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)

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

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.

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.

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...

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

Science.gov (United States)

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

Process for the selective cracking of straight-chained and slightly branched hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Gorring, R L; Shipman, G F

1975-01-23

The invention describes a method for the selective (hydro) cracking of petroleum materials, containing normal straight-chained and/or slightly branched-chained hydrocarbons. The mixture is brought into contact with a selective, crystalline alumino silicate zeolite cracking catalyst housing a silicon oxide/aluminum oxide ratio of at least about 12 and a constraint index of about 1 to 12 under cracking conditions. A zeolite catalyst with a crystal size of up to 0.05 ..mu.. is used. Solidification point and viscosity in particular of oils are to be lowered through the catalytic dewaxing.

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.

Versatility of hydrocarbon production in cyanobacteria.

Science.gov (United States)

Xie, Min; Wang, Weihua; Zhang, Weiwen; Chen, Lei; Lu, Xuefeng

2017-02-01

Cyanobacteria are photosynthetic microorganisms using solar energy, H 2 O, and CO 2 as the primary inputs. Compared to plants and eukaryotic microalgae, cyanobacteria are easier to be genetically engineered and possess higher growth rate. Extensive genomic information and well-established genetic platform make cyanobacteria good candidates to build efficient biosynthetic pathways for biofuels and chemicals by genetic engineering. Hydrocarbons are a family of compounds consisting entirely of hydrogen and carbon. Structural diversity of the hydrocarbon family is enabled by variation in chain length, degree of saturation, and rearrangements of the carbon skeleton. The diversified hydrocarbons can be used as valuable chemicals in the field of food, fuels, pharmaceuticals, nutrition, and cosmetics. Hydrocarbon biosynthesis is ubiquitous in bacteria, yeasts, fungi, plants, and insects. A wide variety of pathways for the hydrocarbon biosynthesis have been identified in recent years. Cyanobacteria may be superior chassis for hydrocabon production in a photosynthetic manner. A diversity of hydrocarbons including ethylene, alkanes, alkenes, and terpenes can be produced by cyanobacteria. Metabolic engineering and synthetic biology strategies can be employed to improve hydrocarbon production in cyanobacteria. This review mainly summarizes versatility and perspectives of hydrocarbon production in cyanobacteria.

Cuticle hydrocarbons in saline aquatic beetles

Directory of Open Access Journals (Sweden)

María Botella-Cruz

2017-07-01

Full Text Available Hydrocarbons are the principal component of insect cuticle and play an important role in maintaining water balance. Cuticular impermeability could be an adaptative response to salinity and desiccation in aquatic insects; however, cuticular hydrocarbons have been poorly explored in this group and there are no previous data on saline species. We characterized cuticular hydrocarbons of adults and larvae of two saline aquatic beetles, namely Nebrioporus baeticus (Dytiscidae and Enochrus jesusarribasi (Hydrophilidae, using a gas chromatograph coupled to a mass spectrometer. The CHC profile of adults of both species, characterized by a high abundance of branched alkanes and low of unsaturated alkenes, seems to be more similar to that of some terrestrial beetles (e.g., desert Tenebrionidae compared with other aquatic Coleoptera (freshwater Dytiscidae. Adults of E. jesusarribasi had longer chain compounds than N. baeticus, in agreement with their higher resistance to salinity and desiccation. The more permeable cuticle of larvae was characterized by a lower diversity in compounds, shorter carbon chain length and a higher proportion of unsaturated hydrocarbons compared with that of the adults. These results suggest that osmotic stress on aquatic insects could exert a selection pressure on CHC profile similar to aridity in terrestrial species.

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.

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

Programmable Self-assembly of Hydrocarbon-capped Nanoparticles: Role of Chain Conformations

Science.gov (United States)

Waltmann, Curt; Horst, Nathan; Travesset, Alex

Nanoparticle superlattices (NPS), i.e. crystalline arrangements of nanoparticles, are materials with fascinating structures, which in many cases are not possible to attain from simple atoms or molecules. They also span a wide range of possible applications such as metamaterials, new energy sources, catalysis, and many others. In this talk, we present a theoretical and computational description of the self-assembly of nanoparticles with hydrocarbons as capping ligands. Usually, these systems have been described with hard sphere packing models. In this talk, we show that the conformations of the hydrocarbon chains play a fundamental role in determining the equilibrium phases, including and especially in binary systems. The work of CW was supported by a DOE-SULI internship from May-December 2016, and by NSF, DMR-CMMT 1606336 CDS&E: Design Principles for Ordering Nanoparticles into Super-crystals after January 1st.

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

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.

Linear C32H66 hydrocarbon in the mixed state with C10H22 ...

Indian Academy of Sciences (India)

Unknown

S R Research Laboratory for Studies in Crystallization Phenomena, 10-1-96, ... mixed state with certain shorter chain length homologues (SMOLLENCs), estimated ... Methods. Five hydrocarbons of even carbon numbers, C10, C12, C14, C16 ...

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.

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.

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

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.

Hydrocarbon phenotyping of algal species using pyrolysis-gas chromatography mass spectrometry

Directory of Open Access Journals (Sweden)

Kothari Shankar L

2010-05-01

Full Text Available Abstract Background Biofuels derived from algae biomass and algae lipids might reduce dependence on fossil fuels. Existing analytical techniques need to facilitate rapid characterization of algal species by phenotyping hydrocarbon-related constituents. Results In this study, we compared the hydrocarbon rich algae Botryococcus braunii against the photoautotrophic model algae Chlamydomonas reinhardtii using pyrolysis-gas chromatography quadrupole mass spectrometry (pyGC-MS. Sequences of up to 48 dried samples can be analyzed using pyGC-MS in an automated manner without any sample preparation. Chromatograms of 30-min run times are sufficient to profile pyrolysis products from C8 to C40 carbon chain length. The freely available software tools AMDIS and SpectConnect enables straightforward data processing. In Botryococcus samples, we identified fatty acids, vitamins, sterols and fatty acid esters and several long chain hydrocarbons. The algae species C. reinhardtii, B. braunii race A and B. braunii race B were readily discriminated using their hydrocarbon phenotypes. Substructure annotation and spectral clustering yielded network graphs of similar components for visual overviews of abundant and minor constituents. Conclusion Pyrolysis-GC-MS facilitates large scale screening of hydrocarbon phenotypes for comparisons of strain differences in algae or impact of altered growth and nutrient conditions.

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

Mixed-chain phosphatidylcholine bilayers: structure and properties

International Nuclear Information System (INIS)

Mattai, J.; Sripada, P.K.; Shipley, G.G.

1987-01-01

Calorimetric and x-ray diffraction data are reported for two series of saturated mixed-chain phosphatidylcholines (PCs), 18:0/n:0-PC and n:0/18:0-PC, where the sn-1 and sn-2 fatty acyl chains on the glycerol backbone are systematically varied by two methylene groups from 18:0 to 10:0 (n = 18, 16, 14, 12, or 10). Fully hydrated PCs were annealed at -4 0 C and their multilamellar dispersions characterized by differential scanning calorimetry and x-ray diffraction. All mixed-chain PCs form low-temperature crystalline bilayer phases following low-temperature incubation, except 18:0/10:0-PC. The subtransition temperature (T/sub s/) shifts toward the main (chain melting) transition temperature (T/sub m/) as the sn-1 or sn-2 fatty acyl chain is reduced in length. T/sub m/ decreases with acyl chain length for both series of PCs except 18:0/10:0-PC, while for the positional isomers, n:0/18:0-PC and 18:0/n:0-PC, T/sub m/ is higher for the isomer with the longer acyl chain in the sn-2 position of the glycerol backbone. The conversion from the crystalline bilayer L/sub c/phase to the liquid-crystalline L/sub α/ phase with melted hydrocarbon chains occurs through a series of phase changes which are chain length dependent. Molecular models indicate that the bilayer gel phases for the more asymmetric PC series, 18:0/n:0-PC, must undergo progressive interdigitation with chain length reduction to maintain maximum chain-chain interaction. The L/sub β/* phase of 18:0/10:p-PC is the most stable structure for this PC below T/sub m/. The formation and stability of the triple-chain structures can be rationalized from molecular models

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.

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.

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.

A novel high-performance thin layer chromatography method for quantification of long chain aliphatic hydrocarbons from Cissus quadrangularis

Directory of Open Access Journals (Sweden)

Vandana Jain

2016-08-01

Full Text Available Context: A high-performance thin layer chromatography (HPTLC is an analytical technique, which can be used for the determination of constituents or marker components in various parts of the plants. Earlier studies have estimated phytoconstituents from the stem and other aerial plant parts of Cissus quadrangularis Linn. Estimation of hydrocarbons can also be successfully done using HPTLC technique using suitable derivatization. Aims: To develop and validate a simple and rapid method for the estimation of long chain aliphatic hydrocarbons from the leaves of C. quadrangularis using HPTLC technique. Methods: Precoated silica gel 60 F254 plates were used as stationary phase. The mobile phase used was hexane (100 %. The detection of spots was carried out using berberine sulphate as detecting reagent. Results: The method was validated in terms of linearity, sensitivity, accuracy, and precision. Linearity range was found to be 2-10 µg/mL, limit of detection 0.127 µg/mL, and limit of quantification 0.384 µg/mL. Conclusions: A novel, simple, accurate, precise and sensitive HPTLC method has been developed and validated for the estimation of long chain aliphatic hydrocarbons obtained from the leaves of C. quadrangularis Linn.

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

International Nuclear Information System (INIS)

Wolfe, M. F.; Schwartz, G. J. B.; Singaram, S.; Tjeerdema, R. S.

1997-01-01

Experiments were conducted to determine the impact of dispersing agents on petroleum hydrocarbons (PH) bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation and metabolic transformation of a model PH, ( 1 4C)naphthalene, were measured and compared with Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527, and undispersed preparations of PBCO. The model food chain consisted of a primary algae producer and a primary rotifer consumer. Results showed that uptake of naphthalene increased significantly in the presence of a dispersant in algae. A significant increase in uptake was also recorded in rotifers via trophic transfer. Trophic transfer played a significant, sometimes even dominant, role in uptake and bioaccumulation. 27 refs., 6 figs

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

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

Energy Technology Data Exchange (ETDEWEB)

Wolfe, M.; Tjeerdema, R. [Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry; Sowby, M. [California Dept. of Fish and Game, Sacramento, CA (United States)

1995-12-31

When crude oil is accidentally released into the ocean, it threatens many levels of marine life. Intervention, in the form of chemical dispersing agents, alters the normal behavior of petroleum hydrocarbons (PH) by increasing their functional water solubility and the extent of their exposure to sub-surface organisms. Dispersing agents may modify bioavailability as a result of altered interactions between dispersed PH droplets and organismal cell membranes.The objective of this research was to determine the impact of dispersing agents on PH bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation, depuration, and metabolic transformation of a model PH, {sup 14}C-naphthalene, were measured and compared for Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527 and undispersed preparations of the water-accommodated fractions (WAF) of PBCO at two salinities and temperatures. The model food chain consisted of Isochrysis galbana and Brachionus plicatilis. Direct aqueous exposure was compared with combined aqueous and dietary exposure. Fractionation and identification of metabolites was done by HPLC co-chromatography with analytical standards, and quantitation was done by liquid scintillation counting. GC-FID characterization of WAF and dispersed oil (DO) preparations shows higher concentrations of petroleum hydrocarbons and a greater number of individual constituents in the dispersed oil preparations.

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

International Nuclear Information System (INIS)

Wolfe, M.; Tjeerdema, R.

1995-01-01

When crude oil is accidentally released into the ocean, it threatens many levels of marine life. Intervention, in the form of chemical dispersing agents, alters the normal behavior of petroleum hydrocarbons (PH) by increasing their functional water solubility and the extent of their exposure to sub-surface organisms. Dispersing agents may modify bioavailability as a result of altered interactions between dispersed PH droplets and organismal cell membranes.The objective of this research was to determine the impact of dispersing agents on PH bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation, depuration, and metabolic transformation of a model PH, 14 C-naphthalene, were measured and compared for Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527 and undispersed preparations of the water-accommodated fractions (WAF) of PBCO at two salinities and temperatures. The model food chain consisted of Isochrysis galbana and Brachionus plicatilis. Direct aqueous exposure was compared with combined aqueous and dietary exposure. Fractionation and identification of metabolites was done by HPLC co-chromatography with analytical standards, and quantitation was done by liquid scintillation counting. GC-FID characterization of WAF and dispersed oil (DO) preparations shows higher concentrations of petroleum hydrocarbons and a greater number of individual constituents in the dispersed oil preparations

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)

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)

Volatile Short-chain Chlorinated Hydrocarbons in the Groundwater of the City of Zagreb

OpenAIRE

Marijanović-Rajčić, M.; Senta, A.

2008-01-01

The aim of the study was to assess the quality of the groundwater sampled from private wells and the public water-supply system in terms of estimating the contamination caused by short-chain chlorinated hydrocarbons, as well as to estimate the exposure of the citizens dwelling in different suburbs to these pollutants of their drinking water (Fig. 1). The aim of the study was also to determine which suburb is supplied through the public water-supply system with water originating from the Sašna...

Correlation between length and tilt of lipid tails

Science.gov (United States)

Kopelevich, Dmitry I.; Nagle, John F.

2015-10-01

It is becoming recognized from simulations, and to a lesser extent from experiment, that the classical Helfrich-Canham membrane continuum mechanics model can be fruitfully enriched by the inclusion of molecular tilt, even in the fluid, chain disordered, biologically relevant phase of lipid bilayers. Enriched continuum theories then add a tilt modulus κθ to accompany the well recognized bending modulus κ. Different enrichment theories largely agree for many properties, but it has been noticed that there is considerable disagreement in one prediction; one theory postulates that the average length of the hydrocarbon chain tails increases strongly with increasing tilt and another predicts no increase. Our analysis of an all-atom simulation favors the latter theory, but it also shows that the overall tail length decreases slightly with increasing tilt. We show that this deviation from continuum theory can be reconciled by consideration of the average shape of the tails, which is a descriptor not obviously includable in continuum theory.

Correlation between length and tilt of lipid tails

Energy Technology Data Exchange (ETDEWEB)

Kopelevich, Dmitry I., E-mail: dkopelevich@che.ufl.edu [Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611 (United States); Nagle, John F., E-mail: nagle@cmu.edu [Department of Physics, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 (United States)

2015-10-21

It is becoming recognized from simulations, and to a lesser extent from experiment, that the classical Helfrich-Canham membrane continuum mechanics model can be fruitfully enriched by the inclusion of molecular tilt, even in the fluid, chain disordered, biologically relevant phase of lipid bilayers. Enriched continuum theories then add a tilt modulus κ{sub θ} to accompany the well recognized bending modulus κ. Different enrichment theories largely agree for many properties, but it has been noticed that there is considerable disagreement in one prediction; one theory postulates that the average length of the hydrocarbon chain tails increases strongly with increasing tilt and another predicts no increase. Our analysis of an all-atom simulation favors the latter theory, but it also shows that the overall tail length decreases slightly with increasing tilt. We show that this deviation from continuum theory can be reconciled by consideration of the average shape of the tails, which is a descriptor not obviously includable in continuum theory.

Lowering of the critical concentration for micelle formation in aqueous soap solutions by action of truly dissolved hydrocarbon at various temperatures

Energy Technology Data Exchange (ETDEWEB)

Markina, Z.N.; Kostova, N.Z.; Rebinder, P.A.

1970-03-01

The effect of dissolved hydrocarbons (octane, benzene, and ethylbenzene) on critical micelle concentration of aqueous solutions of sodium salts of fatty acids from caproate to sodium myristate at various temperatures was studied. Experimental results showed that formation of micelles is promoted by presence of hydrocarbons dissolved in the water phase. Such solutions have below normal critical micelle concentration. The change in critical micelle concentration decreases with increase in length of hydrocarbon chain in the soap molecule and with decrease of hydrocarbon solubility in pure water. The nature of the hydrocarbon also affects the forms and dimension of the micelle. Aromatic hydrocarbons increase micelle volume and greatly decrease C.M.C., while aliphatic hydrocarbons decrease C.M.C. slightly. (12 refs.)

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)

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.

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

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

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.

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.

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.

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.

Volatile Short-chain Chlorinated Hydrocarbons in the Groundwater of the City of Zagreb

Directory of Open Access Journals (Sweden)

Marijanović-Rajčić, M.

2008-01-01

Full Text Available The aim of the study was to assess the quality of the groundwater sampled from private wells and the public water-supply system in terms of estimating the contamination caused by short-chain chlorinated hydrocarbons, as well as to estimate the exposure of the citizens dwelling in different suburbs to these pollutants of their drinking water (Fig. 1. The aim of the study was also to determine which suburb is supplied through the public water-supply system with water originating from the Sašnak spring that is contaminated with volatile chlorinated short-chain hydrocarbons.Drinking water samples were taken from 3 private wells and 1 public water-supply system situated in 3 Zagreb suburbs - Pešćenica, Trnje, and Trešnjevka. The sampling was carried out during 2003 and was undertaken on a seasonal basis. Short-chain chlorinated hydrocarbons - 1,1,1-trichloroethane, carbon tetrachloride, 1,1,2-trichloroethene and 1,1,2,2-tetrachloroethene - were determined by gas chromatography, following "liquid-liquid extraction" in pentane. For that purpose, we applied the gas chromatograph equipped with an electron-capture detector, thermo-programmable operations, and a suitable capillary column. The technique applied was that of split-injection.The groundwater of the City of Zagreb was found to be contaminated with volatile chlorinated hydrocarbons. The concentration level of 1,1,1-trichloroethane, determined in most of the samples, was found to be low (Fig. 2. On the other hand, 1,1,2-trichloroethene was present in all samples in concentrations of about 1 µg l-1- (Fig. 3. Only the drinking water samples taken from private wells in the suburb of Trnje contained somewhat higher mass concentrations of 1,1,1-trichloroethane, with the peak value of 19.03 µg l-1, measured in the winter season. In the samples taken from private wells in Trnje, the mass concentrations of 1,1,2,2-tetrachloroethene rangedfrom 15.30 µg l-1 to 18.65 µg l-1, as measured in autumn

Development changes of cuticular hydrocarbons in Chrysomya rufifacies larvae: potential for determining larval age.

Science.gov (United States)

Zhu, G H; Ye, G Y; Hu, C; Xu, X H; Li, K

2006-12-01

Age determination is the basis of determining the postmortem interval using necrophagous fly larvae. To explore the potential of using cuticular hydrocarbons for determining the ages of fly larvae, changes of cuticular hydrocarbons in developing larvae of Chrysomya rufifacies (Macquart) (Diptera: Calliphoridae) were investigated using gas chromatography with flame-ionization detection and gas chromatography-mass spectrometry. This study showed that the larvae produced cuticular hydrocarbons typical of insects. Most of the hydrocarbons identified were alkanes with the carbon chain length of 21-31, plus six kinds of alkenes. The hydrocarbon composition of the larvae correlated with age. The statistical results showed that simple peak ratios of n-C29 divided by another eight selected peaks increased significantly with age; their relationships with age could be modelled using exponential or power functions with R(2) close to or > 0.80. These results suggest that cuticular hydrocarbon composition is a useful indicator for determining the age of larval C. rufifacies, especially for post-feeding larvae, which are difficult to differentiate by morphology.

