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Sample records for n-alkane chain lengths

  1. Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Seungtaik Hwang

    2018-03-01

    Full Text Available Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n-pentane concentrations exceeding the (eventually attained equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

  2. Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks.

    Science.gov (United States)

    Hwang, Seungtaik; Gopalan, Arun; Hovestadt, Maximilian; Piepenbreier, Frank; Chmelik, Christian; Hartmann, Martin; Snurr, Randall Q; Kärger, Jörg

    2018-03-15

    Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n- alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n- butane was observed, followed by an increase for n- pentane, and another decrease for n- hexane. This observation was confirmed by uptake measurements with n- butane/ n -pentane mixtures, which yield faster uptake of n- pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n- pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n- alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

  3. Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes.

    Science.gov (United States)

    Hilger, Bettina; Fromme, Hermann; Völkel, Wolfgang; Coelhan, Mehmet

    2011-04-01

    Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.

  4. Crystallisation and chain conformation of long chain n-alkanes

    International Nuclear Information System (INIS)

    Gorce, J.

    2000-06-01

    Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as ''internal standards'' for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C 44 H 90 for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm -1 and 1368 cm -1 as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm -1 , increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C 198 H 398 and n-C 246 H 494 . The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with

  5. C14–22 n-Alkanes in Soil from the Freetown Layered Intrusion, Sierra Leone: Products of Pt Catalytic Breakdown of Natural Longer Chain n-Alkanes?

    Directory of Open Access Journals (Sweden)

    John F. W. Bowles

    2018-03-01

    Full Text Available Soil above a platinum-group element (PGE-bearing horizon within the Freetown Layered Intrusion, Sierra Leone, contains anomalous concentrations of n-alkanes (CnH2n+2 in the range C14 to C22 not readily attributable to an algal or lacustrine origin. Longer chain n-alkanes (C23 to C31 in the soil were derived from the breakdown of leaf litter beneath the closed canopy humid tropical forest. Spontaneous breakdown of the longer chain n-alkanes to form C14–22 n-alkanes without biogenic or abiogenic catalysts is unlikely as the n-alkanes are stable. In the Freetown soil, the catalytic properties of the PGE (Pt in particular may lower the temperature at which oxidation of the longer chain n-alkanes can occur. Reaction between these n-alkanes and Pt species, such as Pt2+(H2O2(OH2 and Pt4+(H2O2(OH4 can bend and twist the alkanes, and significantly lower the Heat of Formation. Microbial catalysis is a possibility. Since a direct organic geochemical source of the lighter n-alkanes has not yet been identified, this paper explores the theoretical potential for abiogenic Pt species catalysis as a mechanism of breakdown of the longer n-alkanes to form C14–22 alkanes. This novel mechanism could offer additional evidence for the presence of the PGE in solution, as predicted by soil geochemistry.

  6. Contamination profiles of short-chain polychlorinated n-alkanes in foodstuff samples from Japan

    Energy Technology Data Exchange (ETDEWEB)

    Matsukami, Hidenori; Kurunthachalam, S; Ohi, Etsumasa; Takasuga, Takumi [Shimadzu Techno Research, Inc., Kyoto (Japan); Iino, Fukuya; Nakanishi, Junko [National Inst. of Advanced Industrial Science and Technology, Tsukuba (Japan)

    2004-09-15

    Polychlorinated n-alkanes (PCAs) are group of chemicals manufactured by chlorination of liquid n-paraffin or paraffin wax that contain 30 to 70% chlorine by weight. Large amounts of PCAs are widely used as plasticizers for vinyl chloride, lubricants, paints, and flame retardants and number of other industrial applications. Annual global production of PCAs is approximately 300 kilo tones, with a majority having medium-carbon-chain (C14-C19) length. According to the investigation made by Kagaku Kogyo Nippon-Sha, the annual consumption of PCAs in Japan was about 83,000 tons in between 1986-2001. Short-carbon-chain (C10-C13) has been placed on the Priority Substance List under Canadian Environmental Protection Act and on the Environmental Protection Agency Toxic Release Inventory in the USA due to its potential to act as tumor promoters in mammals. Data on environment levels of PCAs is meager, nevertheless, PCAs have been measured at relatively high concentrations in biota from Sweden, biota, sediment from Canada and marine biota and human milk from the Canadian Arctic. In our earlier study, we reported concentrations of short-chain PCAs from sewage treatment plant (STP) collected from Tama River, Tokyo and river water and sediment from Tokyo and Osaka. STP influent water contained greater shortchain PCAs concentrations than STP effluent. In addition, some river water and sediment samples contained detectable concentrations of short-chain PCAs, which was similar to other industrial countries. However, there is no study conducted to explore the contamination profiles of short-chain PCAs in human foodstuff samples. In the present study, we analyzed eleven foodstuff samples that were purchased from various supermarkets in order to know the short-chain PCAs concentrations in the foodstuff and possible human total daily intake (TDI) amounts.

  7. Solid-Liquid equilibrium of n-alkanes using the Chain Delta Lattice Parameter model

    DEFF Research Database (Denmark)

    Coutinho, João A.P.; Andersen, Simon Ivar; Stenby, Erling Halfdan

    1996-01-01

    The formation of a solid phase in liquid mixtures with large paraffinic molecules is a phenomenon of interest in the petroleum, pharmaceutical, and biotechnological industries among onters. Efforts to model the solid-liquid equilibrium in these systems have been mainly empirical and with different...... degrees of success.An attempt to describe the equilibrium between the high temperature form of a paraffinic solid solution, commonly known as rotator phase, and the liquid phase is performed. The Chain Delta Lattice Parameter model (CDLP) is developed allowing a successful description of the solid-liquid...... equilibrium of n-alkanes ranging from n-C_20 to n-C_40.The model is further modified to achieve a more correct temperature dependence because it severely underestimates the excess enthalpy. It is shown that the ratio of excess enthalpy and entropy for n-alkane solid solutions, as happens for other solid...

  8. Molecular sieve isolation technique for use in stable carbon isotope analysis of individual long-chain n-alkanes in crude oil

    International Nuclear Information System (INIS)

    Yamada, Keita; Kon, Makoto; Naraoka, Hiroshi; Ishiwatari, Ryoshi; Uzaki, Minoru.

    1994-01-01

    An isolation procedure of microgram amounts of long-chain n-alkanes from crude oil using molecular sieve was examined for its applicability to stable carbon isotope analysis by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The procedure examined is as follows: molecular sieve (type 5A, 200 mg) in 1 ml of isooctane solvent are mixed with a saturated hydrocarbon fraction extracted from an appropriate amount (approx. 20 mg) of crude oil and stayed at room temperatures for more than 3 hours. Long-chain n-alkanes are isolated by extraction with n-hexane after dissolution of the resulting molecular sieve with 47% hydrofluoric acid solution. The recoveries were 90±6% for C 15 -C 34 n-alkanes when their total amounts applied do not exceed 1.4 mg. No effect of the isolation procedure on carbon isotope ratios of n-alkanes was observed. (author)

  9. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    Science.gov (United States)

    Bush, R. T.; McInerney, F. A.

    2010-12-01

    Long chain n-alkanes (n-C21 to n-C37) are synthesized as part of the epicuticular leaf wax of terrestrial plants and are among the most recognizable and widely used plant biomarkers. n-Alkane distributions have been utilized in previous studies on modern plant chemotaxonomy, testing whether taxa can be identified based on characteristic n-alkane profiles. Dominant n-alkanes (e.g. n-C27 or n-C31) have also been ascribed to major plant groups (e.g. trees or grasses respectively) and have been used in paleoecology studies to reconstruct fluctuations in plant functional types. However, many of these studies have been based on relatively few modern plant data; with the wealth of modern n-alkane studies, a more comprehensive analysis of n-alkanes in modern plants is now possible and can inform the usefulness of n-alkane distributions as paleoecological indicators. The work presented here is a combination of measurements made using plant leaves collected from the Chicago Botanic Garden and a compilation of published literature data from six continents. We categorized plants by type: angiosperms, gymnosperms, woody plants, forbs, grasses, ferns and pteridophytes, and mosses. We then quantified n-alkane distribution parameters such as carbon preference index (CPI), average chain length (ACL), and dispersion (a measure of the spread of the profile over multiple chain lengths) and used these to compare plant groups. Among all plants, one of the emergent correlations is a decrease in dispersion with increasing CPI. Within and among plant groups, n-alkane distributions show a very large range of variation, and the results show little or no correspondence between broad plant groups and a single dominant n-alkane or a ratio of n-alkanes. These findings are true both when data from six continents are combined and when plants from a given region are compared (North America). We also compared the n-alkane distributions of woody angiosperms, woody gymnosperms, and grasses with one

  10. The phase behavior of a hard sphere chain model of a binary n-alkane mixture

    International Nuclear Information System (INIS)

    Malanoski, A. P.; Monson, P. A.

    2000-01-01

    Monte Carlo computer simulations have been used to study the solid and fluid phase properties as well as phase equilibrium in a flexible, united atom, hard sphere chain model of n-heptane/n-octane mixtures. We describe a methodology for calculating the chemical potentials for the components in the mixture based on a technique used previously for atomic mixtures. The mixture was found to conform accurately to ideal solution behavior in the fluid phase. However, much greater nonidealities were seen in the solid phase. Phase equilibrium calculations indicate a phase diagram with solid-fluid phase equilibrium and a eutectic point. The components are only miscible in the solid phase for dilute solutions of the shorter chains in the longer chains. (c) 2000 American Institute of Physics

  11. Molecular dynamics simulations of diffusion and clustering along critical isotherms of medium-chain n-alkanes.

    Science.gov (United States)

    Mutoru, J W; Smith, W; O'Hern, C S; Firoozabadi, A

    2013-01-14

    Understanding the transport properties of molecular fluids in the critical region is important for a number of industrial and natural systems. In the literature, there are conflicting reports on the behavior of the self diffusion coefficient D(s) in the critical region of single-component molecular systems. For example, D(s) could decrease to zero, reach a maximum, or remain unchanged and finite at the critical point. Moreover, there is no molecular-scale understanding of the behavior of diffusion coefficients in molecular fluids in the critical regime. We perform extensive molecular dynamics simulations in the critical region of single-component fluids composed of medium-chain n-alkanes-n-pentane, n-decane, and n-dodecane-that interact via anisotropic united-atom potentials. For each system, we calculate D(s), and average molecular cluster sizes κ(cl) and numbers N(cl) at various cluster lifetimes τ, as a function of density ρ in the range 0.2ρ(c) ≤ ρ ≤ 2.0ρ(c) at the critical temperature T(c). We find that D(s) decreases with increasing ρ but remains finite at the critical point. Moreover, for any given τ critical point.

  12. Photochemical oxidation of short-chain polychlorinated n-alkane mixtures using H2O2/UV and the photo-Fenton reaction

    OpenAIRE

    Ken J. Friesen; Taha M. El-Morsi; Alaa S. Abd-El-Aziz

    2004-01-01

    The photochemical oxidation of a series of short-chain polychlorinated n-alkane (PCA) mixtures was investigated using H2O2/UV and modified photo-Fenton conditions (Fe3+/H2O2/UV) in both Milli-Q and lake water. All PCA mixtures, including chlorinated (Cl5 to Cl8) decanes, undecanes, dodecanes and tridecanes degraded in 0.02 M H2O2/UV at pH 2.8 in pure water, with 80±4% disappearance after 3 h of irradiation using a 300 nm light source. Degradation was somewhat enhanced under similar conditions...

  13. Preferential methanogenic biodegradation of short-chain n-alkanes by microbial communities from two different oil sands tailings ponds.

    Science.gov (United States)

    Mohamad Shahimin, Mohd Faidz; Foght, Julia M; Siddique, Tariq

    2016-05-15

    Oil sands tailings ponds harbor diverse anaerobic microbial communities capable of methanogenic biodegradation of solvent hydrocarbons entrained in the tailings. Mature fine tailings (MFT) from two operators (Albian and CNRL) that use different extraction solvents were incubated with mixtures of either two (n-pentane and n-hexane) or four (n-pentane, n-hexane, n-octane and n-decane) n-alkanes under methanogenic conditions for ~600 d. Microbes in Albian MFT began methane production by ~80 d, achieving complete depletion of n-pentane and n-hexane in the two-alkane mixture and their preferential biodegradation in the four-alkane mixture. Microbes in CNRL MFT preferentially metabolized n-octane and n-decane in the four-alkane mixture after a ~80 d lag but exhibited a lag of ~360 d before commencing biodegradation of n-pentane and n-hexane in the two-alkane mixture. 16S rRNA gene pyrosequencing revealed Peptococcaceae members as key bacterial n-alkane degraders in all treatments except CNRL MFT amended with the four-alkane mixture, in which Anaerolineaceae, Desulfobacteraceae (Desulfobacterium) and Syntrophaceae (Smithella) dominated during n-octane and n-decane biodegradation. Anaerolineaceae sequences increased only in cultures amended with the four-alkane mixture and only during n-octane and n-decane biodegradation. The dominant methanogens were acetoclastic Methanosaetaceae. These results highlight preferential n-alkane biodegradation by microbes in oil sands tailings from different producers, with implications for tailings management and reclamation. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Leaf wax n-alkane distributions in and across modern plants: Implications for paleoecology and chemotaxonomy

    Science.gov (United States)

    Bush, Rosemary T.; McInerney, Francesca A.

    2013-09-01

    Long chain (C21 to C37) n-alkanes are among the most long-lived and widely utilized terrestrial plant biomarkers. Dozens of studies have examined the range and variation of n-alkane chain-length abundances in modern plants from around the world, and n-alkane distributions have been used for a variety of purposes in paleoclimatology and paleoecology as well as chemotaxonomy. However, most of the paleoecological applications of n-alkane distributions have been based on a narrow set of modern data that cannot address intra- and inter-plant variability. Here, we present the results of a study using trees from near Chicago, IL, USA, as well as a meta-analysis of published data on modern plant n-alkane distributions. First, we test the conformity of n-alkane distributions in mature leaves across the canopy of 38 individual plants from 24 species as well as across a single growing season and find no significant differences for either canopy position or time of leaf collection. Second, we compile 2093 observations from 86 sources, including the new data here, to examine the generalities of n-alkane parameters such as carbon preference index (CPI), average chain length (ACL), and chain-length ratios for different plant groups. We show that angiosperms generally produce more n-alkanes than do gymnosperms, supporting previous observations, and furthermore that CPI values show such variation in modern plants that it is prudent to discard the use of CPI as a quantitative indicator of n-alkane degradation in sediments. We also test the hypotheses that certain n-alkane chain lengths predominate in and therefore can be representative of particular plant groups, namely, C23 and C25 in Sphagnum mosses, C27 and C29 in woody plants, and C31 in graminoids (grasses). We find that chain-length distributions are highly variable within plant groups, such that chemotaxonomic distinctions between grasses and woody plants are difficult to make based on n-alkane abundances. In contrast

  15. Excess molar enthalpies of binary mixtures containing 2-decanone or dipentyl ether with long-chain n-alkanes at T = 298.15 K

    International Nuclear Information System (INIS)

    Liao, Wei-Chen; Lin, Ho-mu; Lee, Ming-Jer

    2011-01-01

    Research highlights: → An isothermal titration calorimeter was used for enthalpy data measurment. → The investigated systems are 2-decanone or dipentyl ether with long-chain n-alkanes. → The excess enthalpies are all positive over entire composition range. → The Patel-Teja equation of state with two parameters gives the best representation. - Abstract: Excess molar enthalpies (H E ) of binary mixtures of 2-decanone or dipentyl ether with n-alkanes, including n-dodecane, n-tetradecane, and n-hexadecane, were measured with an isothermal titration calorimeter (ITC) at T = 298.15 K under atmospheric pressure. All the measured H E values are positive over the entire range of composition, indicating that all these mixing processes are endothermic. The H E values varying with composition are found to be nearly symmetric for each binary system. It was also shown that the H E values follow the order of n-hexadecane > n-tetradecane > n-dodecane at a given composition in either the 2-decanone or dipentyl ether binary systems. An empirical Redlich-Kister equation correlated quantitatively these new H E data. The Peng-Robinson and the Patel-Teja equations of state, and the NRTL model were also applied to fit the H E results. Among these tested correlative models, the Patel-Teja equation of state with two adjustable binary interaction parameters generally yielded the best representation.

  16. n-Alkane adsorption to polar silica surfaces.

    Science.gov (United States)

    Brindza, Michael R; Ding, Feng; Fourkas, John T; Walker, Robert A

    2010-03-21

    The structures of medium-length n-alkane species (C(8)-C(11)) adsorbed to a hydrophilic silica/vapor interface were examined using vibrational sum frequency spectroscopy. Experiments sampling out-of-plane orientation show a clear pattern in vibrational band intensities that implies chains having primarily all-trans conformations lying flat along the interface. Further analysis shows that the methylene groups of the alkane chains have their local symmetry axes directed into and away from the surface. Spectra acquired under different polarization conditions interlock to reinforce this picture of interfacial structure and organization. Variation in signal intensities with chain length suggests that correlation between adsorbed monomers weakens with increasing chain length. This result stands in contrast with alkane behavior at neat liquid/vapor interfaces where longer length alkanes show considerably more surface induced ordering than short chain alkanes.

  17. Distribution and sources of n-alkanes and polycyclic aromatic hydrocarbons in shellfish of the Egyptian Red Sea coast

    Directory of Open Access Journals (Sweden)

    Ahmed El Nemr

    2016-06-01

    Full Text Available Aromatic hydrocarbons and n-alkanes were analyzed in shellfish collected from 13 different sites along the Egyptian Red Sea coast. All samples were analyzed for n-alkanes (C8–C40 and polycyclic aromatic hydrocarbons (EPA list of PAHs. n-Alkanes in shellfish samples from 13 locations were found to be in the range of 71.0–701.1 ng/g with a mean value of 242.2 ± 192.1 ng/g dry wt. Different indices were calculated for the n-alkanes to assess their sources. These were carbon preference index (CPI, average chain length (ACL, terrigenous/aquatic ratio (TAR, natural n-alkane ratio (NAR and proxy ratio (Paq. Most of the collected samples of n-alkanes were discovered to be from natural sources. Aromatic hydrocarbons (16 PAHs from 13 sites varied between 1.3 and 160.9 ng/g with an average of 47.9 ± 45.5 ng/g dry wt. Benzo(apyrine (BaP, a cancer risk assessment, was calculated for the PAHs and resulted in ranges between 0.08 and 4.47 with an average of 1.25 ng/g dry wt.

  18. Distribution and sources of n-alkanes in surface sediments of Taihu Lake, China

    Directory of Open Access Journals (Sweden)

    Yu Yunlong

    2016-03-01

    Full Text Available The last study on n-alkanes in surface sediments of Taihu Lake was in 2000, only 13 surface sediment samples were analysed, in order to have a comprehensive and up-to-date understanding of n-alkanes in the surface sediments of Taihu Lake, 41 surface sediment samples were analyzed by GC-MS. C10 to C37 were detected, the total concentrations of n-alkanes ranged from 2109 ng g−1 to 9096 ng g−1 (dry weight. There was strong odd carbon predominance in long chain n-alkanes and even carbon predominance in short chain n-alkanes. When this finding was combined with the analysis results of wax n-alkanes (WaxCn, carbon preference index (CPI, unresolved complex mixture (UCM, hopanes and steranes, it was considered that the long chain n-alkanes were mainly from terrigenous higher plants, and that the short chain n-alkanes mainly originated from bacteria and algae in the lake, compared with previous studies, there were no obvious anthropogenic petrogenic inputs. Terrestrial and aquatic hydrocarbons ratio (TAR and C21−/C25+ indicated that terrigenous input was higher than aquatic sources and the nearshore n-alkanes were mainly from land-derived sources. Moreover, the distribution of short chain n-alkanes presented a relatively uniform pattern, while the long chain n-alkanes presented a trend that concentrations dropped from nearshore places to the middle of lake.

  19. A nonequilibrium simulation method for calculating tracer diffusion coefficients of small solutes in n-alkane liquids and polymers

    NARCIS (Netherlands)

    van der Vegt, N.F.A.; Briels, Willem J.; Wessling, Matthias; Strathmann, H.

    1998-01-01

    The tracer diffusion coefficients of methane in n-alkane liquids of increasing chain length were calculated by measuring the friction from short time nonequilibrium molecular dynamics simulations. The frictional constant was calculated from the exponentially decaying distance between two methane

  20. Bulk and compound-specific isotope analysis of long-chain n-alkanes from a 85,000 year sediment core from Lake Peten Petén Itzá, Guatemala

    Science.gov (United States)

    Mays, J.; Brenner, M.; Curtis, J. H.; Curtis, K.; Hodell, D. A.; Correa-Metrio, A.; Escobar, J.; Dutton, A. L.; Zimmerman, A. R.; Guilderson, T. P.

    2013-12-01

    Sediment core PI-6 from Lake Petén Itzá, Guatemala possesses an 85-ka record of climate from lowland Central America. Variations in sediment lithology suggest large, abrupt changes in precipitation during the last glacial and deglacial periods, and into the early Holocene. Study of cores from nearby Lake Quexil demonstrated the utility of using the carbon isotopic composition of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al. 2001). Forty-nine samples were taken from composite Petén Itzá core PI-6 to measure carbon isotopes of bulk organic carbon and long-chain n alkanes. Changes in δ13C values indicate shifts in the relative proportion of C3 to C4 biomass. The record shows largest δ13C variations are associated with Heinrich Events. Carbon isotope values in sediments deposited during the Last Glacial Maximum (LGM) indicate moderate precipitation and little rainfall fluctuation. The deglacial was a period of pronounced climate variability, e.g. the Bölling-Allerod and Younger Dryas. Arid times of the deglacial were inferred from samples with the greatest δ13C values in organic matter, reflecting the largest proportion of C4 plants. Such inferences are supported by stable isotope measurements on ostracod shells and analysis of pollen from the same sample depths in core PI-6. Carbon stable isotope measures on bulk organic carbon and n alkane compounds show similar trends throughout the record and the C:N ratio of Petén Itzá sediments indicates a predominantly allochthonous source for bulk organic matter. Hence, isotope measures on bulk organic carbon (δ13CTOC) in sediments from this lake are sufficient to infer climate-driven shifts in vegetation, making n-alkane extraction and isotope analysis superfluous.

  1. Phase Behavior and Evaporation Profile of Tween 20 - Eugenol System. Effect of Different Alkane Chain Length and Solvent System

    International Nuclear Information System (INIS)

    Kassim, A.; Lim, W.H.; Kuangl, D.; Rusmawati, W.W.M.; Abdullah, A.H.; Teoh, S.P.

    2003-01-01

    The isotropic region of Tween 20/eugenol/n-alkane in aqueous systems was determined. The solubilisation trend of isotropic solution formed in the presence of eugenol was studied as a function of different alkyl chain length of n-alkane. The solubility of solvent in surfactant solution is dependent on their molecular polarity. An increase in n-alkane chain length (lower polarity) lead to smaller isotropic region which will affect the surfactant partitioning between the interface, the oil phase and the aqueous phase of the microemulsion as the oil chain length is varied. The changes of evaporation behaviour were affected strongly by the types of phases existed in the systems. The increment of n-alkane and water content led to higher evaporation rate. But the formation of w/o microemulsion would lower the evaporation rate because water molecules were trapped in the core of aggregates. In solubilisation system, evaporation rate is dependent on the solvent content and the interaction between Tween 20 and solvent molecules in the mixed composition. (author)

  2. Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation

    Science.gov (United States)

    Diama, A.; Matthies, B.; Herwig, K. W.; Hansen, F. Y.; Criswell, L.; Mo, H.; Bai, M.; Taub, H.

    2009-08-01

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C24H50 denoted as C24) and dotriacontane (n-C32H66 denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 Å=√3 ag, where ag=2.46 Å is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by ˜10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  3. Secretive production of long-chain fatty acids, triacylglycerols and n-alkane-2-ones by fermentation processes; Hakkoho ni yoru ekitai nenryo no seisan wa kanoka (shishitsu no bunpi seisan)

    Energy Technology Data Exchange (ETDEWEB)

    Fukui, S. [University of Fukuyama, Hiroshima (Japan). Faculty of Engineering

    1995-10-20

    Secretive production of lipids, which are useful source for engine-driving fuel, by microbial process using carbohydrate biomasses as substrate has been investigated in our laboratory. This review consists of four parts concerning breedings and selection of lipid-secretive microorganisms : (1) breedings of long-chain fatty acid-secretive strains from Candida lipolytica L-1 by a step-wise mutagenesis process, (2) selection of a triacylglycerol (TG)-secretive and accumulative yeast strain Trichosporon sp. SH45Y, (3) breedings of mutants, SH45Y-derivatieves, having potent ability to produce TG secretively from glucose, a typical biomass charbohydrate, and (4) selection of microorganisms which produce liquid-n-alkane in culture medium by utilizing long-chain fatty acids and TG; a strain of Penicillium decumbens can produce liquid alkalis with a yield of approximately 60 % in weight from palm kernel oil, a commercial TG. 10 refs., 7 figs., 7 tabs.

  4. Investigating C4 Grass Contributions to N-alkane Based Paleoclimate Reconstructions

    Science.gov (United States)

    Doman, C. E.; Enders, S. K.; Chadwick, O.; Freeman, K. H.

    2014-12-01

    Plant wax n-alkanes are long-chain, saturated hydrocarbons contained within the protective waxy cuticle on leaves. These lipids are pervasive and persistent in soils and sediments and thus are ideal biomarkers of ancient terrestrial organic matter. In ecosystems dominated by C3 plants, the relationship between the carbon isotopic value of whole leaves and lipids is fairly well documented, but this relationship has not been fully investigated for plants that use C4 photosynthesis. In both cases, it is unclear if the isotopic relationships are sensitive to environmental conditions, or reflect inherited characteristics. This study used a natural climate gradient on the Kohala peninsula of Hawaii to investigate relationships between climate and the δ13C and δ2H values of n-alkanes in C3 and C4 plants. δ13C of C3 leaves and lipids decreased 5 ‰ from the driest to the wettest sites, consistent with published data. Carbon isotope values of C4 plants showed no relationship to moisture up to 1000 mm mean annual precipitation (MAP). Above this threshold, δ 13C values were around 10‰ more depleted, likely due to a combination of canopy effects and C4 grasses growing in an uncharacteristically wet and cold environment. In C3 plants, the fractionation between leaf and lipid carbon isotopes did not vary with MAP, which allows estimations of δ13C leaf to be made from alkanes preserved in ancient sediments. Along this transect, C3 plants produce around twice the quantity of n-alkanes as C4 grasses. C4 grasses produce longer carbon chains. As a result, n-alkanes in the geologic record will be biased towards C3 plants, but the presence of alkanes C33 and C35 indicate the contributions of C4 grasses. In both C3 and C4 plants, average chain length increased with mean annual precipitation, but the taxonomic differences in chain length were greater than environmental differences. Hydrogen isotopes of n-alkanes show no trends with MAP, but do show clear differences between plant

  5. Biodegradation of n-alkanes on oil-seawater interfaces at different temperatures and microbial communities associated with the degradation.

    Science.gov (United States)

    Lofthus, Synnøve; Netzer, Roman; Lewin, Anna S; Heggeset, Tonje M B; Haugen, Tone; Brakstad, Odd Gunnar

    2018-04-01

    Oil biodegradation studies have mainly focused on microbial processes in dispersions, not specifically on the interfaces between the oil and the seawater in the dispersions. In this study, a hydrophobic adsorbent system, consisting of Fluortex fabrics, was used to investigate biodegradation of n-alkanes and microbial communities on oil-seawater interfaces in natural non-amended seawater. The study was performed over a temperature range from 0 to 20 °C, to determine how temperature affected biodegradation at the oil-seawater interfaces. Biodegradation of n-alkanes were influenced both by seawater temperature and chain-length. Biotransformation rates of n-alkanes decreased by reduced seawater temperature. Low rate coefficients at a seawater temperature of 0 °C were probably associated with changes in physical-chemical properties of alkanes. The primary bacterial colonization of the interfaces was predominated by the family Oceanospirillaceae at all temperatures, demonstrating the wide temperature range of these hydrocarbonoclastic bacteria. The mesophilic genus Oleibacter was predominant at the seawater temperature of 20 °C, and the psychrophilic genus Oleispira at 5 and 0 °C. Upon completion of n-alkane biotransformation, other oil-degrading and heterotrophic bacteria became abundant, including Piscirickettsiaceae (Cycloclasticus), Colwelliaceae (Colwellia), Altermonadaceae (Altermonas), and Rhodobacteraceae. This is one of a few studies that describe the biodegradation of oil, and the microbial communities associated with the degradation, directly at the oil-seawater interfaces over a large temperature interval.

  6. Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation

    DEFF Research Database (Denmark)

    Diama, A.; Matthies, B.; Herwig, K. W.

    2009-01-01

    measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows...... show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously...

  7. Effect of Thermal Maturation on n-alkanes and Kerogen in Preserved Organic Matter: Implications for Paleoenvironment Biomarkers

    Science.gov (United States)

    Craven, O. D.; Longbottom, T. L.; Hockaday, W. C.; Blackaby, E.

    2017-12-01

    Understanding the effects of maturity on biomarkers is vital in assessing biomarker reliability in mature sediments. It is well known for n-alkanes that increased maturity shortens chain lengths and decreases the odd over even preference however, the amount of change in these variables has not been determined for different maturities and types of preserved organic matter. For this reason, it is difficult to judge the trustworthiness of even lightly matured samples for paleoenvironment reconstruction. Another complication is the difficulty of accurately determining maturity as many maturity indicators are error-prone or not appropriate at low maturities. Using hydrous pyrolysis, we artificially matured black shale samples with type I (lacustrine) and type II (marine) kerogen to measure changes in n-alkane length and odd over even preference. Whole rock samples underwent hydrous pyrolysis for 72 hours, at 250 °C, 300 °C, 325 °C, 350 °C, and 375 °C to cover a wide maturity range. From the immature and artificially matured samples, the bitumen was extracted and the saturate fraction was separated using column chromatography. The saturate fraction was analyzed for n-alkanes using gas chromatography-mass spectroscopy. Kerogen structural changes were also measured using solid-state 13C NMR to relate changes in n-alkane biomarkers to changes in kerogen structure. Results show that for type I bitumen the n-alkanes did not change at low maturities considered premature in terms of oil generation (<325 °C). The NMR spectra of the type I kerogen support the lack of change, at low maturities no changes in the aliphatic portion (Fal) were observed, however, after 325 °C Fal decreased with increasing maturity. The loss of Fal indicates kerogen contributing hydrocarbons to bitumen that cause changes in n-alkane measurements. The type II kerogen's Fal also decreased with increasing maturity, but unlike the type I kerogen Fal loss started at low maturities. The differences

  8. Anaerobic Coculture of Microalgae with Thermosipho globiformans and Methanocaldococcus jannaschii at 68°C Enhances Generation of n-Alkane-Rich Biofuels after Pyrolysis

    Science.gov (United States)

    Matsuyama, Shigeru; Igarashi, Kensuke; Utsumi, Motoo; Shiraiwa, Yoshihiro; Kuwabara, Tomohiko

    2013-01-01

    We tested different alga-bacterium-archaeon consortia to investigate the production of oil-like mixtures, expecting that n-alkane-rich biofuels might be synthesized after pyrolysis. Thermosipho globiformans and Methanocaldococcus jannaschii were cocultured at 68°C with microalgae for 9 days under two anaerobic conditions, followed by pyrolysis at 300°C for 4 days. Arthrospira platensis (Cyanobacteria), Dunaliella tertiolecta (Chlorophyta), Emiliania huxleyi (Haptophyta), and Euglena gracilis (Euglenophyta) served as microalgal raw materials. D. tertiolecta, E. huxleyi, and E. gracilis cocultured with the bacterium and archaeon inhibited their growth and CH4 production. E. huxleyi had the strongest inhibitory effect. Biofuel generation was enhanced by reducing impurities containing alkanenitriles during pyrolysis. The composition and amounts of n-alkanes produced by pyrolysis were closely related to the lipid contents and composition of the microalgae. Pyrolysis of A. platensis and D. tertiolecta containing mainly phospholipids and glycolipids generated short-carbon-chain n-alkanes (n-tridecane to n-nonadecane) and considerable amounts of isoprenoids. E. gracilis also produced mainly short n-alkanes. In contrast, E. huxleyi containing long-chain (31 and 33 carbon atoms) alkenes and very long-chain (37 to 39 carbon atoms) alkenones, in addition to phospholipids and glycolipids, generated a high yield of n-alkanes of various lengths (n-tridecane to n-pentatriacontane). The gas chromatography-mass spectrometry (GC-MS) profiles of these n-alkanes were similar to those of native petroleum crude oils despite containing a considerable amount of n-hentriacontane. The ratio of phytane to n-octadecane was also similar to that of native crude oils. PMID:23183975

  9. Use of n-alkanes and long-chain alcohols as faecal markers to estimate diet composition on small ruminants grazing/browsing mountain grasslands

    OpenAIRE

    Magalhães, Rui José Ribeiro Ferreira de

    2018-01-01

    Knowledge on the grazing/browsing behaviour, especially diet selection, of the different domestic herbivorous species under diverse vegetation communities is of particular importance for the development and application of appropriate grazing management strategies that increase the efficiency of the utilization of the existing vegetation and, consequently, the sustainability of the animal production system. Plant-wax components, namely alkanes and long-chain alcohols (LCOH), have been suggeste...

  10. Vapor phase nucleation of the short-chain n-alkanes (n-pentane, n-hexane and n-heptane): Experiments and Monte Carlo simulations

    Science.gov (United States)

    Ogunronbi, Kehinde E.; Sepehri, Aliasghar; Chen, Bin; Wyslouzil, Barbara E.

    2018-04-01

    We measured the nucleation rates of n-pentane through n-heptane in a supersonic nozzle at temperatures ranging from ca. 109 K to 168 K. For n-pentane and n-hexane, these are the first nucleation rate measurements that have been made, and the trends in the current data agree well with those in the earlier work of Ghosh et al. [J. Chem. Phys. 132, 024307 (2010)] for longer chain alkanes. Complementary Monte Carlo simulations, using the transferable potentials for phase equilibria-united atom potentials, suggest that despite the high degree of supercooling, the critical clusters remain liquid like under experimental conditions for n-pentane through n-heptane, but adopt more ordered structures for n-octane and n-nonane. For all three alkanes, the experimental and simulated nucleation rates are offset by ˜3 orders of magnitude when plotted as a function of ln S/(Tc/T - 1)1.5. Explicitly accounting for the surface tension difference between the real and model substances, or alternatively using the Hale [Phys. Rev. A 33, 4156 (1986); Metall. Mater. Trans. A 23, 1863 (1992)] scaling parameter, Ω, consistent with the model potential, increases the offset to ˜6 orders of magnitude.

  11. Degradation of Hydrocarbons by Members of the Genus Candida II. Oxidation of n-Alkanes and 1-Alkenes by Candida lipolytica

    Science.gov (United States)

    Klug, M. J.; Markovetz, A. J.

    1967-01-01

    Candida lipolytica ATCC 8661 was grown in a mineral-salts hydrocarbon medium. n-Alkanes and 1-alkenes with 14 through 18 carbon atoms were used as substrates. Ether extracts of culture fluids and cells obtained from cultures grown on the various substrates were analyzed by thin-layer and gas-liquid chromatography. Analyses of fluids from cultures grown on n-alkanes indicated a predominance of fatty acids and alcohols of the same chain length as the substrate. In addition, numerous other fatty acids and alcohols were present. Analyses of saponifiable and nonsaponifiable material obtained from the cells revealed essentially the same products. The presence of primary and secondary alcohols, as well as fatty acids, of the same chain length as the n-alkane substrate suggested that attack on both the methyl and α-methylene group was occurring. The significance of these two mechanisms in the degradation of n-alkanes by this organism was not evident from the data presented. Analyses of fluids from cultures grown on 1-alkenes indicated the presence of 1,2-diols, as well as ω-unsaturated fatty acids, of the same chain length as the substrate. Alcohols present were all unsaturated. Saponifiable and nonsaponifiable material obtained from cells contained essentially the same products. The presence of 1,2-diols and ω-unsaturated fatty acids of the same chain length as the substrate from cultures grown on 1-alkenes indicated that both the terminal methyl group and the terminal double bond were being attacked. PMID:6025303

  12. Nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives

    International Nuclear Information System (INIS)

    Taggart, Audrey M.

    1996-01-01

    A detailed study has been performed on the nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives in an attempt to gain a clearer appreciation of the interaction mechanisms behind wax / additive crystallisation. Kinetic and structural assessment of melt phase n-alkanes illustrate the different crystallographic forms present within the homologous series. Studies demonstrate the alternating behaviour of the even and odd numbered homologues which converges as a function of increasing molecular weight. Greater crystal lattice stabilities were found for those n-alkanes which have an even carbon number and which crystallise into the triclinic crystal structure. Solid state phase behaviour of the n-alkanes was found to vary depending on the number and parity of n. Nucleation kinetic studies of n-alkanes and homologous mixtures from model diesel fuel solvents (dodecane, m-xylene, decalin, pristane and a dewaxed fuel) are assessed using turbidity as the method of crystallite detection. Saturation temperatures are found to be related to both alkane structure and molecular chain length for all solvent systems. N-alkane solubilities are lower for n-alkane like solvents. The width of the meta stable zone varies as a function of solvent in order of dodecane ≅ pristane 19 H 40 and solvent m-xylene. Wax precipitation from distillate fuels in the presence of flow improving additives (di-alkyl di-amino xylene, phthalic acid and sulphobenzene acid derivatives and high molecular weight polymers) reveal responsive wax crystal nucleator and growth inhibitor additives. The crystal morphology of heptacosane, C 27 H 56 to simulate a model wax crystal is assessed in addition to its response to blocker 'tailor made' additives: methyl substituted C 27 H 56 and di-alkyl substituted phenyl additives [additive (A) and (B)]. Pure C 27 H 56 reveals a thin lozenge shaped platelet. All additives studied induce growth

  13. Optimized cleanup method for the determination of short chain polychlorinated n-alkanes in sediments by high resolution gas chromatography/electron capture negative ion-low resolution mass spectrometry

    International Nuclear Information System (INIS)

    Gao Yuan; Zhang Haijun; Chen Jiping; Zhang Qing; Tian Yuzeng; Qi Peipei; Yu Zhengkun

    2011-01-01

    Graphical abstract: The sediment sample could be purified by the optimized cleanup method, and satisfying cleanup efficiency was obtained. Highlights: → The elution characters of sPCAs and interfering substances were evaluated on three adsorbents. → An optimized cleanup method was developed for sPCAs with satisfying cleanup efficiency. → The cleanup method combined with HRGC/ECNI-LRMS was applied for sPCAs analysis. → The sPCAs levels range from 53.6 ng g -1 to 289.3 ng g -1 in tested sediment samples. - Abstract: The performances of three adsorbents, i.e. silica gel, neutral and basic alumina, in the separation of short chain polychlorinated n-alkanes (sPCAs) from potential interfering substances such as polychlorinated biphenyls (PCBs) and organochlorine pesticides were evaluated. To increase the cleanup efficiency, a two-step cleanup method using silica gel column and subsequent basic alumina column was developed. All the PCB and organochlorine pesticides could be removed by this cleanup method. The very satisfying cleanup efficiency of sPCAs has been achieved and the recovery in the cleanup method reached 92.7%. The method detection limit (MDL) for sPCAs in sediments was determined to be 14 ng g -1 . Relative standard deviation (R.S.D.) of 5.3% was obtained for the mass fraction of sPCAs by analyzing four replicates of a spiked sediment sample. High resolution gas chromatography/electron capture negative ion-low resolution mass spectrometry (HRGC/ECNI-LRMS) was used for sPCAs quantification by monitoring [M-HCl]· - ions. When applied to the sediment samples from the mouth of the Daliao River, the optimized cleanup method in conjunction with HRGC/ECNI-LRMS allowed for highly selective identifications for sPCAs. The sPCAs levels in sediment samples are reported to range from 53.6 ng g -1 to 289.3 ng g -1 . C 10 - and C 11 -PCAs are the dominant residue in most of investigated sediment samples.

  14. Plant Wax n-Alkane and n-Alkanoic Acid Signatures Overprinted by Microbial Contributions and Old Carbon in Meromictic Lake Sediments

    Science.gov (United States)

    Makou, Matthew; Eglinton, Timothy; McIntyre, Cameron; Montluçon, Daniel; Antheaume, Ingrid; Grossi, Vincent

    2018-01-01

    Specific n-alkanes and n-alkanoic acids are commonly used as biomarkers in paleoenvironmental reconstruction, yet any individual homologue may originate from multiple biological sources. Here we improve source and age controls for these compounds in meromictic systems by measuring the radiocarbon (14C) ages of specific homologues preserved in twentieth century Lake Pavin (France) sediments. In contrast to many studies, 14C ages generally decreased with increasing carbon chain length, from 7.3 to 2.6 ka for the C14-C30 n-alkanoic acids and from 9.2 to 0.3 ka for the C21-C33 n-alkanes. Given a known hard water effect, these values suggest that aquatic microbial sources predominate and contributed to most of the homologues measured. Only the longest chain n-alkanes exclusively represent inputs of higher plant waxes, which were previously sequestered in soils over centennial to millennial timescales prior to transport and deposition. These findings suggest that biomarker source and age should be carefully established for lacustrine settings.

  15. The structure of n-alkane binary mixtures adsorbed on graphite

    International Nuclear Information System (INIS)

    Espeau, Philippe; White, John W.; Papoular, Robert J.

    2005-01-01

    The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A 1-x B x try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations

  16. The structure of n-alkane binary mixtures adsorbed on graphite

    Energy Technology Data Exchange (ETDEWEB)

    Espeau, Philippe [Laboratoire de Chimie Physique et Minerale, Faculte de Pharmacie, Universite Rene Descartes-Paris V, F-75006 Paris (France)]. E-mail: philippe.espeau@univ-paris5.fr; White, John W. [Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia); Papoular, Robert J. [Laboratoire Leon Brillouin, CEA-CEN Saclay, F-91191 Gif-sur-Yvette Cedex (France)

    2005-12-15

    The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A{sub 1-x}B {sub x} try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations.

  17. Re-evaluating the isotopic divide between angiosperms and gymnosperms using n-alkane δ13C values

    Science.gov (United States)

    Bush, R. T.; McInerney, F. A.

    2009-12-01

    Angiosperm δ13C values are typically 1-3‰ more negative than those of co-occurring gymnosperms. This is known for both bulk leaf and compound-specific values from n-alkanes, which are stable, straight-chain hydrocarbons (C23-C35) found in the epicuticular leaf wax of vascular plants. For n-alkanes, there is a second distinction between the δ13C values of angiosperms and gymnosperms—δ13C values generally decrease with increasing chain-length in angiosperms, while in gymnosperms they increase. These two distinctions have been used to support the ‘plant community change hypothesis’ explaining the difference between the terrestrial and marine carbon isotope excursions during the Paleocene-Eocene Thermal Maximum (PETM.) Preserved n-alkanes from terrestrial paleosols in the Bighorn Basin, Wyoming reveal a negative carbon isotope excursion during the PETM of 4-5‰, which is 1-2‰ greater than the excursion recorded by marine carbonates. The local plant community, known from macrofossils as well as palynoflora, shifted from a deciduous, mixed angiosperm/gymnosperm flora to a suite of evergreen angiosperm species during the PETM. At the end of the PETM, the community returned to a mixed deciduous flora very similar to the original. This change in the plant community could thus magnify the terrestrial negative carbon isotope excursion to the degree necessary to explain its divergence from the marine record. However, the comparison between modern angiosperms and gymnosperms has been made mostly between broadleaf, deciduous angiosperms and evergreen, coniferous gymnosperms. New data analyzing deciduous, coniferous gymnosperms, including Metasequoia glyptostroboides and Taxodium distichum, suggests that the division previously ascribed to taxonomy may actually be based on leaf habit and physiology, specifically broadleaf, deciduous versus needle-leaf, evergreen plants. If differences in n-alkane δ13C values can be described not as angiosperms versus gymnosperms

  18. Solvent extraction of thiophene from n-alkanes (C7, C12, and C16) using the ionic liquid [C8mim][BF4

    International Nuclear Information System (INIS)

    Alonso, Luisa; Arce, Alberto; Francisco, Maria; Soto, Ana

    2008-01-01

    In the last years, new strict environmental regulations to reduce sulfur content in liquid fuels have been established. Thiophene derivates can be considered as the key substances to be separated from liquid fuel oils. This paper reports the ability of the ionic liquid 1-methyl-3-octylimidazolium tetrafluoroborate to act as solvent in the (liquid + liquid) extraction of thiophene from aliphatic hydrocarbons. Tie-line data have been determined for ternary systems containing the ionic liquid, thiophene, and some n-alkanes at T = 298.15 K. Extraction process has been analyzed by means of thiophene distribution ratio and selectivity. The solute distribution coefficient decreases and the selectivity increases as the chain length of n-alkane increases. The use of 1-methyl-3-octylimidazolium tetrafluoroborate as potential solvent for separation of thiophene from n-alkanes is feasible using the necessary quantity of solvent. A correlation of the equilibrium data reported here has also been made, using the NRTL activity coefficient model, in order to facilitate their use in simulation and design processes

  19. The effect of n-alkane selection depth on the quality of denormalizate

    Energy Technology Data Exchange (ETDEWEB)

    Dorodnova, V.S.; Bayburskaya, E.L.; Martynenko, A.G.

    1982-01-01

    The effect of n-alkane selection depth from crude diesel fuel on the quality of denormalization on a carbamide deparaffination G-64 device at the Gorknefteorgsintez Production Association. Diesel fuel with o.c. 210/sup 0/, c.c. 315/sup 0/, 828 kg/m/sup 3/ density, -25, n/sup 20/ D 1.4620, aniline point 66.9/sup 0/ and n-alkane content 14.7% was used. The regime of the stage of complex formation was maximal approximation of industrial conditions: ratio Cr: ben. 1:2.6 mass. no, complex formation 25/sup 0/, length of contact 30 min, levels of washing, 2; methanol, 2.0% in Cr. Changing the quantity of carbamide aided the various extraction depths of n-alkanes from the Cr. Following distillation of the solution the following parameters were examined: refraction, density, aniline point, diesel index; Obtained: the dependencies for changes in these indicators depending on the depth of the selection of n-alkanes from the potential or from their content in the denormalizate; as well as the dependence of the component composition of paraffins on the degree of their extraction from the Cr. To simultaneously obtain paraffins and diesel fuel of export quality with a diesel index no lower than 55, it is necessary to guarantee up to 50% (no higher) of paraffin selection from the potential Cr containing 14.7% n-alkanes; the sediment content of n-alkanes in the denormalizate must be found at the 7.4% level.

  20. n-Alkane distributions as indicators of novel ecosystem development in western boreal forest soils

    Science.gov (United States)

    Norris, Charlotte; Dungait, Jennifer; Quideau, Sylvie

    2013-04-01

    Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following surface mining in the Athabasca Oil Sands Region. Sphagnum peat is the primary organic matter amendment used to reconstruct soils in the novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel reconstructed soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. In this study, we evaluated the use of the homologous series of very long chain (>C20) n-alkanes with odd-over-even predominance as biomarker signatures to monitor the re-establishment of boreal forests on reconstructed soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. We observed unique very long n-alkane signatures of the source vegetation, e.g. Sphagnum sp. was dominated by C31 and aspen (Populus tremuloides Michx.) leaves by C25. Greater concentrations of very long chain n-alkanes were extracted from natural than novel ecosystem SOM (puse of n-alkanes as biomarkers of ecosystem development is a promising method.

  1. Plant n-alkane production from litterfall altered the diversity and community structure of alkane degrading bacteria in litter layer in lowland subtropical rainforest in Taiwan

    Science.gov (United States)

    Huang, Tung-Yi; Hsu, Bing-Mu; Chao, Wei-Chun; Fan, Cheng-Wei

    2018-03-01

    n-Alkane and alkane-degrading bacteria have long been used as crucial biological indicators of paleoecology, petroleum pollution, and oil and gas prospecting. However, the relationship between n-alkane and alkane-degrading bacteria in natural forests is still poorly understood. In this study, long-chain n-alkane (C14-C35) concentrations in litterfall, litter layer, and topsoil as well as the diversity and abundance of n-alkane-degrading bacterial communities in litter layers were investigated in three habitats across a lowland subtropical rainforest in southern Taiwan: ravine, windward, and leeward habitats in Nanjenshan. Our results demonstrate that the litterfall yield and productivity of long-chain n-alkane were highest in the ravine habitats. However, long-chain n-alkane concentrations in all habitats were decreased drastically to a similar low level from the litterfall to the bulk soil, suggesting a higher rate of long-chain n-alkane degradation in the ravine habitat. Operational taxonomic unit (OTU) analysis using next-generation sequencing data revealed that the relative abundances of microbial communities in the windward and leeward habitats were similar and different from that in the ravine habitat. Data mining of community amplicon sequencing using the NCBI database revealed that alkB-gene-associated bacteria (95 % DNA sequence similarity to alkB-containing bacteria) were most abundant in the ravine habitat. Empirical testing of litter layer samples using semi-quantitative polymerase chain reaction for determining alkB gene levels confirmed that the ravine habitat had higher alkB gene levels than the windward and leeward habitats. Heat map analysis revealed parallels in pattern color between the plant and microbial species compositions of the habitats, suggesting a causal relationship between the plant n-alkane production and microbial community diversity. This finding indicates that the diversity and relative abundance of microbial communities in the

  2. Thermodiffusion in multicomponent n-alkane mixtures.

    Science.gov (United States)

    Galliero, Guillaume; Bataller, Henri; Bazile, Jean-Patrick; Diaz, Joseph; Croccolo, Fabrizio; Hoang, Hai; Vermorel, Romain; Artola, Pierre-Arnaud; Rousseau, Bernard; Vesovic, Velisa; Bou-Ali, M Mounir; Ortiz de Zárate, José M; Xu, Shenghua; Zhang, Ke; Montel, François; Verga, Antonio; Minster, Olivier

    2017-01-01

    Compositional grading within a mixture has a strong impact on the evaluation of the pre-exploitation distribution of hydrocarbons in underground layers and sediments. Thermodiffusion, which leads to a partial diffusive separation of species in a mixture due to the geothermal gradient, is thought to play an important role in determining the distribution of species in a reservoir. However, despite recent progress, thermodiffusion is still difficult to measure and model in multicomponent mixtures. In this work, we report on experimental investigations of the thermodiffusion of multicomponent n -alkane mixtures at pressure above 30 MPa. The experiments have been conducted in space onboard the Shi Jian 10 spacecraft so as to isolate the studied phenomena from convection. For the two exploitable cells, containing a ternary liquid mixture and a condensate gas, measurements have shown that the lightest and heaviest species had a tendency to migrate, relatively to the rest of the species, to the hot and cold region, respectively. These trends have been confirmed by molecular dynamics simulations. The measured condensate gas data have been used to quantify the influence of thermodiffusion on the initial fluid distribution of an idealised one dimension reservoir. The results obtained indicate that thermodiffusion tends to noticeably counteract the influence of gravitational segregation on the vertical distribution of species, which could result in an unstable fluid column. This confirms that, in oil and gas reservoirs, the availability of thermodiffusion data for multicomponent mixtures is crucial for a correct evaluation of the initial state fluid distribution.

  3. Molecular dynamics simulation studies of mid-size liquid n-Alkanes, C12–C160

    International Nuclear Information System (INIS)

    Kwon, Tae Woo; Lee, Song Hi

    2015-01-01

    In this study, we report the results of molecular dynamics simulations (MD) for model systems of mid-size liquid n-alkanes (C 12 –C 160 ) at several temperatures (⁓2700 K) in canonical ensembles to calculate structural and dynamic properties (viscosity η, self-diffusion constant D, and monomeric friction constant ζ). For the small n-alkanes for n ≤ 80, the chains are clearly ≥ 1, which leads to the conclusion that the liquid n-alkanes are far away from the Rouse regime, but for the n-alkanes for n ≥ 120, the chains are ⁓ 1 and they are Gaussian. It is found that the long chains of these n-alkanes at high temperatures show abnormalities in density, viscosity, and monomeric friction constant. The mass and temperature dependences of structural and dynamic properties (η, D, and ζ) are discussed

  4. Mechanism of trans-vinylene groups formation in the radiolysis of polyethylene and n-alkanes

    International Nuclear Information System (INIS)

    Borzov, S.M.; Sukhov, F.F.; Slovokhotova, N.A.

    1984-01-01

    Infrared spectra of polyethylene and some n-alkanes were studied after their irradiation at 20 K with 1-MeV electrons and subsequent heating to 160 K. The mechanism of trans-vinylene groups formation is suggested, which takes into account the decay of excited states of molecules in primary processes and the intra-chain recombination of free radicals in post-irradiation reactions. (author)

  5. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-08-01

    Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

  6. Predictive Local Composition Models for Solid/Liquid Equilibrium in n-Alkane Systems: Wilson Equation for Multicomponent Systems

    DEFF Research Database (Denmark)

    Coutinho, João A.P.; Stenby, Erling Halfdan

    1996-01-01

    The predictive local composition model is applied to multicomponent hydrocarbon systems with long-chain n-alkanes as solutes. The results show that it can successfully be extended to highorder systems and accurately predict the solid appearance temperature, also known as cloud point, in solutions...

  7. Carbon isotope analysis of n-alkanes in dust from the lower atmosphere over the eastern Atlantic

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schefuß, E.; Ratmeyer, V.; Stuut, J-B.W.; Jansen, J.H.F.

    2003-01-01

    Atmospheric dust samples collected along a transect off the West African coast have been investigated for their lipid content and compound-specific stable carbon isotope compositions. The saturated hydrocarbon fractions of the organic solvent extracts consist mainly of long-chain n-alkanes derived

  8. Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

    Science.gov (United States)

    Wilkes, Heinz; Buckel, Wolfgang; Golding, Bernard T; Rabus, Ralf

    2016-01-01

    The glycyl radical enzyme-catalyzed addition of n-alkanes to fumarate creates a C-C-bond between two concomitantly formed stereogenic carbon centers. The configurations of the two diastereoisomers of the product resulting from n-hexane activation by the n-alkane-utilizing denitrifying bacterium strain HxN1, i.e. (1-methylpentyl)succinate, were assigned as (2S,1'R) and (2R,1'R). Experiments with stereospecifically deuterated n-(2,5-2H2)hexanes revealed that exclusively the pro-S hydrogen atom is abstracted from C2 of the n-alkane by the enzyme and later transferred back to C3 of the alkylsuccinate formed. These results indicate that the alkylsuccinate-forming reaction proceeds with an inversion of configuration at the carbon atom (C2) of the n-alkane forming the new C-C-bond, and thus stereochemically resembles a SN2-type reaction. Therefore, the reaction may occur in a concerted manner, which may avoid the highly energetic hex-2-yl radical as an intermediate. The reaction is associated with a significant primary kinetic isotope effect (kH/kD ≥3) for hydrogen, indicating that the homolytic C-H-bond cleavage is involved in the first irreversible step of the reaction mechanism. The (1-methylalkyl)succinate synthases of n-alkane-utilizing anaerobic bacteria apparently have very broad substrate ranges enabling them to activate not only aliphatic but also alkyl-aromatic hydrocarbons. Thus, two denitrifiers and one sulfate reducer were shown to convert the nongrowth substrate toluene to benzylsuccinate and further to the dead-end product benzoyl-CoA. For this purpose, however, the modified β-oxidation pathway known from alkylbenzene-utilizing bacteria was not employed, but rather the pathway used for n-alkane degradation involving CoA ligation, carbon skeleton rearrangement and decarboxylation. Furthermore, various n-alkane- and alkylbenzene-utilizing denitrifiers and sulfate reducers were found to be capable of forming benzyl alcohols from diverse alkylbenzenes

  9. Neutron chain length distributions in subcritical systems

    International Nuclear Information System (INIS)

    Nolen, S.D.; Spriggs, G.

    1999-01-01

    In this paper, the authors present the results of the chain-length distribution as a function of k in subcritical systems. These results were obtained from a point Monte Carlo code and a three-dimensional Monte Carlo code, MC++. Based on these results, they then attempt to explain why several of the common neutron noise techniques, such as the Rossi-α and Feynman's variance-to-mean techniques, are difficult to perform in highly subcritical systems using low-efficiency detectors

  10. Solid acid catalysts in heterogeneous n-alkanes hydroisomerisation ...

    African Journals Online (AJOL)

    As the current global environmental concerns have prompted regulations to reduce the level of aromatic compounds, particularly benzene and its derivatives in gasoline, ydroisomerisation of n-alkanes is becoming a major alternative for enhancing octane number. Series of solid acid catalysts comprising of Freidel crafts, ...

  11. Theoretical study of n-alkane adsorption on metal surfaces

    DEFF Research Database (Denmark)

    Morikawa, Yoshitada; Ishii, Hisao; Seki, Kazuhiko

    2004-01-01

    The interaction between n-alkane and metal surfaces has been studied by means of density-functional theoretical calculations within a generalized gradient approximation (GGA). We demonstrate that although the GGA cannot reproduce the physisorption energy well, our calculations can reproduce the e...

  12. Degradation of n-alkanes and PAHs from the heavy crude oil using salt-tolerant bacterial consortia and analysis of their catabolic genes.

    Science.gov (United States)

    Gurav, Ranjit; Lyu, Honghong; Ma, Jianli; Tang, Jingchun; Liu, Qinglong; Zhang, Hairong

    2017-04-01

    In the present study, salt-tolerant strains, Dietzia sp. HRJ2, Corynebacterium variabile HRJ4, Dietzia cinnamea HRJ5 and Bacillus tequilensis HRJ6 were isolated from the Dagang oil field, China. These strains degraded n-alkanes and polycyclic aromatic hydrocarbons (PAHs) aerobically from heavy crude oil (HCO) in an experiment at 37 °C and 140 rpm. The GC/MS investigation for degradation of different chain lengths of n-alkanes (C8-C40) by individual strains showed the highest degradation of C8-C19 (HRJ5), C20-C30 (HRJ4) and C31-C40 (HRJ5), respectively. Moreover, degradation of 16 PAHs with individual strains demonstrated that the bicyclic and pentacyclic aromatic hydrocarbons (AHs) were mostly degraded by HRJ5, tricyclic and tetracyclic AHs by HRJ6 and hexacyclic AHs by HRJ2. However, the highest degradation of total petroleum hydrocarbons (TPHs), total saturated hydrocarbons (TSH), total aromatic hydrocarbons (TAH), n-alkanes (C8-C40) and 16 PAHs was achieved by a four-membered consortium (HRJ2 + 4 + 5 + 6) within 12 days, with the predominance of HRJ4 and HRJ6 strains which was confirmed by denaturing gradient gel electrophoresis. The abundance of alkB and nah genes responsible for catabolism of n-alkanes and PAHs was quantified using the qPCR. Maximum copy numbers of genes were observed in HRJ2 + 4 + 5 + 6 consortium (gene copies l -1 ) 2.53 × 10 4 (alkB) and 3.47 × 10 3 (nah) at 12 days, which corresponded to higher degradation rates of petroleum hydrocarbons. The superoxide dismutase (SOD) (total SOD (T-SOD), Cu 2+ Zn 2+ -SOD), catalase (CAT) and ascorbate peroxidase (APX) activities in Allium sativum and Triticum aestivum were lower in the HRJ2 + 4 + 5 + 6-treated HCO as compared to the plantlets exposed directly to HCO. The present results revealed the effective degradation of HCO-contaminated saline medium using the microbial consortium having greater metabolic diversity.

  13. Paleoclimate and Asian monsoon variability inferred from n-alkanes and their stable isotopes at lake Donggi Cona, NE Tibetan Plateau

    Science.gov (United States)

    Saini, Jeetendra; Guenther, Franziska; Mäusbacher, Roland; Gleixner, Gerd

    2015-04-01

    The Tibetan Plateau is one of the most extensive and sensitive region of elevated topography affecting global climate. The interplay between the Asian summer monsoon and the westerlies greatly influences the lake systems at the Tibetan Plateau. Despite a considerable number of research efforts in last decade, possible environmental reactions to change in monsoon dynamics are still not well understood. Here we present results from a sediment core of lake Donggi Cona, which dates back to late glacial period. Distinct organic geochemical proxies and stable isotopes are used to study the paleoenvironmental and hydrological changes in late glacial and Holocene period. Sedimentary n-alkanes of lake Donggi Cona are used as a proxy for paleoclimatic and monsoonal reconstruction. The hydrogen (δD) and carbon (δ13C) isotopes of n-alkanes are used as proxy for hydrological and phytoplankton productivity, respectively . Qualitative and quantitative analysis were performed for n-alkanes over the sediment core. δD proxy for sedimentary n-alkanes is used to infer lake water and rainfall signal. δD of (n-alkane C23) records the signal of the lake water, whereas δD of (n-alkane C29) record the precipitation signal, hence act as an appropriate proxy to track Asian monsoon. Long chain n-alkanes dominate over the sediment core while unsaturated mid chain n-alkenes have high abundance in some samples. From 18.4-13.8 cal ka BP, sample shows low organic productivity due to cold and arid climate. After 13.8-11.8 cal ka BP, slight increase in phytoplankton productivity indicate onset of weaker monsoon. From 11.8-6.8 cal ka BP, high content of organic matter indicates rise in productivity and strong monsoon with high inflow. After 6.8 cal ka BP, decrease in phytoplankton productivity indicating cooler climate and show terrestrial signal. Our results provide new insight into the variability of east Asian monsoon and changes in phytoplankton productivity for last 18.4 ka. Keywords: n-alkanes

  14. Finite fission chain length and symmetry around prompt-criticality

    International Nuclear Information System (INIS)

    Xie Qilin; Yin Yanpeng; Gao Hui; Huang Po; Fang Xiaoqiang

    2012-01-01

    Probability distribution of finite fission chain length was derived by assuming that all neutrons behave identically. Finite fission chain length was also calculated using a zero-dimension Monte-Carlo method based on point kinetics. Then symmetry of finite fission chain length probability distribution around prompt-criticality was deduced, which helps understanding the emission rate of delayed neutrons and initiation of fission chain in super-prompt-critical system. (authors)

  15. Flash Points of Secondary Alcohol and n-Alkane Mixtures.

    Science.gov (United States)

    Esina, Zoya N; Miroshnikov, Alexander M; Korchuganova, Margarita R

    2015-11-19

    The flash point is one of the most important characteristics used to assess the ignition hazard of mixtures of flammable liquids. To determine the flash points of mixtures of secondary alcohols with n-alkanes, it is necessary to calculate the activity coefficients. In this paper, we use a model that allows us to obtain enthalpy of fusion and enthalpy of vaporization data of the pure components to calculate the liquid-solid equilibrium (LSE) and vapor-liquid equilibrium (VLE). Enthalpy of fusion and enthalpy of vaporization data of secondary alcohols in the literature are limited; thus, the prediction of these characteristics was performed using the method of thermodynamic similarity. Additionally, the empirical models provided the critical temperatures and boiling temperatures of the secondary alcohols. The modeled melting enthalpy and enthalpy of vaporization as well as the calculated LSE and VLE flash points were determined for the secondary alcohol and n-alkane mixtures.

  16. Stable hydrogen isotopic composition of n-alkanes in atmospheric aerosols as a tracer for the source region of terrestrial plant waxes

    Science.gov (United States)

    Yamamoto, S.; Kawamura, K.

    2009-12-01

    growing leaves in Tokyo, which confirms the usefulness of the δD of long chain n-alkanes as a tracer for the source region of terrestrial plant waxes in atmospheric aerosols.

  17. Physical properties of {anisole + n-alkanes} at temperatures between (293.15 and 303.15) K

    International Nuclear Information System (INIS)

    Al-Jimaz, Adel S.; Al-Kandary, Jasem A.; Abdul-latif, Abdul-Haq M.; Al-Zanki, Adnan M.

    2005-01-01

    Density ρ, viscosity η, and refractive index n D , values of {anisole + hexane, or heptane, or octane, or nonane, or decane, or dodecane} binary mixtures over the entire range of mole fraction at temperatures (293.15, 298.15, and 303.15) K, have been investigated at atmospheric pressure. The excess molar volume V E , has been calculated from the experimental measurements. These results were fitted to Redlich and Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of Grunberg and Nissan, and McAllister. The refractive indices data were used to calculate the specific refractivity R 12 , and also correlated with Lorentz-Lorenz equation. While the excess molar volumes of {anisole + hexane} are negative, and {anisole + heptane} are sigmoidal S-shaped, the remaining binary mixtures are positive. The effects of n-alkanes chain length as well as the temperature on the excess molar volume have been studied. The calculated values have been qualitatively used to explain the intermolecular interaction between the mixing components

  18. Terrestrial environmental changes around the Gulf of Aden over the last 210 kyr deduced from the sediment n-alkane record: Implications for the dispersal of Homo sapiens

    Science.gov (United States)

    Isaji, Yuta; Kawahata, Hodaka; Ohkouchi, Naohiko; Murayama, Masafumi; Tamaki, Kensaku

    2015-03-01

    We analyzed long-chain (C25-C36) n-alkanes and pollen grains in sediments from the Gulf of Aden covering the last 212 kyr to reconstruct the surrounding terrestrial environment, a critical region for the dispersal of Homo sapiens. Substantial increases in the flux of n-alkanes during 200-185, 120-95, and 70-50 ka were interpreted to indicate enhanced vegetation biomass in the Arabian Peninsula and the northern part of the Horn of Africa or increase in lithogenic material inputs. Periods of enhanced n-alkane flux occurred during or immediately after pluvial episodes, indicating that the increased precipitation may have induced substantially enhanced vegetation biomass, creating favorable conditions for Homo sapiens. Additionally, vegetation may have increased due to moderate precipitation unrecorded by speleothems or in accordance with the lowering of sea level, indicating that the dispersal might have been possible even after the shift to an arid environment indicated by the speleothems.

  19. Variation in the Apparent Biosynthetic Fractionation for N-alkane δD Among Terrestrial Plants: Patterns, Mechanisms, and Implications

    Science.gov (United States)

    Johnson, J. E.; Tipple, B. J.; Betancourt, J. L.; Ehleringer, J. R.; Leavitt, S. W.; Monson, R. K.

