaerobic incubation of mixed culture rumen fluid, rates of free fatty acid production (nmol/mL per h) for the 6 and 20% glycerol-supplemented samples were decreased by 80 and 86%, respectively, compared with rates from nonsupplemented control cultures (12.4±1.0; mean ± SE). Conversely, assay of the prominent ruminal lipase-producing bacteria Anaerovibrio lipolyticus 5S, Butyrivibrio fibrisolvens 49, and Propionibacterium species avidum and acnes revealed no effect of 2 or 10% (vol/vol) added glycerol on lipolytic activity by these organisms. Supplementing glycerol at 6% on a vol/vol basis, equivalent to supplementing glycerol at approximately 8 to 15% of diet dry matter, effectively reduced lipolysis. However, the mechanism of glycerol inhibition of ruminal lipolysis remains to be demonstrated. PMID:22916923

  14. Forming and steering of symmetrical multiple laser beams in optical phased array

    NASA Astrophysics Data System (ADS)

    Liu, Xiang; Zhang, Jian; Wu, Liying; Gan, Yu; Wang, Dong; Ge, Jiajia

    2010-04-01

    Multi-beam technology is one of the key technologies in optical phased array systems for multi-object treatment and multi-task operation. A multi-beam forming and steering method was proposed. This method uses isosceles triangle multilevel phase grating (ITMPG) to form multiple beams simultaneously. Phase profile of the grating is a quantized isosceles triangle with stairs. By changing the phase difference corresponding to the triangle height, multiple beams can be steered symmetrically. It took 34 ms to calculate a set of parameters for one ITMPG, namely one steering. A liquid crystal spatial light modulator was used for the experiment, which formed 6 gratings. The distortion of which had been compensated with the accuracy of 0.0408 λ. Each grating included 16 phase elements with the same period. Steering angle corresponded to the triangle height, which is the phase difference. Relative diffraction efficiency for multiple beams was greater than 81%, intensity nonuniformity was less than 0.134, and the deflection resolution was 2.263 mrad. Experimental results demonstrate that the proposed method can be used to form and steer symmetrical multiple beams simultaneously with the same intensity and high diffraction efficiency in the far field, the deflection resolution is related to the reciprocal of grating period.

  15. Calibrating the glycerol dialkyl glycerol tetraether temperature signal in speleothems

    NASA Astrophysics Data System (ADS)

    Blyth, Alison J.; Schouten, Stefan

    2013-05-01

    Palaeotemperature proxies based on glycerol dialkyl glycerol tetraethers (GDGTs) lipids have been established for marine and lacustrine environments, but there has been relatively little study of their application in speleothems. In this study we analyse the GDGT content of 33 speleothem samples from 16 different sites around the globe, and test whether proxies based on isoprenoid tetraethers (TEX86) or branched tetraethers (MBT/CBT) are correlated with measured surface and cave mean annual air temperature (MAT). The results show that the TEX86 has a strong relationship with measured temperature (r2 = 0.78, standard error of the estimate 2.3 °C, when calibrated with surface MAT). Furthermore, the MBT/CBT also showed a significant relationship with temperature (r2 = 0.73, standard error of the estimate 2.7 °C, when calibrated with surface MAT). Some issues remain requiring future work, in particular the development of a larger calibration sample set with measured cave temperature data, and the investigation of controls other than temperature on GDGT distribution, but overall the results indicate that GDGT based proxies derived from speleothems may be highly viable new methods for reconstructing continental palaeotemperatures.

  16. Striped Phase of 3-Hexylthiophene Self-Assembled Monolayers on Au(1 11) Formed by Vapor Phase Deposition.

    PubMed

    Kim, Youngwoo; Kang, Hungu; Tsunoi, Azuho; Hayashi, Tomohiro; Hara, Masahiko; Noh, Jaegeun

    2016-03-01

    The formation and surface structure of 3-hexylthiophene (HTP) self-assembled monolayers (SAMs) on Au(111) prepared by solution and ambient-pressure vapor deposition at room temperature (RT) for 24 h were examined by means of scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging revealed that HTP SAMs formed by solution deposition have a disordered phase, whereas those formed by vapor deposition exhibit a striped phase with a unidirectional orientation. The distance between the rows in the striped phase was measured to be 1.3 ± 0.1 nm, and the hexyl molecular backbones of HTP in the SAMs on Au(111) are oriented parallel to the Au(111) surface with the head-to-head orientation. From this STM observation, we suggest that the formation of this striped phase in HTP SAMs prepared by vapor deposition were mainly driven by the optimization of van der Waals interactions between the hexyl chains on the surface. CV measurements also demonstrated that HTP SAMs show a high blocking efficiency for electron transfer reactions between electrolytes and the gold electrode, suggesting the formation of SAMs on Au(111) from the vapor phase. Our results obtained here will be very useful for understanding the formation and structure of HTP SAMs on Au(111) surfaces and how they are influenced by deposition method. PMID:27455710

  17. Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof

    PubMed Central

    Shao, Hua

    2010-01-01

    The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by 29Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m2/g) and zeolite end members (8.9 - 40 m2/g), as well as their unique mixed phase composites (124 - 329 m2/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils. PMID:21709774

  18. Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

    PubMed

    Shao, Hua; Pinnavaia, Thomas J

    2010-09-01

    The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils. PMID:21709774

  19. Final waste forms project: Performance criteria for phase I treatability studies

    SciTech Connect

    Gilliam, T.M.; Hutchins, D.A.; Chodak, P. III

    1994-06-01

    This document defines the product performance criteria to be used in Phase I of the Final Waste Forms Project. In Phase I, treatability studies will be performed to provide {open_quotes}proof-of-principle{close_quotes} data to establish the viability of stabilization/solidification (S/S) technologies. This information is required by March 1995. In Phase II, further treatability studies, some at the pilot scale, will be performed to provide sufficient data to allow treatment alternatives identified in Phase I to be more fully developed and evaluated, as well as to reduce performance uncertainties for those methods chosen to treat a specific waste. Three main factors influence the development and selection of an optimum waste form formulation and hence affect selection of performance criteria. These factors are regulatory, process-specific, and site-specific waste form standards or requirements. Clearly, the optimum waste form formulation will require consideration of performance criteria constraints from each of the three categories. Phase I will focus only on the regulatory criteria. These criteria may be considered the minimum criteria for an acceptable waste form. In other words, a S/S technology is considered viable only if it meet applicable regulatory criteria. The criteria to be utilized in the Phase I treatability studies were primarily taken from Environmental Protection Agency regulations addressed in 40 CFR 260 through 265 and 268; and Nuclear Regulatory Commission regulations addressed in 10 CFR 61. Thus the majority of the identified criteria are independent of waste form matrix composition (i.e., applicable to cement, glass, organic binders etc.).

  20. Phase Behavior of Different Forms of Ice Filled with Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

    Hakim, Lukman; Koga, Kenichiro; Tanaka, Hideki

    2010-03-01

    A hybrid grand-canonical Monte Carlo simulation has been performed to investigate the hydrogen hydrate compounds in which hydrogen molecules are stored in ice II and ice Ic. A simple theoretical model, which can reproduce the simulation results, provides the phase diagrams of the two-component system in the pressure-composition plane. Stability enhancement of the two ice forms by hydrogen is quantified by the chemical potential calculation of water. The phase transitions among various phases including the two hydrogen hydrates are predicted as functions of pressure, hydrogen occupancy, and temperature.

  1. Phase behavior of different forms of ice filled with hydrogen molecules.

    PubMed

    Hakim, Lukman; Koga, Kenichiro; Tanaka, Hideki

    2010-03-19

    A hybrid grand-canonical Monte Carlo simulation has been performed to investigate the hydrogen hydrate compounds in which hydrogen molecules are stored in ice II and ice I{c}. A simple theoretical model, which can reproduce the simulation results, provides the phase diagrams of the two-component system in the pressure-composition plane. Stability enhancement of the two ice forms by hydrogen is quantified by the chemical potential calculation of water. The phase transitions among various phases including the two hydrogen hydrates are predicted as functions of pressure, hydrogen occupancy, and temperature. PMID:20366485

  2. Aqueous Two-Phase Systems formed by Biocompatible and Biodegradable Polysaccharides and Acetonitrile

    PubMed Central

    de Brito Cardoso, Gustavo; Souza, Isabela Nascimento; Pereira, Matheus M.; Freire, Mara G.; Soares, Cleide Mara Faria; Lima, Álvaro Silva

    2015-01-01

    In this work, it is shown that novel aqueous two-phase systems can be formed by the combination of acetonitrile and polysaccharides, namely dextran. Several ternary phase diagrams were determined at 25 °C for the systems composed of water + acetonitrile + dextran. The effect of the dextran molecular weight (6,000, 40,000 and 100,000 g.mol−1) was ascertained toward their ability to undergo liquid-liquid demixing. An increase in the dextran molecular weight favors the phase separation. Furthermore, the effect of temperature (25, 35 and 45 °C) was evaluated for the system constituted by the dextran of higher molecular weight. Lower temperatures are favorable for phase separation since lower amounts of dextran and acetonitrile are required for the creation of aqueous two-phase systems. In general, acetonitrile is enriched in the top phase while dextran is majorly concentrated in the bottom phase. The applicability of this new type of two-phase systems as liquid-liquid extraction approaches was also evaluated by the study of the partition behavior of a well-known antioxidant – vanillin - and used here as a model biomolecule. The optimized conditions led to an extraction efficiency of vanillin of 95% at the acetonitrile-rich phase. PMID:25729320

  3. Pseudocapacitive Properties of Two-Dimensional Surface Vanadia Phases Formed Spontaneously on Titania.

    PubMed

    Samiee, Mojtaba; Luo, Jian

    2016-05-25

    Pseudocapacitive properties of V2O5-based adsorbates supported on TiO2 nanoparticles, which form spontaneously as two-dimensional (2-D) nonautonomous surface phases (complexions) at thermodynamic equilibria, have been systematically measured. Surprisingly, surface amorphous films (SAFs), which form naturally at thermodynamic equilibria at 550-600 °C with self-regulating or "equilibrium" thicknesses on the order of 1 nm, exhibit superior electrochemical performance at moderate and high scan rates (20-500 mV/s) that are of prime importance for supercapacitor applications, as compared with submonolayer and monolayer adsorbates formed at lower equilibration temperatures. This study suggests a new direction to design and fabricate a novel class of supercapacitors and other functional devices via utilizing 2-D interfacial phases that can form spontaneously via facile, cost-effective, and highly scalable synthesis routes. PMID:27144457

  4. RUMINAL FERMENTATION OF PROPYLENE GLYCOL AND GLYCEROL

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bovine rumen fluid was fermented anaerobically with 25 mM R-propylene glycol, S-propylene glycol, or glycerol added. After 24 h all of the propylene glycol enantiomers and approximately 80% of the glycerol were metabolized. Acetate, propionate, butyrate, valerate, and caproate concentrations, in dec...

  5. Formulation and Applications of Glycerol Polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Increased production of biodiesel in the U.S. and Europe during the past several years has created an oversupply of glycerol, creating lower domestic profitability. In addition, increased petroleum prices have driven up the cost of synthetic polymers made from petrochemicals. Glycerol can be polym...

  6. Thermal and physical characterization of glycerol polyesters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glycerol polyesters were prepared by the condensation of glycerol and adipic acid, azelaic acid, sebacic acid, or suberic acids. After 48 hours at 125 deg C the polymers were clear and flexible. Samples of the reaction mixtures were analyzed by modulated differential scanning calorimetry to identi...

  7. Correlation spectroscopy applied to glycerol polyester spectra

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The recent development of glycerol polyesters for use as controlled release matrix materials in the nutraceuticals and pharmaceuticals industries presented a unique opportunity to apply correlation spectroscopy. In a typical formulation the glycerol is reacted with a polyfunctional acid such as citr...

  8. From ether to acid: A plausible degradation pathway of glycerol dialkyl glycerol tetraethers

    NASA Astrophysics Data System (ADS)

    Liu, Xiao-Lei; Birgel, Daniel; Elling, Felix J.; Sutton, Paul A.; Lipp, Julius S.; Zhu, Rong; Zhang, Chuanlun; Könneke, Martin; Peckmann, Jörn; Rowland, Steven J.; Summons, Roger E.; Hinrichs, Kai-Uwe

    2016-06-01

    Glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous microbial lipids with extensive demonstrated and potential roles as paleoenvironmental proxies. Despite the great attention they receive, comparatively little is known regarding their diagenetic fate. Putative degradation products of GDGTs, identified as hydroxyl and carboxyl derivatives, were detected in lipid extracts of marine sediment, seep carbonate, hot spring sediment and cells of the marine thaumarchaeon Nitrosopumilus maritimus. The distribution of GDGT degradation products in environmental samples suggests that both biotic and abiotic processes act as sinks for GDGTs. More than a hundred newly recognized degradation products afford a view of the stepwise degradation of GDGT via (1) ether bond hydrolysis yielding hydroxyl isoprenoids, namely, GDGTol (glycerol dialkyl glycerol triether alcohol), GMGD (glycerol monobiphytanyl glycerol diether), GDD (glycerol dibiphytanol diether), GMM (glycerol monobiphytanol monoether) and bpdiol (biphytanic diol); (2) oxidation of isoprenoidal alcohols into corresponding carboxyl derivatives and (3) chain shortening to yield C39 and smaller isoprenoids. This plausible GDGT degradation pathway from glycerol ethers to isoprenoidal fatty acids provides the link to commonly detected head-to-head linked long chain isoprenoidal hydrocarbons in petroleum and sediment samples. The problematic C80 to C82 tetraacids that cause naphthenate deposits in some oil production facilities can be generated from H-shaped glycerol monoalkyl glycerol tetraethers (GMGTs) following the same process, as indicated by the distribution of related derivatives in hydrothermally influenced sediments.

  9. Process for forming a homogeneous oxide solid phase of catalytically active material

    DOEpatents

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  10. Stability of intermediate phases forming on interaction of silicon and germanium with phosphorus and arsenic

    SciTech Connect

    Ugai, Ya.A.; Goncharov, E.G.; Sokolov, L.I.; Pshestanchik, V.R.

    1987-12-01

    By comparing the comparative stability of the intermediate phases in the systems Si(Ge)-P(As) we showed that for the compounds formed by adjacent components in the periodic system the determining factors in the interaction are the electronic configuration and the relative difference of the covalent radii.

  11. Looking for phase-space structures in star-forming regions: an MST-based methodology

    NASA Astrophysics Data System (ADS)

    Alfaro, Emilio J.; González, Marta

    2016-03-01

    We present a method for analysing the phase space of star-forming regions. In particular we are searching for clumpy structures in the 3D sub-space formed by two position coordinates and radial velocity. The aim of the method is the detection of kinematic segregated radial velocity groups, that is, radial velocity intervals whose associated stars are spatially concentrated. To this end we define a kinematic segregation index, tilde{Λ }(RV), based on the Minimum Spanning Tree graph algorithm, which is estimated for a set of radial velocity intervals in the region. When tilde{Λ }(RV) is significantly greater than 1 we consider that this bin represents a grouping in the phase space. We split a star-forming region into radial velocity bins and calculate the kinematic segregation index for each bin, and then we obtain the spectrum of kinematic groupings, which enables a quick visualization of the kinematic behaviour of the region under study. We carried out numerical models of different configurations in the sub-space of the phase space formed by the coordinates and the that various case studies illustrate. The analysis of the test cases demonstrates the potential of the new methodology for detecting different kind of groupings in phase space.

  12. Metabolic Engineering of a Glycerol-Oxidative Pathway in Lactobacillus panis PM1 for Utilization of Bioethanol Thin Stillage: Potential To Produce Platform Chemicals from Glycerol

    PubMed Central

    Kang, Tae Sun; Korber, Darren R.

    2014-01-01

    Lactobacillus panis PM1 has the ability to produce 1,3-propanediol (1,3-PDO) from thin stillage (TS), which is the major waste material after bioethanol production, and is therefore of significance. However, the fact that L. panis PM1 cannot use glycerol as a sole carbon source presents a considerable problem in terms of utilization of this strain in a wide range of industrial applications. Accordingly, L. panis PM1 was genetically engineered to directly utilize TS as a fermentable substrate for the production of valuable platform chemicals without the need for exogenous nutrient supplementation (e.g., sugars and nitrogen sources). An artificial glycerol-oxidative pathway, comprised of glycerol facilitator, glycerol kinase, glycerol 3-phosphate dehydrogenase, triosephosphate isomerase, and NADPH-dependent aldehyde reductase genes of Escherichia coli, was introduced into L. panis PM1 in order to directly utilize glycerol for the production of energy for growth and value-added chemicals. A pH 6.5 culture converted glycerol to mainly lactic acid (85.43 mM), whereas a significant amount of 1,3-propanediol (59.96 mM) was formed at pH 7.5. Regardless of the pH, ethanol (82.16 to 83.22 mM) was produced from TS fermentations, confirming that the artificial pathway metabolized glycerol for energy production and converted it into lactic acid or 1,3-PDO and ethanol in a pH-dependent manner. This study demonstrates the cost-effective conversion of TS to value-added chemicals by the engineered PM1 strain cultured under industrial conditions. Thus, application of this strain or these research findings can contribute to reduced costs of bioethanol production. PMID:25281374

  13. Metabolic engineering of a glycerol-oxidative pathway in Lactobacillus panis PM1 for utilization of bioethanol thin stillage: potential to produce platform chemicals from glycerol.