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.

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

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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 ...

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

Effect of hydrocarbon radical length of fatty acid collectors on flotation separation process of thorium ions

International Nuclear Information System (INIS)

Skrylev, L.D.; Perlova, O.V.; Sazonova, V.F.

1991-01-01

It is shown experimentally that the degree of flotation separation of thorium ions collected by their means increases firstly (potassium laurate), then decreases (potassium tridecanate) and after that increases again (potassium palminate) when increasing the length of the hydrocarbon radical of potassium soaps of saturated fatty acids. The first increase of the collector efficiency is due to the decrease of solubility of thorium-containing sublates, and drop and further increase is due to the change in colloidchemical properties of sublates

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.

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

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.

Effect of a Long Chain Carboxylate Acid on Sodium Dodecyl Sulfate Micelle Structure: A Small-angle Neutron Scattering Study

International Nuclear Information System (INIS)

Arum Patriati; Edy Giri Rachman Putra

2009-01-01

The effect of different hydrocarbon chain length of carboxylate acid, i.e. dodecanoic acid, CH 3 (CH 2 ) 10 COOH and hexadecanoic acid, CH 3 (CH 2 ) 14 COOH as a co-surfactant in the 0.3M SDS micellar solution has been studied using small angle neutron scattering (SANS). Here, the present of dodecanoic acid has induced the SDS structural micelles. The ellipsoid micelles structures changed significantly in length (major axis) from 21.7 Armstrong to 35.5 Armstrong at a fixed minor axis of 16.7 Armstrong in the present of 0.005M to 0.1M dodecanoic acid. Nevertheless, this effect was not shown in the present of hexadecanoic acid with the same concentration range. The present of hexadecanoic acid molecules gave a small effect on growth of SDS micelles where the major axis of the micelle was simply elongated from 21.5 Armstrong to 23.5 Armstrong. It showed that the appropriate hydrocarbon chain length between surfactant and co-surfactant molecules is one of the determining factors in forming a mixed micelles structure. (author)

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.

Inhibition of telomerase by linear-chain fatty acids: a structural analysis.

Science.gov (United States)

Oda, Masako; Ueno, Takamasa; Kasai, Nobuyuki; Takahashi, Hirotada; Yoshida, Hiromi; Sugawara, Fumio; Sakaguchi, Kengo; Hayashi, Hideya; Mizushina, Yoshiyuki

2002-01-01

In the present study, we have found that mono-unsaturated linear-chain fatty acids in the cis configuration with C(18) hydrocarbon chains (i.e. oleic acid) strongly inhibited the activity of human telomerase in a cell-free enzymic assay, with an IC(50) value of 8.6 microM. Interestingly, fatty acids with hydrocarbon chain lengths below 16 or above 20 carbons substantially decreased the potency of inhibition of telomerase. Moreover, the cis-mono-unsaturated C(18) linear-chain fatty acid oleic acid was the strongest inhibitor of all the fatty acids tested. A kinetic study revealed that oleic acid competitively inhibited the activity of telomerase ( K (i)=3.06 microM) with respect to the telomerase substrate primer. The energy-minimized three-dimensional structure of the linear-chain fatty acid was calculated and modelled. A molecule width of 11.53-14.26 A (where 1 A=0.1 nm) in the C(16) to C(20) fatty acid structure was suggested to be important for telomerase inhibition. The three-dimensional structure of the telomerase active site (i.e. the substrate primer-binding site) appears to have a pocket that could bind oleic acid, with the pocket being 8.50 A long and 12.80 A wide. PMID:12121150

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.

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.

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.

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.

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

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.

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.

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.

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.

The Effect of the Chain Length on MMA Free Radicl Polymerization

Institute of Scientific and Technical Information of China (English)

无

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.

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.

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.

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.

Velocity Dependence of Friction of Confined Hydrocarbons

DEFF Research Database (Denmark)

Sivebæk, Ion Marius; Samoilov, Vladimir N.; Persson, Bo N. J.

2010-01-01

We present molecular dynamics friction calculations for confined hydrocarbon “polymer” solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: (a) polymer sliding against a hard substrate and (b) polymer sliding on polymer. We discuss the velocity dependence of the f......We present molecular dynamics friction calculations for confined hydrocarbon “polymer” solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: (a) polymer sliding against a hard substrate and (b) polymer sliding on polymer. We discuss the velocity dependence...... of the frictional shear stress for both cases. In our simulations, the polymer films are very thin (∼3 nm), and the solid walls are connected to a thermostat at a short distance from the polymer slab. Under these circumstances we find that frictional heating effects are not important, and the effective temperature...... in the polymer film is always close to the thermostat temperature. In the first setup (a), for hydrocarbons with molecular lengths from 60 to 1400 carbon atoms, the shear stresses are nearly independent of molecular length, but for the shortest hydrocarbon C20H42 the frictional shear stress is lower. In all...

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.

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

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

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

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.

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.

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.

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.

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...

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....

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

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

Methanol to olefin Conversion on HSAPO-34 zeolite from periodic density functional theory calculations: a complete cycle of side chain hydrocarbon pool mechanism

Energy Technology Data Exchange (ETDEWEB)

Wang, C.M.; Wang, Y.D.; Xie, Z.K.; Liu, Z.P. [SINOPEC, Shanghai (China)

2009-03-15

For its unique position in the coal chemical industry, the methanol to olefin (MTO) reaction has been a hot topic in zeolite catalysis. Due to the complexities of catalyst structure and reaction networks, many questions such as how the olefin chain is built from methanol remain elusive. On the basis of periodic density functional theory calculations, this work establishes the first complete catalytic cycle for MTO reaction via hexamethylbenzene (HMB) trapped in HSAPO-34 zeolite based on the so-called side chain hydrocarbon pool mechanism. The cycle starts from the methylation of HMB that leads to heptamethylbenzenium ion (heptaMB{sup +}) intermediate. This is then followed by the growth of side chain via repeated deprotonation of benzenium ions and methylation of the exocyclic double bond. Ethene and propene can finally be released from the side ethyl and isopropyl groups of benzenium ions by deprotonation and subsequent protonation steps. We demonstrate that (i) HMB/HSAPO-34 only yields propene as the primary product based on the side chain hydrocarbon pool mechanism and (ii) an indirect proton-shift step mediated by water that is always available in the system is energetically more favorable than the traditionally regarded internal hydrogen-shift step. Finally, the implications of our results toward understanding the effect of acidity of zeolite on MTO activity are also discussed.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

Science.gov (United States)

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2018-04-03

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

Science.gov (United States)

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2017-09-26

Systems, processes, and catalysts are disclosed for obtaining fuels and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

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.

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.

Synthesis of Ag Nanocubes 18–32 nm in Edge Length: The Effects of Polyol on Reduction Kinetics, Size Control, and Reproducibility

OpenAIRE

Wang, Yi; Zheng, Yiqun; Huang, Cheng Zhi; Xia, Younan

2013-01-01

This article describes a robust method for the facile synthesis of small Ag nanocubes with edge lengths controlled in the range of 18–32 nm. The success of this new method relies on the substitution of ethylene glycol (EG) -- the solvent most commonly used in a polyol synthesis -- with diethylene glycol (DEG). Owing to the increase in hydrocarbon chain length, DEG possesses a higher viscosity and a lower reducing power relative to EG. As a result, we were able to achieve a nucleation burst in...

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.

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.

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)

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.

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

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

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,

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...

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.

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.

Insights into hydrocarbon formation by nitrogenase cofactor homologs.

Science.gov (United States)

Lee, Chi Chung; Hu, Yilin; Ribbe, Markus W

2015-04-14

The L-cluster is an all-iron homolog of nitrogenase cofactors. Driven by europium(II) diethylenetriaminepentaacetate [Eu(II)-DTPA], the isolated L-cluster is capable of ATP-independent reduction of CO and CN(-) to C1 to C4 and C1 to C6 hydrocarbons, respectively. Compared to its cofactor homologs, the L-cluster generates considerably more CH4 from the reduction of CO and CN(-), which could be explained by the presence of a "free" Fe atom that is "unmasked" by homocitrate as an additional site for methanation. Moreover, the elevated CH4 formation is accompanied by a decrease in the amount of longer hydrocarbons and/or the lengths of the hydrocarbon products, illustrating a competition between CH4 formation/release and C-C coupling/chain extension. These observations suggest the possibility of designing simpler synthetic clusters for hydrocarbon formation while establishing the L-cluster as a platform for mechanistic investigations of CO and CN(-) reduction without complications originating from the heterometal and homocitrate components. Nitrogenase is a metalloenzyme that is highly complex in structure and uniquely versatile in function. It catalyzes two reactions that parallel two important industrial processes: the reduction of nitrogen to ammonia, which parallels the Haber-Bosch process in ammonia production, and the reduction of carbon monoxide to hydrocarbons, which parallels the Fischer-Tropsch process in fuel production. Thus, the significance of nitrogenase can be appreciated from the perspective of the useful products it generates: (i) ammonia, the "fixed" nitrogen that is essential for the existence of the entire human population; and (ii) hydrocarbons, the "recycled" carbon fuel that could be used to directly address the worldwide energy shortage. This article provides initial insights into the catalytic characteristics of various nitrogenase cofactors in hydrocarbon formation. The reported assay system provides a useful tool for mechanistic

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.

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)

Thermotropic phase behavior of long-chain alkylammonium-alkylcarbamates

International Nuclear Information System (INIS)

Holas, Tomas; Zbytovska, Jarmila; Vavrova, Katerina; Berka, Pavel; Madlova, Michaela; Klimentova, Jana; Hrabalek, Alexandr

2006-01-01

A series of alkylammonium-alkylcarbamates with different chain length including transdermal permeation enhancer Transkarbam 12 have been prepared and characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), temperature-dependent Fourier transform infrared spectroscopy (FTIR) and temperature-dependent X-ray powder diffraction. Four transitions have been observed including solid-solid transition (I), melting (II), decomposition of the carbamate salt (III) and boiling of the released amine (IV). The first transition was connected with rearrangement of the hydrocarbon chain packing and unusual shift of symmetric CH 2 stretching vibration in the IR spectra to lower wavenumbers indicated increase of conformational order. The second transition represented melting of the molecule and the third one was attributed to the decomposition of the carbamate salt into two amine molecules and carbon dioxide as evidenced by combination of DSC and TGA curves

Distribution and Fractional Composition of Petroleum Hydrocarbons in Roadside Soils

Directory of Open Access Journals (Sweden)

Larysa Mykhailova

2013-01-01

Full Text Available Total petroleum hydrocarbon (TPH concentrations and their fractional composition (medium fraction: n-alkane chain-length C15 to C27, heavy fraction: >C27 were determined at distances from 1 to 60 m from roads and at soil depths from 0.5 to 15 cm. The traffic intensities were up to 25000 vehicles per day. Soil TPH concentrations were highest within 15 m distance (665 and 3198 mg kg−1 at the windward and leeward sides, resp., followed by a rapid drop to background values beyond (196 and 115 mg kg−1 in 60 m distance at the windward and leeward sides, resp.. The data variability was lowest at distances of 1 m and highest within tree plantations at distances of 15 m from the road. The TPH concentrations decreased with depth but were significantly higher than the background at all depths investigated. A principal component analysis revealed a positive relation between the medium-to-heavy fraction ratio and soil depth. A fractional differentiation of hydrocarbons with distance from road was not observed. It was concluded that the assessment of the potential of hydrocarbons to translocate, accumulate, or degrade in soil necessitates their subdivision into fractions based on their physicochemical and metabolic properties.

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

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.

Superlattice configurations in linear chain hydrocarbon binary mixtures

Indian Academy of Sciences (India)

monoclinic, monoclinic-monoclinic) are realizable, because of discrete orientational changes in the alignment of molecules of -C28H58 hydrocarbon, through an angle , where = 1, 2, 3 … and angle has an average value of 3.3°.

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...

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.

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.

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.

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.

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.

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.

Predictable weathering of puparial hydrocarbons of necrophagous flies for determining the postmortem interval: a field experiment using Chrysomya rufifacies.

Science.gov (United States)

Zhu, Guang-Hui; Jia, Zheng-Jun; Yu, Xiao-Jun; Wu, Ku-Sheng; Chen, Lu-Shi; Lv, Jun-Yao; Eric Benbow, M

2017-05-01

Preadult development of necrophagous flies is commonly recognized as an accurate method for estimating the minimum postmortem interval (PMImin). However, once the PMImin exceeds the duration of preadult development, the method is less accurate. Recently, fly puparial hydrocarbons were found to significantly change with weathering time in the field, indicating their potential use for PMImin estimates. However, additional studies are required to demonstrate how the weathering varies among species. In this study, the puparia of Chrysomya rufifacies were placed in the field to experience natural weathering to characterize hydrocarbon composition change over time. We found that weathering of the puparial hydrocarbons was regular and highly predictable in the field. For most of the hydrocarbons, the abundance decreased significantly and could be modeled using a modified exponent function. In addition, the weathering rate was significantly correlated with the hydrocarbon classes. The weathering rate of 2-methyl alkanes was significantly lower than that of alkenes and internal methyl alkanes, and alkenes were higher than the other two classes. For mono-methyl alkanes, the rate was significantly and positively associated with carbon chain length and branch position. These results indicate that puparial hydrocarbon weathering is highly predictable and can be used for estimating long-term PMImin.

Waste Plastic Converting into Hydrocarbon Fuel Materials

Energy Technology Data Exchange (ETDEWEB)

Sarker, Moinuddin; Mamunor Rashid, Mohammad; Molla, Mohammad

2010-09-15

The increased demand and high prices for energy sources are driving efforts to convert organic compounds into useful hydrocarbon fuels. Although much of this work has focused on biomass, there are strong benefits to deriving fuels from waste plastic material. Natural State Research Inc. (NSR) has invented a simple and economically viable process to decompose the hydrocarbon polymers of waste plastic into the shorter chain hydrocarbon of liquid fuel (patent pending). The method and principle of the production / process will be discussed. Initial tests with several widely used polymers indicate a high potential for commercialization.

Raman spectra of long chain hydrocarbons: anharmonic calculations, experiment and implications for imaging of biomembranes.

Science.gov (United States)

Šebek, Jiří; Pele, Liat; Potma, Eric O; Gerber, R Benny

2011-07-28

First-principles anharmonic vibrational calculations are carried out for the Raman spectrum of the C-H stretching bands in dodecane, and for the C-D bands in the deuterated molecule. The calculations use the Vibrational Self-Consistent Field (VSCF) algorithm. The results are compared with liquid-state experiments, after smoothing the isolated-molecule sharp-line computed spectra. Very good agreement between the computed and experimental results is found for the two systems. The combined theoretical and experimental results provide insights into the spectrum, elucidating the roles of symmetric and asymmetric CH(3) and CH(2) hydrogenic stretches. This is expected to be very useful for the interpretation of spectra of long-chain hydrocarbons. The results show that anharmonic effects on the spectrum are large. On the other hand, vibrational degeneracy effects seem to be rather modest at the resolution of the experiments. The degeneracy effects may have more pronounced manifestations in higher-resolution experiments. The results show that first-principles anharmonic vibrational calculations for hydrocarbons are feasible, in good agreement with experiment, opening the way for applications to many similar systems. The results may be useful for the analysis of CARS imaging of lipids, for which dodecane is a representative molecule. It is suggested that first-principles vibrational calculations may be useful also for CARS imaging of other systems. This journal is © the Owner Societies 2011

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.

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.

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.

Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery.

Science.gov (United States)

Terrón-Mejía, Ketzasmin A; López-Rendón, Roberto; Goicochea, Armando Gama

2017-08-29

The need to extract oil from wells where it is embedded on the surfaces of rocks has led to the development of new and improved enhanced oil recovery techniques. One of those is the injection of surfactants with water vapor, which promotes desorption of oil that can then be extracted using pumps, as the surfactants encapsulate the oil in foams. However, the mechanisms that lead to the optimal desorption of oil and the best type of surfactants to carry out desorption are not well known yet, which warrants the need to carry out basic research on this topic. In this work, we report non equilibrium dissipative particle dynamics simulations of model surfactants and oil molecules adsorbed on surfaces, with the purpose of studying the efficiency of the surfactants to desorb hydrocarbon chains, that are found adsorbed over flat surfaces. The model surfactants studied correspond to nonionic and cationic surfactants, and the hydrocarbon desorption is studied as a function of surfactant concentration under increasing Poiseuille flow. We obtain various hydrocarbon desorption isotherms for every model of surfactant proposed, under flow. Nonionic surfactants are found to be the most effective to desorb oil and the mechanisms that lead to this phenomenon are presented and discussed.

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

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

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.

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...

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.

Microbial Hydrocarbon and ToxicPollutant Degradation Method

Energy Technology Data Exchange (ETDEWEB)

Schlueter, Dietrich [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Janabi, Mustafa [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); O' Neil, James [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Budinger, Thomas [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2011-08-16

The goal of this project is to determine optimum conditions for bacterial oxidation of hydrocarbons and long-chain alkanes that are representative of petroleum contamination of the environment. Polycyclic Aromatic Hydrocarbons (PAHs) are of concern because of their toxicity, low volatility, and resistance to microbial degradation, especially under anaerobic conditions. The uniqueness of our approach is to use carbon-11 in lieu of the traditional use of carbon-14.

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

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.

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.

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.

Rationalization and Prediction of the Equivalent Alkane Carbon Number (EACN) of Polar Hydrocarbon Oils with COSMO-RS σ-Moments.

Science.gov (United States)

Lukowicz, Thomas; Benazzouz, Adrien; Nardello-Rataj, Véronique; Aubry, Jean-Marie

2015-10-20

The equivalent alkane carbon numbers (EACNs) of 20 polar hydrocarbon oils are determined by the fishtail method. These values supplemented by 43 already reported EACNs of other hydrocarbons are rationalized by using the COSMO-RS σ-moments as descriptors for a QSPR analysis. A reliable model, with only two meaningful physicochemical parameters, namely the surface area (M0(X)) and the overall polarity (M2(X)) of the oil X, is able to predict the EACN values of a large variety of oils including (cyclo)alkanes, (cyclo)alkenes, terpenes, aromatics, alkynes, and chloroalkanes and to rationalize structural effects on EACNs. Furthermore, the dependence of the EACN of homologous oils on the chain length provides some molecular insight into how the different oils penetrate into the interfacial film of surfactants.

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...

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

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...

Chain chemical reactions during matrix devitrification

International Nuclear Information System (INIS)

Barkalov, I.M.

1980-01-01

Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

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...

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.

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.

Formation of hydrocarbon compounds during the hydrocracking of non-edible vegetable oils with cobalt-nickel supported on hierarchical HZSM-5 catalyst

Science.gov (United States)

Marlinda, L.; Al-Muttaqii, M.; Roesyadi, A.; Prajitno, D. H.