    2016-12-01

    Long-chain normal alkanes (n-alkanes) are a component of the leaf cuticle of all terrestrial plants. Since the hydrogen in the n-alkanes is derived from the hydrogen in plants' water sources and is non-exchangeable, the stable hydrogen isotopic composition (δD) of the n-alkanes provides information about the δD of environmental waters. While this relationship creates opportunities for using n-alkane δD for process-based reconstructions of δD of environmental waters, progress in this direction is currently constrained by the observation that terrestrial plants exhibit a startlingly wide range of apparent biosynthetic fractionations. To understand the mechanisms responsible for variation in the apparent biosynthetic fractionations, we compared measurements and models of δD for n-C29 in a water-limited ecosystem where the timing of primary and secondary cuticle deposition is closely coupled to water availability (Tumamoc Hill, Tucson, Arizona, USA). During the 2014-2015 hydrologic year, the most widespread and abundant plant species at this site exhibited δD for n-C29 varying over a total range of 102‰. Discrete samples of leaf water collected at the same time as the n-C29 samples exhibited δD varying over a total range of only 53‰, but a continuous model of leaf water through the annual cycle predicted δD varying over a total range of 190‰. These results indicate that the observed variation in the apparent biosynthetic fractionation for n-C29 δD could be primarily attributable to leaf water dynamics that are temporally uncoupled from primary and secondary cuticle deposition. If a single biosynthetic fractionation does describe the relationship between the δD of n-alkanes and leaf water during intervals of cuticle deposition, it will facilitate process-based interpretations of n-alkane δD values in ecological, hydrological, and climatological studies of modern and ancient terrestrial environments.

  20. Abundance and diversity of n-alkane-degrading bacteria in a forest soil co-contaminated with hydrocarbons and metals: a molecular study on alkB homologous genes.

    Science.gov (United States)

    Pérez-de-Mora, Alfredo; Engel, Marion; Schloter, Michael

    2011-11-01

    Unraveling functional genes related to biodegradation of organic compounds has profoundly improved our understanding of biological remediation processes, yet the ecology of such genes is only poorly understood. We used a culture-independent approach to assess the abundance and diversity of bacteria catalyzing the degradation of n-alkanes with a chain length between C(5) and C(16) at a forest site co-contaminated with mineral oil hydrocarbons and metals for nearly 60 years. The alkB gene coding for a rubredoxin-dependent alkane monooxygenase enzyme involved in the initial activation step of aerobic aliphatic hydrocarbon metabolism was used as biomarker. Within the area of study, four different zones were evaluated: one highly contaminated, two intermediately contaminated, and a noncontaminated zone. Contaminant concentrations, hydrocarbon profiles, and soil microbial respiration and biomass were studied. Abundance of n-alkane-degrading bacteria was quantified via real-time PCR of alkB, whereas genetic diversity was examined using molecular fingerprints (T-RFLP) and clone libraries. Along the contamination plume, hydrocarbon profiles and increased respiration rates suggested on-going natural attenuation at the site. Gene copy numbers of alkB were similar in contaminated and control areas. However, T-RFLP-based fingerprints suggested lower diversity and evenness of the n-alkane-degrading bacterial community in the highly contaminated zone compared to the other areas; both diversity and evenness were negatively correlated with metal and hydrocarbon concentrations. Phylogenetic analysis of alkB denoted a shift of the hydrocarbon-degrading bacterial community from Gram-positive bacteria in the control zone (most similar to Mycobacterium and Nocardia types) to Gram-negative genotypes in the contaminated zones (Acinetobacter and alkB sequences with little similarity to those of known bacteria). Our results underscore a qualitative rather than a quantitative response of

  1. Abundance of macroalgal organic matter in biofilms: Evidence from n-alkane biomarkers

    Digital Repository Service at National Institute of Oceanography (India)

    Garg, A; Bhosle, N.B.

    carbon (OC), organic nitrogen (ON), chlorophyll a, diatoms and bacterial numbers on the titanium panels generally increased over the period of immersion. Total lipids and n-alkane concentration also showed similar trends. n-alkanes from C sub(12) to C sub...

  2. Study of factors that influence complex-formation of n-alkanes with crystal carbamide

    Energy Technology Data Exchange (ETDEWEB)

    Dorodnova, V.S.; Korzhov, Yu.A.; Martynenko, A.G.

    1982-01-01

    Studies effect of temperature, solid phase content in the suspension and amount of MeOH on extent of n-alkane extraction during carbamide deparaffinization. A most thorough extraction of n-alkanes is achieved with a graduated temperature regimen of complex-formation.

  3. Constraints on food chain length arising from regional metacommunity dynamics

    Science.gov (United States)

    Calcagno, Vincent; Massol, François; Mouquet, Nicolas; Jarne, Philippe; David, Patrice

    2011-01-01

    Classical ecological theory has proposed several determinants of food chain length, but the role of metacommunity dynamics has not yet been fully considered. By modelling patchy predator–prey metacommunities with extinction–colonization dynamics, we identify two distinct constraints on food chain length. First, finite colonization rates limit predator occupancy to a subset of prey-occupied sites. Second, intrinsic extinction rates accumulate along trophic chains. We show how both processes concur to decrease maximal and average food chain length in metacommunities. This decrease is mitigated if predators track their prey during colonization (habitat selection) and can be reinforced by top-down control of prey vital rates (especially extinction). Moreover, top-down control of colonization and habitat selection can interact to produce a counterintuitive positive relationship between perturbation rate and food chain length. Our results show how novel limits to food chain length emerge in spatially structured communities. We discuss the connections between these constraints and the ones commonly discussed, and suggest ways to test for metacommunity effects in food webs. PMID:21367786

  4. Effect of Amphiphilic Alkyl Chain Length Upon Purified LATEX Stability

    International Nuclear Information System (INIS)

    Amira Amir Hassan; Amir Hashim Mohd Yatim

    2015-01-01

    Rubber particles in purified latex (PL) are stabilized by a film of protein and fatty acid soap (surfactant). Saturated straight-chain fatty acid soaps can assist an enhancement of latex stability. However, whether the alkyl chain length plays an important role in increasing the stability is still an issue. The aim of this study is to investigate the effect of alkyl chain length of anionic surfactant on the stability of purified latex. The fatty acid soap of decanoate (9), laurate (11), sodium dodecyl sulphate (SDS) (12) and palmitate (15) were used. The numbers in parentheses indicating the number of carbon present in alkyl chain of the soap. The results showed that the impact of alkyl chain length on the stability of latex is in the order of laurate > decanoate > SDS > palmitate > purified latex accordingly. The alkyl chain length does giving a significant effect on latex stability after longer stirring time. The particle size of latex with the presence of surfactant is greater compare to a single particle itself due to extension of particles diameter. Thus suitable interaction of the nonpolar tail of surfactant with the hydrophobic regions of latex surface played a major role in maintaining a stable latex system. (author)

  5. Deposition of radiation energy in solids as visualized by the distribution, structure and properties of alkyl radicals in γ-irradiated n-alkane single crystals

    International Nuclear Information System (INIS)

    Gillbro, T.; Lund, A.

    1976-01-01

    This paper summarizes results obtained earlier from ESR studies of γ-irradiated n-alkane single crystals. It also contains some new experimental results that serve to give a more complete picture of the deposition of radiation energy in solid alkanes. The experiments performed with solid n-alkanes have thus far provided structural data that permit the nature and even the conformation of alkyl radicals to be clearly understood. Two types of radical exist namely, one where the unpaired electron is located next to the end methyl group and one with the unpaired electron in the interior of the chain. The first type has a conformation which differs from that of the undamaged molecule. Microwave saturation data show that there is a difference in relaxation properties of these radicals which can be understood in terms of a difference in mobility. Relative yield measurements give the distribution of isomeric alkyl, the result differing from that obtained using product analysis in liquids. For protiated n-alkanes n-alkyl is lacking and the 2-alkyl concentration is higher than expected. For deuterated n-alkanes the ESR spectrum is mainly that of radicals with the unpaired electron located in the interior of the carbon chain. This isotope effect is again contrary to observations in liquid n-alkanes. The broad lines observed in protiated alkanes irradiated at 77 K and deuterated alkanes irradiated at 4.2 K are not believed to arise from strong spin-spin interactions. They are thought instead to arise from distorted crystal and radical structures relating to the damaged regions of the crystals. (Auth.)

  6. Analysis of polychlorinated n-alkanes in environmental samples.

    Science.gov (United States)

    Santos, F J; Parera, J; Galceran, M T

    2006-10-01

    Polychlorinated n-alkanes (PCAs), also known as chlorinated paraffins (CPs), are highly complex technical mixtures that contain a huge number of structural isomers, theoretically more than 10,000 diastereomers and enantiomers. As a consequence of their persistence, tendency to bioaccumulation, and widespread and unrestricted use, PCAs have been found in aquatic and terrestrial food webs, even in rural and remote areas. Recently, these compounds have been included in regulatory programs of several international organizations, including the US Environmental Protection Agency and the European Union. Consequently, there is a growing demand for reliable methods with which to analyze PCAs in environmental samples. Here, we review current trends and recent developments in the analysis of PCAs in environmental samples such as air, water, sediment, and biota. Practical aspects of sample preparation, chromatographic separation, and detection are covered, with special emphasis placed on analysis of PCAs using gas chromatography-mass spectrometry. The advantages and limitations of these techniques as well as recent improvements in quantification procedures are discussed.

  7. Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes

    KAUST Repository

    Wang, Zhandong

    2016-01-20

    Comprehensive low-temperature oxidation mechanisms are needed to accurately predict fuel auto-ignition properties. This paper studies the effects of a previously unconsidered third O2 addition reaction scheme on the simulated auto-ignition of n-alkanes. We demonstrate that this extended low-temperature oxidation scheme has a minor effect on the simulation of n-pentane ignition; however, its addition significantly improves the prediction of n-hexane auto-ignition under low-temperature rapid compression machine conditions. Additional simulations of n-hexane in a homogeneous charge compression ignition engine show that engine-operating parameters (e.g., intake temperature and combustion phasing) are significantly altered when the third O2 addition kinetic mechanism is considered. The advanced combustion phasing is initiated by the formation and destruction of additional radical chain-branching intermediates produced in the third O2 addition process, e.g. keto-dihydroperoxides and/or keto-hydroperoxy cyclic ethers. Our results indicate that third O2 addition reactions accelerate low-temperature radical chain branching at conditions of relevance to advance engine technologies, and therefore these chemical pathways should also be considered for n-alkanes with 6 or more carbon atoms. © 2015 The Combustion Institute.

  8. Application of a Crossover Equation of State to Describe Phase Equilibrium and Critical Properties of n-Alkanes and Methane/n-Alkane Mixtures

    DEFF Research Database (Denmark)

    P. C. M. Vinhal, Andre; Yan, Wei; Kontogeorgis, Georgios M.

    2018-01-01

    and the asymptotic one near the critical point. Although several crossover EOSs have been developed in the last decades their use in modeling industrial processes is rather limited. In this work, we use the crossover Soave–Redlich–Kwong (CSRK) to describe phase equilibrium and critical properties of pure n......-alkanes and methane/n-alkane binary mixtures and compare the results to two other modeling approaches of the SRK EOS. In the case of the pure fluids, CSRK gives an accurate overall description of the phase equilibrium and critical properties; nevertheless, a minor increase in the deviation of the saturation pressure...

  9. A kinetic theory description of the viscosity of dense fluids consisting of chain molecules.

    Science.gov (United States)

    de Wijn, Astrid S; Vesovic, Velisa; Jackson, George; Trusler, J P Martin

    2008-05-28

    An expression for the viscosity of a dense fluid is presented that includes the effect of molecular shape. The molecules of the fluid are approximated by chains of equal-sized, tangentially jointed, rigid spheres. It is assumed that the collision dynamics in such a fluid can be approximated by instantaneous collisions between two rigid spheres belonging to different chains. The approach is thus analogous to that of Enskog for a fluid consisting of rigid spheres. The description is developed in terms of two molecular parameters, the diameter sigma of the spherical segment and the chain length (number of segments) m. It is demonstrated that an analysis of viscosity data of a particular pure fluid alone cannot be used to obtain independently effective values of both sigma and m. Nevertheless, the chain lengths of n-alkanes are determined by assuming that the diameter of each rigid sphere making up the chain can be represented by the diameter of a methane molecule. The effective chain lengths of n-alkanes are found to increase linearly with the number C of carbon atoms present. The dependence can be approximated by a simple relationship m=1+(C-1)3. The same relationship was reported within the context of a statistical associating fluid theory equation of state treatment of the fluid, indicating that both the equilibrium thermodynamic properties and viscosity yield the same value for the chain lengths of n-alkanes.

  10. The Chain-Length Distribution in Subcritical Systems

    International Nuclear Information System (INIS)

    Nolen, Steven Douglas

    2000-01-01

    The individual fission chains that appear in any neutron multiplying system provide a means, via neutron noise analysis, to unlock a wealth of information regarding the nature of the system. This work begins by determining the probability density distributions for fission chain lengths in zero-dimensional systems over a range of prompt neutron multiplication constant (K) values. This section is followed by showing how the integral representation of the chain-length distribution can be used to obtain an estimate of the system's subcritical prompt multiplication (MP). The lifetime of the chains is then used to provide a basis for determining whether a neutron noise analysis will be successful in assessing the neutron multiplication constant, k, of the system in the presence of a strong intrinsic source. A Monte Carlo transport code, MC++, is used to model the evolution of the individual fission chains and to determine how they are influenced by spatial effects. The dissertation concludes by demonstrating how experimental validation of certain global system parameters by neutron noise analysis may be precluded in situations in which the system K is relatively low and in which realistic detector efficiencies are simulated

  11. The Chain-Length Distribution in Subcritical Systems

    Energy Technology Data Exchange (ETDEWEB)

    Nolen, Steven Douglas [Texas A & M Univ., College Station, TX (United States)

    2000-06-01

    The individual fission chains that appear in any neutron multiplying system provide a means, via neutron noise analysis, to unlock a wealth of information regarding the nature of the system. This work begins by determining the probability density distributions for fission chain lengths in zero-dimensional systems over a range of prompt neutron multiplication constant (K) values. This section is followed by showing how the integral representation of the chain-length distribution can be used to obtain an estimate of the system's subcritical prompt multiplication (MP). The lifetime of the chains is then used to provide a basis for determining whether a neutron noise analysis will be successful in assessing the neutron multiplication constant, k, of the system in the presence of a strong intrinsic source. A Monte Carlo transport code, MC++, is used to model the evolution of the individual fission chains and to determine how they are influenced by spatial effects. The dissertation concludes by demonstrating how experimental validation of certain global system parameters by neutron noise analysis may be precluded in situations in which the system K is relatively low and in which realistic detector efficiencies are simulated.

  12. Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

    Science.gov (United States)

    Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

    2011-07-21

    In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

  13. High frequency of Thermodesulfovibrio spp. and Anaerolineaceae in association with Methanoculleus spp. in a long-term incubation of n-alkanes-degrading methanogenic enrichment culture

    Directory of Open Access Journals (Sweden)

    Bo Liang

    2016-09-01

    Full Text Available In the present study, the microbial community and functional gene composition of a long-term active alkane-degrading methanogenic culture was established after two successive enrichment culture transfers and incubated for a total period of 1750 days. Molecular analysis was conducted after the second transfer (incubated for 750 days for both the active alkanes-degrading methanogenic enrichment cultures (T2-AE and the background control (T2-BC. A net increase of methane as the end product was detected in the headspace of the enrichment cultures amended with long-chain n-alkanes and intermediate metabolites, including octadecanoate, hexadecanoate, isocaprylate, butyrate, isobutyrate, propionate, acetate and formate were measured in the liquid cultures. The composition of microbial community shifted through the successive transfers over time of incubation. Sequences of bacterial and archaeal 16S rRNA gene (16S rDNA and mcrA functional gene indicated that bacterial sequences affiliated to Thermodesulfovibrio spp. and Anaerolineaceae and archaeal sequences falling within the genus Methanoculleus were the most frequently encountered and thus represented the dominant members performing the anaerobic degradation of long-chain n-alkanes and methanogenesis. In addition, the presence of assA functional genes encoding the alkylsuccinate synthase α subunit indicated that fumarate addition mechanism could be considered as a possible initial activation step of n-alkanes in the present study. The succession pattern of microbial communities indicates that Thermodesulfovibrio spp. could be a generalist participating in the metabolism of intermediates, while Anaerolineaceae plays a key role in the initial activation of long-chain n-alkane biodegradation.

  14. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    Directory of Open Access Journals (Sweden)

    Monisha Rastogi

    2015-05-01

    Full Text Available The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  15. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Monisha [School of Engineering, Indian Institute of Technology Mandi, Himachal Pradesh 175 001 (India); Vaish, Rahul, E-mail: rahul@iitmandi.ac.in [School of Engineering, Indian Institute of Technology Mandi, Himachal Pradesh 175 001 (India); Materials Research Centre, Indian Institute of Science, Bangalore 560 012 (India)

    2015-05-15

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  16. Stochastic Simulation of a Full-Chain Reptation Model with Constraint Release, Chain-Length Fluctuations and Chain Stretching

    DEFF Research Database (Denmark)

    Neergaard, Jesper; Schieber, Jay D.

    1999-01-01

    A self-consistent reptation model that includes chain stretching, chain-length fluctuations, segment connectivity and constraint release is used to predict transient and steady flows. Quantitative comparisons are made with entangledsolution data. The model is able to capture quantitatively all...

  17. Growth of Rhodococcus sp. strain BCP1 on gaseous n-alkanes: new metabolic insights and transcriptional analysis of two soluble di-iron monooxygenase genes

    Directory of Open Access Journals (Sweden)

    Martina eCappelletti

    2015-05-01

    Full Text Available Rhodococcus sp. strain BCP1 was initially isolated for its ability to grow on gaseous n-alkanes, which act as inducers for the co-metabolic degradation of low-chlorinated compounds. Here, both molecular and metabolic features of BCP1 cells grown on gaseous and short-chain n-alkanes (up to n-heptane were examined in detail. We show that propane metabolism generated terminal and sub-terminal oxidation products such as 1- and 2-propanol, whereas 1-butanol was the only terminal oxidation product detected from butane metabolism. Two gene clusters, prmABCD and smoABCD – coding for soluble di-iron monooxgenases (SDIMOs involved in gaseous n-alkanes oxidation – were detected in the BCP1 genome. By means of reverse transcriptase-quantitative PCR (RT-qPCR analysis, a set of substrates inducing the expression of the sdimo genes in BCP1 were assessed as well as their transcriptional repression in the presence of sugars, organic acids or during the cell growth on rich medium (Luria Bertani broth. The transcriptional start sites of both the sdimo gene clusters were identified by means of primer extension experiments. Finally, proteomic studies revealed changes in the protein pattern induced by growth on gaseous- (n-butane and/or liquid (n-hexane short-chain n-alkanes as compared to growth on succinate. Among the differently expressed protein spots, two chaperonins and an isocytrate lyase were identified along with oxidoreductases involved in oxidation reactions downstream of the initial monooxygenase reaction step.

  18. Growth of Rhodococcus sp. strain BCP1 on gaseous n-alkanes: new metabolic insights and transcriptional analysis of two soluble di-iron monooxygenase genes

    Science.gov (United States)

    Cappelletti, Martina; Presentato, Alessandro; Milazzo, Giorgio; Turner, Raymond J.; Fedi, Stefano; Frascari, Dario; Zannoni, Davide

    2015-01-01

    Rhodococcus sp. strain BCP1 was initially isolated for its ability to grow on gaseous n-alkanes, which act as inducers for the co-metabolic degradation of low-chlorinated compounds. Here, both molecular and metabolic features of BCP1 cells grown on gaseous and short-chain n-alkanes (up to n-heptane) were examined in detail. We show that propane metabolism generated terminal and sub-terminal oxidation products such as 1- and 2-propanol, whereas 1-butanol was the only terminal oxidation product detected from n-butane metabolism. Two gene clusters, prmABCD and smoABCD—coding for Soluble Di-Iron Monooxgenases (SDIMOs) involved in gaseous n-alkanes oxidation—were detected in the BCP1 genome. By means of Reverse Transcriptase-quantitative PCR (RT-qPCR) analysis, a set of substrates inducing the expression of the sdimo genes in BCP1 were assessed as well as their transcriptional repression in the presence of sugars, organic acids, or during the cell growth on rich medium (Luria–Bertani broth). The transcriptional start sites of both the sdimo gene clusters were identified by means of primer extension experiments. Finally, proteomic studies revealed changes in the protein pattern induced by growth on gaseous- (n-butane) and/or liquid (n-hexane) short-chain n-alkanes as compared to growth on succinate. Among the differently expressed protein spots, two chaperonins and an isocytrate lyase were identified along with oxidoreductases involved in oxidation reactions downstream of the initial monooxygenase reaction step. PMID:26029173

  19. Determination of Short-Chain Chlorinated Paraffins by Carbon Skeleton Gas Chromatography

    OpenAIRE

    PELLIZZATO FRANCESCA; RICCI MARINA; HELD ANDREA; EMONS HENDRIK

    2008-01-01

    Short-Chain Chlorinated Paraffins (SCCPs) are highly complex technical mixtures of polychlorinated n-alkanes with a chlorination degree between 50 and 70 % by mass, and a linear carbon chain length from C10 to C13, constituted by thousands of homologues, diastereomers and enantiomers. They have been used in many different applications, such as extreme pressure additives in lubricants and cutting fluids, plasticizers in PVC, and flame retardants in paints, adhesives and sealants. SCCPs are tox...

  20. Expected value of finite fission chain lengths of pulse reactors

    International Nuclear Information System (INIS)

    Liu Jianjun; Zhou Zhigao; Zhang Ben'ai

    2007-01-01

    The average neutron population necessary for sponsoring a persistent fission chain in a multiplying system, is discussed. In the point reactor model, the probability function θ(n, t 0 , t) of a source neutron at time t 0 leading to n neutrons at time t is dealt with. The non-linear partial differential equation for the probability generating function G(z; t 0 , t) is derived. By solving the equation, we have obtained an approximate analytic solution for a slightly prompt supercritical system. For the pulse reactor Godiva-II, the mean value of finite fission chain lengths is estimated in this work and shows that the estimated value is reasonable for the experimental analysis. (authors)

  1. Flow reactor studies of non-equilibrium plasma-assisted oxidation of n-alkanes.

    Science.gov (United States)

    Tsolas, Nicholas; Lee, Jong Guen; Yetter, Richard A

    2015-08-13

    The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  2. Glycogen with short average chain length enhances bacterial durability

    Science.gov (United States)

    Wang, Liang; Wise, Michael J.

    2011-09-01

    Glycogen is conventionally viewed as an energy reserve that can be rapidly mobilized for ATP production in higher organisms. However, several studies have noted that glycogen with short average chain length in some bacteria is degraded very slowly. In addition, slow utilization of glycogen is correlated with bacterial viability, that is, the slower the glycogen breakdown rate, the longer the bacterial survival time in the external environment under starvation conditions. We call that a durable energy storage mechanism (DESM). In this review, evidence from microbiology, biochemistry, and molecular biology will be assembled to support the hypothesis of glycogen as a durable energy storage compound. One method for testing the DESM hypothesis is proposed.

  3. ESR study of n-alkane cation structure and photodecomposition in γ-irradiated frozen solutions of CF3CCl3

    International Nuclear Information System (INIS)

    Tabata, M.; Lund, A.

    1984-01-01

    Cations of several n-alkanes produced by γ-irradiation at 77 K of a CF 3 CCl 3 matrix containing 0.1 to 2 mole% of solute have been investigated with special emphasis on their photo-induced decomposition. A general route of reaction of n-alkane cations containing 4 to 7 chain carbon atoms involves the formation of 2-butene cation probably in a process of the type Csub(n)H + sub(2n+2) -> 2-C 4 H 8 + + Csub(n-4)Hsub(2n-6). This reaction is exothermic, but does not occur thermally over the temperature interval 77 to 140 K. The variation of the ESR spectral data of the parent cations have been investigated over the temperature interval 4 to 140 K and have been compared with data obtained using other matrices. It is concluded that the assumption of an extended conformation of the n-alkane cation is not always valid and that the structure is sensitive to matrix and temperature effects. (author)

  4. Long n-alkanes isomerization by medium pore zeolites with pore mouth and key lock mechanisms; Isomerisation des paraffines longues par des zeolithes a pores moyens selon les mecanismes ouverture de pore et cle serrure

    Energy Technology Data Exchange (ETDEWEB)

    Claude, M.

    1999-10-01

    Skeletal isomerization of long n-alkanes is practiced to improve cold flow properties of diesel and lubricant fractions. In this work, model long n-alkanes (n-C{sub 10} - n-C{sub 24}) were hydro-isomerized in a fixed bed down flow vapour phase reactor loaded with bifunctional Pt/H-ZSM-22 zeolite catalyst. The skeletal isomers were analysed and identified with GC/MS. High isomer yields were obtained. The distribution of positional mono-methyl-branched isomers obtained from n-C{sub 12} to n-C{sub 24} are typically bimodal. This is explained by adsorption and reaction of the alkanes in pore mouths and locks on the external surface of the zeolite crystals. The pore mouth mode favours branching at C{sub 2} and C{sub 3}. The 'key lock' type proceeds by penetration of the two ends of the hydrocarbon chain into a different pore opening and favours more central mono-branching of the chain. The contribution of the key lock mode increases with increasing chain length and with the reaction temperature. The preferentially formed dimethyl-branched isomers have a separation between branchings of three up to fourteen carbon atoms. The formation of the second methyl-branching occurs preferentially from a centrally branched mono-methyl-branched isomer, so that the second branching is generated always more toward the end of the chain. Owing to the differences in adsorption entropy among the locks, at higher temperatures the largest lock is preferred and the distance between the two branching along the carbon chain in the preferred isomers is biggest. Thus the work resulted in the formulation of structure-selectivity relationships. n-C{sub 18} was hydro-isomerized on other zeolites. The nature and distribution of the isomers obtained suggest that the tubular 10-ring zeolites ZSM-23, ZSM-35 and SAPO-11 also operate according to pore mouth and key lock concepts. Zeolites with 12-rings show typical product patterns for catalysis in absence of steric hindrance. (author)

  5. Evaluation of n-alkanes and their carbon isotope enrichments (d13C) as diet composition markers

    NARCIS (Netherlands)

    Derseh, M.B.; Pellikaan, W.F.; Tolera, A.; Hendriks, W.H.

    2011-01-01

    Plant cuticular n-alkanes have been successfully used as markers to estimate diet composition and intake of grazing herbivores. However, additional markers may be required under grazing conditions in botanically diverse vegetation. This study was conducted to describe the n-alkane profiles and the

  6. Stable isotope labeled n-alkanes to assess digesta passage kinetics through the digestive tract of ruminants

    NARCIS (Netherlands)

    Warner, D.; Ferreira, L.M.M.; Breuer, M.J.H.; Dijkstra, J.; Pellikaan, W.F.

    2013-01-01

    We describe the use of carbon stable isotope (13C) labeled n-alkanes as a potential internal tracer to assess passage kinetics of ingested nutrients in ruminants. Plant cuticular n-alkanes originating from intrinsically 13C labeled ryegrass plants were pulse dosed intraruminally in four

  7. Cool-flame Extinction During N-Alkane Droplet Combustion in Microgravity

    Science.gov (United States)

    Nayagam, Vedha; Dietrich, Daniel L.; Hicks, Michael C.; Williams, Forman A.

    2014-01-01

    Recent droplet combustion experiments onboard the International Space Station (ISS) have revealed that large n-alkane droplets can continue to burn quasi-steadily following radiative extinction in a low-temperature regime, characterized by negative-temperaturecoefficient (NTC) chemistry. In this study we report experimental observations of n-heptane, n-octane, and n-decane droplets of varying initial sizes burning in oxygen/nitrogen/carbon dioxide and oxygen/helium/nitrogen environments at 1.0, 0.7, and 0.5 atmospheric pressures. The oxygen concentration in these tests varied in the range of 14% to 25% by volume. Large n-alkane droplets exhibited quasi-steady low-temperature burning and extinction following radiative extinction of the visible flame while smaller droplets burned to completion or disruptively extinguished. A vapor-cloud formed in most cases slightly prior to or following the "cool flame" extinction. Results for droplet burning rates in both the hot-flame and cool-flame regimes as well as droplet extinction diameters at the end of each stage are presented. Time histories of radiant emission from the droplet captured using broadband radiometers are also presented. Remarkably the "cool flame" extinction diameters for all the three n-alkanes follow a trend reminiscent of the ignition delay times observed in previous studies. The similarities and differences among the n-alkanes during "cool flame" combustion are discussed using simplified theoretical models of the phenomenon

  8. Topological analysis of polymeric melts: chain-length effects and fast-converging estimators for entanglement length.

    Science.gov (United States)

    Hoy, Robert S; Foteinopoulou, Katerina; Kröger, Martin

    2009-09-01

    Primitive path analyses of entanglements are performed over a wide range of chain lengths for both bead spring and atomistic polyethylene polymer melts. Estimators for the entanglement length N_{e} which operate on results for a single chain length N are shown to produce systematic O(1/N) errors. The mathematical roots of these errors are identified as (a) treating chain ends as entanglements and (b) neglecting non-Gaussian corrections to chain and primitive path dimensions. The prefactors for the O(1/N) errors may be large; in general their magnitude depends both on the polymer model and the method used to obtain primitive paths. We propose, derive, and test new estimators which eliminate these systematic errors using information obtainable from the variation in entanglement characteristics with chain length. The new estimators produce accurate results for N_{e} from marginally entangled systems. Formulas based on direct enumeration of entanglements appear to converge faster and are simpler to apply.

  9. Effect of temperature on atom-atom collision chain length in metals

    International Nuclear Information System (INIS)

    Makarov, A.A.; Demkin, N.A.; Lyashchenko, B.G.

    1981-01-01

    Focused atom-atom collision chain lengths are calculated for fcc-crystals with account of thermal oscillations. The model of solid spheres with the Born-Merier potential has been used in the calculations. The dependence of chain lengths on the temperature, energy and movement direction of the first chain atom for Cu, Au, Ag, Pb, Ni is considered. The plot presented shows that the chain lengths strongly decrease with temperature growth, for example, for the gold at T=100 K the chain length equals up to 37 interatomic spacings, whereas at T=1000 K their length decreases down to 5 interatomic distances. The dependence of the energy loss by the chain atoms on the atom number in the chain is obtained in a wide range of crystal temperature and the primary chain atom energy [ru

  10. Self-Assembly of Alkylammonium Chains on Montmorillonite: Effect of Interlayer Cations, CEC, and Chain Length

    Science.gov (United States)

    Chen, Hua; Li, Yingjun; Zhou, Yuanlin; Wang, Shanqiang; Zheng, Jian; He, Jiacai

    2017-12-01

    Recently, polymeric materials have been filled with synthetic or natural inorganic compounds in order to improve their properties. Especially, polymer clay nanocomposites have attracted both academic and industrial attention. Currently, the structure and physical phenomena of organoclays at molecular level are difficultly explained by existing experimental techniques. In this work, molecular dynamics (MD) simulation was executed using the CLAYFF and CHARMM force fields to evaluate the structural properties of organoclay such as basal spacing, interlayer density, energy and the arrangement of alkyl chains in the interlayer spacing. Our results are in good agreement with available experimental or other simulation data. The effects of interlayer cations (Na+, K+, Ca2+), the cation exchange capacity, and the alkyl chain length on the basal spacing and the structural properties are estimated. These simulations are expected to presage the microstructure of organo-montmorillonite and lead relevant engineering applications.

  11. Biodegradation of crude oil and n-alkanes by fungi isolated from Oman

    Energy Technology Data Exchange (ETDEWEB)

    Elshafie, Abdulkadir [Department of Biology, College of Science, Sultan Qaboos University, P.O. Box 36 Al Khod, Muscat (Oman)], E-mail: Elshafie@squ.edu.om; AlKindi, Abdulaziz Yahya [Department of Biology, College of Science, Sultan Qaboos University, P.O. Box 36 Al Khod, Muscat (Oman); Al-Busaidi, Sultan [Oman Refinery Company Laboratories, LLC, P.O. Box 3568 Ruwi PC112 (Oman); Bakheit, Charles [Department of Mathematics and Statistics, College of Science, Sultan Qaboos University, P.O. Box 36 Al Khod, Muscat (Oman); Albahry, S.N. [Department of Biology, College of Science, Sultan Qaboos University, P.O. Box 36 Al Khod, Muscat (Oman)

    2007-11-15

    Ten fungal species isolated from tar balls collected from the beaches of Oman were tested for their abilities to grow and degrade n-alkanes and crude oil. The abilities of Aspergillus niger, A. ochraceus and Penicillium chrysogenum to degrade n-alkanes (C13-C18), crude oil were compared and their mycelial biomass was measured. Significant differences were found in the utilization of C15, C16, C17 and C18 by the three fungi. Similarly, significant differences we found in the amount of biomass produced by the three fungi growing on C13, C17, C18 and crude oil. The correlation coefficient of biomass and oil utilization was not statistically significant for Aspergillus niger, significant for Aspergillus terreus and highly significant for P. chrysogenum.

  12. Application of statistical experimental methodology to optimize bioremediation of n-alkanes in aquatic environment

    International Nuclear Information System (INIS)

    Zahed, Mohammad Ali; Aziz, Hamidi Abdul; Mohajeri, Leila; Mohajeri, Soraya; Kutty, Shamsul Rahman Mohamed; Isa, Mohamed Hasnain

    2010-01-01

    Response surface methodology (RSM) was employed to optimize nitrogen and phosphorus concentrations for removal of n-alkanes from crude oil contaminated seawater samples in batch reactors. Erlenmeyer flasks were used as bioreactors; each containing 250 mL dispersed crude oil contaminated seawater, indigenous acclimatized microorganism and different amounts of nitrogen and phosphorus based on central composite design (CCD). Samples were extracted and analyzed according to US-EPA protocols using a gas chromatograph. During 28 days of bioremediation, a maximum of 95% total aliphatic hydrocarbons removal was observed. The obtained Model F-value of 267.73 and probability F < 0.0001 implied the model was significant. Numerical condition optimization via a quadratic model, predicted 98% n-alkanes removal for a 20-day laboratory bioremediation trial using nitrogen and phosphorus concentrations of 13.62 and 1.39 mg/L, respectively. In actual experiments, 95% removal was observed under these conditions.

  13. Experimental measurements and prediction of liquid densities for n-alkane mixtures

    International Nuclear Information System (INIS)

    Ramos-Estrada, Mariana; Iglesias-Silva, Gustavo A.; Hall, Kenneth R.

    2006-01-01

    We present experimental liquid densities for n-pentane, n-hexane and n-heptane and their binary mixtures from (273.15 to 363.15) K over the entire composition range (for the mixtures) at atmospheric pressure. A vibrating tube densimeter produces the experimental densities. Also, we present a generalized correlation to predict the liquid densities of n-alkanes and their mixtures. We have combined the principle of congruence with the Tait equation to obtain an equation that uses as variables: temperature, pressure and the equivalent carbon number of the mixture. Also, we present a generalized correlation for the atmospheric liquid densities of n-alkanes. The average absolute percentage deviation of this equation from the literature experimental density values is 0.26%. The Tait equation has an average percentage deviation of 0.15% from experimental density measurements

  14. Biodegradation of crude oil and n-alkanes by fungi isolated from Oman

    International Nuclear Information System (INIS)

    Elshafie, Abdulkadir; AlKindi, Abdulaziz Yahya; Al-Busaidi, Sultan; Bakheit, Charles; Albahry, S.N.

    2007-01-01

    Ten fungal species isolated from tar balls collected from the beaches of Oman were tested for their abilities to grow and degrade n-alkanes and crude oil. The abilities of Aspergillus niger, A. ochraceus and Penicillium chrysogenum to degrade n-alkanes (C13-C18), crude oil were compared and their mycelial biomass was measured. Significant differences were found in the utilization of C15, C16, C17 and C18 by the three fungi. Similarly, significant differences we found in the amount of biomass produced by the three fungi growing on C13, C17, C18 and crude oil. The correlation coefficient of biomass and oil utilization was not statistically significant for Aspergillus niger, significant for Aspergillus terreus and highly significant for P. chrysogenum

  15. Chain length dependence of the critical density of organic homologous series

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios M.; Fredenslund, Aage; Tassios, Dimitrios P.

    1995-01-01

    Whether the critical density of organic compounds belonging to a certain homologous series increases or decreases with (increasing) molecular weight has been a challenging question over the years. Two sets of experimental data have recently appeared in the literature for the critical density of n......-alkanes: Steele's data (up to n-decane) suggest that critical density increases with carbon number and reaches a limiting value. On the other hand, the data of Teja et al., 1990 which cover a broader range of n-alkanes (up to n-octadecane), reveal a decreasing trend of the critical density after a maximum at n......-heptane. Teja et al. have also presented critical density measurements for 1-alkenes (up to 1-decene) and 1-alkanols (up to 1-undecanol). These data follow the same decreasing trend with the molecular weight as n-alkanes. This trend is not in agreement with the predictions of most group-contribution methods...

  16. n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

    Science.gov (United States)

    Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

    2007-06-01

    Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism.

  17. Structural Insights into Diversity and n-Alkane Biodegradation Mechanisms of Alkane Hydroxylases

    Directory of Open Access Journals (Sweden)

    Yurui eJi

    2013-03-01

    Full Text Available Environmental microbes utilize four degradation pathways for the oxidation of n-alkanes. Although the enzymes degrading n-alkanes in different microbes may vary, enzymes functioning in the first step in the aerobic degradation of alkanes all belong to the alkane hydroxylases. Alkane hydroxylases are a class of enzymes that insert oxygen atoms derived from molecular oxygen into different sites of the alkane terminus (or termini depending on the type of enzymes. In this review, we summarize the different types of alkane hydroxylases, their degrading steps and compare typical enzymes from various classes with regard to their three dimensional structures, in order to provide insights into how the enzymes mediate their different roles in the degradation of n-alkanes and what determines their different substrate ranges. Through the above analyses, the degrading mechanisms of enzymes can be elucidated and molecular biological methods can be utilized to expand their catalytic roles in the petrochemical industry or in bioremediation of oil-contaminated environments.

  18. The roles of productivity and ecosystem size in determining food chain length in tropical terrestrial ecosystems.

    Science.gov (United States)

    Young, Hillary S; McCauley, Douglas J; Dunbar, Robert B; Hutson, Michael S; Ter-Kuile, Ana Miller; Dirzo, Rodolfo

    2013-03-01

    Many different drivers, including productivity, ecosystem size, and disturbance, have been considered to explain natural variation in the length of food chains. Much remains unknown about the role of these various drivers in determining food chain length, and particularly about the mechanisms by which they may operate in terrestrial ecosystems, which have quite different ecological constraints than aquatic environments, where most food chain length studies have been thus far conducted. In this study, we tested the relative importance of ecosystem size and productivity in influencing food chain length in a terrestrial setting. We determined that (1) there is no effect of ecosystem size or productive space on food chain length; (2) rather, food chain length increases strongly and linearly with productivity; and (3) the observed changes in food chain length are likely achieved through a combination of changes in predator size, predator behavior, and consumer diversity along gradients in productivity. These results lend new insight into the mechanisms by which productivity can drive changes in food chain length, point to potential for systematic differences in the drivers of food web structure between terrestrial and aquatic systems, and challenge us to consider how ecological context may control the drivers that shape food chain length.

  19. Structure-guided investigation of lipopolysaccharide O-antigen chain length regulators reveals regions critical for modal length control.

    Science.gov (United States)

    Kalynych, Sergei; Ruan, Xiang; Valvano, Miguel A; Cygler, Miroslaw

    2011-08-01

    The O-antigen component of the lipopolysaccharide (LPS) represents a population of polysaccharide molecules with nonrandom (modal) chain length distribution. The number of the repeat O units in each individual O-antigen polymer depends on the Wzz chain length regulator, an inner membrane protein belonging to the polysaccharide copolymerase (PCP) family. Different Wzz proteins confer vastly different ranges of modal lengths (4 to >100 repeat units), despite having remarkably conserved structural folds. The molecular mechanism responsible for the selective preference for a certain number of O units is unknown. Guided by the three-dimensional structures of PCPs, we constructed a panel of chimeric molecules containing parts of two closely related Wzz proteins from Salmonella enterica and Shigella flexneri which confer different O-antigen chain length distributions. Analysis of the O-antigen length distribution imparted by each chimera revealed the region spanning amino acids 67 to 95 (region 67 to 95), region 200 to 255, and region 269 to 274 as primarily affecting the length distribution. We also showed that there is no synergy between these regions. In particular, region 269 to 274 also influenced chain length distribution mediated by two distantly related PCPs, WzzB and FepE. Furthermore, from the 3 regions uncovered in this study, region 269 to 274 appeared to be critical for the stability of the oligomeric form of Wzz, as determined by cross-linking experiments. Together, our data suggest that chain length determination depends on regions that likely contribute to stabilize a supramolecular complex.

  20. How Chain Length and Charge Affect Surfactant Denaturation of Acyl Coenzyme A Binding Protein (ACBP)

    DEFF Research Database (Denmark)

    Andersen, Kell Kleiner; Otzen, Daniel

    2009-01-01

    maltoside (DDM). The aim has been to determine how surfactant chain length and micellar charge affect the denaturation mechanism. ACBP denatures in two steps irrespective of surfactant chain length, but with increasing chain length, the potency of the denaturant rises more rapidly than the critical micelle......Using intrinsic tryptophan fluorescence, equilibria and kinetics of unfolding of acyl coenzyme A binding protein (ACBP) have been investigated in sodium alkyl sulfate surfactants of different chain length (8-16 carbon atoms) and with different proportions of the nonionic surfactant dodecyl...... constants increases linearly with denaturant concentration below the cmc but declines at higher concentrations. Both shortening chain length and decreasing micellar charge reduce the overall kinetics of unfolding and makes the dependence of unfolding rate constants on surfactant concentration more complex...

  1. Polyurethanes elastomers with amide chain extenders of uniform length

    NARCIS (Netherlands)

    van der Schuur, J.M.; Noordover, B.A.J.; Noordover, Bart; Gaymans, R.J.

    2006-01-01

    Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

  2. Polyuretehane elastomers with amide chain extenders of uniform length

    NARCIS (Netherlands)

    Schuur, van der M.; Noordover, B.A.J.; Gaymans, R.J.

    2006-01-01

    Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

  3. n-Alkanes in surficial sediments of Visakhapatnam harbour, east coast of India

    Digital Repository Service at National Institute of Oceanography (India)

    Punyu, V.R.; Harji, R.R.; Bhosle, N.B.; Sawant, S.S.; Venkat, K.

    -alkanes mainly at C15, C17 and C19 Keywords. Sediments; lipids; n-alkanes; Visakhapatnam harbour. J. Earth Syst. Sci. 122, No. 2, April 2013, pp. 467–477 c© Indian Academy of Sciences 467 468 V R Punyu et al while terrestrial plants exhibit predominance of long... steel plant, a fertilizer plant and a lead and zinc smelter in the vicinity are discharged into this harbour. The harbour handles items such as man- ganese and iron ore, coal and oil products. Added to this, it receives most of the urban run...

  4. Quantum discord length is enhanced while entanglement length is not by introducing disorder in a spin chain.

    Science.gov (United States)

    Sadhukhan, Debasis; Roy, Sudipto Singha; Rakshit, Debraj; Prabhu, R; Sen De, Aditi; Sen, Ujjwal

    2016-01-01

    Classical correlation functions of ground states typically decay exponentially and polynomially, respectively, for gapped and gapless short-range quantum spin systems. In such systems, entanglement decays exponentially even at the quantum critical points. However, quantum discord, an information-theoretic quantum correlation measure, survives long lattice distances. We investigate the effects of quenched disorder on quantum correlation lengths of quenched averaged entanglement and quantum discord, in the anisotropic XY and XYZ spin glass and random field chains. We find that there is virtually neither reduction nor enhancement in entanglement length while quantum discord length increases significantly with the introduction of the quenched disorder.

  5. Determination of molecular diffusion coefficient in n-alkane binary mixtures: empirical correlations.

    Science.gov (United States)

    De Mezquia, D Alonso; Bou-Ali, M Mounir; Larrañaga, M; Madariaga, J A; Santamaría, C

    2012-03-08

    In this work we have measured the molecular diffusion coefficient of the n-alkane binary series nC(i)-nC(6), nC(i)-nC(10), and nC(i)-nC(12) at 298 K and 1 atm and a mass fraction of 0.5 by using the so-called sliding symmetric tubes technique. The results show that the diffusion coefficient at this concentration is proportional to the inverse viscosity of the mixture. In addition, we have also measured the diffusion coefficient of the systems nC(12)-nC(6), nC(12)-nC(7), and nC(12)-nC(8) as a function of concentration. From the data obtained, it is shown that the diffusion coefficient of the n-alkane binary mixtures at any concentration can be calculated from the molecular weight of the components and the dynamic viscosity of the corresponding mixture at 50% mass fraction.

  6. Dependence of the product chain-length on detergents for long-chain E-polyprenyl diphosphate synthases

    Science.gov (United States)

    Pan, Jian-Jung; Ramamoorthy, Gurusankar; Poulter, C. Dale

    2013-01-01

    Long-chain E-polyprenyl diphosphate synthases (E-PDS) catalyze repetitive addition of isopentenyl diphosphate (IPP) to the growing prenyl chain of an allylic diphosphate. The polyprenyl diphosphate products are required for the biosynthesis of ubiquinones and menaquinones required for electron transport during oxidative phosphorylation to generate ATP. In vitro, the long-chain PDSs require addition of phospholipids or detergents to the assay buffer to enhance product release and maintain efficient turnover. During preliminary assays of product chain-length with anionic, zwitterionic, and non-ionic detergents, we discovered considerable variability. Examination of a series of non-ionic PEG detergents with several long-chain E-PDSs from different organisms revealed that in vitro incubations with nonaethylene glycol monododecyl ether or Triton X-100 typically gave chain lengths that corresponded to those of the isoprenoid moieties in respiratory quinones synthesized in vivo. In contrast incubations in buffer with n-butanol, CHAPS, DMSO, n-octyl-β-glucopyranoside, or β-cyclodextrin or in buffer without detergent typically proceeded more slowly and gave a broad range of chain lengths. PMID:23802587

  7. Sublethal Toxic Effects and Induction of gGutathione S-transferase by Short-Chain Chlorinated Paraffins (SCCPs) and C-12 alkane (dodecane) in Xenopus laevis Frog Embryos

    OpenAIRE

    B. Burýšková; L. Bláha; D. Vršková; K. Šimková; B. Maršálek

    2006-01-01

    Short chain chlorinated paraffins (SCCPs) are important industrial chemicals with high persistence in the environment but poorly characterized ecotoxicological effects. We studied embryotoxic effects of commercial mixture of SCCP (carbon length C-12, 56% of chlorine; CP56-12) and non-chlorinated n-alkane (dodecane, C-12) in the 96h Frog Embryo Teratogenesis Assay - Xenopus (FETAX). Only weak lethal effects were observed for both substances (the highest tested concentration 500 mg/L of both ch...

  8. Exploring the impact of the side-chain length on peptide/RNA binding events.

    Science.gov (United States)

    Sbicca, Lola; González, Alejandro López; Gresika, Alexandra; Di Giorgio, Audrey; Closa, Jordi Teixido; Tejedor, Roger Estrada; Andréola, Marie-Line; Azoulay, Stéphane; Patino, Nadia

    2017-07-19

    The impact of the amino-acid side-chain length on peptide-RNA binding events has been investigated using HIV-1 Tat derived peptides as ligands and the HIV-1 TAR RNA element as an RNA model. Our studies demonstrate that increasing the length of all peptide side-chains improves unexpectedly the binding affinity (K D ) but reduces the degree of compactness of the peptide-RNA complex. Overall, the side-chain length appears to modulate in an unpredictable way the ability of the peptide to compete with the cognate TAR RNA partner. Beyond the establishment of non-intuitive fundamental relationships, our results open up new perspectives in the design of effective RNA ligand competitors, since a large number of them have already been identified but few studies report on the modulation of the biological activity by modifying in the same way the length of all chains connecting RNA recognition motives to the central scaffold of a ligand.

  9. Novel odd/even effect of alkylene chain length on the photopolymerizability of organogelators.

    Science.gov (United States)

    Aoki, Ken'ichi; Kudo, Masabumi; Tamaoki, Nobuyuki

    2004-10-28

    [reaction: see text] Starting from diactylene diacarboxylic acids, we have synthesized a series of photopolymerizable organogelators that possess simple amide structures, different alkylene chain lengths, and either optically active or racemic 3,7-dimethyl-1-octylamine units. The alkylene chain length of these compounds exhibits a prominent odd/even effect with respect to the photopolymerization in the gel state and is accompanied by a stereostructural effect on the gelation ability.

  10. Paleoclimatic implications of the hydrogen isotopic composition of terrigenous n-alkanes from Lake Yamzho, southern Tibetan Plateau

    International Nuclear Information System (INIS)

    Xia Zhonghuan; Xu Baiqing; Wu Guangjian; Zhu Liping; Muegler Ines; Gleixner, Gerd; Sachse, Dirk

    2009-01-01

    The hydrogen isotopic composition (δD) of leaf water used for biosynthesis of n-alkanes can be modified by climate. Therefore, the δD can be considered as potential paleolimatic proxy to explore. We compared measured δD values of alkanes (n-C 25 to n-C 31 ) extracted from a short sediment profile spanning the past 50 years with a 7-year resolution from Lake Yamzho, southern Tibetan Plateau. Climatic control was reconstructed using meteorological records of the nearby Langkazi and Lhasa weather stations. We found that the δD values of the n-alkanes correlated with the mean annular air temperature and significantly correlated with the mean growing season air temperature. On the other hand, the δD values show poor correlations with both rainfall amount and relative humidity. These results indicate that stable isotope composition of n-alkanes could be an excellent proxy for paleotemperature reconstruction. (author)

  11. n-Alkanes in sediments from the Yellow River Estuary, China: Occurrence, sources and historical sedimentary record.

    Science.gov (United States)

    Wang, Shanshan; Liu, Guijian; Yuan, Zijiao; Da, Chunnian

    2018-04-15

    A total of 21 surface sediments from the Yellow River Estuary (YRE) and a sediment core from the abandoned Old Yellow River Estuary (OYRE) were analyzed for n-alkanes using gas chromatography-mass spectrometry (GC-MS). n-Alkanes in the range C 12 -C 33 and C 13 -C 34 were identified in the surface sediments and the core, respectively. The homologous series were mainly bimodal distribution pattern without odd/even predominance in the YRE and OYRE. The total n-alkanes concentrations in the surface sediments ranged from 0.356 to 0.572mg/kg, with a mean of 0.434mg/kg on dry wt. Evaluation of n-alkanes proxies indicated that the aliphatic hydrocarbons in the surface sediments were derived mainly from a petrogenic source with a relatively low contribution of submerged/floating macrophytes, terrestrial and emergent plants. The dated core covered the time period 1925-2012 and the mean sedimentation rate was ca. 0.5cm/yr. The total n-alkanes concentrations in the core ranged from 0.0394 to 0.941mg/kg, with a mean of 0.180mg/kg. The temporal evolution of n-alkanes reflected the historical input of aliphatic hydrocarbons and was consistent with local and regional anthropogenic activity. In general, the investigation on the sediment core revealed a trend of regional environmental change and the role of anthropogenic activity in environmental change. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Predictions of homogeneous nucleation rates for n-alkanes accounting for the diffuse phase interface and capillary waves.

    Science.gov (United States)

    Planková, Barbora; Vinš, Václav; Hrubý, Jan

    2017-10-28

    Homogeneous droplet nucleation has been studied for almost a century but has not yet been fully understood. In this work, we used the density gradient theory (DGT) and considered the influence of capillary waves (CWs) on the predicted size-dependent surface tensions and nucleation rates for selected n-alkanes. The DGT model was completed by an equation of state (EoS) based on the perturbed-chain statistical associating fluid theory and compared to the classical nucleation theory and the Peng-Robinson EoS. It was found that the critical clusters are practically free of CWs because they are so small that even the smallest wavelengths of CWs do not fit into their finite dimensions. The CWs contribute to the entropy of the system and thus decrease the surface tension. A correction for the effect of CWs on the surface tension is presented. The effect of the different EoSs is relatively small because by a fortuitous coincidence their predictions are similar in the relevant range of critical cluster sizes. The difference of the DGT predictions to the classical nucleation theory computations is important but not decisive. Of the effects investigated, the most pronounced is the suppression of CWs which causes a sizable decrease of the predicted nucleation rates. The major difference between experimental nucleation rate data and theoretical predictions remains in the temperature dependence. For normal alkanes, this discrepancy is much stronger than observed, e.g., for water. Theoretical corrections developed here have a minor influence on the temperature dependency. We provide empirical equations correcting the predicted nucleation rates to values comparable with experiments.

  13. Predictions of homogeneous nucleation rates for n-alkanes accounting for the diffuse phase interface and capillary waves

    Science.gov (United States)

    Planková, Barbora; Vinš, Václav; Hrubý, Jan

    2017-10-01

    Homogeneous droplet nucleation has been studied for almost a century but has not yet been fully understood. In this work, we used the density gradient theory (DGT) and considered the influence of capillary waves (CWs) on the predicted size-dependent surface tensions and nucleation rates for selected n-alkanes. The DGT model was completed by an equation of state (EoS) based on the perturbed-chain statistical associating fluid theory and compared to the classical nucleation theory and the Peng-Robinson EoS. It was found that the critical clusters are practically free of CWs because they are so small that even the smallest wavelengths of CWs do not fit into their finite dimensions. The CWs contribute to the entropy of the system and thus decrease the surface tension. A correction for the effect of CWs on the surface tension is presented. The effect of the different EoSs is relatively small because by a fortuitous coincidence their predictions are similar in the relevant range of critical cluster sizes. The difference of the DGT predictions to the classical nucleation theory computations is important but not decisive. Of the effects investigated, the most pronounced is the suppression of CWs which causes a sizable decrease of the predicted nucleation rates. The major difference between experimental nucleation rate data and theoretical predictions remains in the temperature dependence. For normal alkanes, this discrepancy is much stronger than observed, e.g., for water. Theoretical corrections developed here have a minor influence on the temperature dependency. We provide empirical equations correcting the predicted nucleation rates to values comparable with experiments.

  14. Viscosity and Liquid Density of Asymmetric n-Alkane Mixtures: Measurement and Modelling

    DEFF Research Database (Denmark)

    Queimada, António J.; Marrucho, Isabel M.; Coutinho, João A.P.

    2005-01-01

    Viscosity and liquid density Measurements were performed, at atmospheric pressure. in pure and mixed n-decane. n-eicosane, n-docosane, and n-tetracosane from 293.15 K (or above the melting point) up to 343.15 K. The viscosity was determined with a rolling ball viscometer and liquid densities...... with a vibrating U-tube densimeter. Pure component results agreed, oil average, with literature values within 0.2% for liquid density and 3% for viscosity. The measured data were used to evaluate the performance of two models for their predictions: the friction theory coupled with the Peng-Robinson equation...... of state and a corresponding states model recently proposed for surface tension, viscosity, vapor pressure, and liquid densities of the series of n-alkanes. Advantages and shortcoming of these models are discussed....

  15. Self-consistent molecular dynamics calculation of diffusion in higher n-alkanes.

    Science.gov (United States)

    Kondratyuk, Nikolay D; Norman, Genri E; Stegailov, Vladimir V

    2016-11-28

    Diffusion is one of the key subjects of molecular modeling and simulation studies. However, there is an unresolved lack of consistency between Einstein-Smoluchowski (E-S) and Green-Kubo (G-K) methods for diffusion coefficient calculations in systems of complex molecules. In this paper, we analyze this problem for the case of liquid n-triacontane. The non-conventional long-time tails of the velocity autocorrelation function (VACF) are found for this system. Temperature dependence of the VACF tail decay exponent is defined. The proper inclusion of the long-time tail contributions to the diffusion coefficient calculation results in the consistency between G-K and E-S methods. Having considered the major factors influencing the precision of the diffusion rate calculations in comparison with experimental data (system size effects and force field parameters), we point to hydrogen nuclear quantum effects as, presumably, the last obstacle to fully consistent n-alkane description.

  16. Measurement and modelling of hydrogen bonding in 1-alkanol plus n-alkane binary mixtures

    DEFF Research Database (Denmark)

    von Solms, Nicolas; Jensen, Lars; Kofod, Jonas L.

    2007-01-01

    Two equations of state (simplified PC-SAFT and CPA) are used to predict the monomer fraction of 1-alkanols in binary mixtures with n-alkanes. It is found that the choice of parameters and association schemes significantly affects the ability of a model to predict hydrogen bonding in mixtures, eve...... studies, which is clarified in the present work. New hydrogen bonding data based on infrared spectroscopy are reported for seven binary mixtures of alcohols and alkanes. (C) 2007 Elsevier B.V. All rights reserved....... though pure-component liquid densities and vapour pressures are predicted equally accurately for the associating compound. As was the case in the study of pure components, there exists some confusion in the literature about the correct interpretation and comparison of experimental data and theoretical...

  17. Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

    Science.gov (United States)

    Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

    2011-02-01

    Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

  18. Degradability of n-alkanes during ex situ natural bioremediation of soil contaminated by heavy residual fuel oil (mazut

    Directory of Open Access Journals (Sweden)

    Ali Ramadan Mohamed Muftah

    2013-01-01

    Full Text Available It is well known that during biodegradation of oil in natural geological conditions, or oil pollutants in the environment, a degradation of hydrocarbons occurs according to the well defined sequence. For example, the major changes during the degradation process of n-alkanes occur in the second, slight and third, moderate level (on the biodegradation scale from 1 to 10. According to previous research, in the fourth, heavy level, when intensive changes of phenanthrene and its methyl isomers begin, n-alkanes have already been completely removed. In this paper, the ex situ natural bioremediation (unstimulated bioremediation, without addition of biomass, nutrient substances and biosurfactant of soil contaminated with heavy residual fuel oil (mazut was conducted during the period of 6 months. Low abundance of n-alkanes in the fraction of total saturated hydrocarbons in the initial sample (identification was possible only after concentration by urea adduction technique showed that the investigated oil pollutant was at the boundary between the third and the fourth biodegradation level. During the experiment, an intense degradation of phenanthrene and its methyl-, dimethyl-and trimethyl-isomers was not followed by the removal of the remaining n-alkanes. The abundance of n-alkanes remained at the initial low level, even at end of the experiment when the pollutant reached one of the highest biodegradation levels. These results showed that the unstimulated biodegradation of some hydrocarbons, despite of their high biodegradability, do not proceed completely to the end, even at final degradation stages. In the condition of the reduced availability of some hydrocarbons, microorganisms tend to opt for less biodegradable but more accessible hydrocarbons.

  19. Resonance chains in open systems, generalized zeta functions and clustering of the length spectrum

    International Nuclear Information System (INIS)

    Barkhofen, S; Faure, F; Weich, T

    2014-01-01

    In many non-integrable open systems in physics and mathematics, resonances have been found to be surprisingly ordered along curved lines in the complex plane. In this article we provide a unifying approach to these resonance chains by generalizing dynamical zeta functions. By means of a detailed numerical study we show that these generalized zeta functions explain the mechanism that creates the chains of quantum resonance and classical Ruelle resonances for three-disk systems as well as geometric resonances on Schottky surfaces. We also present a direct system-intrinsic definition of the continuous lines on which the resonances are strung together as a projection of an analytic variety. Additionally, this approach shows that the existence of resonance chains is directly related to a clustering of the classical length spectrum on multiples of a base length. Finally, this link is used to construct new examples where several different structures of resonance chains coexist. (paper)

  20. Effect of hydrocarbon chain length of aliphatic diluents on hydrodynamic properties of irradiated solutions of extractant

    International Nuclear Information System (INIS)

    Gumenyuk, V.E.; Pribush, A.G.; Egorov, G.F.

    1990-01-01

    To optimize the composition of n-paraffin mixtures with different molecular weight, used as a diluent (D) of extractant during extraction reprocessing of spent fuel, interrelation between D hydrocarbon chain length and change in hydrodynamic properties of extraction mixture on D basis depending on the dose has been considered. It is shown that the value of threshold dose loading (D crit ), at which a sharp change in hydrodynamic properties of tri-n-butyl phosphate solutions in D is observed, decreases with hydrocarbon chain length growth. Empiric ratio relating D crit value and the number of carbon atoms of D is obtained

  1. Knotting dynamics of DNA chains of different length confined in nanochannels

    International Nuclear Information System (INIS)

    Suma, Antonio; Micheletti, Cristian; Orlandini, Enzo

    2015-01-01

    Langevin dynamics simulations are used to characterize the typical mechanisms governing the spontaneous tying, untying and the dynamical evolution of knots in coarse-grained models of DNA chains confined in nanochannels. In particular we focus on how these mechanisms depend on the chain contour length, L c , at a fixed channel width D = 56 nm corresponding to the onset of the Odijk scaling regime where chain backfoldings and hence knots are disfavoured but not suppressed altogether. We find that the lifetime of knots grows significantly with L c , while that of unknots varies to a lesser extent. The underlying kinetic mechanisms are clarified by analysing the evolution of the knot position along the chain. At the considered confinement, in fact, knots are typically tied by local backfoldings of the chain termini where they are eventually untied after a stochastic motion along the chain. Consequently, the lifetime of unknots is mostly controlled by backfoldings events at the chain ends, which is largely independent of L c . The lifetime of knots, instead, increases significantly with L c because knots can, on average, travel farther along the chain before being untied. The observed interplay of knots and unknots lifetimes underpins the growth of the equilibrium knotting probability of longer and longer chains at fixed channel confinement. (paper)

  2. Direct observation of the edge spin structure and chain length dependence of a finite haldane chain by high field ESR measurements

    International Nuclear Information System (INIS)

    Yoshida, Makoto; Ohta, Hitoshi; Ito, Toshimitsu; Ajiro, Yoshitami

    2006-01-01

    We have performed high field and multi-frequency ESR measurements of finite length S=1 antiferromagnetic chains in Y 2 BaNi 0.96 Mg 0.04 O 5 . Owing to the high spectral resolution by high fields and high frequencies, observed ESR signals can be separated into the contributions of the finite chains with various chain lengths. Our results clearly show that the edge spins actually interact with each other through the quantum spin chain and the interaction depends on the chain length N. (author)

  3. Characterization of Binary Organogels Based on Some Azobenzene Compounds and Alkyloxybenzoic Acids with Different Chain Lengths

    Directory of Open Access Journals (Sweden)

    Yongmei Hu

    2014-01-01

    Full Text Available In this work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and alkyloxybenzoic acids with different lengths of alkyl chains in various organic solvents were investigated and characterized. The corresponding gelation behaviors in 20 solvents were characterized and shown as new binary organic systems. It showed that the lengths of substituent alkyl chains in compounds have played an important role in the gelation formation of gelator mixtures in present tested organic solvents. Longer methylene chains in molecular skeletons in these gelators seem more suitable for the gelation of present solvents. Morphological characterization showed that these gelator molecules have the tendency to self-assemble into various aggregates from lamella, wrinkle, and belt to dot with change of solvents and gelator mixtures. Spectral characterization demonstrated different H-bond formation and hydrophobic force existing in gels, depending on different substituent chains in molecular skeletons. Meanwhile, these organogels can self-assemble to form monomolecular or multilayer nanostructures owing to the different lengths of due to alkyl substituent chains. Possible assembly modes for present xerogels were proposed. The present investigation is perspective to provide new clues for the design of new nanomaterials and functional textile materials with special microstructures.

  4. Phase behaviour of an ionic microemulsion system as a function of the cosurfactant chain length

    NARCIS (Netherlands)

    Kegel, W.K.; Lekkerkerker, H.N.W.

    1993-01-01

    The phase behaviour of a microemulsion system consisting of equal volumes of brine and oil, sodium dodecyl sulphate (SDS) as surfactant and alcohols of different chain lengths (pentanol, hexanol and heptanol) as cosurfactant was studied. In the case of pentanol, at low surfactant concentrations and

  5. Vaporization enthalpies of imidazolium based ionic liquids. A thermogravimetric study of the alkyl chain length dependence

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emel’yanenko, Vladimir N.; Ralys, Ricardas V.; Yermalayeu, Andrei V.; Schick, Christoph

    2012-01-01

    Highlights: ► Enthalpies of vaporization of ionic liquids were measured with thermogravimetry. ► We studied 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide. ► The linear alkyl chain length was 4, 6, 8, 10, 12, 14, 16, and 18 C-atoms. ► A linear dependence on the chain length of the alkyl-imidazolium cation was found. - Abstract: Vaporization enthalpies for a series of ten ionic liquids (ILs) 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide [C n mim][NTf 2 ], with the alkyl chain length n = 4, 6, 8, 10, 12, 14, 16, and 18 were determined using the thermogravimetric method. An internally consistent set of experimental data and vaporization enthalpies at 540 K was obtained. Vaporization enthalpies at 540 K have shown a linear dependence on the chain length of the alkyl-imidazolium cation in agreement with the experimental results measured previously with a quartz crystal microbalance. Ambiguity of Δ l g C pm o -values required for the extrapolation of experimental vaporization enthalpies to the reference temperature 298 K has been discussed.

  6. Biosynthesis of medium chain length alkanes for bio-aviation fuel by metabolic engineered Escherichia coli.

    Science.gov (United States)

    Wang, Meng; Nie, Kaili; Cao, Hao; Xu, Haijun; Fang, Yunming; Tan, Tianwei; Baeyens, Jan; Liu, Luo

    2017-09-01

    The aim of this work was to study the synthesis of medium-chain length alkanes (MCLA), as bio-aviation product. To control the chain length of alkanes and increase the production of MCLA, Escherichia coli cells were engineered by incorporating (i) a chain length specific thioesterase from Umbellularia californica (UC), (ii) a plant origin acyl carrier protein (ACP) gene and (iii) the whole fatty acid synthesis system (FASs) from Jatropha curcas (JC). The genetic combination was designed to control the product spectrum towards optimum MCLA. Decanoic, lauric and myristic acid were produced at concentrations of 0.011, 0.093 and 1.657mg/g, respectively. The concentration of final products nonane, undecane and tridecane were 0.00062mg/g, 0.0052mg/g, and 0.249mg/g respectively. Thioesterase from UC controlled the fatty acid chain length in a range of 10-14 carbons and the ACP gene with whole FASs from JC significantly increased the production of MCLA. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. The effect of chain length and lipid phase transitions on the selective permeability properties of liposomes

    NARCIS (Netherlands)

    Blok, M.C.; Neut-Kok, E.C.M. van der; Deenen, L.L.M. van; Gier, J. de

    1975-01-01

    This paper describes experiments showing the importance of the fatty acid chain length on the barrier properties of liposomal bilayers, prepared from saturated lecithins, under conditions of lateral phase separation. 1. 1.|Above the gel to liquid crystalline phase transition temperature,

  8. The importance of chain length for the polyphosphate enhancement of acidic potassium permanganate chemiluminescence.

    Science.gov (United States)

    Holland, Brendan J; Adcock, Jacqui L; Nesterenko, Pavel N; Peristyy, Anton; Stevenson, Paul G; Barnett, Neil W; Conlan, Xavier A; Francis, Paul S

    2014-09-09

    Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV). Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Modification of eucalyptus pulp fiber using silane coupling agents with aliphatic side chains of different length

    Science.gov (United States)

    The objective of this work was to evaluate the effect of three silane coupling agents with different aliphatic chain lengths on the hydrophobicity of eucalyptus pulp fiber. The three silanes coupling agents used (isobutyltrimethoxysilane, methyltrimethoxysilane, and n-octyltriethoxysilane [OTES]) we...