    PubMed

    Kang, Tae Sun; Korber, Darren R; Tanaka, Takuji

    2014-12-01

    Lactobacillus panis PM1 has the ability to produce 1,3-propanediol (1,3-PDO) from thin stillage (TS), which is the major waste material after bioethanol production, and is therefore of significance. However, the fact that L. panis PM1 cannot use glycerol as a sole carbon source presents a considerable problem in terms of utilization of this strain in a wide range of industrial applications. Accordingly, L. panis PM1 was genetically engineered to directly utilize TS as a fermentable substrate for the production of valuable platform chemicals without the need for exogenous nutrient supplementation (e.g., sugars and nitrogen sources). An artificial glycerol-oxidative pathway, comprised of glycerol facilitator, glycerol kinase, glycerol 3-phosphate dehydrogenase, triosephosphate isomerase, and NADPH-dependent aldehyde reductase genes of Escherichia coli, was introduced into L. panis PM1 in order to directly utilize glycerol for the production of energy for growth and value-added chemicals. A pH 6.5 culture converted glycerol to mainly lactic acid (85.43 mM), whereas a significant amount of 1,3-propanediol (59.96 mM) was formed at pH 7.5. Regardless of the pH, ethanol (82.16 to 83.22 mM) was produced from TS fermentations, confirming that the artificial pathway metabolized glycerol for energy production and converted it into lactic acid or 1,3-PDO and ethanol in a pH-dependent manner. This study demonstrates the cost-effective conversion of TS to value-added chemicals by the engineered PM1 strain cultured under industrial conditions. Thus, application of this strain or these research findings can contribute to reduced costs of bioethanol production. PMID:25281374

  14. Rich Phase Behavior of Sphere-Forming Asymmetric ABA'C Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Chanpuriya, Sid; Arora, Akash; Kim, Kyungtae; Dorfman, Kevin; Bates, Frank

    Motivated by self-consistent field theory simulations, the effect of ABA' corona block length asymmetry on the phase behavior of ABA'C-type tetrablock terpolymers has been examined. The chosen model system, poly(styrene)- b-poly(isoprene)- b-poly(styrene)- b-poly(ethylene oxide) (SIS'O), has been characterized using a combination of small-angle X-ray scattering, transmission electron microscopy, and dynamic mechanical spectroscopy. Asymmetric SIS'O tetrablocks reveal a rich variety of sphere-forming phases over compositions and molecular weights where symmetric SISO polymers formed only hexagonally oriented cylinders. These include FCC, HCP, and complex symmetries such as the Frank-Kasper σ and A15 phases. NSF Award 1333669.

  15. Influence of heat shock on glycerol production in alcohol fermentation.

    PubMed

    Berovic, Marin; Pivec, Aleksandra; Kosmerl, Tatjana; Wondra, Mojmir; Celan, Stefan

    2007-02-01

    The influence of single and double heat shocks induced during the exponential growth phase of the Saccharomyces cerevisiae fermentation of cultivar Sauvignon Blanc grape must was examined. Rapid temperature changes from 18 degrees C to 34 degrees C have been applied. The effect of the duration of exposure to a high temperature has been analyzed. By the applications of a single heat shock and a double heat shock, up to 8.2 g l(-1) and 11.0 g l(-1) glycerol have been produced, respectively. To prevent the evaporation of fine wine bouquet compounds during the temperature changes, reflux coolers on the top of bioreactors have been employed. By using this method, glycerol production was increased by up to 65%. PMID:17368395

  16. Constituent phases of the passive film formed on 2205 stainless steel by dynamic electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Cheng, Xue-Qun; Li, Cheng-Tao; Dong, Chao-Fang; Li, Xiao-Gang

    2011-02-01

    The passive film formed on 2205 duplex stainless steel (DSS) in 0.5 M NaHCO3+0.5 M NaCl aqueous solution was characterized by electrochemical measurements, including potentiodynamic anodic polarization and dynamic electrochemical impedance spectroscopy (DEIS). The results demonstrate that there is a great difference between the passive film evolutions of ferrite and austenite. The impedance values of ferrite are higher than those of austenite. The impedance peaks of ferritic and austenitic phases correspond to the potential of 0.15 and 0.25 V in the low potential range and correspond to 0.8 and 0.75 V in the high potential range. The evolutions of the capacitance of both phases are reverse compared to the evolutions of impedance. The thickness variations obtained from capacitance agree well with those of impedance analysis. The results can be used to explain why pitting corrosion occurs more easily in austenite phase than in ferrite phase.

  17. Aqueous polymer two-phase systems formed by new thermoseparating polymers.

    PubMed

    Persson, J; Johansson, H O; Galaev, I; Mattiasson, B; Tjerneld, F

    2000-01-01

    A set of new polymers that can be used as phase forming components in aqueous two-phase systems is presented. All polymers studied have thermoseparating properties i.e. form one separate polymer enriched phase and one aqueous solution when heated above the critical temperature. This property makes the polymers attractive alternatives to the polymers used in traditional aqueous two-phase systems such as poly(ethylene glycol) (PEG) and dextran. The thermal phase separation simplifies recycling of the polymers, thus making the aqueous two-phase systems more cost efficient and suitable for use in large scale. Thermoseparating polymers studied have been copolymers of ethylene oxide and propylene oxide (EO-PO), poly (N-isopropylacrylamide) (poly-NIPAM), poly vinyl caprolactam (poly-VCL) and copolymers of N-isopropylacrylamide and vinyl caprolactam with vinyl imidazole (poly(NIPAM-VI) and poly(VCL-VI), respectively). In addition, the copolymer poly(NIPAM-VI) has the property to be uncharged at pH above 7.0 and positively charged at lower pH. This allows the partitioning of protein to be directed by changing the pH in the system instead of the traditional addition of salt to direct the partitioning. Hydrophobically modified EO-PO copolymer (HM-(EO-PO)) with alkyl groups (C14) at both ends forms two-phase system with for example poly(NIPAM-VI). The phase diagram for poly(NIPAM-VI)/HM-(EO-PO) was determined and the model proteins lysozyme and BSA were partitioned in this system. For BSA in poly(NIPAM-VI)/HM-(EO-PO) system a change in pH from 8.0 to 5.4 results in a change of partition coefficient from K = 0.8 to K = 5.1, i.e. BSA could be transferred from the HM-(EO-PO) phase to the poly(NIPAM-VI) phase. BSA partitioning in poly(NIPAM-VI)/HM-(EO-PO) system allows quantitative BSA recovery, and recoveries of poly(NIPAM-VI) and HM-(EO-PO) were 53% and 92%, respectively, after the thermoseparation step. PMID:10892544

  18. Epitaxy, phase separation and band-edge emission of spontaneously formed InGaN nanorods

    NASA Astrophysics Data System (ADS)

    De, Arpan; Shivaprasad, S. M.

    2016-09-01

    An In-flux dependent study of the nature of epitaxy, compositional phase separation and band-edge emission of spontaneously formed c-oriented InGaN nanorods on c-sapphire is performed. At higher In flux-rates, m-faceted thick nanorods (≈700 nm) form with two in-plane epitaxial orientations, and display compositional phases with In composition varying from 14 to 63%. In these rods, photo-luminescent (PL) emission is seen to originate only from the localized high-In phase (63%) that is embedded in the low-In (14%) InGaN matrix. As the In flux-rate is reduced, nanorods of smaller diameter (≈60 nm) and a coalesced nanorod network are formed, with In incorporation of 15% and 9%, respectively. These faceted, c-aligned thinner nanorods are of a single compositional phase and epitaxy and display room-temperature PL emission. Optical absorption and emission properties of these nanostructures follow Vegard’s law of band-gaps, and the observed bowing parameter and Stokes shifts correlate to the observed compositional inhomogeneity and carrier localization.

  19. Hermite-Gaussian beams with self-forming spiral phase distribution

    NASA Astrophysics Data System (ADS)

    Zinchik, Alexander A.; Muzychenko, Yana B.

    2014-05-01

    Spiral laser beams is a family of laser beams that preserve the structural stability up to scale and rotate with the propagation. Properties of spiral beams are of practical interest for laser technology, medicine and biotechnology. Researchers use a spiral beams for movement and manipulation of microparticles. Spiral beams have a complicated phase distribution in cross section. This paper describes the results of analytical and computer simulation of Hermite-Gaussian beams with self-forming spiral phase distribution. In the simulation used a laser beam consisting of the sum of the two modes HG TEMnm and TEMn1m1. The coefficients n1, n, m1, m were varied. Additional phase depending from the coefficients n, m, m1, n1 imposed on the resulting beam. As a result, formed the Hermite Gaussian beam phase distribution which takes the form of a spiral in the process of distribution. For modeling was used VirtualLab 5.0 (manufacturer LightTrans GmbH).

  20. pn-homojunction organic solar cells formed in phase-separated co-deposited films

    NASA Astrophysics Data System (ADS)

    Kubo, Masayuki; Kaji, Toshihiko; Hiramoto, Masahiro

    2013-12-01

    Simultaneous control of the doping and phase-separation in organic co-deposited films consisting of metal-free phthalocyanine and fullerene was performed. The doping was used to form pn-homojunctions in the phase-separated co-deposited films. The diffusion length of the minority carriers reached 0.3 μm allowing the fabrication of very thick cells up to 0.5 μm thick. It was shown that suppression of the interfacial recombination processes is crucial for obtaining cells with high performance.

  1. Insect glycerol transporters evolved by functional co-option and gene replacement

    PubMed Central

    Finn, Roderick Nigel; Chauvigné, François; Stavang, Jon Anders; Belles, Xavier; Cerdà, Joan

    2015-01-01

    Transmembrane glycerol transport is typically facilitated by aquaglyceroporins in Prokaryota and Eukaryota. In holometabolan insects however, aquaglyceroporins are absent, yet several species possess polyol permeable aquaporins. It thus remains unknown how glycerol transport evolved in the Holometabola. By combining phylogenetic and functional studies, here we show that a more efficient form of glycerol transporter related to the water-selective channel AQP4 specifically evolved and multiplied in the insect lineage, resulting in the replacement of the ancestral branch of aquaglyceroporins in holometabolan insects. To recapitulate this evolutionary process, we generate specific mutants in distantly related insect aquaporins and human AQP4 and show that a single mutation in the selectivity filter converted a water-selective channel into a glycerol transporter at the root of the crown clade of hexapod insects. Integration of phanerozoic climate models suggests that these events were associated with the emergence of complete metamorphosis and the unparalleled radiation of insects. PMID:26183829

  2. Insect glycerol transporters evolved by functional co-option and gene replacement.

    PubMed

    Finn, Roderick Nigel; Chauvigné, François; Stavang, Jon Anders; Belles, Xavier; Cerdà, Joan

    2015-01-01

    Transmembrane glycerol transport is typically facilitated by aquaglyceroporins in Prokaryota and Eukaryota. In holometabolan insects however, aquaglyceroporins are absent, yet several species possess polyol permeable aquaporins. It thus remains unknown how glycerol transport evolved in the Holometabola. By combining phylogenetic and functional studies, here we show that a more efficient form of glycerol transporter related to the water-selective channel AQP4 specifically evolved and multiplied in the insect lineage, resulting in the replacement of the ancestral branch of aquaglyceroporins in holometabolan insects. To recapitulate this evolutionary process, we generate specific mutants in distantly related insect aquaporins and human AQP4 and show that a single mutation in the selectivity filter converted a water-selective channel into a glycerol transporter at the root of the crown clade of hexapod insects. Integration of phanerozoic climate models suggests that these events were associated with the emergence of complete metamorphosis and the unparalleled radiation of insects. PMID:26183829

  3. Cyanamide mediated synthesis under plausible primitive earth conditions. VI - The synthesis of glycerol and glycerophosphates

    NASA Technical Reports Server (NTRS)

    Epps, D. E.; Nooner, D. W.; Eichberg, J.; Sherwood, E.; Oro, J.

    1979-01-01

    The formation of glycerol occurs when a solution of DL-glyceraldehyde is heated in the presence of hydrogen sulfide at room temperature. DL-glyceraldehyde and dihydroxyacetone treated with hydrazine, as well as DL-glyceraldehyde incubated with formaldehyde are also partially converted to glycerol. The yields of the above reactions are from approximately 1% to about 3%. The formation of glycerophosphates occurs when glycerol is heated with ammonium dihydrogen phosphate and either urea or cyanamide. The yield of glycerophosphates is about 30%, most of which is sn-glycero-1(3)-phosphate. These findings indicate that glycerol and sn-glycero-3-phosphate, which are moieties of glycerolipids, could have been formed under conditions which may have prevailed on the primitive earth.

  4. Zeolitic Core@Shell Adsorbents for the Selective Removal of Free Glycerol from Crude Biodiesel.

    PubMed

    Masoumifard, Nima; Arnal, Pablo M; Kaliaguine, Serge; Kleitz, Freddy

    2015-06-22

    Selective adsorption of free glycerol from crude biodiesel was investigated by using mesoporous silica spheres coated with a thin shell of microporous silicalite-1. A polycrystalline silicalite-1 shell was formed upon first covering the external surfaces of various core templates with discrete silicalite-1 nanocrystals, and this was followed by short hydrothermal treatment to ensure shell uniformity. Batch glycerol adsorption experiments were conducted to evaluate the ability of the sorbents to remove free glycerol selectively from crude biodiesel mixtures at various temperatures, also in comparison to that of conventional sorbents, for example, bare mesoporous silica gel spheres and zeolites. The silicalite-1 shell provided a microporous membrane that hindered the diffusion of fatty acid methyl esters into the mesopores of the composite sorbent, whereas the large pore volume of the mesoporous core enabled multilayer glycerol adsorption; this ultimately substantially enhanced the performance in terms of purification yield and adsorption capacity. PMID:26059701

  5. Characterization of the ordered phase formed by sphingomyelin analogues and cholesterol binary mixtures

    PubMed Central

    Kinoshita, Masanao; Goretta, Sarah; Tsuchikawa, Hiroshi; Matsumori, Nobuaki; Murata, Michio

    2013-01-01

    The influences of structural alterations of sphingomyelin (SM) on its interactions with cholesterol (chol) and on ordered phase formation were examined by density measurements and surface pressure vs. molecular area isotherm measurements. In addition, we quantitatively characterized the ordered phase formed in each SM and chol binary mixture on the basis of the molecular compressional modulus of SM ( Cmol−1). Density measurements demonstrated that the ordered phase formation in threo-SM (tSM)/chol and dihydrosphingomyelin (DHSM)/chol binary bilayers shows similar chol concentration-dependency to that of natural erythro-SM (eSM)/chol bilayers; the ordered phase formation was completed in the presence of 25 mol% chol. In contrast, SM bearing a triple bond in the place of a double bond (tripleSM) required a greater concentration of chol to completely transform the bilayer into the ordered phase (at 40 mol% chol). Surface pressure vs. molecular area isotherms showed that the DHSM molecule ( Cmol−1 = 290 mN/m) is more rigid than eSM ( Cmol−1 = 240 mN/m) above 30 mol% chol (in the ordered phase), although these values are similar (140–150 mN/m) in the absence of chol (liquid condensed phase). Most likely, the DHSM/chol mixture forms a more ordered membrane than the eSM/chol mixture does. Moreover, in the absence of chol, the rigidity of the tripleSM molecule ( Cmol−1 = 250 mN/m) is significantly higher as compared with that of the eSM molecule ( Cmol−1 = 150 mN/m), which is probably due to the presence of a triple bond. PMID:27493539

  6. The role of chemisorbed hydroxyl species in alkaline electrocatalysis of glycerol on gold.

    PubMed

    Shi, X; Simpson, D E; Roy, D

    2015-05-01

    The mechanism of energy conversion in a direct glycerol fuel cell (DGFC) is governed by the anode supported heterogeneous steps of glycerol electro-oxidation. In aerated alkaline electrolytes, glycerol also participates in a base catalyzed process, which can release certain species mixing with the anode catalyzed surface products. As a result, selective probing of the surface catalytic reactions involving such systems can be difficult. The present work addresses this issue for a gold anode by using the analytical capability of cyclic voltammetry (CV). In addition, surface plasmon resonance measurements are used to optically probe the adsorption characteristics of the electrolyte species. The net exchange current of the oxidation process and the transfer coefficient of the rate determining step are evaluated by analyzing the CV data. The interfacial reactions and their products on Au are identified by measuring the number of electrons released during the electro-oxidation of glycerol. The results indicate that these reactions are facilitated by the surface bound hydroxyl species on Au (chemisorbed OH(-) and faradaically formed Au-OH). By comparing the findings for stationary and rotating electrodes, it is shown that, convective mass transport is critical to maintaining efficient progression of the consecutive oxidation steps of glycerol. In the absence of hydrodynamic support, the main surface products of glycerol oxidation appear to be glyceraldehyde, glycerate and malonate, formed through a net six-electron route. In the presence of controlled convection, a ten-electron process is activated, where mesaxolate is the likely additional product. PMID:25855265

  7. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    NASA Technical Reports Server (NTRS)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) Program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163 (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The Orion MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a single-piece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment were the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  8. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    NASA Technical Reports Server (NTRS)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163, (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a singlepiece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment are the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  9. Influence of Cooling Rate on Phase Formationin Spray-Formed H13 Tool Steel

    SciTech Connect

    K. M. Mchugh; Y. Lin; Y. Zhou; E. J. Lavernia

    2006-04-01

    Spray forming is an effective way to process many tool steels into near-net-shape molds, dies and related tooling. The general approach involves depositing atomized droplets onto a refractory pattern in order to image the pattern’s features. The pattern is removed and the die is fitted into a standard holding fixture. This approach results in significant cost and lead-time savings compared to conventional machining, Spray-formed dies perform well in many industrial forming operations, oftentimes exhibiting extended die life over conventional dies. Care must be exercised when spray forming tool steel dies to minimize porosity and control the nature and distribution of phases and residual stresses. Selection of post-deposition heat treatment is important to tailor the die’s properties (hardness, strength, impact energy, etc.) for a particular application. This paper examines how the cooling rate and other processing parameters during spray processing and heat treatment of H13 tool steel influence phase formation. Results of case studies on spray-formed die performance in forging, extrusion and die casting, conducted by industry during production runs, will be described.

  10. The Production Phase for the National Compact Stellarator Experiment (NCSX) Modular Coil Winding Forms

    SciTech Connect

    Heitzenroeder, P.; Brown, T.; Neilson, G.; Malinowski, F.; Sutton, L.; Nelson, B.; Williamson, D.; Horton, N.; Goddard, B.; Edwards, J.; Bowling, K.; Hatzilias, K.

    2005-10-20

    The production phase for the NCSX modular coil winding forms has been underway for approximately one year as of this date. This is the culmination of R&D efforts performed in 2001-4. The R&D efforts included limited manufacturing studies while NCSX was in its conceptual design phase followed by more detailed manufacturing studies by two teams which included the fabrication of full scale prototypes. This provided the foundation necessary for the production parts to be produced under a firm price and schedule contract that was issued in September 2004. This paper will describe the winding forms, the production team and team management, details of the production process, and the achievements for the first year.