2017-05-01

The hierarchical Co-Ni/HZSM-5 catalyst with hierarchical pore structure was prepared by desilication and incipient wetness impregnation. Hydrocracking of non-edible vegetable oils at temperature of 400 °C, 20±5 bar for 2 h was performed in the presence of this type of catalyst under hydrogen initial pressure in pressured batch reactor. Non-edible vegetable oils, such as Reutealis trisperma (Blanco) airy shaw (sunan candlenut) and Hevea brasiliensis (rubber seed) were chosen to study the effect of the degree of saturation and lateral chain length on hydrocarbon compounds obtained through hydrocracking. Cerbera manghas oil was also tested for comparison because the composition of fatty acid was different with the other oils The hydrocracking test indicated that liquid product produced has a similar hydrocarbon compounds with petroleum diesel. The most abundant hydrocarbon is pentadecane (n-C15) and heptadecane (n-C17). The high aromatic compounds were found in liquid product produced in hydrocracking of Sunan candlenut oil.

Enabling the synthesis of medium chain alkanes and 1-alkenes in yeast

DEFF Research Database (Denmark)

Zhu, Zhiwei; Zhou, Yongjin J.; Kang, Min Kyoung

2017-01-01

Microbial synthesis of medium chain aliphatic hydrocarbons, attractive drop-in molecules to gasoline and jet fuels, is a promising way to reduce our reliance on petroleum-based fuels. In this study, we enabled the synthesis of straight chain hydrocarbons (C7–C13) by yeast Saccharomyces cerevisiae...

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

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.

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

Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

International Nuclear Information System (INIS)

Westbrook, C.K.

2000-01-01

Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignition in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical combustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant. However, there are many combustion factors that can influence these two major reactions, and these are the features that vary from one practical system to another

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.

Application of positron annihilation techniques to the study of micels and microemulsions

International Nuclear Information System (INIS)

Olea C, O.

1981-01-01

The molecular auto-association mechanisms in sodium-oleate-alcohol-alkane-water systems were studied, applying positron and positronium annihilation techniques. The effects of the different component structures of these systems and of their concentrations on the swelled micel formation process which eventually produce microemulsions, were also investigated. The influences studied were: a) co-surfactant (alcohol) hydrocarbon chain lengths, b) alkane (oil) hydrocarbon chain lengths, c) surfactant concentrations, and d) surfactant double link alkylic chains. (author)

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.

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...

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

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

Energy Technology Data Exchange (ETDEWEB)

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Drummond, Calum J. (CSIRO/MSE)

2014-09-24

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.

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.

Kinetic particularities of strained alicyclic compounds formation in catalytic methanol to hydrocarbon transformation process

OpenAIRE

Doluda V.; Brovko R.; Giniatullina N.; Sulman M.

2017-01-01

The catalytic transformation of methanol into hydrocarbons is a complex chemical process, accompanied by chain parallel chemical transformation reactions. The most valuable products of the methanol to hydrocarbons catalytic transformation reaction are the strained hydrocarbons — cyclopropane derivatives. These compounds can be used as a high-energy fuel, and also as a valuable chemical raw material. However, the yield of strained compounds in methanol to hydrocarbons catalytic transformation ...

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.

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.

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

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.

Isolation and Characterization of Hydrocarbon-Degrading Yeast Strains from Petroleum Contaminated Industrial Wastewater

Science.gov (United States)

Gargouri, Boutheina; Mhiri, Najla; Karray, Fatma; Aloui, Fathi; Sayadi, Sami

2015-01-01

Two yeast strains are enriched and isolated from industrial refinery wastewater. These strains were observed for their ability to utilize several classes of petroleum hydrocarbons substrates, such as n-alkanes and aromatic hydrocarbons as a sole carbon source. Phylogenetic analysis based on the D1/D2 variable domain and the ITS-region sequences indicated that strains HC1 and HC4 were members of the genera Candida and Trichosporon, respectively. The mechanism of hydrocarbon uptaking by yeast, Candida, and Trichosporon has been studied by means of the kinetic analysis of hydrocarbons-degrading yeasts growth and substrate assimilation. Biodegradation capacity and biomass quantity were daily measured during twelve days by gravimetric analysis and gas chromatography coupled with mass spectrometry techniques. Removal of n-alkanes indicated a strong ability of hydrocarbon biodegradation by the isolated yeast strains. These two strains grew on long-chain n-alkane, diesel oil, and crude oil but failed to grow on short-chain n-alkane and aromatic hydrocarbons. Growth measurement attributes of the isolates, using n-hexadecane, diesel oil, and crude oil as substrates, showed that strain HC1 had better degradation for hydrocarbon substrates than strain HC4. In conclusion, these yeast strains can be useful for the bioremediation process and decreasing petroleum pollution in wastewater contaminated with petroleum hydrocarbons. PMID:26339653

Isolation and Characterization of Hydrocarbon-Degrading Yeast Strains from Petroleum Contaminated Industrial Wastewater

Directory of Open Access Journals (Sweden)

Boutheina Gargouri

2015-01-01

Full Text Available Two yeast strains are enriched and isolated from industrial refinery wastewater. These strains were observed for their ability to utilize several classes of petroleum hydrocarbons substrates, such as n-alkanes and aromatic hydrocarbons as a sole carbon source. Phylogenetic analysis based on the D1/D2 variable domain and the ITS-region sequences indicated that strains HC1 and HC4 were members of the genera Candida and Trichosporon, respectively. The mechanism of hydrocarbon uptaking by yeast, Candida, and Trichosporon has been studied by means of the kinetic analysis of hydrocarbons-degrading yeasts growth and substrate assimilation. Biodegradation capacity and biomass quantity were daily measured during twelve days by gravimetric analysis and gas chromatography coupled with mass spectrometry techniques. Removal of n-alkanes indicated a strong ability of hydrocarbon biodegradation by the isolated yeast strains. These two strains grew on long-chain n-alkane, diesel oil, and crude oil but failed to grow on short-chain n-alkane and aromatic hydrocarbons. Growth measurement attributes of the isolates, using n-hexadecane, diesel oil, and crude oil as substrates, showed that strain HC1 had better degradation for hydrocarbon substrates than strain HC4. In conclusion, these yeast strains can be useful for the bioremediation process and decreasing petroleum pollution in wastewater contaminated with petroleum hydrocarbons.

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.

Identifying future directions for subsurface hydrocarbon migration research

Science.gov (United States)

Leifer, I.; Clark, J. F.; Luyendyk, B.; Valentine, D.

Subsurface hydrocarbon migration is important for understanding the input and impacts of natural hydrocarbon seepage on the environment. Great uncertainties remain in most aspects of hydrocarbon migration, including some basic mechanisms of this four-phase flow of tar, oil, water, and gas through the complex fracture-network geometry particularly since the phases span a wide range of properties. Academic, government, and industry representatives recently attended a workshop to identify the areas of greatest need for future research in shallow hydrocarbon migration.Novel approaches such as studying temporal and spatial seepage variations and analogous geofluid systems (e.g., geysers and trickle beds) allow deductions of subsurface processes and structures that remain largely unclear. Unique complexities exist in hydrocarbon migration due to its multiphase flow and complex geometry, including in-situ biological weathering. Furthermore, many aspects of the role of hydrocarbons (positive and negative) in the environment are poorly understood, including how they enter the food chain (respiration, consumption, etc.) and “percolate” to higher trophic levels. But understanding these ecological impacts requires knowledge of the emissions' temporal and spatial variability and trajectories.

Hydrocarbons on Phoebe, Iapetus, and Hyperion: Quantitative Analysis

Science.gov (United States)

Cruikshank, Dale P.; MoreauDalleOre, Cristina; Pendleton, Yvonne J.; Clark, Roger Nelson

2012-01-01

We present a quantitative analysis of the hydrocarbon spectral bands measured on three of Saturn's satellites, Phoebe, Iaperus, and Hyperion. These bands, measured with the Cassini Visible-Infrared Mapping Spectrometer on close fly-by's of these satellites, are the C-H stretching modes of aromatic hydrocarbons at approximately 3.28 micrometers (approximately 3050 per centimeter), and the are four blended bands of aliphatic -CH2- and -CH3 in the range approximately 3.36-3.52 micrometers (approximately 2980- 2840 per centimeter) bably indicating the presence of polycyclic aromatic hydrocarbons (PAH), is unusually strong in comparison to the aliphatic bands, resulting in a unique signarure among Solar System bodies measured so far, and as such offers a means of comparison among the three satellites. The ratio of the C-H bands in aromatic molecules to those in aliphatic molecules in the surface materials of Phoebe, NAro:NAliph approximately 24; for Hyperion the value is approximately 12, while laperus shows an intermediate value. In view of the trend of the evolution (dehydrogenation by heat and radiation) of aliphatic complexes toward more compact molecules and eventually to aromatics, the relative abundances of aliphatic -CH2- and -CH3- is an indication of the lengths of the molecular chain structures, hence the degree of modification of the original material. We derive CH2:CH3 approximately 2.2 in the spectrum of low-albedo material on laperus; this value is the same within measurement errors to the ratio in the diffuse interstellar medium. The similarity in the spectral signatures of the three satellites, plus the apparent weak trend of aromatic/aliphatic abundance from Phoebe to Hyperion, is consistent with, and effectively confirms that the source of the hydrocarbon-bearing material is Phoebe, and that the appearance of that material on the other two satellites arises from the deposition of the inward-spiraling dust that populates the Phoebe ring.

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...

The aliphatic hydrocarbon distributions of terrestrial plants around an alpine lake: a pilot study from Lake Ximencuo, Eastern Qinghai-Tibet Plateau

Science.gov (United States)

Pu, Yang; Jia, Jihong; Cao, Jicheng

2017-12-01

As part of an investigation of the sources of aliphatic hydrocarbons to the sediments of alpine Lake Ximencuo, leaves of the eight dominant vascular plants were collected and their hydrocarbon contents were analyzed. A series of unsaturated aliphatic hydrocarbons were identified in the plant leaves; in particular, Festuca sp. contain a series of n-alkadienes that have rarely been reported in previous studies. The comparison of n-alkane proxies (ACL 27-33, ACL T, P aq, and CPI) and δ13Corg among plant leaves, surface soils, and lake sediments suggests that organic proxies have been altered to varying degrees during the transport and burial process of organic materials. It is believed that microbial reworking and source changes have great impacts on organic proxies in the alpine lake system. In addition, the cluster analysis for plant leaves depending on n-alkane compositions and the ACL T proxy generates similar results. Accordingly, we postulate that the average chain length of plant waxes might be a potential indicator of plant classification in regions such as the Qinghai-Tibet Plateau.

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...

Screening of hydrocarbons as supercritical ORCs working fluids by thermal stability

International Nuclear Information System (INIS)

Dai, Xiaoye; Shi, Lin; An, Qingsong; Qian, Weizhong

2016-01-01

Highlights: • A rapid evaluation method for thermal stability of hydrocarbons for ORCs. • Methane and hydrogen are confirmed to be decomposition indicators. • The decomposition temperatures for some hydrocarbons using the rapid method. • Long carbon chain hydrocarbons are not suitable for supercritical ORCs. - Abstract: Organic Rankine Cycle (ORC) systems are widely used for industrial waste heat recovery and renewable energy utilization. The supercritical ORC is currently one of the main development directions due to its low exergy loss, high thermal efficiency and high work output. The thermal stability is the major limitation of organic working fluid selection with high temperature heat sources. This paper presents a rapid experimental method for assessing the thermal stability of hydrocarbons for ORCs. The fluids were tested in a high temperature reactor with methane and hydrogen theoretically and experimentally confirmed to be the indicators of thermal decomposition. The thermal decomposition temperatures were obtained for n-hexane, n-pentane, isopentane, cyclopentane, n-butane and isobutane using the rapid experimental method. The results show that cycloalkanes are not the good choices by thermal stability and long carbon chain hydrocarbons (longer than C6) are not suitable for supercritical ORCs due to the thermal stability limitation.

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.

Comparison between different bio-treatments of a hydrocarbon ...

African Journals Online (AJOL)

Ramya

2011-10-31

Oct 31, 2011 ... We investigated the bio-remediation of a hydrocarbon contaminated soil pile that was slated for landfill ... soils, plants and in the food chain (Kipopoulou et al., ...... Scientific and Social Research, Putra Palace, Perlis, Malaysia.

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

Effective viscosity of confined hydrocarbons

DEFF Research Database (Denmark)

Sivebæk, Ion Marius; Samoilov, V.N.; Persson, B.N.J.

2012-01-01

We present molecular dynamics friction calculations for confined hydrocarbon films with molecular lengths from 20 to 1400 carbon atoms. We find that the logarithm of the effective viscosity ηeff for nanometer-thin films depends linearly on the logarithm of the shear rate: log ηeff=C-nlog γ̇, where...

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

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...

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.

Phase behavior of fluorocarbon and hydrocarbon double-chain hydroxylated and galactosylated amphiphiles and bolaamphiphiles. Long-term shelf-stability of their liposomes.

Science.gov (United States)

Clary, L; Gadras, C; Greiner, J; Rolland, J P; Santaella, C; Vierling, P; Gulik, A

1999-06-01

This paper describes the morphological characterization, by freeze-fracture electron microscopy, and the thermotropic phase behavior, by differential scanning calorimetry and/or X-ray scattering, of aqueous dispersions of various hydroxylated and galactosylated double-chain amphiphiles and bolaamphiphiles, several of them containing one or two hydrophobic fluorocarbon chains. Colloidal systems are observed in water with the hydroxylated hydrocarbon or fluorocarbon bolaamphiphiles only when they are dispersed with a co-amphiphile such as rac-1,2-dimyristoylphosphatidylcholine (DMPC) or rac-1,2-distearoylphosphatidylcholine (DSPC). Liposomes are formed providing the relative content of bolaamphiphiles does not exceed 20% mol. Most of these liposomes can be thermally sterilized and stored at room temperature for several months without any significant modification of their size and size distribution. The hydrocarbon galactosylated bolaamphiphile HO[C24][C12]Gal forms in water a lamellar phase (the gel to liquid-crystal phase transition is complete at 45 degrees C) and a Im3m cubic phase above 47 degrees C. The fluorocarbon HO[C24][F6C5]Gal analog displays a more complex and metastable phase behavior. The fluorinated non-bolaform galactosylated [F8C7][C16]AEGal and SerGal amphiphiles form lamellar phases in water. Low amounts (10% molar ratio) of the HO[C24][F6C5]Gal or HO[C24][C12]Gal bolaamphiphiles or of the single-headed [F8C7][C16]AEGal improve substantially the shelf-stability of reference phospholipon/cholesterol 2/1 liposomes. These liposomes when co-formulated with a single-headed amphiphile from the SerGal series are by far less stable.

Potential for biodegradation of polycyclic aromatic hydrocarbons by ...

African Journals Online (AJOL)

WiTT

2012-05-08

May 8, 2012 ... Full Length Research Paper. Biodegradation of ... organic compounds, including some organometallic ... is a major source of toxic PAHs that contributes signi- ficantly to ... microorganisms for bioremediation of hydrocarbon-.

Use of nuclear magnetic resonance of hydrogen in the characterization of saturated hydrocarbonic chains

International Nuclear Information System (INIS)

Costa Neto, A.; Soares, V.L.P.; Costa Neto, C.

1979-01-01

Alkanes and cycloalkanes are characterized by a methyl-methylene-methine groups proportion, the percentual absorption in prefixed regions and the pattern of the spectrum of nuclear magnetic resonance of hydrogen. The GPI is calculated from the contribution of the areas corresponding to prefixed regions of the hydrogen magnetic resonance spectra (60 Mc). These regions are (for the saturated hydrocarbons): 0,5-1,05ppm (X), 1,05ppm (Y) and 1,50-2,00ppm (Z). The validity of the index was verified for the homologous series of linear hydrocarbons and methyl-, dimethyl-, ethyl-, cyclopentyl- and cyclohexyl-branched hydrocarbons. Its application to shale oil chemistry (xistoquimica) is discussed. (author) [pt

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

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.

Impact of Branched-Chain Amino Acid Catabolism on Fatty Acid and Alkene Biosynthesis in Micrococcus luteus.

Science.gov (United States)

Surger, Maximilian J; Angelov, Angel; Stier, Philipp; Übelacker, Maria; Liebl, Wolfgang

2018-01-01

Micrococcus luteus naturally produces alkenes, unsaturated aliphatic hydrocarbons, and represents a promising host to produce hydrocarbons as constituents of biofuels and lubricants. In this work, we identify the genes for key enzymes of the branched-chain amino acid catabolism in M. luteus , whose first metabolic steps lead also to the formation of primer molecules for branched-chain fatty acid and olefin biosynthesis, and demonstrate how these genes can be used to manipulate the production of specific olefins in this organism. We constructed mutants of several gene candidates involved in the branched-chain amino acid metabolism or its regulation and investigated the resulting changes in the cellular fatty acid and olefin profiles by GC/MS. The gene cluster encoding the components of the branched-chain α-keto acid dehydrogenase (BCKD) complex was identified by deletion and promoter exchange mutagenesis. Overexpression of the BCKD gene cluster resulted in about threefold increased olefin production whereas deletion of the cluster led to a drastic reduction in branched-chain fatty acid content and a complete loss of olefin production. The specificities of the acyl-CoA dehydrogenases of the branched amino acid degradation pathways were deduced from the fatty acid and olefin profiles of the respective deletion mutant strains. In addition, growth experiments with branched amino acids as the only nitrogen source were carried out with the mutants in order to confirm our annotations. Both the deletion mutant of the BCKD complex, responsible for the further degradation of all three branched-chain amino acids, as well as the deletion mutant of the proposed isovaleryl-CoA dehydrogenase (specific for leucine degradation) were not able to grow on leucine in contrast to the parental strain. In conclusion, our experiments allow the unambigous assignment of specific functions to the genes for key enzymes of the branched-chain amino acid metabolism of M. luteus . We also show how

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

Mesoscale simulation of semiflexible chains. I. Endpoint distribution and chain dynamics

Science.gov (United States)

Groot, Robert D.

2013-06-01

The endpoint distribution and dynamics of semiflexible fibers are studied by numerical simulation. A brief overview is given over the analytical theory of flexible and semiflexible polymers. In particular, a closed expression is given for the relaxation spectrum of wormlike chains, which determines polymer diffusion and rheology. Next a simulation model for wormlike chains with full hydrodynamic interaction is described, and relations for the bending and torsion modulus are given. Two methods are introduced to include torsion stiffness into the model. The model is validated by simulating single chains in a heat bath, and comparing the endpoint distribution of the chains with established Monte Carlo results. It is concluded that torsion stiffness leads to a slightly shorter effective persistence length for a given bending stiffness. To further validate the simulation model, polymer diffusion is studied for fixed persistence length and varying polymer length N. The diffusion constant shows crossover from Rouse (D ∝ N-1) to reptation behaviour (D ∝ N-2). The terminal relaxation time obtained from the monomer displacement is consistent with the theory of wormlike chains. The probability for chain crossing has also been studied. This probability is so low that it does not influence the present results.