  10. effect of side chain length on the stability and structural properties of 3

    African Journals Online (AJOL)

    Preferred Customer

    We report on the effect of the alkoxy chain length on the thermodynamic ... studied by Hartree-Fock (HF) and Density Functional Theory (DFT) methods. ..... with longer alkoxy substituents on the phenyl ring have lesser value of change in Gibbs ...

  11. Chain length distribution and kinetic characteristics of an enzymatically produced polymer

    NARCIS (Netherlands)

    Mulders, K.J.M.; Beeftink, H.H.

    2013-01-01

    Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model

  12. Characterization of amylose nanoparticles prepared via nanoprecipitation: Influence of chain length distribution.

    Science.gov (United States)

    Chang, Yanjiao; Yang, Jingde; Ren, Lili; Zhou, Jiang

    2018-08-15

    The influence of chain length distribution of amylose on size and structure of the amylose nanoparticles (ANPs) prepared through nanoprecipitation was investigated. Amylose with different chain length distributions was obtained by β-amylase treating amylose paste for different times and measured by size exclusion chromatography (SEC) and fluorophore-assisted carbohydrate electrophoresis (FACE). ANPs prepared via precipitation were characterized by using dynamic light scattering (DLS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Results showed that the β-amylase treatments led to decrease in chain length of amylose, and it was the most important factor affecting size of ANPs. When hydrolysis degree of amylose was 52.8%, mean size of ANPs decreased from 206.4 nm to 102.7 nm. All the ANPs displayed a V-type crystalline structure and the effect of amylose chain length on crystallinity of the precipitated ANPs was negligible in the investigated range. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Photoluminescence decay lifetime measurements of hemicyanine derivatives of different alkyl chain lengths

    International Nuclear Information System (INIS)

    Shim, Taekyu; Lee, Myounghee; Kim, Sungho; Sung, Jaeho; Rhee, Bum Ku; Kim, Doseok; Kim, Hyunsung; Yoon, Kyung Byung

    2004-01-01

    The fluorescence upconversion setup for the detection of photoluminescence (PL) decay lifetime with subpicosecond time resolution was constructed, and the photoluminescence phenomena of several hemicyanine dyes with alkyl chains of different chain lengths tethered to the N atom of the pyridine moiety (HC-n, n=6, 15, 22) in methanol were investigated. The average decay lifetimes of the solutions determined from the measured data by multi-order exponential decay curve fitting were ∼27 ps at the PL peak wavelength. It was found that the PL decay properties did not depend on the alkyl chain length in the molecule, implying that the twist of the alkylpyridinium ring of the molecule is not possible as a nonfluorescing relaxation pathway. The time-dependent PL spectra constructed from the PL lifetime data showed the dynamic Stokes shift of ∼1000 cm -1

  14. Infinite coherence time of edge spins in finite-length chains

    Science.gov (United States)

    Maceira, Ivo A.; Mila, Frédéric

    2018-02-01

    Motivated by the recent observation that exponentially long coherence times can be achieved for edge spins in models with strong zero modes, we study the impact of level crossings in finite-length spin chains on the dynamics of the edge spins. Focusing on the X Y spin-1 /2 chain with a transverse or longitudinal magnetic field, two models relevant to understanding recent experimental results on cobalt adatoms, we show that the edge spins can remain coherent for an infinite time even for a finite-length chain if the magnetic field is tuned to a value at which there is a level crossing. Furthermore, we show that the edge spins remain coherent for any initial state for the integrable case of a transverse field because all states have level crossings at the same value of the field, while the coherence time is increasingly large for lower temperatures in the case of a longitudinal field, which is nonintegrable.

  15. PEGylation on mixed monolayer gold nanoparticles: Effect of grafting density, chain length, and surface curvature.

    Science.gov (United States)

    Lin, Jiaqi; Zhang, Heng; Morovati, Vahid; Dargazany, Roozbeh

    2017-10-15

    PEGylation on nanoparticles (NPs) is widely used to prevent aggregation and to mask NPs from the fast clearance system in the body. Understanding the molecular details of the PEG layer could facilitate rational design of PEGylated NPs that maximize their solubility and stealth ability without significantly compromising the targeting efficiency and cellular uptake. Here, we use molecular dynamics (MD) simulation to understand the structural and dynamic the PEG coating of mixed monolayer gold NPs. Specifically, we modeled gold NPs with PEG grafting densities ranging from 0-2.76chain/nm 2 , chain length with 0-10 PEG monomers, NP core diameter from 5nm to 500nm. It is found that the area accessed by individual PEG chains gradually transits from a "mushroom" to a "brush" conformation as NP surface curvature become flatter, whereas such a transition is not evident on small NPs when grafting density increases. It is shown that moderate grafting density (∼1.0chain/nm 2 ) and short chain length are sufficient enough to prevent NPs from aggregating in an aqueous medium. The effect of grafting density on solubility is also validated by dynamic light scattering measurements of PEGylated 5nm gold NPs. With respect to the shielding ability, simulations predict that increase either grafting density, chain length, or NP diameter will reduce the accessibility of the protected content to a certain size molecule. Interestingly, reducing NP surface curvature is estimated to be most effective in promoting shielding ability. For shielding against small molecules, increasing PEG grafting density is more effective than increasing chain length. A simple model that includes these three investigated parameters is developed based on the simulations to roughly estimate the shielding ability of the PEG layer with respect to molecules of different sizes. The findings can help expand our current understanding of the PEG layer and guide rational design of PEGylated gold NPs for a particular

  16. Optimization of the alkyl side chain length of fluorine-18-labeled 7α-alkyl-fluoroestradiol

    International Nuclear Information System (INIS)

    Okamoto, Mayumi; Shibayama, Hiromitsu; Naka, Kyosuke; Kitagawa, Yuya; Ishiwata, Kiichi; Shimizu, Isao; Toyohara, Jun

    2016-01-01

    Introduction: Several lines of evidence suggest that 7α-substituted estradiol derivatives bind to the estrogen receptor (ER). In line with this hypothesis, we designed and synthesized 18 F-labeled 7α-fluoroalkylestradiol (Cn-7α-[ 18 F]FES) derivatives as molecular probes for visualizing ERs. Previously, we successfully synthesized 7α-(3-[ 18 F]fluoropropyl)estradiol (C3-7α-[ 18 F]FES) and showed promising results for quantification of ER density in vivo, although extensive metabolism was observed in rodents. Therefore, optimization of the alkyl side chain length is needed to obtain suitable radioligands based on Cn-7α-substituted estradiol pharmacophores. Methods: We synthesized fluoromethyl (23; C1-7α-[ 18 F]FES) to fluorohexyl (26; C6-7α-[ 18 F]FES) derivatives, except fluoropropyl (C3-7α-[ 18 F]FES) and fluoropentyl derivatives (C5-7α-[ 18 F]FES), which have been previously synthesized. In vitro binding to the α-subtype (ERα) isoform of ERs and in vivo biodistribution studies in mature female mice were carried out. Results: The in vitro IC 50 value of Cn-7α-FES tended to gradually decrease depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the highest uptake in ER-rich tissues such as the uterus. Uterus uptake also gradually decreased depending on the alkyl side chain length. As a result, in vivo uterus uptake reflected the in vitro ERα affinity of each compound. Bone uptake, which indicates de-fluorination, was marked in 7α-(2-[ 18 F]fluoroethyl)estradiol (C2-7α-[ 18 F]FES) (24) and 7α-(4-[ 18 F]fluorobutyl)estradiol (C4-7α-[ 18 F]FES) (25) derivatives. However, C1-7α-[ 18 F]FES (23) and C6-7α-[ 18 F]FES (26) showed limited uptake in bone. As a result, in vivo bone uptake (de-fluorination) showed a bell-shaped pattern, depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the same levels of uptake in uterus and bone compared with those of 16α-[ 18 F]fluoro-17β-estradiol. Conclusions: The optimal alkyl

  17. Critical wetting of n-alkanes on water; Mouillage critique des alcanes sur l`eau

    Energy Technology Data Exchange (ETDEWEB)

    Ragil, K

    1996-10-18

    This study concerns the wetting properties of n-alkanes on water under thermodynamic equilibrium conditions, a problem that is interesting for the petroleum industry as well as for the fundamental understanding of wetting phenomena. An experimental study using ellipsometry reveals that pentane on water undergoes a continuous or critical wetting transition at a temperature equal to 53.1 deg. C. This is the first experimental observation of such a transition, confirming theoretical predictions made on this subject over ten years. This transition is characterized by a continuous and reversible evolution of the thickness of the film of pentane with temperature from a thick (but finite film) to a macroscopic film. The critical wetting transition occurs when the Hamaker constant of the system, which gives the net interaction between the two interfaces bounding the wetting layer of pentane in terms of the van der Waals forces, changes sign. A theoretical approach based on the Cahn-Landau theory, which takes into account long range forces (van der Waals forces), enables us to explain the mechanism of the critical wetting transition and to show that a first-order wetting transition should precede it. Because of their similar dispersive properties, linear alkanes could all be able to show such a succession of transitions. An ellipsometry study performed on a brine/hexane/vapor system confirms that a discontinuous transition from a thin microscopic film to a thick but finite adsorbed film takes place. THis study demonstrates that the wetting of alkanes on water is determined by subtle interplay between short range and long range forces, which can lead to an intermediary state between partial and complete wetting. (author)

  18. Hopane, sterane and n-alkane distributions in shallow sediments hosting high arsenic groundwaters in Cambodia

    International Nuclear Information System (INIS)

    Dongen, Bart E. van; Rowland, Helen A.L.; Gault, Andrew G.; Polya, David A.; Bryant, Charlotte; Pancost, Richard D.

    2008-01-01

    The presence of elevated As in ground waters exploited for drinking water and irrigation in South-East Asia is causing serious impacts on human health. A key mechanism that causes the mobilization of As in these waters is microbially mediated reductive transformation of As-bearing Fe(III) hydrated oxides and the role of degradable organic matter (OM) in this process is widely recognized. A number of different types of OM that drive As release in these aquifers have been suggested, including petroleum derived hydrocarbons naturally seeping into shallow sediments from deeper thermally mature source rocks. However, the amount of information on the characteristics of the OM in South-East Asian aquifers is limited. Here the organic geochemical analyses of the saturated hydrocarbon fractions and radiocarbon analysis, of two additional sites in SE Asia are reported. The results show that the OM in a given sedimentary horizon likely derives from multiple sources including naturally occurring petroleum. The importance of naturally occurring petroleum as one of the sources was clearly indicated by the n-alkane CPI of approximately 1, the presence of an unresolved complex mixture, and hopane (dominated by 17α(H),21β(H) hopanes) and sterane distribution patterns. The results also indicate that the OM in these aquifers varies tremendously in content, character and potential bioavailability. Furthermore, the presence of petroleum derived OM in sediments at both sites doubles the number of locations where their presence has been observed in association with As-rich, shallow aquifers, suggesting that the role of petroleum derived OM in microbially mediated As release might occur over a wider range of geographical locations than previously thought

  19. Dependence of adenine isolation efficiency on the chain length evidenced using paramagnetic particles and voltammetry measurements

    Energy Technology Data Exchange (ETDEWEB)

    Huska, Dalibor [Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University of Agriculture and Forestry, Zemedelska 1, CZ-613 00 Brno (Czech Republic); Adam, Vojtech [Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University of Agriculture and Forestry, Zemedelska 1, CZ-613 00 Brno (Czech Republic); Department of Animal Nutrition and Forage Production, Faculty of Agronomy, Mendel University of Agriculture and Forestry, Zemedelska 1, CZ-613 00 Brno (Czech Republic); Trnkova, Libuse [Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-625 00 Brno (Czech Republic); Kizek, Rene [Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University of Agriculture and Forestry, Zemedelska 1, CZ-613 00 Brno (Czech Republic)], E-mail: kizek@sci.muni.cz

    2009-05-15

    The main aim of this work was to study the dependence of oligoadenine isolation efficiency on the chain length by using paramagnetic particles covered by homo-deoxythymidines ((dT)25) with subsequent detection by adsorptive transfer technique coupled with square wave voltammetry. For this purpose, the oligonucleotides of the length A5, A10, A15, A20, A25, A30, A35, A40 and poly(A) in various concentrations were chosen. We determined that the isolation efficiency defined as 'isolated oligonucleotide concentration'/'given oligonucleotide concentration' was about 55% on average. Sequence A25 demonstrated the best binding onto microparticles surface.

  20. Dependence of adenine isolation efficiency on the chain length evidenced using paramagnetic particles and voltammetry measurements

    International Nuclear Information System (INIS)

    Huska, Dalibor; Adam, Vojtech; Trnkova, Libuse; Kizek, Rene

    2009-01-01

    The main aim of this work was to study the dependence of oligoadenine isolation efficiency on the chain length by using paramagnetic particles covered by homo-deoxythymidines ((dT)25) with subsequent detection by adsorptive transfer technique coupled with square wave voltammetry. For this purpose, the oligonucleotides of the length A5, A10, A15, A20, A25, A30, A35, A40 and poly(A) in various concentrations were chosen. We determined that the isolation efficiency defined as 'isolated oligonucleotide concentration'/'given oligonucleotide concentration' was about 55% on average. Sequence A25 demonstrated the best binding onto microparticles surface.

  1. Influence of the chain length on the biological behaviour of 131I fatty acids

    International Nuclear Information System (INIS)

    Riche, F.; Mathieu, J.P.; Comet, M.; Vidal, M.; Pernin, C.; Marti-Batlle, D.; Busquet, G.; Bardy, A.

    1983-01-01

    Saturated and acetylenic fatty acids labeled with 131 I in ω position, differing by their chain length (C8 to C20) and the number odd or even of their carbon atoms are injected in mice. The evolution of the activity in myocardium, blood, liver and kidney is measured until 10 minutes after injection. The myocardial activity increases with chain length from C8 to C16 then decreases for C18 and C20. The odd or even number of carbon atoms does not influence myocardial activity but in the liver, activity is inferior with the odd fatty acids. The presence of a triple bond accelerates the output of activity from the myocardium and these fatty acids are not well suited for the study of myocardial metabolism [fr

  2. Influence of the chain length on the biological behaviour of /sup 131/I fatty acids

    Energy Technology Data Exchange (ETDEWEB)

    Riche, F.; Mathieu, J.P.; Comet, M.; Vidal, M.; Pernin, C.; Marti-Batlle, D.; Busquet, G. (Universite de Grenoble, 38 (France)); Bardy, A. (C.E.A.-ORIS, 91 - Gif-sur-Yvette (France))

    1983-01-01

    Saturated and acetylenic fatty acids labeled with /sup 131/I in ..omega.. position, differing by their chain length (C8 to C20) and the number odd or even of their carbon atoms are injected in mice. The evolution of the activity in myocardium, blood, liver and kidney is measured until 10 minutes after injection. The myocardial activity increases with chain length from C8 to C16 then decreases for C18 and C20. The odd or even number of carbon atoms does not influence myocardial activity but in the liver, activity is inferior with the odd fatty acids. The presence of a triple bond accelerates the output of activity from the myocardium and these fatty acids are not well suited for the study of myocardial metabolism.

  3. Communication disruption of guava moth (Coscinoptycha improbana) using a pheromone analog based on chain length.

    Science.gov (United States)

    Suckling, D M; Dymock, J J; Park, K C; Wakelin, R H; Jamieson, L E

    2013-09-01

    The guava moth, Coscinoptycha improbana, an Australian species that infests fruit crops in commercial and home orchards, was first detected in New Zealand in 1997. A four-component pheromone blend was identified but is not yet commercially available. Using single sensillum recordings from male antennae, we established that the same olfactory receptor neurons responded to two guava moth sex pheromone components, (Z)-11-octadecen-8-one and (Z)-12-nonadecen-9-one, and to a chain length analog, (Z)-13-eicosen-10-one, the sex pheromone of the related peach fruit moth, Carposina sasakii. We then field tested whether this non-specificity of the olfactory neurons might enable disruption of sexual communication by the commercially available analog, using male catch to synthetic lures in traps in single-tree, nine-tree and 2-ha plots. A disruptive pheromone analog, based on chain length, is reported for the first time. Trap catches for guava moth were disrupted by three polyethylene tubing dispensers releasing the analog in single-tree plots (86% disruption of control catches) and in a plots of nine trees (99% disruption). Where peach fruit moth pheromone dispensers were deployed at a density of 1000/ha in two 2-ha areas, pheromone traps for guava moth were completely disrupted for an extended period (up to 470 days in peri-urban gardens in Mangonui and 422 days in macadamia nut orchards in Kerikeri). In contrast, traps in untreated areas over 100 m away caught 302.8 ± 128.1 moths/trap in Mangonui and 327.5 ± 78.5 moths/ trap in Kerikeri. The longer chain length in the pheromone analog has greater longevity than the natural pheromone due to its lower volatility. Chain length analogs may warrant further investigation for mating disruption in Lepidoptera, and screening using single-sensillum recording is recommended.

  4. Productivity, Disturbance and Ecosystem Size Have No Influence on Food Chain Length in Seasonally Connected Rivers

    OpenAIRE

    Warfe, Danielle M.; Jardine, Timothy D.; Pettit, Neil E.; Hamilton, Stephen K.; Pusey, Bradley J.; Bunn, Stuart E.; Davies, Peter M.; Douglas, Michael M.

    2013-01-01

    The food web is one of the oldest and most central organising concepts in ecology and for decades, food chain length has been hypothesised to be controlled by productivity, disturbance, and/or ecosystem size; each of which may be mediated by the functional trophic role of the top predator. We characterised aquatic food webs using carbon and nitrogen stable isotopes from 66 river and floodplain sites across the wet-dry tropics of northern Australia to determine the relative importance of produ...

  5. The Effect of the Chain Length on MMA Free Radicl Polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In the polymerization process of methyl methacrylate (MMA), the Arrhenius parameters (activation energy and frequency factor) of propagating reaction monotonically decrease with increasing monomer conversion. At the beginning and middle stage of the propagating reaction, the increase of radical chain length is the main reason of above mentioned change. And at the end stage, the sharp decrease of kp indicates that the activation energy is approximately incline to zero and the propagating reaction is controlled by molecular diffusion motion.

  6. Effect of side chain length on charge transport, morphology, and photovoltaic performance of conjugated polymers in bulk heterojunction solar cells

    NARCIS (Netherlands)

    Duan, C.; Willems, R.E.M.; van Franeker, J.J.; Bruijnaers, B.J.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    The effect of side chain length on the photovoltaic properties of conjugated polymers is systematically investigated with two sets of polymers that bear different alkyl side chain lengths based on benzodithiophene and benzo[2,1,3]thiadiazole or 5,6-difluorobenzo[2,1,3]thiadiazole. Characterization

  7. Abnormal glycogen chain length pattern, not hyperphosphorylation, is critical in Lafora disease.

    Science.gov (United States)

    Nitschke, Felix; Sullivan, Mitchell A; Wang, Peixiang; Zhao, Xiaochu; Chown, Erin E; Perri, Ami M; Israelian, Lori; Juana-López, Lucia; Bovolenta, Paola; Rodríguez de Córdoba, Santiago; Steup, Martin; Minassian, Berge A

    2017-07-01

    Lafora disease (LD) is a fatal progressive epilepsy essentially caused by loss-of-function mutations in the glycogen phosphatase laforin or the ubiquitin E3 ligase malin. Glycogen in LD is hyperphosphorylated and poorly hydrosoluble. It precipitates and accumulates into neurotoxic Lafora bodies (LBs). The leading LD hypothesis that hyperphosphorylation causes the insolubility was recently challenged by the observation that phosphatase-inactive laforin rescues the laforin-deficient LD mouse model, apparently through correction of a general autophagy impairment. We were for the first time able to quantify brain glycogen phosphate. We also measured glycogen content and chain lengths, LBs, and autophagy markers in several laforin- or malin-deficient mouse lines expressing phosphatase-inactive laforin. We find that: (i) in laforin-deficient mice, phosphatase-inactive laforin corrects glycogen chain lengths, and not hyperphosphorylation, which leads to correction of glycogen amounts and prevention of LBs; (ii) in malin-deficient mice, phosphatase-inactive laforin confers no correction; (iii) general impairment of autophagy is not necessary in LD We conclude that laforin's principle function is to control glycogen chain lengths, in a malin-dependent fashion, and that loss of this control underlies LD. © 2017 The Authors. Published under the terms of the CC BY 4.0 license.

  8. Productivity, disturbance and ecosystem size have no influence on food chain length in seasonally connected rivers.

    Science.gov (United States)

    Warfe, Danielle M; Jardine, Timothy D; Pettit, Neil E; Hamilton, Stephen K; Pusey, Bradley J; Bunn, Stuart E; Davies, Peter M; Douglas, Michael M

    2013-01-01

    The food web is one of the oldest and most central organising concepts in ecology and for decades, food chain length has been hypothesised to be controlled by productivity, disturbance, and/or ecosystem size; each of which may be mediated by the functional trophic role of the top predator. We characterised aquatic food webs using carbon and nitrogen stable isotopes from 66 river and floodplain sites across the wet-dry tropics of northern Australia to determine the relative importance of productivity (indicated by nutrient concentrations), disturbance (indicated by hydrological isolation) and ecosystem size, and how they may be affected by food web architecture. We show that variation in food chain length was unrelated to these classic environmental determinants, and unrelated to the trophic role of the top predator. This finding is a striking exception to the literature and is the first published example of food chain length being unaffected by any of these determinants. We suggest the distinctive seasonal hydrology of northern Australia allows the movement of fish predators, linking isolated food webs and potentially creating a regional food web that overrides local effects of productivity, disturbance and ecosystem size. This finding supports ecological theory suggesting that mobile consumers promote more stable food webs. It also illustrates how food webs, and energy transfer, may function in the absence of the human modifications to landscape hydrological connectivity that are ubiquitous in more populated regions.

  9. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  10. Productivity, disturbance and ecosystem size have no influence on food chain length in seasonally connected rivers.

    Directory of Open Access Journals (Sweden)

    Danielle M Warfe

    Full Text Available The food web is one of the oldest and most central organising concepts in ecology and for decades, food chain length has been hypothesised to be controlled by productivity, disturbance, and/or ecosystem size; each of which may be mediated by the functional trophic role of the top predator. We characterised aquatic food webs using carbon and nitrogen stable isotopes from 66 river and floodplain sites across the wet-dry tropics of northern Australia to determine the relative importance of productivity (indicated by nutrient concentrations, disturbance (indicated by hydrological isolation and ecosystem size, and how they may be affected by food web architecture. We show that variation in food chain length was unrelated to these classic environmental determinants, and unrelated to the trophic role of the top predator. This finding is a striking exception to the literature and is the first published example of food chain length being unaffected by any of these determinants. We suggest the distinctive seasonal hydrology of northern Australia allows the movement of fish predators, linking isolated food webs and potentially creating a regional food web that overrides local effects of productivity, disturbance and ecosystem size. This finding supports ecological theory suggesting that mobile consumers promote more stable food webs. It also illustrates how food webs, and energy transfer, may function in the absence of the human modifications to landscape hydrological connectivity that are ubiquitous in more populated regions.

  11. Estimativa da ingestão e digestibilidade de erva e bolota em porcos alentejanos pela técnica dos n-alcanos Estimation of intake and digestibility of pasture and acorns by alentejano pigs using n-alkanes

    Directory of Open Access Journals (Sweden)

    C. Mendes

    2007-01-01

    Full Text Available Com o objectivo de estimar, em porcos Alentejanos, a ingestão e a digestibilidade de erva e bolota, foi realizado um ensaio utilizando n-alcanos de cadeia longa como marcadores fecais. Oito animais, alojados em caixas metabólicas, distribuídos aleatoriamente em 2 grupos de 4 animais cada, foram sujeitos a dois tratamentos. Cada animal do grupo 1 recebeu um bolinho por dia, contendo 100 mg de C32 e 150 mg de C36 e do grupo 2, dois bolinhos por dia contendo 50 mg de C32 e 75 mg de C36. Os animais foram alimentados com erva e bolota ao longo de todo o ensaio. A ingestão e a digestibilidade da dieta foram determinadas individualmente, através da medição das quantidades de alimento ingeridas e de fezes produzidas durante 5 dias e estimadas através da utilização da técnica dos n-alcanos. As estimativas da digestibilidade feitas através da utilização dos n-alcanos naturais C25 e C27 permitiram a obtenção de resultados muito próximos das medições in vivo. Os C29 e C31, em combinação com os nalcanos artificiais (C32 e C36, forneceram as estimativas da digestibilidade mais próximas da determinada, sendo os pares C29:C32 e C29:C36 os que forneceram as melhores estimativas para a ingestão. A administração dos C32 e C36 uma ou duas vezes por dia não demonstrou ter qualquer influência nas estimativas realizadas. A composição da dieta (bolota e erva, estimada pelos n-alcanos, apresentou valores próximos dos medidos in vivo, sendo as melhores estimativas dadas pelas combinações dos n-alcanos C29 e C31.The aim of this experiment was to estimate intake and digestibility of grass and acorns in Alentejano pigs, using long chain n-alkanes as fecal markers. Eight male Alentejano pigs, housed in metabolic cages were randomly allocated into two groups. Group 1 received one small cake per animal per day containing 100 mg of C32 and 150 mg of C36 and group 2 received two small cakes per animal per day containing 50 mg of C32 and 75 mg of C

  12. Does alkyl chain length really matter? Structure–property relationships in thermochemistry of ionic liquids

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emel’yanenko, Vladimir N.; Ralys, Ricardas V.; Yermalayeu, Andrei V.; Schick, Christoph

    2013-01-01

    Graphical abstract: We have shown that enthalpies of formation, enthalpies of vaporization, and lattice potential energies of alkylsubstituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with Cl and Br anions are linearly dependant on the alkyl chain length. The thermochemical properties of ILs are generally obey the group additivity rules and the values of the additivity parameters for enthalpies of formation and vaporization are very close to those for molecular compounds. - Highlights: • Alkyl substituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with anions [Cl] and [Br] were studied using DSC and ab initio methods. • The thermochemical properties of ILs generally obey the group additivity rules. • A linear dependence on the chain length of the alkyl chain of cation was found. - Abstract: DSC was used for determination of reaction enthalpies of synthesis of ionic liquids [C n mim][Cl]. A combination of DSC with quantum chemical calculations presents an indirect way to study thermodynamics of ionic liquids. The indirect procedure for vaporization enthalpy was validated with the direct experimental measurements by using thermogravimetry. First-principles calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the CBS-QB3 and G3 (MP2) theory. Experimental DSC data for homologous series of alkyl substituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with anions [Cl] and [Br] were collected from the literature. We have shown that enthalpies of formation, enthalpies of vaporization, and lattice potential energies are linearly dependant on the alkyl chain length. The thermochemical properties of ILs generally obey the group additivity rules and the values of the additivity parameters for enthalpies of formation and vaporization seem to be very close to those for molecular compounds

  13. Liposomes coated with hydrophobically modified hydroxyethyl cellulose: Influence of hydrophobic chain length and degree of modification.

    Science.gov (United States)

    Smistad, Gro; Nyström, Bo; Zhu, Kaizheng; Grønvold, Marthe Karoline; Røv-Johnsen, Anne; Hiorth, Marianne

    2017-08-01

    Nanoparticulate systems with an uncharged hydrophilic surface may have a great potential in mucosal drug delivery. In the present study liposomes were coated with hydrophobically modified hydroxyethyl cellulose (HM-HEC) to create a sterically stabilized liposomal system with an uncharged surface. The aim was to clarify the influence of the amount of hydrophobic modification of HEC and the length of the hydrophobic moiety, on the stability of the system and on the release properties. HM-HEC with different degrees of hydrophobic modification (1 and 2mol%) and hydrophobic groups with different chain lengths (C8, C12, C16) were included in the study, as well as fluid phase and gel phase liposomes. Both types of liposomes were successfully coated with HM-HEC containing 1mol% of hydrophobic groups, while 2mol% did not work for the intended pharmaceutical applications. The polymer coated gel phase liposomes were stable (size, zeta potential, leakage) for 24 weeks at 4°C, with no differences between the C8 and C16 HM-HEC coating. For the fluid phase liposomes a size increase was observed after 24 weeks at 4°C for all formulations; the C8 HM-HEC coated liposomes increased the most. No differences in the leakage during storage at 4°C or in the release at 35°C were observed between the fluid phase formulations. To conclude; HM-HEC with a shorter hydrophobic chain length resulted in a less stable product for the fluid phase liposomes, while no influence of the chain length was observed for the gel phase liposomes (1mol% HM). Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Size distributions of n-alkanes, fatty acids and fatty alcohols in springtime aerosols from New Delhi, India.

    Science.gov (United States)

    Kang, Mingjie; Fu, Pingqing; Aggarwal, Shankar G; Kumar, Sudhanshu; Zhao, Ye; Sun, Yele; Wang, Zifa

    2016-12-01

    Size-segregated aerosol samples were collected in New Delhi, India from March 6 to April 6, 2012. Homologous series of n-alkanes (C 19 C 33 ), n-fatty acids (C 12 C 30 ) and n-alcohols (C 16 C 32 ) were measured using gas chromatography/mass spectrometry. Results showed a high-variation in the concentrations and size distributions of these chemicals during non-haze, haze, and dust storm days. In general, n-alkanes, n-fatty acids and n-alcohols presented a bimodal distribution, peaking at 0.7-1.1 μm and 4.7-5.8 μm for fine modes and coarse modes, respectively. Overall, the particulate matter mainly existed in the coarse mode (≥2.1 μm), accounting for 64.8-68.5% of total aerosol mass. During the haze period, large-scale biomass burning emitted substantial fine hydrophilic smoke particles into the atmosphere, which leads to relatively larger GMDs (geometric mean diameter) of n-alkanes in the fine mode than those during the dust storms and non-haze periods. Additionally, the springtime dust storms transported a large quantity of coarse particles from surrounding or local areas into the atmosphere, enhancing organic aerosol concentration and inducing a remarkable size shift towards the coarse mode, which are consistent with the larger GMDs of most organic compounds especially in total and coarse modes. Our results suggest that fossil fuel combustion (e.g., vehicular and industrial exhaust), biomass burning, residential cooking, and microbial activities could be the major sources of lipid compounds in the urban atmosphere in New Delhi. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Kinetics and mechanistic study of n-alkane hydroisomerization reaction on Pt-doped γ-alumina catalyst

    Directory of Open Access Journals (Sweden)

    Abhishek Dhar

    2017-12-01

    Full Text Available The catalysts γ-alumina (GA, the reference catalyst and Pt doped γ-alumina (PGA-s were synthesized using a simple sol-gel technique, in which at first preparation of porous base (GA, then impregnation of platinum salt over the base and finally reduction of platinum in the surface of the support were done. These catalysts prepared in different mole ratios of Pt:Al as 2:1, 1:1 and 1:2 are named as PGA-1, PGA-2 and PGA-3 respectively. The isomerization of n-alkanes (n-hexane, n-heptane and n-octane were investigated over the synthesized catalysts. The 2-methyl pentane (2-MP, 2,2-dimethyl pentane (2,2-DMP and 2,3-dimethyl hexane (2,3-DMH are the major products of respective isomerization of n-hexane, n-heptane and n-octane, besides a small amount of other branched isomers are also produced. The product distribution is comparable to that reported for Pt based other catalysts. The optimal mole ratios of Pt:Al is 1:1 (PGA-2 gives quite good catalytic activity for isomerization of n-alkane. Even through in reusability study, PGA-2 gives better performance than others. We have mainly focused on kinetic study, reaction mechanism behind isomerization and calculated the order of reactions and activation energies of the isomerization reactions in the present work. Keywords: Isomerization, n-alkanes, Catalyst, Reaction mechanism, Kinetics study, Activation energy

  16. Diversion of phagosome trafficking by pathogenic Rhodococcus equi depends on mycolic acid chain length.

    Science.gov (United States)

    Sydor, Tobias; von Bargen, Kristine; Hsu, Fong-Fu; Huth, Gitta; Holst, Otto; Wohlmann, Jens; Becken, Ulrike; Dykstra, Tobias; Söhl, Kristina; Lindner, Buko; Prescott, John F; Schaible, Ulrich E; Utermöhlen, Olaf; Haas, Albert

    2013-03-01

    Rhodococcus equi is a close relative of Mycobacterium spp. and a facultative intracellular pathogen which arrests phagosome maturation in macrophages before the late endocytic stage. We have screened a transposon mutant library of R. equi for mutants with decreased capability to prevent phagolysosome formation. This screen yielded a mutant in the gene for β-ketoacyl-(acyl carrier protein)-synthase A (KasA), a key enzyme of the long-chain mycolic acid synthesizing FAS-II system. The longest kasA mutant mycolic acid chains were 10 carbon units shorter than those of wild-type bacteria. Coating of non-pathogenic E. coli with purified wild-type trehalose dimycolate reduced phagolysosome formation substantially which was not the case with shorter kasA mutant-derived trehalose dimycolate. The mutant was moderately attenuated in macrophages and in a mouse infection model, but was fully cytotoxic.Whereas loss of KasA is lethal in mycobacteria, R. equi kasA mutant multiplication in broth was normal proving that long-chain mycolic acid compounds are not necessarily required for cellular integrity and viability of the bacteria that typically produce them. This study demonstrates a central role of mycolic acid chain length in diversion of trafficking by R. equi. © 2012 Blackwell Publishing Ltd.

  17. The role of discharge variation in scaling of drainage area and food chain length in rivers

    Science.gov (United States)

    Sabo, John L.; Finlay, Jacques C.; Kennedy, Theodore A.; Post, David M.

    2010-01-01

    Food chain length (FCL) is a fundamental component of food web structure. Studies in a variety of ecosystems suggest that FCL is determined by energy supply, environmental stability, and/or ecosystem size, but the nature of the relationship between environmental stability and FCL, and the mechanism linking ecosystem size to FCL, remain unclear. Here we show that FCL increases with drainage area and decreases with hydrologic variability and intermittency across 36 North American rivers. Our analysis further suggests that hydrologic variability is the mechanism underlying the correlation between ecosystem size and FCL in rivers. Ecosystem size lengthens river food chains by integrating and attenuating discharge variation through stream networks, thereby enhancing environmental stability in larger river systems.

  18. Micellar dipolar rearrangement is sensitive to hydrophobic chain length: Implication for structural switchover of piroxicam.

    Science.gov (United States)

    Sethy, Dasaratha; Chakraborty, Hirak

    2016-10-01

    The interfacial properties of the membrane are exceptionally vital in drug-membrane interaction. They not only select out a particular prototropic form of the drug molecule for incorporation, but are also potent enough to induce structural switchover of these drugs in several cases. In this work, we quantitatively monitored the change in dipolar rearrangement of the micellar interface (as a simplified membrane mimic) by measuring the dielectric constant and dipole potential with the micellization of SDS at pH 3.6. The dielectric constant and dipole potential were measured utilizing the fluorescence of polarity sensitive probe, pyrene and potential-sensitive probe, di-8-ANEPPS, respectively. Our study demonstrates that the change in dipolar rearrangement directly influences the switchover equilibrium between the anionic and neutral from of piroxicam. We have further extended our work to evaluate the effect of hydrophobic chain length of the surfactants on the dipolar rearrangement and its effect on the structural switchover of piroxicam. It is interesting that the extent of switchover of piroxicam is directly correlated with the dipolar rearrangement induced bythe varying hydrophobic chain length of the surfactants. To the best of our knowledge, our results constitute the first report to show the dependence of dipole potential on the hydrophobic chain length of the surfactant and demonstrate that the dipolar rearrangement directly tunes the extent of structural switchover of piroxicam, which was so far only intuitive. We consider that this new finding would have promising implication in drug distribution and drug efficacy. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  19. Dependence of micelle size and shape on detergent alkyl chain length and head group.

    Directory of Open Access Journals (Sweden)

    Ryan C Oliver

    Full Text Available Micelle-forming detergents provide an amphipathic environment that can mimic lipid bilayers and are important tools for solubilizing membrane proteins for functional and structural investigations in vitro. However, the formation of a soluble protein-detergent complex (PDC currently relies on empirical screening of detergents, and a stable and functional PDC is often not obtained. To provide a foundation for systematic comparisons between the properties of the detergent micelle and the resulting PDC, a comprehensive set of detergents commonly used for membrane protein studies are systematically investigated. Using small-angle X-ray scattering (SAXS, micelle shapes and sizes are determined for phosphocholines with 10, 12, and 14 alkyl carbons, glucosides with 8, 9, and 10 alkyl carbons, maltosides with 8, 10, and 12 alkyl carbons, and lysophosphatidyl glycerols with 14 and 16 alkyl carbons. The SAXS profiles are well described by two-component ellipsoid models, with an electron rich outer shell corresponding to the detergent head groups and a less electron dense hydrophobic core composed of the alkyl chains. The minor axis of the elliptical micelle core from these models is constrained by the length of the alkyl chain, and increases by 1.2-1.5 Å per carbon addition to the alkyl chain. The major elliptical axis also increases with chain length; however, the ellipticity remains approximately constant for each detergent series. In addition, the aggregation number of these detergents increases by ∼16 monomers per micelle for each alkyl carbon added. The data provide a comprehensive view of the determinants of micelle shape and size and provide a baseline for correlating micelle properties with protein-detergent interactions.

  20. Lipid polymorphism of mixtures of dioleoylphosphatidylethanolamine and saturated and monounsaturated phosphatidylcholines of various chain lengths

    International Nuclear Information System (INIS)

    Tate, M.W.; Gruner, S.M.

    1987-01-01

    The L/sub α/-H/sub II/ phase transition behavior of many lipid-water liquid crystals is dominated by the competition between the tendency to curl the lipid layers to an intrinsic radius of curvature and opposing hydrocarbon packing constraints. In particular, packing constraints can increase the free energy of the inverted hexagonal (H/sub II/) phase as compared to that of the lamellar (L/sub α/) phase. This is especially true where the lipid molecule is not long enough to reach into the corners of the lattice in large hexagonal structures necessitated by a large radius of curvature.In this paper it is shown that the addition of a minor fraction long-chain lipid to a system of otherwise uniform chain composition can also relax packing constraints, thereby lowering the lamellar to hexagonal transition temperature. For the specific systems used, dioleoylphosphatidylethanolamine (di-18:1/sub c/-PE) with minor fractions of 1,2-diacyl-sn-glycero-3-phosphocholines [di-n:1/sub c/-PC (n = 14, 18, 22, and 24)], the observed H/sub II/lattices systematically increased in size with increasing chain length suggesting that the chain length also may affect the intrinsic curvature of the mixture. These experiments demonstrate that the lipid shape concept, which is a qualitative expression of the concept quantitatively described by the intrinsic radius of curvature, is insufficient to understand the L/sub α/-H/sub II/ transition. It is necessary to, at least, consider the competition between curvature and packing

  1. Alkyl chain length impacts the antioxidative effect of lipophilized ferulic acid in fish oil enriched milk

    DEFF Research Database (Denmark)

    Sørensen, Ann-Dorit Moltke; Lyneborg, Karina Sieron; Villeneuve, Pierre

    2015-01-01

    Lipophilization of phenolics by esterification with fatty alcohols may alter their localization in an emulsion and thereby their antioxidant efficacy. In this study, synthesized unbranched alkyl ferulates were evaluated as antioxidants in fish oil enriched milk. Lipid oxidation was determined...... by peroxide values and concentration of volatile oxidation products. A cut-off effect in the antioxidant efficacy in relation to the alkyl chain length was observed. The most efficient alkyl ferulate was methyl ferulate followed by ferulic acid and butyl ferulate, whereas octyl ferulate was prooxidative...

  2. Perspectives of medium chain length poly(hydroxyalkanoates), a versatile set of bacterial bioplastics

    Science.gov (United States)

    Witholt; Kessler

    1999-06-01

    Medium chain length (mcl) poly(hydroxyalkanoic acids) (PHAs) are polyesters accumulated by fluorescent Pseudomonads and other bacteria. Work on the genetics of mcl-PHA formation has led to polymer synthesis in recombinant bacteria and plants. Several high and medium cost applications are now emerging. With optimized bacterial mcl-PHA synthesis on inexpensive agro-substrates and the development of plant-based mcl-PHAs in the next decade, the production economics of these bioplastics will ultimately permit their sustainable production for bulk applications.

  3. Shape control of the magnetic iron oxide nanoparticles under different chain length of reducing agents

    International Nuclear Information System (INIS)

    Ngoi, Kuan Hoon; Chia, Chin-Hua; Zakaria, Sarani; Chiu, Wee Siong

    2015-01-01

    We report on the effect of using reducing agents with different chain-length on the synthesis of iron oxide nanoparticles by thermal decomposition of iron (III) acetylacetonate in 1-octadecene. This modification allows us to control the shape of nanoparticles into spherical and cubic iron oxide nanoparticles. The highly monodisperse 14 nm spherical nanoparticles are obtained under 1,2-dodecanediol and average 14 nm edge-length cubic iron oxide nanoparticles are obtained under 1,2-tetradecanediol. The structural characterization such as transmission electron microscope (TEM) and X-ray diffraction (XRD) shows similar properties between two particles with different shapes. The vibrating sample magnetometer (VSM) shows no significant difference between spherical and cubic nanoparticles, which are 36 emu/g and 37 emu/g respectively and superparamagnetic in nature

  4. Shape control of the magnetic iron oxide nanoparticles under different chain length of reducing agents

    Energy Technology Data Exchange (ETDEWEB)

    Ngoi, Kuan Hoon; Chia, Chin-Hua, E-mail: chia@ukm.edu.my; Zakaria, Sarani [School of Applied Physics, Faculty Science and Technology, University Kebangsaan Malaysia 43600 UKM Bangi, Selangor (Malaysia); Chiu, Wee Siong [Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University of Malaya, 50603 Lembah Pantai, Kuala Lumpur (Malaysia)

    2015-09-25

    We report on the effect of using reducing agents with different chain-length on the synthesis of iron oxide nanoparticles by thermal decomposition of iron (III) acetylacetonate in 1-octadecene. This modification allows us to control the shape of nanoparticles into spherical and cubic iron oxide nanoparticles. The highly monodisperse 14 nm spherical nanoparticles are obtained under 1,2-dodecanediol and average 14 nm edge-length cubic iron oxide nanoparticles are obtained under 1,2-tetradecanediol. The structural characterization such as transmission electron microscope (TEM) and X-ray diffraction (XRD) shows similar properties between two particles with different shapes. The vibrating sample magnetometer (VSM) shows no significant difference between spherical and cubic nanoparticles, which are 36 emu/g and 37 emu/g respectively and superparamagnetic in nature.

  5. Effect of Chain Length Compatibility of Alcohols on Muscovite Flotation by Dodecyl Amine

    Directory of Open Access Journals (Sweden)

    Li Wang

    2018-04-01

    Full Text Available A portion of dodecyl amine (DDA in a muscovite flotation system was replaced with alcohols with different carbon-chain lengths. These alcohols included octanol (OCT; decanol (DEC; dodecanol (DOD; and tetradecanol (TER. The muscovite adsorption behavior of the mixed DDA and alcohol systems were investigated through zeta potential; contact angle; and adsorption quantity tests. Single-mineral flotation tests showed that the muscovite-collecting power of the mixed DDA/alcohol (OCT, DEC, or DOD system was stronger than that of the pure DDA system. The muscovite-collecting power of the collector systems decreased in the following order: DDA/DEC > DDA/OCT > DDA/DEC > DDA > DDA/TER. Zeta potential and contact angle analysis indicated that when combined with DDA; alcohols physically adsorbed on the surfaces of muscovite. This behavior improved the hydrophobicity of muscovite. Furthermore, adsorption analysis revealed that synergy between DDA and alcohol enhanced the adsorption of alcohol on muscovite. DDA has a dominant role in synergistic adsorption; whereas alcohol has a supporting role. Among all tested alcohols; DDA and DOD exhibit the highest synergetic adsorption effect because of their similar carbon-chain lengths. This similarity promotes the formation of a compact adsorption layer on the muscovite surface.

  6. Effect of the Alkyl Chain Length on the Adsorption Properties of Malonamide Chelating Resins

    International Nuclear Information System (INIS)

    Ismail, I.M.; Nogami, M.; Suzuki, K.

    2004-01-01

    In order to investigate the effect of the alkyl chain length of malonamide chelating resins on the rate of uptake of U(VI) ions and Ce(III) Ions, lV,N,N',N'-tetraethyl malonamide (TEMA), N,N,N',N'-tetra-n-propyl malonamide (TPrMA), lV,lV,N',N'-tetra-n-butyl malonamide (TBMA) and N,l V,N',N'-tetra-n-pentyl malonamide (Tamp) chelating resins were synthesized by chemically bonding these function groups to CMS-DVB co-polymer beads. N,lV,N',N'-tetraphenyl malonamide (TPhMA) chelating resin was also investigated and the results of these resins were compared with those of N,lY,N',N-tetra methylmalonamide (TMMA) previously reported. The batch technique was used to study the thermodynamic equilibrium, in terms of distribution coefficient, and the kinetics of the adsorption U(VI) and Ce(III) ions from 3 M HNO 3 , Acid, and 3 M NaNO 3 + 0.05 M HNO 3 , Salt, media. The introduction ratio of the function group into the polymer base and the uptake of U(VI) ions and C(III) ions were found to decrease with the increase in the alkyl chain length. The uptake was found to diminish in case of TPhMA resin due to the decrease of the function group ratio and the steric-hinder effect

  7. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  8. Pruned-enriched Rosenbluth method: Simulations of θ polymers of chain length up to 1000000

    International Nuclear Information System (INIS)

    Grassberger, P.

    1997-01-01

    We present an algorithm for simulating flexible chain polymers. It combines the Rosenbluth-Rosenbluth method with recursive enrichment. Although it can be applied also in more general situations, it is most efficient for three-dimensional θ polymers on the simple-cubic lattice. There it allows high statistics simulations of chains of length up to N=10 6 . For storage reasons, this is feasable only for polymers in a finite volume. For free θ polymers in infinite volume, we present very high statistics runs with N=10000. These simulations fully agree with previous simulations made by Hegger and Grassberger [J. Chem. Phys. 102, 6681 (1995)] with a similar but less efficient algorithm, showing that logarithmic corrections to mean field behavior are much stronger than predicted by field theory. But the finite volume simulations show that the density inside a collapsed globule scales with the distance from the θ point as predicted by mean field theory, in contrast to claims in the work mentioned above. In addition to the simple-cubic lattice, we also studied two versions of the bond fluctuation model, but with much shorter chains. Finally, we show that our method can be applied also to off-lattice models, and illustrate this with simulations of a model studied in detail by Freire et al. [Macromolecules 19, 452 (1986) and later work]. copyright 1997 The American Physical Society

  9. Alignment-free Transcriptomic and Metatranscriptomic Comparison Using Sequencing Signatures with Variable Length Markov Chains.

    Science.gov (United States)

    Liao, Weinan; Ren, Jie; Wang, Kun; Wang, Shun; Zeng, Feng; Wang, Ying; Sun, Fengzhu

    2016-11-23

    The comparison between microbial sequencing data is critical to understand the dynamics of microbial communities. The alignment-based tools analyzing metagenomic datasets require reference sequences and read alignments. The available alignment-free dissimilarity approaches model the background sequences with Fixed Order Markov Chain (FOMC) yielding promising results for the comparison of microbial communities. However, in FOMC, the number of parameters grows exponentially with the increase of the order of Markov Chain (MC). Under a fixed high order of MC, the parameters might not be accurately estimated owing to the limitation of sequencing depth. In our study, we investigate an alternative to FOMC to model background sequences with the data-driven Variable Length Markov Chain (VLMC) in metatranscriptomic data. The VLMC originally designed for long sequences was extended to apply to high-throughput sequencing reads and the strategies to estimate the corresponding parameters were developed. The flexible number of parameters in VLMC avoids estimating the vast number of parameters of high-order MC under limited sequencing depth. Different from the manual selection in FOMC, VLMC determines the MC order adaptively. Several beta diversity measures based on VLMC were applied to compare the bacterial RNA-Seq and metatranscriptomic datasets. Experiments show that VLMC outperforms FOMC to model the background sequences in transcriptomic and metatranscriptomic samples. A software pipeline is available at https://d2vlmc.codeplex.com.

  10. Characterization of a Novel Subgroup of Extracellular Medium-Chain-Length Polyhydroxyalkanoate Depolymerases from Actinobacteria

    Science.gov (United States)

    Gangoiti, Joana; Santos, Marta; Prieto, María Auxiliadora; de la Mata, Isabel; Llama, María J.

    2012-01-01

    Nineteen medium-chain-length (mcl) poly(3-hydroxyalkanoate) (PHA)-degrading microorganisms were isolated from natural sources. From them, seven Gram-positive and three Gram-negative bacteria were identified. The ability of these microorganisms to hydrolyze other biodegradable plastics, such as short-chain-length (scl) PHA, poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), and poly(l-lactide) (PLA), has been studied. On the basis of the great ability to degrade different polyesters, Streptomyces roseolus SL3 was selected, and its extracellular depolymerase was biochemically characterized. The enzyme consisted of one polypeptide chain of 28 kDa with a pI value of 5.2. Its maximum activity was observed at pH 9.5 with chromogenic substrates. The purified enzyme hydrolyzed mcl PHA and PCL but not scl PHA, PES, and PLA. Moreover, the mcl PHA depolymerase can hydrolyze various substrates for esterases, such as tributyrin and p-nitrophenyl (pNP)-alkanoates, with its maximum activity being measured with pNP-octanoate. Interestingly, when poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate [11%]) was used as the substrate, the main hydrolysis product was the monomer (R)-3-hydroxyoctanoate. In addition, the genes of several Actinobacteria strains, including S. roseolus SL3, were identified on the basis of the peptide de novo sequencing of the Streptomyces venezuelae SO1 mcl PHA depolymerase by tandem mass spectrometry. These enzymes did not show significant similarity to mcl PHA depolymerases characterized previously. Our results suggest that these distinct enzymes might represent a new subgroup of mcl PHA depolymerases. PMID:22865072

  11. Changes in the n-alkane composition of avocado pulp oil ( Persea americana, Mill. during fruit ripening

    Directory of Open Access Journals (Sweden)

    Giuffrè, A. M.

    2005-03-01

    Full Text Available The n-alkane composition of Avocado pulp oil (cv. Hass was investigated during fruit ripening. Three samples of fruit were harvested on March 3, 2003, March 18, 2003 and April 2, 2003. Glass gravity column chromatography was employed to separate n-alkanes from other minor components contained in the unsaponifiable fraction. Gas chromatography was used to analyze the eluate. Fourteen compounds were detected ranging from n -C21 to n -C34; mainly n -C24, followed by n -C25 and then by n -C23. Quantities of n -C21, n -C22, n -C23, n -C27 and n -C28 progressively increased during ripening, whereas n -C24, n -C25, n -C26, n -C29, n -C30 and n -C34 decreased from the first harvest date to the third harvest date. While odd-numbered carbon n-alkanes increased (52.38 %, 52.85 % and 53.06 % for the three samples respectively, even-numbered carbon n-alkanes decreased as the fruit ripened (47.62 %, 47.15 % and 46.94 %. The total n-alkane content decreased during ripening, from 25.20 mg/Kg (first harvest date to 16.77 mg/Kg (third harvest date. In order to minimize.Se ha analizado la composición en hidrocarburos lineales saturados del aceite de la pulpa de aguacate (variedad Hass. Tres muestras fueron recolectadas: el 3 de marzo 2003, el 18 de marzo 2003 y el 2 de abril 2003. La separación de los hidrocarburos lineales saturados se realizó mediante fraccionamiento del insaponificable por cromatografía gravimétrica de adsorción en columna y la determinación de los mismos hidrocarburos por cromatografía gaseosa. 14 compuestos fueron detectados del n- C21 al n- C34. El n- C24 fue el mayoritario, seguido del n- C25 y el n- C23. El porcentaje de n- C21, n- C22, n- C23, n- C27 y n- C28, aumentó durante la maduración, mientras que el porcentaje de n- C24, n- C25, n- C26, n- C29, n- C30 y C34 disminuyó desde el 3 de marzo 2003 hasta el 2 de abril 2003. Los hidrocarburos lineales saturados con número impar de átomos de carbono aumentaron (52.38 %, 52

  12. The effect of carbon chain length of starting materials on the formation of carbon dots and their optical properties

    Science.gov (United States)

    Pan, Xiaohua; Zhang, Yan; Sun, Xiaobo; Pan, Wei; Yu, Guifeng; Si, Shuxin; Wang, Jinping

    2018-04-01

    Carbon dots (CDs) have attracted increasing attention due to their high performances and potential applications in wide range of areas. However, their emission mechanism is not clear so far. In order to reveal more factors contributing to the emission of CDs, the effect of carbon chain length of starting materials on the formation of CDs and their optical properties was experimentally investigated in this work. In order to focus on the effect of carbon chain length, the starting materials with C, O, N in fully identical forms and only carbon chain lengths being different were selected for synthesizing CDs, including citric acid (CA) and adipic acid (AA) as carbon sources, and diamines with different carbon chain lengths (H2N(CH2)nNH2, n = 2, 4, 6) as nitrogen sources, as well as ethylenediamine (EDA) as nitrogen source and diacids with different carbon chain lengths (HOOC(CH2)nCOOH, n = 0, 2, 4, 6) as carbon sources. Therefore, the effect of carbon chain length of starting materials on the formation and optical properties of CDs can be systematically investigated by characterizing and comparing the structures and optical properties of as-prepared nine types of CDs. Moreover, the density of –NH2 on the surface of the CDs was quantitatively detected by a spectrophotometry so as to elucidate the relationship between the –NH2 related surface state and the optical properties.

  13. Soliton scatterings by impurities in a short-length sine-Gordon chain

    International Nuclear Information System (INIS)

    Dikande, A.M.; Kofane, T.C.

    1995-07-01

    The scattering of soliton by impurities at the frontiers of a finite-length region of an infinite sine-Gordon chain is analyzed. The impurities consist of two isotopic inhomogeneities installed at the boundaries of the finite-length region. The soliton solution in the region is found in term of snoidal sine-Gordon soliton which properly takes into account the effects of the boundaries. By contrast, the soliton solutions in the neighboring sides of the region are obtained in terms of the so-called large-amplitude, localized kinks with limiting spatial extensions at x → ± ∞, which is equal ±π. Using the continuity of these soliton solutions at the frontiers as well as appropriate boundary conditions, it is shown that the soliton may be either i) reflected by the incident impurity; ii) trapped (with oscillating motions) between the two impurities (i.e. inside the infinite region); or iii) transmitted by the second impurity into the third, infinitely extended region. The threshold velocities for the reflection and transmission into different regions are found and shown to vary exponentially as a function of the length of the bounded region. The frequency of soliton oscillations between the impurities has also been calculated in some acceptable limit. (author). 28 refs, 1 fig

  14. Seasonal variation of the particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) in urban aerosol of Guangzhou, China.

    Science.gov (United States)

    Tang, X L; Bi, X H; Sheng, G Y; Tan, J H; Fu, J M

    2006-06-01

    Seasonal aerosol samples have been collected by Andersen Hi-Vol pumping system equipped with a five stage cascade impactor and a backup filter (size range: 10-7.2 microm, 7.2-3.0 microm, 3.0-1.5 microm, 1.5-0.95 microm, 0.95-0.49 microm, gas chromatography and PAHs were measured using gas chromatography/mass spectrometry analysis. The bimodal log-normal distributions of n-alkanes and semi-volatile PAHs were found, while for non-volatile PAHs that was unimodal, so much as the mode of semi-volatile PAHs was similar with that of the particles. The n-alkanes and PAHs were preferably associated with fine particles. C (max) (carbon number maximum) (C(22)-C(26)), CPI (carbon preference index) (1.12-1.21), U/R (unresolved to resolved components ratio) (7.42-10.7), wax% (0.9-3.12%) and the diagnostic ratios for PAHs revealed that vehicular emission was the major source of these organic compounds during the study periods, while the contribution of epicuticular waxes emitted by terrestrial plants was minor. CPI(2) (values for petrogenic hydrocarbons), CPI(3) (values for biogenic n-alkanes) and wax% revealed that the natural preferentially accumulated in the larger aerosol while the anthropogenic in the smaller. In addition, the different MMDs (mass median diameters) for n-alkanes and PAHs were observed in different seasons. The MMDs for n-alkanes and PAHs were higher in autumn/winter than those in spring/summer. The seasonal effect was related to the hydrocarbon content in the individual particulate fractions, showing a preferential association of n-alkanes and PAHs with larger particles in the autumn/winter season.

  15. Chain length effects on the vibrational structure and molecular interactions in the liquid normal alkyl alcohols

    Science.gov (United States)

    Kiefer, Johannes; Wagenfeld, Sabine; Kerlé, Daniela

    2018-01-01

    Alkyl alcohols are widely used in academia, industry, and our everyday lives, e.g. as cleaning agents and solvents. Vibrational spectroscopy is commonly used to identify and quantify these compounds, but also to study their structure and behavior. However, a comprehensive investigation and comparison of all normal alkanols that are liquid at room temperature has not been performed, surprisingly. This study aims at bridging this gap with a combined experimental and computational effort. For this purpose, the alkyl alcohols from methanol to undecan-1-ol have been analyzed using infrared and Raman spectroscopy. A detailed assignment of the individual peaks is presented and the influence of the alkyl chain length on the hydrogen bonding network is discussed. A 2D vibrational mapping allows a straightforward visualization of the effects. The conclusions drawn from the experimental data are backed up with results from Monte Carlo simulations using the simulation package Cassandra.

  16. Synthesis of medium-chain length capsinoids from coconut oil catalyzed by Candida rugosa lipases.

    Science.gov (United States)

    Trbojević Ivić, Jovana; Milosavić, Nenad; Dimitrijević, Aleksandra; Gavrović Jankulović, Marija; Bezbradica, Dejan; Kolarski, Dušan; Veličković, Dušan

    2017-03-01

    A commercial preparation of Candida rugosa lipases (CRL) was tested for the production of capsinoids by esterification of vanillyl alcohol (VA) with free fatty acids (FA) and coconut oil (CO) as acyl donors. Screening of FA chain length indicated that C8-C12 FA (the most common FA found in CO triglycerides) are the best acyl-donors, yielding 80-85% of their specific capsinoids. Hence, when CO, which is rich in these FA, was used as the substrate, a mixture of capsinoids (vanillyl caprylate, vanillyl decanoate and vanillyl laurate) was obtained. The findings presented here suggest that our experimental method can be applied for the enrichment of CO with capsinoids, thus giving it additional health promoting properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. The Role of Chain Length in Nonergodicity Factor and Fragility of Polymers

    DEFF Research Database (Denmark)

    Dalle-Ferrie, Cecile; Niss, Kristine; Sokolov, Alexei

    2010-01-01

    The mechanism that leads to different fragility values upon approaching the glass transition remains a topic of active discussion. Many researchers are trying to find an answer in the properties of the frozen glassy state. Following this approach, we focus here on a previously proposed relationship...... between the fragility of glass-formers and their nonergodicity factor, determined by inelastic X-ray scattering (IXS) in the glass. We extend this molecular liquid study to two model polymers— polystyrene (PS) and polyisobutylene (PIB)—for which we change the molecular weight. Polymers offer...... the opportunity to change the fragility without altering the chemical structure, just by changing the chain length. Thus, we specifically chose PS and PIB because they exhibit opposite dependences of fragility with molecular weight. Our analysis for these two polymers reveals no unique correlation between...

  18. Effect of surfactant chain length on drug release kinetics from microemulsion-laden contact lenses.

    Science.gov (United States)

    Maulvi, Furqan A; Desai, Ankita R; Choksi, Harsh H; Patil, Rahul J; Ranch, Ketan M; Vyas, Bhavin A; Shah, Dinesh O

    2017-05-30

    The effect of surfactant chain lengths [sodium caprylate (C 8 ), Tween 20 (C 12 ), Tween 80 (C 18 )] and the molecular weight of block copolymers [Pluronic F68 and Pluronic F 127] were studied to determine the stability of the microemulsion and its effect on release kinetics from cyclosporine-loaded microemulsion-laden hydrogel contact lenses in this work. Globule size and dilution tests (transmittance) suggested that the stability of the microemulsion increases with increase in the carbon chain lengths of surfactants and the molecular weight of pluronics. The optical transmittance of direct drug-laden contact lenses [DL-100] was low due to the precipitation of hydrophobic drugs in the lenses, while in microemulsion-laden lenses, the transmittance was improved when stability of the microemulsion was achieved. The results of in vitro release kinetics revealed that drug release was sustained to a greater extent as the stability of microemulsion was improved as well. This was evident in batch PF127-T80, which showed sustained release for 15days in comparison to batch DL-100, which showed release up to 7days. An in vivo drug release study in rabbit tear fluid showed significant increase in mean residence time (MRT) and area under curve (AUC) with PF-127-T80 lenses (stable microemulsion) in comparison to PF-68-SC lenses (unstable microemulsion) and DL-100 lenses. This study revealed the correlation between the stability of microemulsion and the release kinetics of drugs from contact lenses. Thus, it was inferred that the stable microemulsion batches sustained the release of hydrophobic drugs, such as cyclosporine from contact lenses for an extended period of time without altering critical lens properties. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Tuning the Mechanical Properties of Polymer Nanocomposites Filled with Grafted Nanoparticles by Varying the Grafted Chain Length and Flexibility

    Directory of Open Access Journals (Sweden)

    Zixuan Wang

    2016-08-01

    Full Text Available By employing coarse-grained molecular dynamics simulation, we simulate the spatial organization of the polymer-grafted nanoparticles (NPs in homopolymer matrix and the resulting mechanical performance, by particularly regulating the grafted chain length and flexibility. The morphologies ranging from the agglomerate, cylinder, sheet, and string to full dispersion are observed, by gradually increasing the grafted chain length. The radial distribution function and the total interaction energy between NPs are calculated. Meanwhile, the stress–strain behavior of each morphology and the morphological evolution during the uniaxial tension are simulated. In particular, the sheet structure exhibits the best mechanical reinforcement compared to other morphologies. In addition, the change of the grafted chain flexibility to semi-flexibility leads to the variation of the morphology. We also find that at long grafted chain length, the stress–strain behavior of the system with the semi-flexible grafted chain begins to exceed that of the system with the flexible grafted chain, attributed to the physical inter-locking interaction between the matrix and grafted polymer chains. A similar transition trend is as well found in the presence of the interfacial chemical couplings between grafted and matrix polymer chains. In general, this work is expected to help to design and fabricate high performance polymer nanocomposites filled with grafted NPs with excellent and controllable mechanical properties.

  20. Supplemental Dietary Inulin of Variable Chain Lengths Alters Intestinal Bacterial Populations in Young Pigs123

    Science.gov (United States)

    Patterson, Jannine K.; Yasuda, Koji; Welch, Ross M.; Miller, Dennis D.; Lei, Xin Gen

    2010-01-01

    Previously, we showed that supplementation of diets with short-chain inulin (P95), long-chain inulin (HP), and a 50:50 mixture of both (Synergy 1) improved body iron status and altered expression of the genes involved in iron homeostasis and inflammation in young pigs. However, the effects of these 3 types of inulin on intestinal bacteria remain unknown. Applying terminal restriction fragment length polymorphism analysis, we determined the abundances of luminal and adherent bacterial populations from 6 segments of the small and large intestines of pigs (n = 4 for each group) fed an iron-deficient basal diet (BD) or the BD supplemented with 4% of P95, Synergy 1, or HP for 5 wk. Compared with BD, all 3 types of inulin enhanced (P inulin on bacterial populations in the lumen contents were found. Meanwhile, all 3 types of inulin suppressed the less desirable bacteria Clostridium spp. and members of the Enterobacteriaceae in the lumen and mucosa of various gut segments. Our findings suggest that the ability of dietary inulin to alter intestinal bacterial populations may partially account for its iron bioavailability-promoting effect and possibly other health benefits. PMID:20980641

  1. Critical temperatures and a critical chain length in saturated diacylphosphatidylcholines: calorimetric, ultrasonic and Monte Carlo simulation study of chain-melting/ordering in aqueous lipid dispersions.

    Science.gov (United States)

    Kharakoz, Dmitry P; Panchelyuga, Maria S; Tiktopulo, Elizaveta I; Shlyapnikova, Elena A

    2007-12-01

    Chain-ordering/melting transition in a series of saturated diacylphosphatidylcholines (PCs) in aqueous dispersions have been studied experimentally (calorimetric and ultrasonic techniques) and theoretically (an Ising-like lattice model). The shape of the calorimetric curves was compared with the theoretical data and interpreted in terms of the lateral interactions and critical temperatures determined for each lipid studied. A critical chain length has been found (between 16 and 17 C-atoms per chain) which subdivides PCs into two classes with different phase behavior. In shorter lipids, the transition takes place above their critical temperatures meaning that this is an intrinsically continuous transition. In longer lipids, the transition occurs below the critical temperatures of the lipids, meaning that the transition is intrinsically discontinuous (first-order). This conclusion was supported independently by the ultrasonic relaxation sensitive to density fluctuations. Interestingly, it is this length that is the most abundant among the saturated chains in biological membranes.