  11. Cornucopia of Nanoscale Ordered Phases in Sphere-Forming Tetrablock Terpolymers.

    PubMed

    Chanpuriya, Siddharth; Kim, Kyungtae; Zhang, Jingwen; Lee, Sangwoo; Arora, Akash; Dorfman, Kevin D; Delaney, Kris T; Fredrickson, Glenn H; Bates, Frank S

    2016-05-24

    We report the phase behavior of a series of poly(styrene)-b-poly(isoprene)-b-poly(styrene)'-b-poly(ethylene oxide) (SIS'O) tetrablock terpolymers. This study was motivated by self-consistent field theory (SCFT) calculations that anticipate a rich array of sphere-forming morphologies with variations in the molecular symmetry parameter τ = NS/(NS + NS'), where N is the block degree of polymerization and the volume fraction of O is less than about 0.22. Eight SIS'O samples, with τ ranging from 0.21 to 0.73, were synthesized and investigated using small-angle X-ray scattering and transmission electron microscopy, yielding evidence of nine different spherical phases: hexagonal, FCC, HCP, BCC, rhombohedral (tentative), liquid-like packing, dodecagonal quasicrystal, and Frank-Kasper σ and A15 phases. At temperatures close to the order-disorder transition, these tetrablocks behave as pseudo-[SIS']-O diblocks and form equilibrium morphologies mediated by facile chain exchange between micelles. Transition from equilibrium to nonequilibrium behavior occurs at a temperature (Terg) several tens of degrees below the order-disorder transition temperature, speculated to be coincident with the loss of ergodicity, as chain exchange is arrested due to increased segregation strength between the core (O) and corona (SIS') blocks. Nonequilibrium ordered structures form when T < Terg; these are interpreted using SCFT calculations to elucidate the free energy landscape driving ordering in the S and I block matrix. These experiments demonstrate a profound dependence on phase stability with variations in τ and temperature, providing insights into the formation of ordered phase symmetry in this class of asymmetric multiblock polymers. PMID:27055118

  12. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Rathz, T. J.; Krishnan, S.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    The local atomic structures of undercooled liquid metals are presumed to be icosahedral; this order is incompatible with translational periodicity, constituting a barrier to the nucleation of the crystal phase. The extended atomic structure of the icosahedral quasicrystal (i-phase) is similar to that presumed in the undercooled liquid. Therefore, a comparison of the maximum undercooling in alloys that form the i-phase with those that form crystal phases provides a probe of the liquid structure.

  13. Efficient green methanol synthesis from glycerol

    NASA Astrophysics Data System (ADS)

    Haider, Muhammad H.; Dummer, Nicholas F.; Knight, David W.; Jenkins, Robert L.; Howard, Mark; Moulijn, Jacob; Taylor, Stuart H.; Hutchings, Graham J.

    2015-12-01

    The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry.

  14. Production of 3-Hydroxypropionaldehyde from Glycerol

    PubMed Central

    Slininger, Patricia J.; Bothast, Rodney J.; Smiley, Karl L.

    1983-01-01

    3-Hydroxypropionaldehyde is a precursor to acrolein, which can be used as an intermediate for making acrylic acid and a variety of other useful industrial chemicals. Conversion of glycerol, a renewable resource, to 3-hydroxypropionaldehyde was attempted via action of glycerol dehydrase isolated from Lactobacillus sp. strain NRRL B-1720. This method, however, was unsatisfactory because enzyme activity was lost within 60 to 90 min after the reaction initiation. Fermentation of glycerol by whole cells of Klebsiella pneumoniae NRRL B-199 in the presence of optimal semicarbazide hydrochloride proved more effective. Using this technique, glycerol solutions of 30 g/liter yielded 3-hydroxypropionaldehyde solutions of 13.1 g/liter. Thus, a conversion efficiency equal to 55% of the theoretical maximum was realized. PMID:16346353

  15. Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

    PubMed Central

    Schrader, Alex M.; Cheng, Chi-Yuan; Han, Songi

    2016-01-01

    Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relative to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity. PMID:27475340

  16. Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

    NASA Astrophysics Data System (ADS)

    Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.; Han, Songi

    2016-07-01

    Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relative to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.

  17. Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces.

    PubMed

    Schrader, Alex M; Cheng, Chi-Yuan; Israelachvili, Jacob N; Han, Songi

    2016-07-28

    Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relative to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity. PMID:27475340

  18. Crude Glycerol as Cost-Effective Fuel for Combined Heat and Power to Replace Fossil Fuels, Final Technical Report

    SciTech Connect

    Roberts, William L

    2012-10-31

    The primary objectives of this work can be summed into two major categories. Firstly, the fundamentals of the combustion of glycerol (in both a refined and unrefined form) were to be investigated, with emphasis of the development of a system capable of reliably and repeatedly combusting glycerol as well as an analysis of the emissions produced during glycerol combustion. Focus was placed on quantifying common emissions in comparison to more traditional fuels and this work showed that the burner developed was able to completely combust glycerol within a relatively wide range of operating conditions. Additionally, focus was placed on examining specific emissions in more detail, namely interesting NOx emissions observed in initial trials, acrolein and other volatile organic emissions, and particulate and ash emissions. This work showed that the combustion of crude glycerol could result in significantly reduced NOx emissions as a function of the high fuel bound oxygen content within the glycerol fuel. It also showed that when burned properly, the combustion of crude glycerol did not result in excessive emissions of acrolein or any other VOC compared to the combustion from more traditional fuels. Lastly however, this work has shown that in any practical application in which glycerol is being burned, it will be necessary to explore ash mitigation techniques due to the very high particulate matter concentrations produced during glycerol combustion. These emissions are comparable to unfiltered coal combustion and are directly tied to the biodiesel production method. The second focus of this work was directed to developing a commercialization strategy for the use of glycerol as a fuel replacement. This strategy has identified a 30 month plan for the scaling up of the laboratory scale burner into a pre-pilot scale system. Additionally, financing options were explored and an assessment was made of the economics of replacing a traditional fuel (namely natural gas) with crude

  19. Hopf normal form with SN symmetry and reduction to systems of nonlinearly coupled phase oscillators

    NASA Astrophysics Data System (ADS)

    Ashwin, Peter; Rodrigues, Ana

    2016-06-01

    Coupled oscillator models where N oscillators are identical and symmetrically coupled to all others with full permutation symmetry SN are found in a variety of applications. Much, but not all, work on phase descriptions of such systems consider the special case of pairwise coupling between oscillators. In this paper, we show this is restrictive-and we characterize generic multi-way interactions between oscillators that are typically present, except at the very lowest order near a Hopf bifurcation where the oscillations emerge. We examine a network of identical weakly coupled dynamical systems that are close to a supercritical Hopf bifurcation by considering two parameters, ɛ (the strength of coupling) and λ (an unfolding parameter for the Hopf bifurcation). For small enough λ > 0 there is an attractor that is the product of N stable limit cycles; this persists as a normally hyperbolic invariant torus for sufficiently small ɛ > 0. Using equivariant normal form theory, we derive a generic normal form for a system of coupled phase oscillators with SN symmetry. For fixed N and taking the limit 0 < ɛ ≪ λ ≪ 1, we show that the attracting dynamics of the system on the torus can be well approximated by a coupled phase oscillator system that, to lowest order, is the well-known Kuramoto-Sakaguchi system of coupled oscillators. The next order of approximation generically includes terms with up to four interacting phases, regardless of N. Using a normalization that maintains nontrivial interactions in the limit N → ∞, we show that the additional terms can lead to new phenomena in terms of coexistence of two-cluster states with the same phase difference but different cluster size.

  20. Glycerol-3-Phosphate-Induced Catabolite Repression in Escherichia coli

    PubMed Central

    Eppler, Tanja; Postma, Pieter; Schütz, Alexandra; Völker, Uwe; Boos, Winfried

    2002-01-01

    The formation of glycerol-3-phosphate (G3P) in cells growing on TB causes catabolite repression, as shown by the reduction in malT expression. For this repression to occur, the general proteins of the phosphoenolpyruvate-dependent phosphotransferase system (PTS), in particular EIIAGlc, as well as the adenylate cyclase and the cyclic AMP-catabolite activator protein system, have to be present. We followed the level of EIIAGlc phosphorylation after the addition of glycerol or G3P. In contrast to glucose, which causes a dramatic shift to the dephosphorylated form, glycerol or G3P only slightly increased the amount of dephosphorylated EIIAGlc. Isopropyl-β-d-thiogalactopyranoside-induced overexpression of EIIAGlc did not prevent repression by G3P, excluding the possibility that G3P-mediated catabolite repression is due to the formation of unphosphorylated EIIAGlc. A mutant carrying a C-terminally truncated adenylate cyclase was no longer subject to G3P-mediated repression. We conclude that the stimulation of adenylate cyclase by phosphorylated EIIAGlc is controlled by G3P and other phosphorylated sugars such as d-glucose-6-phosphate and is the basis for catabolite repression by non-PTS compounds. Further metabolism of these compounds is not necessary for repression. Two-dimensional polyacrylamide gel electrophoresis was used to obtain an overview of proteins that are subject to catabolite repression by glycerol. Some of the prominently repressed proteins were identified by peptide mass fingerprinting. Among these were periplasmic binding proteins (glutamine and oligopeptide binding protein, for example), enzymes of the tricarboxylic acid cycle, aldehyde dehydrogenase, Dps (a stress-induced DNA binding protein), and d-tagatose-1,6-bisphosphate aldolase. PMID:12003946

  1. Stability conditions and mechanism of cream soaps: role of glycerol.

    PubMed

    Sagitani, Hiromichi

    2014-01-01

    Fatty acids, fatty acid potassium soaps, glycerol and water are essential ingredients in the production of stable cream soaps. In this study, the behavior of these components in solution was investigated to elucidate the stability conditions and mechanism of cream soaps. It was determined that the cream soaps were a dispersion of 1:1 acid soap (1:1 molar ratio of potassium soap/fatty acid) crystals in the lamellar gel phase, which has confirmed from the phase behavior diagrams and small angle X-ray scattering data. Glycerol was crucial ingredient in the formation of the lamellar gel phase. The cleansing process of the cream soaps was also evaluated using the same diagrams. The structure of the continuous phase in cream soaps changed from lamellar gel to a micellar aqueous solution upon the addition of water. This structural change during the washing process is important in producing the foaming activity of acid soaps to wash away dirt or excess fats from the skin surface. PMID:24671023

  2. Glass polymorphism in glycerol-water mixtures: I. A computer simulation study.

    PubMed

    Jahn, David A; Wong, Jessina; Bachler, Johannes; Loerting, Thomas; Giovambattista, Nicolas

    2016-04-28

    We perform out-of-equilibrium molecular dynamics (MD) simulations of water-glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA-HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ(g) = 0-13% and find that, for the present mixture models and rates, the LDA-HDA transformation is detectable up to χ(g) ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ(g) ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ(g) > 5%. We present an analysis of the molecular-level changes underlying the LDA-HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA-HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA-HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that

  3. PLGA in situ implants formed by phase inversion: critical physicochemical parameters to modulate drug release.

    PubMed

    Parent, Marianne; Nouvel, Cécile; Koerber, Martin; Sapin, Anne; Maincent, Philippe; Boudier, Ariane

    2013-11-28

    In situ forming implants (ISI) based on phase separation by solvent exchange represent an attractive alternative to conventional preformed implants and microparticles for parenteral applications. They are indeed easier to manufacture and their administration does not require surgery, therefore improving patient compliance. They consist of polymeric solutions precipitating at the site of injection and thus forming a drug eluting depot. Drug release from ISI is typically divided into three phases: burst during precipitation of the depot, diffusion of drug through the polymeric matrix and finally drug release by system degradation. This review gives a comprehensive overview on (i) the theoretical bases of these three phases, (ii) the parameters influencing them and (iii) the remaining drawbacks which have to be addressed to enlarge their commercial opportunities. Indeed, although some of them are already commercialized, ISI still suffer from limitations: mainly lack of reproducibility in depot shape, burst during solidification and potential toxicity. Nevertheless, depending on the targeted therapeutic application, these shortcomings may be transformed into advantages. As a result, keys are given in order to tailor these formulations in view of the desired application so that ISI could gain further clinical importance in the following years. PMID:24001947

  4. Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-08-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  5. Biomass Pretreatment using Ionic Liquid and Glycerol Mixtures

    NASA Astrophysics Data System (ADS)

    Lynam, Joan Goerss

    Lignocellulosic biomass is a renewable, sustainable resource that can replace or supplement fossil fuels use for liquid fuels and chemicals. However, its recalcitrant structure including interwoven cellulose, hemicelluloses, and lignin biomacromolecules is challenging to deconstruct. Pretreating biomass so that it can be converted to useful liquids dominates process economics. Many pretreatment methods exist, but most require hazardous chemicals or processing conditions. Many ionic liquids (ILs), salts molten below 100°C, can be used to deconstruct lignocellulosic biomass and are less hazardous than the volatile organic compounds typically used. While effective, relatively safe, and recyclable, ILs are expensive. To reduce costs, dilution with other safe compounds is desirable, if there is no impact on deconstruction efficiency. Glycerol, a food additive, is inexpensive and becoming even more so since it is a by-product of the burgeoning biodiesel industry. Use of glycerol as an additive or diluent for ILs is extensively evaluated in this work. Rice hulls are an abundant biomass, with over 100 million tons produced per year, but with little practical use. The IL 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH] or EMIM Form) when mixed with an equal amount of glycerol has been shown to be effective in pretreating rice hulls. Ambient pressure, a pretreatment temperature of 110°C, and a reaction time of three hours produced rice hulls that could be enzymatically hydrolyzed to give reasonably good glucose and xylose yields considering the recalcitrance of this silica-armored biomass. The IL [C2mim][O2CH] was also effective when mixed with an equal amount of glycerol to pretreat loblolly pine, a fast-growing softwood. Loblolly pine was pretreated at 140°C for three hours to produce a solid rich in cellulose and hemicelluloses, while a lignin-rich product could be precipitated from the IL. Similar products were obtained from pretreatment with a mixture of 75% 1

  6. Temperature-Dependent Phase Behaviors in Cylinder-Forming Block Copolymers

    PubMed Central

    Ahn, Dae Up; Sancaktar, Erol

    2009-01-01

    We demonstrate that the temperature-dependent phase behaviors of parallel and perpendicular cylinder-forming block copolymers are governed by domain-domain segregation forces inherently present in block copolymer material itself. With increasing temperature, a parallel cylinder-forming block copolymer experienced a parallel cylinder straightening process before the order-disorder transition (ODT) and did not show long-range composition fluctuations near the ODT temperature due to the weak segregation forces between the block domains. A perpendicular cylinder-forming block copolymer with a strong segregation force between the block domains displayed cylinder orientation transition from perpendicular to parallel below the ODT temperature. On the other hand, a perpendicular cylinder-forming block copolymer material with an exceptionally strong segregation force between the block domains maintained its initial perpendicular cylinder orientation up to near the ODT temperature. In both cases of perpendicular cylinder-forming block copolymers, submicrometer-scale long-range composition fluctuations were observed well above the ODT temperature due to their intrinsically strong segregation forces between the block domains. PMID:19564947

  7. Characterization of secondary phases formed during MOVPE growth of InSbBi mixed crystals

    NASA Astrophysics Data System (ADS)

    Wagener, M. C.; Botha, J. R.; Leitch, A. W. R.

    2000-05-01

    Secondary phases, formed during the growth of InSbBi, a III-V compound with potential for infrared applications in the 8-12 μm range, are reported. Layers were prepared by atmospheric pressure metal-organic vapour-phase epitaxy at 455°C in a horizontal quartz reactor. The source materials used were trimethylindium (TMIn), trimethylantimony (TMSb), and trimethylbismuth (TMBi). Scanning electron microscopy and X-ray diffraction spectra showed the formation of extra phases on the surfaces of the layers. The compositions of these condensed phases were influenced by the V/III ratio at the growth interface. Bi precipitates were observed by cross-sectional transmission electron microscopy for layers grown on InSb substrates. Attempts to grow InSbBi on GaAs substrates produced InAsSb layers. The As composition showed a dependence on the availability of Bi, increasing from 7.5 to 26 mol% InAs when increasing the Bi/V ratio from 0.04 to 2%. The incorporation of As has been related to the formation of Bi-Ga inclusions at the GaAs interface.

  8. Synthesis of Glycerol Carbonate by Transesterification of Glycerol with Urea Over Zn/Al Mixed Oxide.

    PubMed

    Ryu, Young Bok; Baek, Jae Ho; Kim, Yangdo; Lee, Man Sig

    2015-01-01

    Reactions of glycerol carbonate using glycerol and urea have been carried out previously using ZnSO4 and ZnO catalysts, and high yields have been reported using ZnSO4 as catalyst. However, this salt is soluble in glycerol, and recycling of catalyst is difficult after the reaction. In this study, we prepared a mixed metal oxide catalyst using Zn and Al, and this catalyst consisted of a mixture of ZnO and ZnAl2O4. We confirmed the conversion of glycerol and the yield of glycerol carbonate of the amount of Al. As a result, we obtained a yield of 82.3% and a conversion of 82.7%. In addition we obtained high yield in recycling of catalyst. The yield of the glycerol carbonate increases with an increase of acid and base site of catalysts and the highest catalytic activity was obtained when acid/base ratio was approx. 1. From this result, we may conclude that the acid and base site density and ratio of catalysts were very important parameters in the synthesis of glycerol carbonate from urea and glycerol. PMID:26328352

  9. Alkyl-bis(imidazolium) salts: a new amphiphile platform that forms thermotropic and non-aqueous lyotropic bicontinuous cubic phases

    SciTech Connect

    Robertson, LA; Schenkel, MR; Wiesenauer, BR; Gin, DL

    2013-01-01

    New ionic amphiphiles with a hexyl-bridged bis(imidazolium) headgroup; Br-, BF4-, or Tf2N- anions; and a long n-alkyl tail can form thermotropic bicontinuous cubic liquid crystal phases in neat form and/or lyotropic bicontinuous cubic phases with several non-aqueous solvents or water.

  10. Radiometric assays for glycerol, glucose, and glycogen

    SciTech Connect

    Bradley, D.C.; Kaslow, H.R. )

    1989-07-01

    We have developed radiometric assays for small quantities of glycerol, glucose and glycogen, based on a technique described by Thorner and Paulus for the measurement of glycerokinase activity. In the glycerol assay, glycerol is phosphorylated with (32P)ATP and glycerokinase, residual (32P)ATP is hydrolyzed by heating in acid, and free (32P)phosphate is removed by precipitation with ammonium molybdate and triethylamine. Standard dose-response curves were linear from 50 to 3000 pmol glycerol with less than 3% SD in triplicate measurements. Of the substances tested for interference, only dihydroxyacetone gave a slight false positive signal at high concentration. When used to measure glycerol concentrations in serum and in media from incubated adipose tissue, the radiometric glycerol assay correlated well with a commonly used spectrophotometric assay. The radiometric glucose assay is similar to the glycerol assay, except that glucokinase is used instead of glycerokinase. Dose response was linear from 5 to 3000 pmol glucose with less than 3% SD in triplicate measurements. Glucosamine and N-acetylglucosamine gave false positive signals when equimolar to glucose. When glucose concentrations in serum were measured, the radiometric glucose assay agreed well with hexokinase/glucose-6-phosphate dehydrogenase (H/GDH)-based and glucose oxidase/H2O2-based glucose assays. The radiometric method for glycogen measurement incorporates previously described isolation and digestion techniques, followed by the radiometric assay of free glucose. When used to measure glycogen in mouse epididymal fat pads, the radiometric glycogen assay correlated well with the H/GDH-based glycogen assay. All three radiometric assays offer several practical advantages over spectral assays.