Desiccation resistance: effect of cuticular hydrocarbons and water content in Drosophila melanogaster adults

Directory of Open Access Journals (Sweden)

Jean-Francois Ferveur

2018-02-01

Full Text Available Background The insect cuticle covers the whole body and all appendages and has bi-directionnal selective permeability: it protects against environmental stress and pathogen infection and also helps to reduce water loss. The adult cuticle is often associated with a superficial layer of fatty acid-derived molecules such as waxes and long chain hydrocarbons that prevent rapid dehydration. The waterproofing properties of cuticular hydrocarbons (CHs depend on their chain length and desaturation number. Drosophila CH biosynthesis involves an enzymatic pathway including several elongase and desaturase enzymes. Methods The link between desiccation resistance and CH profile remains unclear, so we tested (1 experimentally selected desiccation-resistant lines, (2 transgenic flies with altered desaturase expression and (3 natural and laboratory-induced CH variants. We also explored the possible relationship between desiccation resistance, relative water content and fecundity in females. Results We found that increased desiccation resistance is linked with the increased proportion of desaturated CHs, but not with their total amount. Experimentally-induced desiccation resistance and CH variation both remained stable after many generations without selection. Conversely, flies with a higher water content and a lower proportion of desaturated CHs showed reduced desiccation resistance. This was also the case in flies with defective desaturase expression in the fat body. Discussion We conclude that rapidly acquired desiccation resistance, depending on both CH profile and water content, can remain stable without selection in a humid environment. These three phenotypes, which might be expected to show a simple relationship, turn out to have complex physiological and genetic links.

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

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.

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

Radiation induced solid-state polymerization of long-chain acrylates containing fluorocarbon chain

International Nuclear Information System (INIS)

Shibasaki, Y.; Zhu, Zhi-Qin

1995-01-01

γ-Ray irradiation post-polymerizations of long-chain acrylates containing fluorocarbon chain, H(CF 2 ) 10 CH 2 OCOCH=CH 2 and H(CF 2 ) 8 CH 2 OCOCH=CH 2 , were investigated and also the structures and thermal properties of comb-like polymers obtained were studied. It was found that these monomers exhibited very high polymerizability at wide temperature ranges around the melting points. Because the fluorocarbon chains are less flexible and thicker than the hydrocarbon chains, it can be expected that the aggregation force among the monomer molecules is strong and the conformational freedom of functional group for polymerization is large. According to the DSC and the X-ray diffraction measurements of the comb-like polymers obtained, the fluorocarbon chains are aggregated in a mode of hexagonal packing in the lamellar crystals. This situation can be considered as an optimum condition for the γ-ray irradiation post-polymerization. (author)

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.

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.

Noble gas and hydrocarbon tracers in multiphase unconventional hydrocarbon systems: Toward integrated advanced reservoir simulators

Science.gov (United States)

Darrah, T.; Moortgat, J.; Poreda, R. J.; Muehlenbachs, K.; Whyte, C. J.

2015-12-01

Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noble gas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

Microbial communities involved in methane production from hydrocarbons in oil sands tailings.

Science.gov (United States)

Siddique, Tariq; Penner, Tara; Klassen, Jonathan; Nesbø, Camilla; Foght, Julia M

2012-09-04

Microbial metabolism of residual hydrocarbons, primarily short-chain n-alkanes and certain monoaromatic hydrocarbons, in oil sands tailings ponds produces large volumes of CH(4) in situ. We characterized the microbial communities involved in methanogenic biodegradation of whole naphtha (a bitumen extraction solvent) and its short-chain n-alkane (C(6)-C(10)) and BTEX (benzene, toluene, ethylbenzene, and xylenes) components using primary enrichment cultures derived from oil sands tailings. Clone libraries of bacterial 16S rRNA genes amplified from these enrichments showed increased proportions of two orders of Bacteria: Clostridiales and Syntrophobacterales, with Desulfotomaculum and Syntrophus/Smithella as the closest named relatives, respectively. In parallel archaeal clone libraries, sequences affiliated with cultivated acetoclastic methanogens (Methanosaetaceae) were enriched in cultures amended with n-alkanes, whereas hydrogenotrophic methanogens (Methanomicrobiales) were enriched with BTEX. Naphtha-amended cultures harbored a blend of these two archaeal communities. The results imply syntrophic oxidation of hydrocarbons in oil sands tailings, with the activities of different carbon flow pathways to CH(4) being influenced by the primary hydrocarbon substrate. These results have implications for predicting greenhouse gas emissions from oil sands tailings repositories.

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.

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.

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.

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.)

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

Chlorinated hydrocarbons in a pelagic community

International Nuclear Information System (INIS)

Elder, D.; Fowler, S.W.

1976-01-01

For several years data have been accruing on the distribution of chlorinated hydrocarbon pollutants in marine ecosystems. An overall picture of ambient levels in biota, water and sediments is now emerging however, despite the vast amount of data collected to date, questions still arise as to whether certain pollutants such as chlorinated hydrocarbons are indeed magnified through the marine food web. Evidence both for and against trophic concentration of PCB and DDT compounds has been cited. The answer to this question remains unclear due to lack of adequate knowledge on the relative importance of food and water in the uptake of these compounds as well as the fact that conclusions are often confounded by comparing pollutant concentrations in successive links in the food chain sampled at different geographical locations and/or at different points in time. The situation is further complicated by complex prey-predator relationships that exist in many marine communities. In the present study we have tried to eliminate some of these problems by examining PCB and DOT concentrations in species belonging to a relatively well-defined pelagic food chain sampled at one point in space and time

Toxicity of jet fuel aliphatic and aromatic hydrocarbon mixtures on human epidermal Keratinocytes: evaluation based on in vitro cytotoxicity and interleukin-8 release

Energy Technology Data Exchange (ETDEWEB)

Yang, Jen-Hung (Chung-Shan Medical University Hospital, Department of Dermatology, Taichung, Taiwan, R.O.C); Lee, Chia-Hue; Tsang, Chau-Loong [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); Monteiro-Riviere, Nancy A.; Riviere, Jim E. [North Carolina State University, Center for Chemical Toxicology Research and Pharmacokinetics (CCTRP), Raleigh, NC (United States); Chou, Chi-Chung [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan)

2006-08-15

Jet fuels are complex mixtures of aliphatic (ALI) and aromatic (ARO) hydrocarbons that vary significantly in individual cytotoxicity and proinflammatory activity in human epidermal keratinocytes (HEK). In order to delineate the toxicological interactions among individual hydrocarbons in a mixture and their contributions to cutaneous toxicity, nine ALI and five ARO hydrocarbons were each divided into five (high/medium/low cytotoxic and strong/weak IL-8 induction) groups and intra/inter-mixed to assess for their mixture effects on HEK mortality and IL-8 release. Addition of single hydrocarbon to JP-8 fuel was also evaluated for their changes in fuel dermatotoxicity. The results indicated that when hydrocarbons were mixed, HEK mortality and IL-8 release were not all predictable by their individual ability affecting these two parameters. The lowest HEK mortality (7%) and the highest IL-8 production were induced with mixtures including high cytotoxic and weak IL-8 inductive ARO hydrocarbons. Antagonistic reactions not consistently correlated with ALI carbon chain length and ARO structure were evident and carried different weight in the overall mixture toxicities. Single addition of benzene, toluene, xylene or ethylbenzene for up to tenfold in JP-8 did not increase HEK mortality while single addition of ALI hydrocarbons exhibited dose-related differential response in IL-8. In an all ALI environment, no single hydrocarbon is the dominating factor in the determination of HEK cytotoxicity while deletion of hexadecane resulted in a 2.5-fold increase in IL-8 production. Overall, decane, undecane and dodecane were the major hydrocarbons associated with high cytotoxicity while tetradecane, pentadecane and hexadecane were those which had the greatest buffering effect attenuating dermatotoxicity. The mixture effects must be considered when evaluating jet fuel toxicity to HEK. (orig.)

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.

Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

Energy Technology Data Exchange (ETDEWEB)

Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

1993-12-01

Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

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.

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 

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.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis

Energy Technology Data Exchange (ETDEWEB)

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-11-04

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis.

Science.gov (United States)

Goblirsch, Brandon R; Jensen, Matthew R; Mohamed, Fatuma A; Wackett, Lawrence P; Wilmot, Carrie M

2016-12-23

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety-unusual for a thiolase-are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys 143 ) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C 12 and C 14 ) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ 117 ) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

Science.gov (United States)

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-01-01

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. PMID:27815501

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

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.

Evaluation of synthetic hydrocarbons for mark-recapture studies on the red milkweed beetle.

Science.gov (United States)

Ginzel, Matthew D; Hanks, Lawrence M

2002-05-01

This study evaluates the potential for using blends of synthetic hydrocarbons in mark-recapture studies of insects. To test the durability of hydrocarbons, we applied a blend of five straight-chain hydrocarbons (C24, C21, C26. C28, C30) to detached elytra of the red milkweed beetle, Tetraopes tetrophthalmus (Forster) (Coleoptera: Cerambycidae), mounted the elytra on pins, and placed them in an exposed location outdoors. The amount of hydrocarbons on the elytra did not change over time, even after two months of exposure to sun and rain. Synthetic hydrocarbons applied to the elytra of living beetles did not significantly influence their longevity or mating success in a laboratory study. and the amounts of hydrocarbons did not change with age. The invariability of hydrocarbon ratios over time suggests that blends could provide a nearly infinite variety of ratios to mark individual insects uniquely and indelibly with a hydrocarbon "fingerprint." This technique offers a convenient, safe, and durable means of individually marking insects and may find application in field studies of larger bodied insects that are long-lived and sedentary.

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....

Predicting the environmental fate properties of petroleum hydrocarbon mixtures

International Nuclear Information System (INIS)

Pisigan, R.A. Jr.; Tucker, W.A.

1995-01-01

The environmental fate and transport of petroleum products for risk assessment can be evaluated based on the physico-chemical properties of an indicator chemical or a surrogate compound, or the whole mixture. A study was conducted to develop a simple representation of the hydrocarbon mixture as if it contained only few constituents, each of which represents a large number of compounds. The products considered are gasoline, diesel fuel, and jet fuel (JP4). Each petroleum hydrocarbon was characterized as a mixture of six constituents: short chain alkanes, long chain alkanes, short chain cycloalkanes and alkenes, long chain cycloalkanes and alkenes, BTEX, and other aromatics. The carbon number used as a cut-off between short and long chain alkanes, alkenes, and cycloalkanes varies with the type of product. Each mixture has different average molecular weight, water solubility, vapor pressure, organic carbon partition coefficient, and air diffusivity. The properties of each constituent of gasoline were derived from the weighted average of all compounds belonging to each constituent group. For diesel fuel and JP4, the properties of each constituent were generated from the properties of the component most representative of the group. Any property that is missing or not available from common literature sources was derived from regression equations developed from the data base for gasoline. These regression equations express the property as function of the number of carbon atoms. The R 2 values of the regression equations range from 0.82--0.92. Some case studies involving petroleum product contamination in which the estimated properties were applied are presented

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

Superlattice configurations in linear chain hydrocarbon binary mixtures

Indian Academy of Sciences (India)

Unknown

Long-chain alkanes; binary mixtures; superlattices; discrete orientational changes. 1. Introduction ... tem and a model of superlattice configuration was proposed4, in terms of .... C18 system,4 the angle with value = 3⋅3° was seen to play an ...

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...

[Compositions and residual properties of petroleum hydrocarbon in contaminated soil of the oilfields].

Science.gov (United States)

Hu, Di; Li, Chuan; Dong, Qian-Qian; Li, Li-Ming; Li, Guang-He

2014-01-01

The aims of this study were to determine the compositions and residual properties of petroleum hydrocarbon in soil, as well as to identify the source and weathering degree of the pollution. A total of 5 producing wells in Gudao and Hekou oil producing region of Shengli oilfields were analyzed. More than 50 individual target compounds including straight-and branched-chain alkanes( n-alkanes, pristine and phytane) and polycyclic aromatic hydrocarbons (PAHs) in soil samples and crude oil were determined by gas chromatography-mass spectrometry (GC-MS). The percentages of chain alkanes and PAHs in total solvent extractable matters(TSEM) of soil samples were both much lower than those in the crude oil samples. The compositions of petroleum hydrocarbon in soil samples differed from those in crude oil, which indicated the n-alkanes with carbon numbers contaminated soils, the relationship between the index and petroleum hydrocarbon compounds was analyzed using principal component analysis (PCA). The results showed that the n-alkanes with carbon numbers > 33 and the PAHs with rings between 3 and 5 were much harder to degrade. PCA of 4 indexes for source identification revealed more than 50% of the soil samples were polluted by crude oil, which needs more attention during remediation.

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)

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.

Shearing Nanometer-Thick Confined Hydrocarbon Films: Friction and Adhesion

DEFF Research Database (Denmark)

Sivebæk, I. M.; Persson, B. N. J.

2016-01-01

We present molecular dynamics (MD) friction and adhesion calculations for nanometer-thick confined hydrocarbon films with molecular lengths 20, 100 and 1400 carbon atoms. We study the dependency of the frictional shear stress on the confining pressure and sliding speed. We present results...

Partnership in an application of RBCA: Case study for quantitative assessment of total petroleum hydrocarbons

International Nuclear Information System (INIS)

Srinivasan, K.; Shepherd, D.

1995-01-01

Risk-Based Corrective Action (RBCA) was successfully applied at a site contaminated with weathered Total Petroleum Hydrocarbons (TPH) from a past release of Diesel Fuel No. 2. In partnership with the state regulatory agency, an approach was developed to assess the toxicity of TPH by the evaluation of its individual classes/constituents. Historically, assessments of petroleum product releases have focused solely on TPH as an analytical parameter and not its individual fractions and/or constituents which represent the actual toxicity of the released product. Soil and groundwater TPH data by Modified California Method 8015 (GC/MS) were reviewed. Based on analytical standards, typical Diesel Fuel No. 2 carbon ranges/fractions were identified. In addition, site-specific carbon-chain lengths were identified based on the aforementioned standard. In consultation with state regulators and according to state draft RBCA guidance, site-specific polycyclic aromatic hydrocarbons (PAHs) and three TPH carbon-range fractions were identified as constituents of concern. In order to quantify the three TPH fractions, appropriate toxicological surrogates were identified. Site-specific exposures to potential human and ecological receptors were evaluated in close consultation with the state regulators. Limited contaminant fate and transport analysis was conducted. Subsequently, complete exposure pathways were quantified

Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

Science.gov (United States)

Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A; Alsberg, Tomas; de Wit, Cynthia A

2017-09-19

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 referred to as a "congener group" C n Cl m . Recently, we resolved individual C n Cl m by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying C n Cl m by introducing C n Cl m specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each C n Cl m are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. C n Cl m concentrations determined with the three instruments were highly correlated (R 2 > 0.90) with each other.

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.

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

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.

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)

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...

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

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...

Effect of alkyl length of cationic surfactants on desorption of Cs from contaminated clay

Energy Technology Data Exchange (ETDEWEB)

Kim, Bo Hyun; Park, Chan Woo; Yang, Hee Man; Seo, Bum Kyoung; Lee, Kune Woo [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Park, So Jin [Chungnam National University, Daejeon (Korea, Republic of)

2017-03-15

In this study, desorption characteristics of Cs from clay according to the hydrophobic alkyl chain length of the cationic surfactant were investigated. Alkyltrimethylammonium bromide was used as a cationic surfactant, and the length of the hydrophobic alkyl chain of the cationic surfactant was varied from –octyl to –cetyl. The adsorbed amount of the cationic surfactant on montmorillonite increased with the length of the hydrophobic alkyl chain, and intercalation of the cationic surfactant into the clay interlayer increased the interlayer distances. The Cs removal efficiency was also enhanced with increasing alkyl chain length, and the cationic surfactant with the cetyl group showed a maximum Cs removal efficiency of 99±2.9%.

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)

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.

Degradation of hydrocarbons in soil samples analyzed within accepted analytical holding times

International Nuclear Information System (INIS)

Jackson, J.; Thomey, N.; Dietlein, L.F.

1992-01-01

Samples which are collected in conjunction with subsurface investigations at leaking petroleum storage tank sites and petroleum refineries are routinely analyzed for benzene, toluene, ethylbenzene, xylenes (BTEX), and total petroleum hydrocarbons (TPH). Water samples are preserved by the addition of hydrochloric acid and maintained at four degrees centigrade prior to analysis. This is done to prevent bacterial degradation of hydrocarbons. Chemical preservation is not presently performed on soil samples. Instead, the samples are cooled and maintained at four degrees centigrade. This study was done to measure the degree of degradation of hydrocarbons in soil samples which are analyzed within accepted holding times. Soil samples were collected and representative subsamples were prepared from the initial sample. Subsamples were analyzed in triplicate for BTEX and TPH throughout the length of the approved holding times to measure the extent of sample constituent degradation prior to analysis. Findings imply that for sandy soils, BTEX and TPH concentrations can be highly dependent upon the length of time which elapses between sample collection and analysis

Fluid Phase Lipid Areas and Bilayer Thicknesses of Commonly Used Phosphatidylcholines as a Function of Temperature

International Nuclear Information System (INIS)

Kucerka, Norbert; Nieh, Mu-Ping; Katsaras, John

2011-01-01

The structural parameters of fluid phase bilayers composed of phosphatidylcholines with fully saturated, mixed, and branched fatty acid chains, at several temperatures, have been determined by simultaneously analyzing small-angle neutron and X-ray scattering data. Bilayer parameters, such as area per lipid and overall bilayer thickness have been obtained in conjunction with intrabilayer structural parameters (e.g. hydrocarbon region thickness). The results have allowed us to assess the effect of temperature and hydrocarbon chain composition on bilayer structure. For example, we found that for all lipids there is, not surprisingly, an increase in fatty acid chain trans-gauche isomerization with increasing temperature. Moreover, this increase in trans-gauche isomerization scales with fatty acid chain length in mixed chain lipids. However, in the case of lipids with saturated fatty acid chains, trans-gauche isomerization is increasingly tempered by attractive chain-chain van der Waals interactions with increasing chain length. Finally, our results confirm a strong dependence of lipid chain dynamics as a function of double bond position along fatty acid chains.

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.

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.

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...

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

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):

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):

CARBON-CHAIN SPECIES IN WARM-UP MODELS

International Nuclear Information System (INIS)

Hassel, George E.; Harada, Nanase; Herbst, Eric

2011-01-01

In previous warm-up chemical models of the low-mass star-forming region L1527, we investigated the evolution of carbon-chain unsaturated hydrocarbon species when the envelope temperature is slightly elevated to T ≈ 30 K. These models demonstrated that enhanced abundances of such species can be explained by gas-phase ion-molecule chemistry following the partial sublimation of methane from grain surfaces. We also concluded that the abundances of hydrocarbon radicals such as the C n H family should be further enhanced as the temperatures increase to higher values, but this conclusion stood in contrast with the lack of unambiguous detection of these species toward hot core and corino sources. Meanwhile, observational surveys have identified C 2 H, C 4 H, CH 3 CCH, and CH 3 OH toward hot corinos (especially IRAS 16293–2422) as well as toward L1527, with lower abundances for the carbon-chain radicals and higher abundances for the other two species toward the hot corinos. In addition, the Herschel Space Telescope has detected the bare linear chain C 3 in 50 K material surrounding young high-mass stellar objects. To understand these new results, we revisit previous warm-up models with an augmented gas-grain network that incorporated reactions from a gas-phase network that was constructed for use with increased temperature up to 800 K. Some of the newly adopted reactions between carbon-chain species and abundant H 2 possess chemical activation energy barriers. The revised model results now better reproduce the observed abundances of unsaturated carbon chains under hot corino (100 K) conditions and make predictions for the abundances of bare carbon chains in the 50 K regions observed by the Herschel HIFI detector.