  2. Source apportionment of PAHs and n-alkanes bound to PM1 collected near the Venice highway.

    Science.gov (United States)

    Valotto, Gabrio; Rampazzo, Giancarlo; Gonella, Francesco; Formenton, Gianni; Ficotto, Silvia; Giraldo, Giorgia

    2017-04-01

    n-Alkanes and polycyclic aromatic hydrocarbons (PAHs) bound to atmospheric particulate matter (PM 1 ) were investigated in a traffic site located in an urban area of Venice Province (Eastern Po Valley, Italy) during the cold season. Considering the critical situation affecting the Veneto Region concerning the atmospheric pollution and the general lack of information on PM 1 composition and emission in this area, this experimental study aims at determining the source profile, their relative contributions and the dispersion of finer particles. Four sources were identified and quantified using the Positive Matrix Factorization receptor model: (1) mixed combustions related to the residential activities, (2) agricultural biomass burning in addition to the resuspension of anthropogenic and natural debris carried by the wind, (3) gasoline and (4) diesel traffic-related combustions. The role of local atmospheric circulation was also investigated to identify the pollutant sources. Copyright © 2016. Published by Elsevier B.V.

  3. Oh Magadi! Interpreting isoGDGTs and n-alkanes in a saline tropical lake: Lake Magadi, Kenya

    Science.gov (United States)

    Ferland, T. M.; Werne, J. P.; Castañeda, I. S.; Cohen, A. S.; Lowenstein, T. K.; Deocampo, D.; Renaut, R.; Bernhart, O. R.

    2017-12-01

    The Hominin Sites and Paleolakes Drilling Project (HSPDP) seeks to understand the paleoclimatic and paleoenvironmental context of hominin adaptation and evolution by analysis of paleolacustrine cores taken near key hominin fossil and artifact localities in Kenya and Ethiopia. We present biomarker and compound specific isotope data from a 200 m drill core from Lake Magadi, Kenya. Located 20 km from the Koora Plain in the southern Kenya Rift, and adjacent to the Olorgesailie basin, Lake Magadi is in one of the richest Early-Late Pleistocene archaeological localities in Africa, a region that has been key in debates about the relationship between climate and evolution. Present-day Lake Magadi is a saline pan, a descendant of a series of paleolakes that have occupied its drainage basin and progressively dried for approximately one million years. Nearly 70% of samples analyzed for n-alkanes recorded a robust terrestrial signal. The majority of samples did not contain the complete suite of branched GDGTs necessary to reconstruct temperature from the Methylation of Branched Tetraethers and Cyclisation of Branched Tetraethers (MBT/CBT; Weijers et al., 2007) proxy. The TetraEther indeX with 86 carbon atoms (TEX86; Schouten et al., 2002) temperature proxy was established for 90% of samples analyzed for isoGDGTs, however the Methane and Ring Indices (Zhang et al., 2011; Zhang et al., 2016) suggest that the TEX86 is not applicable to temperature reconstruction at Magadi. Despite this, the Magadi TEX86 temperature reconstruction appears to agree with not only the trends in our n-alkane data but with other regional and global records, including the GRIP-2 δ18O record. We compare our temperature data to other records in the region, and investigate influences on our TEX86 data including microbial community turnover and lake drying.

  4. The effect of environmental factors on stable isotopic composition of n-alkanes in Mediterranean olive oils

    Science.gov (United States)

    Pedentchouk, Nikolai; Mihailova, Alina; Abbado, Dimitri

    2014-05-01

    Traceability of the geographic origin of olive oils is an important issue from both commercial and health perspectives. This study evaluates the impact of environmental factors on stable C and H isotope compositions of n-alkanes in extra virgin olive oils from Croatia, France, Greece, Italy, Morocco, Portugal, Slovenia, and Spain. The data are used to investigate the applicability of stable isotope methodology for olive oil regional classification in the Mediterranean region. Analysis of stable C isotope composition of n-C29 alkane showed that extra virgin olive oils from Portugal and Spain have the most positive n-C29 alkane delta13C values. Conversely, olive oils from Slovenia, northern and central Italy are characterized by the most negative values. Overall, the n-C29 alkane delta13C values show a positive correlation with the mean air temperature during August-December and a negative correlation with the mean relative humidity during these months. Analysis of stable H isotope composition of n-C29 alkane revealed that the deltaD values are the most positive in olive oils from Greece and Morocco and the most negative in oils from northern Italy. The deltaD values of oils show significant correlation with all the analyses geographical parameters: the mean air temperature and relative humidity during August-December, the total amount of rainfall (the same months) and the annual deltaD values of precipitation. As predictor variables in the Categorical Data Analysis, the n-C29 alkane deltaD values show the most significant discriminative power, followed by the n-C29 alkane delta13C values. Overall, 93.4% of olive oil samples have been classified correctly into one of the production regions. Our findings suggest that an integrated analysis of C and H isotope compositions of n-alkanes extracted from extra virgin olive oil could become a useful tool for geographical provenancing of this highly popular food commodity.

  5. Well-defined block copolymers for gene delivery to dendritic cells: probing the effect of polycation chain-length.

    Science.gov (United States)

    Tang, Rupei; Palumbo, R Noelle; Nagarajan, Lakshmi; Krogstad, Emily; Wang, Chun

    2010-03-03

    The development of safe and efficient polymer carriers for DNA vaccine delivery requires mechanistic understanding of structure-function relationship of the polymer carriers and their interaction with antigen-presenting cells. Here we have synthesized a series of diblock copolymers with well-defined chain-length using atom transfer radical polymerization and characterized the influence of polycation chain-length on the physico-chemical properties of the polymer/DNA complexes as well as the interaction with dendritic cells. The copolymers consist of a hydrophilic poly(ethylene glycol) block and a cationic poly(aminoethyl methacrylate) (PAEM) block. The average degree of polymerization (DP) of the PAEM block was varied among 19, 39, and 75, with nearly uniform distribution. With increasing PAEM chain-length, polyplexes formed by the diblock copolymers and plasmid DNA had smaller average particle size and showed higher stability against electrostatic destabilization by salt and heparin. The polymers were not toxic to mouse dendritic cells (DCs) and only displayed chain-length-dependent toxicity at a high concentration (1mg/mL). In vitro gene transfection efficiency and polyplex uptake in DCs were also found to correlate with chain-length of the PAEM block with the longer polymer chain favoring transfection and cellular uptake. The polyplexes induced a modest up-regulation of surface markers for DC maturation that was not significantly dependent on PAEM chain-length. Finally, the polyplex prepared from the longest PAEM block (DP of 75) achieved an average of 20% enhancement over non-condensed anionic dextran in terms of uptake by DCs in the draining lymph nodes 24h after subcutaneous injection into mice. Insights gained from studying such structurally well-defined polymer carriers and their interaction with dendritic cells may contribute to improved design of practically useful DNA vaccine delivery systems. Copyright 2009 Elsevier B.V. All rights reserved.

  6. Scaling behaviour of the correlation length for the two-point correlation function in the random field Ising chain

    Energy Technology Data Exchange (ETDEWEB)

    Lange, Adrian; Stinchcombe, Robin [Theoretical Physics, University of Oxford, Oxford (United Kingdom)

    1996-07-07

    We study the general behaviour of the correlation length {zeta}(kT:h) for two-point correlation function of the local fields in an Ising chain with binary distributed fields. At zero field it is shown that {zeta} is the same as the zero-field correlation length for the spin-spin correlation function. For the field-dominated behaviour of {zeta} we find an exponent for the power-law divergence which is smaller than the exponent for the spin-spin correlation length. The entire behaviour of the correlation length can be described by a single crossover scaling function involving the new critical exponent. (author)

  7. Control of in vivo disposition and immunogenicity of polymeric micelles by adjusting poly(sarcosine) chain lengths on surface

    Science.gov (United States)

    Kurihara, Kensuke; Ueda, Motoki; Hara, Isao; Ozeki, Eiichi; Togashi, Kaori; Kimura, Shunsaku

    2017-07-01

    Four kinds of A3B-type amphiphilic polydepsipeptides, (poly(sarcosine))3- b-poly( l-lactic acid) (the degree of polymerization of poly(sarcosine) are 10, 33, 55, and 85; S10 3 , S33 3 , S55 3 , and S85 3 ) were synthesized to prepare core-shell type polymeric micelles. Their in vivo dispositions and stimulations to trigger immune system to produce IgM upon multiple administrations to mice were examined. With increasing poly(sarcosine) chain lengths, the hydrophilic shell became thicker and the surface density at the most outer surface decreased on the basis of dynamic and static light scattering measurements. These two physical elements of polymeric micelles elicited opposite effects on the immune response in light of the chain length therefore to show an optimized poly(sarcosine) chain length existing between 33mer and 55mer to suppress the accelerated blood clearance phenomenon associated with polymeric micelles.

  8. Difference equation model for isothermal gas chromatography expresses retention behavior of homologues of n-alkanes excluding the influence of holdup time

    Science.gov (United States)

    Wu, Liejun; Chen, Yongli; Caccamise, Sarah A.L.; Li, Qing X.

    2012-01-01

    A difference equation (DE) model is developed using the methylene retention increment (Δtz) of n-alkanes to avoid the influence of gas holdup time (tM). The effects of the equation orders (1st–5th) on the accuracy of a curve fitting show that a linear equation (LE) is less satisfactory and it is not necessary to use a complicated cubic or higher order equation. The relationship between the logarithm of Δtz and the carbon number (z) of the n-alkanes under isothermal conditions closely follows the quadratic equation for C3–C30 n-alkanes at column temperatures of 24–260 °C. The first and second order forward differences of the expression (Δlog Δtz and Δ2log Δtz, respectively) are linear and constant, respectively, which validates the DE model. This DE model lays a necessary foundation for further developing a retention model to accurately describe the relationship between the adjusted retention time and z of n-alkanes. PMID:22939376

  9. Distribution and origins of n-alkanes, hopanes, and steranes in rivers and marine sediments from Southwest Caspian coast, Iran: implications for identifying petroleum hydrocarbon inputs.

    Science.gov (United States)

    Shirneshan, Golshan; Bakhtiari, Alireza Riyahi; Memariani, Mahmoud

    2016-09-01

    The occurrence of n-alkanes and biomarkers (hopane and sterane) in surface sediments from Southwestern coasts of Caspian Sea and 28 rivers arriving to this lake, determined with a gas chromatography-mass spectrometry method, was used to assess the impacts of anthropogenic activities in the studied area. The concentrations of total n-alkanes (Σ21 n-alkane) in costal and riverine sediments varied from 249.2 to 3899.5 and 56 to 1622.4 μg g(-1), respectively. An evaluation of the source diagnostic indices indicated that petroleum related sources (petrogenic) were mainly contributed to n-alkanes in costal and most riverine sediments. Only the hydrocarbons in sediment of 3 rivers were found to be mainly of biogenic origin. Principal component analysis using hopane diagnostic ratios in costal and riverine sediments, and Anzali, Turkmenistan, and Azerbaijan oils were used to identify the sources of hydrocarbons in sediments. It was indicated that the anthropogenic contributions in most of the costal sediment samples are dominated with inputs of oil spills from Turkmenistan and Azerbaijan countries.

  10. Heat capacity and Joule-Thomson coefficient of selected n-alkanes at 0.1 and 10 MPa in broad temperature ranges

    DEFF Research Database (Denmark)

    Regueira Muñiz, Teresa; Varzandeh, Farhad; Stenby, Erling Halfdan

    2017-01-01

    Isobaric heat capacity of six n-alkanes, i.e. n-hexane, n-octane, n-decane, n-dodecane, n-tetradecane and n-hexadecane, was determined with a Calvet type differential heat-flux calorimeter at 0.1 and 10 MPa in a broad temperature range. The measured isobaric heat capacity data were combined...

  11. Transport properties of mixtures by the soft-SAFT + free-volume theory: application to mixtures of n-alkanes and hydrofluorocarbons.

    Science.gov (United States)

    Llovell, F; Marcos, R M; Vega, L F

    2013-05-02

    In a previous paper (Llovell et al. J. Phys. Chem. B, submitted for publication), the free-volume theory (FVT) was coupled with the soft-SAFT equation of state for the first time to extend the capabilities of the equation to the calculation of transport properties. The equation was tested with molecular simulations and applied to the family of n-alkanes. The capability of the soft-SAFT + FVT treatment is extended here to other chemical families and mixtures. The compositional rules of Wilke (Wilke, C. R. J. Chem. Phys. 1950, 18, 517-519) are used for the diluted term of the viscosity, while the dense term is evaluated using very simple mixing rules to calculate the viscosity parameters. The theory is then used to predict the vapor-liquid equilibrium and the viscosity of mixtures of nonassociating and associating compounds. The approach is applied to determine the viscosity of a selected group of hydrofluorocarbons, in a similar manner as previously done for n-alkanes. The soft-SAFT molecular parameters are taken from a previous work, fitted to vapor-liquid equilibria experimental data. The application of FVT requires three additional parameters related to the viscosity of the pure fluid. Using a transferable approach, the α parameter is taken from the equivalent n-alkane, while the remaining two parameters B and Lv are fitted to viscosity data of the pure fluid at several isobars. The effect of these parameters is then investigated and compared to those obtained for n-alkanes, in order to better understand their effect on the calculations. Once the pure fluids are well characterized, the vapor-liquid equilibrium and the viscosity of nonassociating and associating mixtures, including n-alkane + n-alkane, hydrofluorocarbon + hydrofluorocarbon, and n-alkane + hydrofluorocarbon mixtures, are calculated. One or two binary parameters are used to account for deviations in the vapor-liquid equilibrium diagram for nonideal mixtures; these parameters are used in a

  12. On optimal length of hydrocarbon chain of fatty-acid collectors of rare earth ions

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Sazonova, V.F.; Markina, Eh.L.

    1978-01-01

    The mechanism of the effect of the length of alkyl chain in fatty-acid collectors on the efficiency of flotation separation of the ions of rare earth elements (REE) collected by them has been investigated. REE flotation separation was studied on gadolinium chloride. Aqueous solutions of potassium caprinata, indecanate, laurate, tridecanate, myristate, pentadecanate and palmitate were used as collectors of Gd ions. The interaction of Gd ions with these compounds proceeds rapidly and is accompanied by stable colloidal solutions of Gd soaps being formed. Infrared spectra and radiograms of the sublates have been studied. It has been found that, with the number of carbon atoms in the collector molecule increasing from 10 to 16, the rate of flotation separation of Gd ions from solutions with pH 6 and 8 at first practically does not change (for potassium caprinate, undecanate and laurate), then drops sharply (potassium tridecanate and myristate), after which is again increases sharply (potassium pentadecanata and palmitate). The separation rate of Gd ions does not rise in solutions with pH 10. The nature of the sublate is shown to be determined by the solubility of the corresponing fatty acids and gadolinium soaps

  13. The interacting effects of temperature and food chain length on trophic abundance and ecosystem function.

    Science.gov (United States)

    Beveridge, Oliver S; Humphries, Stuart; Petchey, Owen L

    2010-05-01

    1. While much is known about the independent effects of trophic structure and temperature on density and ecosystem processes, less is known about the interaction(s) between the two. 2. We manipulated the temperature of laboratory-based bacteria-protist communities that contained communities with one, two, or three trophic levels, and recorded species' densities and bacterial decomposition. 3. Temperature, food chain length and their interaction produced significant responses in microbial density and bacterial decomposition. Prey and resource density expressed different patterns of temperature dependency during different phases of population dynamics. The addition of a predator altered the temperature-density relationship of prey, from a unimodal trend to a negative one. Bacterial decomposition was greatest in the presence of consumers at higher temperatures. 4. These results are qualitatively consistent with a recent model of direct and indirect temperature effects on resource-consumer population dynamics. Results highlight and reinforce the importance of indirect effects of temperature mediated through trophic interactions. Understanding and predicting the consequences of environmental change will require that indirect effects, trophic structure, and individual species' tolerances be incorporated into theory and models.

  14. Molecular identification of Giardia duodenalis in Ecuador by polymerase chain reaction-restriction fragment length polymorphism

    Directory of Open Access Journals (Sweden)

    Richard Atherton

    2013-06-01

    Full Text Available The aim of this study was to determine the genetic diversity of Giardia duodenalis present in a human population living in a northern Ecuadorian rain forest. All Giardia positive samples (based on an ELISA assay were analysed using a semi-nested polymerase chain reaction-restriction fragment length polymorphism assay that targets the glutamate dehydrogenase (gdh gene; those amplified were subsequently genotyped using NlaIV and RsaI enzymes. The gdh gene was successfully amplified in 74 of 154 ELISA positive samples; 69 of the 74 samples were subsequently genotyped. Of these 69 samples, 42 (61% were classified as assemblage B (26 as BIII and 16 as BIV, 22 (32% as assemblage A (3 as AI and 19 as AII and five (7% as mixed AII and BIII types. In this study site we observe similar diversity in genotypes to other regions in Latin America, though in contrast to some previous studies, we found similar levels of diarrheal symptoms in those individuals infected with assemblage B compared with those infected with assemblage A.

  15. Chain length dependence of the helix orientation in Langmuir-Blodgett monolayers of alpha-helical diblock copolypeptides

    NARCIS (Netherlands)

    Nguyen, Le-Thu T.; Ardana, Aditya; Vorenkamp, Eltjo J.; ten Brinke, Gerrit; Schouten, Arend J.

    2010-01-01

    The effect of chain length on the helix orientation of alpha-helical diblock copolypeptides in Langmuir and Langmuir-Blodgett monolayers is reported for the first time. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and

  16. Biosynthesis of Colabomycin E, a New Manumycin-Family Metabolite, Involves an Unusual Chain-Length Factor

    Czech Academy of Sciences Publication Activity Database

    Petříčková, Kateřina; Pospíšil, Stanislav; Kuzma, Marek; Tylová, Tereza; Jágr, Michal; Tomek, P.; Chroňáková, Alica; Brabcová, E.; Anděra, Ladislav; Krištůfek, Václav; Petříček, Miroslav

    2014-01-01

    Roč. 15, č. 9 (2014), s. 1334-1345 ISSN 1439-4227 R&D Projects: GA MZd(CZ) NT13012 Institutional support: RVO:61388971 ; RVO:60077344 ; RVO:68378050 Keywords : biosynthesis * chain-length factors * manumycins Subject RIV: CE - Biochemistry Impact factor: 3.088, year: 2014

  17. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder

    NARCIS (Netherlands)

    Walle, van der G.A.M.; Buisman, F.J.H.; Weusthuis, R.A.; Eggink, G.

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of

  18. Density and Compressibility of Multicomponent n-Alkane Mixtures up to 463 K and 140 MPa

    DEFF Research Database (Denmark)

    Regueira, Teresa; Glykioti, Maria-Lito; Stenby, Erling Halfdan

    2017-01-01

    Density measurements of two ternary alkane mixtures (methane/n-butane/n-decane and methane/n-butane/n-dodecane) and two multicomponent mixtures composed of methane/n-butane/n-octane/n-dodecane/n-hexadecane/n-eicosane were performed in the temperature range from (278.15 to 463.15) K and pressures ......–Redlich–Kwong (SRK), Peng–Robinson (PR), Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT), and Soave-Benedict-Webb-Rubin (Soave-BWR) were used for predicting the experimental density values as well as the excess volumes....... to 140 MPa. The isothermal compressibility values of these mixtures were obtained by differentiation from a Tait-type fitting of experimental densities as a function of temperature and pressure. Excess volume of the studied mixtures was also determined. Four different equations of state, that is, Soave...

  19. Measurement and modelling of high pressure density and interfacial tension of (gas + n-alkane) binary mixtures

    International Nuclear Information System (INIS)

    Pereira, Luís M.C.; Chapoy, Antonin; Burgass, Rod; Tohidi, Bahman

    2016-01-01

    Highlights: • (Density + IFT) measurements are performed in synthetic reservoir fluids. • Measured systems include CO_2, CH_4 and N_2 with n-decane. • Novel data are reported for temperatures up to 443 K and pressures up to 69 MPa. • Predictive models are tested in 16 (gas + n-alkane) systems. • Best modelling results are achieved with the Density Gradient Theory. - Abstract: The deployment of more efficient and economical extraction methods and processing facilities of oil and gas requires the accurate knowledge of the interfacial tension (IFT) of fluid phases in contact. In this work, the capillary constant a of binary mixtures containing n-decane and common gases such as carbon dioxide, methane and nitrogen was measured. Experimental measurements were carried at four temperatures (313, 343, 393 and 442 K) and pressures up to 69 MPa, or near the complete vaporisation of the organic phase into the gas-rich phase. To determine accurate IFT values, the capillary constants were combined with saturated phase density data measured with an Anton Paar densitometer and correlated with a model based on the Peng–Robinson 1978 equation of state (PR78 EoS). Correlated density showed an overall percentage absolute deviation (%AAD) to measured data of (0.2 to 0.5)% for the liquid phase and (1.5 to 2.5)% for the vapour phase of the studied systems and P–T conditions. The predictive capability of models to accurately describe both the temperature and pressure dependence of the saturated phase density and IFT of 16 (gas + n-alkane) binary mixtures was assessed in this work by comparison with data gathered from the literature and measured in this work. The IFT models considered include the Parachor, the Linear Gradient Theory (LGT) and the Density Gradient Theory (DGT) approaches combined with the Volume-Translated Predictive Peng–Robinson 1978 EoS (VT-PPR78 EoS). With no adjustable parameters, the VT-PPR78 EoS allowed a good description of both solubility and

  20. Pseudomonas aeruginosa cytochrome c551 denaturation by five systematic urea derivatives that differ in the alkyl chain length.

    Science.gov (United States)

    Kobayashi, Shinya; Fujii, Sotaro; Koga, Aya; Wakai, Satoshi; Matubayasi, Nobuyuki; Sambongi, Yoshihiro

    2017-07-01

    Reversible denaturation of Pseudomonas aeruginosa cytochrome c 551 (PAc 551 ) could be followed using five systematic urea derivatives that differ in the alkyl chain length, i.e. urea, N-methylurea (MU), N-ethylurea (EU), N-propylurea (PU), and N-butylurea (BU). The BU concentration was the lowest required for the PAc 551 denaturation, those of PU, EU, MU, and urea being gradually higher. Furthermore, the accessible surface area difference upon PAc 551 denaturation caused by BU was found to be the highest, those by PU, EU, MU, and urea being gradually lower. These findings indicate that urea derivatives with longer alkyl chains are stronger denaturants. In this study, as many as five systematic urea derivatives could be applied for the reversible denaturation of a single protein, PAc 551 , for the first time, and the effects of the alkyl chain length on protein denaturation were systematically verified by means of thermodynamic parameters.

  1. Molecular dynamics simulation of radiation grafted FEP films as proton exchange membranes: Effects of the side chain length

    DEFF Research Database (Denmark)

    Li, Xue; Zhao, Yang; Li, Weiwei

    2017-01-01

    In order to study the microstructure of the prepared potential proton exchange membrane (PEM), molecular dynamics (MD) simulations were used to lucubrate the transport behavior of water molecules and hydronium ions inside the hydrated sulfonated styrene grafted fluorinated ethylene propylene (FEP...... whereas larger water clusters formed. The results of the mean square displacements (MSDs) show that the proton conductivities of the membranes with the proposed side chain lengths were about three fifths of the experimental data, of which the membrane with side chain length of 7 sulfonic styrene units...... was supposed to exhibit the highest proton conductivity, that is 115.69 mS cm-1. All of the supposed membrane models presented good proton conductivity that could definitely meet the application requirements of the proton exchange membranes. The MD simulations can provide an insight to the chain structure...

  2. Effects of cloud-point grafting, chain length, and density of PEG layers on competitive adsorption of ocular proteins

    DEFF Research Database (Denmark)

    Kingshott, P.; Thissen, H.; Griesser, H.J.

    2002-01-01

    The effects of pinning density, chain length, and 'cloud point' (CP) versus non-CP grafting conditions have been studied on the ability of polyethylene glycol (PEG) layers to minimize adsorption from a multicomponent (lysozyme, human serum albumin (HSA), IgG and lactoferrin) protein solution...... density) r.f.g.d. polymer layers. The PEG graft density was varied also by increasing the temperature and salt (K2SO4) content of the grafting solution; it reached a maximum at the CP of the PEGs. The CP reaction conditions were critical for producing PEG layers capable of minimizing protein adsorption. X...... density and chain length are interrelated, but the key factor is optimization of PEG chain density by use of the CP conditions, provided that a sufficient density of pinning sites exists. (C) 2002 Elsevier Science Ltd. Al l rights reserved....

  3. Dual influences of ecosystem size and disturbance on food chain length in streams.

    Science.gov (United States)

    McHugh, Peter A; McIntosh, Angus R; Jellyman, Phillip G

    2010-07-01

    The number of trophic transfers occurring between basal resources and top predators, food chain length (FCL), varies widely in the world's ecosystems for reasons that are poorly understood, particularly for stream ecosystems. Available evidence indicates that FCL is set by energetic constraints, environmental stochasticity, or ecosystem size effects, although no single explanation has yet accounted for FCL patterns in a broad sense. Further, whether environmental disturbance can influence FCL has been debated on both theoretical and empirical grounds for quite some time. Using data from sixteen South Island, New Zealand streams, we determined whether the so-called ecosystem size, disturbance, or resource availability hypotheses could account for FCL variation in high country fluvial environments. Stable isotope-based estimates of maximum trophic position ranged from 2.6 to 4.2 and averaged 3.5, a value on par with the global FCL average for streams. Model-selection results indicated that stream size and disturbance regime best explained across-site patterns in FCL, although resource availability was negatively correlated with our measure of disturbance; FCL approached its maximum in large, stable springs and was disturbed streams. Community data indicate that size influenced FCL, primarily through its influence on local fish species richness (i.e., via trophic level additions and/or insertions), whereas disturbance did so via an effect on the relative availability of intermediate predators (i.e., predatory invertebrates) as prey for fishes. Overall, our results demonstrate that disturbance can have an important food web-structuring role in stream ecosystems, and further imply that pluralistic explanations are needed to fully understand the range of structural variation observed for real food webs.

  4. Inelastic neutron scattering study on the polytypism of even-numbered n-alkanes

    Science.gov (United States)

    Kubota, Hideki; Kaneko, Fumitoshi; Kawaguchi, Tatsuya

    2005-02-01

    The thermodynamic properties of the two polytypes of n-hexatriacontane ( n- C36H74), single-layered structure Mon and double-layered structure Orth II, have been studied with incoherent inelastic neutron scattering and solubility measurements. The solubility measurements show that Orth II is more stable than Mon, because of its larger entropy. The neutron scattering measurements reveal that the vibrational modes of Orth II shift to the lower frequencies compared with those of Mon in the frequency region below 120 cm-1. The vibrational modes in this region make a dominant contribution to the vibrational entropy of a system, and the advantage of Orth II in vibrational entropy due to the low-frequency shifts is estimated to be 7.8 J K-1 mol-1 at 288 K under the harmonic approximation, which is in good agreement with the entropy difference between Mon and Orth II determined by solubility measurements. These results suggest that the relative stability of polytypic structures of long-chain compounds is mainly determined by the vibrational entropy of the low-frequency modes.

  5. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yongli [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)] [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China); Fang Xiaomin, E-mail: fangxm@itpcas.ac.cn [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China)] [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Zhang Tongwei [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2010-10-15

    Research highlights: {yields} This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. {yields} Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. {yields} These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. {yields} A close correspondence among the low ratio of n-C{sub 27}/n-C{sub 31}, the heavy {delta}{sup 13}C values of TOC and a strong even carbon-number predominance (low OEP{sub 16-20} values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C{sub 16}-n-C{sub 20} with maximum values at n-C{sub 18} and n-C{sub 27}-n-C{sub 31} as well as at n-C{sub 29}. The first mode shows a strong even C-number predominance (OEP{sub 16-20} 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP{sub 27-31} 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded

  6. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    International Nuclear Information System (INIS)

    Wang Yongli; Fang Xiaomin; Zhang Tongwei; Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao

    2010-01-01

    Research highlights: → This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. → Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. → These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. → A close correspondence among the low ratio of n-C 27 /n-C 31 , the heavy δ 13 C values of TOC and a strong even carbon-number predominance (low OEP 16-20 values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C 16 -n-C 20 with maximum values at n-C 18 and n-C 27 -n-C 31 as well as at n-C 29 . The first mode shows a strong even C-number predominance (OEP 16-20 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP 27-31 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.

  7. Transport behavior of n-alkane penetrants into castor oil based polyurethane-polyester nonwoven fabric composites

    International Nuclear Information System (INIS)

    Satheesh Kumar, M.N.; Manjula, K.S.; Siddaramaiah

    2007-01-01

    Castor oil based polyurethane (PU)-polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. Composites were fabricated with two different isocyanates such as toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Transport behavior of n-alkane penetrants (pentane, hexane and heptane) into both PUs and PU-polyester nonwoven fabric composites were studied. Sorption studies were carried out at different temperatures. From the sorption results, the diffusion (D) and permeation (P) coefficients of penetrants have been calculated. Significant increase in the diffusion and permeation coefficients was observed with increase in the temperature of sorption experiments. Drastical reduction in diffusion and permeation coefficients was noticed in the composites compared to neat PUs. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport and K is a constant depends on the structural characteristics of the composite in addition to its interaction with penetrants. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameter for diffusion (E D ) and permeation (E P ) processes from Arrhenius plots. Furthermore, the sorption results have been interpreted in terms of the thermodynamic parameters such as enthalpy (ΔH) and entropy (ΔS)

  8. Fabrication, thermal properties and thermal stabilities of microencapsulated n-alkane with poly(lauryl methacrylate) as shell

    International Nuclear Information System (INIS)

    Qiu, Xiaolin; Lu, Lixin; Wang, Ju; Tang, Guoyi; Song, Guolin

    2015-01-01

    Highlights: • Microencapsulation of octadecane and paraffin by crosslinked poly(lauryl methacrylate). • Octadecane microcapsules have a melting enthalpy of about 118 J g −1 . • Weight loss temperatures of the microcapsules were increased by 67 °C and 28 °C. • Phase change enthalpies decreased by around 10 wt% after 500 thermal cycles. • Foams with microcapsules can be applied for passive temperature control. - Abstract: Microencapsulation of n-octadecane or paraffin with poly(lauryl methacrylate) (PLMA) shell was performed by a suspension-like polymerization. The polymer shell was crosslinked by pentaerythritol tetraacrylate (PETRA). The surface morphologies of microcapsules were investigated by scanning electron microscopy (SEM). Phase change properties, thermal reliabilities and thermal stabilities of microcapsules were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The n-octadecane microcapsule exhibits higher melting enthalpy (118.0 J g −1 ) and crystallization enthalpy (108.3 J g −1 ) compared with the paraffin microcapsule. The thermal resistant temperatures were enhanced by more than 25 °C when n-alkanes were microencapsulated by PLMA. The PCM contents of microcapsules decreased by less than 4 wt% and 6 wt% after 500 and 1000 thermal cycles, respectively. Heat-up experiments indicated that microcapsule-treated foams exhibited upgraded thermal regulation capacities. Consequently, microencapsulated n-octadecane or paraffin with PLMA as shell possesses good potentials for heat storage and thermal regulation.

  9. High Amounts of n-Alkanes in the Composition of Asphodelus aestivus Brot. Flower Essential Oil from Cyprus.

    Science.gov (United States)

    Polatoğlu, Kaan; Demirci, Betül; Can Başer, Kemal Hüsnü

    2016-10-01

    There is only a couple of reports indicating essential oil composition of Asphodelus species in the literature. However, from the members of this genus many non-volatile secondary metabolites were isolated. In Cyprus, Asphodelus aestivus Brot. can be found abundantly in all regions of the island. This plant has various ethnobotanical uses in Cyprus. There is no report on the volatiles nor the essential oil composition of A. aestivus. The smell of A. aestivus flowers resembles that of a cat pee which caught our attention. Therefore, we have carried out GC, GC/MS analysis of the essential oil (yield: 0.01 v/w) obtained from Asphodelus aestivus flowers. Seventeen compounds were identified in the essential oil comprising 96.2% of the oil. The major components of the essential oil were hexadecanoic acid 35.6%, pentacosane 17.4%, tricosane 13.4% and heptacosane 8.4%. In our results, we expected to see sulfur containing cat pee odorants due to the odor of the flower whereas high amounts of n-alkanes, saturated fatty acids and minor amounts of acyclic diterpenes were observed.

  10. Fabrication, thermal properties and thermal stabilities of microencapsulated n-alkane with poly(lauryl methacrylate) as shell

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Xiaolin, E-mail: shirleyqiu2009@gmail.com [Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology, School of Mechanical Engineering, Jiangnan University, Wuxi 214122 (China); Lu, Lixin; Wang, Ju [Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology, School of Mechanical Engineering, Jiangnan University, Wuxi 214122 (China); Tang, Guoyi [Advanced Materials Institute and Clearer Production Key Laboratory, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Key Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Haidian District, Beijing 100084 (China); Song, Guolin [Advanced Materials Institute and Clearer Production Key Laboratory, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2015-11-20

    Highlights: • Microencapsulation of octadecane and paraffin by crosslinked poly(lauryl methacrylate). • Octadecane microcapsules have a melting enthalpy of about 118 J g{sup −1}. • Weight loss temperatures of the microcapsules were increased by 67 °C and 28 °C. • Phase change enthalpies decreased by around 10 wt% after 500 thermal cycles. • Foams with microcapsules can be applied for passive temperature control. - Abstract: Microencapsulation of n-octadecane or paraffin with poly(lauryl methacrylate) (PLMA) shell was performed by a suspension-like polymerization. The polymer shell was crosslinked by pentaerythritol tetraacrylate (PETRA). The surface morphologies of microcapsules were investigated by scanning electron microscopy (SEM). Phase change properties, thermal reliabilities and thermal stabilities of microcapsules were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The n-octadecane microcapsule exhibits higher melting enthalpy (118.0 J g{sup −1}) and crystallization enthalpy (108.3 J g{sup −1}) compared with the paraffin microcapsule. The thermal resistant temperatures were enhanced by more than 25 °C when n-alkanes were microencapsulated by PLMA. The PCM contents of microcapsules decreased by less than 4 wt% and 6 wt% after 500 and 1000 thermal cycles, respectively. Heat-up experiments indicated that microcapsule-treated foams exhibited upgraded thermal regulation capacities. Consequently, microencapsulated n-octadecane or paraffin with PLMA as shell possesses good potentials for heat storage and thermal regulation.

  11. Relationship between Length and Surface-Enhanced Raman Spectroscopy Signal Strength in Metal Nanoparticle Chains: Ideal Models versus Nanofabrication

    Directory of Open Access Journals (Sweden)

    Kristen D. Alexander

    2012-01-01

    Full Text Available We have employed capillary force deposition on ion beam patterned substrates to fabricate chains of 60 nm gold nanospheres ranging in length from 1 to 9 nanoparticles. Measurements of the surface-averaged SERS enhancement factor strength for these chains were then compared to the numerical predictions. The SERS enhancement conformed to theoretical predictions in the case of only a few chains, with the vast majority of chains tested not matching such behavior. Although all of the nanoparticle chains appear identical under electron microscope observation, the extreme sensitivity of the SERS enhancement to nanoscale morphology renders current nanofabrication methods insufficient for consistent production of coupled nanoparticle chains. Notwithstanding this fact, the aggregate data also confirmed that nanoparticle dimers offer a large improvement over the monomer enhancement while conclusively showing that, within the limitations imposed by current state-of-the-art nanofabrication techniques, chains comprising more than two nanoparticles provide only a marginal signal boost over the already considerable dimer enhancement.

  12. Association mapping of starch chain length distribution and amylose content in pea (Pisum sativum L.) using carbohydrate metabolism candidate genes.

    Science.gov (United States)

    Carpenter, Margaret A; Shaw, Martin; Cooper, Rebecca D; Frew, Tonya J; Butler, Ruth C; Murray, Sarah R; Moya, Leire; Coyne, Clarice J; Timmerman-Vaughan, Gail M

    2017-08-01

    Although starch consists of large macromolecules composed of glucose units linked by α-1,4-glycosidic linkages with α-1,6-glycosidic branchpoints, variation in starch structural and functional properties is found both within and between species. Interest in starch genetics is based on the importance of starch in food and industrial processes, with the potential of genetics to provide novel starches. The starch metabolic pathway is complex but has been characterized in diverse plant species, including pea. To understand how allelic variation in the pea starch metabolic pathway affects starch structure and percent amylose, partial sequences of 25 candidate genes were characterized for polymorphisms using a panel of 92 diverse pea lines. Variation in the percent amylose composition of extracted seed starch and (amylopectin) chain length distribution, one measure of starch structure, were characterized for these lines. Association mapping was undertaken to identify polymorphisms associated with the variation in starch chain length distribution and percent amylose, using a mixed linear model that incorporated population structure and kinship. Associations were found for polymorphisms in seven candidate genes plus Mendel's r locus (which conditions the round versus wrinkled seed phenotype). The genes with associated polymorphisms are involved in the substrate supply, chain elongation and branching stages of the pea carbohydrate and starch metabolic pathways. The association of polymorphisms in carbohydrate and starch metabolic genes with variation in amylopectin chain length distribution and percent amylose may help to guide manipulation of pea seed starch structural and functional properties through plant breeding.

  13. The effect of the chain length distribution of free fatty acids on the mixing properties of stratum corneum model membranes.

    Science.gov (United States)

    Oguri, Masashi; Gooris, Gert S; Bito, Kotatsu; Bouwstra, Joke A

    2014-07-01

    The stratum corneum (SC) plays a fundamental role in the barrier function of the skin. The SC consists of corneocytes embedded in a lipid matrix. The main lipid classes in the lipid matrix are ceramides (CERs), cholesterol (CHOL) and free fatty acids (FFAs). The aim of this study was to examine the effect of the chain length of FFAs on the thermotropic phase behavior and mixing properties of SC lipids. Fourier transform infrared spectroscopy and Raman imaging spectroscopy were used to study the mixing properties using either protonated or deuterated FFAs. We selected SC model lipid mixtures containing only a single CER, CHOL and either a single FFA or a mixture of FFAs mimicking the FFA SC composition. The single CER consists of a sphingoid base with 18 carbon atoms and an acyl chain with a chain length of 24 carbon atoms. When using lignoceric acid (24 carbon atoms) or a mixture of FFAs, the CER and FFAs participated in mixed crystals, but hydration of the mixtures induced a slight phase separation between CER and FFA. The mixed crystalline structures did not phase separate during storage even up to a time period of 3months. When using palmitic acid (16 carbon atoms), a slight phase separation was observed between FFA and CER. This phase separation was clearly enhanced during hydration and storage. In conclusion, the thermotropic phase behavior and the mixing properties of the SC lipid mixtures were shown to strongly depend on the chain length and chain length distribution of FFAs, while hydration enhanced the phase separation. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Proton conducting graft copolymers with tunable length and density of phosphonated side chains for fuel cell membranes

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja

    2014-01-01

    Polysulfones functionalized with highly phosphonated poly(pentafluorostyrene) side chains of different lengths were synthesized applying controlled polymerization and modification methods. The graft copolymers' thermal properties were evaluated by differential scanning calorimetry and thermal...... gravimetrical analyses. The proton conductivity of membrane prepared from the graft copolymer with the shortest phosphonated side chains was 134 mS cm(-1) at 100 degrees C under fully immersed conditions. The graft copolymer TEM image shows a nanophase separation of ion-rich segments within the polysulfone...

  15. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder.

    Science.gov (United States)

    van der Walle, G A; Buisman, G J; Weusthuis, R A; Eggink, G

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of unsaturated alkyl side chains incorporated into the PHA resins resulted in oxidative drying PHA paints having excellent coating properties. The homogeneously pigmented PHA coatings yielded high-gloss, smooth and strong films upon curing and showed an excellent flexibility, a good adhesion to different substrates, cohesive film properties and resistance to chipping.

  16. σ-Bond Electron Delocalization in Oligosilanes as Function of Substitution Pattern, Chain Length, and Spatial Orientation

    Directory of Open Access Journals (Sweden)

    Johann Hlina

    2016-08-01

    Full Text Available Polysilanes are known to exhibit the interesting property of σ-bond electron delocalization. By employing optical spectroscopy (UV-vis, it is possible to judge the degree of delocalization and also differentiate parts of the molecules which are conjugated or not. The current study compares oligosilanes of similar chain length but different substitution pattern. The size of the substituents determines the spatial orientation of the main chain and also controls the conformational flexibility. The chemical nature of the substituents affects the orbital energies of the molecules and thus the positions of the absorption bands.

  17. The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids.

    Science.gov (United States)

    Filippov, Andrei; Taher, Mamoun; Shah, Faiz Ullah; Glavatskih, Sergei; Antzutkin, Oleg N

    2014-12-28

    The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature.

  18. Effect of side chain length on the stability and structural properties of 3

    African Journals Online (AJOL)

    thiophene (DOOPT) and their dimers studied by Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The DFT calculations suggest that dimers of the dialkoxyphenylthiophenes with longer side chains are thermodynamically more ...

  19. Carbon and Hydrogen Isotopic Composition of Plant Wax n-Alkanes: A Tool for Characterizing Soil Provenance in Forensic Science

    Science.gov (United States)

    Pedentchouk, N.; Wagner, T.; Jones, M.

    2009-04-01

    Forensic science is an integrative discipline that requires material evidence from diverse sources. Geochemical evidence derived from inorganic and organic substances is becoming increasingly popular among law enforcement agencies in industrialized countries. Previous investigations indicate that the relative distributions of individual plant-derived biomarkers found in soils are linked to the biomarker patterns found in the overlying vegetation. However, identification of soil provenance based on the distribution of plant-derived biomarkers for forensic purposes is inhibited by the fact that a significant number of terrestrial plant species have overlapping biomarker distributions. In order to enhance the resolving power of plant-derived biomarker signal, we propose to enhance the molecular approach by adding a stable isotope component, i.e. the delta13C/deltaD values of individual biomarkers. The first objective of this project is to determine the delta13C/deltaD signatures of n-alkanes derived from various higher plant types commonly growing in the UK. The second objective is to investigate whether the same species/plant types differ isotopically between two locations affected by different weather patterns in the UK: a relatively warmer and drier Norwich, Norfolk and a cooler and wetter Newcastle-upon-Tyne in NE England. The n-C29 alkane data from 14 tree species sampled during July 2007 and August 2008 in Newcastle show a clear negative trend between delta13C and deltaD values. When these data are plotted against each other, the six deciduous angiosperms (delta13C: c. -39 to -35 per mil; deltaD: c. -155 to -130 per mil) are completely separated from four evergreen angiosperms (delta13C: c. -33 to -28 per mil; deltaD: c. -195 to -165 per mil). The four gymnosperm species data plot between those of the deciduous and evergreen angiosperms. Because all 14 species in Newcastle experience the same environmental conditions, we suggest that the observed isotopic

  20. Effect of Difference in Fatty Acid Chain Lengths of Medium- Chain Lipids on Lipid/Surfactant/Water Phase Diagrams and Drug Solubility

    Directory of Open Access Journals (Sweden)

    Hetal N. Prajapati

    2011-09-01

    Full Text Available Lipids consisting of medium chain fatty acids are commonly used in the development of lipid-based selfemulsifying and self-microemulsifying drug delivery systems. However, no systematic approach to selecting one lipid over another has been reported in the literature. In this study, propylene glycol (PG monoester (PG monocaprylate, Capmul PG-8® and PG diester (PG dicaprylocaprate, Captex 200P® of C8-fatty acids were compared with PG monoester (PG monolaurate, Capmul PG-12® and PG diester (PG dilaurate, Capmul PG-2L® of C12-fatty acids with respect to their phase diagrams, and especially for their ability to form microemulsions in the presence of a common surfactant, Cremophor EL®, and water. The solubility of two model drugs, danazol and probucol, in the lipids and lipid/surfactant mixtures were also compared. The effect of the chain length of medium-chain fatty acids (C8 versus C12 on the phase diagrams of the lipids was minimal. Both shorter and longer chain lipids formed essentially similar microemulsion and emulsion regions in the presence of Cremophor EL® and water, although the C12-fatty acid esters formed larger gel regions in the phase diagrams than the C8-fatty acid esters. When monoesters were mixed with their respective diesters at 1:1 ratios, larger microemulsion regions with lower lipid particle sizes were observed compared to those obtained with individual lipids alone. While the solubility of both danazol and probucol increased greatly in all lipids studied, compared to their aqueous solubility, the solubility in C12-fatty acid esters was found to be lower than in C8-fatty acid esters when the lipids were used alone. This difference in solubility due to the difference in fatty acid chain length, practically disappeared when the lipids were combined with the surfactant.

  1. Characterization of sorbent properties of soil organic matter and carbonaceous geosorbents using n-alkanes and cycloalkanes as molecular probes.

    Science.gov (United States)

    Endo, Satoshi; Grathwohl, Peter; Haderlein, Stefan B; Schmidt, Torsten C

    2009-01-15

    Nonspecific interactions and modes (i.e., adsorption vs absorption) of sorption by noncondensed, amorphous organic phases (here termed organic matter; OM) in soils and by rigid, aromatic, and condensed phases (termed carbonaceous geosorbents; CGs) were investigated using n-alkanes and cycloalkanes as molecular probes. Sorption isotherms of n- and cyclooctane from water for seven CGs (charcoal, lignite coke, activated carbon, graphite, partially oxidized graphite, diesel soot, bituminous coal), four sorbents with a predominance of OM (lignite, peat, two sapric soils), and two soils containing OM and high amounts of CGs were measured in batch systems. The peat and the sapric soils showed extensively linear sorption, while the CGs exhibited highly nonlinear (Freundlich exponents 0.2-0.7) and strong (Koc values being up to 10(5) times those for the OM-rich materials at low concentrations) sorption for the alkanes studied, showing that enhanced sorption by CGs can occur to completely apolar sorbates that do not undergo any specific interaction. Sorption by CGs was generally stronger and more nonlinear for n-octane than for cyclooctane, which suggests a strong dependence of sorption on the 3-D structure of sorbate molecules. The n-octane-to-cyclooctane sorption coefficient ratios (Kn/Kc) for adsorption to CGs were > or = 1, being distinctly different from those for absorption to the OM-rich materials (Kn/Kc soils determined by quantitative petrography analysis suggest, however, that CGs occurring in soils may be far less effective sorbents than the reference CGs used in the sorption experiments at least for nonspecifically interacting sorbates, probably because of competitive sorption and/or pore blocking by natural OM. The presented approaches and results offer a basis for interpreting sorption data for other organic compounds, as nonspecific interactions and sorption modes are relevant for any compound.

  2. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han

    2014-06-01

    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  3. Impact of the alkyl chain length on binding of imidazolium-based ionic liquids to bovine serum albumin

    Science.gov (United States)

    Zhang, Mengyue; Wang, Ying; Zhang, Hongmei; Cao, Jian; Fei, Zhenghao; Wang, Yanqing

    2018-05-01

    The effects of six imidazolium-based ionic liquids (ILs) with different alkyl chain length ([CnMim]Cl, n = 2, 4, 6, 8, 10, 12) on the structure and functions of bovine serum albumin (BSA) were studied by multi-spectral methods and molecular docking. ILs with the longer alkyl chain length have the stronger binding interaction with BSA and the greater conformational damage to protein. The effects of ILs on the functional properties of BSA were further studied by the determination of non-enzyme esterase activity, β-fibrosis and other properties of BSA. The thermal stability of BSA was reduced, the rate of the formation of beta sheet structures of BSA was lowered, and the esterase-like activity of BSA were decreased with the increase of ILs concentration. Simultaneous molecular modeling technique revealed the favorable binding sites of ILs on protein. The hydrophobic force and polar interactions were the mainly binding forces of them. The calculated results are in a good agreement with the spectroscopic experiments. These studies on the impact of the alkyl chain length on binding of imidazolium-based ionic liquids to BSA are of great significance for understanding and developing the application of ionic liquid in life and physiological system.

  4. Size-distributions of n-alkanes, PAHs and hopanes and their sources in the urban, mountain and marine atmospheres over East Asia

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2009-11-01

    Full Text Available Size-segregated (9 stages n-alkanes, polycyclic aromatic hydrocarbons (PAHs and hopanes in the urban (Baoji city in inland China, mountain (Mt. Tai in east coastal China and marine (Okinawa Island, Japan atmospheres over East Asia were studied using a GC/MS technique. Ambient concentrations of n-alkanes (1698±568 ng m−3 in winter and 487±145 ng m−3 in spring, PAHs (536±80 and 161±39 ng m−3, and hopanes (65±24 and 20±2.4 ng m−3 in the urban air are 1–2 orders of magnitude higher than those in the mountain aerosols and 2–3 orders of magnitude higher than those in the marine samples. Mass ratios of n-alkanes, PAHs and hopanes clearly demonstrate coal-burning emissions as their major source. Size distributions of fossil fuel derived n-alkane, PAHs and hopanes were found to be unimodal in most cases, peaking at 0.7–1.1 μm size. In contrast, plant wax derived n-alkanes presented a bimodal distribution with two peaks at the sizes of 0.7–1.1 μm and >4.7 μm in the summer mountain and spring marine samples. Among the three types of samples, geometric mean diameter (GMD of the organics in fine mode (<2.1 μm was found to be smallest (av. 0.63 μm in spring for the urban samples and largest (1.01 μm for the marine samples, whereas the GMD in coarse mode (≥2.1 μm was found to be smallest (3.48 μm for the marine aerosols and largest (4.04 μm for the urban aerosols. The fine mode GMDs of the urban and mountain samples were larger in winter than in spring and summer. Moreover, GMDs of 3- and 4-ring PAHs were larger than those of 5- and 6-ring PAHs in the three types of atmospheres. Such differences in GMDs can be interpreted by the repartitioning of organic compounds and the coagulation and hygroscopic growth of particles during a long-range transport from the inland continent to the marine area, as well as the difference in their sources among the three regions.

  5. Spectral sensitization of TiO2 by new hemicyanine dyes in dye solar cell yielding enhanced photovoltage: Probing chain length effect on performance

    International Nuclear Information System (INIS)

    Fadadu, Kishan B.; Soni, Saurabh S.

    2013-01-01

    Graphical abstract: New hemicyanine dyes based on indolenine moiety were utilized as light harvesting materials in dye sensitized solar cell. Chain lengths of the molecules were varied in order to study its effect of chain length on the performance of DSSC. Electron transfer kinetic of the solar cell was studied and it was found that the chain length changes the electron transfer kinetic. We have achieved remarkable photovoltage and overall performance of DSSC. Highlights: ► New hemicyanine dyes based on indolenine moiety were utilized as light harvesting materials in dye sensitized solar cell. ► Chain lengths of the molecules were varied in order to study its effect of chain length on the performance of DSSC. ► Electron transfer kinetic of the solar cell was studied and it was found that the chain length changes the electron transfer kinetic. -- Abstract: New hemicyanine dyes having indole nucleus with different alkyl chain length were synthesized and characterized using 1 H NMR and mass spectroscopy. These dyes were used to sensitize the TiO 2 film in dye sensitized solar cell. Nanocrystalline dye solar cells were fabricated and characterized using various electrochemical techniques. It has been found that the alkyl chain length present in the dye molecules greatly affects the overall performance of dye solar cell. Molecules having longer alkyl chain are having better sensitizers which enhance V oc to significant extent. Chain length dependent performance was further investigated using Tafel polarization and impedance method. Hemicyanine dye having hexyl chain has outperformed by attaining 2.9% solar to electricity conversion efficiency

  6. Prediction of the vapor–liquid equilibria and speed of sound in binary systems of 1-alkanols and n-alkanes with the simplified PC-SAFT equation of state

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Thomsen, Kaj; Yan, Wei

    2013-01-01

    (or other derivative properties) with satisfactory accuracy over wide temperature, pressure and composition conditions. This work presents the prediction of the vapor–liquid equilibria and speed of sound in binary mixtures of 1-alkanols and n-alkanes using the simplified PC-SAFT equation of state...... of sound with a satisfactory accuracy for 1-alkanols and n-alkanes binary systems within the PC-SAFT framework....

  7. Thermoresponsive Poly(2-oxazoline) Molecular Brushes by Living Ionic Polymerization: Kinetic Investigations of Pendant Chain Grafting and Cloud Point Modulation by Backbone and Side Chain Length Variation

    KAUST Repository

    Zhang, Ning

    2012-04-17

    Molecular brushes of poly(2-oxazoline)s were prepared by living anionic polymerization of 2-iso-propenyl-2-oxazoline to form the backbone and subsequent living cationic ring-opening polymerization of 2-n- or 2-iso-propyl-2-oxazoline for pendant chain grafting. In situ kinetic studies indicate that the initiation efficiency and polymerization rates are independent from the number of initiator functions per initiator molecule. This was attributed to the high efficiency of oxazolinium salt and the stretched conformation of the backbone, which is caused by the electrostatic repulsion of the oxazolinium moieties along the macroinitiator. The resulting molecular brushes showed thermoresponsive properties, that is, having a defined cloud point (CP). The dependence of the CP as a function of backbone and side chain length as well as concentration was studied. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Perfil de n-alcanos em cinco espécies de plantas forrageiras tropicais - DOI: 10.4025/actascianimsci.v27i3.1207 Profile of n-alkanes in five species of plants tropical forages - DOI: 10.4025/actascianimsci.v27i3.1207

    Directory of Open Access Journals (Sweden)

    Antônio Ferriani Branco

    2005-03-01

    Full Text Available O objetivo do experimento foi estudar o perfil de n-alcanos em espécies de gramíneas (Brachiaria brizantha, Cynodon dactylon e Panicum maximum e leguminosas (Arachis pintoi e Glycine wightii. Foram identificados e quantificados por meio de cromatografia gasosa, os n-alcanos C24 a C35, sendo C32 e C34 padrões internos. As concentrações dos n-alcanos nas diferentes espécies e respectivas frações (lâminas foliares, colmos porções superior e inferior e matéria morta para gramíneas; folhas, caule porção superior e inferior e matéria morta para leguminosas foram submetidas à análise de variância e teste de média (Tukey. Nos períodos de primavera e inverno, para a maioria das espécies e frações, há predomínio dos n-alcanos de cadeia ímpar. Houve maior concentração de C29, C31 e C33 na primavera, C27, C28, C29, C30 e C31, no verão e C27, C29, C31 e C33 no invernoThis experiment aimed to study the profile of n-alkanes in tropical grasses species (Brachiaria brizantha, Cynodon dactylon and Panicum maximum and legumes (Arachis pintoi and Glycine wightii. They were identified and quantified, through gas cromatography, the n-alkanes C24 to C35, being the alkanes C32 and C34 internal indices. The n-alkanes concentrations in the different species and respective fractions (leaf blade, stem higher and lower portion and dead matter for grasses; leaves, stem higher portion, stem lower portion and dead matter for legumes were submitted to variance analysis and mean test (Tukey. For most of the species and fractions, there is prevalence of odd chain n-alkanes during springtime and winter. There was larger concentration of the alkanes C29, C31 and C33 in springtime, C27, C28, C29, C30 and C31 in summer and C27, C29, C31 and C33 in winter

  9. Simulated glass-forming polymer melts: dynamic scattering functions, chain length effects, and mode-coupling theory analysis.

    Science.gov (United States)

    Frey, S; Weysser, F; Meyer, H; Farago, J; Fuchs, M; Baschnagel, J

    2015-02-01

    We present molecular-dynamics simulations for a fully flexible model of polymer melts with different chain length N ranging from short oligomers (N = 4) to values near the entanglement length (N = 64). For these systems we explore the structural relaxation of the supercooled melt near the critical temperature T c of mode-coupling theory (MCT). Coherent and incoherent scattering functions are analyzed in terms of the idealized MCT. For temperatures T > T c we provide evidence for the space-time factorization property of the β relaxation and for the time-temperature superposition principle (TTSP) of the α relaxation, and we also discuss deviations from these predictions for T ≈ T c. For T larger than the smallest temperature where the TTSP holds we perform a quantitative analysis of the dynamics with the asymptotic MCT predictions for the late β regime. Within MCT a key quantity, in addition to T c, is the exponent parameter λ. For the fully flexible polymer models studied we find that λ is independent of N and has a value (λ = 0.735 ) typical of simple glass-forming liquids. On the other hand, the critical temperature increases with chain length toward an asymptotic value T c (∞) . This increase can be described by T c (∞) - T c(N) ∼ 1/N and may be interpreted in terms of the N dependence of the monomer density ρ, if we assume that the MCT glass transition is ruled by a soft-sphere-like constant coupling parameter Γ c = ρ c T c (-1/4), where ρ c is the monomer density at T c. In addition, we also estimate T c from a Hansen-Verlet-like criterion and MCT calculations based on structural input from the simulation. For our polymer model both the Hansen-Verlet criterion and the MCT calculations suggest T c to decrease with increasing chain length, in contrast to the direct analysis of the simulation data.

  10. Novel Strategies for Production of Medium and High Chain Length Alcohols

    NARCIS (Netherlands)

    Lopez Contreras, A.M.; Kuit, W.; Springer, J.; Claassen, P.A.M.

    2011-01-01

    Fermentation-derived ethanol is currently widely used as transport fuel, both as such or as a blending component in gasoline (Antoni et al. 2007; Mielenz 2001). However, longer chain alcohols have higher energy densities and are less soluble in water than ethanol, which are important advantages for

  11. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

    Science.gov (United States)

    Nakamura, Issei

    2014-05-29

    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  12. Electrical contacts to nanorod networks at different length scales: From macroscale ensembles to single nanorod chains

    KAUST Repository

    Lavieville, Romain; Zhang, Yang; Di Fabrizio, Enzo M.; Krahne, Roman

    2013-01-01

    The nature of metal-semiconductor interfaces at the nanoscale is an important issue in micro- and nanoelectronic engineering. The study of charge transport through chains of CdSe semiconductor nanorods linked by Au particles represents an ideal model system for this matter, because the metal semiconductor interface is an intrinsic feature of the nanosystem. Here we show the controlled fabrication of all-inorganic hybrid metal-semiconductor networks with different size, in which the semiconductor nanorods are linked by Au domains at their tips. We demonstrate different approaches to selectively contact the networks and single nanorod chains with planar electrodes, and we investigate their charge transport at room temperature. © 2013 Elsevier B.V. All rights reserved.

  13. Electrical contacts to nanorod networks at different length scales: From macroscale ensembles to single nanorod chains

    KAUST Repository

    Lavieville, Romain

    2013-11-01

    The nature of metal-semiconductor interfaces at the nanoscale is an important issue in micro- and nanoelectronic engineering. The study of charge transport through chains of CdSe semiconductor nanorods linked by Au particles represents an ideal model system for this matter, because the metal semiconductor interface is an intrinsic feature of the nanosystem. Here we show the controlled fabrication of all-inorganic hybrid metal-semiconductor networks with different size, in which the semiconductor nanorods are linked by Au domains at their tips. We demonstrate different approaches to selectively contact the networks and single nanorod chains with planar electrodes, and we investigate their charge transport at room temperature. © 2013 Elsevier B.V. All rights reserved.

  14. The effect of the alkyl chain length on physicochemical features of (ionic liquids + γ-butyrolactone) binary mixtures

    International Nuclear Information System (INIS)

    Papović, Snežana; Bešter-Rogač, Marija; Vraneš, Milan; Gadžurić, Slobodan

    2016-01-01

    Highlights: • Influence of alkyl substituent length on IL properties was studied. • Nature of interactions between studied [C_nC_1im][NTf_2] and GBL were discussed. • Angell strength parameter indicates [C_nC_1im][NTf_2] are fragile liquids. • ILs properties regularly change with increase of the alkyl chain length. • Absence of GBL self-association upon addition of IL is observed. - Abstract: Densities and viscosities were determined and analysed for γ-butyrolactone (GBL) binary mixtures with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids (where alkyl = ethyl, hexyl, octyl) as a function of temperature at atmospheric pressure (p = 0.1 MPa) and over the whole composition range. Excess molar volumes have been calculated from the experimental densities and were fitted using Redlich–Kister’s polynomial equation. Other volumetric parameters have been also calculated in order to obtain information about interactions between GBL and imidazolium based ionic liquids with different alkyl chain length. From the viscosity measurements, the Angell strength parameter was calculated for pure ionic liquids indicating that all investigated electrolytes are “fragile” liquids.

  15. Room temperature ionic liquids: A simple model. Effect of chain length and size of intermolecular potential on critical temperature.

    Science.gov (United States)

    Chapela, Gustavo A; Guzmán, Orlando; Díaz-Herrera, Enrique; del Río, Fernando

    2015-04-21

    A model of a room temperature ionic liquid can be represented as an ion attached to an aliphatic chain mixed with a counter ion. The simple model used in this work is based on a short rigid tangent square well chain with an ion, represented by a hard sphere interacting with a Yukawa potential at the head of the chain, mixed with a counter ion represented as well by a hard sphere interacting with a Yukawa potential of the opposite sign. The length of the chain and the depth of the intermolecular forces are investigated in order to understand which of these factors are responsible for the lowering of the critical temperature. It is the large difference between the ionic and the dispersion potentials which explains this lowering of the critical temperature. Calculation of liquid-vapor equilibrium orthobaric curves is used to estimate the critical points of the model. Vapor pressures are used to obtain an estimate of the triple point of the different models in order to calculate the span of temperatures where they remain a liquid. Surface tensions and interfacial thicknesses are also reported.

  16. Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects.

    Science.gov (United States)

    Zaidi, A; Gainer, J L; Carta, G; Mrani, A; Kadiri, T; Belarbi, Y; Mir, A

    2002-02-28

    The esterification of long-chain fatty acids in n-hexane catalyzed by nylon-immobilized lipase from Candida rugosa has been investigated. Butyl oleate (22 carbon atoms), oleyl butyrate (22 carbon atoms) and oleyl oleate (36 carbon atoms) were produced at maximum reaction rates of approximately equal to 60 mmol h(-1) g(-1) immobilized enzyme when the substrates were present in equimolar proportions at an initial concentration of 0.6 mol l(-1). The observed kinetic behavior of all the esterification reactions is found to follow a ping-pong bi-bi mechanism with competitive inhibition by both substrates. The effect of the chain-length of the fatty acids and the alcohols could be correlated to some mechanistic models, in accordance with the calculated kinetic parameters.

  17. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Directory of Open Access Journals (Sweden)

    Jiqian Wang

    Full Text Available BACKGROUND: Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. METHODOLOGY/PRINCIPAL FINDINGS: Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18 modified Fe(3O(4 were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. CONCLUSIONS/SIGNIFICANCE: The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for

  18. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Science.gov (United States)

    Wang, Jiqian; Meng, Gang; Tao, Kai; Feng, Min; Zhao, Xiubo; Li, Zhen; Xu, Hai; Xia, Daohong; Lu, Jian R

    2012-01-01

    Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18) modified Fe(3)O(4) were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for enzyme immobilization enabling efficient enzyme recovery and recycling.

  19. Collapse of Langmuir monolayer at lower surface pressure: Effect of hydrophobic chain length

    Energy Technology Data Exchange (ETDEWEB)

    Das, Kaushik, E-mail: kaushikdas2089@gmail.com; Kundu, Sarathi [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam 781035 (India)

    2016-05-23

    Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba{sup 2+} ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (π{sub c} > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structure at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.

  20. Polycyclic aromatic hydrocarbons (PAHs) and n-Alkanes in beaked sea snake Enhydrina schistose (Daudin, 1803) from the Mandovi Estuary, Goa

    Digital Repository Service at National Institute of Oceanography (India)

    Mote, S.; RanjeetKumar; Naik, B.G.; Ingole, B.S.

    , occur in high abundances (Voris H K 1985; Aaron Lobo et al. 2004) Present study demonstrates the tissue specific distribution of 15 EPA priority PAHs and 27 n-alkanes compounds in two individuals of E. schistose. We used GC-MS for analysis, which... in 20 ml dichloromethane/hexane (1:3 v/v) with surrogate internal standard (SIS) 20 ppm-200μl Tetracosane-d50 for alkane, 5ppm-200μl Chrysene-d12 for PAHs were spiked and transferred to 5% H2O deactivated silica gel column (1 cm i.dx 9 cm). Elution...

  1. Equation of state modeling of the phase equilibria of asymmetric CO2+n-alkane binary systems using mixing rules cubic with respect to mole fraction

    DEFF Research Database (Denmark)

    Cismondi, Martin; Mollerup, Jørgen M.; Zabaloy, Marcelo S.

    2010-01-01

    for a great diversity of mixtures. Nevertheless, the models for representing phase equilibria and physico-chemical properties of asymmetric systems may require more flexible mixing rules than the classical quadratic van der Waals (vdW) mixing rules or their equivalent (with regard to the number of available...... interaction parameters) in modern equations of state.In particular, the phase equilibria of binary mixtures containing CO2 and heavy n-alkanes have been studied by an important number of authors and using different types of models, achieving only partially accurate results and realizing the difficulties...

  2. Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

    Science.gov (United States)

    Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

    2011-05-21

    In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles

  3. Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties

    KAUST Repository

    Shi, Xueliang

    2014-01-01

    Recent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal is

  4. Evaluation of clay hybrid nanocomposites of different chain length as reinforcing agent for natural and synthetic rubbers

    International Nuclear Information System (INIS)

    Yehia, A.A.; Akelah, A.M.; Rehab, A.; El-Sabbagh, S.H.; El Nashar, D.E.; Koriem, A.A.

    2012-01-01

    Highlights: → The modified organo-clay (MMT-ATBN) markedly reinforce natural and synthetic rubbers. → The reinforcing efficiency of the organo-clay is much higher than HAF carbon black. → The reinforcing efficiency of MMT modified with different alkylamines greatly depend on the chain length. → The good compatibility of modified organo-clay with NBR can be attributed to the chemical nature. -- Abstract: Polymer nanocomposites are one of the highly discussed research topics in recent time. It has been reported in the present paper the preparation and the properties of different nanoclays based on sodium montmorillonite (bentonite) and some organic amines of varying chain lengths (dodecylamine, hexadecylamine and octadecylamine) beside amine-terminated butadiene-acrylonitrile copolymer (ATBN). The hybrid clays have been characterized with the help of Fourier Transform Infrared spectroscopy (FTIR). Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Wide angle X-ray diffractions (WXRD), and Thermogravimetric analysis (TGA). X-ray results showed that the intergallery distance of the clay is increased as a result of the intercalation of the amines and ATBN. The nanocomposite clays were incorporated in natural and synthetic rubbers (NR, SBR and NBR). The physico-mechanical properties are greatly improved with loading low concentrations of the nanocomposite clays compared with carbon black.

  5. Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

    Science.gov (United States)

    Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

    2015-08-07

    A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

  6. Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

    International Nuclear Information System (INIS)

    Heinze, D.; Mang, Th.; Popescu, C.; Weichold, O.