  11. Radiometric assays for glycerol, glucose, and glycogen.

    PubMed

    Bradley, D C; Kaslow, H R

    1989-07-01

    We have developed radiometric assays for small quantities of glycerol, glucose and glycogen, based on a technique described by Thorner and Paulus (1971, J. Biol. Chem. 246, 3885-3894) for the measurement of glycerokinase activity. In the glycerol assay, glycerol is phosphorylated with [32P]ATP and glycerokinase, residual [32P]ATP is hydrolyzed by heating in acid, and free [32P]phosphate is removed by precipitation with ammonium molybdate and triethylamine. Standard dose-response curves were linear from 50 to 3000 pmol glycerol with less than 3% SD in triplicate measurements. Of the substances tested for interference, only dihydroxyacetone gave a slight false positive signal at high concentration. When used to measure glycerol concentrations in serum and in media from incubated adipose tissue, the radiometric glycerol assay correlated well with a commonly used spectrophotometric assay. The radiometric glucose assay is similar to the glycerol assay, except that glucokinase is used instead of glycerokinase. Dose response was linear from 5 to 3000 pmol glucose with less than 3% SD in triplicate measurements. Glucosamine and N-acetylglucosamine gave false positive signals when equimolar to glucose. When glucose concentrations in serum were measured, the radiometric glucose assay agreed well with hexokinase/glucose-6-phosphate dehydrogenase (H/GDH)-based and glucose oxidase/H2O2-based glucose assays. The radiometric method for glycogen measurement incorporates previously described isolation and digestion techniques, followed by the radiometric assay of free glucose. When used to measure glycogen in mouse epididymal fat pads, the radiometric glycogen assay correlated well with the H/GDH-based glycogen assay. All three radiometric assays offer several practical advantages over spectral assays. PMID:2817333

  12. Reduced catabolic protein expression in Clostridium butyricum DSM 10702 correlate with reduced 1,3-propanediol synthesis at high glycerol loading

    PubMed Central

    2014-01-01

    Higher initial glycerol loadings (620 mM) have a negative effect on growth and 1,3-propanediol (1,3-PDO) synthesis in Clostridium butyricum DSM 10702 relative to lower initial glycerol concentrations (170 mM). To help understand metabolic shifts associated with elevated glycerol, protein expression levels were quantified by LC/MS/MS analyses. Thirty one (31) proteins involved in conversion of glycerol to 1,3-PDO and other by-products were analyzed by multiple reaction monitoring (MRM). The analyses revealed that high glycerol concentrations reduced cell growth. The expression levels of most proteins in glycerol catabolism pathways were down-regulated, consistent with the slower growth rates observed. However, at high initial glycerol concentrations, some of the proteins involved in the butyrate synthesis pathways such as a putative ethanol dehydrogenase (CBY_3753) and a 3-hydroxybutyryl-CoA dehydrogenase (CBY_3045) were up-regulated in both exponential and stationary growth phases. Expression levels of proteins (CBY_0500, CBY_0501 and CBY_0502) involved in the reductive pathway of glycerol to 1,3-PDO were consistent with glycerol consumption and product concentrations observed during fermentation at both glycerol concentrations, and the molar yields of 1,3-PDO were similar in both cultures. This is the first report that correlates expression levels of glycerol catabolism enzymes with synthesis of 1,3-PDO in C. butyricum. The results revealed that significant differences in the expression of a small subset of proteins were observed between exponential and stationary growth phases at both low and high glycerol concentrations. PMID:25401066

  13. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  14. Solid phase synthesis of functionalised SAM-forming alkanethiol-oligoethyleneglycols.

    PubMed

    Murray, James; Nowak, Dominika; Pukenas, Laurynas; Azhar, Rizuan; Guillorit, Mathieu; Wälti, Christoph; Critchley, Kevin; Johnson, Steven; Bon, Robin S

    2014-06-28

    We present an efficient solid phase synthesis methodology that provides easy access to a range of functionalised long-chain alkanethiol-oligoethyleneglycols that form well-defined self-assembled monolayers on gold and are compatible with pre- or post-assembly conjugation of (bio)molecules. We demonstrate the versatility of our synthetic route by synthesising LCAT-OEGs with a range of functional moieties, including peptides, electro-active redox groups, chemical handles for post-assembly conjugation of (bio)molecules, and demonstrate the application of our LCAT-OEG monolayers in immunosensing, where they show good biocompatibility with minimal biofouling. PMID:25400934

  15. WENO wavelet method for a hyperbolic model of two-phase flow in conservative form

    NASA Astrophysics Data System (ADS)

    Zeidan, Dia; Kozakevicius, Alice J.; Schmidt, Alex A.; Jakobsson, Stefan

    2016-06-01

    The current work presents a WENO wavelet adaptive method for solving multiphase flow problems. The grid adaptivity in each time step is obtained by the application of a thresholded interpolating wavelet transform, which allows the construction of a small yet effective sparse point representation of the solution. The spatial operator is solved by the Lax-Friedrich flux splitting approach in which the flux derivatives are approximated by the WENO scheme. Hyperbolic models of two-phase flow in conservative form are efficiently solved since shocks and rarefaction waves are precisely captured by the chosen methodology. Substantial computational gains are obtained through the grid reduction feature while maintaining the quality of the solutions.

  16. Catalytic glycerol steam reforming for hydrogen production

    SciTech Connect

    Dan, Monica Mihet, Maria Lazar, Mihaela D.

    2015-12-23

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H{sub 2}. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al{sub 2}O{sub 3}. The catalyst was prepared by wet impregnation method and characterized through different methods: N{sub 2} adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H{sub 2}, CH{sub 4}, CO, CO{sub 2}. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H{sub 2}O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  17. Catalytic glycerol steam reforming for hydrogen production

    NASA Astrophysics Data System (ADS)

    Dan, Monica; Mihet, Maria; Lazar, Mihaela D.

    2015-12-01

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H2. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al2O3. The catalyst was prepared by wet impregnation method and characterized through different methods: N2 adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H2, CH4, CO, CO2. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H2O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  18. Solid-state NMR identification and quantification of newly formed aluminosilicate phases in weathered kaolinite systems.

    PubMed

    Crosson, Garry S; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary Kay; O'Day, Peggy A; Mueller, Karl T

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3-, 1 mol kg-1 of OH-, and pH approximately 13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10(-3), 10(-4), and 10(-5) molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10(-5) m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10(-3) m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and

  19. Solid-State NMR Identification and Quantification of Newly Formed Aluminosilicate Phases in Weathered Kaolinite Systems

    SciTech Connect

    Crosson, Garry S.; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary K.; O'Day, Peggy A.; Mueller, Karl T.

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3 -, 1 mol kg-1 of OH-, and pH ~13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10-3, 10-4, and 10-5 molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10-5 m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10-3 m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and the quantitative

  20. Direct phase-sensitive identification of a d-form factor density wave in underdoped cuprates

    PubMed Central

    Fujita, Kazuhiro; Hamidian, Mohammad H.; Edkins, Stephen D.; Kim, Chung Koo; Kohsaka, Yuhki; Azuma, Masaki; Takano, Mikio; Takagi, Hidenori; Eisaki, Hiroshi; Uchida, Shin-ichi; Allais, Andrea; Lawler, Michael J.; Kim, Eun-Ah; Sachdev, Subir; Davis, J. C. Séamus

    2014-01-01

    The identity of the fundamental broken symmetry (if any) in the underdoped cuprates is unresolved. However, evidence has been accumulating that this state may be an unconventional density wave. Here we carry out site-specific measurements within each CuO2 unit cell, segregating the results into three separate electronic structure images containing only the Cu sites [Cu(r)] and only the x/y axis O sites [Ox(r) and Oy(r)]. Phase-resolved Fourier analysis reveals directly that the modulations in the Ox(r) and Oy(r) sublattice images consistently exhibit a relative phase of π. We confirm this discovery on two highly distinct cuprate compounds, ruling out tunnel matrix-element and materials-specific systematics. These observations demonstrate by direct sublattice phase-resolved visualization that the density wave found in underdoped cuprates consists of modulations of the intraunit-cell states that exhibit a predominantly d-symmetry form factor. PMID:24989503

  1. Augmented ciliary reorientation response and cAMP-dependent protein phosphorylation induced by glycerol in triton-extracted Paramecium.

    PubMed

    Noguchi, Munenori; Kitani, Takayuki; Ogawa, Tokushige; Inoue, Hiroshi; Kamachi, Hiroyuki

    2005-01-01

    In the presence of 30% glycerol, the cilia of a permeabilized cell model from Paramecium exhibit dynamic orientation changes while displaying only a restricted cyclic beating with a very small amplitude. The direction of cilia under these conditions corresponds to the direction of the effective power stroke of cilia beating in the absence of glycerol, i.e., pointing posteriorly in the absence of Ca2+ and anteriorly at > 10(-6) M Ca2+. Ciliary reorientation toward the posterior in response to the removal of Ca2+ is particularly conspicuous; all the cilia become predominantly pointing to the posterior end all through their beating phases. Previous studies suggested that the effect of glycerol is caused through modification of cAMP-dependent protein phosphorylation. To determine whether glycerol in fact affects ciliary reorientation through changes in protein phosphorylation, here we examined protein phosphorylation in the axonemes. Glycerol stimulated cAMP-induced phosphorylation of 29-kDa and 65-kDa proteins. The stimulation of phosphorylation was found to be partly due to the inhibition of endogenous phosphodiesterase (PDE), and partly due to the inhibition of the dephosphorylation of the 29-kDa and 65-kDa phosphoproteins within the axoneme. Thus glycerol appears to cause predominant posterior orientation of cilia by stimulating cAMP-dependent phosphorylation on those proteins. In addition, glycerol appears to inhibit ciliary beating through inhibition of dynein ATPase. PMID:15684582

  2. Esterification of glycerol 3-phosphate in lactating guinea-pig mammary gland

    PubMed Central

    Kuhn, N. J.

    1967-01-01

    1. The presence of palmitoyl-CoA–l-glycerol 3-phosphate palmitoyltransferase (EC 2.3.1.15) has been demonstrated in a particulate fraction of mammary tissue from lactating guinea pigs. 2. Cell-free preparations also catalysed the activation of palmitate and oleate, and the conversion of enzymically formed phosphatidic acid into glycerides, in accord with the Kennedy pathway of glyceride formation. 3. The properties of the system that esterifies l-glycerol 3-phosphate were studied with respect to substrates and cofactors, and the reaction product was shown to be phosphatidic acid (1,2-diacyl glycerol 3-phosphate). 4. The extent to which newly formed phosphatidic acid was converted into glyceride in a cell-free system was dependent on the nature of the acyl donor, the concentration of subcellular particles, the time of incubation and the concentration of Mg2+. PMID:6070127

  3. Bioconversion of glycerol to ethanol by a mutant Enterobacter aerogenes

    PubMed Central

    2012-01-01

    The main objective of this research is to develop, by adaptive evolution, mutant strains of Enterobacter aerogenes ATCC 13048 that are capable of withstanding high glycerol concentration as well as resisting ethanol-inhibition. The mutant will be used for high ethanol fermentation from glycerol feedstock. Ethanol production from pure (P-) and recovered (R-) glycerol using the stock was evaluated. A six-tube-subculture-generations method was used for developing the mutant. This involved subculturing the organism six consecutive times in tubes containing the same glycerol and ethanol concentrations at the same culture conditions. Then, the glycerol and/or ethanol concentration was increased and the six subculture generations were repeated. A strain capable of growing in 200 g/L glycerol and 30 g/L ethanol was obtained. The ability of this mutant, vis-à-vis the original strain, in utilizing glycerol in a high glycerol containing medium, with the concomitant ethanol yield, was assessed. Tryptic soy broth without dextrose (TSB) was used as the fermentation medium. Fermentation products were analyzed using HPLC. In a 20 g/L glycerol TSB, E. aerogenes ATCC 13048 converted 18.5 g/L P-glycerol and 17.8 g/L R-glycerol into 12 and 12.8 g/L ethanol, respectively. In a 50 g/L P-glycerol TSB, it utilized only 15.6 g/L glycerol; but the new strain used up 39 g/L, yielding 20 g/L ethanol after 120 h, an equivalence of 1.02 mol ethanol/mol-glycerol. This is the highest ethanol yield reported from glycerol bioconversion. The result of this P-glycerol fermentation can be duplicated using the R-glycerol from biodiesel production. PMID:22455837

  4. Biorefinery for Glycerol Rich Biodiesel Industry Waste.

    PubMed

    Kalia, Vipin Chandra; Prakash, Jyotsana; Koul, Shikha

    2016-06-01

    The biodiesel industry has the potential to meet the fuel requirements in the future. A few inherent lacunae of this bioprocess are the effluent, which is 10 % of the actual product, and the fact that it is 85 % glycerol along with a few impurities. Biological treatments of wastes have been known as a dependable and economical direction of overseeing them and bring some value added products as well. A novel eco-biotechnological strategy employs metabolically diverse bacteria, which ensures higher reproducibility and economics. In this article, we have opined, which organisms and what bioproducts should be the focus, while exploiting glycerol as feed. PMID:27570302

  5. Tandem transformation of glycerol to esters.

    PubMed

    Sotenko, Maria V; Rebroš, Martin; Sans, Victor S; Loponov, Konstantin N; Davidson, Matthew G; Stephens, Gill; Lapkin, Alexei A

    2012-12-31

    Tandem transformation of glycerol via microbial fermentation and enzymatic esterification is presented. The reaction can be performed with purified waste glycerol from biodiesel production in a continuous mode, combining continuous fermentation with membrane-supported enzymatic esterification. Continuous anaerobic fermentation was optimized resulting in the productivity of 2.4 g L⁻¹ h⁻¹ of 1,3-propanediol. Biphasic esterification of 1,3-propanediol was optimized to achieve ester yield of up to 75%. A hollow fibre membrane contactor with immobilized Rhizomucor miehei lipase was demonstrated for the continuous tandem fermentation-esterification process. PMID:22796408

  6. Effects of intravenous infusion of glycerol on blood parameters and urinary glycerol concentrations.

    PubMed

    Okano, Masato; Nishitani, Yasunori; Dohi, Michiko; Kageyama, Shinji

    2016-05-01

    In sports, the oral intake and intravenous administration of glycerol as a potential masking agent have been prohibited. The effect of glycerol on blood parameters was investigated by comparing the intravenous administration of glycerol (20g/200mL) with that of an electrolyte (8g glucose/200mL) as a comparator (n=7, fixed-dose-rate i.v. infusion, 200mL in 1h). This study was also designed to evaluate whether the urinary concentrations reached the positivity threshold after the intravenous infusion of glycerol. Significant decreases of the haemoglobin (HGB, g/dL), haematocrit (HCT, %) and OFF-h Score (OFF-score) values were observed after the infusion of glycerol (P<0.05 at 1-6h). The differences in the HGB, HCT and OFF-score between pre- and post-administration were -0.49±0.23g/dL (2h), -1.54±0.73% (2h) and -3.89±3.66 (2h), respectively. Glycerol infusion significantly increased the plasma volume by 12.1% (1h), 6.3% (2h) and 5.7% (3h) compared with the initial values. The infusion of the comparator also increased the plasma volume by 9.6% (1h), 5.8% (2h) and 4.9% (3h) compared with the values before infusion. There were no significant differences in the change of the plasma volume between the intravenous infusions of glycerol and the glucose-based electrolyte (as the comparator) (P≥0.05). This finding might indicate that glycerol itself only exhibited limited effects on the expansion of plasma. After administration of glycerol, the urinary glycerol concentrations increased from 0.0013±0.0004mg/mL to 6.86±2.86mg/mL at 1h and 6.45±3.08mg/mL at 2h. The intravenous infusion of glycerol can most likely be detected using the current urine analysis; however, the dependence of the concentration of urinary glycerol on the urine volume should be considered. PMID:26986972

  7. Structural Characterizations of Glycerol Kinase: Unraveling Phosphorylation-Induced Long-Range Activation

    SciTech Connect

    Yeh, Joanne I.; Kettering, Regina; Saxl, Ruth; Bourand, Alexa; Darbon, Emmanuelle; Joly, Nathalie; Briozzo, Pierre; Deutscher, Josef

    2009-09-11

    Glycerol metabolism provides a central link between sugar and fatty acid catabolism. In most bacteria, glycerol kinase plays a crucial role in regulating channel/facilitator-dependent uptake of glycerol into the cell. In the firmicute Enterococcus casseliflavus, this enzyme's activity is enhanced by phosphorylation of the histidine residue (His232) located in its activation loop, approximately 25 A from its catalytic cleft. We reported earlier that some mutations of His232 altered enzyme activities; we present here the crystal structures of these mutant GlpK enzymes. The structure of a mutant enzyme with enhanced enzymatic activity, His232Arg, reveals that residues at the catalytic cleft are more optimally aligned to bind ATP and mediate phosphoryl transfer. Specifically, the position of Arg18 in His232Arg shifts by approximately 1 A when compared to its position in wild-type (WT), His232Ala, and His232Glu enzymes. This new conformation of Arg18 is more optimally positioned at the presumed gamma-phosphate location of ATP, close to the glycerol substrate. In addition to structural changes exhibited at the active site, the conformational stability of the activation loop is decreased, as reflected by an approximately 35% increase in B factors ('thermal factors') in a mutant enzyme displaying diminished activity, His232Glu. Correlating conformational changes to alteration of enzymatic activities in the mutant enzymes identifies distinct localized regions that can have profound effects on intramolecular signal transduction. Alterations in pairwise interactions across the dimer interface can communicate phosphorylation states over 25 A from the activation loop to the catalytic cleft, positioning Arg18 to form favorable interactions at the beta,gamma-bridging position with ATP. This would offset loss of the hydrogen bonds at the gamma-phosphate of ATP during phosphoryl transfer to glycerol, suggesting that appropriate alignment of the second substrate of glycerol kinase

  8. Genetic construction of recombinant Pseudomonas chlororaphis for improved glycerol utilization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this study is to improve by genetic engineering the glycerol metabolic capability of Pseudomonas chlororaphis which is capable of producing commercially valuable biodegradable poly(hydroxyalkanoate) (PHA) and biosurfactant rhamnolipids (RLs). In the study, glycerol uptake facilitat...