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

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos)

Science.gov (United States)

Hoffman, D.J.

1979-01-01

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

Directory of Open Access Journals (Sweden)

R. E. Dunmore

2015-09-01

Full Text Available Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London, which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

Selection of bacteria with hydrocarbon degrading capacity isolated from Colombian Caribbean sediments

International Nuclear Information System (INIS)

Narvaez Florez, Silvia; Gomez, Martha L; Martinez Maria M

2008-01-01

Thirty one bacterial isolations in minimal salts supplemented medium with hydrocarbons (ACPM or crude oil) as sole carbon source were isolated from sediment samples from the Colombian Caribbean. Bacterial strains underwent selection tests in different concentrations of hydrocarbons; 11 tolerant crude oil and ACPM strains in a range of 1-8%v/v were chosen. A mixed bacterial culture was created and assessed its ability to degrade hydrocarbons in a laboratory-scale test, with a concentration of 2% v/v of ACPM over a period of 21 days. Measurements of biomass in Colony Forming Units (CFU)/mL were used to develop the growth curve of the mixed culture. Hydrocarbons remotion was measured by mass chromatography. The mixed culture was able to degrade the 68.6% of aliphatic hydrocarbons in preference of long chain n- alkenes (C12- C31), reaching a maximum growth of 3.13 x 10 9 UFC / mL. Degradation of aromatic hydrocarbons was not evidenced under the observation time. Nine of the eleven strains were identified using the biochemical systems BBL and API 50 CHB/E; they belonged to the genus Klebsiella, Chromobacterium, Flavimonas, Enterobacter,Pseudomonas, and Bacillus. The evaluated strains have enzymatic potential to degrade hydrocarbons and it is necessary to characterize them at molecular level in order to develop and effective consortium for field application

Primitive-path statistics of entangled polymers: mapping multi-chain simulations onto single-chain mean-field models

International Nuclear Information System (INIS)

Steenbakkers, Rudi J A; Schieber, Jay D; Tzoumanekas, Christos; Li, Ying; Liu, Wing Kam; Kröger, Martin

2014-01-01

We present a method to map the full equilibrium distribution of the primitive-path (PP) length, obtained from multi-chain simulations of polymer melts, onto a single-chain mean-field ‘target’ model. Most previous works used the Doi–Edwards tube model as a target. However, the average number of monomers per PP segment, obtained from multi-chain PP networks, has consistently shown a discrepancy of a factor of two with respect to tube-model estimates. Part of the problem is that the tube model neglects fluctuations in the lengths of PP segments, the number of entanglements per chain and the distribution of monomers among PP segments, while all these fluctuations are observed in multi-chain simulations. Here we use a recently proposed slip-link model, which includes fluctuations in all these variables as well as in the spatial positions of the entanglements. This turns out to be essential to obtain qualitative and quantitative agreement with the equilibrium PP-length distribution obtained from multi-chain simulations. By fitting this distribution, we are able to determine two of the three parameters of the model, which govern its equilibrium properties. This mapping is executed for four different linear polymers and for different molecular weights. The two parameters are found to depend on chemistry, but not on molecular weight. The model predicts a constant plateau modulus minus a correction inversely proportional to molecular weight. The value for well-entangled chains, with the parameters determined ab initio, lies in the range of experimental data for the materials investigated. (paper)

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...

Evaluation of mineral oil saturated hydrocarbons (MOSH and mineral oil aromatic hydrocarbons (MOAH in pure mineral hydrocarbon-based cosmetics and cosmetic raw materials using 1H NMR spectroscopy [version 2; referees: 3 approved

Directory of Open Access Journals (Sweden)

Dirk W. Lachenmeier

2017-08-01

Full Text Available Mineral hydrocarbons consist of two fractions, mineral oil saturated hydrocarbons (MOSH and mineral oil aromatic hydrocarbons (MOAH. MOAH is a potential public health hazard because it may include carcinogenic polycyclic compounds. In the present study, 400 MHz nuclear magnetic resonance (NMR spectroscopy was introduced, in the context of official controls, to measure MOSH and MOAH in raw materials or pure mineral hydrocarbon final products (cosmetics and medicinal products. Quantitative determination (qNMR has been established using the ERETIC methodology (electronic reference to access in vivo concentrations based on the PULCON principle (pulse length based concentration determination. Various mineral hydrocarbons (e.g., white oils, paraffins or petroleum jelly were dissolved in deuterated chloroform. The ERETIC factor was established using a quantification reference sample containing ethylbenzene and tetrachloronitrobenzene. The following spectral regions were integrated: MOSH δ 3.0 – 0.2 ppm and MOAH δ 9.2 - 6.5, excluding solvent signals. Validation showed a sufficient precision of the method with a coefficient of variation <6% and a limit of detection <0.1 g/100 g. The applicability of the method was proven by analysing 27 authentic samples with MOSH and MOAH contents in the range of 90-109 g/100 g and 0.02-1.10 g/100 g, respectively. It is important to distinguish this new NMR-approach from the hyphenated liquid chromatography-gas chromatography methodology previously used to characterize MOSH/MOAH amounts in cosmetic products. For mineral hydrocarbon raw materials or pure mineral hydrocarbon-based cosmetic products, NMR delivers higher specificity without any sample preparation besides dilution. Our sample survey shows that previous methods may have overestimated the MOAH amount in mineral oil products and opens new paths to characterize this fraction. Therefore, the developed method can be applied for routine monitoring of consumer

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.

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.

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.

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.

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.

Biogeochemistry of Halogenated Hydrocarbons

Science.gov (United States)

Adriaens, P.; Gruden, C.; McCormick, M. L.

2003-12-01

Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

Microbial activity and soil organic matter decay in roadside soils polluted with petroleum hydrocarbons

Science.gov (United States)

Mykhailova, Larysa; Fischer, Thomas; Iurchenko, Valentina

2015-04-01

It has been demonstrated previously that hydrocarbon addition to soil provokes soil organic matter priming (Zyakun et al., 2011). It has further been shown that petroleum hydrocarbons deposit to roadside soils bound to fine mineral particles and together with vehicle spray (Mykhailova et al., 2014), and that hydrocarbon concentrations decrease to safe levels within the first 15 m from the road, reaching background concentrations at 60-100 m distance (Mykhailova et al., 2013). It was the aim of this study to (I) identify the bioavailability of different petroleum hydrocarbon fractions to degradation and to (II) identify the native (i.e. pedogenic) C fraction affected by hydrocarbon-mediated soil organic matter priming during decay. To address this aim, we collected soil samples at distances from 1 to 100 m (sampling depth 15 cm) near the Traktorostroiteley avenue and the Pushkinskaya street in Kharkov, as well as near the country road M18 near Kharkov, Ukraine. The roads have been under exploitation for several decades, so microbial adaptation to enhanced hydrocarbon levels and full expression of effects could be assumed. The following C fractions were quantified using 13C-CP/MAS-NMR: Carbohydrates, Proteins, Lignin, Aliphates, Carbonyl/Carboxyl as well as black carbon according to Nelson and Baldock (2005). Petroleum hydrocarbons were determind after hexane extraction using GC-MS and divided into a light fraction (chain-length C27, Mykhailova et al., 2013). Potential soil respiration was determined every 48 h by trapping of CO2 evolving from 20 g soil in NaOH at 20 ° C and at 60% of the maximum water holding capacity and titration after a total incubation period of 4 weeks in the lab. It was found that soil respiration positively correlated with the ratio of the light fraction to the sum of medium and heavy fractions of petroleum hydrocarbons, which indicates higher biodegradation primarily of the light petroleum hydrocarbon fraction. Further, soil respiration was

Calculating in situ degradation rates of hydrocarbon compounds in deep waters of the Gulf of Mexico.

Science.gov (United States)

Thessen, Anne E; North, Elizabeth W

2017-09-15

Biodegradation is an important process for hydrocarbon weathering that influences its fate and transport, yet little is known about in situ biodegradation rates of specific hydrocarbon compounds in the deep ocean. Using data collected in the Gulf of Mexico below 700m during and after the Deepwater Horizon oil spill, we calculated first-order degradation rate constants for 49 hydrocarbons and inferred degradation rate constants for an additional 5 data-deficient hydrocarbons. Resulting calculated (not inferred) half-lives of the hydrocarbons ranged from 0.4 to 36.5days. The fastest degrading hydrocarbons were toluene (k=-1.716), methylcyclohexane (k=-1.538), benzene (k=-1.333), and C1-naphthalene (k=-1.305). The slowest degrading hydrocarbons were the large straight-chain alkanes, C-26 through C-33 (k=-0.0494 through k=-0.007). Ratios of C-18 to phytane supported the hypothesis that the primary means of degradation in the subsurface was microbial biodegradation. These degradation rate constants can be used to improve models describing the fate and transport of hydrocarbons in the event of an accidental deep ocean oil spill. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain under critical conditions.

Science.gov (United States)

Skvortsov, A M; Leermakers, F A M; Fleer, G J

2013-08-07

In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration φ by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from φ = 0 (single grafted chain) to φ = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of φ, for several chain lengths and substrate∕polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate∕polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate∕polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of φ, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided

PREBIOTIC HYDROCARBON SYNTHESIS IN IMPACTING REDUCED ASTROPHYSICAL ICY MIXTURES

International Nuclear Information System (INIS)

Koziol, Lucas; Goldman, Nir

2015-01-01

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials

PREBIOTIC HYDROCARBON SYNTHESIS IN IMPACTING REDUCED ASTROPHYSICAL ICY MIXTURES

Energy Technology Data Exchange (ETDEWEB)

Koziol, Lucas; Goldman, Nir, E-mail: lucas.koziol@exxonmobil.com, E-mail: ngoldman@llnl.gov [Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States)

2015-04-20

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.

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.

OleA Glu117 is key to condensation of two fatty-acyl coenzyme A substrates in long-chain olefin biosynthesis

Energy Technology Data Exchange (ETDEWEB)

Jensen, Matthew R.; Goblirsch, Brandon R.; Christenson, James K.; Esler, Morgan A.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M. (UMM)

2017-10-12

In the interest of decreasing dependence on fossil fuels, microbial hydrocarbon biosynthesis pathways are being studied for renewable, tailored production of specialty chemicals and biofuels. One candidate is long-chain olefin biosynthesis, a widespread bacterial pathway that produces waxy hydrocarbons. Found in three- and four-gene clusters, oleABCD encodes the enzymes necessary to produce cis-olefins that differ by alkyl chain length, degree of unsaturation, and alkyl chain branching. The first enzyme in the pathway, OleA, catalyzes the Claisen condensation of two fatty acyl-coenzyme A (CoA) molecules to form a β-keto acid. In this report, the mechanistic role of Xanthomonas campestris OleA Glu117 is investigated through mutant enzymes. Crystal structures were determined for each mutant as well as their complex with the inhibitor cerulenin. Complemented by substrate modeling, these structures suggest that Glu117 aids in substrate positioning for productive carbon–carbon bond formation. Analysis of acyl-CoA substrate hydrolysis shows diminished activity in all mutants. When the active site lacks an acidic residue in the 117 position, OleA cannot form condensed product, demonstrating that Glu117 has a critical role upstream of the essential condensation reaction. Profiling of pH dependence shows that the apparent pKa for Glu117 is affected by mutagenesis. Taken together, we propose that Glu117 is the general base needed to prime condensation via deprotonation of the second, non-covalently bound substrate during turnover. This is the first example of a member of the thiolase superfamily of condensing enzymes to contain an active site base originating from the second monomer of the dimer.

Aromatic hydrocarbons

International Nuclear Information System (INIS)

Roder, M.

1985-01-01

Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

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.

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...

Characterization of cyanobacterial hydrocarbon composition and distribution of biosynthetic pathways.

Directory of Open Access Journals (Sweden)

R Cameron Coates

Full Text Available Cyanobacteria possess the unique capacity to naturally produce hydrocarbons from fatty acids. Hydrocarbon compositions of thirty-two strains of cyanobacteria were characterized to reveal novel structural features and insights into hydrocarbon biosynthesis in cyanobacteria. This investigation revealed new double bond (2- and 3-heptadecene and methyl group positions (3-, 4- and 5-methylheptadecane for a variety of strains. Additionally, results from this study and literature reports indicate that hydrocarbon production is a universal phenomenon in cyanobacteria. All cyanobacteria possess the capacity to produce hydrocarbons from fatty acids yet not all accomplish this through the same metabolic pathway. One pathway comprises a two-step conversion of fatty acids first to fatty aldehydes and then alkanes that involves a fatty acyl ACP reductase (FAAR and aldehyde deformylating oxygenase (ADO. The second involves a polyketide synthase (PKS pathway that first elongates the acyl chain followed by decarboxylation to produce a terminal alkene (olefin synthase, OLS. Sixty-one strains possessing the FAAR/ADO pathway and twelve strains possessing the OLS pathway were newly identified through bioinformatic analyses. Strains possessing the OLS pathway formed a cohesive phylogenetic clade with the exception of three Moorea strains and Leptolyngbya sp. PCC 6406 which may have acquired the OLS pathway via horizontal gene transfer. Hydrocarbon pathways were identified in one-hundred-forty-two strains of cyanobacteria over a broad phylogenetic range and there were no instances where both the FAAR/ADO and the OLS pathways were found together in the same genome, suggesting an unknown selective pressure maintains one or the other pathway, but not both.

Adsorption of short-chain fluids at solid substrates from density functional theory

International Nuclear Information System (INIS)

Bryk, P.; Bucior, K.; Sokolowski, S.; Zukocinski, G.

2005-01-01

We use microscopic density functional theory to investigate the adsorption of short-chains at solid surfaces. The fluid is modeled as freely-jointed tangent spheres that interact via a short-ranged attractive potential. Within the framework of fundamental measure theory we study how the structure and surface phase behaviour of adsorbed fluid changes when the chain length is increased. We observe that the wetting temperature rescaled by the bulk critical temperature decreases with an increase of the chain length. For longer chains this temperature reaches a plateau. For the surface critical temperature an inverse effect is observed, i.e. the surface critical temperature increases with the chain length and then attains a plateau. Furthermore, we analyze how the layering transitions change with the change of the chain length and with relative strength of the fluid-solid interaction. The critical temperature of the first layering transition, rescaled by the bulk critical temperature increases slightly with an increase of the chain length. We have found that for longer chains the layering transitions within consecutive layers are shifted towards very low temperatures and that their sequence is finally replaced by a single transition. Finally we investigate capillary condensation of chain fluid in slit-like pores. We find that for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. (author)

The reduction of petroleum hydrocarbons in soil under saline conditions using ultrasound

Energy Technology Data Exchange (ETDEWEB)

McMillan, D. [SNC-Lavallin, Vancouver, BC (Canada); Northern British Columbia Univ., Prince George, BC (Canada)

2010-07-01

Petroleum hydrocarbons (PHCs) and salts are two of the most common soil contaminants found at oil and gas extraction sites. High concentrations of salt from brine spills may amplify the challenges of soil remediation by reducing bioavailability for remediation. This PowerPoint presentation described an ultrasonic soil flushing technology that used sonic cavitation to break down contaminants. Long chain and aromatic hydrocarbons with complex structures were broken down by the direct oxidation under high temperature and pressure environments created by the sonic cavitation process. The cavitation waves broke up the aggregates of solid particles and increased the turbulence and transportation of the contaminants. A laboratory study evaluated the ability of the treatment process to remediate salt and hydrocarbon contaminated soil samples. The adsorption isotherms of the samples were analyzed. Sand, clay, and muskeg samples were treated. Results of the study suggested that the treatment is more effective when treating granular soils with high hydraulic conductivity. Even small amounts of salt were found to have a negative impact on the reduction of hydrocarbon contaminants. tabs., figs.

Forced reptation revealed by chain pull-out simulations.

Science.gov (United States)

Bulacu, Monica; van der Giessen, Erik

2009-08-14

We report computation results obtained from extensive molecular dynamics simulations of tensile disentanglement of connector chains placed at the interface between two polymer bulks. Each polymer chain (either belonging to the bulks or being a connector) is treated as a sequence of beads interconnected by springs, using a coarse-grained representation based on the Kremer-Grest model, extended to account for stiffness along the chain backbone. Forced reptation of the connectors was observed during their disentanglement from the bulk chains. The extracted chains are clearly seen following an imaginary "tube" inside the bulks as they are pulled out. The entropic and energetic responses to the external deformation are investigated by monitoring the connector conformation tensor and the modifications of the internal parameters (bonds, bending, and torsion angles along the connectors). The work needed to separate the two bulks is computed from the tensile force induced during debonding in the connector chains. The value of the work reached at total separation is considered as the debonding energy G. The most important parameters controlling G are the length (n) of the chains placed at the interface and their areal density. Our in silico experiments are performed at relatively low areal density and are disregarded if chain scission occurs during disentanglement. As predicted by the reptation theory, for this pure pull-out regime, the power exponent from the scaling G proportional, variant n(a) is a approximately 2, irrespective of chain stiffness. Small variations are found when the connectors form different number of stitches at the interface, or when their length is randomly distributed in between the two bulks. Our results show that the effects of the number of stitches and of the randomness of the block lengths have to be considered together, especially when comparing with experiments where they cannot be controlled rigorously. These results may be significant for

GC-MS analysis of cuticular lipids in recent and older scavenger insect puparia. An approach to estimate the postmortem interval (PMI).

Science.gov (United States)

Frere, B; Suchaud, F; Bernier, G; Cottin, F; Vincent, B; Dourel, L; Lelong, A; Arpino, P

2014-02-01

An analytical method was developed to characterize puparia cuticular lipids (hydrocarbons, waxes) and to compare the molecular distribution patterns in the extracts from either recent or older puparia. Acid-catalyzed transesterification and solvent extraction and purification, followed by combined gas chromatography coupled to mass spectrometry, were optimized for the determination of hydrocarbons and fatty acid ethyl esters from transesterified waxes, extracted from a single species of a fly scavenger (Hydrotaea aenescens Wiedemann, 1830). Comparison between recent (2012) or older (1997) puparia contents has highlighted significant composition differences, in particular, a general decrease of the chain length in the n-alkane distribution pattern and, on the contrary, an increase of the ester chain length. Both extracts contain traces of three hopane hydrocarbon congeners. Preliminary results evidence the change in puparia lipid composition over time, thus potentially providing new indices for estimating postmortem interval.

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

Energy Technology Data Exchange (ETDEWEB)

Putra, Edy Giri Rachman [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Patriati, Arum [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Gadjah Mada, Bulaksumur, Yogyakarta 55281, Indonesia giri@batan.go.id (Indonesia)

2015-04-16

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

International Nuclear Information System (INIS)

Putra, Edy Giri Rachman; Patriati, Arum

2015-01-01

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations

The snakelike chain character of unstructured RNA.