    2016-01-01

    Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl_3–(CH_2CH (OCO(CH_2)_mCH_3))_n–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

  7. Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Heinze, D.; Mang, Th. [Aachen University of Applied Sciences, Heinrich-Mussmann-Str. 1, 52428 Jülich (Germany); Popescu, C., E-mail: crisan.popescu@kao.com [KAO Germany GmbH, Pfungstädterstr. 98-100, 64297 Darmstadt (Germany); Weichold, O., E-mail: weichold@ibac.rwth-aachen.de [Institute of Building Materials Research, Schinkelstr. 3, 52062 Aachen (Germany)

    2016-08-10

    Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl{sub 3}–(CH{sub 2}CH (OCO(CH{sub 2}){sub m}CH{sub 3})){sub n}–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

  8. Effects of Chain Length and Saturability of Fatty Acids on Phospholipids and Proteins in Plasma Membranes of Bovine Mammary Gland.

    Science.gov (United States)

    Yan, Qiongxian; Tang, Shaoxun; Han, Xuefeng; Bamikole, Musibau Adungbe; Zhou, Chuanshe; Kang, Jinhe; Wang, Min; Tan, Zhiliang

    2016-12-01

    Free fatty acids (FFAs) in plasma are essential substrates for de novo synthesis of milk fat, or directly import into mammary cells. The physico-chemical properties of mammary cells membrane composition affected by FFAs with different chain lengths and saturability are unclear yet. Employing GC, FTIR and fluorescence spectroscopy, the adsorption capacity, phospholipids content, membrane proteins conformation, lipid peroxidation product, and free sulfhydryl of plasma membranes (PMs) interacted with different FFAs were determined. The mammary cells PMs at 38 and 39.5 °C showed different adsorption capacities: acetic acid (Ac) > stearic acid (SA) > β-hydroxybutyric acid (BHBA) > trans10, cis12 CLA. In the FTIR spectrum, the major adsorption peaks appeared at 2920 and 2850 cm -1 for phospholipids, and at 1628 and 1560 cm -1 for membrane proteins. The intensities of PMs-FFAs complexes were varied with the FFAs species and their initial concentrations. The β-sheet and turn structures of membrane proteins were transferred into random coil and α-helix after BHBA, SA and trans10, cis12 CLA treatments compared with Ac treatment. The quenching effects on the fluorescence of endogenous membrane protein, 1, 8-ANS, NBD-PE, and DHPE entrapped in PMs by LCFA were different from those of short chain FFAs. These results indicate that the adsorption of FFAs could change membrane protein conformation and polarity of head group in phospholipids. This variation of the mammary cells PMs was regulated by carbon chain length and saturability of FFAs.

  9. 4-N, 4-S & 4-O Chloroquine Analogues: Influence of Side Chain Length and Quinolyl Nitrogen pKa on Activity vs. Chloroquine Resistant Malaria+, #

    OpenAIRE

    Natarajan, Jayakumar K.; Alumasa, John; Yearick, Kimberly; Ekoue-Kovi, Kekeli A.; Casabianca, Leah B.; de Dios, Angel C.; Wolf, Christian; Roepe, Paul D.

    2008-01-01

    Using predictions from heme – quinoline antimalarial complex structures, previous modifications of chloroquine (CQ), and hypotheses for chloroquine resistance (CQR), we synthesize and assay CQ analogues that test structure – function principles. We vary side chain length for both monoethyl and diethyl 4N CQ derivatives. We alter the pKa of the quinolyl N by introducing alkylthio or alkoxy substituents into the 4 position, and vary side chain length for these analogues. We introduce an additio...

  10. Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

    Science.gov (United States)

    Chen, Yuehua; Wang, Huiyong; Wang, Jianji

    2014-05-01

    Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

  11. Application of nitrogen and carbon stable isotopes (δ(15N and δ(13C to quantify food chain length and trophic structure.

    Directory of Open Access Journals (Sweden)

    Matthew J Perkins

    Full Text Available Increasingly, stable isotope ratios of nitrogen (δ(15N and carbon (δ(13C are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR using δ(15N, and carbon range (CR using δ(13C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ(15N or δ(13C from source to consumer between trophic levels and among food chains. δ(15N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰, and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ(13C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ(13C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority

  12. Application of Nitrogen and Carbon Stable Isotopes (δ15N and δ13C) to Quantify Food Chain Length and Trophic Structure

    Science.gov (United States)

    Perkins, Matthew J.; McDonald, Robbie A.; van Veen, F. J. Frank; Kelly, Simon D.; Rees, Gareth; Bearhop, Stuart

    2014-01-01

    Increasingly, stable isotope ratios of nitrogen (δ15N) and carbon (δ13C) are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR) using δ15N, and carbon range (CR) using δ13C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ15N or δ13C from source to consumer) between trophic levels and among food chains. δ15N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰), and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ13C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ13C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority of ecological systems

  13. Application of nitrogen and carbon stable isotopes (δ(15)N and δ(13)C) to quantify food chain length and trophic structure.

    Science.gov (United States)

    Perkins, Matthew J; McDonald, Robbie A; van Veen, F J Frank; Kelly, Simon D; Rees, Gareth; Bearhop, Stuart

    2014-01-01

    Increasingly, stable isotope ratios of nitrogen (δ(15)N) and carbon (δ(13)C) are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR) using δ(15)N, and carbon range (CR) using δ(13)C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ(15)N or δ(13)C from source to consumer) between trophic levels and among food chains. δ(15)N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰), and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ(13)C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ(13)C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority of

  14. CD2 probe infrared method for determining polymethylene chain conformation

    International Nuclear Information System (INIS)

    Maroncelli, M.; Strauss, H.L.; Snyder, R.G.

    1985-01-01

    The rocking mode frequency of a CD 2 group substituted in a polymethylene chain is sensitive to conformation in the immediate vicinity of the CD 2 group. This sensitivity forms the basis of a commonly used infrared method for determining site-specific conformation in polymethylene systems. In the present work, the CD 2 probe method has been extended and quantified with the use of infrared data on model CD 2 -substituted n-alkanes. The frequency of the CD 2 rocking band is determined primarily by the conformation of adjoining CC bonds, i.e., by tt, gt, and gg pairs. However, we have found that there are significant frequency shifts associated with other factors. These include the conformation of the next nearest CC bonds, both with the CD 2 positioned at the end and in the interior of the chain, and chain length. In addition, the ratio of the absorptivities of the tt to gt bands has been established. These results enable the method to provide new details about the conformation of the chains in polymethylene systems and reliable estimates of the concentrations of specific kinds of short conformational sequences. 14 references, 6 figures, 2 tables

  15. Excess molar volumes of the ternary system {methylcyclohexane (1)+cyclohexane (2)+n-alkanes (3)} at T=298.15 K

    International Nuclear Information System (INIS)

    Iloukhani, Hossein; Rezaei-Sameti, Mahdi

    2005-01-01

    Densities were experimentally determined in the whole range of composition at T=298.15 K for the ternary system {methylcyclohexane (1)+cyclohexane (2)+n-alkanes (3)} and for the seven corresponding binary systems. The n-alkanes include n-hexane, n-heptane, and n-octane. Excess molar volumes, V E , were calculated for the binaries and ternaries systems. The V 123 E data are positive over the entire range of composition for the systems {methylcyclohexane (1)+cyclohexane (2)+n-heptane (3) or n-octane (3)} at three fixed compositions (f m =X 1 /X 2 ). For the system {methylcyclohexane (1)+cyclohexane (2)+n-hexane (3)}, the V E values showed positive for f m =0.3 and negative for f m =3. The V E data exhibit, an inversion in sign in the mixture containing f m =1 for later ternary system. Several empirical expressions are used to predict and correlate the ternary excess molar volumes from experimental results on the constituted binaries and analyzed to gain insight about liquid mixture interactions

  16. n-Alkane and clofibrate, a peroxisome proliferator, activate transcription of ALK2 gene encoding cytochrome P450alk2 through distinct cis-acting promoter elements in Candida maltosa

    International Nuclear Information System (INIS)

    Kogure, Takahisa; Takagi, Masamichi; Ohta, Akinori

    2005-01-01

    The ALK2 gene, encoding one of the n-alkane-hydroxylating cytochromes P450 in Candida maltosa, is induced by n-alkanes and a peroxisome proliferator, clofibrate. Deletion analysis of this gene's promoter revealed two cis-acting elements-an n-alkane-responsive element (ARE2) and a clofibrate-responsive element (CRE2)-that partly overlap in sequence but have distinct functions. ARE2-mediated activation responded to n-alkanes but not to clofibrate and was repressed by glucose. CRE2-mediated activation responded to polyunsaturated fatty acids and steroid hormones as well as to peroxisome proliferators but not to n-alkanes, and it was not repressed by glucose. Both elements mediated activation by oleic acid. Mutational analysis demonstrated that three CCG sequences in CRE2 were critical to the activation by clofibrate as well as to the in vitro binding of a specific protein to this element. These findings suggest that ALK2 is induced by peroxisome proliferators and steroid hormones through a specific CRE2-mediated regulatory mechanism

  17. PEGylation of Phytantriol-Based Lyotropic Liquid Crystalline Particles-The Effect of Lipid Composition, PEG Chain Length, and Temperature on the Internal Nanostructure

    DEFF Research Database (Denmark)

    Nilsson, Christa; Ostergaard, Jesper; Larsen, Susan Weng

    2014-01-01

    of these lipidic nonlamellar liquid crystalline particles by using DSPE-mPEGs with three different block lengths of the hydrophilic PEG segment. The effects of lipid composition, PEG chain length, and temperature on the morphology and internal nanostructure of these self-assembled lipidic aqueous dispersions based...

  18. Effect of Hydrophobic Chain Length on the Stability and Guest Exchange Behavior of Shell-Sheddable Micelles Formed by Disulfide-Linked Diblock Copolymers.

    Science.gov (United States)

    Fan, Haiyan; Li, Yixia; Yang, Jinxian; Ye, Xiaodong

    2017-10-19

    Reduction-responsive micelles hold enormous promise for application as drug carriers due to the fast drug release triggered by reducing conditions and high anticancer activity. However, the effect of hydrophobic chain length on the stability and guest exchange of reduction-responsive micelles, especially for the micelles formed by diblock copolymers containing single disulfide group, is not fully understood. Here, shell-sheddable micelles formed by a series of disulfide-linked copolymer poly(ethylene glycol)-b-poly(ε-caprolactone) (PEG-SS-PCL) containing the same chain length of PEG but different chain lengths of hydrophobic block PCL were prepared and well characterized. The influence of the chain length of hydrophobic PCL block on the stability and guest exchange of PEG-SS-PCL micelles was studied by the use of both dynamic laser light scattering (DLS) and fluorescence resonance energy transfer (FRET). The results show that longer PCL chains lead to a slower aggregation rate and guest exchange of micelles in the aqueous solutions containing 10 mM dithiothreitol (DTT). The cell uptake of the shell-sheddable PEG-SS-PCL micelles in vitro shows that the amount of internalization of dyes loaded in PEG-SS-PCL micelles increases with the chain length of hydrophobic PCL block investigated by flow cytometric analysis and confocal fluorescence microscopy.

  19. HLA-DPB1 typing with polymerase chain reaction and restriction fragment length polymorphism technique in Danes

    DEFF Research Database (Denmark)

    Hviid, Thomas Vauvert F.; Madsen, Hans O; Morling, Niels

    1992-01-01

    We have used the polymerase chain reaction (PCR) in combination with the restriction fragment length polymorphism (RFLP) technique for HLA-DBP1 typing. After PCR amplification of the polymorphic second exon of the HLA-DPB1 locus, the PCR product was digested with seven allele-specific restriction...... endonucleases: RsaI, FokI, ApaI, SacI, BstUI, EcoNI, and DdeI, and the DNA fragments were separated by electrophoresis in agarose gels. Altogether, 71 individuals were investigated and 16 different HLA-DPB1 types were observed in 26 different heterozygotic combinations, as well as five possible homozygotes....... Four heterozygotes could not be unequivocally typed with the PCR-RFLP method. The HLA-DPB1 typing results obtained with the PCR-RFLP method were compared with the typing results obtained with PCR allele-specific oligonucleotides (PCR-ASO) in 50 individuals. The results obtained with the two methods...

  20. Modulation of saturation and chain length of fatty acids in Saccharomyces cerevisiae for production of cocoa butter-like lipids

    DEFF Research Database (Denmark)

    Bergenholm, David; Gossing, Michael; Wei, Yongjun

    2018-01-01

    Chain length and degree of saturation plays an important role for the characteristics of various products derived from fatty acids, such as fuels, cosmetics, and food additives. The seeds of Theobroma cacao are the source of cocoa butter, a natural lipid of high interest for the food and cosmetics...... as the saturated fatty acid stearic acid is typically found only in low abundance. Demand for cocoa butter is increasing, yet T. cacao can only be cultivated in some parts of the tropics. Alternative means of production of cocoa butter lipids (CBLs) are, therefore, sought after. Yeasts also store fatty acids...... industry. Cocoa butter is rich in saturated fatty acids that are stored in the form of triacylglycerides (TAGs). One of the major TAG species of cocoa butter, consisting of two stearic acid molecules and one oleic acid molecule (stearic acid-oleic acid-stearic acid, sn-SOS), is particularly rare in nature...

  1. A kinetic model for growth and biosynthesis of medium-chain-length poly-(3-hydroxyalkanoates in Pseudomonas putida

    Directory of Open Access Journals (Sweden)

    M. S. M. Annuar

    2008-06-01

    Full Text Available A kinetic model is presented giving a mathematical description of batch culture of Pseudomonas putida PGA1 grown using saponified palm kernel oil as carbon source and ammonium as the limiting nutrient. The growth of the micro-organism is well-described using Tessier-type model which takes into account the inhibitory effect of ammonium at high concentrations. The ammonium consumption rate by the cells is related in proportion to the rate of growth. The intracellular production of medium-chain-length poly-(3-hydroxyalkanoates (PHA MCL by P. putida PGA1 cells is reasonably modeled by the modified Luedeking-Piret kinetics, which incorporate a function of product synthesis inhibition (or reduction by ammonium above a threshold level.

  2. The Relationship between the Monomer Chain Length and the Electro-Optical Properties of Polymer Dispersed Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Liu J.

    2016-03-01

    Full Text Available Five polymers dispersed liquid crystalline (LC films were fabricated using photo-polymerizable monomers with different lengths of carbon chains. These LC films have shown different electro-optical (EO properties. Through their SEM pictures, the relationship between the linear electro-optical effect and the mesh size of the polymer network was explored. With the increase of number of photo-polymerizable monomers, the mesh size of the polymer network would become larger. So the liquid crystal molecules would be easily oriented in the electric field and therefore, the threshold voltage and saturation voltage would decrease. The open state response times were also reduced and the off state response times would be extended. The DFT simulations have shown principal role of the ground state dipole moments in the observed electro-optical efficiency.

  3. Production of Medium Chain Length Polyhydroxyalkanoates From Oleic Acid Using Pseudomonas putida PGA1 by Fed Batch Culture

    Directory of Open Access Journals (Sweden)

    Sidik Marsudi

    2010-10-01

    Full Text Available Bacterial polyhydroxyalkanoates (PHAs are a class of p0lymers currently receiving much attention because of their potential as renewable and biodegradable plastics. A wide variety of bacteria has been reported to produce PHAs including Pseudomonas strains. These strains are known as versatile medium chain length PHAs (PHAs-mcl producers using fatty acids as carbon source. Oleic acid was used to produce PHAs-mcl using Pseudomonas putida PGA 1 by continuous feeding of both nitrogen and carbon source, in a fed batch culture. During cell growth, PHAs also accumulated, indicating that PHA production in this organism is growth associated. Residual cell increased until the nitrogen source was depleted. At the end of fermentation, final cell concentration, PHA content, and roductivity were 30.2 g/L, 44.8 % of cell dry weight, and 0.188 g/l/h, respectively.

  4. Synthesis of Medium-Chain-Length Polyhydroxyalkanoate Homopolymers, Random Copolymers, and Block Copolymers by an Engineered Strain of Pseudomonas entomophila.

    Science.gov (United States)

    Wang, Ying; Chung, Ahleum; Chen, Guo-Qiang

    2017-04-01

    Medium-chain-length polyhydroxyalkanoates (mcl-PHAs), widely used in medical area, are commonly synthesized by Pseudomonas spp. This study tries to use β-oxidation pathways engineered P. entomophila to achieve single source of a series of mcl-monomers for microbial production of PHA homopolymers. The effort is proven successful for the first time to obtain a wide range of mcl-PHA homopolymers from engineered P. entomophila LAC23 grown on various fatty acids, respectively, ranging from poly(3-hydroxyheptanoate) to poly(3-hydroxytetradecanoate). Effects of a PHA monomer chain length on thermal and crystallization properties including the changes of T m , T g , and T d5% are investigated. Additionally, strain LAC23 is used to synthesize random copolymers of 3-hydroxyoctanoate (3HO) and 3-hydroxydodecanoate (3HDD) or 3-hydroxytetradecanoates, their compositions could be controlled by adjusting the ratios of two related fatty acids. Meanwhile, block copolymer P(3HO)-b-P(3HDD) is synthesized by the same strain. It is found for the first time that even- and odd number mcl-PHA homopolymers have different physical properties. When the gene of the PHA synthase in the engineered P. entomophila is replaced by phaC from Aeromonas hydrophila 4AK4, poly(3-hydroxybutyrate-co-30 mol%-3-hydroxyhexanoate) is synthesized. Therefore, P. entomophila can be used to synthesize the whole range of PHA (C7-C14) homopolymers, random- and block copolymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

    International Nuclear Information System (INIS)

    Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit

    2014-01-01

    Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH 2 + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH 2 ) considered are acetamide (CH 3 CONH 2 ), propionamide (CH 3 CH 2 CONH 2 ), and butyramide (CH 3 CH 2 CH 2 CONH 2 ); the electrolytes (LiX) are lithium perchlorate (LiClO 4 ), lithium bromide (LiBr), and lithium nitrate (LiNO 3 ). Differential scanning calorimetric measurements reveal glass transition temperatures (T g ) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T g s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH 3 CONH 2 + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in terms of temporal heterogeneity and amide clustering in these multi

  6. Influence of alkyl chain length and temperature on thermophysical properties of ammonium-based ionic liquids with molecular solvent.

    Science.gov (United States)

    Kavitha, T; Attri, Pankaj; Venkatesu, Pannuru; Devi, R S Rama; Hofman, T

    2012-04-19

    Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R(4)N](+) with commonly used anion hydroxide [OH](-) were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R(4)N](+)[OH](-) are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH(3))(4)N](+)[OH](-) (TMAH), tetraethyl ammonium hydroxide [(C(2)H(5))(4)N](+)[OH](-) (TEAH), tetrapropyl ammonium hydroxide [(C(3)H(7))(4)N](+)[OH](-) (TPAH) and tetrabutyl ammonium hydroxide [(C(4)H(9))(4)N](+)[OH](-) (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (V(E)), the deviation in isentropic compressibility (Δκ(s)) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.

  7. Effect of the number, position and length of alkyl chains on the physical properties of polysubstituted pyridinium ionic liquids

    International Nuclear Information System (INIS)

    Verdía, Pedro; Hernaiz, Marta; González, Emilio J.; Macedo, Eugénia A.; Salgado, Josefa; Tojo, Emilia

    2014-01-01

    Highlights: • Synthesis of five polysubstituted pyridinium based-ionic liquids. • Physical properties of the pure ionic liquids were measured at several temperatures. • Thermal analysis of the pure ionic liquids was carried out by DSC and TGA techniques. • Density, speed of sound, and refractive index were fitted with a linear expression. • Viscosity data were correlated using the VFT equation. -- Abstract: The knowledge of the physical properties of ionic liquids is of high importance in order to evaluate their potential applicability for a given purpose. In the last few years, ionic liquids have been proposed as promising solvents for extractive desulfurization of fuels. Among them, recent studies have shown that ionic liquids derived from pyridinium affords excellent S-compounds removal capacity. In this work, the thermal analysis of five ionic liquids derived from pyridinium cation polysubstituted with different alkyl chains was carried out by Differencial Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA). Furthermore, the density, speed of sound, refractive index and dynamic viscosity for all the pure ionic liquids were also measured from T = (298.15 to 343.15) K. The effect of the number of cation alkyl chains, their length, and their position on the pyridinium ring, on the ionic liquid physical properties is also analyzed and discussed

  8. Increased mean aliphatic lipid chain length in left ventricular hypertrophy secondary to arterial hypertension: A cross-sectional study.

    Science.gov (United States)

    Evaristi, Maria Francesca; Caubère, Céline; Harmancey, Romain; Desmoulin, Franck; Peacock, William Frank; Berry, Matthieu; Turkieh, Annie; Barutaut, Manon; Galinier, Michel; Dambrin, Camille; Polidori, Carlo; Miceli, Cristina; Chamontin, Bernard; Koukoui, François; Roncalli, Jerôme; Massabuau, Pierre; Smih, Fatima; Rouet, Philippe

    2016-11-01

    About 77.9 million (1 in 4) American adults have high blood pressure. High blood pressure is the primary cause of left ventricular hypertrophy (LVH), which represents a strong predictor of future heart failure and cardiovascular mortality. Previous studies have shown an altered metabolic profile in hypertensive patients with LVH. The goal of this study was to identify blood metabolomic LVH biomarkers by H NMR to provide novel diagnostic tools for rapid LVH detection in populations of hypertensive individuals. This cross-sectional study included 48 hypertensive patients with LVH matched with 48 hypertensive patients with normal LV size, and 24 healthy controls. Two-dimensional targeted M-mode echocardiography was performed to measure left ventricular mass index. Partial least squares discriminant analysis was used for the multivariate analysis of the H NMR spectral data. From the H NMR-based metabolomic profiling, signals coming from methylene (-CH2-) and methyl (-CH3) moieties of aliphatic chains from plasma lipids were identified as discriminant variables. The -CH2-/-CH3 ratio, an indicator of the mean length of the aliphatic lipid chains, was significantly higher (P hypertensive group without LVH and controls. Receiver operating characteristic curve showed that a cutoff of 2.34 provided a 52.08% sensitivity and 85.42% specificity for discriminating LVH (AUC = 0.703, P-value hypertension.

  9. Fatty acid biosynthesis VII. Substrate control of chain-length of products synthesised by rat liver fatty acid synthetase

    DEFF Research Database (Denmark)

    Hansen, Heinz Johs. Max; Carey, E.M.; Dils, R.

    1970-01-01

    - 1. Gas-liquid and paper chromatography have been used to determine the chain-lengths of fatty acids synthesised by purified rat liver fatty acid synthetase from [1-14C]acetyl-CoA, [1,3-14C2]malonyl-CoA and from [1-14C]acetyl-CoA plus partially purified rat liver acetyl-CoA carboxylase. - 2....... A wide range (C4:0–C18:0) of fatty acids was synthesised and the proportions were modified by substrate concentrations in the same manner as for purified rabbit mammary gland fatty acid synthetase. - 3. The relative amount of radioactivity incorporated from added acetyl-CoA and malonyl-CoA depended...... of long-chain fatty acids was synthesised from carboxylated acetyl-CoA than from added malonyl-CoA. - 5. It is suggested that acetyl-CoA carboxylase may carboxylate acetate bound to fatty acid synthetase....

  10. Influence of the chain length of surfactant in the modification of zeolites and clays. Removal of atrazine from water solutions.

    Science.gov (United States)

    Toledo-Jaldin, Helen Paola; Blanco-Flores, Alien; Sánchez-Mendieta, Víctor; Martín-Hernández, Osnieski

    2017-08-30

    Removal potentials of a surfactant modified zeolite (SMZ) and clay (SMC) for atrazine adsorption were evaluated. Materials were modified with hexadecyl trimethyl ammonium bromide (HDTMA-Br) and benzyl octadecyl dimethyl ammonium (BODA) chloride considering the critical micellar concentration (CMC) of each one (0.94 and 0.041 meq/L, respectively). The influence of the surfactant was analyzed in detail, particularly the formation of surfactant layers (complete or partial) connected with the length of the surfactant tail (16 and 18 methyl groups or number of carbons in the chain). Raw materials were characterized by XRD and Fourier transform infrared spectroscopy (FTIR), SMZ and SMC were analyzed by FTIR. Results obtained from kinetic adsorption experiments shown that equilibrium time is less for materials modified with HDTMA (8 h) than materials with BODA (10 and 12 h). Materials modified with the largest chain surfactant (BODA) showed more resistance to atrazine masse transference. The chemisorption was presented in the adsorption mechanisms of atrazine and adsorbent materials. Based on the results of adsorption isotherms Langmuir isotherms showed the better correlation coefficients value. The q max is greater for materials modified with BODA (0.9232 and 4.2448 mg/g) than for materials modified with HDTMA (0.6731 and 3.9121 mg/g). Therefore, SMZ and SMC modified with the largest chain surfactant has more affinity for the pesticide. The removal process at high concentration of atrazine depends of the partition process but at lower concentration, it occurs not only by this process but also by absorption process.

  11. Effects of hydrophobic helix length and side chain chemistry on biomimicry in peptoid analogues of SP-C.

    Science.gov (United States)

    Brown, Nathan J; Wu, Cindy W; Seurynck-Servoss, Shannon L; Barron, Annelise E

    2008-02-12

    The hydrophobic proteins of lung surfactant (LS), SP-B and SP-C, are critical constituents of an effective surfactant replacement therapy for the treatment of respiratory distress syndrome. Because of concerns and difficulties associated with animal-derived surfactants, recent investigations have focused on the creation of synthetic analogues of the LS proteins. However, creating an accurate mimic of SP-C that retains its biophysical surface activity is extraordinarily challenging given the lipopeptide's extreme hydrophobicity and propensity to misfold and aggregate. One successful approach that overcomes these difficulties is the use of poly-N-substituted glycines, or peptoids, to mimic SP-C. To develop a non-natural, bioactive mimic of SP-C and to investigate the effects of side chain chemistry and length of the helical hydrophobic region, we synthesized, purified, and performed in vitro testing of two classes of peptoid SP-C mimics: those having a rigid alpha-chiral aromatic helix and those having a biomimetic alpha-chiral aliphatic helix. The length of the two classes of mimics was also systematically altered. Circular dichroism spectroscopy gave evidence that all of the peptoid-based mimics studied here emulated SP-C's secondary structure, forming stable helical structures in solution. Langmuir-Wilhelmy surface balance, fluorescence microscopy, and pulsating bubble surfactometry experiments provide evidence that the aromatic-based SP-C peptoid mimics, in conjunction with a synthetic lipid mixture, have superior surface activity and biomimetic film morphology in comparison to the aliphatic-based mimics and that there is an increase in surface activity corresponding to increasing helical length.

  12. Aggregation behavior and intermicellar interactions of cationic Gemini surfactants: Effects of alkyl chain, spacer lengths and temperature

    International Nuclear Information System (INIS)

    Hajy Alimohammadi, Marjan; Javadian, Soheila; Gharibi, Hussein; Tehrani-Bagha, Ali reza; Alavijeh, Mohammad Rashidi; Kakaei, Karim

    2012-01-01

    Graphical abstract: Highlights: → Enthalpy-entropy compensation relation was found between and for gemini surfactants. → The intermicellar interaction parameters are influenced with increasing the lengths of the tail and the spacer of gemini surfactants. → Increasing temperature decreases the intermicellar interaction parameters. → The changes in micellar surface charge density, and phase transition between spherical and rod geometries explain the data. - Abstract: The aggregation behavior of the cationic Gemini surfactants C m H 2m+1 N(CH 3 ) 2 (CH 2 ) S (CH 3 ) 2 N C m H 2m+1 ,2Br - with m = 12, 14 and s = 2, 4 were studied by performing surface tension, electrical conductivity, pulsed field gradient nuclear magnetic resonance (PFG-NMR), and cyclic voltammetry (CV) measurements over the temperature range 298 K to 323 K. The critical micelle concentration (CMC), surface excess (Γ max ), mean molecular surface area (A min ), degree of counter ion dissociation (α), and the thermodynamic parameters of micellization were determined from the surface tension and conductance data. An enthalpy-entropy compensation effect was observed and all the plots of enthalpy-entropy compensation exhibit excellent linearity. The micellar self-diffusion coefficients (D m ) and intermicellar interaction parameters (k d ) were obtained from the PFG-NMR and CV measurements. These results are discussed in terms of the intermicellar interactions, the effects of the chain and spacer lengths on the micellar surface charge density, and the phase transition between spherical and rod geometries. The intermicellar interaction parameters were found to decrease slightly with increasing temperature for 14-4-14, which suggests that the micellar surface charge density decreases with increasing temperature. The mean values of the hydrodynamic radius, R h , and the aggregation number, N agg , of the Gemini surfactants'm-4-m micelles were calculated from the micellar self-diffusion coefficient

  13. Heat and Mass Transfer during Solid-Liquid Phase Transition of n-Alkanes in the C{sub 16} to C{sub 19} Range

    Energy Technology Data Exchange (ETDEWEB)

    Holmen, Rune

    2002-07-01

    The main goal of this project has been to study heat and mass transfer during solid-liquid phase transition of n-alkanes in the in the C{sub 16} to C{sub 19} range. Phase transitions of both mixtures and pure components have been investigated. All experiments and simulations have been performed without any convection. Thermal conductivities have been determined at the melting point for solid and liquid unbranched alkanes ranging from C{sub 16} to C{sub 19}. An assessment of the error of the method has been performed. The measurements of solid conductivities are in accordance with measurements reported previously and confirm the applicability of the method. Liquid conductivities are higher than extrapolated values from the literature. The enhanced conductivity is believed to be caused by structural changes close to the melting point which is not taken into account when extrapolating values from the literature. Experiments have been performed for the purpose of investigating the freezing of mixtures of n-alkanes in the C{sub 16}-C{sub 19} range. The positions of the solid-liquid interfaces have been measured as freezing occurred. Calculations of the ratio of liquid and solid conductivities show that the solid structure of mixtures of the investigated n-alkanes is predominantly in a rotator structure at the temperatures investigated. There are indications of a transformation into an orthorhombic structure at lower temperatures. The temperatures on the solid-liquid interface have been measured, and compared with calculated values from chapter 4. The temperature of the interface is represented better by the measured interfacial temperatures than by the calculated interfacial temperatures. The experimental results indicate that the diffusion of heat is the limiting mechanism of phase transition. This result in a homogeneous liquid composition. A numerical model has been developed in order to simulate the experimental freezing of mixtures. The model represents the results

  14. Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes

    KAUST Repository

    Wang, Zhandong; Sarathy, Mani

    2016-01-01

    kinetic mechanism is considered. The advanced combustion phasing is initiated by the formation and destruction of additional radical chain-branching intermediates produced in the third O2 addition process, e.g. keto-dihydroperoxides and/or keto

  15. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    Energy Technology Data Exchange (ETDEWEB)

    Huo, Lixia [National Key Laboratory of Science and Technology on Vacuum Technology and Physics, Lanzhou Institute of Physics, Lanzhou, Gansu 730010 (China); Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China); Du, Pengcheng [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China); Zhou, Hui; Zhang, Kaifeng [National Key Laboratory of Science and Technology on Vacuum Technology and Physics, Lanzhou Institute of Physics, Lanzhou, Gansu 730010 (China); Liu, Peng, E-mail: pliu@lzu.edu.cn [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China)

    2017-02-28

    Highlights: • n-Alkyltrimethoxysilanes with various chain lengths were self-assembled on silicon. • Effect of alkyl chain lengths (C6, C12, or C18) on the SAMs was investigated. • Surface roughness of the SAMs decreased with increasing the alkyl chain lengths. • The C{sub 12}-SAM possessed superior friction reduction and wear resistance. - Abstract: It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C{sub 6}, C{sub 12}, or C{sub 18}) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (R{sub a}) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al{sub 2}O{sub 3} ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C{sub 12} alkyl chain (C{sub 12}-SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C{sub 12}-SAM with desirable alkyl chain length.

  16. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    International Nuclear Information System (INIS)

    Huo, Lixia; Du, Pengcheng; Zhou, Hui; Zhang, Kaifeng; Liu, Peng

    2017-01-01

    Highlights: • n-Alkyltrimethoxysilanes with various chain lengths were self-assembled on silicon. • Effect of alkyl chain lengths (C6, C12, or C18) on the SAMs was investigated. • Surface roughness of the SAMs decreased with increasing the alkyl chain lengths. • The C 12 -SAM possessed superior friction reduction and wear resistance. - Abstract: It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C 6 , C 12 , or C 18 ) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (R a ) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al 2 O 3 ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C 12 alkyl chain (C 12 -SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C 12 -SAM with desirable alkyl chain length.

  17. Critical constants and acentric factors for long-chain alkanes suitable for corresponding states applications

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Dimitrios, Tassios

    1997-01-01

    Several methods for the estimation of the critical temperature T-c, the critical pressure P-c, and the acentric factor omega for long-chain n-alkanes are reviewed and evaluated for the prediction of vapor pressures using Corresponding States (CS) methods, like the Lee-Kesler equation and the cubic....... Anselme, Correlation of the critical properties of alkanes and alkanols, Fluid Phase Equilibria, 56 (1990) 153-169; W. Hu, J. Lovland and P. Vonka. Generalized vapor pressure equations for n-alkanes, 1-alkenes, and 1-alkanols, Presented at the 11th Int. Congress of Chemical Engineering, Chemical Equipment...

  18. Comparison of Chain-Length Preferences and Glucan Specificities of Isoamylase-Type α-Glucan Debranching Enzymes from Rice, Cyanobacteria, and Bacteria.

    Directory of Open Access Journals (Sweden)

    Taiki Kobayashi

    Full Text Available It has been believed that isoamylase (ISA-type α-glucan debranching enzymes (DBEs play crucial roles not only in α-glucan degradation but also in the biosynthesis by affecting the structure of glucans, although molecular basis on distinct roles of the individual DBEs has not fully understood. In an attempt to relate the roles of DBEs to their chain-length specificities, we analyzed the chain-length distribution of DBE enzymatic reaction products by using purified DBEs from various sources including rice, cyanobacteria, and bacteria. When DBEs were incubated with phytoglycogen, their chain-length specificities were divided into three groups. First, rice endosperm ISA3 (OsISA3 and Eschericia coli GlgX (EcoGlgX almost exclusively debranched chains having degree of polymerization (DP of 3 and 4. Second, OsISA1, Pseudomonas amyloderamosa ISA (PsaISA, and rice pullulanase (OsPUL could debranch a wide range of chains of DP≧3. Third, both cyanobacteria ISAs, Cyanothece ATCC 51142 ISA (CytISA and Synechococcus elongatus PCC7942 ISA (ScoISA, showed the intermediate chain-length preference, because they removed chains of mainly DP3-4 and DP3-6, respectively, while they could also react to chains of DP5-10 and 7-13 to some extent, respectively. In contrast, all these ISAs were reactive to various chains when incubated with amylopectin. In addition to a great variation in chain-length preferences among various ISAs, their activities greatly differed depending on a variety of glucans. Most strikingly, cyannobacteria ISAs could attack branch points of pullulan to a lesser extent although no such activity was found in OsISA1, OsISA3, EcoGlgX, and PsaISA. Thus, the present study shows the high possibility that varied chain-length specificities of ISA-type DBEs among sources and isozymes are responsible for their distinct functions in glucan metabolism.

  19. Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity.

    Science.gov (United States)

    Lebrón-Aguilar, Rosa; Quintanilla-López, Jesús Eduardo; Santiuste, José María

    2010-12-03

    A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (Δ(sol)H(o)) has been carried out. Those methods based on the fitting of lnV(g) or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T(a)) are the most adequate ones for obtaining Δ(sol)H(o) values. However, the latter is the only reliable option for Δ(sol)H(o) estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V(g) determination is less accurate or even impossible. Consequently, in this paper, Δ(sol)H(o) obtained from ln(k/T) vs. (1/T+T(a)) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (Δ(sol)C(p)(o)) have also been calculated using this method. A clear influence on Δ(sol)H(o) of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of Δ(sol)C(p)(o) with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. Effect of isothermal dilution on emission factors of organic carbon and n-alkanes in the particle and gas phases of diesel exhaust

    Science.gov (United States)

    Fujitani, Yuji; Saitoh, Katsumi; Fushimi, Akihiro; Takahashi, Katsuyuki; Hasegawa, Shuich; Tanabe, Kiyoshi; Kobayashi, Shinji; Furuyama, Akiko; Hirano, Seishiro; Takami, Akinori

    2012-11-01

    To investigate the effect of isothermal dilution (30 °C) on emission factors (EFs) of semivolatile and nonvolatile compounds of heavy-duty diesel exhaust, we measured EFs for particulate matter (PM), organic carbon (OC), and elemental carbon (EC) in the particle phase, and EFs for n-alkanes in both the particle phase and the gas phase of exhaust produced under high-idle engine operating conditions at dilution ratios (DRs) ranging from 8 to 1027. The EC EFs did not vary with DR, whereas the OC EFs in the particle phase determined at DR = 1027 were 13% of the EFs determined at DR = 8, owing to evaporation of organic compounds. Using partitioning theory and n-alkane EFs measured at DR = 14 and 238, we calculated the distributions of compounds between the particle and gas phases at DR = 1760, which corresponds to the DR for tailpipe emissions as they move from the tailpipe to the roadside atmosphere. The gas-phase EF of a compound with a vapor pressure of 10-7 Pa was 0.01 μg kg-1-fuel at DR = 14, and this value is 1/330 the value derived at DR = 1760. Our results suggest that the EFs of high-volatility compounds in the particle phase will be overestimated and that the EFs of low-volatility compounds in the gas phase will be underestimated if the estimates are derived from data obtained at the low DRs and they are applied to the real world. Therefore, extrapolation from EFs derived at low DR values to EFs at atmospherically relevant DRs will be a source of error in predictions of the concentrations of particulate matter and gas-phase precursors to secondary organic aerosols in air quality models.

  1. Gas chromatographic-mass spectrometric investigation of n-alkanes and carboxylic acids in bottom sediments of the northern Caspian Sea

    Science.gov (United States)

    Kenzhegaliev, Akimgali; Zhumagaliev, Sagat; Kenzhegalieva, Dina; Orazbayev, Batyr

    2018-03-01

    Prior to the start of experimental oil production in the Kashagan field (northern part of the Caspian Sea), n-alkanes and carboxylic acids contained in samples obtained from bottom sediments in the area of artificial island "D" were investigated by gas chromatography-mass spectrometry. Concentrations of 10 n-alkanes (composed of C10-C13, C15-C20) and 11 carboxylic acids (composed of C6-C12, C14-C16) were identified and measured. Concentrations of individual alkanes and carboxylic acids in bottom sediments of the various samples varied between 0.001 ÷ 0.88 μg/g and 0.001 ÷ 1.94 μg/g, respectively. Mass spectra, in particular the M+ molecular ion peak and the most intense peaks of fragment ions, are given. The present study illustrates the stability of molecular ions to electronic ionisation and the main fragment ions to the total ion current and shows that the initial fragmentation of alkanes implies radical cleavage of C2H5 rather than CH3. All aliphatic monocarboxylic acids studied were characterised by McLafferty rearrangement leading to the formation of F4 cation-radical with m/z 60 and F3 cation-radical with m/z 88 in the case of ethylhexanoic acid. The formation of oxonium ions presents another important aspect of acid fragmentation. Using mass numbers of oxonium ions and rearrangement ions allows determination of the substitution character in α- and β- C atoms. The essence of our approach is to estimate the infiltration of hydrocarbon fluids from the enclosing formation into sea water, comprising an analysis of derivatives of organic compounds in bottom sediments. Thus, concentrations of derived organic molecules can serve as a basis for estimates of the depth at which hydrocarbon fluids leak, i.e., to serve as an auxiliary technique in the search for hydrocarbon deposits and to repair well leaks.

  2. Bacterial membrane activity of a-peptide/b-peptoid chimeras: Influence of amino acid composition and chain length on the activity against different bacterial strains

    DEFF Research Database (Denmark)

    Hein-Kristensen, Line; Knapp, Kolja M; Franzyk, Henrik

    2011-01-01

    and subsequent killing is usually not tested. In this report, six α-peptide/β-peptoid chimeras were examined for the effect of amino acid/peptoid substitutions and chain length on the membrane perturbation and subsequent killing of food-borne and clinical bacterial isolates. RESULTS: All six AMP analogues...... acid only had a minor effect on MIC values, whereas chain length had a profound influence on activity. All chimeras were less active against Serratia marcescens (MICs above 46 μM). The chimeras were bactericidal and induced leakage of ATP from Staphylococcus aureus and S. marcescens with similar time...... of onset and reduction in the number of viable cells. EDTA pre-treatment of S. marcescens and E. coli followed by treatment with chimeras resulted in pronounced killing indicating that disintegration of the Gram-negative outer membrane eliminated innate differences in susceptibility. Chimera chain length...

  3. On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends.

    Science.gov (United States)

    Morse, David C; Chung, Jun Kyung

    2009-06-14

    The self-consistent field (SCF) approach to the thermodynamics of dense polymer liquids is based on the idea that short-range correlations in a polymer liquid are almost independent of how monomers are connected into polymers over larger scales. Some limits of this idea are explored in the context of a perturbation theory for symmetric polymer blends. We consider mixtures of two structurally identical polymers, A and B, in which the AB monomer pair interaction differs slightly from the AA and BB interactions by an amount proportional to a parameter alpha. An expansion of the free energy to first order in alpha yields an excess free energy of mixing per monomer of the form alphaz(N)phi(A)phi(B) in both lattice and continuum models, where z(N) is a measure of the number of intermolecular near neighbors per monomer in a one-component (alpha=0) reference liquid with chains of length N. The quantity z(N) decreases slightly with increasing N because the concentration of intramolecular near neighbors is slightly higher for longer chains, creating a slightly deeper intermolecular correlation hole. We predict that z(N)=z(infinity)[1+betaN(-1/2)], where N is an invariant degree of polymerization and beta=(6/pi)(3/2) is a universal coefficient. This and related predictions about the slight N dependence of local correlations are confirmed by comparison to simulations of a continuum bead-spring model and to published lattice Monte Carlo simulations. We show that a renormalized one-loop theory for blends correctly describes this N dependence of local liquid structure. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of perturbation theory to the limit N-->infinity.

  4. Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

    Energy Technology Data Exchange (ETDEWEB)

    Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit, E-mail: ranjit@bose.res.in [Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India)

    2014-03-14

    Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH{sub 2} + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH{sub 2}) considered are acetamide (CH{sub 3}CONH{sub 2}), propionamide (CH{sub 3}CH{sub 2}CONH{sub 2}), and butyramide (CH{sub 3}CH{sub 2}CH{sub 2}CONH{sub 2}); the electrolytes (LiX) are lithium perchlorate (LiClO{sub 4}), lithium bromide (LiBr), and lithium nitrate (LiNO{sub 3}). Differential scanning calorimetric measurements reveal glass transition temperatures (T{sub g}) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T{sub g}s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH{sub 3}CONH{sub 2} + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in

  5. Influence of trehalose 6,6'-diester (TDX) chain length on the physicochemical and immunopotentiating properties of DDA/TDX liposomes

    DEFF Research Database (Denmark)

    Kallerup, Rie Selchau; Madsen, Cecilie Maria; Schiøth, Mikkel Lohmann

    2015-01-01

    Linking physicochemical characterization to functional properties is crucial for defining critical quality attributes during development of subunit vaccines toward optimal safety and efficacy profiles. We investigated how the trehalose 6,6'-diester (TDX) chain length influenced the physicochemical...... and immunopotentiating properties of the clinically tested liposomal adjuvant composed of dimethyldioctadecylammonium (DDA) bromide and analogues of trehalose-6,6'-dibehenate (TDB). TDB analogues with symmetrically shortened acyl chains [denoted X: arachidate (A), stearate (S), palmitate (P), myristate (Myr) and laurate...

  6. Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

    International Nuclear Information System (INIS)

    Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei

    2017-01-01

    Highlights: • CsPbBr_3 perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr_3 nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr_3 nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr_3 nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr_3 NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr_3 NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr_3 NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr_3 NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the product synthesized in the presence of

  7. Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei, E-mail: awtang@bjtu.edu.cn

    2017-05-31

    Highlights: • CsPbBr{sub 3} perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr{sub 3} nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr{sub 3} nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr{sub 3} nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr{sub 3} NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr{sub 3} NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr{sub 3} NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr{sub 3} NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the

  8. Evaluation of medium-chain-length polyhydroxyalkanoate production by Pseudomonas putida LS46 using biodiesel by-product streams.

    Science.gov (United States)

    Fu, Jilagamazhi; Sharma, Umesh; Sparling, Richard; Cicek, Nazim; Levin, David B

    2014-07-01

    Medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida LS46 was analyzed in shake-flask-based batch reactions, using pure chemical-grade glycerol (PG), biodiesel-derived "waste" glycerol (WG), and biodiesel-derived "waste" free fatty acids (WFA). Cell growth, substrate consumption, mcl-PHA accumulation within the cells, and the monomer composition of the synthesized biopolymers were monitored. The patterns of mcl-PHA synthesis in P. putida LS46 cells grown on PG and WG were similar but differed from that of cells grown with WFA. Polymer accumulation in glycerol-based cultures was stimulated by nitrogen limitation and plateaued after 48 h in both PG and WG cultures, with a total accumulation of 17.9% cell dry mass and 16.3% cell dry mass, respectively. In contrast, mcl-PHA synthesis was independent of nitrogen concentration in P. putida LS46 cells cultured with WFA, which accumulated to 29% cell dry mass. In all cases, the mcl-PHAs synthesized consisted primarily of 3-hydroxyoctanoate (C(8)) and 3-hydroxydecanoate (C(10)). WG and WFA supported similar or greater cell growth and mcl-PHA accumulation than PG under the experimental conditions used. These results suggest that biodiesel by-product streams could be used as low-cost carbon sources for sustainable mcl-PHA production.

  9. Identification of Echinococcus granulosus strains using polymerase chain reaction-restriction fragment length polymorphism amongst livestock in Moroto district, Uganda.

    Science.gov (United States)

    Chamai, Martin; Omadang, Leonard; Erume, Joseph; Ocaido, Michael; Oba, Peter; Othieno, Emmanuel; Bonaventure, Straton; Kitibwa, Annah

    2016-07-29

    A descriptive study was conducted to identify the different strains of Echinococcus granulosus occurring in livestock in Moroto district, Uganda. Echinococcus cysts from 104 domestic animals, including cattle, sheep, goats and camels, were taken and examined by microscopy, polymerase chain reaction with restriction fragment length polymorphism and Sanger DNA sequencing. Echinococcus granulosus genotypes or strains were identified through use of Bioinformatics tools: BioEdit, BLAST and MEGA6. The major finding of this study was the existence of a limited number of E. granulosus genotypes from cattle, goats, sheep and camels. The most predominant genotype was G1 (96.05%), corresponding to the common sheep strain. To a limited extent (3.95%), the study revealed the existence of Echinococcus canadensis G6/7 in three (n = 3) of the E. granulosus-positive samples. No other strains of E. granulosus were identified. It was concluded that the common sheep strain of Echinococcus sensu stricto and G6/7 of E. canadensis were responsible for echinococcal disease in Moroto district, Uganda.

  10. Effects of Odd–Even Side Chain Length of Alkyl-Substituted Diphenylbithiophenes on First Monolayer Thin Film Packing Structure

    KAUST Repository

    Akkerman, Hylke B.

    2013-07-31

    Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5′bis(4-alkylphenyl)-2,2′-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified SiO2 surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd-even effect in the strength of the intermolecular electronic coupling. © 2013 American Chemical Society.

  11. Medium-chain-length poly-3-hydroxyalkanoates-carbon nanotubes composite anode enhances the performance of microbial fuel cell.

    Science.gov (United States)

    Hindatu, Y; Annuar, M S M; Subramaniam, R; Gumel, A M

    2017-06-01

    Insufficient power generation from a microbial fuel cell (MFC) hampers its progress towards utility-scale development. Electrode modification with biopolymeric materials could potentially address this issue. In this study, medium-chain-length poly-3-hydroxyalkanoates (PHA)/carbon nanotubes (C) composite (CPHA) was successfully applied to modify the surface of carbon cloth (CC) anode in MFC. Characterization of the functional groups on the anodic surface and its morphology was carried out. The CC-CPHA composite anode recorded maximum power density of 254 mW/m 2 , which was 15-53% higher than the MFC operated with CC-C (214 mW/m 2 ) and pristine CC (119 mW/m 2 ) as the anode in a double-chambered MFC operated with Escherichia coli as the biocatalyst. Electrochemical impedance spectroscopy and cyclic voltammetry showed that power enhancement was attributed to better electron transfer capability by the bacteria for the MFC setup with CC-CPHA anode.

  12. Distinguishing Heterodera filipjevi and H. avenae using polymerase chain reaction-restriction fragment length polymorphism and cyst morphology.

    Science.gov (United States)

    Yan, Guiping; Smiley, Richard W

    2010-03-01

    The cereal cyst nematodes Heterodera filipjevi and H. avenae impede wheat production in the Pacific Northwest (PNW). Accurate identification of cyst nematode species and awareness of high population density in affected fields are essential for designing effective control measures. Morphological methods for differentiating these species are laborious. These species were differentiated using polymerase chain reaction restriction fragment length polymorphism (PCR-RFLP) of internal transcribed spacer (ITS)-ribosomal (r)DNA with up to six restriction endonucleases (TaqI, HinfI, PstI, HaeIII, RsaI, and AluI). The method was validated by inspecting underbridge structures of cyst vulval cones. Grid soil sampling of an Oregon field infested by both species revealed that H. filipjevi was present at most of the infested grid sites but mixtures of H. avenae and H. filipjevi also occurred. These procedures also detected and differentiated H. filipjevi and H. avenae in soil samples from nearby fields in Oregon and H. avenae in samples from Idaho and Washington. Intraspecific polymorphism was not observed within H. filipjevi or PNW H. avenae populations based on the ITS-rDNA. However, intraspecific variation was observed between H. avenae populations occurring in the PNW and France. Methods described here will improve detection and identification efficiencies for cereal cyst nematodes in wheat fields.

  13. The Impact of Polyether Chain Length on the Iron Clearing Efficiency and Physiochemical Properties of Desferrithiocin Analogues

    Science.gov (United States)

    Bergeron, Raymond J.; Bharti, Neelam; Wiegand, Jan; McManis, James S.; Singh, Shailendra; Abboud, Khalil A.

    2010-01-01

    (S)-2-(2,4-Dihydroxyphenyl)-4,5-dihydro-4-methyl-4-thiazolecarboxylic acid (2) was abandoned in clinical trials as an iron chelator for the treatment of iron overload disease because of its nephrotoxicity. However, subsequent investigations revealed that replacing the 4′-(HO) of 2 with a 3,6,9-trioxadecyloxy group, ligand 4, increased iron clearing efficiency (ICEa) and ameliorated the renal toxicity of 2. This compelled a closer look at additional polyether analogues, the subject of this work. The 3,6,9,12-tetraoxatridecyloxy analogue of 4, chelator 5, an oil, had twice the ICE in rodents of 4, although its ICE in primates was reduced relative to 4. The corresponding 3,6-dioxaheptyloxy analogue of 2, 6 (a crystalline solid), had high ICEs in both the rodent and primate models. It significantly decorporated hepatic, renal, and cardiac iron, with no obvious histopathologies. These findings suggest that polyether chain length has a profound effect on ICE, tissue iron decorporation, and ligand physiochemical properties. PMID:20232803

  14. Limits of a rapid identification of common Mediterranean sandflies using polymerase chain reaction-restriction fragment length polymorphism

    Directory of Open Access Journals (Sweden)

    Azzedine Bounamous

    2014-07-01

    Full Text Available A total of 131 phlebotomine Algerian sandflies have been processed in the present study. They belong to the species Phlebotomus bergeroti, Phlebotomus alexandri, Phlebotomus sergenti, Phlebotomus chabaudi, Phlebotomus riouxi, Phlebotomus perniciosus, Phlebotomus longicuspis, Phlebotomus perfiliewi, Phlebotomus ariasi, Phlebotomus chadlii, Sergentomyia fallax, Sergentomyia minuta, Sergentomyia antennata, Sergentomyia schwetzi, Sergentomyia clydei, Sergentomyia christophersi and Grassomyia dreyfussi. They have been characterised by sequencing of a part of the cytochrome b (cyt b, t RNA serine and NADH1 on the one hand and of the cytochrome C oxidase I of the mitochondrial DNA (mtDNA on the other hand. Our study highlights two sympatric populations within P. sergenti in the area of its type-locality and new haplotypes of P. perniciosus and P. longicuspis without recording the specimens called lcx previously found in North Africa. We tried to use a polymerase chain reaction-restriction fragment length polymorphism method based on a combined double digestion of each marker. These method is not interesting to identify sandflies all over the Mediterranean Basin.

  15. Effects of Odd–Even Side Chain Length of Alkyl-Substituted Diphenylbithiophenes on First Monolayer Thin Film Packing Structure

    KAUST Repository

    Akkerman, Hylke B.; Mannsfeld, Stefan C. B.; Kaushik, Ananth P.; Verploegen, Eric; Burnier, Luc; Zoombelt, Arjan P.; Saathoff, Jonathan D.; Hong, Sanghyun; Atahan-Evrenk, Sule; Liu, Xueliang; Aspuru-Guzik, Alá n; Toney, Michael F.; Clancy, Paulette; Bao, Zhenan

    2013-01-01

    Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5′bis(4-alkylphenyl)-2,2′-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified SiO2 surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd-even effect in the strength of the intermolecular electronic coupling. © 2013 American Chemical Society.

  16. Haplotyping the human T-cell receptor β-chain gene complex by use of restriction fragment length polymorphisms

    International Nuclear Information System (INIS)

    Charmley, P.; Chao, A.; Gatti, R.A.; Concannon, P.; Hood, L.

    1990-01-01

    The authors have studied the genetic segregation of human T-cell receptor β-chain (TCRβ) genes on chromosome 7q in 40 CEPH (Centre d'Etude du Polymorphisme Humain) families by using restriction fragment length polymorphisms (RFLPs). They constructed haplotypes from eight RFLPs by using variable- and constant-region cDNA probes, which detect polymorphisms that span more than 600 kilobases of the TCRβ gene complex. Analysis of allele distributions between TCRβ genes revealed significant linkage disequilibrium between only 6 of the 28 different pairs of RFLPs. This linkage disequilibrium strongly influences the most efficient order to proceed for typing of these RFLPs in order to achieve maximum genetic informativeness, which in this study revealed a 97.3% level of heterozygosity within the TCRβ gene complex. The results should provide new insight into recent reports of disease associations with the TCRβ gene complex and should assist in designing future experiments to detect or confirm the existence of disease-susceptibility loci in this region of the human genome

  17. Rapid differentiation of closely related isolates of two plant viruses by polymerase chain reaction and restriction fragment length polymorphism analysis.

    Science.gov (United States)

    Barbara, D J; Morton, A; Spence, N J; Miller, A

    1995-09-01

    Immunocapture reverse transcriptase-polymerase chain reaction (RT-PCR) followed by restriction fragment length polymorphism (RFLP) analysis of the product has been shown to be an effective procedure for discriminating serologically indistinguishable isolates of two plant viruses, raspberry bushy dwarf (RBDV) and zucchini yellow mosaic (ZYMV). For both viruses, only limited sequence information was available at the time of primer design, but most of the isolates which were tested could be amplified (the one exception being a serologically quite distinct isolate of ZYMV). Restriction endonucleases revealing diagnostic RFLPs were readily identified. Each of two isolates of ZYMV could be detected in the presence of the other and the relative proportions approximately quantified by visual estimation of the relative intensity of the appropriate bands. A range of isolates of different RBDV pathotypes were compared; isolates were grouped in ways that accorded with their known history. Computer analysis of the published sequence from which the primers had been derived showed the sequenced isolate to be identical with an isolate imported from the USSR. The PCR/RFLP procedure is rapid (it can be completed in less than 2 days), effective and will probably be generally applicable to distinguishing closely related virus isolates, even where little sequence information is available.

  18. Lyme disease with facial nerve palsy: rapid diagnosis using a nested polymerase chain reaction-restriction fragment length polymorphism analysis.

    Science.gov (United States)

    Hashimoto, Y; Takahashi, H; Kishiyama, K; Sato, Y; Nakao, M; Miyamoto, K; Iizuka, H

    1998-02-01

    A 64-year-old woman with Lyme disease and manifesting facial nerve palsy had been bitten by a tick on the left frontal scalp 4 weeks previously. Erythema migrans appeared on the left forehead, accompanied by left facial paralysis. Nested polymerase chain reaction-restriction fragment length polymorphism analysis (nested PCR-RFLP) was performed on DNA extracted from a skin biopsy of the erythema on the left forehead. Borrelia flagellin gene DNA was detected and its RFLP pattern indicated that the organism was B. garinii, Five weeks later, B. garinii was isolated by conventional culture from the erythematous skin lesion, but not from the cerebrospinal fluid. After treatment with ceftriaxone intravenously for 10 days and oral administration of minocycline for 7 days, both the erythema and facial nerve palsy improved significantly. Nested PCR and culture taken after the lesion subsided, using skin samples obtained from a site adjacent to the original biopsy, were both negative. We suggest that nested PCR-RFLP analysis might be useful for the rapid diagnosis of Lyme disease and for evaluating therapy.

  19. An Assessment of Weight-Length Relationships for Muskellunge,Northern Pike, and Chain Pickerel In Carlander's Handbook of Freshwater Fishery Biology

    OpenAIRE

    Daviscourt, Joshua; Huertas, Joshua; Courtney, Michael

    2011-01-01

    Carlander's Handbook of Freshwater Fishery Biology (1969) contains life history data from many species of freshwater fish found in North America. It has been cited over 1200 times and used to produce standard-weight curves for some species. Recent work (Cole-Fletcher et al. 2011) suggests Carlander (1969) contains numerous errors in listed weight-length equations. This paper assesses the weight-length relationships listed in Carlander for muskellunge, northern pike, and chain pickerel by comp...

  20. Determination of n-alkanes in C. annuum (bell pepper) fruit and seed using GC-MS: comparison of extraction methods and application to samples of different geographical origin

    NARCIS (Netherlands)

    de Rijke, E.; Fellner, C.; Westerveld, J.; Lopatka, M.; Cerli, C.; Kalbitz, K.; de Koster, C.G.

    2015-01-01

    An efficient extraction and analysis method was developed for the isolation and quantification of n-alkanes from bell peppers of different geographical locations. Five extraction techniques, i.e., accelerated solvent extraction (ASE), ball mill extraction, ultrasonication, rinsing, and shaking, were

  1. Inhibition of nuclear T3 binding by fatty acids: dependence on chain length, unsaturated bonds, cis-trans configuration and esterification

    NARCIS (Netherlands)

    Wiersinga, W. M.; Platvoet-ter Schiphorst, M.

    1990-01-01

    1. Fatty acids have the capacity for inhibition of nuclear T3 binding (INB). The present studies were undertaken to describe the INB-activity of fatty acids as a function of chain length, unsaturated bonds, cis-trans configuration, and esterification. 2. Isolated rat liver nuclei were incubated with

  2. Characterisation of Toxoplasma gondii isolates using polymerase chain reaction (PCR) and restriction fragment length polymorphism (RFLP) of the non-coding Toxoplasma gondii (TGR)-gene sequences

    DEFF Research Database (Denmark)

    Høgdall, Estrid; Vuust, Jens; Lind, Peter

    2000-01-01

    of using TGR gene variants as markers to distinguish among T. gondii isolates from different animals and different geographical sources. Based on the band patterns obtained by restriction fragment length polymorphism (RFLP) analysis of the polymerase chain reaction (PCR) amplified TGR sequences, the T...

  3. Lid opening and conformational stability of T1 Lipase is mediated by increasing chain length polar solvents

    Directory of Open Access Journals (Sweden)

    Jonathan Maiangwa

    2017-05-01

    Full Text Available The dynamics and conformational landscape of proteins in organic solvents are events of potential interest in nonaqueous process catalysis. Conformational changes, folding transitions, and stability often correspond to structural rearrangements that alter contacts between solvent molecules and amino acid residues. However, in nonaqueous enzymology, organic solvents limit stability and further application of proteins. In the present study, molecular dynamics (MD of a thermostable Geobacillus zalihae T1 lipase was performed in different chain length polar organic solvents (methanol, ethanol, propanol, butanol, and pentanol and water mixture systems to a concentration of 50%. On the basis of the MD results, the structural deviations of the backbone atoms elucidated the dynamic effects of water/organic solvent mixtures on the equilibrium state of the protein simulations in decreasing solvent polarity. The results show that the solvent mixture gives rise to deviations in enzyme structure from the native one simulated in water. The drop in the flexibility in H2O, MtOH, EtOH and PrOH simulation mixtures shows that greater motions of residues were influenced in BtOH and PtOH simulation mixtures. Comparing the root mean square fluctuations value with the accessible solvent area (SASA for every residue showed an almost correspondingly high SASA value of residues to high flexibility and low SASA value to low flexibility. The study further revealed that the organic solvents influenced the formation of more hydrogen bonds in MtOH, EtOH and PrOH and thus, it is assumed that increased intraprotein hydrogen bonding is ultimately correlated to the stability of the protein. However, the solvent accessibility analysis showed that in all solvent systems, hydrophobic residues were exposed and polar residues tended to be buried away from the solvent. Distance variation of the tetrahedral intermediate packing of the active pocket was not conserved in organic solvent

  4. 4-N-, 4-S-, and 4-O-chloroquine analogues: influence of side chain length and quinolyl nitrogen pKa on activity vs chloroquine resistant malaria.

    Science.gov (United States)

    Natarajan, Jayakumar K; Alumasa, John N; Yearick, Kimberly; Ekoue-Kovi, Kekeli A; Casabianca, Leah B; de Dios, Angel C; Wolf, Christian; Roepe, Paul D

    2008-06-26

    Using predictions from heme-quinoline antimalarial complex structures, previous modifications of chloroquine (CQ), and hypotheses for chloroquine resistance (CQR), we synthesize and assay CQ analogues that test structure-function principles. We vary side chain length for both monoethyl and diethyl 4-N CQ derivatives. We alter the pKa of the quinolyl N by introducing alkylthio or alkoxy substituents into the 4 position and vary side chain length for these analogues. We introduce an additional titratable amino group to the side chain of 4-O analogues with promising CQR strain selectivity and increase activity while retaining selectivity. We solve atomic resolution structures for complexes formed between representative 4-N, 4-S, and 4-O derivatives vs mu-oxo dimeric heme, measure binding constants for monomeric vs dimeric heme, and quantify hemozoin (Hz) formation inhibition in vitro. The data provide additional insight for the design of CQ analogues with improved activity vs CQR malaria.

  5. 4-N, 4-S & 4-O Chloroquine Analogues: Influence of Side Chain Length and Quinolyl Nitrogen pKa on Activity vs. Chloroquine Resistant Malaria+, #

    Science.gov (United States)

    Natarajan, Jayakumar K.; Alumasa, John; Yearick, Kimberly; Ekoue-Kovi, Kekeli A.; Casabianca, Leah B.; de Dios, Angel C.; Wolf, Christian; Roepe, Paul D.

    2009-01-01

    Using predictions from heme – quinoline antimalarial complex structures, previous modifications of chloroquine (CQ), and hypotheses for chloroquine resistance (CQR), we synthesize and assay CQ analogues that test structure – function principles. We vary side chain length for both monoethyl and diethyl 4N CQ derivatives. We alter the pKa of the quinolyl N by introducing alkylthio or alkoxy substituents into the 4 position, and vary side chain length for these analogues. We introduce an additional titratable amino group to the side chain of 4O analogues with promising CQR strain selectivity and increase activity while retaining selectivity. We solve atomic resolution structures for complexes formed between representative 4N, 4S and 4O derivatives vs. μ-oxo dimeric heme, measure binding constants for monomeric vs. dimeric heme, and quantify hemozoin (Hz) formation inhibition in vitro. The data provide additional insight for the design of CQ analogues with improved activity vs. CQR malaria. PMID:18512900

  6. Comparison of CHROMagar, polymerase chain reaction-restriction fragment length polymorphism, and polymerase chain reaction-fragment size for the identification of Candida species.

    Science.gov (United States)

    Jafari, Zahra; Motamedi, Marjan; Jalalizand, Nilufar; Shokoohi, Gholam R; Charsizadeh, Arezu; Mirhendi, Hossein

    2017-09-01

    The epidemiological alteration in the distribution of Candida species, as well as the significantly increasing trend of either intrinsic or acquired resistance of some of these fungi highlights the need for a reliable method for the identification of the species. Polymerase chain reaction (PCR) is one of the methods facilitating the quick and precise identification of Candida species. The aim of this study was to compare the efficiency of CHROMagar, PCR-restriction fragment length polymorphism (PCR-RFLP), and PCR-fragment size polymorphism (PCR-FSP) assays in the identification of Candida species to determine the benefits and limitations of these methods. This study was conducted on 107 Candida strains, including 20 standard strains and 87 clinical isolates. The identification of the isolates was accomplished by using CHROMagar as a conventional method. The PCR-RFLP assay was performed on the entire internal transcribed spacer (ITS) region of ribosomal DNA (rDNA), and the consequent enzymatic digestion was compared with PCR-FSP results in which ITS1 and ITS2 regions were separately PCR amplified. In both molecular assays, yeast identification was carried out through the specific electrophoretic profiles of the PCR products. According to the results, the utilization of CHROMagar resulted in the identification of 29 (33.3%) Candida isolates, while the PCR-RFLP and PCR-FSP facilitated the identification of 83 (95.4%) and 80 (91.9%) clinical isolates, respectively. The obtained concordances between CHROMagar and PCR-RFLP, between CHROMagar and PCR-FSP, as well as between PCR-RFLP and PCR-FSP were 0.23, 0.20, and 0.77, respectively. The recognition of the benefits and limitations of PCR methods allows for the selection of the most efficient technique for a fast and correct differentiation. The PCR-RFLP and PCR-FSP assays had satisfactory concordance. The PCR-FSP provides a rapid, technically simple, and cost-effective method for the identification of Candida species

  7. Modulation of saturation and chain length of fatty acids in Saccharomyces cerevisiae for production of cocoa butter-like lipids.