  9. Sorption behavior of mixtures of glycerol and starch.

    PubMed

    Enrione, Javier I; Hill, Sandra E; Mitchell, John R

    2007-04-18

    Glycerol is often added to starches to plasticize the product, but the presence of glycerol may also affect the water content of the samples. To evaluate the effect of glycerol on the sorption properties of starches, waxy maize, rice, and wheat starch were thermomechanically extruded in the presence of glycerol. Sorption isotherms of these extruded samples were ascertained using dynamic vapor sorption (DVS). BET and GAB modeling showed a monolayer (mo) significantly higher for waxy maize than for rice and wheat. Glycerol inclusion changed the model values, indicating reduction in sorption energy at the monolayer and restructuring of the multilayer. An interaction factor (xi) based on weight fraction models was calculated. Differences in xi were obtained when glycerol was added, varying from approximately 0.9 for 5% glycerol to approximately 0.8 for 20% glycerol, supporting the hypothesis of interactions between starch and this polyol. PMID:17362027

  10. Single-electron transport in InAs nanowire quantum dots formed by crystal phase engineering

    NASA Astrophysics Data System (ADS)

    Nilsson, Malin; Namazi, Luna; Lehmann, Sebastian; Leijnse, Martin; Dick, Kimberly A.; Thelander, Claes

    2016-05-01

    We report electrical characterization of quantum dots formed by introducing pairs of thin wurtzite (WZ) segments in zinc blende (ZB) InAs nanowires. Regular Coulomb oscillations are observed over a wide gate voltage span, indicating that WZ segments create significant barriers for electron transport. We find a direct correlation of transport properties with quantum dot length and corresponding growth time of the enclosed ZB segment. The correlation is made possible by using a method to extract lengths of nanowire crystal phase segments directly from scanning electron microscopy images, and with support from transmission electron microscope images of typical nanowires. From experiments on controlled filling of nearly empty dots with electrons, up to the point where Coulomb oscillations can no longer be resolved, we estimate a lower bound for the ZB-WZ conduction-band offset of 95 meV.

  11. Partition of synaptic membranes in aqueous two-phase systems at subzero temperatures by using anti-freeze solvent.

    PubMed

    Johansson, G; Joelsson, M; Olde, B

    1990-11-16

    The freezing point of aqueous two-phase (liquid-liquid) systems containing water, dextran and poly(ethylene glycol) has been lowered by including glycerol. Biological membranes, obtained by fragmentation of a crude synaptosomal preparation from calf brain cortex, have been included in the two-phase systems. The effects of temperature and the concentration of glycerol on the partition of the membranes within the systems have been investigated. Considerable stabilisation of the membranes was noticed when they were partitioned at -10 degrees C compared with 0 degrees C. The influences of glycerol, ethylene glycol, N,N-dimethylformamide and tetrahydrofuran on the phase-forming properties of the systems and on enzyme activities are also presented. Possible use of the above systems for studies and separation of biological membranes are discussed. PMID:2245213

  12. Corrosion properties of S-phase layers formed on medical grade austenitic stainless steel.

    PubMed

    Buhagiar, Joseph; Dong, Hanshan

    2012-02-01

    The corrosion properties of S-phase surface layers formed in AISI 316LVM (ASTM F138) and High-N (ASTM F1586) medical grade austenitic stainless steels by plasma surface alloying with nitrogen (at 430°C), carbon (at 500°C) and both carbon and nitrogen (at 430°C) has been investigated. The corrosion behaviour of the S-phase layers in Ringer's solutions was evaluated using potentiodynamic and immersion corrosion tests. The corrosion damage was evaluated using microscopy, hardness testing, inductive coupled plasma mass spectroscopy and X-ray diffraction. The experimental results have demonstrated that low-temperature nitriding, carburising and carbonitriding can improve the localised corrosion resistance of both industrial and medical grade austenitic stainless steels as long as the threshold sensitisation temperature is not reached. Carburising at 500°C has proved to be the best hardening treatment with the least effect on the corrosion resistance of the parent alloy. PMID:22160745

  13. Coarse-grained models of stripe forming systems: Phase diagrams, anomalies, and scaling hypothesis

    NASA Astrophysics Data System (ADS)

    Mendoza-Coto, Alejandro; Stariolo, Daniel A.

    2012-11-01

    Two coarse-grained models which capture some universal characteristics of stripe forming systems are studied. At high temperatures, the structure factors of both models attain their maxima on a circle in reciprocal space, as a consequence of generic isotropic competing interactions. Although this is known to lead to some universal properties, we show that the phase diagrams have important differences, which are a consequence of the particular k⃗ dependence of the fluctuation spectrum in each model. The phase diagrams are computed in a mean field approximation and also after inclusion of small fluctuations, which are shown to modify drastically the mean field behavior. Observables like the modulation length and magnetization profiles are computed for the whole temperature range accessible to both models and some important differences in behavior are observed. A stripe compression modulus is computed, showing an anomalous behavior with temperature as recently reported in related models. Also, a recently proposed scaling hypothesis for modulated systems is tested and found to be valid for both models studied.

  14. 1,2-Isopropylidene glycerol carbonate: preparation, characterization, and hydrolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The utilization of excess glycerol supplies derived from the burgeoning biodiesel industry is of major importance to the oleochemical industry as the economic viability of the biodiesel and oleochemical industries are closely linked to glycerol prices. Carbonate compounds based on glycerol, such as...

  15. Determining Atmospheric Pressure with a Eudiometer and Glycerol

    ERIC Educational Resources Information Center

    Brody, Jed; Rohald, Kate; Sutton, Atasha

    2010-01-01

    We consider a volume of air trapped over a glycerol column in a eudiometer. We demonstrate that there is an approximately linear relationship between the volume of trapped air and the height of the glycerol column. Simply by moving the eudiometer up and down, we cause the glycerol-column height and trapped-air volume to vary. The plot of volume…

  16. 21 CFR 172.735 - Glycerol ester of rosin.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Glycerol ester of rosin. 172.735 Section 172.735 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... CONSUMPTION Other Specific Usage Additives § 172.735 Glycerol ester of rosin. Glycerol ester of wood...

  17. 21 CFR 172.735 - Glycerol ester of rosin.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Glycerol ester of rosin. 172.735 Section 172.735 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... CONSUMPTION Other Specific Usage Additives § 172.735 Glycerol ester of rosin. Glycerol ester of wood...

  18. Digestable and Metabolizable Energy of Crude Glycerol in Growing Pigs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The apparent DE and ME value of crude glycerol for growing pigs was determined in a series of 5 experiments using crude glycerol (86.95% glycerol) from a biodiesel production facility with soybean oil used as the initial feedstock (AG Processing Inc., Sergeant Bluff, IA). Dietary treatments were 0, ...

  19. Conversion of glycerol to hydrogen rich gas.

    PubMed

    Tran, Nguyen H; Kannangara, G S Kamali

    2013-12-21

    Presently there is a glut of glycerol as the by-product of biofuel production and it will grow as production increases. The conundrum is how we can consume this material and convert it into a more useful product. One potential route is to reform glycerol to hydrogen rich gas including synthesis gas (CO + H2) and hydrogen. However, there is recent literature on various reforming techniques which may have a bearing on the efficiency of such a process. Hence in this review reforming of glycerol at room temperature (normally photo-catalytic), catalysis at moderate and high temperature and a non-catalytic pyrolysis process are presented. The high temperature processes allow the generation of synthesis gas with the hydrogen to carbon monoxide ratios being suitable for synthesis of dimethyl ether, methanol and for the Fischer-Tropsch process using established catalysts. Efficient conversion of synthesis gas to hydrogen involves additional catalysts that assist the water gas shift reaction, or involves in situ capture of carbon dioxide and hydrogen. Reforming at reduced temperatures including photo-reforming offers the opportunity of producing synthesis gas or hydrogen using single catalysts. Together, these processes will assist in overcoming the worldwide glut of glycerol, increasing the competitiveness of the biofuel production and reducing our dependency on the fossil based, hydrogen rich gas. PMID:24043264

  20. Crystallographic Stability of Metastable Phase Formed by Containerless Processing in REFeO3 (RE: Rare-Earth Element)

    NASA Technical Reports Server (NTRS)

    Kuribayashi, Kazuhiko; Kumar, M. S. Vijaya

    2012-01-01

    Undercooling a melt often facilitates a metastable phase to nucleate preferentially. Although the classical nucleation theory shows that the most critical factor for forming a metastable phase is the interface free energy, the crystallographic stability is also indispensable for the phase to be frozen at ambient temperature. In compound materials such as oxides, authors have suggested that the decisive factors for forming a critical nucleus are not only the free energy difference but also the difference of the entropy of fusion between stable and metastable phases. In the present study, using REFeO3 (RE: rare-earth element) as a model material, we investigate the formation of a metastable phase from undercooled melts with respect to the competitive nucleation and crystallographical stabilities of both phases.

  1. Phase transition method to form Group 6A nanoparticles on carbonaceous templates.

    PubMed

    Youn, Hee-Chang; Jegal, Jong-Pil; Park, Sang-Hoon; Kim, Hyun-Kyung; Park, Ho Seok; Roh, Kwang Chul; Kim, Kwang-Bum

    2014-03-25

    Considerable effort has been made to develop unique methods of preparing and characterizing nanoparticles and nanocomposites in order to exploit the true potential of nanotechnology. We used a facile, versatile phase-transition method for forming Group 6A nanoparticles on carbonaceous templates to produce homogeneous 5-10 nm diameter Group 6A nanoparticles on carbon nanotubes (CNTs) and reduced graphene oxide (RGO), to obtain nanocomposites. The method involved melting and recrystallizing mixtures of elemental sulfur and either CNTs or RGO on carbonaceous templates. The surface tension and hydrophilicity of the molten Group 6A species surfaces and the oxygen functional groups on the carbonaceous template surfaces were considered in depth to provide important guidelines for forming Group 6A nanoparticles on carbonaceous templates. The surface tension of the molten Group 6A species should be intrinsically low, leading to effective wetting on the carbonaceous template. In addition, the molten Group 6A species hydrophilic surfaces were essential for enabling hydrophilic-hydrophilic interaction for selective wetting at the oxygen functional groups on the carbonaceous template, leading to the heterogeneous nucleation of nanoparticles. Furthermore, the size and morphology (isolated vs layer-like) of the Group 6A nanoparticles were tuned by adjusting the oxidation state of the carbonaceous template. We investigated the potential application of the nanocomposites prepared using this method to cathode materials in lithium-sulfur secondary batteries. PMID:24499384

  2. Preparation of porous microsphere-scaffolds by electrohydrodynamic forming and thermally induced phase separation.

    PubMed

    Ghanbar, Hanif; Luo, C J; Bakhshi, Poonam; Day, Richard; Edirisinghe, Mohan

    2013-07-01

    The availability of forming technologies able to mass produce porous polymeric microspheres with diameters ranging from 150 to 300 μm is significant for some biomedical applications where tissue augmentation is required. Moreover, appropriate assembly of microspheres into scaffolds is an important challenge to enable direct usage of the as-formed structures in treatments. This work reports the production of poly (glycolic-co-lactic acid) and poly (ε-caprolactone) microspheres under ambient conditions using one-step electrohydrodynamic jetting (traditionally known as atomisation) and thermally induced phase separation (TIPS). To ensure robust production for practical uses, this work presents 12 comprehensive parametric mode mappings of the diameter distribution profiles of the microspheres obtained over a broad range of key processing parameters and correlating of this with the material parameters of 5 different polymer solutions of various concentrations. Poly (glycolic-co-lactic acid) (PLGA) in Dimethyl carbonate (DMC), a low toxicity solvent with moderate conductivity and low dielectric constant, generated microspheres within the targeted diameter range of 150-300 μm. The fabrication of the microspheres suitable for formation of the scaffold structure is achieved by changing the collection method from distilled water to liquid nitrogen and lyophilisation in a freeze dryer. PMID:23623059

  3. Depletion Interactions: Effects of Added Homopolymer on Ordered Phases Formed by Spherical Block Copolymer Micelles

    SciTech Connect

    Abbas, Sayeed; Lodge, Timothy P.

    2008-12-09

    Three distinct poly(styrene-b-isoprene) (SI) diblock copolymers with molecular weights of 16-16, 38-14, and 50-13 kDa for styrene and isoprene, respectively, formed spherical micelles when dissolved in diethyl phthalate (DEP). Since DEP is a styrene-selective solvent, micelles with polyisoprene in the core and polystyrene in the corona were formed. At block copolymer concentrations of 20%, 16%, and 14% in DEP, the spherical micelles of SI(16-16), SI(38-14), and SI(50-13) pack onto a face-centered cubic (FCC) lattice, a mixture of FCC and body-centered cubic (BCC) lattices, and a BCC lattice, respectively. Polystyrene homopolymers with molecular weights of 4, 48, and 180 kDa were added to these ordered solutions. The following general trends were observed: the FCC phase tended to disorder, and samples that originally behaved like soft solids exhibited liquidlike flow behavior. The effect increased strongly with both the molecular weight and concentration of homopolymer in the solution. Furthermore, the BCC lattice tended to be displaced by the FCC lattice, or to disorder, when homopolymer was added. These results can be explained by invoking depletion interactions, which have been studied extensively in colloid/polymer mixtures. However, the phenomenon differs in certain details from colloidal systems because the addition of homopolymer can also influence the aggregation number of the micelles, which in turn affects the lattice packing of the micelles.

  4. Isomers and conformational barriers of gas phase nicotine, nornicotine and their protonated forms

    SciTech Connect

    Yoshida, Tomoki; Farone, William A.; Xantheas, Sotiris S.

    2014-07-17

    We report extensive conformational searches of the neutral nicotine, nornicotine and their protonated analogs that are based on ab-initio second order Møller-Plesset perturbation (MP2) electronic structure calculations. Initial searches were performed with the 6-31G(d,p) and the energetics of the most important structures were further refined from geometry optimizations with the aug-cc-pVTZ basis set. Based on the calculated free energies at T=298 K for the gas phase molecules, neutral nicotine has two dominant trans conformers, whereas neutral nornicotine is a mixture of several conformers. For nicotine, the protonation on both the pyridine and the pyrrolidine sites is energetically competitive, whereas nornicotine prefers protonation on the pyridine nitrogen. The protonated form of nicotine is mainly a mixture of two pyridine-protonated trans conformers and two pyrrolidine-protonated trans conformers, whereas the protonated form of nornicotine is a mixture of four pyridine-protonated trans conformers. Nornicotine is conformationally more flexible than nicotine, however it is less protonated at the biologically important pyrrolidine nitrogen site. The lowest energy isomers for each case were found to interconvert via low (< 6 kcal/mol) rotational barriers around the pyridine-pyrrolidine bond.

  5. Hydrogenolysis of Glycerol to Propylene Glycol on Nanosized Cu-Zn-Al Catalysts Prepared Using Microwave Process.

    PubMed

    Kim, Dong Won; Ha, Sang Ho; Moon, Myung Jun; Lim, Kwon Taek; Ryu, Young Bok; Lee, Sun Do; Lee, Man Sig; Hong, Seong-Soo

    2015-01-01

    Cu-Zn-Al catalysts were prepared using microwave-assisted process and co-precipitation methods. The prepared catalysts were characterized by XRD, BET, XPS and TPD of ammonia and their catalytic activity for the hydrogenolysis of glycerol to propylene glycol was also examined. The XRD patterns of Cu/Zn/Al mixed catalysts show CuO and ZnO crystalline phase regardless of preparation method. The highest glycerol hydrogenolysis conversion is obtained with the catalyst having a Cu/Zn/Al ratio of 2:2:1. Hydrogen pre-reduction of catalysts significantly enhanced both glycerol conversions and selectivity to propylene glycol. The glycerol conversion increased with an increase of reaction temperature. However, the selectivity to propylene glycol increased with an increase of temperature, and then declined to 30.5% at 523 K. PMID:26328420

  6. Glycerol oxidation using gold-containing catalysts.

    PubMed

    Villa, Alberto; Dimitratos, Nikolaos; Chan-Thaw, Carine E; Hammond, Ceri; Prati, Laura; Hutchings, Graham J

    2015-05-19

    Glycerol is an important byproduct of biodiesel production, and it is produced in significant amounts by transesterification of triglycerides with methanol. Due to the highly functionalized nature of glycerol, it is an important biochemical that can be utilized as a platform chemical for the production of high-added-value products. At present, research groups in academia and industry are exploring potential direct processes for the synthesis of useful potential chemicals using catalytic processes. Over the last 10 years, there has been huge development of potential catalytic processes using glycerol as the platform chemical. One of the most common processes investigated so far is the catalytic oxidation of glycerol at mild conditions for the formation of valuable oxygenated compounds used in the chemical and pharmaceutical industry. The major challenges associated with the selective oxidation of glycerol are (i) the control of selectivity to the desired products, (ii) high activity and resistance to poisoning, and (iii) minimizing the usage of alkaline conditions. To address these challenges, the most common catalysts used for the oxidation of glycerol are based on supported metal nanoparticles. The first significant breakthrough was the successful utilization of supported gold nanoparticles for improving the selectivity to specific products, and the second was the utilization of supported bimetallic nanoparticles based on gold, palladium, and platinum for improving activity and controlling the selectivity to the desired products. Moreover, the utilization of base-free reaction conditions for the catalytic oxidation of glycerol has unlocked new pathways for the production of free-base products, which facilitates potential industrial application. The advantages of using gold-based catalysts are the improvement of the catalyst lifetime, stability, and reusability, which are key factors for potential commercialization. In this Account, we discuss the advantages of the