Science.gov (United States)

Jacobson, David R; McIntosh, Dustin B; Saleh, Omar A

2013-12-03

In the absence of base-pairing and tertiary structure, ribonucleic acid (RNA) assumes a random-walk conformation, modulated by the electrostatic self-repulsion of the charged, flexible backbone. This behavior is often modeled as a Kratky-Porod "wormlike chain" (WLC) with a Barrat-Joanny scale-dependent persistence length. In this study we report measurements of the end-to-end extension of poly(U) RNA under 0.1 to 10 pN applied force and observe two distinct elastic-response regimes: a low-force, power-law regime characteristic of a chain of swollen blobs on long length scales and a high-force, salt-valence-dependent regime consistent with ion-stabilized crumpling on short length scales. This short-scale structure is additionally supported by force- and salt-dependent quantification of the RNA ion atmosphere composition, which shows that ions are liberated under stretching; the number of ions liberated increases with increasing bulk salt concentration. Both this result and the observation of two elastic-response regimes directly contradict the WLC model, which predicts a single elastic regime across all forces and, when accounting for scale-dependent persistence length, the opposite trend in ion release with salt concentration. We conclude that RNA is better described as a "snakelike chain," characterized by smooth bending on long length scales and ion-stabilized crumpling on short length scales. In monovalent salt, these two regimes are separated by a characteristic length that scales with the Debye screening length, highlighting the determining importance of electrostatics in RNA conformation. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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.

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.

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

Antibacterial Activity of Long-Chain Fatty Alcohols against Staphylococcus aureus

Directory of Open Access Journals (Sweden)

Yoshihiro Inoue

2007-02-01

Full Text Available The antibacterial activity against Staphylococcus aureus of long-chain fatty alcohols was investigated, with a focus on normal alcohols. The antibacterial activity varied with the length of the aliphatic carbon chain and not with the water/octanol partition coefficient. 1-Nonanol, 1-decanol and 1-undecanol had bactericidal activity and membrane-damaging activity. 1-Dodecanol and 1-tridecanol had the highest antibacterial activity among the long-chain fatty alcohols tested, but had no membrane-damaging activity. Consequently, it appears that not only the antibacterial activity but also the mode of action of long-chain fatty alcohols might be determined by the length of the aliphatic carbon chain.

Thermal conductivity of the Lennard-Jones chain fluid model.

Science.gov (United States)

Galliero, Guillaume; Boned, Christian

2009-12-01

Nonequilibrium molecular dynamics simulations have been performed to estimate, analyze, and correlate the thermal conductivity of a fluid composed of short Lennard-Jones chains (up to 16 segments) over a large range of thermodynamic conditions. It is shown that the dilute gas contribution to the thermal conductivity decreases when the chain length increases for a given temperature. In dense states, simulation results indicate that the residual thermal conductivity of the monomer increases strongly with density, but is weakly dependent on the temperature. Compared to the monomer value, it has been noted that the residual thermal conductivity of the chain was slightly decreasing with its length. Using these results, an empirical relation, including a contribution due to the critical enhancement, is proposed to provide an accurate estimation of the thermal conductivity of the Lennard-Jones chain fluid model (up to 16 segments) over the domain 0.8values of the Lennard-Jones chain fluid model merge on the same "universal" curve when plotted as a function of the excess entropy. Furthermore, it is shown that the reduced configurational thermal conductivity of the Lennard-Jones chain fluid model is approximately proportional to the reduced excess entropy for all fluid states and all chain lengths.

Problems of selectivity in liquid-phase oxidation

Energy Technology Data Exchange (ETDEWEB)

Emanuel, N M

1978-07-01

Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

Risk assessment of metals and organic pollutants for herbivorous and carnivorous small mammal food chains in a polluted floodplain (Biesbosch, The Netherlands)

NARCIS (Netherlands)

Hamers, T.H.M.; Berg, van den J.H.J.; Gestel, van C.A.M.; Schooten, van F.J.; Murk, A.J.

2006-01-01

A risk assessment was made for a carnivorous and a herbivorous food chain in a heavily polluted natural estuary (Biesbosch), by determining the most critical pollutants and the food chain most at risk. Exposure of food chains to metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated

The liquid-vapour interface of chain molecules investigated using a density functional approach

International Nuclear Information System (INIS)

Bryk, P; Bucior, K; Sokolowski, S; Zukocinski, G

2004-01-01

A microscopic density functional theory is used to investigate the liquid-vapour interface of fluids composed of short linear chains. We analyse the structure of the interface and evaluate the dependence of the surface tension and of the interfacial width on the temperature. The difference in chain length leads to differences in the thermodynamic properties of the fluids. The liquid-phase parts of the interfacial profiles of shorter chains exhibit oscillations at low temperatures. These oscillations vanish for longer chains. The surface tension and the interfacial width at a given temperature are found to increase with the chain length. Both the surface tension and the interfacial width scale as power laws upon approaching the critical point with critical exponents characteristic of mean-field-type theories and with prefactors depending on the chain length only

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)

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...

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®

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

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.

Emissions of hydrocarbons from marine phytoplankton—Some results from controlled laboratory experiments

Science.gov (United States)

McKay, W. A.; Turner, M. F.; Jones, B. M. R.; Halliwell, C. M.

Laboratory experiments have been carried out to help assess and quantify the role of marine phytoplankton in the production of non-methane hydrocarbons. Evidence is presented here that supports the hypothesis that some short-chain hydrocarbons are produced during diatom and dinoflagellate lifecycles. The pattern of their emissions to the air above axenic unicultures of diatoms and dinoflagellates has been followed. The results suggest that ethane, ethene, propane and propene are produced during the autolysis of some phytoplankton, possibly by the oxidation of polyunsaturated lipids released into their culture medium. In contrast, isoprene and hexane appear during phytoplankton growth and are thus most likely produced either directly by the plankton or through the oxidation of exuded dissolved organic carbon.

Dominant petroleum hydrocarbon-degrading bacteria in the Archipelago Sea in South-West Finland (Baltic Sea) belong to different taxonomic groups than hydrocarbon degraders in the oceans.

Science.gov (United States)

Reunamo, Anna; Riemann, Lasse; Leskinen, Piia; Jørgensen, Kirsten S

2013-07-15

The natural petroleum hydrocarbon degrading capacity of the Archipelago Sea water in S-W Finland was studied in a microcosm experiment. Pristine and previously oil exposed sites were examined. Bacterial community fingerprinting was performed using terminal restriction fragment length polymorphism (T-RFLP) and samples from selected microcosms were sequenced. The abundance of PAH degradation genes was measured by quantitative PCR. Bacterial communities in diesel exposed microcosms diverged from control microcosms during the experiment. Gram positive PAH degradation genes dominated at both sites in situ, whereas gram negative PAH degrading genes became enriched in diesel microcosms. The dominant bacterial groups after a 14 days of diesel exposure were different depending on the sampling site, belonging to the class Actinobacteria (32%) at a pristine site and Betaproteobacteria (52%) at a previously oil exposed site. The hydrocarbon degrading bacteria in the Baltic Sea differ from those in the oceans, where most hydrocarbon degraders belong to Gammaproteobacteria. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Ion beam focusing by the atomic chains of a crystal lattice

International Nuclear Information System (INIS)

Shulga, V.I.

1975-01-01

A study is made of the focusing of a parallel ion beam by a pair of close packed atomic chains of a crystal. The focal length of this system has been calculated to the approximation of continuous potential of chain in the general form and also for a number of specific potentials of ion-atom interactions. Ar ion beam focusing by a Cu chain pair is discusssed in detail. For this case, the focal length has been calculated as a function of ion energy using the method of computer simulation of ion trajectories in the chain field. The calculations were made on the basis of the Born-Mayer potential with various constants. A pronounced dependence of focal length on the constant in this potential has been found. (author)

Electrostatic stiffening and induced persistence length for coassembled molecular bottlebrushes

Science.gov (United States)

Storm, Ingeborg M.; Stuart, Martien A. Cohen; de Vries, Renko; Leermakers, Frans A. M.

2018-03-01

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 addition to an intrinsic rigidity, an electrostatic stiffening effect, because the electric double layer resists bending. For molecular bottlebrushes, there is an induced contribution due to the grafts. We explore cases beyond the classical phantom main-chain approximation and elaborate molecularly more realistic models where the backbone has a finite volume, which is necessary for treating coassembled bottlebrushes. We find that the way in which the linear charge density or the grafting density is regulated is important. Typically, the stiffening effect is reduced when there is freedom for these quantities to adapt to the curvature stresses. Electrostatically driven coassembled bottlebrushes, however, are relatively stiff because the chains have a low tendency to escape from the compressed regions and the electrostatic binding force is largest in the convex part. For coassembled bottlebrushes, the induced persistence length is a nonmonotonic function of the polymer concentration: For low polymer concentrations, the stiffening grows quadratically with coverage; for semidilute polymer concentrations, the brush chains retract and regain their Gaussian size. When doing so, they lose their induced persistence length contribution. Our results correlate well with observed physical characteristics of electrostatically driven coassembled DNA-bioengineered protein-polymer bottlebrushes.

Hydrocarbon-degrading sulfate-reducing bacteria in marine hydrocarbon seep sediments

OpenAIRE

Kleindienst, Sara

2012-01-01

Microorganisms are key players in our biosphere because of their ability to degrade various organic compounds including a wide range of hydrocarbons. At marine hydrocarbon seeps, more than 90% of sulfate reduction (SR) is potentially coupled to non-methane hydrocarbon oxidation. Several hydrocarbon-degrading sulfate-reducing bacteria (SRB) were enriched or isolated from marine sediments. However, in situ active SRB remained largely unknown. In the present thesis, the global distribution and a...

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.

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

Optimized CO{sub 2} miscible hydrocarbon fracturing fluids

Energy Technology Data Exchange (ETDEWEB)

Taylor, R.S.; Funkhouser, G.P.; Fyten, G.; Attaway, D.; Watkins, H. [Halliburton Energy Services, Calgary, AB (Canada); Lestz, R.S. [Chevron Canada Resources, Calgary, AB (Canada); Loree, D. [FracEx Inc. (Canada)

2006-07-01

Carbon dioxide (CO{sub 2}) miscible hydrocarbon fracturing fluids address issues of fluid retention in low-permeability gas reservoirs, including undersaturated and underpressured reservoirs. An optimized surfactant gel technology using carbon dioxide (CO{sub 2}) hydrocarbon fracturing fluids applicable to all gas-well stimulation applications was discussed in this paper. The crosslinked surfactant gel technology improved proppant transport, leakoff control, and generation of effective fracture half-length. Tests indicated that application of the surfactant cooled the fracture face, which had the effect of extending break times and increasing viscosity during pumping periods. Rapid recovery of the fracturing fluid eliminated the need for swabbing in some cases, and the fluid system was not adversely affected by shear. However, rheological test equipment capable of mixing liquid CO{sub 2} and viscosified hydrocarbons at downhole temperatures is required to determine rheology and required chemical concentrations. It was recommended that to achieve an effective methane-drive cleanup mechanism, treatments should be designed so that the gellant system can be effective with up to 50 per cent CO{sub 2} dissolved in oil. It was concluded that it should be possible to apply the technology to low permeability gas reservoirs. Viscosity curves and friction data were presented. Issues concerning the selection of tubulars and flowback procedures were also discussed. It was suggested that the cost of the hydrocarbon fracturing fluid can be recovered by the sale of recovered load fluid. 6 refs., 4 figs.

A model for the chain-to-plane charge transfer in YBa2Cu3O6+x

International Nuclear Information System (INIS)

Matic, V. M.; Lazarov, N. Dj.; Milic, M.

2012-01-01

A model for the chain-to-plane charge transfer is proposed to account for the two plateaus, at 60 K and at 90 K, of the T c (x) characteristics of the YBa 2 Cu 3 O 6+x high-T c superconductor. It is assumed that the number of holes transferred from a CuO chain of length l to two nearby CuO 2 sheets is proportional to l (that is, to the number of oxygen atoms in the chain), if the chain length is greater than, or equal to, a certain critical chain length, l cr , that is required to trigger the charge transfer process. No holes are assumed to have been transferred from chains of length l cr . The calculated T c (x) dependence is found to be in excellent agreement with the experimentally reported T c (x). The critical chain length parameter is estimated to be equal to l cr = 11 (eleven oxygen atoms in a chain), which is a greater value than that obtained in the previously proposed model for the chain-to-plane charge transfer (l cr = 4). The results obtained out of the proposed model are briefly discussed

Two-step processing of oil shale to linear hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Ryzhov, A.N.; Latypova, D.Zh.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry; Avakyan, T.A. [Gubkin Russian State University of Oil and Gas, Moscow (Russian Federation)

2013-11-01

Thermal and catalytic steam reforming of oil shale mined from Leningrad and Kashpir deposits was studied. Experiments were performed in fixed bed reactor by varying temperature and steam flow rate. Data obtained were approximated by empirical formulas containing some parameters calculated by least-squares method. Thus predicting amount of hydrogen, carbon monoxide and methane in producer gas is possible for given particular kind of oil shale, temperature and steam flow rate. Adding Ni catalyst enriches hydrogen and depletes CO content in effluent gas at low gasification temperatures. Modeling gas simulating steam reforming gases (H{sub 2}, CO, CO{sub 2}, and N{sub 2} mixture) was tested in hydrocarbon synthesis over Co-containing supported catalyst. Selectivity of CO conversion into C{sub 5+} hydrocarbons reaches 84% while selectivity to methane is 7%. Molecular weight distribution of synthesized alkanes obeys Anderson-Schulz-Flory equation and chain growth probability 0.84. (orig.)

Analysing destruction channels of interstellar hydrocarbon anions with a 22pol ion-trap

Energy Technology Data Exchange (ETDEWEB)

Endres, Eric; Lakhmanskaya, Olga; Best, Thorsten; Hauser, Daniel; Kumar, Sunil; Wester, Roland [Universitaet Innsbruck, Institut fuer Ionenphysik und Angewandte Physik (Austria)

2014-07-01

In the interstellar medium (ISM), ion-molecule reactions are considered to play a key role in the formation of complex molecules. The detection of the first interstellar anions, which happen to be carbon chain anions, has raised new interest in the quantitative composition of the ISM and the underlying reaction network. To understand the observed abundance of these carbon chain anions, a detailed analysis of the possible destruction channels is indispensable. A cryogenic 22-pol radio frequency ion trap is an ideal tool to observe reactions that take place slowly, such as carbon chain anions with molecular hydrogen. Furthermore, measurements over a large temperature scale are feasible. Longitudinal optical access to the trap also provides the possibility to make precise photodetachment measurements. Temperature dependent measurements of the reaction rates for the reaction between hydrocarbon chain anions and H{sub 2} are presented.

Diversity Analysis of the Immunoglobulin M Heavy Chain Gene in ...

African Journals Online (AJOL)

A full-length cDNA encoding the immunoglobulin (IgM) heavy chain gene of Nile tilapia was successfully cloned using the 5' and 3' RACE techniques. The complete cDNA of the Nile tilapia IgM heavy chain gene is 1,921 bp in length and has an open reading frame (ORF) of 1,740 bp, which corresponds to 580 amino acid ...

Hydrodynamic slip length as a surface property

Science.gov (United States)

Ramos-Alvarado, Bladimir; Kumar, Satish; Peterson, G. P.

2016-02-01

Equilibrium and nonequilibrium molecular dynamics simulations were conducted in order to evaluate the hypothesis that the hydrodynamic slip length is a surface property. The system under investigation was water confined between two graphite layers to form nanochannels of different sizes (3-8 nm). The water-carbon interaction potential was calibrated by matching wettability experiments of graphitic-carbon surfaces free of airborne hydrocarbon contamination. Three equilibrium theories were used to calculate the hydrodynamic slip length. It was found that one of the recently reported equilibrium theories for the calculation of the slip length featured confinement effects, while the others resulted in calculations significantly hindered by the large margin of error observed between independent simulations. The hydrodynamic slip length was found to be channel-size independent using equilibrium calculations, i.e., suggesting a consistency with the definition of a surface property, for 5-nm channels and larger. The analysis of the individual trajectories of liquid particles revealed that the reason for observing confinement effects in 3-nm nanochannels is the high mobility of the bulk particles. Nonequilibrium calculations were not consistently affected by size but by noisiness in the smallest systems.

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.

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

Biodegradation of diesel fuel by a microbial consortium in the presence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues

DEFF Research Database (Denmark)

Chrzanowski, L; Stasiewicz, M; Owsianiak, Mikolaj

2009-01-01

hypothesize that in the presence of diesel fuel low-water-soluble ionic liquids may become more toxic to hydrocarbon-degrading microorganisms. In this study the influence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues (side-chain length from C-3 to C-18) on biodegradation of diesel fuel...... by a bacterial consortium was investigated. Whereas test performed for the consortium cultivated on disodium succinate showed that toxicity of the investigated ionic liquids decreased with increase in side-chain length, only higher homologues (C-8-C-18) caused a decrease in diesel fuel biodegradation......, respectively. We conclude that in the presence of hydrocarbons acting as a solvent, the increased bioavailability of hydrophobic homologues is responsible for the decrease in biodegradation efficiency of diesel fuel....

Self-assembled monolayers of semi-fluorinated thiols and disulfides with a potentially antibacterial terminal fragment on gold surfaces

International Nuclear Information System (INIS)

Thebault, P.; Taffin de Givenchy, E.; Guittard, F.; Guimon, C.; Geribaldi, S.

2008-01-01

Attempts to elaborate the best organized cationic self-assembled monolayers (SAMs) with sulfur derivatives containing potentially bactericidal quaternary ammonium salt moieties have been performed on gold with the final aim to obtain contact-active antibacterial surfaces. Four molecules bearing two hydrocarbon spacers with different lengths between the sulfur atom and the quaternized nitrogen atom, and two different terminal semi-fluorinated alkyl chains have been synthesised and used in view to evaluate their capacity for leading to the highest densities and the highest organization of potentially active molecules on the metal surface. The formation and quality of SAMs characterized by X-ray photoelectron spectroscopy, Internal Reflexion Infra Red Imaging, contact angle and blocking factor measurements depend on the lengths of both the hydrocarbon spacer and terminal perfluorinated chain

Consistent energy barrier distributions in magnetic particle chains

International Nuclear Information System (INIS)

Laslett, O.; Ruta, S.; Chantrell, R.W.; Barker, J.; Friedman, G.; Hovorka, O.

2016-01-01

We investigate long-time thermal activation behaviour in magnetic particle chains of variable length. Chains are modelled as Stoner–Wohlfarth particles coupled by dipolar interactions. Thermal activation is described as a hopping process over a multidimensional energy landscape using the discrete orientation model limit of the Landau–Lifshitz–Gilbert dynamics. The underlying master equation is solved by diagonalising the associated transition matrix, which allows the evaluation of distributions of time scales of intrinsic thermal activation modes and their energy representation. It is shown that as a result of the interaction dependence of these distributions, increasing the particle chain length can lead to acceleration or deceleration of the overall relaxation process depending on the initialisation procedure.

Geometric distribution of CuO chains in YBa2Cu3O6+x

International Nuclear Information System (INIS)

Matic, V.M.; Lazarov, N.Dj.