    Science.gov (United States)

    Bergenholm, David; Gossing, Michael; Wei, Yongjun; Siewers, Verena; Nielsen, Jens

    2018-04-01

    Chain length and degree of saturation plays an important role for the characteristics of various products derived from fatty acids, such as fuels, cosmetics, and food additives. The seeds of Theobroma cacao are the source of cocoa butter, a natural lipid of high interest for the food and cosmetics industry. Cocoa butter is rich in saturated fatty acids that are stored in the form of triacylglycerides (TAGs). One of the major TAG species of cocoa butter, consisting of two stearic acid molecules and one oleic acid molecule (stearic acid-oleic acid-stearic acid, sn-SOS), is particularly rare in nature as the saturated fatty acid stearic acid is typically found only in low abundance. Demand for cocoa butter is increasing, yet T. cacao can only be cultivated in some parts of the tropics. Alternative means of production of cocoa butter lipids (CBLs) are, therefore, sought after. Yeasts also store fatty acids in the form of TAGs, but these are typically not rich in saturated fatty acids. To make yeast an attractive host for microbial production of CBLs, its fatty acid composition needs to be optimized. We engineered Saccharomyces cerevisiae yeast strains toward a modified fatty acid synthesis. Analysis of the fatty acid profile of the modified strains showed that the fatty acid content as well as the titers of saturated fatty acids and the titers of TAGs were increased. The relative content of potential CBLs in the TAG pool reached up to 22% in our engineered strains, which is a 5.8-fold increase over the wild-type. SOS content reached a level of 9.8% in our engineered strains, which is a 48-fold increase over the wild type. © 2018 Wiley Periodicals, Inc.

  8. The conversion of BTEX compounds by single and defined mixed cultures to medium-chain-length polyhydroxyalkanoate.

    Science.gov (United States)

    Nikodinovic, Jasmina; Kenny, Shane T; Babu, Ramesh P; Woods, Trevor; Blau, Werner J; O'Connor, Kevin E

    2008-09-01

    Here, we report the use of petrochemical aromatic hydrocarbons as a feedstock for the biotechnological conversion into valuable biodegradable plastic polymers--polyhydroxyalkanoates (PHAs). We assessed the ability of the known Pseudomonas putida species that are able to utilize benzene, toluene, ethylbenzene, p-xylene (BTEX) compounds as a sole carbon and energy source for their ability to produce PHA from the single substrates. P. putida F1 is able to accumulate medium-chain-length (mcl) PHA when supplied with toluene, benzene, or ethylbenzene. P. putida mt-2 accumulates mcl-PHA when supplied with toluene or p-xylene. The highest level of PHA accumulated by cultures in shake flask was 26% cell dry weight for P. putida mt-2 supplied with p-xylene. A synthetic mixture of benzene, toluene, ethylbenzene, p-xylene, and styrene (BTEXS) which mimics the aromatic fraction of mixed plastic pyrolysis oil was supplied to a defined mixed culture of P. putida F1, mt-2, and CA-3 in the shake flasks and fermentation experiments. PHA was accumulated to 24% and to 36% of the cell dry weight of the shake flask and fermentation grown cultures respectively. In addition a three-fold higher cell density was achieved with the mixed culture grown in the bioreactor compared to shake flask experiments. A run in the 5-l fermentor resulted in the utilization of 59.6 g (67.5 ml) of the BTEXS mixture and the production of 6 g of mcl-PHA. The monomer composition of PHA accumulated by the mixed culture was the same as that accumulated by single strains supplied with single substrates with 3-hydroxydecanoic acid occurring as the predominant monomer. The purified polymer was partially crystalline with an average molecular weight of 86.9 kDa. It has a thermal degradation temperature of 350 degrees C and a glass transition temperature of -48.5 degrees C.

  9. Manipulating the morphology and textural property of γ-AlOOH by modulating the alkyl chain length of cation in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Zhe, E-mail: tangzhe1983@163.com; Hu, Xiaofu, E-mail: hjj19850922@126.cn; Liang, Jilei, E-mail: liang.jilei_ttplan@126.com; Zhao, Jinchong, E-mail: Dr.zhaojc@gmail.com; Liu, Yunqi, E-mail: liuyq@upc.edu.cn; Liu, Chenguang, E-mail: cgliu@upc.edu.cn

    2013-06-01

    Graphical abstract: - Highlights: • γ-AlOOH was the only product in all experiments. • Different morphology of γ-AlOOH was obtained according to the alkyl chain length. • The textural property of γ-AlOOH was changed according to the alkyl chain length. • The possible formation mechanisms for hollow sphere and microflower were proposed. - Abstract: We demonstrated that the morphology and textural property of γ-AlOOH can be tuned by modulating the alkyl chain length of cation in [C{sub n}mim]{sup +}Cl{sup −} (n = 4, 8, 16). Using the short alkyl chain length-based [C{sub 4}mim]{sup +}Cl{sup −} as the structure-directed reagent, the morphology of γ-AlOOH was not changed and preserved as the hollow sphere structure in all experiments. The specific area and the number of small meso-pores of γ-AlOOH increased with the increase of [C{sub 4}mim]{sup +}Cl{sup −} dosage. While, using the larger alkyl chain length-based ionic liquids as the soft-template, such as [C{sub 8}mim]{sup +}Cl{sup −} and [C{sub 16}mim]{sup +}Cl{sup −}, the morphologies of γ-AlOOH were changed from initiative hollow spheres into the final microflowers. The specific areas of γ-AlOOH firstly increased then decreased with the increase of their dosage. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and Transmission Electron Microscopy (TEM). Furthermore, the possible formation mechanisms of γ-AlOOH have been proposed.

  10. Hydrogen isotope ratios of terrestrial leaf wax n-alkanes from the Tibetan Plateau: Controls on apparent enrichment factors, effect of vapor sources and implication for altimetry

    Science.gov (United States)

    Zhang, Xiaolong; Xu, Baiqing; Günther, Franziska; Mügler, Ines; Lange, Markus; Zhao, Huabiao; Li, Jiule; Gleixner, Gerd

    2017-08-01

    Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large

  11. Digestibilidade determinada pelo método indireto usando o n-alcano C35 Digestibility determinate by indirect method using C35 n-alkane

    Directory of Open Access Journals (Sweden)

    Dimas Estrásulas de Oliveira

    2000-06-01

    Full Text Available Foi feito um trabalho de extração e análise de n-alcanos com o objetivo de investigar o uso do n-alcano (C35 presente nas forragens como um indicador interno para determinação de digestibilidade. Foram utilizadas amostras de experimentos de digestibilidade convencional realizados previamente entre os anos de 1978 e 1982. O C35 subestimou as digestibilidades da matéria seca e orgânica, apresentando diferença média, em relação ao método in vivo, de 4,68 (± 0,69 e 4,43 (± 0,85 unidades percentuais, respectivamente. O coeficiente de regressão não diferiu da unidade, indicando que os métodos foram equivalentes, havendo, porém, a necessidade de um fator de correção. Os coeficientes de correlação para a matéria seca e orgânica, observados entre os dois métodos, foram 0,87 e 0,85, respectivamente. O C35 apresentou recuperação fecal média de 91,76% (± 7,94, que contribuiu para o vício da técnica.An experiment was conducted, on extraction and analysis of n-alkanes, to investigate the use of n-alkane (C35 present in forages as an internal marker for the digestibility determination. Samples of forages and feces were taken from conventional digestibility trials, which were previous conducted from 1978 to 1982. The C35 underestimated the dry matter and organic matter digestibilities, presenting an average difference in relation to in vivo of 4.68 (± 0.69 and 4,43 (± 0.85 perceptual units, respectively. The coefficient of regression did not differ from the unit, indicating that both methods were equivalent, having, however, the necessity of a correction factor. The coefficients of correlation observed for the dry and organic matter between the two methods were 0.87 and 0.85, respectively. The average fecal recovery of C35 was 91.76% (± 7.94, and this contributed to the bias of the method.

  12. Overexpression of O-polysaccharide chain length regulators in Gram-negative bacteria using the Wzx-/Wzy-dependent pathway enhances production of defined modal length O-polysaccharide polymers for use as haptens in glycoconjugate vaccines.

    Science.gov (United States)

    Hegerle, N; Bose, J; Ramachandran, G; Galen, J E; Levine, M M; Simon, R; Tennant, S M

    2018-03-30

    O-polysaccharide (OPS) molecules are protective antigens for several bacterial pathogens, and have broad utility as components of glycoconjugate vaccines. Variability in the OPS chain length is one obstacle towards further development of these vaccines. Introduction of sizing steps during purification of OPS molecules of suboptimal or of mixed lengths introduces additional costs and complexity while decreasing the final yield. The overall goal of this study was to demonstrate the utility of engineering Gram-negative bacteria to produce homogenous O-polysaccharide populations that can be used as the basis of carbohydrate vaccines by overexpressing O-polysaccharide chain length regulators of the Wzx-/Wzy-dependent pathway. The O-polysaccharide chain length regulators wzzB and fepE from Salmonella Typhimurium I77 and wzz2 from Pseudomonas aeruginosa PAO1 were cloned and expressed in the homologous organism or in other Gram-negative bacteria. Overexpression of these Wzz proteins in the homologous organism significantly increased the proportion of long or very long chain O-polysaccharides. The same observation was made when wzzB was overexpressed in Salmonella Paratyphi A and Shigella flexneri, and wzz2 was overexpressed in two other strains of P. aeruginosa. Overexpression of Wzz proteins in Gram-negative bacteria using the Wzx/Wzy-dependant pathway for lipopolysaccharide synthesis provides a genetic method to increase the production of an O-polysaccharide population of a defined size. The methods presented herein represent a cost-effective and improved strategy for isolating preferred OPS vaccine haptens, and could facilitate the further use of O-polysaccharides in glycoconjugate vaccine development. © 2018 The Society for Applied Microbiology.

  13. Surface tension of droplets and Tolman lengths of real substances and mixtures from density functional theory

    Science.gov (United States)

    Rehner, Philipp; Gross, Joachim

    2018-04-01

    The curvature dependence of interfacial properties has been discussed extensively over the last decades. After Tolman published his work on the effect of droplet size on surface tension, where he introduced the interfacial property now known as Tolman length, several studies were performed with varying results. In recent years, however, some consensus has been reached about the sign and magnitude of the Tolman length of simple model fluids. In this work, we re-examine Tolman's equation and how it relates the Tolman length to the surface tension and we apply non-local classical density functional theory (DFT) based on the perturbed chain statistical associating fluid theory (PC-SAFT) to characterize the curvature dependence of the surface tension of real fluids as well as mixtures. In order to obtain a simple expression for the surface tension, we use a first-order expansion of the Tolman length as a function of droplet radius Rs, as δ(Rs) = δ0 + δ1/Rs, and subsequently expand Tolman's integral equation for the surface tension, whereby a second-order expansion is found to give excellent agreement with the DFT result. The radius-dependence of the surface tension of increasingly non-spherical substances is studied for n-alkanes, up to icosane. The infinite diameter Tolman length is approximately δ0 = -0.38 Å at low temperatures. For more strongly non-spherical substances and for temperatures approaching the critical point, however, the infinite diameter Tolman lengths δ0 turn positive. For mixtures, even if they contain similar molecules, the extrapolated Tolman length behaves strongly non-ideal, implying a qualitative change of the curvature behavior of the surface tension of the mixture.

  14. Effect of surfactant alkyl chain length on the dispersion, and thermal and dynamic mechanical properties of LDPE/organo-LDH composites

    Directory of Open Access Journals (Sweden)

    2011-05-01

    Full Text Available Low density polyethylene/layered double hydroxide (LDH composites were prepared via melt compounding using different kinds of organo-LDHs and polyethylene-grafted maleic anhydride as the compatibilizer. The organo-LDHs were successfully prepared by converting a commercial MgAl-carbonate LDH into a MgAl-nitrate LDH, which was later modified by anion exchange with linear and branched sodium alkyl sulfates having different alkyl chain lengths (nc = 6, 12 and 20. It was observed that, depending on the size of the surfactant alkyl chain, different degrees of polymer chain intercalation were achieved, which is a function of the interlayer distance of the organo-LDHs, of the packing level of the alkyl chains, and of the different interaction levels between the surfactant and the polymer chains. In particular, when the number of carbon atoms of the surfactant alkyl chain is larger than 12, the intercalation of polymer chains in the interlayer space and depression of the formation of large aggregates of organo-LDH platelets are favored. A remarkable improvement of the thermal-oxidative degradation was evidenced for all of the composites; whereas only a slight increase of the crystallization temperature and no significant changes of both melting temperature and degree of crystallinity were achieved. By thermodynamic mechanical analysis, it was evidenced that a softening of the matrix is may be due to the plasticizing effect of the surfactant.

  15. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    Science.gov (United States)

    Huo, Lixia; Du, Pengcheng; Zhou, Hui; Zhang, Kaifeng; Liu, Peng

    2017-02-01

    It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C6, C12, or C18) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (Ra) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al2O3 ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C12 alkyl chain (C12-SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C12-SAM with desirable alkyl chain length.

  16. Effects of alkyl chain length and substituent pattern of fullerene bis-adducts on film structures and photovoltaic properties of bulk heterojunction solar cells.

    Science.gov (United States)

    Tao, Ran; Umeyama, Tomokazu; Kurotobi, Kei; Imahori, Hiroshi

    2014-10-08

    A series of alkoxycarbonyl-substituted dihydronaphthyl-based [60]fullerene bis-adduct derivatives (denoted as C2BA, C4BA, and C6BA with the alkyl chain of ethyl, n-butyl, and n-hexyl, respectively) have been synthesized to investigate the effects of alkyl chain length and substituent pattern of fullerene bis-adducts on the film structures and photovoltaic properties of bulk heterojunction polymer solar cells. The shorter alkyl chain length caused lower solubility of the fullerene bis-adducts (C6BA > C4BA > C2BA), thereby resulting in the increased separation difficulty of respective bis-adduct isomers. The device performance based on poly(3-hexylthiophene) (P3HT) and the fullerene bis-adduct regioisomer mixtures was enhanced by shortening the alkyl chain length. When using the regioisomerically separated fullerene bis-adducts, the devices based on trans-2 and a mixture of trans-4 and e of C4BA exhibited the highest power conversion efficiencies of ca. 2.4%, which are considerably higher than those of the C6BA counterparts (ca. 1.4%) and the C4BA regioisomer mixture (1.10%). The film morphologies as well as electron mobilities of the P3HT:bis-adduct blend films were found to affect the photovoltaic properties considerably. These results reveal that the alkyl chain length and substituent pattern of fullerene bis-adducts significantly influence the photovoltaic properties as well as the film structures of bulk heterojunction solar cells.

  17. Probing the Differential Tissue Distribution and Bioaccumulation Behavior of Per- and Polyfluoroalkyl Substances of Varying Chain-Lengths, Isomeric Structures and Functional Groups in Crucian Carp.

    Science.gov (United States)

    Shi, Yali; Vestergren, Robin; Nost, Therese Haugdahl; Zhou, Zhen; Cai, Yaqi

    2018-04-17

    Understanding the bioaccumulation mechanisms of per- and polyfluoroalkyl substances (PFASs) across different chain-lengths, isomers and functional groups represents a monumental scientific challenge with implications for chemical regulation. Here, we investigate how the differential tissue distribution and bioaccumulation behavior of 25 PFASs in crucian carp from two field sites impacted by point sources can provide information about the processes governing uptake, distribution and elimination of PFASs. Median tissue/blood ratios (TBRs) were consistently 90% of the amount of PFASs in the organism. Principal component analyses of TBRs and RBBs showed that the functional group was a relatively more important predictor of internal distribution than chain-length for PFASs. Whole body bioaccumulation factors (BAFs) for short-chain PFASs deviated from the positive relationship with hydrophobicity observed for longer-chain homologues. Overall, our results suggest that TBR, RBB, and BAF patterns were most consistent with protein binding mechanisms although partitioning to phospholipids may contribute to the accumulation of long-chain PFASs in specific tissues.

  18. Effect of stereochemistry, chain length and sequence pattern on antimicrobial properties of short synthetic β-sheet forming peptide amphiphiles.

    Science.gov (United States)

    Ong, Zhan Yuin; Cheng, Junchi; Huang, Yuan; Xu, Kaijin; Ji, Zhongkang; Fan, Weimin; Yang, Yi Yan

    2014-01-01

    In the face of mounting global antibiotics resistance, the identification and development of membrane-active antimicrobial peptides (AMPs) as an alternative class of antimicrobial agent have gained significant attention. The physical perturbation and disruption of microbial membranes by the AMPs have been proposed to be an effective means to overcome conventional mechanisms of drug resistance. Recently, we have reported the design of a series of short synthetic β-sheet folding peptide amphiphiles comprised of recurring (X1Y1X2Y2)n-NH2 sequences where X: hydrophobic amino acids, Y: cationic amino acids and n: number of repeat units. In efforts to investigate the effects of key parameters including stereochemistry, chain length and sequence pattern on antimicrobial effects, systematic d-amino acid substitutions of the lead peptides (IRIK)2-NH2 (IK8-all L) and (IRVK)3-NH2 (IK12-all L) were performed. It was found that the corresponding D-enantiomers exhibited stronger antimicrobial activities with minimal or no change in hemolytic activities, hence translating very high selectivity indices of 407.0 and >9.8 for IK8-all D and IK12-all D respectively. IK8-all D was also demonstrated to be stable to degradation by broad spectrum proteases trypsin and proteinase K. The membrane disrupting bactericidal properties of IK8-all D effectively prevented drug resistance development and inhibited the growth of various clinically isolated MRSA, VRE, Acinetobacter baumanni, Pseudomonas aeruginosa, Cryptococcus. neoformans and Mycobacterium tuberculosis. Significant reduction in intracellular bacteria counts was also observed following treatment with IK8-all D in the Staphylococcus. aureus infected mouse macrophage cell line RAW264.7 (P < 0.01). These results suggest that the d-amino acids substituted β-sheet forming peptide IK8-all D with its enhanced antimicrobial activities and improved protease stability, is a promising therapeutic candidate with potential to combat

  19. An instrument for the examination of nucleation from solution and its applications to the study of precipitation from diesel fuels and solutions of n-alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Gerson, A R; Roberts, K J; Sherwood, J N [Strathclyde Univ., Glasgow (UK). Dept. of Pure and Applied Chemistry

    1991-03-01

    An automated apparatus has been designed and constructed to measure precipitation and dissolution of solids from solution at varying automatically predetermined rates of heating and cooling. The appearance and disappearance of crystals are detected by means of a fibre optic turbidity sensor attached to a Sybron/Brinkman colorimeter. Temperature is measured by a Pt resistance thermometer attached to a constant current source. Both of these measurements are recorded by a personal computer via an analog to digital converter. The temperature of the system and its variation is controlled from the personal computer via a digital to analog interface attached to the control head of a Haake F3Q cryostat. The system has been used for measurements of precipitation and dissolution temperatures for diesel waxes with and without nucleation additives. Studies have been made of the nucleation of a single n-alkane from solution. From these measurements, saturation curves, orders of reactions, interfacial tensions and the critical radii of nuclei can be assessed. (orig.).

  20. Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

    Science.gov (United States)

    Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei

    2017-05-01

    All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr3 nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr3 NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr3 NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55-80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr3 NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr3 NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the product synthesized in the presence of oleylamine (OLAm), but only flat nanoplates are observed in the products in the presence of OTAm at 120 °C. The results indicate that the lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr3 NCs. This work opens up an alternative approach to controllable-synthesis of perovskite NCs through varying the carbon chain length of organic surfactants, and enlightens

  1. Effects of molecular and lattice structure on the thermal behaviours of some long chain length potassium(I) n-alkanoates

    Science.gov (United States)

    Nelson, Peter N.; Ellis, Henry A.; Taylor, Richard A.

    2014-01-01

    Lattice structures and thermal behaviours for some long chain potassium carboxylates (nc = 8-18, inclusive) are investigated using Fourier Transform Infrared spectroscopy, X-ray Powder Diffraction, Solid State spin decoupled 13C NMR spectroscopy, Differential Scanning Calorimetry and Thermogravimetry. The measurements show that the carboxyl groups are coordinated to potassium atoms via asymmetric chelating bidentate bonding, with extensive carboxyl intermolecular interactions to yield tetrahedral metal centers, irrespective of chain length. Furthermore, the hydrocarbon chains are crystallized in the fully extended all-trans configuration and are arranged as non-overlapping lamellar bilayer structures with closely packed methyl groups from opposite layers. Additionally, odd-even alternation, observed in density and methyl group chemical shift, is ascribed to the relative vertical distances between layers in the bilayer, that are not in the same plane. Therefore, for even chain homologues, where this distances is less than for odd chain adducts, more intimate packing is indicated. The phase sequences for all compounds show several reversible crystal-crystal transition associated with kinetically controlled gauche-trans isomerism of the polymethylene chains which undergo incomplete fusion when heated to the melt. The compounds degrade above 785 K to yield carbon dioxide, water, potassium oxide and an alkene.

  2. The critical main-chain length for helix formation in water: determined in a peptide series with alternating Aib and Ala residues exclusively and detected with ECD spectroscopy.

    Science.gov (United States)

    Longo, Edoardo; Moretto, Alessandro; Formaggio, Fernando; Toniolo, Claudio

    2011-10-01

    Critical main-chain length for peptide helix formation in the crystal (solid) state and in organic solvents has been already reported. In this short communication, we describe our results aiming at assessing the aforementioned parameter in water solution. To this goal, we synthesized step-by-step by solution procedures a complete series of N-terminally acetylated, C-terminally methoxylated oligopeptides, characterized only by alternating Aib and Ala residues, from the dimer to the nonamer level. All these compounds were investigated by electronic circular dichroism in the far-UV region in water solution as a function of chemical structure, namely presence/absence of an ester moiety or a negative charge at the C-terminus, and temperature. We find that the critical main-chain lengths for 3(10)- and α-helices, although still formed to a limited extent, in aqueous solution are six and eight residues, respectively. © 2011 Wiley-Liss, Inc.

  3. Synthesis and characterization of novel side-chain liquid crystalline polycarbonates, 4 - Synthesis of side-chain liquid crystalline polycarbonates with mesogenic groups having tails of different lengths

    NARCIS (Netherlands)

    Jansen, J.C.; Addink, R.; Nijenhuis, K.T.; Mijs, W.J.

    1999-01-01

    Side-chain liquid crystalline polycarbonates with alkoxyphenylbenzoate side groups, having a short spacer and tails ranging from 1 to 8 C-atoms, were synthesized. The polymers were prepared by an organo-zinc catalysed copolymerization of carbon dioxide and mesogenic 4-alkoxyphenyl

  4. Synthesis and characterization of novel side-chain liquid crystalline polycarbonates, 5 - Mesophase characterization of side-chain liquid crystalline polycarbonates with tails of different lengths

    NARCIS (Netherlands)

    Jansen, J.C.; Addink, R.; Nijenhuis, K.T.; Mijs, W.J.

    1999-01-01

    The mesomorphic properties and thermal stability of side-chain LC polycarbonates with alkoxyphenyl benzoate side groups having a short spacer and alkoxy tails ranging from 1 to 8 carbon atoms were studied by DSC, X-ray diffraction and polarized light optical microscopy. All polymers have a smectic A

  5. Studies on the solvation dynamics of coumarin 153 in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: dependence on alkyl chain length.

    Science.gov (United States)

    Das, Sudhir Kumar; Sarkar, Moloy

    2012-08-06

    Steady-state and time-resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1-ethyl-3-methylimidazolium alkylsulfate ([C(2)mim][C(n)OSO(3)]) ionic liquids differing only in the length of the linear alkyl chain (n = 4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady-state absorption and emission maxima of C153 on going from the C(4)OSO(3) to the C(8)OSO(3) system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time-zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes-Einstein-Debye (SED), Gierer-Wirtz (GW), and Dote-Kivelson-Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of the Alkyl Chain Length Incorporated into Donor Part on the Optoelectronic Properties of the Carbazole Based Dyes: Theoretical Study

    Directory of Open Access Journals (Sweden)

    Souad El Mzioui

    2017-12-01

    Full Text Available In this paper, we report a theoretical study using density functional theory (DFT and time-dependent (TD-DFT for R-D-π-A systems with various alkyl chains (R. Results show that the LUMO of the dye lies above the semiconductor conduction band, promoting the injection of electrons; the lower HOMO level promotes dye regeneration. The incorporation of methyl chain (CH3 has a significant reduction in the gap energy, improved red-shift absorption spectrum and increase the molar extinction coefficient at the maximum absorption wavelength compared to D. While, the increase in alkyl chain length from C2H5 to C6H13 present a relatively reduce of gap energies, low effect on the wavelength (438 nm and converged excitation energies. DOI: http://dx.doi.org/10.17807/orbital.v9i5.1003 

  7. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

    Science.gov (United States)

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

    2016-04-14

    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

  8. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    International Nuclear Information System (INIS)

    Oeiras, R. Y.; Silva, E. Z. da

    2014-01-01

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed π-bond (MpB) model describes unsaturated carbons that introduce a mobile π-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials

  9. Equivalent chain lengths of all C4-C23 saturated monomethyl branched fatty acid methyl esters on methylsilicone OV-1 stationary phase.

    Science.gov (United States)

    Kubinec, Róbert; Blaško, Jaroslav; Górová, Renáta; Addová, Gabriela; Ostrovský, Ivan; Amann, Anton; Soják, Ladislav

    2011-04-01

    Isomer mixtures of monomethyl branched saturated C7-C23 fatty acid methyl esters (FAME) were prepared by performing a methylene insertion reaction to the straight chain FAME and this study model was completed by using commercially available standards of C4-C7 FAME. The equivalent chain lengths (ECL) of all 220 C4-C23 monomethyl branched FAME on OV-1 stationary phase were measured, achieving an average repeatability of ±0.0004 ECL units. The monomethyl branched FAME was identified by GC on the basis of regularity of the fractional chain lengths (FCL) dependence on the number of carbon atoms (C(z)) of individual homologous series of methyl 2-, 3-, …, 21-FAME. The prediction of retention of the first homologues, having the new position of methyl group beginning at higher carbon atoms number, and analogously for the second, third, fourth, and other members of the homologous series, allowed the dependence FCL=f(C(z)) for the first and subsequent members of beginning homologous of monomethyl derivatives of FAME. The identification was confirmed by mass spectrometry. All of the methyl isomers of FAME, which could not be completely separated by gas chromatography due to having a methyl group in surroundings of the middle of the carbon chain, were resolved by mass spectrometry using deconvolution in a SIM-mode. Measured gas chromatographic and mass spectrometric data were applied for identification of the monomethyl branched saturated FAME in tongue coating. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Is DNA a worm-like chain in Couette flow? In search of persistence length, a critical review.

    Science.gov (United States)

    Rittman, Martyn; Gilroy, Emma; Koohya, Hashem; Rodger, Alison; Richards, Adair

    2009-01-01

    Persistence length is the foremost measure of DNA flexibility. Its origins lie in polymer theory which was adapted for DNA following the determination of BDNA structure in 1953. There is no single definition of persistence length used, and the links between published definitions are based on assumptions which may, or may not be, clearly stated. DNA flexibility is affected by local ionic strength, solvent environment, bound ligands and intrinsic sequence-dependent flexibility. This article is a review of persistence length providing a mathematical treatment of the relationships between four definitions of persistence length, including: correlation, Kuhn length, bending, and curvature. Persistence length has been measured using various microscopy, force extension and solution methods such as linear dichroism and transient electric birefringence. For each experimental method a model of DNA is required to interpret the data. The importance of understanding the underlying models, along with the assumptions required by each definition to determine a value of persistence length, is highlighted for linear dichroism data, where it transpires that no model is currently available for long DNA or medium to high shear rate experiments.

  11. Nighttime oxidation of surfactants at the air-water interface: effects of chain length, head group and saturation

    Science.gov (United States)

    Sebastiani, Federica; Campbell, Richard A.; Rastogi, Kunal; Pfrang, Christian

    2018-03-01

    Reactions of the key atmospheric nighttime oxidant NO3 with organic monolayers at the air-water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO3 at the air-water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8±0.7) × 10-8, (2.4±0.5) × 10-8and (3.3±0.6) × 10-8 cm2 molecule-1 s-1 for fitted initial desorption lifetimes of NO3 at the closely packed organic monolayers, τd, NO3, 1, of 8.1±4.0, 16±4.0 and 8.1±3.0 ns, respectively. The approximately doubled desorption lifetime found in the best fit for POA compared to OA and MO is consistent with a more accessible double bond associated with the shorter alkyl chain of POA facilitating initial NO3 attack at the double bond in a closely packed monolayer. The corresponding uptake coefficients for OA, POA and MO were found to be (2.1±0.5) × 10-3, (1.7±0.3) × 10-3 and (2.1±0.4) × 10-3, respectively. For the much slower NO3-initiated oxidation of the saturated surfactant SA we estimated a loss rate of approximately (5±1) × 10-12 cm2 molecule-1 s-1, which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of ca. (5±1) × 10-7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air-water interface during nighttime given its reactivity is ca. 2 orders of magnitude higher than that of O3. Furthermore, the relative contributions of NO3 and O3 to the oxidative

  12. Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

    Directory of Open Access Journals (Sweden)

    F. Sebastiani

    2018-03-01

    Full Text Available Reactions of the key atmospheric nighttime oxidant NO3 with organic monolayers at the air–water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA, palmitoleic acid (POA, methyl oleate (MO and stearic acid (SA to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR to determine the reaction kinetics of organic monolayers with NO3 at the air–water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8±0.7 × 10−8, (2.4±0.5 × 10−8and (3.3±0.6 × 10−8 cm2 molecule−1 s−1 for fitted initial desorption lifetimes of NO3 at the closely packed organic monolayers, τd, NO3, 1, of 8.1±4.0, 16±4.0 and 8.1±3.0 ns, respectively. The approximately doubled desorption lifetime found in the best fit for POA compared to OA and MO is consistent with a more accessible double bond associated with the shorter alkyl chain of POA facilitating initial NO3 attack at the double bond in a closely packed monolayer. The corresponding uptake coefficients for OA, POA and MO were found to be (2.1±0.5 × 10−3, (1.7±0.3 × 10−3 and (2.1±0.4 × 10−3, respectively. For the much slower NO3-initiated oxidation of the saturated surfactant SA we estimated a loss rate of approximately (5±1 × 10−12 cm2 molecule−1 s−1, which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of ca. (5±1 × 10−7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air–water interface during nighttime given its reactivity is ca. 2 orders of magnitude higher

  13. Critical determinant of intestinal permeability and oral bioavailability of pegylated all trans-retinoic acid prodrug-based nanomicelles: Chain length of poly (ethylene glycol) corona.

    Science.gov (United States)

    Li, Zhenbao; Han, Xiaopeng; Zhai, Yinglei; Lian, He; Zhang, Dong; Zhang, Wenjuan; Wang, Yongjun; He, Zhonggui; Liu, Zheng; Sun, Jin

    2015-06-01

    Pegylation method is widely used to prolong the blood circulation time of proteins and nanoparticles after intravenous administration, but the effect of surface poly (ethylene glycol) (PEG) chain length on oral absorption of the pegylated nanoparticles is poorly reported. The aim of our study was to investigate the influence of PEG corona chain length on membrane permeability and oral bioavailability of the amphiphilic pegylated prodrug-based nanomicelles, taking all trans-retinoic acid (ATRA) as a model drug. The amphiphilic ATRA-PEG conjugates were synthesized by esterification reaction between all trans-retinoic acid and mPEGs (mPEG500, mPEG1000, mPEG2000, and mPEG5000). The conjugates could self-assemble in aqueous medium to form nanomicelles by emulsion-solvent evaporation method. The resultant nanomicelles were in spherical shape with an average diameter of 13-20 nm. The drug loading efficiency of ATRA-PEG500, ATRA-PEG1000, ATRA-PEG2000, and ATRA-PEG5000 was about 38.4, 26.6, 13.1, and 5.68 wt%, respectively. With PEG chain length ranging from 500 to 5000, ATRA-PEG nanomicelles exhibited a bell shape of chemical stability in different pH buffers, intestinal homogenate and plasma. More importantly, they were all rapidly hydrolyzed into the parent drug in hepatic homogenate, with the half-time values being 0.3-0.4h. In comparison to ATRA solution and ATRA prodrug-based nanomicelles, ATRA-PEG1000 showed the highest intestinal permeability. After oral administration, ATRA-PEG2000 and ATRA-PEG5000 nanomicelles were not nearly absorbed, while the oral bioavailability of ATRA-PEG500 and ATRA-PEG1000 demonstrated about 1.2- and 2.0-fold higher than ATRA solution. Our results indicated that PEG1000 chain length of ATRA-PEG prodrug nanomicelles has the optimal oral bioavailability probably due to improved stability and balanced mucus penetration capability and cell binding, and that the PEG chain length on a surface of nanoparticles cannot exceed a key threshold with

  14. Hydrogen Apparent Fractionation between Precipitation and Leaf Wax n-Alkanes from Conifers and Deciduous Angiosperms along a Longitudinal Transect in Eurasia

    Science.gov (United States)

    Pedentchouk, Nikolai; Fisher, Katherine; Wagner, Thomas

    2010-05-01

    D/H composition of individual organic compounds derived from leaf wax may provide a wealth of information regarding plant-water relations in studies of plant ecology and climate change. Extracting that information from the organic D/H signal requires a thorough understanding of hydrogen isotope fractionation between environmental water and organic compounds. The purpose of this project is to investigate the importance of plant types and local climatic conditions on hydrogen apparent fractionation in higher terrestrial plants. We determined D/H composition of n-alkanes derived from leaf wax extracted from several extant plants representing common evergreen and deciduous conifer (Pinus and Larix) and deciduous angiosperm (Betula, Salix, and Sorbus) genera along a longitudinal transect from the UK to central Siberia at 10 different locations. These data were used to calculate the apparent fractionation factor (epsilon) between source water, estimated using the Online Isotopes in Precipitation Calculator, and n-alkanes. Our initial results show the following. First, we found large differences in the epsilon values among different genera at each location, e.g. Betula -63‰ vs. Salix -115‰ in Norwich, UK, and Betula -86‰ vs. Salix -146‰ in Novosibirsk, Russia. Assuming the plants at individual locations utilized soil water of very similar deltaD values, variations in the epsilon values are likely to be explained by differences in plant physiology and biochemistry. Second, we identified extensive shifts in the epsilon values in individual species along the transect from the UK to central Siberia, e.g. Betula -63‰ in Norwich vs. -104‰ in Zotino, Krasnoyarsk Krai, central Siberia and Salix -115‰ in Norwich vs. -164‰ in Sodankyla, Finland. With the exception of Sorbus, there is a positive relationship between the MAT (mean annual temperature) and epsilon values at locations above 2 °C MAT, suggesting a possible climatic effect on isotopic fractionation

  15. GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

    Directory of Open Access Journals (Sweden)

    X. Xu

    2003-01-01

    Full Text Available During the Mediterranean Intensive Oxidant Study (MINOS campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene to 43±36 pptv (toluene. The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and

  16. GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

    Science.gov (United States)

    Xu, X.; Williams, C.; Plass-Dülmer, H.; Berresheim, H.; Salisbury, G.; Lange, L.; Lelieveld, J.

    2003-09-01

    During the Mediterranean Intensive Oxidant Study (MINOS) campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC) at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene) to 43±36 pptv (toluene). The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH) and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and related data

  17. Ecological response to climate change and human activities indicated by n-alkane proxy during the mid- to late Holocene: a case study from an alpine lake

    Science.gov (United States)

    Zhang, C.; Zhao, C.

    2017-12-01

    Paleolimonological records provide long-term dynamics information of past climate, environment, human activities and ecological variations and give evolutionary perspectives to understand responses process of ecological shift to internal or external trigger. In this study, a powerful biomarkers, n-alkanes, was used to reconstruct the past 5000 years organic matter sources and ecological evolution history of Beilianchi Lake in the southwestern of Loess Plateau after preliminary investigation of modern samples. Climate-environment change and human activities were also traced by total organic matter (TOC), magnetic susceptibility (MS) and relevant proxies. The results showed that the ecosystem related to organic matter composition in Beilianchi Lake might be mainly controlled by climate change before 1400 cal B.P., whereas after that, it was significantly influenced by soil erosion induced by increasing population and enhanced human activities. Lake ecosystem experienced periodical change from relatively stable stage with combination of allochthonous-autochthonous organic sources prior to 1400 cal B.P. to extremely instability and final return to steady state with allochthonous-dominant organic source since 300 cal B.P.. During the period of instability, organic matter composition during 1400-800 cal B.P. indicated a obvious bimodal distribution based on probability density distribution analysis, which reflected the lake ecosystem might stay at bistable state and switched repeatedly from more-macrophytes state (regime A with low ACL) towards less-macrophytes state (regime B with high ACL) controlled by disturbance of soil erosion. The flickering during this period could serve as the early warning signal of transition towards more-macrophytes state or less-macrophytes state in lake ecosystems.

  18. Lipid membrane partitioning of lysolipids and fatty acids: Effects of membrane phase structure and detergent chain length

    DEFF Research Database (Denmark)

    Høyrup, Lise Pernille Kristine; Davidsen, Jesper; Jørgensen, Kent

    2001-01-01

    gel phase and at high temperatures in the disordered fluid phase of the phospholipid membrane vesicles. The long saturated acyl chains of the lysolipids and fatty acids varied from 10 to 16 carbon atoms and all titrations were performed below the critical micellar concentrations (cmc...... of magnitude higher when the saturated acyl chain of the detergents increases by two carbon atoms. The obtained partition coefficients are of importance in relation to a deeper understanding of the interplay between global aqueous and local membrane concentrations of the detergents and the functional influence...

  19. Novel extracellular medium-chain-length polyhydroxyalkanoate depolymerase from Streptomyces exfoliatus K10 DSMZ 41693

    DEFF Research Database (Denmark)

    Martinez, Virginia; de Santos, Patricia Gómez; García-Hidalgo, Javier

    2015-01-01

    reaction product. Markedly, PhaZSex2 is able to degrade functionalized polymers containing thioester groups in the side chain (PHACOS), releasing functional thioester-based monomers and oligomers demonstrating the potentiality of this novel biocatalyst for the industrial production of enantiopure (R)-3...

  20. Highly Grafted Polystyrene/polyvinylpyridine Polymer Gold Nanoparticles in a Good Solvent: Effects of Chain Length and Composition.

    Czech Academy of Sciences Publication Activity Database

    Posel, Zbyšek; Posocco, P.; Lísal, Martin; Fermeglia, M.; Pricl, S.

    2016-01-01

    Roč. 12, č. 15 (2016), s. 3600-3611 ISSN 1744-683X R&D Projects: GA ČR(CZ) GA13-02938S; GA MŠk LH12020 Institutional support: RVO:67985858 Keywords : block copolymers * chains * fiber optic sensors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.889, year: 2016

  1. Revisit complexation between DNA and polyethylenimine — Effect of length of free polycationic chains on gene transfection

    DEFF Research Database (Denmark)

    Yue, Yanan; Jin, Fan; Deng, Rui

    2011-01-01

    Our revisit of the complexation between DNA and polyethylenimine (PEI) by using a combination of laser light scattering and gel electrophoresis confirms that nearly all the DNA chains are complexed with PEI to form polyplexes when the molar ratio of nitrogen from PEI to phosphate from DNA (N:P) r...

  2. Influence of alkyl chain length and anion species on ionic liquid structure at the graphite interface as a function of applied potential

    International Nuclear Information System (INIS)

    Li, Hua; Wood, Ross J; Atkin, Rob; Endres, Frank

    2014-01-01

    Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain length and the anion species on ionic liquid (IL) interfacial structure at highly ordered pyrolytic graphite (HOPG) surfaces as a function of potential. Three ILs are examined: 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP), 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] TFSA). The step-wise force-distance profiles indicate the ILs adopt a multilayered morphology near the surface. When the surface is biased positively or negatively versus Pt quasireference electrode, both the number of steps, and the force required to rupture each step increase, indicating stronger interfacial structure. At all potentials, push-through forces for [HMIM] FAP are the highest, because the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed layers that resist the AFM tip. The most layers are observed for [EMIM] FAP, because the C 2 chains are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing. [EMIM] TFSA has the smallest push-through forces and fewest layers, and thus the weakest interfacial structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions are the strongest for [EMIM] TFSA and the weakest for [HMIM] FAP because the interfacial layers are better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which masks the weak attractive forces. (paper)

  3. Effects of Chain Length and Degree of Unsaturation of Fatty Acids on Structure and in Vitro Digestibility of Starch-Protein-Fatty Acid Complexes.

    Science.gov (United States)

    Zheng, Mengge; Chao, Chen; Yu, Jinglin; Copeland, Les; Wang, Shuo; Wang, Shujun

    2018-02-28

    The effects of chain length and degree of unsaturation of fatty acids (FAs) on structure and in vitro digestibility of starch-protein-FA complexes were investigated in model systems. Studies with the rapid visco analyzer (RVA) showed that the formation of ternary complex resulted in higher viscosities than those of binary complex during the cooling and holding stages. The results of differential scanning calorimetry (DSC), Raman, and X-ray diffraction (XRD) showed that the structural differences for ternary complexes were much less than those for binary complexes. Starch-protein-FA complexes presented lower in vitro enzymatic digestibility compared with starch-FAs complexes. We conclude that shorter chain and lower unsaturation FAs favor the formation of ternary complexes but decrease the thermal stability of these complexes. FAs had a smaller effect on the ordered structures of ternary complexes than on those of binary complexes and little effect on enzymatic digestibility of both binary and ternary complexes.

  4. Critical effects of alkyl chain length on fibril structures in benzene-trans(RR)- or (SS)-N,N'-alkanoyl-1,2-diaminocyclohexane gels.

    Science.gov (United States)

    Sato, Hisako; Nakae, Takahiro; Morimoto, Kazuya; Tamura, Kenji

    2012-02-28

    Vibrational circular dichroism (VCD) spectra were recorded on benzene-d(6) gels formed by chiral low molecular mass gelators (LMGs), trans(RR)- or trans(SS)-N,N'-alkanoyl-1,2-diaminocyclohexane (denoted by RR-C(n) or SS-C(n), respectively; n = the number of carbon atoms in an introduced alkanoyl group). Attention was focused on the effects of alkyl chain length on the structures of the gels. When n was changed from 6 to 12, the signs of the coupled peaks around 1550 cm(-1) in the VCD spectra, which were assigned to the symmetric and asymmetric C=O stretching vibrations from the higher to lower wavenumber, respectively, critically depended on the alkyl chain length. In the case of RR-C(n), for example, the signs of the couplet were plus and minus for n = 8, 9, 10 and 12, while the signs of the same couplet were reversed for n = 6 and 7. The conformations of LMGs in fibrils were determined by comparing the observed IR and VCD spectra with those calculated for a monomeric molecule. The observed reversal of signs in the C=O couplet was rationalized in terms of the different modes of hydrogen bonding. In the case of C(8), C(9), C(10) and C(12), gelator molecules were stacked with their cyclohexyl rings in parallel, forming double anti-parallel chains of intermolecular hydrogen bonds using two pairs of >NH and >C=O groups. In case of C(6) and C(7), gelator molecules were stacked through a single chain of intermolecular hydrogen bonds using a pair of >NH and >C=O groups. The remaining pair of >NH and >C=O groups formed an intramolecular hydrogen bond.

  5. Photo-Induced Phase Transitions to Liquid Crystal Phases: Influence of the Chain Length from C8E4 to C14E4

    Directory of Open Access Journals (Sweden)

    Simone Techert

    2009-09-01

    Full Text Available Photo-induced phase transitions are characterized by the transformation from phase A to phase B through the absorption of photons. We have investigated the mechanism of the photo-induced phase transitions of four different ternary systems CiE4/alkane (i with n = 8, 10, 12, 14; cyclohexane/H2O. We were interested in understanding the effect of chain length increase on the dynamics of transformation from the microemulsion phase to the liquid crystal phase. Applying light pump (pulse/x-ray probe (pulse techniques, we could demonstrate that entropy and diffusion control are the driving forces for the kind of phase transition investigated.

  6. Flow behaviour of inulin-milk beverages: Influence of inulin chain length and of milk fat content

    OpenAIRE

    Villegas, Beatriz; Costell, Elvira

    2003-01-01

    Inulin is used either as a macronutrient substitute or as a supplement added in foods mainly for its nutritional properties. Chemically, inulin consists of a long chain made up of fructose molecules and one glucose molecule at one end. The fructose molecules are connected by β-(2-1) bonds and the last fructose is linked with a glucose by an α-(1-2) bond as in sucrose [1, 2]. The average molecular weight and degree of polymerisation of inulin depend on the source of inulin, the time of harvest...

  7. Uso de N-alcanos na estimativa da composição botânica em amostras com diferentes proporções de Brachiaria brizantha e Arachis pintoi Use of N-alkanes for estimations of botanical composition in samples with different proportions of Brachiaria brizantha and Arachis pintoi

    Directory of Open Access Journals (Sweden)

    Cristiano Côrtes

    2005-10-01

    method and identified and quantified by the gas chromatography analysis. Alkane C34 was used as internal marker. The proportions of A. pintoi in the diets were estimated by the minimization of z (sum of the squares of the deviations between the real proportion of the analyzed alkanes and the pre-established proportions (treatments, using Duncan et al. (1999 equation. The prevalence of odd carbonic chains was detected. The total concentration of n-alkanes decreased as the proportion of A. pintoi increased in the mixtures. Good estimates of the botanical composition of the mixtures of A. pintoi with B. brizantha were obtained from the alkanes C29, C31, C33 and C35. The alkane C35 was fundamental for the quality of the estimates. The results indicate the great potential of the technique for studies of grazing animal diet.

  8. Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles.

    Science.gov (United States)

    Wang, Xue-Tong; Zhang, Yuan; Miao, Yi; Ma, Ling-Ling; Li, Yuan-Cheng; Chang, Yue-Ya; Wu, Ming-Hong

    2013-07-01

    Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C10 to C13 and chlorine content between 49 and 70%. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng g(-1), with a median of 9.6 ng g(-1). The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil-air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C13- and C11-congeners were predominant in most soils and C10- and C12-congeners dominated in the remaining soils. Cl7- and Cl8-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.

  9. Solute transport in a single fracture involving an arbitrary length decay chain with rock matrix comprising different geological layers.

    Science.gov (United States)

    Mahmoudzadeh, Batoul; Liu, Longcheng; Moreno, Luis; Neretnieks, Ivars

    2014-08-01

    A model is developed to describe solute transport and retention in fractured rocks. It accounts for advection along the fracture, molecular diffusion from the fracture to the rock matrix composed of several geological layers, adsorption on the fracture surface, adsorption in the rock matrix layers and radioactive decay-chains. The analytical solution, obtained for the Laplace-transformed concentration at the outlet of the flowing channel, can conveniently be transformed back to the time domain by the use of the de Hoog algorithm. This allows one to readily include it into a fracture network model or a channel network model to predict nuclide transport through channels in heterogeneous fractured media consisting of an arbitrary number of rock units with piecewise constant properties. More importantly, the simulations made in this study recommend that it is necessary to account for decay-chains and also rock matrix comprising at least two different geological layers, if justified, in safety and performance assessment of the repositories for spent nuclear fuel. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Critical Length Criterion and the Arc Chain Model for Calculating the Arcing Time of the Secondary Arc Related to AC Transmission Lines

    International Nuclear Information System (INIS)

    Cong Haoxi; Li Qingmin; Xing Jinyuan; Li Jinsong; Chen Qiang

    2015-01-01

    The prompt extinction of the secondary arc is critical to the single-phase reclosing of AC transmission lines, including half-wavelength power transmission lines. In this paper, a low-voltage physical experimental platform was established and the motion process of the secondary arc was recorded by a high-speed camera. It was found that the arcing time of the secondary arc rendered a close relationship with its arc length. Through the input and output power energy analysis of the secondary arc, a new critical length criterion for the arcing time was proposed. The arc chain model was then adopted to calculate the arcing time with both the traditional and the proposed critical length criteria, and the simulation results were compared with the experimental data. The study showed that the arcing time calculated from the new critical length criterion gave more accurate results, which can provide a reliable criterion in term of arcing time for modeling and simulation of the secondary arc related with power transmission lines. (paper)

  11. Effect of temperature and chain length on the viscosity and surface tension of binary systems of N,N-dimethylformamide with 1-octanol, 1-nonanol and 1-decanol

    International Nuclear Information System (INIS)

    Mohammad, Abubaker A.; Alkhaldi, Khaled H.A.E.; AlTuwaim, Mohammad S.; Al-Jimaz, Adel S.

    2014-01-01

    Highlights: • Effect of temperature and chain length on η and σ of DMF + 1-alkanol binary systems. • Viscosity and surface tension were obtained. • Δη, Δσ and G ∗E were calculated using the experimental data. • H σ and S σ were determined using the surface tension data. • Semi-empirical relations were used to estimate the viscosity of liquid mixtures. - Abstract: Viscosity and surface tension of binary systems of N,N-dimethylformamide DMF with higher 1-alkanols (C 8 –C 10 ) were measured at atmospheric pressure and four different temperatures over the entire range of mole fraction. The experimental measurements were used to calculate the deviations in viscosity and surface tension. Furthermore, the excess Gibbs free energy of activation, surface enthalpy and surface entropy of the (DMF + 1-alkanols) binary mixtures were determined. In addition, the deviation and excess properties were fitted to the method of Redlich–Kister (R–K) polynomial. Viscosity data of the binary systems were correlated with three different expressions (Grunberg and Nissan, the three-body, and four-body McAllister). The effects of the chain length of the higher 1-alkanols and temperature were investigated

  12. Individual Impact of Distinct Polysialic Acid Chain Lengths on the Cytotoxicity of Histone H1, H2A, H2B, H3 and H4

    Directory of Open Access Journals (Sweden)

    Kristina Zlatina

    2017-12-01

    Full Text Available Neutrophils are able to neutralize pathogens by phagocytosis, by the release of antimicrobial components, as well as by the formation of neutrophil extracellular traps (NETs. The latter possibility is a DNA-meshwork mainly consisting of highly concentrated extracellular histones, which are not only toxic for pathogens, but also for endogenous cells triggering several diseases. To reduce the negative outcomes initiated by extracellular histones, different approaches like antibodies against histones, proteases, and the polysaccharide polysialic acid (polySia were discussed. We examined whether each of the individual histones is a binding partner of polySia, and analyzed their respective cytotoxicity in the presence of this linear homopolymer. Interestingly, all of the histones (H1, H2A, H2B, H3, and H4 seem to interact with α2,8-linked sialic acids. However, we observed strong differences regarding the required chain length of polySia to bind histone H1, H2A, H2B, H3, and H4. Moreover, distinct degrees of polymerization were necessary to act as a cytoprotective agent in the presence of the individual histones. In sum, the outlined results described polySia-based strategies to bind and/or to reduce the cytotoxicity of individual histones using distinct polySia chain length settings.

  13. Effect of Acylglycerol Composition and Fatty Acyl Chain Length on Lipid Digestion in pH-Stat Digestion Model and Simulated In Vitro Digestion Model.

    Science.gov (United States)

    Qi, Jin F; Jia, Cai H; Shin, Jung A; Woo, Jeong M; Wang, Xiang Y; Park, Jong T; Hong, Soon T; Lee, K-T

    2016-02-01

    In this study, a pH-stat digestion model and a simulated in vitro digestion model were employed to evaluate the digestion degree of lipids depending on different acylglycerols and acyl chain length (that is, diacylglycerol [DAG] compared with soybean oil representing long-chain triacylglycerol compared with medium-chain triacylglycerol [MCT]). In the pH-stat digestion model, differences were observed among the digestion degrees of 3 oils using digestion rate (k), digestion half-time (t1/2 ), and digestion extent (Φmax). The results showed the digestion rate order was MCT > soybean oil > DAG. Accordingly, the order of digestion half-times was MCT digestion model, digestion rates (k') and digestion half-times (t'1/2 ) were also obtained and the results showed a digestion rate order of MCT (k' = 0.068 min(-1) ) > soybean oil (k' = 0.037 min(-1) ) > DAG (k' = 0.024 min(-1) ). Consequently, the order of digestion half-times was MCT (t'1/2 = 10.20 min) digested faster than soybean oil, and that soybean oil was digested faster than DAG. © 2015 Institute of Food Technologists®

  14. Diacyltransferase Activity and Chain Length Specificity of Mycobacterium tuberculosis PapA5 in the Synthesis of Alkyl β-Diol Lipids

    Energy Technology Data Exchange (ETDEWEB)

    Touchette, Megan H.; Bommineni, Gopal R.; Delle Bovi, Richard J.; Gadbery, John; Nicora, Carrie D.; Shukla, Anil K.; Kyle, Jennifer E.; Metz, Thomas O.; Martin, Dwight W.; Sampson, Nicole S.; Miller, W. T.; Tonge, Peter J.; Seeliger, Jessica C.

    2015-09-08

    Although classified as Gram-positive bacteria, Corynebacterineae possess an asymmetric outer membrane that imparts structural and thereby physiological similarity to more distantly related Gram-negative bacteria. Like lipopolysaccharide in Gram-negative bacteria, lipids in the outer membrane of Corynebacterineae have been associated with the virulence of pathogenic species such as Mycobacterium tuberculosis (Mtb). For example, Mtb strains that lack long, branched-chain alkyl esters known as dimycocerosates (DIMs) are significantly attenuated in model infections. The resultant interest in the biosynthetic pathway of these unusual virulence factors has led to the elucidation of many of the steps leading to the final esterification of the alkyl beta-diol, phthiocerol, with branched-chain fatty acids know as mycocerosates. PapA5 is an acyltransferase implicated in these final reactions. We here show that PapA5 is indeed the terminal enzyme in DIM biosynthesis by demonstrating its dual esterification activity and chain-length preference using synthetic alkyl beta-diol substrate analogues. Applying these analogues to a series of PapA5 mutants, we also revise a model for the substrate binding within PapA5. Finally, we demonstrate that the Mtb Ser/Thr kinase PknB modifies PapA5 on three Thr residues, including two (T196, T198) located on an unresolved loop. These results clarify the DIM biosynthetic pathway and suggest possible mechanisms by which DIM biosynthesis may be regulated by the post-translational modification of PapA5.

  15. Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2013-10-10

    Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

  16. Oligothiophene-Indandione-Linked Narrow-Band Gap Molecules: Impact of π-Conjugated Chain Length on Photovoltaic Performance.

    Science.gov (United States)

    Komiyama, Hideaki; To, Takahiro; Furukawa, Seiichi; Hidaka, Yu; Shin, Woong; Ichikawa, Takahiro; Arai, Ryota; Yasuda, Takuma

    2018-04-04

    Solution-processed organic solar cells (OSCs) based on narrow-band gap small molecules hold great promise as next-generation energy-converting devices. In this paper, we focus on a family of A-π-D-π-A-type small molecules, namely, BDT- nT-ID ( n = 1-4) oligomers, consisting of benzo[1,2- b:4,5- b']dithiophene (BDT) as the central electron-donating (D) core, 1,3-indandione (ID) as the terminal electron-accepting (A) units, and two regioregular oligo(3-hexylthiophene)s ( nT) with different numbers of thiophene rings as the π-bridging units, and elucidate their structure-property-function relationships. The effects of the length of the π-bridging nT units on the optical absorption, thermal behavior, morphology, hole mobility, and OSC performance were systematically investigated. All oligomers exhibited broad and intense visible photoabsorption in the 400-700 nm range. The photovoltaic performances of bulk heterojunction OSCs based on BDT- nT-IDs as donors and a fullerene derivative as an acceptor were studied. Among these oligomers, BDT-2T-ID, incorporating bithiophene as the π-bridging units, showed better photovoltaic performance with a maximum power conversion efficiency as high as 6.9% under AM 1.5G illumination without using solvent additives or postdeposition treatments. These favorable properties originated from the well-developed interpenetrating network morphology of BDT-2T-ID, with larger domain sizes in the photoactive layer. Even though all oligomers have the same A-D-A main backbone, structural modulation of the π-bridging nT length was found to impact their self-organization and nanostructure formation in the solid state, as well as the corresponding OSC device performance.

  17. Determination of locust bean gum and guar gum by polymerase chain reaction and restriction fragment length polymorphism analysis.

    Science.gov (United States)

    Meyer, K; Rosa, C; Hischenhuber, C; Meyer, R

    2001-01-01

    A polymerase chain reaction (PCR) was developed to differentiate the thickening agents locust bean gum (LBG) and the cheaper guar gum in finished food products. Universal primers for amplification of the intergenic spacer region between trnL 3' (UAA) exon and trnF (GAA) gene in the chloroplast (cp) genome and subsequent restriction analysis were applied to differentiate guar gum and LBG. The presence of guar gum powder added to LBG powder was detectable. Based on data obtained from sequencing this intergenic spacer region, a second PCR method for the specific detection of guar gum DNA was also developed. This assay detected guar gum powder in LBG in amounts as low as 1% (w/w). Both methods successfully detected guar gum and/or LBG in ice cream stabilizers and in foodstuffs, such as dairy products, ice cream, dry seasoning mixes, a finished roasting sauce, and a fruit jelly product, but not in products with highly degraded DNA, such as tomato ketchup and sterilized chocolate cream. Both methods detected guar gum and LBG in ice cream and fresh cheese at levels <0.1%.

  18. Enterococcus faecalis Responds to Individual Exogenous Fatty Acids Independently of Their Degree of Saturation or Chain Length.

    Science.gov (United States)

    Saito, Holly E; Harp, John R; Fozo, Elizabeth M

    2018-01-01

    Enterococcus faecalis is a commensal of the human gastrointestinal tract that can persist in the external environment and is a leading cause of hospital-acquired infections. Given its diverse habitats, the organism has developed numerous strategies to survive a multitude of environmental conditions. Previous studies have demonstrated that E. faecalis will incorporate fatty acids from bile and serum into its membrane, resulting in an induced tolerance to membrane-damaging agents. To discern whether all fatty acids induce membrane stress protection, we examined how E. faecalis responded to individually supplied fatty acids. E. faecalis readily incorporated fatty acids 14 to 18 carbons in length into its membrane but poorly incorporated fatty acids shorter or longer than this length. Supplementation with saturated fatty acids tended to increase generation time and lead to altered cellular morphology in most cases. Further, exogenously supplied saturated fatty acids did not induce tolerance to the membrane-damaging antibiotic daptomycin. Supplementation with unsaturated fatty acids produced variable growth effects, with some impacting generation time and morphology. Exogenously supplied unsaturated fatty acids that are normally produced by E. faecalis and those that are found in bile or serum could restore growth in the presence of a fatty acid biosynthetic inhibitor. However, only the eukaryote-derived fatty acids oleic acid and linoleic acid provided protection from daptomycin. Thus, exogenous fatty acids do not lead to a common physiological effect on E. faecalis The organism responds uniquely to each, and only host-derived fatty acids induce membrane protection. IMPORTANCE Enterococcus faecalis is a commonly acquired hospital infectious agent with resistance to many antibiotics, including those that target its cellular membrane. We previously demonstrated that E. faecalis will incorporate fatty acids found in human fluids, like serum, into its cellular membrane

  19. Production of medium-chain-length polyhydroxyalkanoate by Pseudomonas oleovorans grown in sugary cassava extract supplemented with andiroba oil

    Directory of Open Access Journals (Sweden)

    Diego Aires da Silva

    2014-12-01

    Full Text Available Pseudomonas oleovorans were grown on sugary cassava extracts supplemented with andiroba oil for the synthesis of a mediumchain- length polyhydroxyalkanoate (PHA MCL. The concentration of total sugars in the extract was approximately: 40 g/L in culture 1, 15 g/L in cultures 2 and 3, and 10 g/L in culture 4. Supplementation with 1% andiroba oil and 0.2 g/L of (NH42HPO4 was performed 6.5 hours after growth in culture 3, and supplementation with the same amount of andiroba oil and 2.4 g/L of (NH42HPO4 was performed at the beginning of growth in culture 4. The synthesis resulted mainly in 3-hydroxy-decanoate and 3-hydroxy-dodecanoate units; 3-hydroxy-butyrate, 3-hydroxy-hexanoate; and 3-hydroxy-octanoate monomers were also produced but in smaller proportions. P. oleovorans significantly accumulated PHA MCL in the deceleration phase of growth with an oxygen limitation but with sufficient nitrogen concentration to maintain cell growth. The sugary cassava extract supplemented with andiroba oil proved to be a potential substrate for PHA MCL production.

  20. Bimolecular encounters and re-encounters (cage effect) of a spin-labeled analogue of cholestane in a series of n-alkanes: effect of anisotropic exchange integral.

    Science.gov (United States)

    Vandenberg, Andrew D; Bales, Barney L; Salikhov, K M; Peric, Miroslav

    2012-12-27

    Electron paramagnetic resonance (EPR) spectra of the nitroxide spin probe 3β-doxyl-5α-cholestane (CSL) are studied as functions of the molar concentration, c, and the temperature, T, in a series of n-alkanes. The results are compared with a similar study of a much smaller spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDT). The Heisenberg spin exchange (HSE) rate constants, K(ex), of CSL are similar in hexane, octane, and decane and are about one-half of those for pDT in the same solvents. They are also about one-half of the Stokes-Einstein-Perrin prediction. This reduction in HSE efficiency is attributed to an effective steric factor, f(eff), which was evaluated by comparing the results with the Stokes-Einstein-Perrin prediction or with pDT, and it is equal to 0.49 ± 0.03, independent of temperature. The unpaired spin density in CSL is localized near one end of the long molecule, so the exchange integral, J, leading to HSE, is expected to be large in some collisions and small in others; thus, J is modeled by an ideal distribution of values of J = J(0) with probability f and J = 0 with probability (1 - f). Because of rotational and translation diffusion during contact and between re-encounters of the probe, the effective steric factor is predicted to be f(eff) = f(1/2). Estimating the fraction of the surface of CSL with rich spin density yields a theoretical estimate of f(eff) = 0.59 ± 0.08, in satisfactory agreement with experiment. HSE is well described by simple hydrodynamic theory, with only a small dependence on solvent-probe relative sizes at the same value of T/η, where η is the viscosity of the solvent. This result is probably due to a fortuitous interplay between long- and short-range effects that describe diffusion processes over relatively large distances. In contrast, dipole-dipole interactions (DD) as measured by the line broadening, B(dip), and the mean time between re-encounters within the cage, τ(RE), vary significantly

  1. Optimization of Water/Oil/Surfactant System for Preparation of Medium-Chain-Length Poly-3-Hydroxyalkanoates (mcl-PHA)-Incorporated Nanoparticles via Nanoemulsion Templating Technique.

    Science.gov (United States)

    Ishak, K A; Annuar, M Suffian M; Ahmad, N

    2017-12-01

    Polymeric nanoparticles gain a widespread interest in food and pharmaceutical industries as delivery systems that encapsulate, protect, and release lipophilic compounds such as omega-3 fatty acids, fat-soluble vitamins, carotenoids, carvedilol, cyclosporine, and ketoprofen. In this study, medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA)-incorporated nanoparticle was developed via facile organic solvent-free nanoemulsion templating technique. The water content (W/surfactant-to-oil (S/O)), S/O, and Cremophor EL-to-Span 80 (Cremo/Sp80) ratios were first optimized using response surface methodology (RSM) to obtain nanoemulsion template prior to incorporation of mcl-PHA. Their effects on nanoemulsion formation were investigated. The mcl-PHA-incorporated nanoparticle system showed a good preservation capability of β-carotene and extended storage stability.

  2. Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

    Directory of Open Access Journals (Sweden)

    Jignesh Lunagariya

    2017-07-01

    Full Text Available The non-ionic triblock copolymer, Pluronic® F127, has been selected to observe its interaction with ionic liquids (ILs in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC of F127 increased with the addition of ILs, which appeared logical since it increases the solubility of PPO (and PEO moiety, making it behaves more like a hydrophilic block copolymer that is micellized at a higher copolymer concentration. The results from DLS data showed good agreement with those obtained from the surface tension measurements. Upon the addition of ILs, the tendency in micellar size reduction was demonstrated by viscosity results, and therefore, intrinsic viscosity decreased compared to pure F127 in aqueous solution. The results were discussed as a function of alkyl chain length and anions of imidazolium based ILs.

  3. Identification of planorbids from Venezuela by polymerase chain reaction amplification and restriction fragment length polymorphism of internal transcriber spacer of the RNA ribosomal gene

    Directory of Open Access Journals (Sweden)

    Caldeira Roberta L

    2000-01-01

    Full Text Available Snails of the genus Biomphalaria from Venezuela were subjected to morphological assessment as well as polymerase chain reaction and restriction fragment length polymorphism (PCR-RFLP analysis. Morphological identification was carried out by comparison of characters of the shell and the male and female reproductive apparatus. The PCR-RFLP involved amplification of the internal spacer region ITS1 and ITS2 of the RNA ribosomal gene and subsequent digestion of this fragment by the restriction enzymes DdeI, MnlI, HaeIII and MspI. The planorbids were compared with snails of the same species and others reported from Venezuela and present in Brazil, Cuba and Mexico. All the enzymes showed a specific profile for each species, that of DdeI being the clearest. The snails were identified as B. glabrata, B. prona and B. kuhniana.

  4. Effects of PEG tethering chain length of vitamin E TPGS with a Herceptin-functionalized nanoparticle formulation for targeted delivery of anticancer drugs.

    Science.gov (United States)

    Zhao, Jing; Feng, Si-Shen

    2014-03-01

    Drug formulation by ligand conjugated nanoparticles of biodegradable polymers has become one of the most important strategies in drug targeting. We have developed in our previous work nanoparticles of a mixture of two vitamin E TPGS based copolymers PLA-TPGS and TPGS-TOOH with the latter for Herceptin conjugation for targeted delivery of anticancer drugs such as docetaxel to the cancer cells of human epidermal growth factor receptor 2 (HER2) overexpression. In this research, we investigated the effects of the PEG chain length in TPGS, which is in fact a PEGylated vitamin E, on the cellular uptake and cytotoxicity of the drug formulated in the Herceptin-conjugated nanoparticles of PLA-TPGS/TPGS-COOH blend (NPs). Such NPs of PEG1000, PEG2000, PEG3350 and PEG5000, i.e. the PEG of molecule weight 1000, 2000, 3350 and 5000, were prepared by the nanoprecipitation method and characterized for their size and size distribution, drug loading, surface morphology, surface charge and surface chemistry as well as in vitro drug release profile, cellular uptake and cytotoxicity. We found among such nanoparticles, those of PEG1000, i.e. of the shortest PEG tethering chain length, could result in the best therapeutic effects, which are 24.1%, 37.3%, 38.1% more efficient in cellular uptake and 68.1%, 90%, 92.6% lower in IC50 (thus higher in cytotoxicity) than the Herceptin-conjugated nanoparticles of PLA-TPGS/TPGS-COOH blend of PEG2000, PEG3350 and PEG5000 respectively in treatment of SK-BR-3 cancer cells which are of high HER2 overexpression. We provided a theoretical explanation from surface mechanics and thermodynamics for endocytosis of nanoparticles. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Crystal structure of heterodimeric hexaprenyl diphosphate synthase from Micrococcus luteus B-P 26 reveals that the small subunit is directly involved in the product chain length regulation.