  7. Anaerobic digestion of glycerol and co-digestion of glycerol and pig manure.

    PubMed

    Nuchdang, Sasikarn; Phalakornkule, Chantaraporn

    2012-06-30

    The potential of glycerol obtained from transesterification of waste cooking oil as a main carbon source for biogas production was investigated. The glycerol was highly contaminated with oils and fats and was pretreated with sulfuric acid. Using a carbon source of glucose as a control, we compared biogas production from the acid-treated glycerol in a synthetic medium and the acid-treated glycerol mixed with pig manure. The anaerobic digestion of acid-treated glycerol with supplement in a synthetic medium was found to be satisfactory at organic loading rates (OLR) between 1.3, 1.6 and 2.6 g chemical oxygen demand (COD) L(-1) d(-1). The maximum methane yield of 0.32 L at Standard temperature and pressure (STP) g(-1) COD removal was achieved at an OLR of 1.6 g COD L(-1) d(-1) and the methane content was 54% on an average. At a higher organic loading rate of 5.4 g COD L(-1) d(-1), the propionic acid to acetic acid ratio was higher than the critical threshold limit for metabolic imbalance. Anaerobic digestion of acid-treated glycerol with pig manure was also investigated at the COD ratio of 80:20 (glycerol:pig manure). The anaerobic digestion of acid-treated glycerol with pig manure was found to be satisfactory at organic loading rates between 1.3, 1.7, 2.9 and 5.0 g COD L(-1) d(-1) in terms of COD reduction (>80%) and methane content of (62% on an average). However, the biogas production rate was found to significantly decrease at the highest load. The maximum methane yield of 0.24 L STP g(-1) COD removal was achieved at an OLR of 1.3 g COD L(-1) d(-1). PMID:22417895

  8. Anaerobic pathways of glycerol dissimilation by Enterobacter agglomerans CNCM 1210: limitations and regulations.

    PubMed

    Barbirato, F; Astruc, S; Soucaille, P; Camarasa, C; Salmon, J M; Bories, A

    1997-07-01

    Continuous cultures of Enterobacter agglomerans CNCM 1210 were performed under regulated pH conditions (pH 7.0) with glycerol or glucose (20 g l-1) as carbon source. Cultures grown on glucose produced mainly acetate, ethanol and formate. In contrast, 1,3-propanediol (PPD) was the main product with glycerol. The carbon flow distribution at branching metabolic points was investigated. Higher PPD yields with increased dilution rate were correlated with an important increase in the relative ratio of glycerol dehydratase to glycerol dehydrogenase. Determination of intracellular triose-phosphate and fructose 1,6-biphosphate concentrations demonstrated that glyceraldehyde-3-phosphate dehydrogenase is the limiting step in glycerol dissimilation. At the pyruvate branching point, pyruvate dehydrogenase (PDH) activity was systematically detected. The pyruvate flow shifted to PDH is suspected to represent up to 22% of the acetyl-CoA formed. In addition, this enzyme pattern combined with the enhanced in vivo lactate dehydrogenase activity at high growth rates, was correlated with a decrease in the pyruvate formate-lyase activity. A regulation of this latter enzyme by the accumulation of triose-phosphate is suspected. PMID:9245823

  9. Micron-sized structure in a thin glycerol film revealed by fluorescent probes.

    PubMed

    Xia, Ted; Xiao, Liantuan; Orrit, Michel

    2009-12-01

    We report on micrometer-sized structures in supercooled glycerol observed by imaging fluorescent probes at the temperatures close to, but above, the glass transition temperature (190 K). Two distinct heterogeneous patterns of the fluorescence intensity were detected, depending on how fast the sample was cooled down. In a slowly cooled sample, we observed a Swiss cheese-like pattern in which many micrometer-sized dark spots were nucleated in a bright background. A quickly cooled sample resulted in a spinodal decomposition pattern where many bright island-like features on micrometer scale were dispersed in a dark matrix. Similar patterns were seen earlier in triphenyl phosphite, another molecular liquid, which shows solid-like behavior at temperatures above its glass transition. Once the heterogeneous patterns are formed in the glycerol, they can persist for days, unless the samples are heated above 260 K for more than 10 h. Such heterogeneous patterns are ascribed to differential dye distributions in the glycerol film, pointing to long-lived and micrometer-scale density fluctuations in supercooled glycerol. The observation of such heterogeneity may provide additional understanding on how supercooled glycerol behaves before it turns into a glass. PMID:19929008

  10. Use of raw glycerol to produce oil rich in polyunsaturated fatty acids by a thraustochytrid.

    PubMed

    Scott, Spencer D; Armenta, Roberto E; Berryman, Kevin T; Norman, Andrew W

    2011-03-01

    Glucose is the typical carbon source for producing microbial polyunsaturated fatty acids (PUFA) with single cell microorganisms such as thraustochytrids. We assessed the use of a fish oil derived glycerol by-product (raw glycerol), produced by a fish oil processing plant, as a carbon source to produce single cell oil rich in polyunsaturated fatty acids (PUFA), notably docosahexaenoic acid (DHA). These results were compared to those obtained when using analytical grade glycerol, and glucose. The thraustochytrid strain tested produced similar amounts of oil and PUFA when grown with both types of glycerol, and results were also similar to those obtained using glucose. After 6 days of fermentation, approximately 320 mg/g of oil, and 145 mg/g of PUFA were produced with all carbon sources tested. All oils produced by our strain were 99.95% in the triacylglycerol form. To date, this is the first report of using raw glycerol derived from fish oil for producing microbial triglyceride oil rich in PUFA. PMID:22112910

  11. Glycerol as a substrate for aerobic succinate production in minimal medium with Corynebacterium glutamicum

    PubMed Central

    Litsanov, Boris; Brocker, Melanie; Bott, Michael

    2013-01-01

    Corynebacterium glutamicum, an established microbial cell factory for the biotechnological production of amino acids, was recently genetically engineered for aerobic succinate production from glucose in minimal medium. In this work, the corresponding strains were transformed with plasmid pVWEx1-glpFKD coding for glycerol utilization genes from Escherichia coli. This plasmid had previously been shown to allow growth of C. glutamicum with glycerol as sole carbon source. The resulting strains were tested in minimal medium for aerobic succinate production from glycerol, which is a by-product in biodiesel synthesis. The best strain BL-1/pVWEx1-glpFKD formed 79 mM (9.3 g l−1) succinate from 375 mM glycerol, representing 42% of the maximal theoretical yield under aerobic conditions. A specific succinate production rate of 1.55 mmol g−1 (cdw) h−1 and a volumetric productivity of 3.59 mM h−1 were obtained, the latter value representing the highest one currently described in literature. The results demonstrate that metabolically engineered strains of C. glutamicum are well suited for aerobic succinate production from glycerol. PMID:22513227

  12. Antioxidant behavior of 1-feruloyl-sn-glycerol and 1,3-diferuloyl-sn-glycerol in phospholipid liposomes 1

    Technology Transfer Automated Retrieval System (TEKTRAN)

    1-Feruloyl-sn-glycerol (FG) and 1,3-diferuloyl-sn-glycerol (DFG) are two natural plant compounds that may be useful in cosmeceutical, food, and skin care applications because of excellent antioxidant properties. FG and DFG enzymatically synthesized through esterification of glycerol and soybean oil...

  13. Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Viscoelastic properties have been determined for poly(glycerol-co-glutaric acid) films synthesized from Lewis acid-catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125 degrees C to form polymer films. The polymers were evaluated ...

  14. Glycerol-3-phosphate is a critical mobile inducer of systemic immunity in plants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Glycerol-3-phosphate (G3P) is an important metabolite that contributes to the growth and disease-related physiologies of prokaryotes, plants, animals and humans alike. Here we show that G3P serves as the inducer of an important form of broad-spectrum immunity in plants, termed systemic acquired resi...

  15. Structure of olefin-imidacloprid and gas-phase fragmentation chemistry of its protonated form.

    PubMed

    Fusetto, Roberto; White, Jonathan M; Hutton, Craig A; O'Hair, Richard A J

    2016-02-01

    One of the major insect metabolites of the widely used neonicotinoid insecticide imidacloprid, 1 (1-[(6-chloro-3-pyridinyl)methyl]-N-nitro-1H-imidazol-2-amine), is the olefin 2. To better understand how the structure of olefin 2 relates to the gas-phase fragmentation of its protonated form, 2H(+), X-ray crystallography, tandem mass spectrometry experiments and DFT calculations were carried out. Olefin 2 was found to be in a tautomeric form where the proton is on the N(1) position of the imidazole ring and forms a hydrogen bond to one of the oxygen atoms of the coplanar nitroamine group. Under conditions of low-energy collision-induced dissociation (CID) in a linear ion trap, 2H(+), formed via electrospray ionization (ESI), fragments via a major loss of water, together with minor competing losses of HNO2 and NO2•.This contrasts with 1H+, which mainly undergoes bond homolysis via NO2• loss. Thus, installation of the double bond in 2 plays a key role in facilitating the loss of water. DFT calculations, carried out using the B3LYP/6-311G++(d,p) level of theory, revealed that loss of water was energetically more favourable compared to HNO2 and NO2• loss. Three multistep, energetically accessible mechanisms were identified for loss of water from 2H(+), and these have the following barriers: (I) direct proton transfer from N(5) of the pyridine to O(1) on the NO2 group (119 kJ mol(-1)); (II) rotation of the N(2)-N(4) bond (117 kJ mol(-1)); (III) 1,3-intramolecular proton transfer between the two oxygen atoms of the NO2 group (145 kJ mol(-1)). Given that the lowest barrier for the losses of HNO2 and NO2• is 156 kJ mol(-1), it is likely that all three water loss mechanisms occur concurrently. PMID:26726997

  16. Yeast Fps1 glycerol facilitator functions as a homotetramer.

    PubMed

    Beese-Sims, Sara E; Lee, Jongmin; Levin, David E

    2011-12-01

    The Saccharomyces cerevisiae Fps1 glycerol channel is a member of the major intrinsic protein (MIP) family of plasma membrane channel proteins that functions in osmoregulatory pathways to transport glycerol passively out of the cell. The MIP family is subdivided into members that are selectively permeable to water (aquaporins) and those permeated by glycerol (aquaglyceroporins or glycerol facilitators). Although aquaporins function as homo-tetramers with each monomer possessing its own channel, previous studies have suggested that aquaglyceroporins may function as monomers. Here we provide both genetic and biochemical evidence that Fps1 functions as a homotetramer to regulate glycerol transport in yeast. PMID:22030956

  17. Acetylcholinesterase from Apis mellifera head. Evidence for amphiphilic and hydrophilic forms characterized by Triton X-114 phase separation.

    PubMed Central

    Belzunces, L P; Toutant, J P; Bounias, M

    1988-01-01

    The polymorphism of bee acetylcholinesterase was studied by sucrose-gradient-sedimentation analysis and non-denaturing electrophoretic analysis of fresh extracts. Lubrol-containing extracts exhibited only one form, which sedimented at 5 S when analysed on high-salt Lubrol-containing gradients and 6 S when analysed on low-salt Lubrol-containing gradients. The 5 S/6 S form aggregated upon removal of the detergent when sedimented on detergent-free gradients and was recovered in the detergent phase after Triton X-114 phase separation. Thus the 5 S/6 S enzyme corresponds to an amphiphilic acetylcholinesterase form. In detergent-free extracts three forms, whose apparent sedimentation coefficients are 14 S, 11 S and 7 S, were observed when sedimentations were performed on detergent-free gradients. Sedimentation analyses on detergent-containing gradients showed only a 5 S peak in high-salt detergent-free extracts and a 6 S peak, with a shoulder at about 7 S, in low-salt detergent-free extracts. Electrophoretic analysis in the presence of detergent demonstrated that the 14 S and 11 S peaks corresponded to aggregates of the 5 S/6 S form, whereas the 7 S peak corresponded to a hydrophilic acetylcholinesterase form which was recovered in the aqueous phase following Triton X-114 phase separation. The 5 S/6 S amphiphilic form could be converted into a 7.1 S hydrophilic form by phosphatidylinositol-specific phospholipase C digestion. Images Fig. 3. Fig. 6. PMID:2849414

  18. Cubic phase-forming dry powders for controlled drug delivery on mucosal surfaces.

    PubMed

    Moebus, K; Siepmann, J; Bodmeier, R

    2012-01-30

    The purpose of this study was to prepare and physicochemically characterize protein-loaded, glycerol monooleate (GMO)-based dry powder systems, which can be used for the controlled mucosal delivery of macromolecules (e.g., nasal, buccal, pulmonary). Bovine serum albumin (BSA)-loaded powders were prepared by spray-drying, freeze-drying and/or spray-freezing using different types of carrier materials, including mannitol, polyvinyl pyrrolidone (PVP 25) and polyethylene glycols (PEGs). The systems were characterized by optical and polarized light microscopy, X-ray powder diffraction, gel electrophoresis and diffusion studies. The type of carrier material strongly affected the resulting particle size and shape. The presence of GMO effectively slowed down BSA release. Importantly, broad ranges of release patterns could be achieved by varying the type of preparation method and composition of the dry powders. In all cases, the primary structure of the BSA remained intact. GMO, which is a wax solid at room temperature, has been successfully converted into dry powder formulations that offer potential for the controlled mucosal delivery of proteins. PMID:21963767

  19. Anaerobic treatment of crude glycerol from biodiesel production.

    PubMed

    Nakazawa, M M; Silva Júnior, W R S; Kato, M T; Gavazza, S; Florencio, L

    2015-01-01

    In this study, we evaluated the use of an up-flow anaerobic sludge blanket (UASB) reactor to treat crude glycerol obtained from cottonseed biodiesel production. The laboratory-scale UASB reactor (7.0 L) was operated at ambient temperature of 26.5°C with chemical oxygen demand (COD) concentrations between 0.5 and 8.0 g/L. The volatile fatty acid contents, pH, inorganic salt contents and biogas production were monitored during a 280-day experimental period. Molecular biology techniques were used to assess the microbial diversity in the bioreactor. The reactor achieved COD removal efficiencies of up to 92% except during one phase when the efficiency decreased to 81%. Biogas production remained stable throughout the experimental period, when the fraction converted to methane reached values as high as 68%. The profile of the denaturing gradient gel electrophoresis (DGGE) bands suggested slight changes in the microbial community during reactor operation. The overall results indicated that the crude glycerol from biodiesel production can serve as a suitable substrate for anaerobic degradation with a stable reactor performance and biogas production as long as the applied organic loads are up to 8.06 kg COD/m3·d. PMID:26465309

  20. Use of molecular dynamics to assess the biophysiological role of hydroxyl groups in glycerol dyalkyl glycerol teraethers

    NASA Astrophysics Data System (ADS)

    Huguet, Carme; Costenaro, Lionel; Fietz, Susanne; Daura, Xavier

    2015-04-01

    The cell membrane of some Archaea is constituted by lipids that span the whole membrane width and contain two alkyl chains bound by two glycerol groups (glycerol dyalkyl glycerol teraethers or GDGTs). These lipids confer stability to the membrane in mesophile to extremophile environments. Besides the more frequently studied isoprenoid archaeal lipids, both mono- and dihydroxy-GDGTs (OH-GDGT) have been recently reported to occur in marine sediments (1). OH-GDGTs contain up to two cyclopentane moieties and have been identified in both core and intact forms. In 2013, a correlation between OH-GDGTs and temperature was reported, with higher relative OH-GDGT abundances at high latitudes (2,3). The physiological function of the hydroxyl group in a GDGT is not yet known, but given the field results, it could be linked to an adaptation of the membrane to changes in temperature. For hydroxydiether lipid cores in methanogenic bacteria, it has been postulated that the hydroxyl group may alter the cell membrane properties: either extending the polar head group region or creating a hydrophilic pocket (4). It has also been suggested that the hydroxylation of the biphytany (l) moiety may result in enhanced membrane rigidity (1). To improve our understanding of the effect of the hydroxylation on physical properties of membranes, we performed molecular-dynamics simulations of GDGT membranes presenting and lacking these additional OH groups. This is an approach with a great development potential in the archaea lipid field, especially in relation to proxy validation. Our results indicate that the addition of an OH increases the membrane fluidity, thus providing an advantage in cold environments. We also observe a widening of the polar head group area, which could enhance transport. 1. Liu et al. 2012, GCA 2. Huguet et al. 2013, Org. Geochem 3. Fietz et al. 2013 4. Sprott et al. 1990. J. Biol. Chem. 265, 13735-13740.

  1. Phase transformations of the FePO4 catalyst in the oxidative dehydrogenation to form an alkyl methacrylate

    NASA Astrophysics Data System (ADS)

    Khan, F. B.; Bharuth-Ram, K.; Friedrich, H. B.

    2010-04-01

    A phase specific iron orthophosphate catalyst, FePO4, was synthesized and subjected to oxidative dehydrogenation reactions to form an alkyl methacrylate. The phases of the catalyst, before and after the reactions, were characterized by Mössbauer spectroscopy. The Mössbauer spectra show the change of the catalyst precursor FePO4, tridymite-like phase (tdm), to the reduced form, iron(II) pyrophosphate, Fe2P2O7, and thereafter the phase change is governed by the temperatures of oxidation. X-ray diffraction and Mössbauer measurements on the spent catalyst, after using organic and water co-feeds, show a transformation of the catalyst to a mixture of phases which are condition specific.

  2. Oblique shock structures formed during the ablation phase of aluminium wire array z-pinches

    SciTech Connect

    Swadling, G. F.; Lebedev, S. V.; Niasse, N.; Chittenden, J. P.; Hall, G. N.; Suzuki-Vidal, F.; Burdiak, G.; Harvey-Thompson, A. J.; Bland, S. N.; De Grouchy, P.; Khoory, E.; Pickworth, L.; Skidmore, J.; Suttle, L.

    2013-02-15

    A series of experiments has been conducted in order to investigate the azimuthal structures formed by the interactions of cylindrically converging plasma flows during the ablation phase of aluminium wire array Z pinch implosions. These experiments were carried out using the 1.4 MA, 240 ns MAGPIE generator at Imperial College London. The main diagnostic used in this study was a two-colour, end-on, Mach-Zehnder imaging interferometer, sensitive to the axially integrated electron density of the plasma. The data collected in these experiments reveal the strongly collisional dynamics of the aluminium ablation streams. The structure of the flows is dominated by a dense network of oblique shock fronts, formed by supersonic collisions between adjacent ablation streams. An estimate for the range of the flow Mach number (M = 6.2-9.2) has been made based on an analysis of the observed shock geometry. Combining this measurement with previously published Thomson Scattering measurements of the plasma flow velocity by Harvey-Thompson et al.[Physics of Plasmas 19, 056303 (2012)] allowed us to place limits on the range of the ZT{sub e} of the plasma. The detailed and quantitative nature of the dataset lends itself well as a source for model validation and code verification exercises, as the exact shock geometry is sensitive to many of the plasma parameters. Comparison of electron density data produced through numerical modelling with the Gorgon 3D MHD code demonstrates that the code is able to reproduce the collisional dynamics observed in aluminium arrays reasonably well.