2006-01-01

Statistics of CuO chains in basal planes of YBa 2 Cu 3 O 6+x high-T c superconductor has been studied in terms of two dimensional asymmetric next-to-nearest-neighbor Ising (ASYNNNI) model, with accentuation on distribution of CuO chains per different chain lengths. It has been shown that the fraction p(l) of CuO chains containing l oxygen ions (i.e., having the length equal to l), satisfies so-called ''law of geometric distribution''p(l)=ω(1-ω) l-1 , where the quantity ω is equal to the inverse of average chain length l av in the system, for given values of oxygen content x and temperature T. In the case of ortho-II (OII) structural phase, the geometric chain probability distribution is shown to hold separately for each of two different sublattices of oxygen sites, commonly known as α 1 and α 2 , with respectively defined l av α 1 (x,T) and l av α 2 (x,T). The theoretically derived result of the chain probability distribution p(l) is shown to be in a remarkable agreement with the results obtained out of extensive Monte Carlo calculations that were made within region of stability of orthorhombic structural phases in (x,T) space. The relevance of chain length distribution for accurate count of the number of transferred electronic holes to superconducting CuO 2 layers has been pointed out and expression for hole concentration has been derived. The concept of critical chain length for charge transfer mechanism was briefly discussed

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.

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.

Equations for the stochastic cumulative multiplying chain

Energy Technology Data Exchange (ETDEWEB)

Lewins, J D [Cambridge Univ. (UK). Dept. of Engineering

1980-01-01

The forward and backward equations for the conditional probability of the neutron multiplying chain are derived in a new generalization accounting for the chain length and admitting time dependent properties. These Kolmogorov equations form the basis of a variational and hence complete description of the 'lumped' multiplying system. The equations reduce to the marginal distribution, summed over all chain lengths, and to the simpler equations previously derived for that problem. The method of derivation, direct and in the probability space with the minimum of mathematical manipulations, is perhaps the chief attraction: the equations are also displayed in conventional generating function form. As such, they appear to apply to number of problems in areas of social anthropology, polymer chemistry, genetics and cell biology as well as neutron reactor theory and radiation damage.

Equations for the stochastic cumulative multiplying chain

International Nuclear Information System (INIS)

Lewins, J.D.

1980-01-01

The forward and backward equations for the conditional probability of the neutron multiplying chain are derived in a new generalization accounting for the chain length and admitting time dependent properties. These Kolmogorov equations form the basis of a variational and hence complete description of the 'lumped' multiplying system. The equations reduce to the marginal distribution, summed over all chain lengths, and to the simpler equations previously derived for that problem. The method of derivation, direct and in the probability space with the minimum of mathematical manipulations, is perhaps the chief attraction: the equations are also displayed in conventional generating function form. As such, they appear to apply to number of problems in areas of social anthropology, polymer chemistry, genetics and cell biology as well as neutron reactor theory and radiation damage. (author)

Physiological tolerance and stoichiometric potential of cyanobacteria for hydrocarbon fuel production.

Science.gov (United States)

Kämäräinen, Jari; Knoop, Henning; Stanford, Natalie J; Guerrero, Fernando; Akhtar, M Kalim; Aro, Eva-Mari; Steuer, Ralf; Jones, Patrik R

2012-11-30

Cyanobacteria are capable of directly converting sunlight, carbon dioxide and water into hydrocarbon fuel or precursors thereof. Many biological and non-biological factors will influence the ability of such a production system to become economically sustainable. We evaluated two factors in engineerable cyanobacteria which could potentially limit economic sustainability: (i) tolerance of the host to the intended end-product, and (ii) stoichiometric potential for production. Alcohols, when externally added, inhibited growth the most, followed by aldehydes and acids, whilst alkanes were the least inhibitory. The growth inhibition became progressively greater with increasing chain-length for alcohols, whilst the intermediate C6 alkane caused more inhibition than both C3 and C11 alkane. Synechocystis sp. PCC 6803 was more tolerant to some of the tested chemicals than Synechococcus elongatus PCC 7942, particularly ethanol and undecane. Stoichiometric evaluation of the potential yields suggested that there is no difference in the potential productivity of harvestable energy between any of the studied fuels, with the exception of ethylene, for which maximal stoichiometric yield is considerably lower. In summary, it was concluded that alkanes would constitute the best choice metabolic end-product for fuel production using cyanobacteria if high-yielding strains can be developed. Copyright © 2012 Elsevier B.V. All rights reserved.

Fast co-pyrolysis of waste newspaper with high-density polyethylene for high yields of alcohols and hydrocarbons.

Science.gov (United States)

Chen, Weimin; Shi, Shukai; Chen, Minzhi; Zhou, Xiaoyan

2017-09-01

Waste newspaper (WP) was first co-pyrolyzed with high-density polyethylene (HDPE) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to enhance the yields of alcohols and hydrocarbons. The effects of WP: HDPE feed ratio (100:0, 75:25, 50:50, 25:75, 0:100) and temperature (500-800°C) on products distribution were investigated and the interaction mechanism during co-pyrolysis was also proposed. Maximum yields of alcohols and hydrocarbons reached 85.88% (feed ratio 50:50wt.%, 600°C). Hydrogen supplements and deoxidation by HDPE and subsequently fragments recombination result in the conversion of aldehydes and ketones into branched hydrocarbons. Radicals from WP degradation favor the secondary crack for HDPE products resulting in the formation of linear hydrocarbons with low carbon number. Hydrocarbons with activated radical site from HDPE degradation were interacted with hydroxyl from WP degradation promoting the formation of linear long chain alcohols. Moreover, co-pyrolysis significantly enhanced condensable oil qualities, which were close to commercial diesel No. 0. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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...

Chains of mean-field models

International Nuclear Information System (INIS)

Hamed Hassani, S; Macris, Nicolas; Urbanke, Ruediger

2012-01-01

We consider a collection of Curie–Weiss (CW) spin systems, possibly with a random field, each of which is placed along the positions of a one-dimensional chain. The CW systems are coupled together by a Kac-type interaction in the longitudinal direction of the chain and by an infinite-range interaction in the direction transverse to the chain. Our motivations for studying this model come from recent findings in the theory of error-correcting codes based on spatially coupled graphs. We find that, although much simpler than the codes, the model studied here already displays similar behavior. We are interested in the van der Waals curve in a regime where the size of each Curie–Weiss model tends to infinity, and the length of the chain and range of the Kac interaction are large but finite. Below the critical temperature, and with appropriate boundary conditions, there appears a series of equilibrium states representing kink-like interfaces between the two equilibrium states of the individual system. The van der Waals curve oscillates periodically around the Maxwell plateau. These oscillations have a period inversely proportional to the chain length and an amplitude exponentially small in the range of the interaction; in other words, the spinodal points of the chain model lie exponentially close to the phase transition threshold. The amplitude of the oscillations is closely related to a Peierls–Nabarro free energy barrier for the motion of the kink along the chain. Analogies to similar phenomena and their possible algorithmic significance for graphical models of interest in coding theory and theoretical computer science are pointed out

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

Sulfonated hydrocarbon graft architectures for cation exchange membranes

DEFF Research Database (Denmark)

Nielsen, Mads Møller; Jankova Atanasova, Katja; Hvilsted, Søren

2013-01-01

A synthetic strategy to hydrocarbon graft architectures prepared from a commercial polysulfone and aimed as ion exchange membrane material is proposed. Polystyrene is grafted from a polysulfone macroinitiator by atom transfer radical polymerization, and subsequently sulfonated with acetyl sulfate...... to various degrees. Series of grafting densities and graft lengths are prepared, and membranes are solvent cast from DMSO. The membrane properties in aqueous environments are evaluated from their water swelling behavior, and their thermal properties and stability are investigated by thermogravimetric...

Mapping bright and dark modes in gold nanoparticle chains using electron energy loss spectroscopy.

Science.gov (United States)

Barrow, Steven J; Rossouw, David; Funston, Alison M; Botton, Gianluigi A; Mulvaney, Paul

2014-07-09

We present a scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) investigation of gold nanosphere chains with lengths varying from 1 to 5 particles. We show localized EELS signals from the chains and identify energy-loss peaks arising due to l = 1, 2, 3, 4, and 5 plasmon modes through the use of EELS mapping. We also show the evolution of the energy of these modes as the length of a given chain increases, and we find that a chain containing N particles can accommodate at least N experimentally observable modes, in addition to the transverse mode. As the chain length is increased by the addition of one more gold particle to the chain, the new N + 1 mode becomes the highest energy mode, while the existing modes lower their energy and eventually asymptote as they delocalize along the chain. We also show that modes become increasingly difficult to detect with the EELS technique as l approaches N. The data are compared to numerical simulations.

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.

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.

Synthesis and characterization of associating polymers which contain siloxanes chains; Synthese et caracterisation de polymeres associatifs porteurs de groupes siloxanes

Energy Technology Data Exchange (ETDEWEB)

Meyer, V

1999-01-11

Polymers that associate via physical interactions in solutions have received much attention as viscosifiers. Such associating polymers are now used in variety of applications due to their unique theological properties coating, food thickeners, paints, enhanced oil recovery, water treatment). They contain a hydrophilic main chain with hydrophobic side chain that is generally constituted of hydrocarbon or fluorocarbon groups. Novel copolymers with sites of association in aqueous solution were prepared by co-polymerizing acrylamide with an hydrophobic monomer containing siloxane parts. Rheological properties were studied as a function of polymer concentration, microstructure, shear rate and frequency in order to show intra intermolecular associations between the hydrophobic parts. The polymer solution viscosity increases as a function of the hydrophobic group content. Tests of adsorption show a high affinity of these copolymers with clay and the amount absorbed increase with the quantity of hydrophobic entities containing in the chain. These properties are enhanced compared to copolymers containing hydrocarbon chains. (authors) 456 refs.

The length-scale dependence of strain in networks by SANS

CERN Document Server

Pyckhout-Hintzen, W; Heinrich, M; Richter, D; Westermann, S; Straube, E

2002-01-01

We present a SANS study of the length-scale dependence of chain deformation by means of a suitable labeling in dense, cross-linked elastomers of the HDH-type. This length scale is controlled by the size of the label as well as the cross-link density. The results are compared to long homopolymers. The data are analyzed by means of the tube model of topology in rubber elasticity in combination with the random-phase approximation (RPA) to account for interchain correlations. Chain degradation during cross linking is treated by the standard RPA approach for polydisperse multicomponent systems. A transition from locally freely fluctuating to tube-constrained segmental motion was observed. (orig.)

The influence of cyclic structure on the radiolysis of hydrocarbons

International Nuclear Information System (INIS)

Foeldiak, G.; Cserep, Gy.; Horvath, Zs.; Wojnarovits, L.

1975-01-01

Aliphatic and cyclic C 3 -C 12 alkanes and alkenes have been irradiated in liquid phase by a 60 Co-γ-source with the nominal activity of 80 000 Ci. The dose rate was 1-2 Mrad/hr, the doses were between 0 and 10 Mrad. The following conclusions can be drawn from the experiments: 1., While no significant difference can be observed between radiolytic decomposition of n-hydrocarbon homologues, that of cyclic hydrocarbons is the function of the size of the ring. 2., Reactivity of cyclic hydrocarbons is influenced not only by their surplus enthalpy of formation (strain energy) but also by the individual components of this surplus enthalpy, e.g. bond deformation or repulsion between hydrogen atoms. 3., The overall yield of decomposition of higher than C 4 straightchain and cyclic alkanes activated by radiation and reacting via either C-C or C-H fission is approximately constant, with a G value of 6.5+-0.5. The structure of the molecules affects mainly the ratio of C-C and C-H bond rupture, i.e. these two processes are in competition. 4., Hydrogen yields from alkenes are affected mainly by the order and number of allylic C-H bonds, and by the possibility of the formation of allyl-type radicals. This latter is facilitated by ''free'' rotation in the case of open-chain hydrocarbons whereas it is hindered in the case of small and medium size cycles. (K.A.)

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.

Anaerobic Microbial Degradation of Hydrocarbons: From Enzymatic Reactions to the Environment.

Science.gov (United States)

Rabus, Ralf; Boll, Matthias; Heider, Johann; Meckenstock, Rainer U; Buckel, Wolfgang; Einsle, Oliver; Ermler, Ulrich; Golding, Bernard T; Gunsalus, Robert P; Kroneck, Peter M H; Krüger, Martin; Lueders, Tillmann; Martins, Berta M; Musat, Florin; Richnow, Hans H; Schink, Bernhard; Seifert, Jana; Szaleniec, Maciej; Treude, Tina; Ullmann, G Matthias; Vogt, Carsten; von Bergen, Martin; Wilkes, Heinz

2016-01-01

Hydrocarbons are abundant in anoxic environments and pose biochemical challenges to their anaerobic degradation by microorganisms. Within the framework of the Priority Program 1319, investigations funded by the Deutsche Forschungsgemeinschaft on the anaerobic microbial degradation of hydrocarbons ranged from isolation and enrichment of hitherto unknown hydrocarbon-degrading anaerobic microorganisms, discovery of novel reactions, detailed studies of enzyme mechanisms and structures to process-oriented in situ studies. Selected highlights from this program are collected in this synopsis, with more detailed information provided by theme-focused reviews of the special topic issue on 'Anaerobic biodegradation of hydrocarbons' [this issue, pp. 1-244]. The interdisciplinary character of the program, involving microbiologists, biochemists, organic chemists and environmental scientists, is best exemplified by the studies on alkyl-/arylalkylsuccinate synthases. Here, research topics ranged from in-depth mechanistic studies of archetypical toluene-activating benzylsuccinate synthase, substrate-specific phylogenetic clustering of alkyl-/arylalkylsuccinate synthases (toluene plus xylenes, p-cymene, p-cresol, 2-methylnaphthalene, n-alkanes), stereochemical and co-metabolic insights into n-alkane-activating (methylalkyl)succinate synthases to the discovery of bacterial groups previously unknown to possess alkyl-/arylalkylsuccinate synthases by means of functional gene markers and in situ field studies enabled by state-of-the-art stable isotope probing and fractionation approaches. Other topics are Mo-cofactor-dependent dehydrogenases performing O2-independent hydroxylation of hydrocarbons and alkyl side chains (ethylbenzene, p-cymene, cholesterol, n-hexadecane), degradation of p-alkylated benzoates and toluenes, glycyl radical-bearing 4-hydroxyphenylacetate decarboxylase, novel types of carboxylation reactions (for acetophenone, acetone, and potentially also benzene and

Properties of Confined Star-Branched and Linear Chains. A Monte Carlo Simulation Study

International Nuclear Information System (INIS)

Romiszowski, P.; Sikorski, A.

2004-01-01

A model of linear and star-branched polymer chains confined between two parallel and impenetrable surfaces was built. The polymer chains were restricted to a simple cubic lattice. Two macromolecular architectures of the chain: linear and star branched (consisted of f = 3 branches of equal length) were studied. The excluded volume was the only potential introduced into the model (the athermal system). Monte Carlo simulations were carried out using a sampling algorithm based on chain's local changes of conformation. The simulations were carried out at different confinement conditions: from light to high chain's compression. The scaling of chain's size with the chain length was studied and discussed. The influence of the confinement and the macromolecular architecture on the shape of a chain was studied. The differences in the shape of linear and star-branched chains were pointed out. (author)

The bio-remediation of the contamination with hydrocarbons

International Nuclear Information System (INIS)

Montoya, Sandra J; Concha, Alexander; Alcalde, Osmar R; Alvarez, Juan C; Garcia, Juan G; Guerra, Fabio W

1999-01-01

The activities of the oil industry comprise many processes that represent environmental risks, usually the pollution of the ecosystems with hydrocarbons. When bulky spills occur, the first measure used for damage repair is the physical gathering, but scattered quantities of oil even remain. The last is typical of chronic leakage's when is necessary to make use of other procedures for the environmental restoration. The bioremediation is an effective and economic technique useful in these cases that rest upon natural processes of the detritivorous tropic chain in all the ecosystems. There are over one-hundred species of bacteria and fungi able to profit the hydrocarbons as energy source for feeding, diminishing the pollutant to levels harmless to the physical, chemical and biological properties of the ecosystems. The current weariest stock belongs to the bacteria species pseudomonas aeruginosa. To apply properly this technique is necessary to know the nature of the pollutant, the properties of the substratum and the indigenous microbiological communities. Moreover it is required to control the environmental conditions, mainly aeration, moisture, temperature, pH, and nutrients status of the substratum

Synthesis of single- and double-chain fluorocarbon and hydrocarbon galactosyl amphiphiles and their anti-HIV-1 activity.

Science.gov (United States)

Faroux-Corlay, B; Clary, L; Gadras, C; Hammache, D; Greiner, J; Santaella, C; Aubertin, A M; Vierling, P; Fantini, J

2000-07-24

Galactosylceramide (GalCer) is an alternative receptor allowing HIV-1 entry into CD4(-)/GalCer(+) cells. This glycosphingolipid recognizes the V3 loop of HIV gp120, which plays a key role in the fusion of the HIV envelope and cellular membrane. To inhibit HIV uptake and infection, we designed and synthesized analogs of GalCer. These amphiphiles and bolaamphiphiles consist of single and double hydrocarbon and/or fluorocarbon chain beta-linked to galactose and galactosamine. They derive from serine (GalSer), cysteine (GalCys), and ethanolamine (GalAE). The anti-HIV activity and cytotoxicity of these galactolipids were evaluated in vitro on CEM-SS (a CD4(+) cell line), HT-29, a CD4(-) cell line expressing high levels of GalCer receptor, and/or HT29 genetically modified to express CD4. GalSer and GalAE derivatives, tested in aqueous medium or as part of liposome preparation, showed moderate anti-HIV-1 activities (IC50 in the 20-220 microM range), whereas none of the GalCys derivatives was found to be active. Moreover, only some of these anti-HIV active analogs inhibited the binding of [3H]suramin (a polysulfonyl compound which displays a high affinity for the V3 loop) to SPC3, a synthetic peptide which contains the conserved GPGRAF region of the V3 loop. Our results most likely indicate that the neutralization of the virion through masking of this conserved V3 loop region is not the only mechanism involved in the HIV-1 antiviral activity of our GalCer analogs.

Distribution of hydrocarbon-utilizing microorganisms and hydrocarbon biodegradation potentials in Alaskan continental shelf areas

International Nuclear Information System (INIS)

Roubal, G.; Atlas, R.M.

1978-01-01

Hydrocarbon-utilizing microogranisms were enumerated from Alaskan continental shelf areas by using plate counts and a new most-probable-number procedure based on mineralization of 14 C-labeled hydrocarbons. Hydrocarbon utilizers were ubiquitously distributed, with no significant overall concentration differences between sampling regions or between surface water and sediment samples. There were, however, significant seasonal differences in numbers of hydrocarbon utilizers. Distribution of hydrocarbon utilizers within Cook Inlet was positively correlated with occurrence of hydrocarbons in the environment. Hydrocarbon biodegradation potentials were measured by using 14 C-radiolabeled hydrocarbon-spiked crude oil. There was no significant correlation between numbers of hydrocarbon utilizers and hydrocarbon biodegradation potentials. The biodegradation potentials showed large seasonal variations in the Beaufort Sea, probably due to seasonal depletion of available nutrients. Non-nutrient-limited biodegradation potentials followed the order hexadecane > naphthalene >> pristane > benzanthracene. In Cook Inlet, biodegradation potentials for hexadecane and naphthalene were dependent on availability of inorganic nutrients. Biodegradation potentials for pristane and benzanthracene were restricted, probably by resistance to attack by available enzymes in the indigenous population

Evaluation of landfarm remediation of hydrocarbon-contaminated soil at the Inveresk Railyard, Launceston, Australia

International Nuclear Information System (INIS)

Line, M.A.; Garland, C.D.; Crowley, M.