    Science.gov (United States)

    Sasaki, Daisuke; Fujihashi, Masahiro; Okuyama, Naomi; Kobayashi, Yukiko; Noike, Motoyoshi; Koyama, Tanetoshi; Miki, Kunio

    2011-02-04

    Hexaprenyl diphosphate synthase from Micrococcus luteus B-P 26 (Ml-HexPPs) is a heterooligomeric type trans-prenyltransferase catalyzing consecutive head-to-tail condensations of three molecules of isopentenyl diphosphates (C(5)) on a farnesyl diphosphate (FPP; C(15)) to form an (all-E) hexaprenyl diphosphate (HexPP; C(30)). Ml-HexPPs is known to function as a heterodimer of two different subunits, small and large subunits called HexA and HexB, respectively. Compared with homooligomeric trans-prenyltransferases, the molecular mechanism of heterooligomeric trans-prenyltransferases is not yet clearly understood, particularly with respect to the role of the small subunits lacking the catalytic motifs conserved in most known trans-prenyltransferases. We have determined the crystal structure of Ml-HexPPs both in the substrate-free form and in complex with 7,11-dimethyl-2,6,10-dodecatrien-1-yl diphosphate ammonium salt (3-DesMe-FPP), an analog of FPP. The structure of HexB is composed of mostly antiparallel α-helices joined by connecting loops. Two aspartate-rich motifs (designated the first and second aspartate-rich motifs) and the other characteristic motifs in HexB are located around the diphosphate part of 3-DesMe-FPP. Despite the very low amino acid sequence identity and the distinct polypeptide chain lengths between HexA and HexB, the structure of HexA is quite similar to that of HexB. The aliphatic tail of 3-DesMe-FPP is accommodated in a large hydrophobic cleft starting from HexB and penetrating to the inside of HexA. These structural features suggest that HexB catalyzes the condensation reactions and that HexA is directly involved in the product chain length control in cooperation with HexB.

  6. Allelic sequence variations in the hypervariable region of a T-cell receptor β chain: Correlation with restriction fragment length polymorphism in human families and populations

    International Nuclear Information System (INIS)

    Robinson, M.A.

    1989-01-01

    Direct sequence analysis of the human T-cell antigen receptor (TCR) V β1 variable gene identified a single base-pair allelic variation (C/G) located within the coding region. This change results in substitution of a histidine (CAC) for a glutamine (CAG) at position 48 of the TCR β chain, a position predicted to be in the TCR antigen binding site. The V β1 polymorphism was found by DNA sequence analysis of V β1 genes from seven unrelated individuals; V β1 genes were amplified by the polymerase chain reaction, the amplified fragments were cloned into M13 phage vectors, and sequences were determined. To determined the inheritance patterns of the V β1 substitution and to test correlation with V β1 restriction fragment length polymorphism detected with Pvu II and Taq I, allele-specific oligonucleotides were constructed and used to characterize amplified DNA samples. Seventy unrelated individuals and six families were tested for both restriction fragment length polymorphism and for the V β1 substitution. The correlation was also tested using amplified, size-selected, Pvu II- and Taq I-digested DNA samples from heterozygotes. Pvu II allele 1 (61/70) and Taq I allele 1 (66/70) were found to be correlated with the substitution giving rise to a histidine at position 48. Because there are exceptions to the correlation, the use of specific probes to characterize allelic forms of TCR variable genes will provide important tools for studies of basic TCR genetics and disease associations

  7. Micelle formation of nonionic surfactants in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: surfactant chain length dependence of the critical micelle concentration.

    Science.gov (United States)

    Inoue, Tohru; Yamakawa, Haruka

    2011-04-15

    Micellization behavior was investigated for polyoxyethylene-type nonionic surfactants with varying chain length (C(n)E(m)) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)). Critical micelle concentration (cmc) was determined from the variation of (1)H NMR chemical shift with the surfactant concentration. The logarithmic value of cmc decreased linearly with the number of carbon atoms in the surfactant hydrocarbon chain, similarly to the case observed in aqueous surfactant solutions. However, the slope of the straight line is much smaller in bmimBF(4) than in aqueous solution. Thermodynamic parameters for micelle formation estimated from the temperature dependence of cmc showed that the micellization in bmimBF(4) is an entropy-driven process around room temperature. This behavior is also similar to the case in aqueous solution. However, the magnitude of the entropic contribution to the overall micellization free energy in bmimBF(4) is much smaller compared with that in aqueous solution. These results suggest that the micellization in bmimBF(4) proceeds through a mechanism similar to the hydrophobic interaction in aqueous surfactant solutions, although the solvophobic effect in bmimBF(4) is much weaker than the hydrophobic effect. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Density functional theory study of silodithiophene thiophenepyrrolopyrroledion-based small molecules: The effect of alkyl side chain length in electron donor materials

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Dong Kyun; Yeo, Hak; Kwak, Kyung Won [Dept. of Chemistry, Chung-Ang University, Seoul (Korea, Republic of); Yoon, Young Woon; Kim, Bong Soo [Photo-electronic Hybrids Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Lee, Kyung Koo [Dept. of Chemistry, Kunsan National University, Gunsan (Korea, Republic of)

    2015-02-15

    Push–pull small molecules are promising electron-donor materials for organic solar cells. Thus, precise prediction of their electronic structures is of paramount importance to control the optical and electrical properties of the solar cells. Various types of alkyl chains are usually introduced to increase solubility and modify the morphology of the resulting molecular films. Here, using density functional theory (DFT) and time-dependent DFT (TD-DFT), we report the precise effect of increasing the length of the alkyl chain on the electronic structure of an electron donor molecule 6,60-((4,4-dialkyl-4H-silolo[3,2-b:4,5-b′]-dithiophene-2,6-diyl) bis(thiophene-5,2-diyl))bis(2,5-alkyl-3-(thiophen-2-yl) -2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (DTS1TDPP). Alkyl groups were attached to the bridging position (silicon atom) of the fused rings and nitrogen atom of the pyrrolopyrroledione groups. We demonstrate that the alkyl groups do not perturb the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, π-delocalized backbone structure, and UV–Vis absorption spectrum when they are placed at the least steric effect positions.

  9. Roles of head group architecture and side chain length on colorimetric response of polydiacetylene vesicles to temperature, ethanol and pH.

    Science.gov (United States)

    Charoenthai, Nipaphat; Pattanatornchai, Thanutpon; Wacharasindhu, Sumrit; Sukwattanasinitt, Mongkol; Traiphol, Rakchart

    2011-08-15

    In this contribution, we report the relationship between molecular structures of polydiacetylene (PDA) vesicles, fabricated by using three monomers, 10,12-tricosadiynoic acid (TCDA), 10,12-pentacosadiynoic acid (PCDA) and N-(2-aminoethyl)pentacosa-10,12-diynamide (AEPCDA), and their color-transition behaviors. The modification of side chain length and head group of the PDA vesicles strongly affects the colorimetric response to temperature, ethanol and pH. A shorter side chain of poly(TCDA) yields weaker inter- and intra-chain dispersion interactions in the bilayers compared to the system of poly(PCDA), which in turn results in a faster color transition upon exposure to all stimuli. A change of head group in poly(AEPCDA) slightly reduces the transition temperature. Interestingly, the colorimetric response of poly(AEPCDA) vesicles to the addition of ethanol is found to occur in a two-step fashion while the response of poly(PCDA) vesicles takes place in a one-step process. The amount of ethanol required for inducing complete color-transition of poly(AEPCDA) vesicles is also much higher, about 87% v/v. The increase of pH to ~9 and ~10 causes a color-transition of poly(TCDA) and poly(PCDA) vesicles, respectively. The poly(AEPCDA) vesicles, on the other hand, change color upon decreasing pH to ~0. The colorimetric response also occurs in a multi-step fashion. These discrepancies are attributed to the architecture of surface layers of poly(AEPCDA), constituting amine and amide groups separated by ethyl linkers. Copyright © 2011 Elsevier Inc. All rights reserved.

  10. Thermosensitive mPEG-b-PA-g-PNIPAM comb block copolymer micelles: effect of hydrophilic chain length and camptothecin release behavior.

    Science.gov (United States)

    Yang, Xiao-Li; Luo, Yan-Ling; Xu, Feng; Chen, Ya-Shao

    2014-02-01

    Block copolymer micelles are extensively used as drug controlled release carriers, showing promising application prospects. The comb or brush copolymers are especially of great interest, whose densely-grafted side chains may be important for tuning the physicochemical properties and conformation in selective solvents, even in vitro drug release. The purpose of this work was to synthesize novel block copolymer combs via atom transfer radical polymerization, to evaluate its physicochemical features in solution, to improve drug release behavior and to enhance the bioavailablity, and to decrease cytotoxicity. The physicochemical properties of the copolymer micelles were examined by modulating the composition and the molecular weights of the building blocks. A dialysis method was used to load hydrophobic camptothecin (CPT), and the CPT release and stability were detected by UV-vis spectroscopy and high-performance liquid chromatography, and the cytotoxicity was evaluated by MTT assays. The copolymers could self-assemble into well-defined spherical core-shell micelle aggregates in aqueous solution, and showed thermo-induced micellization behavior, and the critical micelle concentration was 2.96-27.64 mg L(-1). The micelles were narrow-size-distribution, with hydrodynamic diameters about 128-193 nm, depending on the chain length of methoxy polyethylene glycol (mPEG) blocks and poly(N-isopropylacrylamide) (PNIPAM) graft chains or/and compositional ratios of mPEG to PNIPAM. The copolymer micelles could stably and effectively load CPT but avoid toxicity and side-effects, and exhibited thermo-dependent controlled and targeted drug release behavior. The copolymer micelles were safe, stable and effective, and could potentially be employed as CPT controlled release carriers.

  11. Use of length heterogeneity polymerase chain reaction (LH-PCR as non-invasive approach for dietary analysis of Svalbard reindeer, Rangifer tarandus platyrhynchus.

    Directory of Open Access Journals (Sweden)

    Sungbae Joo

    Full Text Available To efficiently investigate the forage preference of Svalbard reindeer (Rangifer tarandus platyrhynchus, we applied length-heterogeneity polymerase chain reaction (LH-PCR based on length differences of internal transcribed spacer (ITS regions of ribosomal RNA (rRNA to fecal samples from R. tarandus platyrhynchus. A length-heterogeneity (LH database was constructed using both collected potential food sources of Svalbard reindeer and fecal samples, followed by PCR, cloning and sequencing. In total, eighteen fecal samples were collected between 2011 and 2012 from 2 geographic regions and 15 samples were successfully amplified by PCR. The LH-PCR analysis detected abundant peaks, 18.6 peaks on an average per sample, ranging from 100 to 500 bp in size and showing distinct patterns associated with both regions and years of sample collection. Principal component analysis (PCA resulted in clustering of 15 fecal samples into 3 groups by the year of collection and region with a statistically significant difference at 99.9% level. The first 2 principal components (PCs explained 71.1% of the total variation among the samples. Through comparison with LH database and identification by cloning and sequencing, lichens (Stereocaulon sp. and Ochrolechia sp. and plant species (Salix polaris and Saxifraga oppositifolia were detected as the food sources that contributed most to the Svalbard reindeer diet. Our results suggest that the use of LH-PCR analysis would be a non-invasive and efficient monitoring tool for characterizing the foraging strategy of Svalbard reindeer. Additionally, combining sequence information would increase its resolving power in identification of foraged diet components.

  12. Potencial discriminatório dos N-alcanos em plantas forrageiras tropicais por análises multivariadas Discriminatory potential of the N-alkanes in tropical forages by multivariate analysis

    Directory of Open Access Journals (Sweden)

    Cristiano Côrtes

    2005-08-01

    Full Text Available O potencial dos n-alcanos em discriminar frações ou espécies de gramíneas (Brachiaria brizantha Stapf. cv. Marandu, Cynodon dactylon Pers. cv. Coast-cross 1 e Panicum maximum Jacq. cv. Tanzânia 1 e leguminosas tropicais (Arachis pintoi Koprov & Gregory. cv. Amarillo e Glycine wightii Verdc. Soja Perene foi avaliado neste estudo. As forrageiras foram amostradas na primavera, no verão e inverno, com quatro repetições por espécie. Utilizaram-se nas análises os n-alcanos C24 a C35, sendo o C32 e C34 padrões internos. As concentrações dos n-alcanos nas diferentes espécies e respectivas frações (lâminas foliares, haste porções superior e inferior e matéria morta, para gramíneas; folhas, caule porções superior e inferior e matéria morta para leguminosas foram avaliadas mediante análises multivariadas. O potencial discriminatório dos n-alcanos foi determinado pela análise de variáveis canônicas. As espécies e frações foram divididas em grupos por meio da análise de agrupamento. Os alcanos com menor potencial discriminatório foram: C26, C29, C25, C27 e C28 (primavera, C26, C28, C27, C30 e C29 (verão e C28, C26, C25, C29 e C27 (inverno. Nos períodos de primavera e inverno, a técnica de n-alcanos permitiu distinguir a lâmina foliar do coastcross das hastes superior e inferior, bem como das gramíneas e leguminosas. Em pastagens exclusivas de Brachiaria brizantha, no período de verão, seria possível discriminar as frações de importância nutricional, lâmina foliar e haste superior, pela determinação dos n-alcanos. As análises multivariadas, as variáveis canônicas e a análise de agrupamento representam boas alternativas de cálculo para melhorar a aplicabilidade da técnica dos n-alcanos na discriminação das dietas de herbívoros.The discriminatory potential of n-alkanes in tropical grasses (Brachiaria brizantha Stapf. cv. Marandu, Cynodon dactylon Pers. cv. Coast-cross 1 and Panicum maximum Jacq. cv. Tanz

  13. Genotyping of major histocompatibility complex Class II DRB gene in Rohilkhandi goats by polymerase chain reaction-restriction fragment length polymorphism and DNA sequencing

    Directory of Open Access Journals (Sweden)

    Kush Shrivastava

    2015-10-01

    Full Text Available Aim: To study the major histocompatibility complex (MHC Class II DRB1 gene polymorphism in Rohilkhandi goat using polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP and nucleotide sequencing techniques. Materials and Methods: DNA was isolated from 127 Rohilkhandi goats maintained at sheep and goat farm, Indian Veterinary Research Institute, Izatnagar, Bareilly. A 284 bp fragment of exon 2 of DRB1 gene was amplified and digested using BsaI and TaqI restriction enzymes. Population genetic parameters were calculated using Popgene v 1.32 and SAS 9.0. The genotypes were then sequenced using Sanger dideoxy chain termination method and were compared with related breeds/species using MEGA 6.0 and Megalign (DNASTAR software. Results: TaqI locus showed three and BsaI locus showed two genotypes. Both the loci were found to be in Hardy–Weinberg equilibrium (HWE, however, population genetic parameters suggest that heterozygosity is still maintained in the population at both loci. Percent diversity and divergence matrix, as well as phylogenetic analysis revealed that the MHC Class II DRB1 gene of Rohilkhandi goats was found to be in close cluster with Garole and Scottish blackface sheep breeds as compared to other goat breeds included in the sequence comparison. Conclusion: The PCR-RFLP patterns showed population to be in HWE and absence of one genotype at one locus (BsaI, both the loci showed excess of one or the other homozygote genotype, however, effective number of alleles showed that allelic diversity is present in the population. Sequence comparison of DRB1 gene of Rohilkhandi goat with other sheep and goat breed assigned Rohilkhandi goat in divergence with Jamanupari and Angora goats.

  14. Chain-Length Distribution and Hydrogen Isotopic Fraction of n-alkyl Lipids in Aquatic and Terrestrial Plants: Implications for Paleoclimate Reconstructions

    Science.gov (United States)

    Gao, L.; Littlejohn, S.; Hou, J.; Toney, J.; Huang, Y.

    2008-12-01

    Recent studies demonstrate that in lacustrine sediments, aquatic plant lipids (e.g., C22-fatty acid) record lake water D/H ratio variation, while long-chain fatty acids (C26-C32, major components of terrestrial plant leaf waxes), record D/H ratios of precipitation (especially in arid regions). However, there are insufficient literature data for the distribution and hydrogen isotopic fractionation of n-alkyl lipids in aquatic and terrestrial plants. In this study, we determined the chain-length distributions and D/H ratios of n-alkyl lipids from 17 aquatic plant species (9 emergent, 4 floating and 4 submerge species) and 13 terrestrial plant species (7 grasses and 6 trees) from Blood Pond, Massachusetts. Our results are consistent with previous studies and provide a solid basis for the paleoclimatic reconstruction using D/H ratios of aquatic and terrestrial plant biomarkers. In addition, systematic hydrogen isotopic analyses on leaf waxes, leaf, stem and soil waters from trees and grasses significantly advance our understanding of our previously observed large D/H ratio difference between tree and grass leaf waxes. Our data indicate that the observed difference is not due to differences in leaf water D/H ratios. In comparison with grasses, trees use greater proportion of D-enriched residual or stored carbohydrates (as opposed to current photosynthetic carbohydrates) for leaf wax biosynthesis, resulting in higher leaf wax D/H ratios. The residual carbohydrates are enriched in deuterium because of the preferential consumption of light-hydrogen substrates during plant metabolism.

  15. Asymmetric Conjugated Molecules Based on [1]Benzothieno[3,2-b][1]benzothiophene for High-Mobility Organic Thin-Film Transistors: Influence of Alkyl Chain Length.

    Science.gov (United States)

    He, Keqiang; Li, Weili; Tian, Hongkun; Zhang, Jidong; Yan, Donghang; Geng, Yanhou; Wang, Fosong

    2017-10-11

    Herein, we report the synthesis and characterization of a series of [1]benzothieno[3,2-b][1]benzothiophene (BTBT)-based asymmetric conjugated molecules, that is, 2-(5-alkylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene (BTBT-Tn, in which T and n represent thiophene and the number of carbons in the alkyl group, respectively). All of the molecules with n ≥ 4 show mesomorphism and display smectic A, smectic B (n = 4), or smectic E (n > 4) phases and then crystalline phases in succession upon cooling from the isotropic state. Alkyl chain length has a noticeable influence on the microstructures of vacuum-deposited films and therefore on the performance of the organic thin-film transistors (OTFTs). All molecules except for 2-(thiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene and 2-(5-ethylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene showed OTFT mobilities above 5 cm 2 V -1 s -1 . 2-(5-Hexylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene and 2-(5-heptylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene showed the greatest OTFT performance with reliable hole mobilities (μ) up to 10.5 cm 2 V -1 s -1 because they formed highly ordered and homogeneous films with diminished grain boundaries.

  16. Synthetic high-charge organomica: effect of the layer charge and alkyl chain length on the structure of the adsorbed surfactants.

    Science.gov (United States)

    Pazos, M Carolina; Castro, Miguel A; Orta, M Mar; Pavón, Esperanza; Valencia Rios, Jesús S; Alba, María D

    2012-05-15

    A family of organomicas was synthesized using synthetic swelling micas with high layer charge (Na(n)Si(8-n)Al(n)Mg(6)F(4)O(20)·XH(2)O, where n = 2, 3, and 4) exchanged with dodecylammonium and octadecylammonium cations. The molecular arrangement of the surfactant was elucidated on the basis on XRD patterns and DTA. The ordering conformation of the surfactant molecules into the interlayer space of micas was investigated by (13)C, (27)Al, and (29)Si MAS NMR. The arrangement of alkylammonium ions in these high-charge synthetic micas depends on the combined effects of the layer charge of the mica and the chain length of the cation. In the organomicas with dodecylammonium, a transition from a parallel layer to a bilayer-paraffin arrangement is observed when the layer charge of the mica increases. However, when octadecylammonium is the interlayer cation, the molecular arrangement of the surfactant was found to follow the bilayer-paraffin model for all values of layer charge. The amount of ordered conformation all-trans is directly proportional of layer charge.

  17. Identification of Pork Contamination in Meatballs of Indonesia Local Market Using Polymerase Chain Reaction-Restriction Fragment Length Polymorphism (PCR-RFLP Analysis

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    Yuny Erwanto

    2014-10-01

    Full Text Available This research applied and evaluated a polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP using cytochrome b gene to detect pork contamination in meatballs from local markets in Surabaya and Yogyakarta regions, Indonesia. To confirm the effectiveness and specificity of this fragment, thirty nine DNA samples from different meatball shops were isolated and amplified, and then the PCR amplicon was digested by BseDI restriction enzyme to detect the presence of pork in meatballs. BseDI restriction enzyme was able to cleave porcine cytochrome b gene into two fragments (131 bp and 228 bp. Testing the meatballs from the local market showed that nine of twenty meatball shops in Yogyakarta region were detected to have pork contamination, but there was no pork contamination in meatball shops in Surabaya region. In conclusion, specific PCR amplification of cytochrome b gen and cleaved by BseDI restriction enzymes seems to be a powerful technique for the identification of pork presence in meatball because of its simplicity, specificity and sensitivity. Furthermore, pork contamination intended for commercial products of sausage, nugget, steak and meat burger can be checked. The procedure is also much cheaper than other methods based on PCR, immunodiffusion and other techniques that need expensive equipment.

  18. Identification of Pork Contamination in Meatballs of Indonesia Local Market Using Polymerase Chain Reaction-Restriction Fragment Length Polymorphism (PCR-RFLP) Analysis.

    Science.gov (United States)

    Erwanto, Yuny; Abidin, Mohammad Zainal; Sugiyono, Eko Yasin Prasetyo Muslim; Rohman, Abdul

    2014-10-01

    This research applied and evaluated a polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) using cytochrome b gene to detect pork contamination in meatballs from local markets in Surabaya and Yogyakarta regions, Indonesia. To confirm the effectiveness and specificity of this fragment, thirty nine DNA samples from different meatball shops were isolated and amplified, and then the PCR amplicon was digested by BseDI restriction enzyme to detect the presence of pork in meatballs. BseDI restriction enzyme was able to cleave porcine cytochrome b gene into two fragments (131 bp and 228 bp). Testing the meatballs from the local market showed that nine of twenty meatball shops in Yogyakarta region were detected to have pork contamination, but there was no pork contamination in meatball shops in Surabaya region. In conclusion, specific PCR amplification of cytochrome b gen and cleaved by BseDI restriction enzymes seems to be a powerful technique for the identification of pork presence in meatball because of its simplicity, specificity and sensitivity. Furthermore, pork contamination intended for commercial products of sausage, nugget, steak and meat burger can be checked. The procedure is also much cheaper than other methods based on PCR, immunodiffusion and other techniques that need expensive equipment.

  19. Production of Medium-Chain-Length Poly(3-Hydroxyalkanoates from Saponified Palm Kernel Oil by Pseudomonas putida: Kinetics of Batch and Fed-Batch Fermentations

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    Annuar, M. S. M.

    2006-01-01

    Full Text Available The kinetics of medium-chain-length poly(3-hydroxyalkanoates, PHAMCL production by Pseudomonas putida PGA1 in batch and fed-batch fermentations were studied. With saponified palm kernel oil (SPKO supplying the free fatty acids mixture as the sole carbon and energy source, PHAMCL accumulation is encouraged under ammonium-limited condition, which is a nitrogen stress environment. The amount of PHAMCL accumulated and its specific production rate, qPHA were influenced by the residual ammonium concentration level in the culture medium. It was observed that in both fermentation modes, when the residual ammonium was exhausted (< 0.05 gL-1, the PHAMCL accumulation (11.9% and qPHA (0.0062 h-1 were significantly reduced. However, this effect can be reversed by feeding low amount of ammonium to the culture, resulting in significantly improved PHAMCL yield (71.4% and specific productivity (0.6 h-1. It is concluded that the feeding of low ammonium concentration to the culture medium during the PHAMCL accumulation has a positive effect on sustaining the PHAMCL biosynthetic capability of the organism. It was also found that increasing SPKO concentration in the medium significantly reduced (up to 50% the volumetric oxygen transfer coefficient (KLa of the fermentation system.

  20. Molecular identification of Candida species isolated from cases of neonatal candidemia using polymerase chain reaction-restriction fragment length polymorphism in a tertiary care hospital

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    Akeela Fatima

    2017-01-01

    Full Text Available Context: Candida spp. is an emerging cause of bloodstream infections worldwide. Delay in speciation of Candida isolates by conventional methods and resistance to antifungal drugs in various Candida species are responsible for the increase in morbidity and mortality due to candidemia. Hence, the rapid identification of Candida isolates is very important for the proper management of patients with candidemia. Aims: The aim was to re-evaluate the identification of various Candida spp. by polymerase chain reaction (PCR-restriction fragment length polymorphism (RFLP and to evaluate the accuracy, speed, and cost of phenotypic methodology versus PCR-RFLP. Settings and Design: Hospital-based cross-sectional study. Materials and Methods: Ninety consecutive clinical isolates of seven Candida species, isolated from blood of neonates and identified by routine phenotypic methods, were re-evaluated using universal primers internal transcribed spacer 1 (ITS1 and ITS4 for PCR amplification and Msp I restriction enzyme for RFLP. Statistical Analysis Used: Kappa test for agreement. Results: The results of PCR-RFLP were 100% in agreement with those obtained using conventional phenotypic methods. Identification could be achieved within 3 work days by both the methods. Our routine methods proved to be cost effective than PCR-RFLP. Conclusions: We can continue with our routine phenotypic methods and PCR-RFLP can be used for periodic quality control or when conventional methods fail to identify a species.

  1. Molecular identification of similar species of the genus Biomphalaria (Mollusca: Planorbidae determined by a polymerase chain reaction-restriction fragment length polymorphism

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    Caldeira Roberta Lima

    1998-01-01

    Full Text Available The freshwater snails Biomphalaria straminea, B. intermedia, B. kuhniana and B. peregrina, are morphologically similar; based on this similarity the first three species were therefore grouped in the complex B. straminea. The morphological identification of these species is based on characters such as vaginal wrinkling, relation between prepuce: penial sheath:deferens vas and number of muscle layers in the penis wall. In this study the polymerase chain reaction restriction fragment length polymorphism technique was used for molecular identification of these molluscs. This technique is based on the amplification of the internal transcribed spacer regions ITS1 e ITS2 of the ribosomal RNA gene and subsequent digestion of these fragments by restriction enzymes. Six enzymes were tested: Dde I, Mnl I, Hae III, Rsa I, Hpa II e Alu I. The restriction patterns obtained with DdeI presented the best profile for separation of the four species of Biomphalaria. The profiles obtained with all the enzymes were used to estimate the genetic distances among the species through analysis of common banding patterns.

  2. The color tuning of PS-b-P2VP lamellar films with changing the alkyl chain length of 1-iodoalkanes.

    Science.gov (United States)

    Shin, Sung-Eui; Kim, Su-Young; Shin, Dong-Myung

    2011-05-01

    Photonic crystals with tunability in the visible or near-infrared region have drawn increasing attention for controlling and processing light for the active components of future display. We prepared polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) lamellar films which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 57 kg/mol-b-57 kg/mol. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic moiety of PS-b-P2VP, are obtained by exposing the spin coated film under chloroform vapor. The band gaps of the lamellar films interestingly varied after immersion into the quaternizing solvents containing 5 wt% of iodomethane, iodoethane, 1-iodobutane, 1-iodopentane, 1-iodohexane and 1-iodooctane solubilized in n-hexane. The iodoalkanes reacted with pyridine groups in PS-b-P2VP and generated the alkyl pyridinium salts readily. The degree of quaternization, alkyl chain length of iodoalkane and the salt water concentration affects the spacing of layer structure of PS-b-P2VP. The iodomethane and iodohexane produced similar band gaps and salt concentration dependence. These results are very much dependent on the hydrophobic-hydrophilic characters of PS-b-P2VP lamellar surface.

  3. The prevalence of cryptosporidiosis in Turkish children, and geno typing of isolates by nested polymerase chain reaction-restriction fragment length polymorphism

    International Nuclear Information System (INIS)

    Tamer, Gulden S.; Turk, M.; Dagci, H.; Pektas, B.; Guruz, Adnan Y.; Uner, A.; Guy, E.C.

    2007-01-01

    Objective was to verify the incidence of cryptosporidiosis among Turkish elementary school students. The study was conducted in the Dept. of Parasitology, Faculty of Medicine, Ege University, Turkey during a 3-month period in 2006. We assessed the fecal samples of 707 children using modified acid-fast and phenol-auramine staining followed by modified Ritchie concentration method. All cryptosporidium species isolates were analysed by nested polymerase chain reaction (PCR) and restriction fragment length polymorphism (RFLP) to differentiate genotypes of the isolates. After the coprological examination, 4 samples were found to be positive for cryptosporidium species oocysts. In the present study, all 4 oocysts were of zoonotic origin and belonged to cryptoporodium parvum genotype 2 indicating that in Turkey the potential sources of human cryptosporidiosis is from animals. The application of genotyping to clinical isolates of cryptosporidium has significantly increased our knowledge and understanding of the distribution and epidemiology of this parasite. The PCR and RFLP techniques represent a more rapid and simple method of genotyping to support epidemiological and clinical investigations than conventional analytical DNA techniques. (author)

  4. Quinoidal Oligo(9,10-anthryl)s with Chain-Length-Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

    KAUST Repository

    Lim, Zhenglong

    2015-11-12

    Quinoidal π-conjugated polycyclic hydrocarbons have attracted intensive research interest due to their unique optical/electronic properties and possible magnetic activity, which arises from a thermally excited triplet state. However, there is still lack of fundamental understanding on the factors that determine the electronic ground states. Herein, by using quinoidal oligo(9,10-anthryl)s, it is demonstrated that both aromatic stabilisation and steric strain release play balanced roles in determining the ground states. Oligomers with up to four anthryl units were synthesised and their ground states were investigated by electronic absorption and electron spin resonance (ESR) spectroscopy, assisted by density functional theory (DFT) calculations. The quinoidal 9,10-anthryl dimer 1 has a closed-shell ground state, whereas the tri- (2) and tetramers (3) both have an open-shell diradical ground state with a small singlet-triplet gap. Such a difference results from competition between two driving forces: the large steric repulsion between the anthryl/phenyl units in the closed-shell quinoidal form that drives the molecule to a flexible open-shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed-shell form, which drives the molecule towards a contorted quinoidal structure. The ground states of these oligomers thus depend on the overall balance between these two driving forces and show chain-length dependence. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. The normal chain length distribution of the O antigen is required for the interaction of Shigella flexneri 2a with polarized Caco-2 cells

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    Anilei Hoare

    2012-01-01

    Full Text Available Shigella flexneri causes bacillary dysentery in humans. Essential to the establishment of the disease is the invasion of the colonic epithelial cells. Here we investigated the role of the lipopolysaccharide (LPS O antigen in the ability of S. flexneri to adhere to and invade polarized Caco-2 cells. The S. flexneri 2a O antigen has two preferred chain lengths: a short O antigen (S-OAg regulated by the WzzB protein and a very long O antigen (VL-OAg regulated by Wzz pHS2. Mutants with defined deletions of the genes required for O-antigen assembly and polymerization were constructed and assayed for their abilities to adhere to and enter cultured epithelial cells. The results show that both VL- and S-OAg are required for invasion through the basolateral cell membrane. In contrast, the absence of O antigen does not impair adhesion. Purified LPS does not act as a competitor for the invasion of Caco-2 cells by the wild-type strain, suggesting that LPS is not directly involved in the internalization process by epithelial cells.

  6. Diffusional behavior of n-paraffins with various chain lengths in urea adduct channels by pulsed field-gradient spin-echo NMR spectroscopy

    International Nuclear Information System (INIS)

    Kim, Sunmi; Kuroki, Shigeki; Ando, Isao

    2006-01-01

    The diffusion coefficients (D) of n-paraffin molecules (n-C n H 2n+2 ) with various chain-lengths (n = 8, 12, 21, 26, 28 and 32) in the long channels of a deuterated urea-d 4 adduct have been measured at 25 deg. C by means of pulsed field-gradient spin-echo 1 H NMR method. The aim is to clarify diffusional behavior of the n-paraffin molecules in the urea adduct channels. From the experimental results, it is found that n-paraffin molecules are diffusing in the long channels and have two kinds of diffusion components, namely a fast (D ∼ 10 -10 m 2 /s) and a slow diffusion component (D ∼ 10 -11 m 2 /s). The diffusing-time (Δ) dependence of the diffusion coefficients of the n-paraffins shows some likely evidence of restricted diffusion since the n-paraffin molecules are confined in the urea channel. The diffusion coefficients (D) decrease as the carbon number increases from 8 to 28, and very slowly decreases as the carbon number increases from 28 to 32

  7. Simultaneous and rapid differential diagnosis of Mycoplasma genitalium and Ureaplasma urealyticum based on a polymerase chain reaction-restriction fragment length polymorphism

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    R Mirnejad

    2011-01-01

    Full Text Available Objectives: The aim of this investigation was to simultaneously detect and differentiate Mycoplasma genitalium and Ureaplasma urealyticum in female patients suffering from genital complications by polymerase chain reaction (PCR-restriction fragment length polymorphism (RFLP. Materials and Methods : Genital swabs were taken from 210 patients. They were transported to the laboratory in phosphate-buffered saline. For PCR, samples were analysed with genus-specific MyUu-R and MyUu-F primers. This primer set, which was originally designed in our laboratory, amplified a 465 bp fragment (M. genitalium and a 559 bp fragment (U. urealyticum. Samples containing a band of the expected sizes for the Mycoplasma strains were subjected to digestion with a restriction endonuclease enzyme of TaqI and Cac8I. Results: Of the 210 samples, a total of 100 (47.6% samples were found to be positive for Mycoplasmas (seven M. genitalium isolates, 3.3%; and 89 U. urealyticum isolates, 42.4%, and coinfections with both species were detected in four samples (1.9%. The PCR-RFLP results showed that M. genitalium and U. urealyticum are different by enzyme patterns. Conclusion: PCR-RFLP offers a rapid and easily applicable protocol to simultaneous detection and differentiation of M. genitalium and U. urealyticum from clinical samples when specific primers and restriction enzymes are used.

  8. The quantification of short-chain chlorinated paraffins in sediment samples using comprehensive two-dimensional gas chromatography with μECD detection.

    Science.gov (United States)

    Muscalu, Alina M; Morse, Dave; Reiner, Eric J; Górecki, Tadeusz

    2017-03-01

    The analysis of persistent organic pollutants in environmental samples is a challenge due to the very large number of compounds with varying chemical and physical properties. Chlorinated paraffins (CPs) are complex mixtures of chlorinated n-alkanes with varying chain lengths (C 10 to C 30 ) and degree of chlorination (30 to 70% by weight). Their physical-chemical properties make these compounds persistent in the environment and able to bioaccumulate in living organisms. Comprehensive two-dimensional gas chromatography (GC × GC) coupled with micro-electron capture detection (μECD) was used to separate and quantify short-chain chlorinated paraffins (SCCP) in sediment samples. Distinct ordered bands were observed in the GC × GC chromatograms pointing to group separation. Using the Classification function of the ChromaTOF software, summary tables were generated to determine total area counts to set up multilevel-calibration curves for different technical mixes. Fortified sediment samples were analyzed by GC × GC-μECD with minimal extraction and cleanup. Recoveries ranged from 120 to 130%. To further validate the proposed method for the analysis of SCCPs, the laboratory participated in interlaboratory studies for the analysis of standards and sediment samples. The results showed recoveries between 75 and 95% and z-score values <2, demonstrating that the method is suitable for the analysis of SCCPs in soil/sediment samples. Graphical abstract Quantification of SCCPs by 2D-GC-μECD.

  9. Distribution and congener profiles of short-chain chlorinated paraffins in indoor/outdoor glass window surface films and their film-air partitioning in Beijing, China.

    Science.gov (United States)

    Gao, Wei; Wu, Jing; Wang, Yawei; Jiang, Guibin

    2016-02-01

    Short-chain chlorinated paraffins (SCCPs) are a group of n-alkanes with carbon chain length of 10-13. In this work, paired indoor/outdoor samples of organic films on window glass surfaces from urban buildings in Beijing, China, were collected to measure the concentrations and congener distributions of SCCPs. The total SCCP levels ranged from 337 ng/m(2) to 114 μg/m(2), with total organic carbon (TOC) normalized concentrations of 365 μg/m(2)-365 mg/m(2). Overall, the concentrations of SCCPs on the interior films were higher than the concentrations on the exterior films, suggesting an important indoor environmental exposure of SCCPs to the general public. A significant linear relationship was found between the SCCP concentrations and TOC, with a correlation coefficient of R = 0.34 (p film-air partitioning model suggests that the indoor gas-phase SCCPs are related to their corresponding window film levels. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Effect of alkyl chain length of imidazolium cations on the electron transport and recombination kinetics in ionic gel electrolytes based quasi-solid-state dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Huo, Zhipeng; Tao, Li; Wang, Lu; Zhu, Jun; Chen, Shuanghong; Zhang, Changneng; Dai, Songyuan; Zhang, Bing

    2015-01-01

    Highlights: •A series of novel IGEs based on 12-hydroxystearicacid as LMOG were prepared. •The QS-DSSCs exhibit excellent stability during the accelerated aging tests. •The influence of Im + alkyl chain length on the electron kinetic process is investigated. -- Abstract: A series of stable quasi-solid-state dye-sensitized solar cells (QS-DSSCs) are prepared by the 12-hydroxystearicacid as low molecular mass organogelator (LMOG) to gelate the ionic liquid with different alkyl chain lengths (3, 4, and 7). The influence of alkyl chain length of imidazolium cations (Im + ) on the kinetic processes of electron transport and recombination are investigated by Electrochemical impedance spectroscopy (EIS) and intensity-modulated photocurrent spectroscopy/intensity-modulated photovoltage spectroscopy (IMPS/IMVS). It is found that the ionic gel electrolytes (IGEs) with different alkyl chain lengths of Im + can influence the competitive adsorption effects of imidazolium cations (Im + ) and Li + , and further affect the charge diffusion, the electron recombination/transport processes, the shift of TiO 2 conduction band edge and surface states distribution. The IGE with longer alkyl chain length of Im + can prolong the electron recombination lifetime, promote the incidental photon-to-electron conversion efficiency (IPCE) and the short circuit photocurrent density (J sc ). An excellent QS-DSSC based on the IGE with the longer alkyl chain of Im + gives the highest photoelectric conversion efficiency. Moreover, all the QS-DSSCs based on IGEs exhibit excellent durability without losing their photovoltaic performances during the accelerated thermal and light–soaking test. These results are very important to the researches on the electrochemical mechanism and application of QS-DSSCs based on IGEs

  11. (99m)Tc-labeled gastrins of varying peptide chain length: Distinct impact of NEP/ACE-inhibition on stability and tumor uptake in mice.

    Science.gov (United States)

    Kaloudi, Aikaterini; Nock, Berthold A; Lymperis, Emmanouil; Krenning, Eric P; de Jong, Marion; Maina, Theodosia

    2016-06-01

    In situ inhibition of neutral endopeptidase (NEP) has been recently shown to impressively increase the bioavailability and tumor uptake of biodegradable gastrin radioligands. Furthermore, angiotensin converting enzyme (ACE) has been previously shown to cleave gastrin analogs in vitro. In the present study, we have assessed the effects induced by single or dual NEP/ACE-inhibition on the pharmacokinetic profile of three (99m)Tc-labeled gastrins of varying peptide chain length: [(99m)Tc]SG6 ([(99m)Tc-N4-Gln(1)]gastrin(1-17)), [(99m)Tc]DG2 ([(99m)Tc-N4-Gly(4),DGlu(5)]gastrin(4-17)) and [(99m)Tc]DG4 ([(99m)Tc-N4-DGlu(10)]gastrin(10-17)). Mouse blood samples were collected 5min after injection of each of [(99m)Tc]SG6/DG2/DG4 together with: a) vehicle, b) the NEP-inhibitor phosphoramidon (PA), c) the ACE-inhibitor lisinopril (Lis), or d) PA plus Lis and were analyzed by RP-HPLC for radiometabolite detection. Biodistribution was studied in SCID mice bearing A431-CCK2R(+/-) xenografts at 4h postinjection (pi). [(99m)Tc]SG6 or [(99m)Tc]DG4 was coinjected with either vehicle or the above described NEP/ACE-inhibitor regimens; for [(99m)Tc]DG2 control and PA animal groups were only included. Treatment of mice with PA induced significant stabilization of (99m)Tc-radiotracers in peripheral blood, while treatment with Lis or Lis+PA affected the stability of des(Glu)5 [(99m)Tc]DG4 only. In line with these findings, PA coinjection led to notable amplification of tumor uptake of radiopeptides compared to controls (PTc]DG4 profited by single Lis (2.06±0.39%ID/g vs 0.99±0.13%ID/g in controls) or combined Lis+PA coinjection (8.91±1.61%ID/g vs 4.89±1.33%ID/g in PA-group). Furthermore, kidney uptake remained favourably low and unaffected by PA and/or Lis coinjection only in the case of [(99m)Tc]DG4 (Tc-radioligands based on different-length gastrins. Truncated [(99m)Tc]DG4 exhibited overall the most attractive profile during combined NEP/ACE-inhibition in mouse models, providing new

  12. Changes in thyroid parameters of hatchling American kestrels (Falco sparverius) following embryonic exposure to technical short chain chlorinated paraffins (SCCPs; C10-13, 55.5% CL)

    Science.gov (United States)

    Fernie, Kimberly J; Henry, Paula F.; Letcher, Robert J; Palace, Vince; Peters, Lisa; Rattner, Barnett A.; Sverko, Edward; Karouna-Renier, Natalie K.

    2015-01-01

    Chlorinated paraffins (CPs) are complex mixtures of polychlorinated n-alkanes categorized according to their carbon chain length: short chain (SCCPs, C10 – C13), medium (C14 - C17), and long chain (C>17), chlorinated paraffins. SCCPs are primarily used in metalworking applications, as flame retardants, and in paints, adhesives, sealants, textiles, plastics and rubber (UNEP 2012). In 2012, the United Nations Environment Program (UNEP 2012) reported in the Revised Draft Risk Profile for SCCPs, that CPs were produced in the United States, the European Union (EU), Slovakia, Brazil, India, Japan and China. While annual global consumption of SCCPs is large (>25 tonnes/year), it has sharply declined over the past 20 years. SCCPs are released through wastewater, landfills, and air emissions (UNEP 2012). Concentrations of SCCPs have been reported in fish and marine mammals in North and South America, Europe, Japan, Greenland and the Arctic (UNEP 2012 and references therein). Characterization of SCCP concentrations and exposure in terrestrial wildlife is limited. In 2010, SCCP concentrations were reported in the eggs of yellow-legged gulls (Larus michahellis) (4536 ± 40 pg/g wet weight (ww)) and Audouin’s gulls (Larus audouinii) (6364 ± 20 pg/g ww) in Spain (Morales et al. 2012), and little auks (Alle alle) (5 - 88 ng/g ww) and kittiwakes (Rissa tridactyla) (5 - 44 ng/g ww) in the European Arctic (Reth et al. 2006). In Sweden, muscle of ospreys contained CPs of unspecified chain length (Jansson et al. 1993). Although the toxicity of SCCPs has been demonstrated in aquatic invertebrates, fish, frogs, and laboratory rats, there are limited avian studies and these reported no effects of SCCPs on egg parameters of domestic hens (Gallus gallus domesticus) and ducks (Anas platyrhynchos) (UNEP 2012). Despite reported accumulation of SCCPs in wild birds, to our knowledge, exposure-related toxicities and effects with respect to avian wildlife remain unknown.

  13. Soil pretreatment and fast cell lysis for direct polymerase chain reaction from forest soils for terminal restriction fragment length polymorphism analysis of fungal communities

    Directory of Open Access Journals (Sweden)

    Fei Cheng

    Full Text Available Abstract Humic substances in soil DNA samples can influence the assessment of microbial diversity and community composition. Using multiple steps during or after cell lysis adds expenses, is time-consuming, and causes DNA loss. A pretreatment of soil samples and a single step DNA extraction may improve experimental results. In order to optimize a protocol for obtaining high purity DNA from soil microbiota, five prewashing agents were compared in terms of their efficiency and effectiveness in removing soil contaminants. Residual contaminants were precipitated by adding 0.6 mL of 0.5 M CaCl2. Four cell lysis methods were applied to test their compatibility with the pretreatment (prewashing + Ca2+ flocculation and to ultimately identify the optimal cell lysis method for analyzing fungal communities in forest soils. The results showed that pretreatment with TNP + Triton X-100 + skim milk (100 mM Tris, 100 mM Na4P2O7, 1% polyvinylpyrrolidone, 100 mM NaCl, 0.05% Triton X-100, 4% skim milk, pH 10.0 removed most soil humic contaminants. When the pretreatment was combined with Ca2+ flocculation, the purity of all soil DNA samples was further improved. DNA samples obtained by the fast glass bead-beating method (MethodFGB had the highest purity. The resulting DNA was successfully used, without further purification steps, as a template for polymerase chain reaction targeting fungal internal transcribed spacer regions. The results obtained by terminal restriction fragment length polymorphism analysis indicated that the MethodFGB revealed greater fungal diversity and more distinctive community structure compared with the other methods tested. Our study provides a protocol for fungal cell lysis in soil, which is fast, convenient, and effective for analyzing fungal communities in forest soils.

  14. Production of medium-chain-length polyhydroxyalkanoates by sequential feeding of xylose and octanoic acid in engineered Pseudomonas putida KT2440

    Directory of Open Access Journals (Sweden)

    Le Meur Sylvaine

    2012-08-01

    Full Text Available Abstract Background Pseudomonas putida KT2440 is able to synthesize large amounts of medium-chain-length polyhydroxyalkanoates (mcl-PHAs. To reduce the substrate cost, which represents nearly 50% of the total PHA production cost, xylose, a hemicellulose derivate, was tested as the growth carbon source in an engineered P. putida KT2440 strain. Results The genes encoding xylose isomerase (XylA and xylulokinase (XylB from Escherichia coli W3110 were introduced into P. putida KT2440. The recombinant KT2440 exhibited a XylA activity of 1.47 U and a XylB activity of 0.97 U when grown on a defined medium supplemented with xylose. The cells reached a maximum specific growth rate of 0.24 h-1 and a final cell dry weight (CDW of 2.5 g L-1 with a maximal yield of 0.5 g CDW g-1 xylose. Since no mcl-PHA was accumulated from xylose, mcl-PHA production can be controlled by the addition of fatty acids leading to tailor-made PHA compositions. Sequential feeding strategy was applied using xylose as the growth substrate and octanoic acid as the precursor for mcl-PHA production. In this way, up to 20% w w-1 of mcl-PHA was obtained. A yield of 0.37 g mcl-PHA per g octanoic acid was achieved under the employed conditions. Conclusions Sequential feeding of relatively cheap carbohydrates and expensive fatty acids is a practical way to achieve more cost-effective mcl-PHA production. This study is the first reported attempt to produce mcl-PHA by using xylose as the growth substrate. Further process optimizations to achieve higher cell density and higher productivity of mcl-PHA should be investigated. These scientific exercises will undoubtedly contribute to the economic feasibility of mcl-PHA production from renewable feedstock.

  15. Transcriptome analysis of Pseudomonas mediterranea and P. corrugata plant pathogens during accumulation of medium-chain-length PHAs by glycerol bioconversion.

    Science.gov (United States)

    Licciardello, Grazia; Ferraro, Rosario; Russo, Marcella; Strozzi, Francesco; Catara, Antonino F; Bella, Patrizia; Catara, Vittoria

    2017-07-25

    Pseudomonas corrugata and P. mediterranea are soil inhabitant bacteria, generally living as endophytes on symptomless plants and bare soil, but also capable of causing plant diseases. They share a similar genome size and a high proteome similarity. P. corrugata produces many biomolecules which play an important role in bacterial cell survival and fitness. Both species produce different medium-chain-length PHAs (mcl-PHAs) from the bioconversion of glycerol to a transparent film in P. mediterranea and a sticky elastomer in P. corrugata. In this work, using RNA-seq we investigated the transcriptional profiles of both bacteria at the early stationary growth phase with glycerol as the carbon source. Quantitative analysis of P. mediterranea transcripts versus P. corrugata revealed that 1756 genes were differentially expressed. A total of 175 genes were significantly upregulated in P. mediterranea, while 217 were downregulated. The largest group of upregulated genes was related to transport systems and stress response, energy and central metabolism, and carbon metabolism. Expression levels of most genes coding for enzymes related to PHA biosynthesis and central metabolic pathways showed no differences or only slight variations in pyruvate metabolism. The most relevant result was the significantly increased expression in P. mediterranea of genes involved in alginate production, an important exopolysaccharide, which in other Pseudomonas spp. plays a key role as a virulence factor or in stress tolerance and shows many industrial applications. In conclusion, the results provide useful information on the co-production of mcl-PHAs and alginate from glycerol as carbon source by P. mediterranea in the design of new strategies of genetic regulation to improve the yield of bioproducts or bacterial fitness. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Investigation of the role of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene glycol) networks: towards high-performance antifouling coatings

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yapei; Pitet, Louis M.; Finlay, John A.; Brewer, Lenora H.; Cone, Gemma; Betts, Douglas E.; Callow, Maureen E.; Callow, James A.; Wendt, Dean E.; Hillmyer, Marc A.; DeSimone, Joseph M. (Birmingham UK); (NCSU); (UNC); (Cal. Polytech.); (UMM)

    2013-03-07

    The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M{sub w} = 1500 g mol{sup -1}) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M{sub w} = 300, 475, 1100 g mol{sup -1}), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.

  17. Investigation of the role of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene glycol) networks: towards high-performance antifouling coatings.

    Science.gov (United States)

    Wang, Yapei; Pitet, Louis M; Finlay, John A; Brewer, Lenora H; Cone, Gemma; Betts, Douglas E; Callow, Maureen E; Callow, James A; Wendt, Dean E; Hillmyer, Marc A; DeSimonea, Joseph M

    2011-01-01

    The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M(w) = 1500 g mol(-1)) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M(w) = 300, 475, 1100 g mol(-1)), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.

  18. Effect of molecular chain length on the mechanical and thermal properties of amine-functionalized graphene oxide/polyimide composite films prepared by in situ polymerization.

    Science.gov (United States)

    Liao, Wei-Hao; Yang, Shin-Yi; Wang, Jen-Yu; Tien, Hsi-Wen; Hsiao, Sheng-Tsung; Wang, Yu-Sheng; Li, Shin-Ming; Ma, Chen-Chi M; Wu, Yi-Fang

    2013-02-01

    This study fabricates amine (NH(2))-functionalized graphene oxide (GO)/polyimide(PI) composite films with high performance using in situ polymerization. Linear poly(oxyalkylene)amines with two different molecular weights 400 and 2000 (D400 and D2000) have been grafted onto the GO surfaces, forming two types of NH(2)-functionalized GO (D400-GO/D2000-GO). NH(2)-functionalized GO, especially D400-GO, demonstrated better reinforcing efficiency in mechanical and thermal properties. The observed property enhancement are due to large aspect ratio of GO sheets, the uniform dispersion of the GO within the PI matrix, and strong interfacial adhesion due to the chemical bonding between GO and the polymeric matrix. The Young's modulus of the composite films with 0.3 wt % D400-GO loading is 7.4 times greater than that of neat PI, and tensile strength is 240% higher than that of neat PI. Compared to neat PI, 0.3 wt % D400-GO/PI film exhibits approximately 23.96 °C increase in glass transition temperature (T(g)). The coefficient of thermal expansion below T(g) is significantly decreased from 102.6 μm/°C (neat PI) to 53.81 μm/°C (decreasing 48%) for the D400-GO/PI composites with low D400-GO content (0.1 wt %). This work not only provides a method to develop the GO-based polyimide composites with superior performances but also conceptually provides a chance to modulate the interfacial interaction between GO and the polymer through designing the chain length of grafting molecules on NH(2)-functionalized GO.

  19. Novel phytoceramides containing fatty acids of diverse chain lengths are better than a single C18-ceramide N-stearoyl phytosphingosine to improve the physiological properties of human stratum corneum

    Directory of Open Access Journals (Sweden)

    Oh MJ

    2017-09-01

    Full Text Available Myoung Jin Oh,1 Young Hoon Cho,1 So Yoon Cha,1 Eun Ok Lee,2 Jin Wook Kim,2 Sun Ki Kim,2 Chang Seo Park1 1Department of Chemical and Biochemical Engineering, Dongguk University, Chung-gu, Seoul, 2LCS Biotech, Gwonseon-gu, Suwon-si, Gyeonggi-do, Republic of Korea Abstract: Ceramides in the human stratum corneum (SC are a mixture of diverse N-acylated fatty acids (FAs with different chain lengths. C24 is the major class of FAs of ceramides. However, there are also other classes of ceramides with diverse chain lengths of FAs, and these lengths generally range from C16 to C26. This study aimed to prepare several types of phytoceramide containing diverse chain lengths of N-acylated FAs and compare them with C18-ceramide N-stearoyl phytosphingosine (NP in terms of their effects on the physiological properties of the SC. We chose natural oils, such as horse fat oil, shea butter, sunflower oil, and a mixture of macadamia nut, shea butter, moringa, and meadowfoam seed oil, as sources of FAs and phytosphingosine as a sphingoid backbone to synthesize diverse phytoceramides. Each phytoceramide exhibited a distinctive formation of the lamellar structure, and their FA profiles were similar to those of their respective natural oil. The skin barrier properties, as analyzed in human skin, clearly demonstrated that all the phytoceramides improved the recovery rate of the damaged SC and enhanced hydration better than C18-ceramide NP did. In conclusion, natural oil-derived phytoceramides could represent a novel class of ceramides for cosmetic applications in the development of an ideal skin barrier moisturizer. Keywords: fatty acid, chain length, phytoceramide, skin barrier, natural oil

  20. A reduction in growth rate of Pseudomonas putida KT2442 counteracts productivity advances in medium-chain-length polyhydroxyalkanoate production from gluconate

    Directory of Open Access Journals (Sweden)

    Zinn Manfred

    2011-04-01

    Full Text Available Abstract Background The substitution of plastics based on fossil raw material by biodegradable plastics produced from renewable resources is of crucial importance in a context of oil scarcity and overflowing plastic landfills. One of the most promising organisms for the manufacturing of medium-chain-length polyhydroxyalkanoates (mcl-PHA is Pseudomonas putida KT2440 which can accumulate large amounts of polymer from cheap substrates such as glucose. Current research focuses on enhancing the strain production capacity and synthesizing polymers with novel material properties. Many of the corresponding protocols for strain engineering rely on the rifampicin-resistant variant, P. putida KT2442. However, it remains unclear whether these two strains can be treated as equivalent in terms of mcl-PHA production, as the underlying antibiotic resistance mechanism involves a modification in the RNA polymerase and thus has ample potential for interfering with global transcription. Results To assess PHA production in P. putida KT2440 and KT2442, we characterized the growth and PHA accumulation on three categories of substrate: PHA-related (octanoate, PHA-unrelated (gluconate and poor PHA substrate (citrate. The strains showed clear differences of growth rate on gluconate and citrate (reduction for KT2442 > 3-fold and > 1.5-fold, respectively but not on octanoate. In addition, P. putida KT2442 PHA-free biomass significantly decreased after nitrogen depletion on gluconate. In an attempt to narrow down the range of possible reasons for this different behavior, the uptake of gluconate and extracellular release of the oxidized product 2-ketogluconate were measured. The results suggested that the reason has to be an inefficient transport or metabolization of 2-ketogluconate while an alteration of gluconate uptake and conversion to 2-ketogluconate could be excluded. Conclusions The study illustrates that the recruitment of a pleiotropic mutation, whose effects might

  1. Comparative analysis of human cytomegalovirus a-sequence in multiple clinical isolates by using polymerase chain reaction and restriction fragment length polymorphism assays.

    Science.gov (United States)

    Zaia, J A; Gallez-Hawkins, G; Churchill, M A; Morton-Blackshere, A; Pande, H; Adler, S P; Schmidt, G M; Forman, S J

    1990-01-01

    The human cytomegalovirus (HCMV) a-sequence (a-seq) is located in the joining region between the long (L) and short (S) unique sequences of the virus (L-S junction), and this hypervariable junction has been used to differentiate HCMV strains. The purpose of this study was to investigate whether there are differences among strains of human cytomegalovirus which could be characterized by polymerase chain reaction (PCR) amplification of the a-seq of HCMV DNA and to compare a PCR method of strain differentiation with conventional restriction fragment length polymorphism (RFLP) methodology by using HCMV junction probes. Laboratory strains of HCMV and viral isolates from individuals with HCMV infection were characterized by using both RFLPs and PCR. The PCR assay amplified regions in the major immediate-early gene (IE-1), the 64/65-kDa matrix phosphoprotein (pp65), and the a-seq of the L-S junction region. HCMV laboratory strains Towne, AD169, and Davis were distinguishable, in terms of size of the amplified product, when analyzed by PCR with primers specific for the a-seq but were indistinguishable by using PCR targeted to IE-1 and pp65 sequences. When this technique was applied to a characterization of isolates from individuals with HCMV infection, selected isolates could be readily distinguished. In addition, when the a-seq PCR product was analyzed with restriction enzyme digestion for the presence of specific sequences, these DNA differences were confirmed. PCR analysis across the variable a-seq of HCMV demonstrated differences among strains which were confirmed by RFLP in 38 of 40 isolates analyzed. The most informative restriction enzyme sites in the a-seq for distinguishing HCMV isolates were those of MnlI and BssHII. This indicates that the a-seq of HCMV is heterogeneous among wild strains, and PCR of the a-seq of HCMV is a practical way to characterize differences in strains of HCMV. Images PMID:1980680

  2. 99mTc-labeled gastrins of varying peptide chain length: Distinct impact of NEP/ACE-inhibition on stability and tumor uptake in mice

    International Nuclear Information System (INIS)

    Kaloudi, Aikaterini; Nock, Berthold A.; Lymperis, Emmanouil; Krenning, Eric P.; Jong, Marion de; Maina, Theodosia

    2016-01-01

    Introduction: In situ inhibition of neutral endopeptidase (NEP) has been recently shown to impressively increase the bioavailability and tumor uptake of biodegradable gastrin radioligands. Furthermore, angiotensin converting enzyme (ACE) has been previously shown to cleave gastrin analogs in vitro. In the present study, we have assessed the effects induced by single or dual NEP/ACE-inhibition on the pharmacokinetic profile of three 99m Tc-labeled gastrins of varying peptide chain length: [ 99m Tc]SG6 ([ 99m Tc-N 4 -Gln 1 ]gastrin(1–17)), [ 99m Tc]DG2 ([ 99m Tc-N 4 -Gly 4 ,DGlu 5 ]gastrin(4–17)) and [ 99m Tc]DG4 ([ 99m Tc-N 4 -DGlu 10 ]gastrin(10–17)). Methods: Mouse blood samples were collected 5 min after injection of each of [ 99m Tc]SG6/DG2/DG4 together with: a) vehicle, b) the NEP-inhibitor phosphoramidon (PA), c) the ACE-inhibitor lisinopril (Lis), or d) PA plus Lis and were analyzed by RP-HPLC for radiometabolite detection. Biodistribution was studied in SCID mice bearing A431-CCK2R(+/−) xenografts at 4 h postinjection (pi). [ 99m Tc]SG6 or [ 99m Tc]DG4 was coinjected with either vehicle or the above described NEP/ACE-inhibitor regimens; for [ 99m Tc]DG2 control and PA animal groups were only included. Results: Treatment of mice with PA induced significant stabilization of 99m Tc-radiotracers in peripheral blood, while treatment with Lis or Lis + PA affected the stability of des(Glu) 5 [ 99m Tc]DG4 only. In line with these findings, PA coinjection led to notable amplification of tumor uptake of radiopeptides compared to controls (P < 0.01). Only [ 99m Tc]DG4 profited by single Lis (2.06 ± 0.39%ID/g vs 0.99 ± 0.13%ID/g in controls) or combined Lis + PA coinjection (8.91 ± 1.61%ID/g vs 4.89 ± 1.33%ID/g in PA-group). Furthermore, kidney uptake remained favourably low and unaffected by PA and/or Lis coinjection only in the case of [ 99m Tc]DG4 (< 1.9%ID/g) resulting in the most optimal tumor-to-kidney ratios. Conclusions: In situ NEP

  3. Excess molar volumes and dynamic viscosities for binary mixtures of toluene + n-alkanes (C5-C10) at T = 298.15 K - Comparison with Prigogine-Flory-Patterson theory

    International Nuclear Information System (INIS)

    Iloukhani, Hossein; Rezaei-Sameti, Mahdi; Basiri-Parsa, Jalal

    2006-01-01

    Densities ρ, dynamic viscosities η, for binary mixtures of toluene with some n-alkanes, namely, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane have been measured over the complete composition range. Excess molar volumes V E , viscosity deviations Δη, and excess Gibbs free energy of activation ΔG * E , were calculated there from and were correlated by Redlich-Kister type function in terms of mole fractions. For mixtures of toluene with n-pentane and n-hexane the V E is negative and for the remaining systems is positive. The Δη values are negative for all the studied mixtures. The ΔG * E values shows the positive values for the binary mixtures with n-decane, whereas the negative values have been observed for all the remaining binary mixtures. From the results, the excess thermal expansivities at constant pressure α E , is also estimated. The Prigogine-Flory-Patterson (PFP) theory and its applicability in predicting V E is tested. The results obtained for viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg and Nissan, Tamura and Kurata, Hind et al., Katti and Chaudhri, McAllister, Heric, Kendall, and Monroe. The experimental on the constituted binaries are analyzed to discus the nature and strength of intermolecular interactions in these mixtures

  4. Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2012-10-25

    In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

  5. PMMA-g-OEtOx Graft Copolymers: Influence of Grafting Degree and Side Chain Length on the Conformation in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Irina Muljajew

    2018-03-01

    Full Text Available Depending on the degree of grafting (DG and the side chain degree of polymerization (DP, graft copolymers may feature properties similar to statistical copolymers or to block copolymers. This issue is approached by studying aqueous solutions of PMMA-g-OEtOx graft copolymers comprising a hydrophobic poly(methyl methacrylate (PMMA backbone and hydrophilic oligo(2-ethyl-2-oxazoline (OEtOx side chains. The graft copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT copolymerization of methyl methacrylate (MMA and OEtOx-methacrylate macromonomers of varying DP. All aqueous solutions of PMMA-g-OEtOx (9% ≤ DG ≤ 34%; 5 ≤ side chain DP ≤ 24 revealed lower critical solution temperature behavior. The graft copolymer architecture significantly influenced the aggregation behavior, the conformation in aqueous solution and the coil to globule transition, as verified by means of turbidimetry, dynamic light scattering, nuclear magnetic resonance spectroscopy, and analytical ultracentrifugation. The aggregation behavior of graft copolymers with a side chain DP of 5 was significantly affected by small variations of the DG, occasionally forming mesoglobules above the cloud point temperature (Tcp, which was around human body temperature. On the other hand, PMMA-g-OEtOx with elongated side chains assembled into well-defined structures below the Tcp (apparent aggregation number (Nagg = 10 that were able to solubilize Disperse Orange 3. The thermoresponsive behavior of aqueous solutions thus resembled that of micelles comprising a poly(2-ethyl-2-oxazoline (PEtOx shell (Tcp > 60 °C.

  6. Alkyl chain interaction at the surface of room temperature ionic liquids: systematic variation of alkyl chain length (R = C(1)-C(4), C(8)) in both cation and anion of [RMIM][R-OSO(3)] by sum frequency generation and surface tension.

    Science.gov (United States)

    Santos, Cherry S; Baldelli, Steven

    2009-01-29

    The gas-liquid interface of halide-free 1,3-dialkylimidazolium alkyl sulfates [RMIM][R-OSO(3)] with R chain length from C(1)-C(4) and C(8) has been studied systematically using the surface-specific sum frequency generation (SFG) vibrational spectroscopy and surface tension measurements. From the SFG spectra, vibrational modes from the methyl group of both cation and anion are observed for all ionic liquid samples considered in the present study. These results suggest the presence of both ions at the gas-liquid interface, which is further supported by surface tension measurements. Surface tension data show a decreasing trend as the alkyl chain in the imidazolium cation is varied from methyl to butyl chain, with a specific anion. A similar trend is observed when the alkyl chain of the anion is modified and the cation is fixed.

  7. Genomic DNA fingerprinting of clinical Haemophilus influenzae isolates by polymerase chain reaction amplification: comparison with major outer-membrane protein and restriction fragment length polymorphism analysis

    NARCIS (Netherlands)

    van Belkum, A.; Duim, B.; Regelink, A.; Möller, L.; Quint, W.; van Alphen, L.

    1994-01-01

    Non-capsulate strains of Haemophilus influenzae were genotyped by analysis of variable DNA segments obtained by amplification of genomic DNA with the polymerase chain reaction (PCR fingerprinting). Discrete fragments of 100-2000 bp were obtained. The reproducibility of the procedure was assessed by

  8. Probing the effects of the ester functional group, alkyl side chain length and anions on the bulk nanostructure of ionic liquids: a computational study.

    Science.gov (United States)

    Fakhraee, Mostafa; Gholami, Mohammad Reza

    2016-04-14

    The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation.

  9. Integrated Use of n-Alkanes and PAH to Evaluate the Anthropogenic Hydrocarbon Sources and the Toxicity Assessment of Surface Sediments from the Southwestern Coasts of the Caspian Sea

    Directory of Open Access Journals (Sweden)

    Golshan Shirneshan

    2017-07-01

    Full Text Available Polycyclic aromatic hydrocarbon (PAH compounds and normal alkanes form a large group of undegradable environmental contaminats. This study aims to determine the sources and distribution of oil pollution (PAH compounds and normal alkanes in the sediments of the southwestern coastal areas of the Caspian Sea and to compare their levels with the relevant standards. For this purpose, 18 surface sediment samples were collected from depths of 10, 20, and 50 meters along two transects in the vertical direction located in the coastal areas of Sangachin and Hashtpar (Gilan Province. The samples were then examined using mass-spectrometric gas chromatography. The origins of n-alkanes were identified using CPI index (0.76-0.95, U/R (3.30‒6.57, and Pristane/Phytane (0.21‒0.42. The sources of PAHs were determined using the index ratios of LMW/HMW (1.93‒13.37, Phenanthrene/Anthracene (11.44‒ 16.7, Chrysene/Benzo (a anthracene (4.69‒10/33, Fluoranthene/Pyrene (0.53‒0.69, and MP/P (0.05‒0.08. Results confirmed the dominant petrogenic source of the hydrocarbons found in the region. The total concentrations of 30 aliphatic hydrocarbons and PAHs in the sediments ranged from 823.8 to 3899.5 µg/g and from 626.95 to 3842.5362 ng/g, respectively. Comparison of the measured PAH concentrations with US sediment quality guidelines revealed that the levels of naphthalene, fluorine, Acenaphthylene, and Acenaphthene exceeded the ERLs at stations with depths of 50m in Sangachin and Hashtpar while comparisons with Canadian standards indicated that they were higher than PELs at all the stations sampled. A major point of great concern is the high concentration of naphthalene as the most toxic PAH compound, which naturally warrants due attention to adopt appropriate management programs.