  3. Structural Properties, Order-Disorder Phenomena, and Phase Stability of Orotic Acid Crystal Forms.

    PubMed

    Braun, Doris E; Nartowski, Karol P; Khimyak, Yaroslav Z; Morris, Kenneth R; Byrn, Stephen R; Griesser, Ulrich J

    2016-03-01

    Orotic acid (OTA) is reported to exist in the anhydrous (AH), monohydrate (Hy1), and dimethyl sulfoxide monosolvate (SDMSO) forms. In this study we investigate the (de)hydration/desolvation behavior, aiming at an understanding of the elusive structural features of anhydrous OTA by a combination of experimental and computational techniques, namely, thermal analytical methods, gravimetric moisture (de)sorption studies, water activity measurements, X-ray powder diffraction, spectroscopy (vibrational, solid-state NMR), crystal energy landscape, and chemical shift calculations. The Hy1 is a highly stable hydrate, which dissociates above 135 °C and loses only a small part of the water when stored over desiccants (25 °C) for more than one year. In Hy1, orotic acid and water molecules are linked by strong hydrogen bonds in nearly perfectly planar arranged stacked layers. The layers are spaced by 3.1 Å and not linked via hydrogen bonds. Upon dehydration the X-ray powder diffraction and solid-state NMR peaks become broader, indicating some disorder in the anhydrous form. The Hy1 stacking reflection (122) is maintained, suggesting that the OTA molecules are still arranged in stacked layers in the dehydration product. Desolvation of SDMSO, a nonlayer structure, results in the same AH phase as observed upon dehydrating Hy1. Depending on the desolvation conditions, different levels of order-disorder of layers present in anhydrous OTA are observed, which is also suggested by the computed low energy crystal structures. These structures provide models for stacking faults as intergrowth of different layers is possible. The variability in anhydrate crystals is of practical concern as it affects the moisture dependent stability of AH with respect to hydration. PMID:26741914

  4. Structural Properties, Order–Disorder Phenomena, and Phase Stability of Orotic Acid Crystal Forms

    PubMed Central

    2016-01-01

    Orotic acid (OTA) is reported to exist in the anhydrous (AH), monohydrate (Hy1), and dimethyl sulfoxide monosolvate (SDMSO) forms. In this study we investigate the (de)hydration/desolvation behavior, aiming at an understanding of the elusive structural features of anhydrous OTA by a combination of experimental and computational techniques, namely, thermal analytical methods, gravimetric moisture (de)sorption studies, water activity measurements, X-ray powder diffraction, spectroscopy (vibrational, solid-state NMR), crystal energy landscape, and chemical shift calculations. The Hy1 is a highly stable hydrate, which dissociates above 135 °C and loses only a small part of the water when stored over desiccants (25 °C) for more than one year. In Hy1, orotic acid and water molecules are linked by strong hydrogen bonds in nearly perfectly planar arranged stacked layers. The layers are spaced by 3.1 Å and not linked via hydrogen bonds. Upon dehydration the X-ray powder diffraction and solid-state NMR peaks become broader, indicating some disorder in the anhydrous form. The Hy1 stacking reflection (122) is maintained, suggesting that the OTA molecules are still arranged in stacked layers in the dehydration product. Desolvation of SDMSO, a nonlayer structure, results in the same AH phase as observed upon dehydrating Hy1. Depending on the desolvation conditions, different levels of order–disorder of layers present in anhydrous OTA are observed, which is also suggested by the computed low energy crystal structures. These structures provide models for stacking faults as intergrowth of different layers is possible. The variability in anhydrate crystals is of practical concern as it affects the moisture dependent stability of AH with respect to hydration. PMID:26741914

  5. Silicon carbonate phase formed from carbon dioxide and silica under pressure.

    PubMed

    Santoro, Mario; Gorelli, Federico; Haines, Julien; Cambon, Olivier; Levelut, Claire; Garbarino, Gaston

    2011-05-10

    The discovery of nonmolecular carbon dioxide under high-pressure conditions shows that there are remarkable analogies between this important substance and other group IV oxides. A natural and long-standing question is whether compounds between CO(2) and SiO(2) are possible. Under ambient conditions, CO(2) and SiO(2) are thermodynamically stable and do not react with each other. We show that reactions occur at high pressures indicating that silica can behave in a manner similar to ionic metal oxides that form carbonates at room pressure. A silicon carbonate phase was synthesized by reacting silicalite, a microporous SiO(2) zeolite, and molecular CO(2) that fills the pores, in diamond anvil cells at 18-26 GPa and 600-980 K; the compound was then temperature quenched. The material was characterized by Raman and IR spectroscopy, and synchrotron X-ray diffraction. The experiments reveal unique oxide chemistry at high pressures and the potential for synthesis of a class of previously uncharacterized materials. There are also potential implications for CO(2) segregation in planetary interiors and for CO(2) storage. PMID:21518903

  6. Vesicles formed by mixed catanionic surfactants as novel pseudostationary phase in electrokinetic chromatography.

    PubMed

    Lu, Jie; Ni, Xinjiong; Cao, Yuhua; Ma, Xinyu; Cao, Guangqun

    2014-09-12

    In this paper, a novel pseudostationary phase (PSP), the vesicle formed from octyltriethylammonium bromide (C8NE3Br) and sodium dodecyl benzene sulfonate (SDBS), has been developed in electrokinetic chromatography (EKC). Physicochemical parameters of the mixture of catanionic surfactants such as ζ potential and size of the aggregates were characterized as the molar ratio of C8NE3Br to SDBS varied from 2:8 to 8:2 and total concentration of surfactants fixed at 20mM. At any ratio mentioned above, ζ potential of mixture of catanionic surfactants remained negative. The absolute values of ζ potential were even larger than in only SDBS system as the molar ratio of C8NE3Br to SDBS less than 4:6, and they decreased as increasing the ratio of cationic surfactants. The size of the aggregates became smaller as the ratio was close to 1. Unexpectedly, the size was smallest at ratio of 3:7 and 6:4, instead of at 5:5. Notably, coagulation did not occur in the catanionic system at any proportion of each other. TEM testified the formation of vesicles. The performance of the vesicle as PSP was evaluated by separating eight kinds of corticosteroids with EKC, these analytes were separated completely without any additives. Compared with SDS microemulsion modified with ionic liquid (IL) and polymeric micelle, the novel vesicle PSP had better separation performances. PMID:25064530

  7. Rad52 forms DNA repair and recombination centers during S phase

    PubMed Central

    Lisby, Michael; Rothstein, Rodney; Mortensen, Uffe H.

    2001-01-01

    Maintenance of genomic integrity and stable transmission of genetic information depend on a number of DNA repair processes. Failure to faithfully perform these processes can result in genetic alterations and subsequent development of cancer and other genetic diseases. In the eukaryote Saccharomyces cerevisiae, homologous recombination is the major pathway for repairing DNA double-strand breaks. The key role played by Rad52 in this pathway has been attributed to its ability to seek out and mediate annealing of homologous DNA strands. In this study, we find that S. cerevisiae Rad52 fused to green fluorescent protein (GFP) is fully functional in DNA repair and recombination. After induction of DNA double-strand breaks by γ-irradiation, meiosis, or the HO endonuclease, Rad52-GFP relocalizes from a diffuse nuclear distribution to distinct foci. Interestingly, Rad52 foci are formed almost exclusively during the S phase of mitotic cells, consistent with coordination between recombinational repair and DNA replication. This notion is further strengthened by the dramatic increase in the frequency of Rad52 focus formation observed in a pol12-100 replication mutant and a mec1 DNA damage checkpoint mutant. Furthermore, our data indicate that each Rad52 focus represents a center of recombinational repair capable of processing multiple DNA lesions. PMID:11459964

  8. Catalytic etherification of glycerol to produce biofuels over novel spherical silica supported Hyflon® catalysts.

    PubMed

    Frusteri, Francesco; Frusteri, Leone; Cannilla, Catia; Bonura, Giuseppe

    2012-08-01

    Etherification of glycerol (GLY) with isobutylene (IB) to produce biofuels was investigated in liquid phase using spherical silica supported Hyflon® catalysts (SSHC). As reference catalyst, Amberlyst® 15 (A-15) acid ion-exchange resin was used. Experiments were carried out in batch mode at a reaction temperature ranging from 323 to 343 K. SSHC were found to be very effective systems in etherification of glycerol with IB, providing cumulative di- and tri-ethers yields higher than that obtained by using A-15 catalyst. Furthermore, such catalysts were stable and easily reusable; no leaching of active phase was observed. The formation of poly-substituted ethers, suitable additives for conventional fuels, was favored by operating at an isobutylene/glycerol molar ratio >3 and low reaction time (<6 h); however, the concentration of mono-ether reached values lower than 3 wt.% only when SSHC catalyst was used. Turnover frequency of glycerol (TOF(GLY)) highlighted that SSHC systems were much more active than A-15 catalyst: the accessibility and nature of active sites and the surface properties of catalysts were indicated as the main factors affecting the catalytic behavior. A lower acid site density of SSHC than that of A-15 catalyst was decisive in preventing the occurrence of oligomerization reaction which leads to the formation of di-isobutylene (DIB), precursors of gummy products. PMID:22705542

  9. Tricontinuous Cubic Nanostructure and Pore Size Patterning in Mesostructured Silica Films Templated with Glycerol Monooleate

    PubMed Central

    Dunphy, Darren R.; Garcia, Fred L.; Kaehr, Bryan; Khripin, Constantine Y.; Collord, Andrew D.; Baca, Helen K.; Tate, Michael P.; Hillhouse, Hugh W.; Strzalka, Joseph W.; Jiang, Zhang; Wang, Jin; Brinker, C. Jeffrey

    2011-01-01

    The fabrication of nanostructured films possessing tricontinuous minimal surface mesophases with well-defined framework and pore connectivity remains a difficult task. As a new route to these structures, we introduce glycerol monooleate (GMO) as a template for evaporation-induced self-assembly. As deposited, a nanostructured double gyroid phase is formed, as indicated by analysis of grazing-incidence small-angle x-ray scattering data. Removal of GMO by UV/O3 treatment or acid extraction induces a phase change to a nanoporous body-centered structure which we tentatively identify as based on the IW-P surface. To improve film quality, we add a co-surfactant to the GMO in a mass ratio of 1:10; when this co-surfactant is cetyltrimethylammonium bromide, we find an unusually large pore size (8-12 nm) in acid extracted films, while UV/O3 treated films yield pores of only ca. 4 nm. Using this pore size dependence on film processing procedure, we create a simple method for patterning pore size in nanoporous films, demonstrating spatially-defined size-selective molecular adsorption. PMID:21572556

  10. Protease activation in glycerol-based deep eutectic solvents.

    PubMed

    Zhao, Hua; Baker, Gary A; Holmes, Shaletha

    2011-11-01

    Deep eutectic solvents (DESs) consisting of mixtures of a choline salt (chloride or acetate form) and glycerol are prepared as easily accessible, biodegradable, and inexpensive alternatives to conventional aprotic cation-anion paired ionic liquids. These DES systems display excellent fluidity coupled with thermal stability to nearly 200 °C. In this work, the transesterification activities of cross-linked proteases (subtilisin and α-chymotrypsin), immobilized on chitosan, were individually examined in these novel DESs. In the 1:2 molar ratio mixture of choline chloride/glycerol containing 3% (v/v) water, cross-linked subtilisin exhibited an excellent activity (2.9 μmo l min(-1) g(-1)) in conjunction with a selectivity of 98% in the transesterification reaction of N-acetyl-L-phenylalanine ethyl ester with 1-propanol. These highly encouraging results advocate more extensive exploration of DESs in protease-mediated biotransformations of additional polar substrates and use of DESs in biocatalysis more generally. PMID:21909232

  11. Protease activation in glycerol-based deep eutectic solvents

    PubMed Central

    Zhao, Hua; Baker, Gary A.; Holmes, Shaletha

    2011-01-01

    Deep eutectic solvents (DESs) consisting of mixtures of a choline salt (chloride or acetate form) and glycerol are prepared as easily accessible, biodegradable, and inexpensive alternatives to conventional aprotic cation-anion paired ionic liquids. These DES systems display excellent fluidity coupled with thermal stability to nearly 200 °C. In this work, the transesterification activities of cross-linked proteases (subtilisin and α-chymotrypsin), immobilized on chitosan, were individually examined in these novel DESs. In the 1:2 molar ratio mixture of choline chloride/glycerol containing 3% (v/v) water, cross-linked subtilisin exhibited an excellent activity (2.9 μmo l min−1 g−1) in conjunction with a selectivity of 98% in the transesterification reaction of N-acetyl-L-phenylalanine ethyl ester with 1-propanol. These highly encouraging results advocate more extensive exploration of DESs in protease-mediated biotransformations of additional polar substrates and use of DESs in biocatalysis more generally. PMID:21909232

  12. Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate.

    PubMed

    Waghmare, Govind V; Vetal, Mangesh D; Rathod, Virendra K

    2015-01-01

    The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100W), duty cycle 50% and temperature (60°C) in a relatively short reaction time (4h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4h as compared to conventional stirring method (14h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion. PMID:25069889

  13. Laser Annealing to Form High-Temperature Phase of FeS2

    NASA Astrophysics Data System (ADS)

    Umehara, Mitsutaro; Takeda, Yasuhiko; Azuma, Hirozumi; Motohiro, Tomoyoshi

    2012-02-01

    We fabricated single-phase pyrite thin films of FeS2 by laser annealing of multi-phase FeS2 films. Sputter-deposited FeS films followed by sulfurization in sulfur vapor at high temperatures were mainly composed of the high-temperature phase (pyrite) but contained a small amount of the low-temperature phase (marcasite) that likely grew when the samples were naturally cooled after the sulfurization. We applied the rapid cooling feature of laser annealing to preventing the marcasite phase formation. No trace of marcasite phase was observed in Raman spectra and X-ray diffraction patterns of the laser-annealed samples. We analyzed temporal evolution of the sample temperature during the laser-annealing processes to confirm that the laser heating induced phase change of the small amount of marcasite to pyrite and the rapid cooling prevented marcasite regrowth.

  14. Evidence for a glycerol pathway through aquaporin 1 (CHIP28) channels.

    PubMed

    Abrami, L; Tacnet, F; Ripoche, P

    1995-07-01

    Permeabilities to glycerol and small non-electrolytes of three Aquaporin 1 CHIP (AQP1) water channels were measured in AQP1 cRNA-injected Xenopus laevis oocytes and in human AQP1 channels reconstituted in proteoliposomes. By an "osmotic" swelling assay, significant increases of ethylene glycol, glycerol and 1,3-propanediol apparent permeability coefficients (P'solutes) were found in oocytes expressing human, rat and frog AQP1. p-Chloromercuribenzene sulphonate (pCMBS) and CuSO4 inhibited, by 95% and 58% respectively, apparent glycerol permeability (P'gly) in oocytes expressing human AQP1. pCMBS inhibition was reversed by beta-mercaptoethanol and CuSO4 inhibition was partly reversed by the Cu(2+)-binding peptide Gly-Gly-His. Tritiated glycerol uptakes confirmed the augmented P'gly value of AQP1 cRNA-injected oocytes. In contrast, no increases of urea, meso-erythritol, D-or L-threitol, xylitol and mannitol uptakes were detected. Stopped-flow light scattering experiments performed with human AQP1 proteoliposomes also revealed a much greater increase of P'gly than did those with protein-free liposomes; the initial rate of proteoliposomes also swelling was inhibited by 96.2% with HgCl2 and by 72.5% with CuSO4. In AQP1 cRNA-injected oocytes and in proteoliposomes, the value of the glycerol reflection coefficient was 0.74-0.80, indicating that water and glycerol share the same pathway. All these results provide strong evidence that water and certain small solutes permeate the AQP1 channels expressed at the surface of X. laevis oocytes or reconstituted in proteoliposomes. The urea exclusion suggests that the selectivity of the AQP1 channels not only depends on the size of the solutes but probably also on their flexibility and their ability to form H-bonds. PMID:7491270

  15. Biological Conversion of Glycerol to Ethanol by Enterobacter aerogenes

    NASA Astrophysics Data System (ADS)

    Nwachukwu, Raymond E. S.

    In a search to turn the economically and environmentally non-valuable "waste" streams of biodiesel production into a profitable byproduct, a mutant strain of Enterobacter aerogenes ATCC 13048 was developed by six-tube subculturing technique. This technique is based on the principle of adaptive evolution, and involved subculturing the bacterium in a tryptic soy broth without dextrose (TSB) containing specific glycerol and ethanol concentration for six consecutive times. Then, the six consecutive subculturing was repeated in a fresh TSB of higher glycerol and ethanol concentrations. A new mutant strain, E. aerogenes S012, which could withstand a combination of 200 g/l glycerol and 30 g/l ethanol concentrations, was developed. The wild and mutant strains were used for the fermentation of pure (P-) and recovered (R-) glycerol. Taguchi and full factorial methods of design of experiments were used to screen and optimize the important process factors that influence the microbial production of ethanol. A statistically sound regression model was used to establish the mathematical relationship between the process variables and ethanol production. Temperature of 38°C, agitation speed of 200 rpm, pH of 6.3-6.6, and microaerobic condition were the optimum process conditions. Different pretreatment methods to recover glycerol from the crude glycerol and the subsequent fermentation method showed that direct acidification using 85% H3PO4 was the best. The R-glycerol contained 51% pure glycerol and 21% methanol. The wild strain, E. aerogenes ATCC 13048, produced only 12 g/l and 12.8 g/l ethanol from 20 g/l P- and R-glycerol respectively, and could not utilize higher glycerol concentrations. The mutant, E. aerogenes S012, produced ethanol amount and yield of 43 g/l and 1.12 mol/mol-glycerol from P-glycerol, respectively within 96 h. It also produced ethanol amount and yield of 26.8 g/l and 1.07 mol/mol-glycerol, respectively, from R-glycerol within the same duration. In a

  16. Amorphous calcium phosphate is a major component of the forming fin bones of zebrafish: Indications for an amorphous precursor phase.