  10. Influence of chain length of pyrene fatty acids on their uptake and metabolism by Epstein-Barr-virus-transformed lymphoid cell lines from a patient with multisystemic lipid storage myopathy and from control subjects.

    OpenAIRE

    Radom, J; Salvayre, R; Levade, T; Douste-Blazy, L

    1990-01-01

    The uptake and intracellular metabolism of 4-(1-pyrene)butanoic acid (P4), 10-(1-pyrene)decanoic acid (P10) and 12-(1-pyrene)dodecanoic acid (P12) were investigated in cultured lymphoid cell lines from normal individuals and from a patient with multisystemic lipid storage myopathy (MLSM). The cellular uptake was shown to be dependent on the fatty-acid chain length, but no significant difference in the uptake of pyrene fatty acids was observed between MLSM and control lymphoid cells. After inc...

  11. Sublethal Toxic Effects and Induction of gGutathione S-transferase by Short-Chain Chlorinated Paraffins (SCCPs and C-12 alkane (dodecane in Xenopus laevis Frog Embryos

    Directory of Open Access Journals (Sweden)

    B. Burýšková

    2006-01-01

    Full Text Available Short chain chlorinated paraffins (SCCPs are important industrial chemicals with high persistence in the environment but poorly characterized ecotoxicological effects. We studied embryotoxic effects of commercial mixture of SCCP (carbon length C-12, 56% of chlorine; CP56-12 and non-chlorinated n-alkane (dodecane, C-12 in the 96h Frog Embryo Teratogenesis Assay - Xenopus (FETAX. Only weak lethal effects were observed for both substances (the highest tested concentration 500 mg/L of both chemicals caused up to 11% mortality. On the other hand, we observed developmental malformations and reduced embryo growth at 5 mg/l and higher concentrations. However, the effects were not related to chlorination pattern as both SCCPs and dodecane induced qualitatively similar effects. SCCPs also significantly induced phase II detoxification enzyme glutathione S-transferase (GST in Xenopus laevis embryos even at 0.5 mg/L, and this biomarker might be used as another early warning of chronic toxic effects. Our results newly indicate significant developmental toxicity of both SCCPs and n-dodecane to aquatic organisms along with inductions of specific biochemical toxicity mechanisms.

  12. Gamma-irradiation of homodeoxyoligonucleotides 32P-labelled at one end: computer simulation of the chain length distribution of the radioactive fragments

    International Nuclear Information System (INIS)

    Teoule, R.; Duplaa, A.M.

    1987-01-01

    Electrophoresis on polyacrylamide gels of the fragments resulting from γ-irradiation of single-stranded oligodeoxyribonucleotides labelled at their 5'- or 3'-end proved a potent tool for analysis of the radiation-induced chain breakage of DNA. Owing to the fact that the oligonucleotide may be ruptured at more than one site, counting of the electrophoresis bands must be corrected and it is necessary to assess the influence of the cleavage position on the band intensities. A complicating factor is the inhomogeneity of the system due to the presence of the four bases A, T, C and G. To circumvent this problem, the homooligodeoxyribonucleotides (dA) 15 , (dC) 15 , (dT) 15 were used as experimental probes. They were γ-irradiated in solution, heated in alkali and resulting fragments separated by gel electrophoresis. A computer simulation of band intensities was compiled based on the general assumption that the chain breakage is homogeneous. Experimental results obtained from the homooligodeoxyribonucleotides labelled at either the 5' or the 3'-end are in excellent agreement with theoretical calculations. Abacus giving the gel band intensities (percentage) against the nucleotide positions and the remaining intensity of the original oligonucleotide have been obtained. (author)

  13. Influence of chain length of pyrene fatty acids on their uptake and metabolism by Epstein-Barr-virus-transformed lymphoid cell lines from a patient with multisystemic lipid storage myopathy and from control subjects.

    Science.gov (United States)

    Radom, J; Salvayre, R; Levade, T; Douste-Blazy, L

    1990-01-01

    The uptake and intracellular metabolism of 4-(1-pyrene)butanoic acid (P4), 10-(1-pyrene)decanoic acid (P10) and 12-(1-pyrene)dodecanoic acid (P12) were investigated in cultured lymphoid cell lines from normal individuals and from a patient with multisystemic lipid storage myopathy (MLSM). The cellular uptake was shown to be dependent on the fatty-acid chain length, but no significant difference in the uptake of pyrene fatty acids was observed between MLSM and control lymphoid cells. After incubation for 1 h the distribution of fluorescent fatty acids taken up by the lymphoid cell lines also differed with the chain length, most of the fluorescence being associated with phospholipid and triacylglycerols. In contrast with P10 and P12, P4 was not incorporated into neutral lipids. When the cells were incubated for 24 h with the pyrene fatty acids, the amount of fluorescent lipids synthesized by the cells was proportional to the fatty acid concentration in the culture medium. After a 24 h incubation in the presence of P10 or P12, at any concentration, the fluorescent triacylglycerol content of MLSM cells was 2-5-fold higher than that of control cells. Concentrations of pyrene fatty acids higher than 40 microM seemed to be more toxic for mutant cells than for control cells. This cytotoxicity was dependent on the fluorescent-fatty-acid chain length (P12 greater than P10 greater than P4). Pulse-chase experiments permitted one to demonstrate the defect in the degradation of endogenously biosynthesized triacylglycerols in MLSM cells (residual activity was around 10-25% of controls on the basis of half-lives and initial rates of P10- or P12-labelled-triacylglycerol catabolism); MLSM lymphoid cells exhibited a mild phenotypic expression of the lipid storage (less severe than that observed in fibroblasts). P4 was not utilized in the synthesis of triacylglycerols, and thus did not accumulate in MLSM cells: this suggests that natural short-chain fatty acids might induce a lesser

  14. Engineering a disulfide bond in the lid hinge region of Rhizopus chinensis lipase: increased thermostability and altered acyl chain length specificity.

    Directory of Open Access Journals (Sweden)

    Xiao-Wei Yu

    Full Text Available The key to enzyme function is the maintenance of an appropriate balance between molecular stability and structural flexibility. The lid domain which is very important for "interfacial activation" is the most flexible part in the lipase structure. In this work, rational design was applied to explore the relationship between lid rigidity and lipase activity by introducing a disulfide bond in the hinge region of the lid, in the hope of improving the thermostability of R. chinensis lipase through stabilization of the lid domain without interfering with its catalytic performance. A disulfide bridge between F95C and F214C was introduced into the lipase from R. chinensis in the hinge region of the lid according to the prediction of the "Disulfide by Design" algorithm. The disulfide variant showed substantially improved thermostability with an eleven-fold increase in the t(1/2 value at 60°C and a 7°C increase of T(m compared with the parent enzyme, probably contributed by the stabilization of the geometric structure of the lid region. The additional disulfide bond did not interfere with the catalytic rate (k(cat and the catalytic efficiency towards the short-chain fatty acid substrate, however, the catalytic efficiency of the disulfide variant towards pNPP decreased by 1.5-fold probably due to the block of the hydrophobic substrate channel by the disulfide bond. Furthermore, in the synthesis of fatty acid methyl esters, the maximum conversion rate by RCLCYS reached 95% which was 9% higher than that by RCL. This is the first report on improving the thermostability of the lipase from R. chinensis by introduction of a disulfide bond in the lid hinge region without compromising the catalytic rate.

  15. Dynamics of cyanophenyl alkylbenzoate molecules in the bulk and in a surface layer adsorbed onto aerosil. Variation of the lengths of the alkyl chain

    Energy Technology Data Exchange (ETDEWEB)

    Frunza, Stefan [National Institute of Materials Physics, R-077125 Magurele (Romania); Schoenhals, Andreas [BAM Federal Institute of Materials Research and Testing, D-12205 Berlin (Germany); Frunza, Ligia, E-mail: lfrunza@infim.ro [National Institute of Materials Physics, R-077125 Magurele (Romania); Beica, Traian; Zgura, Irina; Ganea, Paul [National Institute of Materials Physics, R-077125 Magurele (Romania); Stoenescu, Daniel [Telecom-Bretagne, Departement d' Optique, Technopole Brest-Iroise 29238 Cedex (France)

    2010-06-16

    Graphical abstract: The temperature dependence of the molecular mobility in composites shows an Arrhenius-type regime at low temperature and a glassy-type one at higher temperature separated by a crossover phenomenon. - Abstract: The molecular mobility of 4-butyl- and 4-pentyl-4'-cyanophenyl benzoate (CP4B, CP5B) and their composites prepared from aerosil A380 was investigated by broadband dielectric spectroscopy in a large temperature range. Thermogravimetric and infrared investigations were additionally performed. High silica density (larger than 7 g aerosil/1 g of liquid crystal) was selected to observe a thin layer adsorbed on the surface of the silica particles. The data were compared with those of the member of the series with six carbon atoms in the alkyl tail. Bulk CP4B and CP5B show the dielectric behaviour expected for liquid crystals. For the composites one relaxation process is observed at frequencies much lower than those for the corresponding bulk, which was assigned to the dynamics of the molecules in a surface layer. The temperature dependence of the relaxation rates (and of the dielectric strength) shows a crossover behaviour with two distinguished regimes. At higher temperatures the data obey the Vogel-Fulcher-Tammann law, whereas an Arrhenius law is observed at lower temperature, in a close similarity to the behaviour of a constrained dynamic glass transition. The estimated Vogel and crossover temperature is independent on the tail length, while the activation energy for the low temperature branch increases weakly with increasing the alkyl tail.

  16. Genetic polymorphism of toll-like receptors 4 gene by polymerase chain reaction-restriction fragment length polymorphisms, polymerase chain reaction-single-strand conformational polymorphism to correlate with mastitic cows

    Directory of Open Access Journals (Sweden)

    Pooja H. Gupta

    2015-05-01

    Full Text Available Aim: An attempt has been made to study the toll-like receptors 4 (TLR4 gene polymorphism from cattle DNA to correlate with mastitis cows. Materials and Methods: In present investigation, two fragments of TLR4 gene named T4CRBR1 and T4CRBR2 of a 316 bp and 382 bp were amplified by polymerase chain reaction (PCR, respectively from Kankrej (22 and Triple cross (24 cattle. The genetic polymorphisms in the two populations were detected by a single-strand conformational polymorphism in the first locus and by digesting the fragments with restriction endonuclease Alu I in the second one. Results: Results showed that both alleles (A and B of two loci were found in all the two populations and the value of polymorphism information content indicated that these were highly polymorphic. Statistical results of χ2 test indicated that two polymorphism sites in the two populations fit with Hardy–Weinberg equilibrium (p˂0.05. Meanwhile, the effect of polymorphism of TLR4 gene on the somatic cell score (SCS indicated the cattle with allele a in T4CRBR1 showed lower SCS than that of allele B (p<0.05. Thus, the allele A might play an important role in mastitis resistance in cows. Conclusion: The relationship between the bovine mastitis trait and the polymorphism of TLR4 gene indicated that the bovine TLR4 gene may play an important role in mastitis resistance.

  17. N-terminal fatty acylated His-dPhe-Arg-Trp-NH(2) tetrapeptides: influence of fatty acid chain length on potency and selectivity at the mouse melanocortin receptors and human melanocytes.

    Science.gov (United States)

    Todorovic, Aleksandar; Holder, Jerry Ryan; Bauzo, Rayna M; Scott, Joseph Walker; Kavanagh, Renny; Abdel-Malek, Zalfa; Haskell-Luevano, Carrie

    2005-05-05

    The melanocortin system is involved in the regulation of a diverse number of physiologically important pathways including pigmentation, feeding behavior, weight and energy homeostasis, inflammation, and sexual function. All the endogenous melanocortin agonist ligands possess the conserved His-Phe-Arg-Trp tetrapeptide sequence that is postulated to be important for melanocortin receptor molecular recognition and stimulation. Previous studies by our laboratory resulted in the discovery that increasing alkyl chain length at the N-terminal "capping" region of the His-dPhe-Arg-Trp-NH(2) tetrapeptide resulted in a 100-fold increased melanocortin receptor agonist potency. This study was undertaken to systematically evaluate the pharmacological effects of increasing N-capping alkyl chain length of the CH(3)(CH(2))(n)CO-His-dPhe-Arg-Trp-NH(2) (n = 6-16) tetrapeptide template. Twelve analogues were synthesized and pharmacologically characterized at the mouse melanocortin receptors MC1R and MC3R-MC5R and human melanocytes known to express the MC1R. These peptides demonstrated melanocortin receptor selectivity profiles different from those of previously published tetrapeptides. The most notable results of enhanced ligand potency (20- to 200-fold) and receptor selectivity were observed at the MC1R. Tetrapeptides that possessed greater than nine alkyl groups were superior to alpha-MSH in terms of the stimulation of human melanocyte tyrosinase activity. Additionally, the n-pentadecanoyl derivative had a residual effect on tyrosinase activity that existed for at least 4 days after the peptide was removed from the human melanocyte culture medium. These data demonstrate the utility, potency, and residual effect of melanocortin tetrapeptides by adding N-terminal fatty acid moieties.

  18. Maternal long chain polyunsaturated fatty acid supplementation in infancy increases length- and weight-for-age but not BMI to 6 years when controlling for effects of maternal smoking

    Science.gov (United States)

    Currie, L.M.; Tolley, E.A.; Thodosoff, J.M.; Kerling, E.H.; Sullivan, D.K.; Colombo, J.; Carlson, S.E.

    2015-01-01

    Summary Long chain polyunsaturated fatty acids (LCPUFA) are added to infant formula but their effect on long-term growth of children is under studied. We evaluated the effects of feeding LCPUFA-supplemented formula (n=54) compared to control formula (n=15) throughout infancy on growth from birth-6 years. Growth was described using separate models developed with the MIXED procedure of SAS® that included maternal smoking history and gender. Compared to children fed control formula, children who consumed LCPUFA supplemented formula had higher length-/stature-/and weight-for-age percentiles but not body mass index (BMI) percentile from birth to 6 years. Maternal smoking predicted lower stature (2-6 years), higher weight-for-length (birth-18 months) and BMI percentile (2-6 years) independent of LCPUFA effects. Gender interacted with the effect of LCPUFA on stature, and the relationship between smoking and BMI, with a larger effect for boys. Energy intake did not explain growth differences. A relatively small control sample is a limitation. PMID:25936840

  19. Fundamental length and relativistic length

    International Nuclear Information System (INIS)

    Strel'tsov, V.N.

    1988-01-01

    It si noted that the introduction of fundamental length contradicts the conventional representations concerning the contraction of the longitudinal size of fast-moving objects. The use of the concept of relativistic length and the following ''elongation formula'' permits one to solve this problem

  20. Flame Length

    Data.gov (United States)

    Earth Data Analysis Center, University of New Mexico — Flame length was modeled using FlamMap, an interagency fire behavior mapping and analysis program that computes potential fire behavior characteristics. The tool...

  1. Analytical calculation of chain length in ferrofluids

    Indian Academy of Sciences (India)

    2Department of Mechanical Engineering, Tezpur University, Assam 784028, India. MS received 4 ... under an external magnetic field applied parallel to the slit containing the ... of competition between magnetic dipolar interaction and.

  2. Chemotaxonomy in some Mediterranean plants and implications for fossil biomarker records

    Science.gov (United States)

    Norström, Elin; Katrantsiotis, Christos; Smittenberg, Rienk H.; Kouli, Katerina

    2017-12-01

    The increasing utilization of n-alkanes as plant-derived paleo-environmental proxies calls for improved chemotaxonomic control of the modern flora in order to calibrate fossil sediment records to modern analogues. Several recent studies have investigated long-chain n-alkane concentrations and chain-length distributions in species from various vegetation biomes, but up to date, the Mediterranean flora is relatively unexplored in this respect. Here, we analyse the n-alkane concentrations and chain-length distributions in some of the most common species of the modern macchia and phrygana vegetation in south western Peloponnese, Greece. We show that the drought adapted phrygana herbs and shrubs, as well as some of the sclerophyll and gymnosperm macchia components, produce high concentrations of n-alkanes, on average more than double n-alkane production in local wetland reed vegetation. Furthermore, the chain-length distribution in the analysed plants is related to plant functionality, with longer chain lengths associated with higher drought adaptive capacities, probably as a response to long-term evolutionary processes in a moisture limited environment. Furthermore, species with relatively higher average chain lengths (ACL) showed more enriched carbon isotope composition in their tissues (δ13Cplant), suggesting a dual imprint from both physiological and biochemical drought adaptation. The findings have bearings on interpretation of fossil sedimentary biomarker records in the Mediterranean region, which is discussed in relation to a case study from Agios Floros fen, Messenian plain, Peloponnese. The 6000 year long n-alkane record from Agios Floros (ACL, δ13Cwax) is linked to the modern analogue and then evaluated through a comparison with other regional-wide as well as local climate and vegetation proxy-data. The high concentration of long chain n-alkanes in phrygana vegetation suggests a dominating imprint from this vegetation type in sedimentary archives from this

  3. Production of n-alkyl lipids in living plants and implications for the geologic past

    Science.gov (United States)

    Diefendorf, Aaron F.; Freeman, Katherine H.; Wing, Scott L.; Graham, Heather V.

    2011-12-01

    Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ 13C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes ( ɛlipid) varies by as much as 10‰ among different chain lengths. Overall, ɛlipid values are slightly lower (-4.5‰) for angiosperm than for gymnosperm (-2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δleaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in 13C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented

  4. Fundamental length

    International Nuclear Information System (INIS)

    Pradhan, T.

    1975-01-01

    The concept of fundamental length was first put forward by Heisenberg from purely dimensional reasons. From a study of the observed masses of the elementary particles known at that time, it is sumrised that this length should be of the order of magnitude 1 approximately 10 -13 cm. It was Heisenberg's belief that introduction of such a fundamental length would eliminate the divergence difficulties from relativistic quantum field theory by cutting off the high energy regions of the 'proper fields'. Since the divergence difficulties arise primarily due to infinite number of degrees of freedom, one simple remedy would be the introduction of a principle that limits these degrees of freedom by removing the effectiveness of the waves with a frequency exceeding a certain limit without destroying the relativistic invariance of the theory. The principle can be stated as follows: It is in principle impossible to invent an experiment of any kind that will permit a distintion between the positions of two particles at rest, the distance between which is below a certain limit. A more elegant way of introducing fundamental length into quantum theory is through commutation relations between two position operators. In quantum field theory such as quantum electrodynamics, it can be introduced through the commutation relation between two interpolating photon fields (vector potentials). (K.B.)

  5. Differentiation of canine distemper virus isolates in fur animals from various vaccine strains by reverse transcription-polymerase chain reaction-restriction fragment length polymorphism according to phylogenetic relations in china

    Directory of Open Access Journals (Sweden)

    Zhao Jianjun

    2011-02-01

    Full Text Available Abstract In order to effectively identify the vaccine and field strains of Canine distemper virus (CDV, a new differential diagnostic test has been developed based on reverse transcription-polymerase chain reaction (RT-PCR and restriction fragment length polymorphism (RFLP. We selected an 829 bp fragment of the nucleoprotein (N gene of CDV. By RFLP analysis using BamHI, field isolates were distinguishable from the vaccine strains. Two fragments were obtained from the vaccine strains by RT-PCR-RFLP analysis while three were observed in the field strains. An 829 nucleotide region of the CDV N gene was analyzed in 19 CDV field strains isolated from minks, raccoon dogs and foxes in China between 2005 and 2007. The results suggest this method is precise, accurate and efficient. It was also determined that three different genotypes exist in CDV field strains in fur animal herds of the north of China, most of which belong to Asian type. Mutated field strains, JSY06-R1, JSY06-R2 and JDH07-F1 also exist in Northern China, but are most closely related to the standard virulent strain A75/17, designated in Arctic and America-2 genetype in the present study, respectively.

  6. Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat; Shekaari, Hemayat; Hosseini, Rahim

    2009-01-01

    The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C 3 ), hexyl (C 6 ), heptyl (C 7 ), and octyl (C 8 )) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol . kg -1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [C n mim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich-Mayer and the Pitzer's equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute-solvent and solute-solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made

  7. Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)], E-mail: rahsadeghi@yahoo.com; Shekaari, Hemayat [Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of); Hosseini, Rahim [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)

    2009-02-15

    The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C{sub 3}), hexyl (C{sub 6}), heptyl (C{sub 7}), and octyl (C{sub 8})) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol . kg{sup -1} were taken. The values of the compressibilities, expansivity and apparent molar properties for [C{sub n}mim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich-Mayer and the Pitzer's equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute-solvent and solute-solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made.

  8. The straight-chain lipid biomarker composition of plant species responsible for the dominant biomass production along two altitudinal transects in the Ecuadorian Andes

    Energy Technology Data Exchange (ETDEWEB)

    Jansen, Boris; Nierop, Klaas G.J.; Verstraten, Jacobus M.; Cleef, Antoine M. [Amsterdam Univ., Center for Geo-ecological Research (ICG), Amsterdam (Netherlands); Hageman, Jos A. [Amsterdam Univ., Swammerdam Inst. for Life Sciences (SILS), Amsterdam (Netherlands)

    2006-11-15

    For a detailed reconstruction of historic upper forest line (UFL) positions, new proxies in addition to traditional pollen and vegetation analyses are needed. If the straight-chain lipid composition in plant leaves and roots is specific enough to allow distinction, their records in soils and peat bogs might be used for this purpose. We tested for such distinctiveness by analyzing the n-alkane, n-alcohol, n-aldehyde and wax ester composition in lipid extracts from the leaves and roots of the 19 plant species responsible for the dominant biomass input into soils and peat bogs along two altitudinal transects in the Ecuadorian Andes. We found the combined n-alkane and n-alcohol composition of the leaves of the studied plants to be unique enough in theory to allow for a distinction of the various plant species. The extractable straight-chain lipid concentrations in the roots were generally much lower than in the leaves of the same species, and were in many cases less specific. The n-fatty acids, n-aldehydes and wax ester compositions in leaves as well as roots appeared to be less suited as biomarkers, due to a lower specificity of the n-fatty acids and the absence of the n-aldehydes and wax ester from a significant number of plant species. Furthermore, using cluster analysis we found the combination of n-alkanes and n-alcohols from leaves to give the most meaningful clustering from the point of view of an UFL reconstruction, with all but one paramo grassland species and all but one peat bog species clustering separately from forest species. In addition, a large C{sub 31} /C{sub 27} n-alkane ratio as well as a large C{sub 26} /C{sub 30} n-alcohol ratio were found to be indicative of paramo vegetation (grasses). Both clustering and ratios can help reconstruct past UFL positions if discerning individual species from soil or peat records proves unfeasible. The preservation of the straight-chain lipid signal was tested in soil and peat samples from the study area predating

  9. Kondo length in bosonic lattices

    Science.gov (United States)

    Giuliano, Domenico; Sodano, Pasquale; Trombettoni, Andrea

    2017-09-01

    Motivated by the fact that the low-energy properties of the Kondo model can be effectively simulated in spin chains, we study the realization of the effect with bond impurities in ultracold bosonic lattices at half filling. After presenting a discussion of the effective theory and of the mapping of the bosonic chain onto a lattice spin Hamiltonian, we provide estimates for the Kondo length as a function of the parameters of the bosonic model. We point out that the Kondo length can be extracted from the integrated real-space correlation functions, which are experimentally accessible quantities in experiments with cold atoms.

  10. SAXS study of transient pre-melting in chain-folded alkanes

    International Nuclear Information System (INIS)

    Ungar, G.; Wills, H.H.

    1990-01-01

    A pronounced pre-melting effect is observed in chain-folded crystals of pure monodisperse n-alkane C 246 H 494 . The effect is reversible on a short time scale, but at longer times the once-folded chain crystals are irreversibly lost as slow chain extension proceeds by solid diffusion well below the melting point. The melting process is thus monitored by rapid time-resolved small-angle X-ray (SAXS) measurements, using synchrotron radiation. The results show that the observed pronounced broadening of the DSC melting endotherm for chain-folded crystals is entirely due to genuine pre-melting of lamellar surfaces. Although a significant portion of material is already molten below the final melting point of chain-folded crystals T F , no recrystallization in the chain-extended form can occur until the cores of the crystalline lamellae melt at T F . Pre-melting of extended chain crystals is significantly less pronounced than that of folded chain crystals

  11. Application of novel catalytic-ceramic-filler in a coupled system for long-chain dicarboxylic acids manufacturing wastewater treatment.

    Science.gov (United States)

    Wu, Suqing; Qi, Yuanfeng; Fan, Chunzhen; He, Shengbing; Dai, Bibo; Huang, Jungchen; Zhou, Weili; Gao, Lei

    2016-02-01

    To gain systematic technology for long-chain dicarboxylic acids (LDCA) manufacturing wastewater treatment, catalytic micro-electrolysis (CME) coupling with adsorption-biodegradation sludge (AB) process was studied. Firstly, novel catalytic-ceramic-filler was prepared from scrap iron, clay and copper sulfate solution and packed in the CME reactor. To remove residual n-alkane and LDCA, the CME reactor was utilized for LDCA wastewater pretreatment. The results revealed that about 94% of n-alkane, 98% of LDCA and 84% of chemical oxygen demand (COD) were removed by the aerated CME reactor at the optimum hydraulic retention time (HRT) of 3.0 h. In this process, catalysis from Cu and montmorillonites played an important role in improving the contaminants removal. Secondly, to remove residual COD in the wastewater, AB process was designed for the secondary biological treatment, about 90% of the influent COD could be removed by biosorption, bio-flocculation and biodegradation effects. Finally, the effluent COD (about 150 mg L(-1)) discharged from the coupled CME-AB system met the requirement of the national discharged standard (COD ≤ 300 mg L(-1)). All of these results suggest that the coupled CME-AB system is a promising technology due to its high-efficient performance, and has the potential to be applied for the real LDCA wastewater treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Uso de n-alcanos na estimativa da composição botânica da dieta em ovinos alimentados com diferentes proporções de Brachiaria decumbens Stapf e Arachis pintoi Koprov e Gregory Use of n-alkanes to estimate the dietary botanical composition in sheep fed different proportions of Brachiaria decumbens Stapf and Arachis pintoi Koprov and Gregory

    Directory of Open Access Journals (Sweden)

    Nelson Massaru Fukumoto

    2007-08-01

    Full Text Available Neste experimento objetivou-se avaliar o poder discriminatório dos n-alcanos para estimar com acurácia e precisão a composição botânica da dieta em ovinos alimentados com diferentes proporções de Arachis pintoi Koprov & Gregory cv. Amarillo (0, 15, 30, 45 e 60% e Brachiaria decumbens Stapf. Foram utilizados 20 ovinos em delineamento inteiramente casualizado, com período experimental de dez dias de adaptação à dieta e cinco dias de coleta de fezes. Nas amostras (compostas de fezes do período e nos fenos, foi analisada a concentração de n-alcanos. Para o cálculo da composição botânica, utilizou-se minimização da soma dos quadrados dos desvios, considerando as concentrações dos alcanos nos componentes da dieta e nas fezes. Para a escolha dos alcanos mais discriminatórios, foram utilizadas as análises multivariadas e as variáveis canônicas. As estimativas calculadas foram submetidas à análise de variância. As médias foram comparadas pelo teste t e as correções dos valores estimados em relação aos valores reais foram ajustadas em regressão linear. As variáveis canônicas indicaram que os alcanos C35, C33, C30, C31, C27, C29 e C36 são os de maior potencial discriminatório. O uso desses alcanos nos cálculos foi mais acurado e preciso para estimar a proporção de A. pintoi na dieta que o uso de apenas dois ou três alcanos com poder discriminatório. O melhor ajuste da regressão também foi encontrado para esses alcanos. O teste t para o intercepto da equação (a e o coeficiente de regressão (b indicaram que a = 0 e b = 1, comprovando que os valores estimados são equivalentes aos valores reais. As análises multivariadas mostraram-se ferramentas de grande importância na escolha dos n-alcanos nos cálculos nas estimativas.The objective of this experiment was to use n-alkane to estimate accurately and precisely the botanical composition of dietary forage in sheep fed different proportions of Arachis pintoi

  13. Adsorption of small hydrocarbons on rutile TiO2(110)

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Long; Smith, R. Scott; Kay, Bruce D.; Dohnalek, Zdenek

    2016-08-01

    Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

  14. GENOMIC DNA-FINGERPRINTING OF CLINICAL HAEMOPHILUS-INFLUENZAE ISOLATES BY POLYMERASE CHAIN-REACTION AMPLIFICATION - COMPARISON WITH MAJOR OUTER-MEMBRANE PROTEIN AND RESTRICTION-FRAGMENT-LENGTH-POLYMORPHISM ANALYSIS

    NARCIS (Netherlands)

    VANBELKUM, A; DUIM, B; REGELINK, A; MOLLER, L; QUINT, W; VANALPHEN, L

    Non-capsulate strains of Haemophilus influenzae were genotyped by analysis of variable DNA segments obtained by amplification of genomic DNA with the polymerase chain reaction (PCR fingerprinting). Discrete fragments of 100-2000 bp were obtained. The reproducibility of the procedure was assessed by

  15. Molecular structure stability of short-chain chlorinated paraffins (SCCPs): Evidence from lattice compatibility and Simha-Somcynsky theories

    Science.gov (United States)

    Yumak, A.; Boubaker, K.; Petkova, P.; Yahsi, U.

    2015-10-01

    In is known that short-chain chlorinated paraffins (SCCPs) are highly complex technical mixtures of polychlorinated n-alkanes with single chlorine content. Due to their physical properties (viscosity, flame resistance) they are used in many different applications, such as lubricant additives, metal processing, leather fat-liquoring, plastics softening, PVC plasticizing and flame retardants in paints, adhesives and sealants. SCCPs are studied here in terms of processing-linked molecular structure stability, under Simha and Somcynsky-EOS theory calculations and elements from Simha-Somcynsky-related Lattice Compatibility Theory. Analyses were carried out on 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro 2-methylane, and 2-chloro 2-methylane as (SCCPs) universal representatives. This paper gives evidence to this stability and reviews the current state of knowledge and highlights the need for further research in order to improve future (SCCPs) monitoring efforts.

  16. Falling chains

    OpenAIRE

    Wong, Chun Wa; Yasui, Kosuke

    2005-01-01

    The one-dimensional fall of a folded chain with one end suspended from a rigid support and a chain falling from a resting heap on a table is studied. Because their Lagrangians contain no explicit time dependence, the falling chains are conservative systems. Their equations of motion are shown to contain a term that enforces energy conservation when masses are transferred between subchains. We show that Cayley's 1857 energy nonconserving solution for a chain falling from a resting heap is inco...

  17. Telomere Length and Mortality

    DEFF Research Database (Denmark)

    Kimura, Masayuki; Hjelmborg, Jacob V B; Gardner, Jeffrey P

    2008-01-01

    Leukocyte telomere length, representing the mean length of all telomeres in leukocytes, is ostensibly a bioindicator of human aging. The authors hypothesized that shorter telomeres might forecast imminent mortality in elderly people better than leukocyte telomere length. They performed mortality...

  18. Thermodynamic parameters for the adsorption of volatile n-alkane ...

    African Journals Online (AJOL)

    alkanes hexane to nonane on ground dried water hyacinth (E. crassipes) root biomass were studied between 40 and 70°C column temperature using inverse gas chromatography, before and after treatment of the root biomass with mineral acid ...

  19. n-Alkanes in surficial sediments of Visakhapatnam harbour, east ...

    Indian Academy of Sciences (India)

    Visakhapatnam harbour, a semi-enclosed water body is one of the .... PDB − 1. } × 1000. 2.5 Extraction of lipids. Total lipids (TL) were extracted from lyophilized sediments following ..... 2010 Sources of OM and microbial community structure.

  20. Unit and internal chain profiles of maca amylopectin.

    Science.gov (United States)

    Zhang, Ling; Li, Guantian; Yao, Weirong; Zhu, Fan

    2018-03-01

    Unit chain length distributions of amylopectin and its φ, β-limit dextrins, which reflect amylopectin internal structure from three maca starches, were determined by high-performance anion-exchange chromatography with pulsed amperometric detection after debranching, and the samples were compared with maize starch. The amylopectins exhibited average chain lengths ranging from 16.72 to 17.16, with ranges of total internal chain length, external chain length, and internal chain length of the maca amylopectins at 12.49 to 13.68, 11.24 to 11.89, and 4.27 to 4.48. The average chain length, external chain length, internal chain length, and total internal chain length were comparable in three maca amylopectins. Amylopectins of the three maca genotypes studied here presented no significant differences in their unit chain length profiles, but did show significant differences in their internal chain profiles. Additional genetic variations between different maca genotypes need to be studied to provide unit- and internal chain profiles of maca amylopectin. Copyright © 2017. Published by Elsevier Ltd.

  1. Chain networking revealed by molecular dynamics simulation

    Science.gov (United States)

    Zheng, Yexin; Tsige, Mesfin; Wang, Shi-Qing

    Based on Kremer-Grest model for entangled polymer melts, we demonstrate how the response of a polymer glass depends critically on the chain length. After quenching two melts of very different chain lengths (350 beads per chain and 30 beads per chain) into deeply glassy states, we subject them to uniaxial extension. Our MD simulations show that the glass of long chains undergoes stable necking after yielding whereas the system of short chains is unable to neck and breaks up after strain localization. During ductile extension of the polymer glass made of long chain significant chain tension builds up in the load-bearing strands (LBSs). Further analysis is expected to reveal evidence of activation of the primary structure during post-yield extension. These results lend support to the recent molecular model 1 and are the simulations to demonstrate the role of chain networking. This work is supported, in part, by a NSF Grant (DMR-EAGER-1444859)

  2. Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments.

    Directory of Open Access Journals (Sweden)

    Arpita eBose

    2013-12-01

    Full Text Available Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2-C5 and longer alkanes. C2-C4 alkanes such as ethane, propane and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1-C4 then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist. Changes in the δ13C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4‰ and 4.5‰ respectively. The concurrent depletion in the δ13C of dissolved inorganic carbon (DIC implies a transfer of carbon from the alkane to the DIC pool (-3.5 and -6.7‰ for C3 and C4 incubations, respectively. Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1-C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3-C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial community

  3. Extraction of pentylbenzene from high molar mass alkanes (C14 and C17) by N-methyl-2-pyrrolidone

    International Nuclear Information System (INIS)

    Fandary, Mohamed S.; Al-Jimaz, Adel S.; Al-Kandary, Jasem A.; Fahim, Mohamed A.

    2006-01-01

    Equilibrium tie line data have been determined for the two ternary liquid systems: {tetradecane, or heptadecane + pentylbenzene + N-methyl-2-pyrrolidone (NMP)} over a temperature range of (298 to 328) K. The two systems studied exhibit type I liquid + liquid phase diagram. The effect of temperature and n-alkane chain length upon solubility, selectivity, and distribution coefficients were investigated experimentally

  4. Partial nucleotide sequences, and routine typing by polymerase chain reaction-restriction fragment length polymorphism, of the brown trout (Salmo trutta) lactate dehydrogenase, LDH-C1*90 and *100 alleles.

    Science.gov (United States)

    McMeel, O M; Hoey, E M; Ferguson, A

    2001-01-01

    The cDNA nucleotide sequences of the lactate dehydrogenase alleles LDH-C1*90 and *100 of brown trout (Salmo trutta) were found to differ at position 308 where an A is present in the *100 allele but a G is present in the *90 allele. This base substitution results in an amino acid change from aspartic acid at position 82 in the LDH-C1 100 allozyme to a glycine in the 90 allozyme. Since aspartic acid has a net negative charge whilst glycine is uncharged, this is consistent with the electrophoretic observation that the LDH-C1 100 allozyme has a more anodal mobility relative to the LDH-C1 90 allozyme. Based on alignment of the cDNA sequence with the mouse genomic sequence, a local primer set was designed, incorporating the variable position, and was found to give very good amplification with brown trout genomic DNA. Sequencing of this fragment confirmed the difference in both homozygous and heterozygous individuals. Digestion of the polymerase chain reaction products with BslI, a restriction enzyme specific for the site difference, gave one, two and three fragments for the two homozygotes and the heterozygote, respectively, following electrophoretic separation. This provides a DNA-based means of routine screening of the highly informative LDH-C1* polymorphism in brown trout population genetic studies. Primer sets presented could be used to sequence cDNA of other LDH* genes of brown trout and other species.

  5. Consumo e digestibilidade da matéria seca de fenos de braquiária decumbens e amendoim forrageiro em ovinos estimados por meio de n-alcanos Use of n-alkanes to estimate intake and digestibility of signalgrass and forage peanut in sheep

    Directory of Open Access Journals (Sweden)

    Nelson Massaru Fukumoto

    2007-04-01

    Full Text Available O experimento foi realizado com os objetivos de avaliar a técnica de n-alcanos para estimar o consumo e a digestibilidade da MS em ovinos e definir a estratégia de coleta de fezes e os alcanos internos a serem utilizados no cálculos. Vinte ovinos foram distribuídos em delineamento inteiramente casualizado e alimentados com dietas formuladas com diferentes proporções de amendoim forrageiro (Arachis pintoi Koprov & Gregory cv. Amarillo e braquiária decumbens [Urochloa decumbens (Stapf, Webster] (0, 15, 30, 45 e 60% de amendoim forrageiro, base da MS. O período experimental teve duração de 18 dias, dez de adaptação à dieta, três para administração do indicador externo (C32 em péletes de celulose e cinco de coleta de fezes. As fezes foram coletadas seis vezes ao dia (9, 13, 17, 21, 1 e 5h, diretamente no reto do animal. Os dados foram submetidos à análise de variância e as comparações das médias estimadas aos valores reais foram feitas utilizando-se o teste t a 5% de significância. Para determinação da digestibilidade aparente da MS, os animais foram equipados com bolsas coletoras de fezes. O consumo foi calculado utilizando-se os alcanos internos C31 e C33 isoladamente ou em conjunto. Para o cálculo da digestibilidade da MS, foram utilizados os alcanos internos C33 a C35. Para obtenção de estimativas adequadas de digestibilidade, é necessária a correção para os valores de recuperação fecal dos indicadores internos, observando-se que os melhores resultados foram obtidos quando se utilizou o alcano interno C33 nos cálculos. Para estimar o consumo de MS, devem-se utilizar, de forma conjunta nos cálculos, os alcanos internos C31 e C33, sem necessidade de correção para recuperação fecal, podendo-se coletar uma única amostra de fezes por animal por dia, pela manhã (9 h ou à tarde (13 h.The objective of this trial was to use n-alkanes to estimate dry matter intake (DMI and DM digestibility in sheep. It was also

  6. Quantifying Short-Chain Chlorinated Paraffin Congener Groups

    NARCIS (Netherlands)

    Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A.; Alsberg, Tomas; Wit, de Cynthia A.

    2017-01-01

    Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are

  7. Chain Assembly and Disassembly Processes Differently Affect the Conformational Space of Ubiquitin Chains.

    Science.gov (United States)

    Kniss, Andreas; Schuetz, Denise; Kazemi, Sina; Pluska, Lukas; Spindler, Philipp E; Rogov, Vladimir V; Husnjak, Koraljka; Dikic, Ivan; Güntert, Peter; Sommer, Thomas; Prisner, Thomas F; Dötsch, Volker

    2018-02-06

    Ubiquitination is the most versatile posttranslational modification. The information is encoded by linkage type as well as chain length, which are translated by ubiquitin binding domains into specific signaling events. Chain topology determines the conformational space of a ubiquitin chain and adds an additional regulatory layer to this ubiquitin code. In particular, processes that modify chain length will be affected by chain conformations as they require access to the elongation or cleavage sites. We investigated conformational distributions in the context of chain elongation and disassembly using pulsed electron-electron double resonance spectroscopy in combination with molecular modeling. Analysis of the conformational space of diubiquitin revealed conformational selection or remodeling as mechanisms for chain recognition during elongation or hydrolysis, respectively. Chain elongation to tetraubiquitin increases the sampled conformational space, suggesting that a high intrinsic flexibility of K48-linked chains may contribute to efficient proteasomal degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Tunnel current across linear homocatenated germanium chains

    International Nuclear Information System (INIS)

    Matsuura, Yukihito

    2014-01-01

    The electronic transport properties of germanium oligomers catenating into linear chains (linear Ge chains) have been theoretically studied using first principle methods. The conduction mechanism of a Ge chain sandwiched between gold electrodes was analyzed based on the density of states and the eigenstates of the molecule in a two-probe environment. Like that of silicon chains (Si chains), the highest occupied molecular orbital of Ge chains contains the extended σ-conjugation of Ge 4p orbitals at energy levels close to the Fermi level; this is in contrast to the electronic properties of linear carbon chains. Furthermore, the conductance of a Ge chain is expected to decrease exponentially with molecular length L. The decay constant β, which is defined as e −βL , of a Ge chain is similar to that of a Si chain, whereas the conductance of the Ge chains is higher than that of Si chains even though the Ge–Ge bond length is longer than the Si–Si bond length

  9. Kinematics and Dynamics of Roller Chain Drives

    DEFF Research Database (Denmark)

    Fuglede, Niels

    There are two main subjects of this work: Kinematic and dynamic modeling and analysis of roller chain drives. In the kinematic analysis we contribute first with a complete treatment of the roller chain drive modeled as a four-bar mechanism. This includes a general, exact and approximate analysis...... which is useful for predicting the characteristic loading of the roller chain drive. As a completely novel contribution, a kinematic model and analysis is presented which includes both spans and sprockets in a simple chain drive system. A general procedure for determination of the total wrapping length...... is presented, which also allows for exact sprocket center positions for a chain with a given number of links. Results show that the total chain wrapping length varies periodically with the tooth frequency. These results are of practical importance to both the design, installation and operation of roller chain...

  10. CHAIN 2

    International Nuclear Information System (INIS)

    Bailey, D.

    1998-04-01

    The Second Processing Chain (CHAIN2) consists of a suite of ten programs which together provide a full local analysis of the bulk plasma physics within the JET Tokamak. In discussing these ten computational models this report is intended to fulfil two broad purposes. Firstly it is meant to be used as a reference source for any user of CHAIN2 data, and secondly it provides a basic User Manual sufficient to instruct anyone in running the CHAIN2 suite of codes. In the main report text each module is described in terms of its underlying physics and any associated assumptions or limitations, whilst deliberate emphasis is put on highlighting the physics and mathematics of the calculations required in deriving each individual datatype in the standard module PPF output. In fact each datatype of the CHAIN2 PPF output listed in Appendix D is cross referenced to the point in the main text where its evaluation is discussed. An effort is made not only to give the equation used to derive a particular data profile but also to explicitly define which external data sources are involved in the computational calculation

  11. Telomere length analysis.

    Science.gov (United States)

    Canela, Andrés; Klatt, Peter; Blasco, María A

    2007-01-01

    Most somatic cells of long-lived species undergo telomere shortening throughout life. Critically short telomeres trigger loss of cell viability in tissues, which has been related to alteration of tissue function and loss of regenerative capabilities in aging and aging-related diseases. Hence, telomere length is an important biomarker for aging and can be used in the prognosis of aging diseases. These facts highlight the importance of developing methods for telomere length determination that can be employed to evaluate telomere length during the human aging process. Telomere length quantification methods have improved greatly in accuracy and sensitivity since the development of the conventional telomeric Southern blot. Here, we describe the different methodologies recently developed for telomere length quantification, as well as their potential applications for human aging studies.

  12. Carbon chain length and the stimulus problem in oldfaction

    NARCIS (Netherlands)

    Boesveldt, S.; Olsson, M.; Lundstrom, J.N.

    2010-01-01

    Understanding how odour quality perception is encoded in its molecular properties arguably poses one of the most significant problems in olfaction. Determining the odour structure–quality relationships of structurally similar odorants could provide a key tool to this problem. We tentatively explored

  13. Electrostatic stiffening and induced persistence length for coassembled molecular bottlebrushes

    NARCIS (Netherlands)

    Storm, Ingeborg M.; Stuart, Martien A.C.; Vries, de Renko; Leermakers, Frans A.M.

    2018-01-01

    A self-consistent field analysis for tunable contributions to the persistence length of isolated semiflexible polymer chains including electrostatically driven coassembled deoxyribonucleic acid (DNA) bottlebrushes is presented. When a chain is charged, i.e., for polyelectrolytes, there is, in

  14. Rapid atmospheric transport and large-scale deposition of recently synthesized plant waxes

    Science.gov (United States)

    Nelson, Daniel B.; Ladd, S. Nemiah; Schubert, Carsten J.; Kahmen, Ansgar

    2018-02-01

    Sedimentary plant wax 2H/1H ratios are important tools for understanding hydroclimate and environmental changes, but large spatial and temporal uncertainties exist about transport mechanisms from ecosystem to sediments. To assess atmospheric pathways, we collected aerosol samples for two years at four locations within a ∼60 km radius in northern Switzerland. We measured n-alkane distributions and 2H/1H ratios in these samples, and from local plants, leaf litter, and soil, as well as surface sediment from six nearby lakes. Increased concentrations and 2H depletion of long odd chain n-alkanes in early summer aerosols indicate that most wax aerosol production occurred shortly after leaf unfolding, when plants synthesize waxes in large quantities. During autumn and winter, aerosols were characterized by degraded n-alkanes lacking chain length preferences diagnostic of recent biosynthesis, and 2H/1H values that were in some cases more than 100‰ higher than growing season values. Despite these seasonal shifts, modeled deposition-weighted average 2H/1H values of long odd chain n-alkanes primarily reflected summer values. This was corroborated by n-alkane 2H/1H values in lake sediments, which were similar to deposition-weighted aerosol values at five of six sites. Atmospheric deposition rates for plant n-alkanes on land were ∼20% of accumulation rates in lakes, suggesting a role for direct deposition to lakes or coastal oceans near similar production sources, and likely a larger role for deposition on land and transport in river systems. This mechanism allows mobilization and transport of large quantities of recently produced waxes as fine-grained material to low energy sedimentation sites over short timescales, even in areas with limited topography. Widespread atmospheric transfer well before leaf senescence also highlights the importance of the isotopic composition of early season source water used to synthesize waxes for the geologic record.

  15. Chain-modified radioiodinated fatty acids

    International Nuclear Information System (INIS)

    Otto, C.A.

    1987-01-01

    Several carbon chain manipulations have been studied in terms of their effects on myocardial activity levels and residence time. The manipulations examined included: chain length, chain branching, chain unsaturation, and carbon-iodine bond stabilization. It was found that chain length affects myocardial activity levels for both straight-chain alkyl acids and branched chain alkyl and aryl acids. Similar results have been reported for the straight-chain aryl acids. Generally, the longer chain lengths correlated with higher myocardial activity levels and longer residence times. This behavior is attributed to storage as triglycerides. Branched chain acids are designed to be anti-metabolites but only the aryl β-methyl acids possessed the expected time course of constant or very slowly decreasing activity levels. The alkyl β-methyl acids underwent rapid deiodination - a process apparently independent of β-oxidation. Inhibition of β-oxidation by incorporation of carbon-carbon double and triple bonds was studied. Deiodination of ω-iodo alkyl fatty acids prevented an assessment of suicide inhibition using an unsaturated alkynoic acid. Stabilization of the carbon-iodine bond by attachment of iodine to a vinylic or aryl carbon was studied. The low myocardial values and high blood values observed for an eleven carbon ω-iodo vinylic fatty acid were not encouraging but ω-iodo aryl fatty acids appear to avoid the problems of rapid deiodination. (Auth.)

  16. Formation and properties of metal-oxygen atomic chains

    DEFF Research Database (Denmark)

    Thijssen, W.H.A.; Strange, Mikkel; de Brugh, J.M.J.A.

    2008-01-01

    of longer atomic chains. The mechanical and electrical properties of these diatomic chains have been investigated by determining local vibration modes of the chain and by measuring the dependence of the average chain-conductance on the length of the chain. Additionally, we have performed calculations......Suspended chains consisting of single noble metal and oxygen atoms have been formed. We provide evidence that oxygen can react with and be incorporated into metallic one-dimensional atomic chains. Oxygen incorporation reinforces the linear bonds in the chain, which facilitates the creation...

  17. Heavy Chain Diseases

    Science.gov (United States)

    ... of heavy chain produced: Alpha Gamma Mu Alpha Heavy Chain Disease Alpha heavy chain disease (IgA heavy ... the disease or lead to a remission. Gamma Heavy Chain Disease Gamma heavy chain disease (IgG heavy ...

  18. Telomere length and depression

    DEFF Research Database (Denmark)

    Wium-Andersen, Marie Kim; Ørsted, David Dynnes; Rode, Line

    2017-01-01

    BACKGROUND: Depression has been cross-sectionally associated with short telomeres as a measure of biological age. However, the direction and nature of the association is currently unclear. AIMS: We examined whether short telomere length is associated with depression cross-sectionally as well...... as prospectively and genetically. METHOD: Telomere length and three polymorphisms, TERT, TERC and OBFC1, were measured in 67 306 individuals aged 20-100 years from the Danish general population and associated with register-based attendance at hospital for depression and purchase of antidepressant medication....... RESULTS: Attendance at hospital for depression was associated with short telomere length cross-sectionally, but not prospectively. Further, purchase of antidepressant medication was not associated with short telomere length cross-sectionally or prospectively. Mean follow-up was 7.6 years (range 0...

  19. Full Length Research Article

    African Journals Online (AJOL)

    MEMUNA

    markovian process could be reduced to a markovian chain with the homogenous .... x and y respectively. n= the value of the strategy i.e. number of dummies/virtual ..... Groove, CA. Feinberg, E. A. & Shwartz, A. (2002), Handbook of Markov.

  20. Extended fuel cycle length

    International Nuclear Information System (INIS)

    Bruyere, M.; Vallee, A.; Collette, C.

    1986-09-01

    Extended fuel cycle length and burnup are currently offered by Framatome and Fragema in order to satisfy the needs of the utilities in terms of fuel cycle cost and of overall systems cost optimization. We intend to point out the consequences of an increased fuel cycle length and burnup on reactor safety, in order to determine whether the bounding safety analyses presented in the Safety Analysis Report are applicable and to evaluate the effect on plant licensing. This paper presents the results of this examination. The first part indicates the consequences of increased fuel cycle length and burnup on the nuclear data used in the bounding accident analyses. In the second part of this paper, the required safety reanalyses are presented and the impact on the safety margins of different fuel management strategies is examined. In addition, systems modifications which can be required are indicated

  1. Grazer-induced chain lenght plasticity reduces grazing risk in a marine diatom

    DEFF Research Database (Denmark)

    Bergkvist, Johanna; Thor, Peter; Jakobsen, Hans Henrik

    2012-01-01

    . marinoi was exposed to chemical cues from caged A. tonsa without physical contact with the responding cells. The reductions in chain length significantly reduced copepod grazing; grazing rates on chains (four cells or more) were several times higher compared to that of single cells. This suggests...... that chain length plasticity is a means for S. marinoi to reduce copepod grazing. In contrast, chain length was not suppressed in cultures exposed to the microzooplankton grazer Gyrodinium dominans. Size-selective predation may have played a key role in the evolution of chain formation and chain length...... plasticity in diatoms...

  2. Relativistic distances, sizes, lengths

    International Nuclear Information System (INIS)

    Strel'tsov, V.N.

    1992-01-01

    Such notion as light or retarded distance, field size, formation way, visible size of a body, relativistic or radar length and wave length of light from a moving atom are considered. The relation between these notions is cleared up, their classification is given. It is stressed that the formation way is defined by the field size of a moving particle. In the case of the electromagnetic field, longitudinal sizes increase proportionally γ 2 with growing charge velocity (γ is the Lorentz-factor). 18 refs

  3. The coprime quantum chain

    Science.gov (United States)

    Mussardo, G.; Giudici, G.; Viti, J.

    2017-03-01

    In this paper we introduce and study the coprime quantum chain, i.e. a strongly correlated quantum system defined in terms of the integer eigenvalues n i of the occupation number operators at each site of a chain of length M. The n i ’s take value in the interval [2,q] and may be regarded as S z eigenvalues in the spin representation j  =  (q  -  2)/2. The distinctive interaction of the model is based on the coprimality matrix \\boldsymbolΦ : for the ferromagnetic case, this matrix assigns lower energy to configurations where occupation numbers n i and n i+1 of neighbouring sites share a common divisor, while for the anti-ferromagnetic case it assigns a lower energy to configurations where n i and n i+1 are coprime. The coprime chain, both in the ferro and anti-ferromagnetic cases, may present an exponential number of ground states whose values can be exactly computed by means of graph theoretical tools. In the ferromagnetic case there are generally also frustration phenomena. A fine tuning of local operators may lift the exponential ground state degeneracy and, according to which operators are switched on, the system may be driven into different classes of universality, among which the Ising or Potts universality class. The paper also contains an appendix by Don Zagier on the exact eigenvalues and eigenvectors of the coprimality matrix in the limit q\\to ∞ .

  4. Phase behaviour of polyethylene knotted ring chains

    International Nuclear Information System (INIS)

    Wen Xiao-Hui; Xia A-Gen; Chen Hong-Ping; Zhang Lin-Xi

    2011-01-01

    The phase behaviour of polyethylene knotted ring chains is investigated by using molecular dynamics simulations. In this paper, we focus on the collapse of the polyethylene knotted ring chain, and also present the results of linear and ring chains for comparison. At high temperatures, a fully extensive knot structure is observed. The mean-square radius of gyration per bond (S 2 )/(Nb 2 ) and the shape factor (δ*) depend on not only the chain length but also the knot type. With temperature decreasing, chain collapse is observed, and the collapse temperature decreases with the chain length increasing. The actual collapse transition can be determined by the specific heat capacity C v , and the knotted ring chain undergoes gas—liquid—solid-like transition directly. The phase transition of a knotted ring chain is only one-stage collapse, which is different from the polyethylene linear and ring chains. This investigation can provide some insights into the statistical properties of knotted polymer chains. (condensed matter: structural, mechanical, and thermal properties)

  5. Chain Dynamics in Magnetorheological Suspensions

    Science.gov (United States)

    Gast, A. P.; Furst, E. M.

    1999-01-01

    fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead

  6. Pion nucleus scattering lengths

    International Nuclear Information System (INIS)

    Huang, W.T.; Levinson, C.A.; Banerjee, M.K.

    1971-09-01

    Soft pion theory and the Fubini-Furlan mass dispersion relations have been used to analyze the pion nucleon scattering lengths and obtain a value for the sigma commutator term. With this value and using the same principles, scattering lengths have been predicted for nuclei with mass number ranging from 6 to 23. Agreement with experiment is very good. For those who believe in the Gell-Mann-Levy sigma model, the evaluation of the commutator yields the value 0.26(m/sub σ//m/sub π/) 2 for the sigma nucleon coupling constant. The large dispersive corrections for the isosymmetric case implies that the basic idea behind many of the soft pion calculations, namely, slow variation of matrix elements from the soft pion limit to the physical pion mass, is not correct. 11 refs., 1 fig., 3 tabs

  7. Gap length distributions by PEPR

    International Nuclear Information System (INIS)

    Warszawer, T.N.

    1980-01-01

    Conditions guaranteeing exponential gap length distributions are formulated and discussed. Exponential gap length distributions of bubble chamber tracks first obtained on a CRT device are presented. Distributions of resulting average gap lengths and their velocity dependence are discussed. (orig.)

  8. Relativistic length agony continued

    Directory of Open Access Journals (Sweden)

    Redžić D.V.

    2014-01-01

    Full Text Available We made an attempt to remedy recent confusing treatments of some basic relativistic concepts and results. Following the argument presented in an earlier paper (Redžić 2008b, we discussed the misconceptions that are recurrent points in the literature devoted to teaching relativity such as: there is no change in the object in Special Relativity, illusory character of relativistic length contraction, stresses and strains induced by Lorentz contraction, and related issues. We gave several examples of the traps of everyday language that lurk in Special Relativity. To remove a possible conceptual and terminological muddle, we made a distinction between the relativistic length reduction and relativistic FitzGerald-Lorentz contraction, corresponding to a passive and an active aspect of length contraction, respectively; we pointed out that both aspects have fundamental dynamical contents. As an illustration of our considerations, we discussed briefly the Dewan-Beran-Bell spaceship paradox and the ‘pole in a barn’ paradox. [Projekat Ministarstva nauke Republike Srbije, br. 171028

  9. Odd Length Contraction

    Science.gov (United States)

    Smarandache, Florentin

    2013-09-01

    Let's denote by VE the speed of the Earth and byVR the speed of the rocket. Both travel in the same direction on parallel trajectories. We consider the Earth as a moving (at a constant speed VE -VR) spacecraft of almost spherical form, whose radius is r and thus the diameter 2r, and the rocket as standing still. The non-proper length of Earth's diameter, as measured by the astronaut is: L = 2 r√{ 1 -|/VE -VR|2 c2 } rocket! Also, let's assume that the astronaut is laying down in the direction of motion. Therefore, he would also shrink, or he would die!

  10. discouraged by queue length

    Directory of Open Access Journals (Sweden)

    P. R. Parthasarathy

    2001-01-01

    Full Text Available The transient solution is obtained analytically using continued fractions for a state-dependent birth-death queue in which potential customers are discouraged by the queue length. This queueing system is then compared with the well-known infinite server queueing system which has the same steady state solution as the model under consideration, whereas their transient solutions are different. A natural measure of speed of convergence of the mean number in the system to its stationarity is also computed.

  11. Chain reaction

    International Nuclear Information System (INIS)

    Balogh, Brian.

    1991-01-01

    Chain Reaction is a work of recent American political history. It seeks to explain how and why America came to depend so heavily on its experts after World War II, how those experts translated that authority into political clout, and why that authority and political discretion declined in the 1970s. The author's research into the internal memoranda of the Atomic Energy Commission substantiates his argument in historical detail. It was not the ravages of American anti-intellectualism, as so many scholars have argued, that brought the experts back down to earth. Rather, their decline can be traced to the very roots of their success after World War II. The need to over-state anticipated results in order to garner public support, incessant professional and bureaucratic specialization, and the sheer proliferation of expertise pushed arcane and insulated debates between experts into public forums at the same time that a broad cross section of political participants found it easier to gain access to their own expertise. These tendencies ultimately undermined the political influence of all experts. (author)

  12. What is the Entanglement Length in a Polymer Melt?

    International Nuclear Information System (INIS)

    Grest, Gary S.; Kremer, Kurt; Putz, Mathias

    1999-01-01

    We present the results of molecular dynamics simulations of very long model polymer chains analyzed by various experimentally relevant techniques. The segment motion of the chains is found to be in very good agreement with the reptation model. We also calculated the plateau modulus G 0 N . The predictions of the entanglement length N e from G 0 N and from the mean square displacement of the chain segments disagree by a factor of about 2.2(2), indicating an error in the prefactor in the standard formula for G 0 N . We show that recent neutron spin echo measurements were carried out for chain lengths which are too small to allow for a correct determination of N e

  13. Applying Best Supply Chain Practices to Humanitarian Relief

    OpenAIRE

    Russell, Roberta S.; Hiller, Janine S.

    2015-01-01

    With the growth in length and breadth of extended supply chains, more companies are employing risk management techniques and resilience planning to deal with burgeoning and costly supply chain disruptions. As companies can learn from humanitarian groups, so can humanitarian groups learn from industry how to respond, recover, and prepare for these disruptive events. This paper looks at industry leaders in supply chain risk management and explores how humanitarian supply chains can learn from i...

  14. Understanding the length dependence of molecular junction thermopower

    DEFF Research Database (Denmark)

    Karlström, Sven Olov Harald; Strange, Mikkel; Solomon, Gemma

    2014-01-01

    Thermopower of molecular junctions is sensitive to details in the junction and may increase, decrease, or saturate with increasing chain length, depending on the system. Using McConnell's theory for exponentially suppressed transport together with a simple and easily interpretable tight binding...... model, we show how these different behaviors depend on the molecular backbone and its binding to the contacts. We distinguish between resonances from binding groups or undercoordinated electrode atoms, and those from the periodic backbone. It is demonstrated that while the former gives a length......-independent contribution to the thermopower, possibly changing its sign, the latter determines its length dependence. This means that the question of which orbitals from the periodic chain that dominate the transport should not be inferred from the sign of the thermopower but from its length dependence. We find...

  15. Aberrant leukocyte telomere length in Birdshot Uveitis.

    Science.gov (United States)

    Vazirpanah, Nadia; Verhagen, Fleurieke H; Rothova, Anna; Missotten, Tom O A R; van Velthoven, Mirjam; Den Hollander, Anneke I; Hoyng, Carel B; Radstake, Timothy R D J; Broen, Jasper C A; Kuiper, Jonas J W

    2017-01-01

    Birdshot Uveitis (BU) is an archetypical chronic inflammatory eye disease, with poor visual prognosis, that provides an excellent model for studying chronic inflammation. BU typically affects patients in the fifth decade of life. This suggests that it may represent an age-related chronic inflammatory disease, which has been linked to increased erosion of telomere length of leukocytes. To study this in detail, we exploited a sensitive standardized quantitative real-time polymerase chain reaction to determine the peripheral blood leukocyte telomere length (LTL) in 91 genotyped Dutch BU patients and 150 unaffected Dutch controls. Although LTL erosion rates were very similar between BU patients and healthy controls, we observed that BU patients displayed longer LTL, with a median of log (LTL) = 4.87 (= 74131 base pair) compared to 4.31 (= 20417 base pair) in unaffected controls (PRTEL1. These findings suggest that BU is accompanied by significantly longer LTL.

  16. Human health risk assessment of long chain alcohols (LCOH)

    DEFF Research Database (Denmark)

    Veenstra, Gauke; Sanderson, Hans; Webb, Catherine

    2009-01-01

    evidence of activity in genetic toxicity tests or to the reproductive system or the developing organism. These chemicals also are not sensitizers. Irritation is dependant on chain length; generally, alcohols in the range C6-C11 are considered as irritant, intermediate chain lengths (C12-C16) alcohols...... are considered to be mild irritants and chain lengths of C18 and above are considered non-irritants. These chemicals are broadly used across the consumer products industry with highest per person consumer exposures resulting from use in personal care products. Margins of exposure adequate for the protection...

  17. CHAINS-PC, Decay Chain Atomic Densities

    International Nuclear Information System (INIS)

    1994-01-01

    1 - Description of program or function: CHAINS computes the atom density of members of a single radioactive decay chain. The linearity of the Bateman equations allows tracing of interconnecting chains by manually accumulating results from separate calculations of single chains. Re-entrant loops can be treated as extensions of a single chain. Losses from the chain are also tallied. 2 - Method of solution: The Bateman equations are solved analytically using double-precision arithmetic. Poles are avoided by small alterations of the loss terms. Multigroup fluxes, cross sections, and self-shielding factors entered as input are used to compute the effective specific reaction rates. The atom densities are computed at any specified times. 3 - Restrictions on the complexity of the problem: Maxima of 100 energy groups, 100 time values, 50 members in a chain

  18. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil

    2012-01-01

    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  19. Buckling of paramagnetic chains in soft gels

    Science.gov (United States)

    Huang, Shilin; Pessot, Giorgio; Cremer, Peet; Weeber, Rudolf; Holm, Christian; Nowak, Johannes; Odenbach, Stefan; Menzel, Andreas M.; Auernhammer, Günter K.

    We study the magneto-elastic coupling behavior of paramagnetic chains in soft polymer gels exposed to external magnetic fields. To this end, a laser scanning confocal microscope is used to observe the morphology of the paramagnetic chains together with the deformation field of the surrounding gel network. The paramagnetic chains in soft polymer gels show rich morphological shape changes under oblique magnetic fields, in particular a pronounced buckling deformation. The details of the resulting morphological shapes depend on the length of the chain, the strength of the external magnetic field, and the modulus of the gel. Based on the observation that the magnetic chains are strongly coupled to the surrounding polymer network, a simplified model is developed to describe their buckling behavior. A coarse-grained molecular dynamics simulation model featuring an increased matrix stiffness on the surfaces of the particles leads to morphologies in agreement with the experimentally observed buckling effects.

  20. Extraction of pentylbenzene from high molar mass alkanes (C{sub 14} and C{sub 17}) by N-methyl-2-pyrrolidone

    Energy Technology Data Exchange (ETDEWEB)

    Fandary, Mohamed S. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait)]. E-mail: mfandary@yahoo.com; Al-Jimaz, Adel S. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait); Al-Kandary, Jasem A. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait); Fahim, Mohamed A. [Chemical Engineering Department, University of Kuwait, P.O. Box 5969, Safat 13060 (Kuwait)

    2006-04-15

    Equilibrium tie line data have been determined for the two ternary liquid systems: {l_brace}tetradecane, or heptadecane + pentylbenzene + N-methyl-2-pyrrolidone (NMP){r_brace} over a temperature range of (298 to 328) K. The two systems studied exhibit type I liquid + liquid phase diagram. The effect of temperature and n-alkane chain length upon solubility, selectivity, and distribution coefficients were investigated experimentally.

  1. Tunable evolutions of shock absorption and energy partitioning in magnetic granular chains

    Science.gov (United States)

    Leng, Dingxin; Liu, Guijie; Sun, Lingyu

    2018-01-01

    In this paper, we investigate the tunable characteristics of shock waves propagating in one-dimensional magnetic granular chains at various chain lengths and magnetic flux densities. According to the Hertz contact theory and Maxwell principle, a discrete element model with coupling elastic and field-induced interaction potentials of adjacent magnetic grains is proposed. We also present hard-sphere approximation analysis to describe the energy partitioning features of magnetic granular chains. The results demonstrate that, for a fixed magnetic field strength, when the chain length is greater than two times of the wave width of the solitary wave, the chain length has little effect on the output energy of the system; for a fixed chain length, the shock absorption and energy partitioning features of magnetic granular chains are remarkably influenced by varying magnetic flux densities. This study implies that the magnetic granular chain is potential to construct adaptive shock absorption components for impulse mitigation.

  2. Electrostatic stiffening and induced persistence length for coassembled molecular bottlebrushes

    Science.gov (United States)

    Storm, Ingeborg M.; Stuart,