    PubMed

    Mahamid, Julia; Sharir, Amnon; Addadi, Lia; Weiner, Steve

    2008-09-01

    A fundamental question in biomineralization is the nature of the first-formed mineral phase. In vertebrate bone formation, this issue has been the subject of a long-standing controversy. We address this key issue using the continuously growing fin bony rays of the Tuebingen long-fin zebrafish as a model for bone mineralization. Employing high-resolution scanning and transmission electron microscopy imaging, electron diffraction, and elemental analysis, we demonstrate the presence of an abundant amorphous calcium phosphate phase in the newly formed fin bones. The extracted amorphous mineral particles crystallize with time, and mineral crystallinity increases during bone maturation. Based on these findings, we propose that this amorphous calcium phosphate phase may be a precursor phase that later transforms into the mature crystalline mineral. PMID:18753619

  17. Optical BEAMTAP beam-forming and jammer-nulling system for broadband phased-array antennas.

    PubMed

    Kriehn, G; Kiruluta, A; Silveira, P E; Weaver, S; Kraut, S; Wagner, K; Weverka, R T; Griffiths, L

    2000-01-10

    We present an approach to receive-mode broadband beam forming and jammer nulling for large adaptive antenna arrays as well as its efficient and compact optical implementation. This broadband efficient adaptive method for true-time-delay array processing (BEAMTAP) algorithm decreases the number of tapped delay lines required for processing an N-element phased-array antenna from N to only 2, producing an enormous savings in delay-line hardware (especially for large broadband arrays) while still providing the full NM degrees of freedom of a conventional N-element time-delay-and-sum beam former that requires N tapped delay lines with M taps each. This allows the system to adapt fully and optimally to an arbitrarily complex spatiotemporal signal environment that can contain broadband signals of interest, as well as interference sources and narrow-band and broadband jammers--all of which can arrive from arbitrary angles onto an arbitrarily shaped array--thus enabling a variety of applications in radar, sonar, and communication. This algorithm is an excellent match with the capabilities of radio frequency (rf) photonic systems, as it uses a coherent optically modulated fiber-optic feed network, gratings in a photorefractive crystal as adaptive weights, a traveling-wave detector for generating time delay, and an acousto-optic device to control weight adaptation. Because the number of available adaptive coefficients in a photorefractive crystal is as large as 10(9), these photonic systems can adaptively control arbitrarily large one- or two-dimensional antenna arrays that are well beyond the capabilities of conventional rf and real-time digital signal processing techniques or alternative photonic techniques. PMID:18337889

  18. Bio-transformation of Glycerol to 3-Hydroxypropionic Acid Using Resting Cells of Lactobacillus reuteri.

    PubMed

    Ramakrishnan, Gopi Gopal; Nehru, Ganesh; Suppuram, Pandiaraj; Balasubramaniyam, Sowmiya; Gulab, Brajesh Raman; Subramanian, Ramalingam

    2015-10-01

    Lactobacillus reuteri grown in MRS broth containing 20 mM glycerol exhibits 3.7-fold up-regulation of 3-hydroxypropionic acid (3-HP) pathway genes during the stationary phase. Concomitantly, the resting cells prepared from stationary phase show enhancement in bio-conversion of glycerol, and the maximum specific productivity (q p) is found to be 0.17 g 3-HP per g CDW per hour. The regulatory elements such as catabolite repression site in the up-stream of 3-HP pathway genes are presumed for the augmentation of glycerol bio-conversion selectively in stationary phase. However, in the repression mutant, the maximum q p of 3-HP persisted in the stationary phase-derived resting cells indicating the role of further regulatory features. In the production stage, the external 3-HP concentration of 35 mM inhibits 3-HP synthesis. In addition, it has also moderated 1,3-propanediol formation, as it is a redox bio-catalysis involving NAD(+)/NADH ratio of 6.5. Repeated batch bio-transformation has been used to overcome product inhibition, and the total yield (Ypx) of 3-HP from the stationary phase-derived biomass is 3.3 times higher than that from the non-repeated mode. With the use of appropriate gene expression condition and repeated transfer of biomass, 3-HP produced in this study can be used for low-volume, high-value applications. PMID:26204968

  19. Codon-Optimized NADH Oxidase Gene Expression and Gene Fusion with Glycerol Dehydrogenase for Bienzyme System with Cofactor Regeneration

    PubMed Central

    Zhou, Qiang; Wang, Shizhen

    2015-01-01

    NADH oxidases (NOXs) play an important role in maintaining balance of NAD+/NADH by catalyzing cofactors regeneration. The expression of nox gene from Lactobacillus brevis in Escherichia coli BL21 (BL21 (DE3)) was studied. Two strategies, the high AT-content in the region adjacent to the initiation codon and codon usage of the whole gene sequence consistent with the host, obtained the NOX activity of 59.9 U/mg and 73.3 U/mg (crude enzyme), with enhanced expression level of 2.0 and 2.5-folds, respectively. Purified NOX activity was 213.8 U/mg. Gene fusion of glycerol dehydrogenase (GDH) and NOX formed bifuctional multi-enzymes for bioconversion of glycerol coupled with coenzyme regeneration. Kinetic parameters of the GDH-NOX for each substrate, glycerol and NADH, were calculated as Vmax(Glycerol) 20 μM/min, Km(Glycerol) 19.4 mM, Vmax (NADH) 12.5 μM/min and Km (NADH) 51.3 μM, respectively, which indicated the potential application of GDH-NOX for quick glycerol analysis and dioxyacetone biosynthesis. PMID:26115038

  20. Investigation of various phases of Fe-Si structures formed in Si by low energy Fe ion implantation

    NASA Astrophysics Data System (ADS)

    Lakshantha, Wickramaarachchige J.; Dhoubhadel, Mangal S.; Reinert, Tilo; McDaniel, Floyd D.; Rout, Bibhudutta

    2015-12-01

    The compositional phases of ion beam synthesized Fe-Si structures at two high fluences (0.50 × 1017 atoms/cm2 and 2.16 × 1017 atoms/cm2) were analyzed using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The distribution of Fe implanted in Si was simulated using a dynamic simulation code (TRIDYN) incorporating target sputtering effects. The Fe depth profiles in the Si matrix were confirmed with Rutherford backscattering spectrometry (RBS) and XPS depth profiling using Ar-ion etching. Based on XPS binding energy shift and spectral asymmetry, the distribution of stable Fe-Si phases in the substrate was analyzed as a function of depth. Results indicate Fe implantation with a fluence of 0.50 × 1017 atoms/cm2 and subsequent thermal annealing produce mainly the β-FeSi2 phase in the whole thickness of the implanted region. But for the samples with a higher fluence Fe implantation, multiple phases are formed. Significant amount of Fe3Si phase are found at depth intervals of 14 nm and 28 nm from the surface. Initially, as-implanted samples show amorphous Fe3Si formation and further thermal annealing at 500 °C for 60 min formed crystalline Fe3Si structures at the same depth intervals. In addition, thermal annealing at 800 °C for 60 min restructures the Fe3Si clusters to form FeSi2 and FeSi phases.

  1. Mulled coal: A beneficiated coal form for use as a fuel or fuel intermediate. Phase 3, Final report

    SciTech Connect

    Not Available

    1993-08-01

    Energy International Corporation (El) was awarded a contract to evaluate a new concept for utilization of the fine coal wetcake produced by many of the physical beneficiation processes now under development. EI proposed development of a stabilized wetcake with properties that would facilitate storage, handling, transport, and subsequent conversion of the material into Coal-Water Fuel (CWF) at the point of use. The effort was performed in three phases. Phase I established the technical feasibility of stabilizing the fine coal ``wetcake`` in a form that can be readily handled and converted into a desired fuel form at the combustion site. The preferred form of stabilized ``wetcake`` was a granular free flowing material with the moisture encapsulated with the fine coal particles. The product was termed Mulled Coal. Phase I results indicated that the Mulled Coal was not only suitable as a CWF intermediate, but also had potential as a solid fuel. Phase II demonstrated the utilization of the Mulled Coal process to store and move fine coal products as a stable ``wetcake.`` Tasks in this phase tested components of the various systems required for storage, handling and combustion of the fine coals. Phase III expanded the technology by: 1. Evaluating Mulled Coal from representative coals from all producing regions in the US. 2. Development of bench-scale tests. 3. Design, construction, and operation of a 1 ton/hr continuous processing unit. 4. Evaluation of the effects of beneficiation. and 5. Developing an estimate of capital and operating costs for commercial units.

  2. Direct visualization of β phase causing intergranular forms of corrosion in Al–Mg alloys

    SciTech Connect

    Yang, Young-Ki Allen, Todd

    2013-06-15

    For a more effective examination of microstructure in Al–Mg alloys, a new etching solution has been developed; dissolved ammonium persulfate in water. It is demonstrated how β phase (Al{sub 3}Mg{sub 2}) in Al–Mg alloys respond to this solution using samples of a binary Al–Mg alloy and a commercial 5083 aluminum alloy. Nanometer sized β phase is clearly visualized for the first time using scanning electron microscopy (SEM) instead of transmission electron microscopy (TEM). It is anticipated that direct and unambiguous visualization of β phase will greatly augment intergranular corrosion research in 5xxx series aluminum alloys. - Highlights: • Nanometer sized β phase in Al-10% Mg is first clearly visualized with SEM. • Nanometer sized β phase in wrought alloy 5083 is first clearly visualized with SEM. • Grain boundary decorating β phase and isolated sponge-like β phase are shown. • This phase is confirmed to be β phase using composition analysis.

  3. Suppressed Release of Clarithromycin from Tablets by Crystalline Phase Transition of Metastable Polymorph Form I.

    PubMed

    Fujiki, Sadahiro; Watanabe, Narumi; Iwao, Yasunori; Noguchi, Shuji; Mizoguchi, Midori; Iwamura, Takeru; Itai, Shigeru

    2015-08-01

    The pharmaceutical properties of clarithromycin (CAM) tablets containing the metastable form I of crystalline CAM were investigated. Although the dissolution rate of form I was higher than that of stable form II, the release of CAM from form I tablet was delayed. Disintegration test and liquid penetration test showed that the disintegration of the tablet delayed because of the slow penetration of an external solution into form I tablet. Investigation by scanning electron microscopy revealed that the surface of form I tablet was covered with fine needle-shaped crystals following an exposure to the external solution. These crystals were identified as form IV crystals by powder X-ray diffraction. The phenomenon that CAM releases from tablet was inhibited by fine crystals spontaneously formed on the tablet surface could be applied to the design of sustained-release formulation systems with high CAM contents by minimizing the amount of functional excipients. PMID:26053058

  4. Synthesis and hydrolytic behaviour of glycerol-1,2-diibuprofenate-3-nitrate, a putative pro-drug of ibuprofen and glycerol-1-nitrate.

    PubMed

    Ingram, M J; Moynihan, H A; Powell, M W; Rostron, C

    2001-03-01

    Nitroxylated derivatives of non-steroidal anti-inflammatory drugs appear to offer protection against the gastrotoxicity normally associated with non-steroidal anti-inflammatory drugs, ostensibly via local production of nitric oxide. A diester of ibuprofen and glycerol-1-mononitrate has been prepared via the condensation of ibuprofen with 3-bromopropan-1,2-diol, followed by silver-(I)-nitrate-mediated nitroxylation. The release of ibuprofen from this diester has been studied in a simulated gastric fluid model with direct analysis by reverse-phase HPLC, using an acetonitrile-water (80%:20%) mobile phase containing trifluoroacetic acid (0.005%). n-Propyl ibuprofen was found to undergo pH-dependent hydrolysis, ranging from negligible hydrolysis at pH 5 to 52% hydrolysis at pH 3, over a 2-h period in this model. The ibuprofen-glycerol mononitrate diester was subjected to the most vigorous model hydrolytic conditions and was found to undergo 50 % hydrolysis during the study period. This study shows that pro-drugs of ibuprofen and glycerol mononitrate can be obtained, and can undergo degradation to the parent drugs under conditions simulating those likely to be encountered in the stomach. PMID:11291749

  5. Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

    PubMed Central

    Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

    2014-01-01

    Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

  6. Glycerol metabolism promotes biofilm formation by Pseudomonas aeruginosa.

    PubMed

    Scoffield, Jessica; Silo-Suh, Laura

    2016-08-01

    Pseudomonas aeruginosa causes persistent infections in the airways of cystic fibrosis (CF) patients. Airway sputum contains various host-derived nutrients that can be utilized by P. aeruginosa, including phosphotidylcholine, a major component of host cell membranes. Phosphotidylcholine can be degraded by P. aeruginosa to glycerol and fatty acids to increase the availability of glycerol in the CF lung. In this study, we explored the role that glycerol metabolism plays in biofilm formation by P. aeruginosa. We report that glycerol metabolism promotes biofilm formation by both a chronic CF isolate (FRD1) and a wound isolate (PAO1) of P. aeruginosa. Moreover, loss of the GlpR regulator, which represses the expression of genes involved in glycerol metabolism, enhances biofilm formation in FRD1 through the upregulation of Pel polysaccharide. Taken together, our results suggest that glycerol metabolism may be a key factor that contributes to P. aeruginosa persistence by promoting biofilm formation. PMID:27392247

  7. Measuring glycerol turnover, gluconeogenesis from glycerol, and total gluconeogenesis with [2-13C] glycerol: role of the infusion-sampling mode.

    PubMed

    Peroni, O; Large, V; Odeon, M; Beylot, M

    1996-07-01

    Mass isotopomer distribution analysis (MIDA) of glucose during infusion of [2-13C]glycerol is a new method for measuring total gluconeogenesis (GNG). Since this method relies on calculation of the isotopic enrichment (IE) of hepatic triose phosphates (TP), the results should be independent of the sites of tracer infusion and blood sampling. Postabsorptive and starved rats were infused with [2-13C]glycerol and sampled either in the arterial-venous (A-V) or venous-arterial (V-A) modes. Blood was also sampled from the portal vein. In both postabsorptive and starved rats, glycerol turnover rate (Rt) and the percent contribution of glycerol to total glucose production were higher in the A-V mode than in the V-A mode (P < .05). Glycerol IE in portal venous blood was intermediate between IE values observed in peripheral arterial and venous blood. Its use for calculating the contribution of glycerol to glucose production reconciled the results obtained with the two infusion-sampling modes in both postabsorptive and starved rats; this contribution was increased by starvation (P < .01). In postabsorptive rats, total GNG calculated from MIDA of glucose accounted for approximately 50% of glucose production whatever the infusion-sampling mode (A-V, 48.8% +/- 4.7%; V-A, 52.2% +/- 3.9%). This contribution increased to 90% in starved rats, again, with no difference between A-V (95.2% +/- 1.8%) and V-A (89.2% +/- 1.3%) modes. In conclusion, during infusion of [2-13C]glycerol, total GNG measured from MIDA of glucose is independent of the infusion-sampling mode, contrary to calculations of Rt and GNG from glycerol. Measurement of glycerol IE in portal venous blood reconciles the results obtained with the two modes with respect to the contribution of glycerol to GNG. PMID:8692028

  8. Glycerol production by Oenococcus oeni during sequential and simultaneous cultures with wine yeast strains.

    PubMed

    Ale, Cesar E; Farías, Marta E; Strasser de Saad, Ana M; Pasteris, Sergio E

    2014-07-01

    Growth and fermentation patterns of Saccharomyces cerevisiae, Kloeckera apiculata, and Oenococcus oeni strains cultured in grape juice medium were studied. In pure, sequential and simultaneous cultures, the strains reached the stationary growth phase between 2 and 3 days. Pure and mixed K. apiculata and S. cerevisiae cultures used mainly glucose, producing ethanol, organic acids, and 4.0 and 0.1 mM glycerol, respectively. In sequential cultures, O. oeni achieved about 1 log unit at 3 days using mainly fructose and L-malic acid. Highest sugars consumption was detected in K. apiculata supernatants, lactic acid being the major end-product. 8.0 mM glycerol was found in 6-day culture supernatants. In simultaneous cultures, total sugars and L-malic acid were used at 3 days and 98% of ethanol and glycerol were detected. This study represents the first report of the population dynamics and metabolic behavior of yeasts and O. oeni in sequential and simultaneous cultures and contributes to the selection of indigenous strains to design starter cultures for winemaking, also considering the inclusion of K. apiculata. The sequential inoculation of yeasts and O. oeni would enhance glycerol production, which confers desirable organoleptic characteristics to wines, while organic acids levels would not affect their sensory profile. PMID:24752716

  9. Probe Dependent Solvation Dynamics Study in a Microscopically Immiscible Dimethyl Sulfoxide-Glycerol Binary Solvent.

    PubMed

    Kaur, Harveen; Koley, Somnath; Ghosh, Subhadip

    2014-06-26

    Excited state dipole solvation of three coumarin dyes with different hydrophobicities was studied in DMSO-glycerol binary solvent. The solvation times obtained from the three dyes are remarkably different. The highly hydrophilic dye coumarin 343 (C343) exhibits the slowest solvation time (>12 ns) among all the dyes we used. This is in contrast to the most hydrophobic dye coumarin 153 (C153), where the solvated state is reached just within ∼104 ps. However, the moderately hydrophobic dye coumarin 480 (C480) demonstrates an intermediate (∼396 ps) solvation time. Unprecedented slowdown of solvation time of C343 is probably due to the slow diffusion of solvent molecules in the glycerol-rich first solvation shell followed by hydrogen bond rearrangements around the solute dipole. On the other hand, fast solvation of hydrophobic dye C153 is most likely caused by the fast reorganization dynamics of hydrophobic -CH3 groups of DMSO or the carbon backbone of the glycerol molecule around the solute dipole. Interestingly, a remarkable probe dependency in solvation dynamics was not observed in the case of DMSO-water binary solvent or in a neat solvent isopropanol. Probe dependent solvation in a DMSO-glycerol mixture is attributed to the microscopic phase segregation and different locations of coumarin dyes within this binary solvent. PMID:24942350

  10. Formation of dAMP-glycerol and dAMP-Tris Derivatives by Thermococcus kodakaraensis DNA Primase*

    PubMed Central

    Chemnitz Galal, Wiebke; Pan, Miao; Giulian, Gary; Yuan, Wei; Li, Shuwei; Edwards, James L.; Marino, John P.; Kelman, Zvi; Hurwitz, Jerard

    2012-01-01

    In the presence of dATP, glycerol, and Tris buffer, the DNA primase isolated from Thermococcus kodakaraensis catalyzed the formation of dAMP and two products that were identified as dAMP-glycerol and dAMP-Tris. These products were formed by the T. kodakaraensis p41 catalytic subunit alone and the T. kodakaraensis p41-p46 complex in the absence of a DNA template. They were not formed with preparations containing the catalytically inactive p41 subunit. Similar glycerol and Tris derivatives as well as dNMPs were also formed with dGTP, dCTP, or dTTP. The mechanism contributing to the formation of these products and its implications in the initiation reaction catalyzed by the T. kodakaraensis primase are discussed. PMID:22427647