1996-01-01

The cost of landfarm bioremediation of hydrocarbon-contaminated soil at a disused railyard site in Tasmania, Australia is reported. The landfarm area was enclosed in an impermeable clay embankment and where necessary the base was also rolled with clay. Microbial inoculation was not deemed to be necessary since suitable degrading biota were found to be present in site samples prior to commencement of the landfarming. Fertilizer amendment comprised primarily ammonium sulphate and superphosphate to give a C:N ratio (TPH:fertilizer) of 28:1 and a C:P ratio of 200:1. The soil was turned regularly and watered as required for the 12-month duration of the operation. Over this period levels of TPH showed a linear decline from a mean of 4,644 mg/kg to near 100 mg/kg or less, with greatest losses being in the chain lengths C10-C28. The cost was determined to be $A13.40c per m 3 , which is at the lower end of the spectrum of reported landfarming costs. The cost of such operations is important since the reported economics will influence others' choice of bioremediation techniques

Community Structure in Methanogenic Enrichments Provides Insight into Syntrophic Interactions in Hydrocarbon-Impacted Environments

DEFF Research Database (Denmark)

Fowler, Jane; Toth, Courtney R. A.; Gieg, Lisa M.

2016-01-01

, but such information has important implications for bioremediation and microbial enhanced energy recovery technologies. Many factors such as changing environmental conditions or substrate variations can influence the composition and biodegradation capabilities of syntrophic microbial communities in hydrocarbon......The methanogenic biodegradation of crude oil involves the conversion of hydrocarbons to methanogenic substrates by syntrophic bacteria and subsequent methane production by methanogens. Assessing the metabolic roles played by various microbial species in syntrophic communities remains a challenge......-impacted environments. In this study, a methanogenic crude oil-degrading enrichment culture was successively transferred onto the single long chain fatty acids palmitate or stearate followed by their parent alkanes, hexadecane or octadecane, respectively, in order to assess the impact of different substrates...

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min Suk

2017-02-16

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured to be submerged in the liquid. The plasma plume from the plasma torch can cause reformation of the hydrocarbon. The device can use a variety of plasma torches that can be arranged in a variety of positions in the liquid container. The devices can be used for the reformation of gaseous hydrocarbons and/or liquid hydrocarbons. The reformation can produce methane, lower hydrocarbons, higher hydrocarbons, hydrogen gas, water, carbon dioxide, carbon monoxide, or a combination thereof.

A metabolomics strategy to assess the combined toxicity of polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated paraffins (SCCPs).

Science.gov (United States)

Wang, Feidi; Zhang, Haijun; Geng, Ningbo; Ren, Xiaoqian; Zhang, Baoqin; Gong, Yufeng; Chen, Jiping

2018-03-01

The combined toxicity of mixed chemicals is usually evaluated according to several specific endpoints, and other potentially toxic effects are disregarded. In this study, we provided a metabolomics strategy to achieve a comprehensive understanding of toxicological interactions between mixed chemicals on metabolism. The metabolic changes were quantified by a pseudotargeted analysis, and the types of combined effects were quantitatively discriminated according to the calculation of metabolic effect level index (MELI). The metabolomics strategy was used to assess the combined effects of polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated paraffins (SCCPs) on the metabolism of human hepatoma HepG2 cells. Our data suggested that exposure to a combination of PAHs and SCCPs at human internal exposure levels could result in an additive effect on the overall metabolism, whereas diverse joint effects were observed on various metabolic pathways. The combined exposure could induce a synergistic up-regulation of phospholipid metabolism, an additive up-regulation of fatty acid metabolism, an additive down-regulation of tricarboxylic acid cycle and glycolysis, and an antagonistic effect on purine metabolism. SCCPs in the mixture acted as the primary driver for the acceleration of phospholipid and fatty acid metabolism. Lipid metabolism disorder caused by exposure to a combination of PAHs and SCCPs should be an important concern for human health. Copyright © 2017 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons in Saccoglossus kowalewskyi (Agassiz)

Science.gov (United States)

Carey, D. A.; Farrington, J. W.

1989-08-01

Hydrocarbon extracts were analyzed from Saccoglossus kowalewskyi, a deposit-feeding enteropneust worm, and from surface sediments from Cape Cod, MA. Worms were held in experimental aquaria in sieved sediments and flowing seawater for four months and then fed sediments mixed with creosote, lampblack or clean sediment for two weeks as analogues of sediments containing degraded oil and pyrogenic compounds. Worms from all treatments contained polyaromatic hydrocarbons (PAHs) in amounts and composition that indicate that the worms were contaminated with weathered No. 2 fuel oil before our experimental treatment and that the contamination persisted for four months in clean conditions. The contamination was not detected in the clean sediments used in the experiment. The worms accumulated steroid transformation products in greater abundance than the odd chain n-alkanes that dominated the sediment extractions. This may indicate selective assimilation of algal detritus and microbial products over salt marsh detritus. Worms, actively feeding during the experiment, contained 1-3 × 10 -6 g g -1 dry weight of unknown brominated compounds which were not detected in the sediments. These compounds are similar to bromopyrroles found elsewhere in enteropneusts, polychaetes and bacteria and may cause substantial interference in analyses for some industrial pollutants.

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

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.

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

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.

Petroleum hydrocarbons

International Nuclear Information System (INIS)

Farrington, J.W.; Teal, J.M.; Parker, P.L.

1976-01-01

Methods for analysis of petroleum hydrocarbons in marine samples are presented. Types of hydrocarbons present and their origins are discussed. Principles and methods of analysis are outlined. Infrared spectrometry, uv spectrometry, gas chromatography, mass spectroscopy, and carbon 14 measurements are described

Small angle neutron scattering study on short and long chain phosphatidylcholine mixture in trehalose solution

Energy Technology Data Exchange (ETDEWEB)

Takahashi, Hiroshi [Department of Physics, Gunma University, Maebashi, Gunma (Japan)

2001-03-01

Trehalose protects cells and proteins against various stresses due to low temperatures or dryness. In order to clarify the molecular mechanism of cryoprotective function of trehalose, we have studied the interaction between trehalose and phosphatidylcholine (PC) which is a main lipid component of cell membranes. In this study, the structural change of a binary PC mixture by the presence of trehalose was investigated by means of small angle neutron scattering. The PC binary mixture studied contains dihexanoyl-PC (diC{sub 6}PC) and dihexadecy-PC (DHPC). The former has short hydrocarbon chains and the latter has long hydrocarbon chains. The scattering profiles from the DHPC/diC{sub 6}PC mixture were changed, depending on trehalose concentrations. This change can be interpreted as suggesting that the presence of trehalose reduces the interfacial area between water and PCs. (author)

A time-dependent density functional theory investigation of plasmon resonances of linear Au atomic chains

International Nuclear Information System (INIS)

Liu Dan-Dan; Zhang Hong

2011-01-01

We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time-dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Newtonian Analysis of a Folded Chain Drop

Science.gov (United States)

Mungan, Carl E.

2018-05-01

Consider a chain of length L that hangs in a U shape with end A fixed to a rigid support and free end E released from rest starting from the same initial height (call it y = 0) as A. Figure 1 sketches the chain after end E has fallen a distance y. Points O and A are assumed to be close enough to each other and the chain flexible enough that the radius of curvature r at the bottom point C can be taken to be negligibly small (compared to the length of the chain). The problem is to compare the speed of descent v(y) = dy/dt of the free end E of the chain to the speed vfree(y )=√{2 g y } of a free-falling point mass that has descended the same distance y. If v(y) > vfree (y) for all y > 0, then, in a race to fall any arbitrary distance Y (where 0 < Y < L), the chain end E will always beat a simultaneously released point mass, because the fall time t for E will be shorter than tfree for the point mass, t = ∫0 Y d/y v (y )

Energetic effects of adsorption of C6-C8 hydrocarbons on hard coal samples of different metamorphism

Directory of Open Access Journals (Sweden)

Orzechowska-Zięba Agnieszka

2017-01-01

Full Text Available The analysis of sorption equilibrium of aliphatic saturated and unsaturated hydrocarbons on low and medium rank coals were performed. Isosteric sorption enthalpy correlation with the degree of fill of sorption capacity was presented for the low rank coal. There was found a crucial role of primary pore structure in the coal grains in the process of sorption, especially in case of temperature anomalies occurrence. Hexane differently than other hydrocarbons of longer chains, represent the property of micropore penetration. Due to literature the presence of double bound in other molecules causes difficulties with penetration into porous structure of coal.

Flexible chain molecules in the marginal and concentrated regimes: universal static scaling laws and cross-over predictions

OpenAIRE

Laso Carbajo, Manuel; Karayiannis, Nikos Ch.

2008-01-01

We present predictions for the static scaling exponents and for the cross-over polymer volumetric fractions in the marginal and concentrated solution regimes. Corrections for finite chain length are made. Predictions are based on an analysis of correlated fluctuations in density and chain length, in a semigrand ensemble in which mers and solvent sites exchange identities. Cross-over volumetric fractions are found to be chain length independent to first order, although reciprocal-N corrections...

From single Debye-Hückel chains to polyelectrolyte solutions: Simulation results

Science.gov (United States)

Kremer, Kurt

1996-03-01

This lecture will present results from simulations of single weakly charged flexible chains, where the electrostatic part of the interaction is modeled by a Debye-Hückel potential,( with U. Micka, IFF, Forschungszentrum Jülich, 52425 Jülich, Germany) as well as simulations of polyelectrolyte solutions, where the counterions are explicitly taken into account( with M. J. Stevens, Sandia Nat. Lab., Albuquerque, NM 87185-1111) ( M. J. Stevens, K. Kremer, JCP 103), 1669 (1995). The first set of the simulations is meant to clear a recent contoversy on the dependency of the persistence length LP on the screening length Γ. While the analytic theories give Lp ~ Γ^x with either x=1 or x=2, the simulations find for all experimentally accessible chain lengths a varying exponent, which is significantly smaller than 1. This causes serious doubts on the applicability of this model for weakly charged polyelectrolytes in general. The second part deals with strongly charged flexible polyelectrolytes in salt free solution. These simulations are performed for multichain systems. The full Coulomb interactions of the monomers and counterions are treated explicitly. Experimental measurements of the osmotic pressure and the structure factor are reproduced and extended. The simulations reveal a new picture of the chain structure based on calculations of the structure factor, persistence length, end-to-end distance, etc. Even at very low density, the chains show significant bending. Furthermore, the chains contract significantly before they start to overlap. We also show that counterion condensation dramatically alters the chain structure, even for a good solvent backbone.

Converting high boiling hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Terrisse, H; DuFour, L

1929-02-12

A process is given for converting high boiling hydrocarbons into low boiling hydrocarbons, characterized in that the high boiling hydrocarbons are heated to 200 to 500/sup 0/C in the presence of ferrous chloride and of such gases as hydrogen, water gas, and the like gases under a pressure of from 5 to 40 kilograms per square centimeter. The desulfurization of the hydrocarbons occurs simultaneously.

Elasticity of short DNA molecules: theory and experiment for contour lengths of 0.6-7 microm.

Science.gov (United States)

Seol, Yeonee; Li, Jinyu; Nelson, Philip C; Perkins, Thomas T; Betterton, M D

2007-12-15

The wormlike chain (WLC) model currently provides the best description of double-stranded DNA elasticity for micron-sized molecules. This theory requires two intrinsic material parameters-the contour length L and the persistence length p. We measured and then analyzed the elasticity of double-stranded DNA as a function of L (632 nm-7.03 microm) using the classic solution to the WLC model. When the elasticity data were analyzed using this solution, the resulting fitted value for the persistence length p(wlc) depended on L; even for moderately long DNA molecules (L = 1300 nm), this apparent persistence length was 10% smaller than its limiting value for long DNA. Because p is a material parameter, and cannot depend on length, we sought a new solution to the WLC model, which we call the "finite wormlike chain (FWLC)," to account for effects not considered in the classic solution. Specifically we accounted for the finite chain length, the chain-end boundary conditions, and the bead rotational fluctuations inherent in optical trapping assays where beads are used to apply the force. After incorporating these corrections, we used our FWLC solution to generate force-extension curves, and then fit those curves with the classic WLC solution, as done in the standard experimental analysis. These results qualitatively reproduced the apparent dependence of p(wlc) on L seen in experimental data when analyzed with the classic WLC solution. Directly fitting experimental data to the FWLC solution reduces the apparent dependence of p(fwlc) on L by a factor of 3. Thus, the FWLC solution provides a significantly improved theoretical framework in which to analyze single-molecule experiments over a broad range of experimentally accessible DNA lengths, including both short (a few hundred nanometers in contour length) and very long (microns in contour length) molecules.

Endophytic Bacteria Associated with Hieracium piloselloides: Their Potential for Hydrocarbon-Utilizing and Plant Growth-Promotion.

Science.gov (United States)

Pawlik, Małgorzata; Piotrowska-Seget, Zofia

2015-01-01

The aim of this study was to assess the potential of 18 crude-oil-degrading endophytic bacteria for removal of hydrocarbons and promotion of plant growth. Strains were isolated from Hieracium piloselloides (tall hawkweed), which grows in soil heavily polluted with petroleum hydrocarbons. Bacteria from the genus Pseudomonas were abundant among the isolates. The potential for hydrocarbon degradation was evaluated by polymerase chain reaction (PCR) analyses of the genes alkB, alkH, C23O, P450, and pah. It was found that 88.89% of the endophytic bacteria contained gene-encoding polycyclic aromatic hydrocarbon (PAH) initial dioxygenase, 61% possessed the 2,3-catechol dioxygenase gene, and 39% of strains that were tested had the cytochrome P-450 hydroxylase gene. All isolates were capable of producing indole-3-acetic acid (1.8-76.4 μg/ml). Only 17% of them were able to produce siderophores, excrete cellulase, and solubilize phosphate. Hydrogen cyanide synthesis occurred in 33% of endophytic bacteria. The 1-aminocyclopropane-1-carboxylate deaminase activity in isolates that were screened was in the range of 2.6 to 74.1 μmol α-ketobutyrate/mg/h. This feature of the bacteria indicated that isolates may enhance the phytoremediation process. Data suggest that crude-oil-degrading endophytic bacteria possess potential to be promising candidates for enhancement of phytoremediation of hydrocarbon-contaminated soil. Further evaluation of these bacteria is needed in order to assess the role played in the degradation of petroleum hydrocarbons.

Behenic acid pyrolysis to produce diesel-like hydrocarbons

International Nuclear Information System (INIS)

Xu, Zhi-Xiang; Liu, Peng; Xu, Gui-Sheng; He, Zhi-Xia; Ji, Heng-Song; Wang, Qian

2017-01-01

Highlights: • Behenic acid is a suitable bio-renewable resource to produce bio-fuel oil using catalytic cracking. • Little fraction of aromatic compounds presented in bio-fuel oil. • Carbon chain of fatty acid was cracked to form short carbon chain carboxyl firstly. • ESI FT-ICR MS experiment was an effective method to analyze bio-fuel oil heavy compounds. - Abstract: In order to obtain diesel-like bio-fuel oil, behenic acid was selected to carry out fast pyrolysis. The decomposition temperature of behenic acid was in the range of 250–450 °C at 20 k/min according to TG experiment. The bio-fuel oil mainly contained alkane, alkene and fatty acid. Components of products were C_1_3–C_2_0 hydrocarbon. Little fraction of aromatic compounds was found in bio-fuel oil. According to ESI FT-ICR MS analysis results, the oxygen containing compounds in bio-fuel oil were mainly O_2–O_4 classes, with the O_3 being the major class. According to GC–MS and ESI FT-ICR MS results, it was found that the carbon chain of behenic acid was cracked to form short carbon chain carboxyl firstly. And then decarboxylation reaction carried out. In other means carboxyl groups were more stable than carbon chain of fatty acid. The probable mechanism of O_4 species was free radical reaction. The recommended pyrolysis path was also proposed. Diesel-like bio-fuel oil can be obtained using behenic acid catalytic cracking.

Ecotoxicological and analytical assessment of hydrocarbon-contaminated soils and application to ecological risk assessment

Energy Technology Data Exchange (ETDEWEB)

Saterbak, A.; Toy, R.J.; Wong, D.C.L.; McMain, B.J.; Williams, M.P.; Dorn, P.B.; Brzuzy, L.P.; Chai, E.Y.; Salanitro, J.P.

1999-07-01

Ecotoxicological assessments of contaminated soil aim to understand the effect of introduced chemicals on the soil flora and fauna. Ecotoxicity test methods were developed and conducted on hydrocarbon-contaminated soils and on adjacent uncontaminated control soils from eight field locations. Tests included 7-d, 14-d, and chronic survival tests and reproduction assays for the earthworm (Eisenia fetida) and seed germination, root length, and plant growth assays for corn, lettuce, mustard, and wheat. Species-specific responses were observed with no-observed effect concentrations (NOECs) ranging from <1 to 100% contaminated soil. The 14-d earthworm survival NOEC was equal to or greater than the reproduction NOEC values for numbers of cocoons and juveniles, which were similar to one another. Cocoon and juvenile production varied among the control soils. Germination and root length NOECs for mustard and lettuce were less than NOECs for corn and wheat. Root length NOECs were similar to or less than seed germination NOECs. Statistically significant correlations for earthworm survival and seed germination as a function of hydrocarbon measurements were found. The 14-d earthworm survival and the seed germination tests are recommended for use in the context of a risk-based framework for the ecological assessment of contaminated sites.

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.

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.

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...

Targeting of insect epicuticular lipids by the entomopathogenic fungus Beauveria bassiana: hydrocarbon oxidation within the context of a host-pathogen interaction

Science.gov (United States)

Pedrini, Nicolás; Ortiz-Urquiza, Almudena; Huarte-Bonnet, Carla; Zhang, Shizhu; Keyhani, Nemat O.

2013-01-01

Broad host range entomopathogenic fungi such as Beauveria bassiana attack insect hosts via attachment to cuticular substrata and the production of enzymes for the degradation and penetration of insect cuticle. The outermost epicuticular layer consists of a complex mixture of non-polar lipids including hydrocarbons, fatty acids, and wax esters. Long chain hydrocarbons are major components of the outer waxy layer of diverse insect species, where they serve to protect against desiccation and microbial parasites, and as recognition molecules or as a platform for semiochemicals. Insect pathogenic fungi have evolved mechanisms for overcoming this barrier, likely with sets of lipid degrading enzymes with overlapping substrate specificities. Alkanes and fatty acids are substrates for a specific subset of fungal cytochrome P450 monooxygenases involved in insect hydrocarbon degradation. These enzymes activate alkanes by terminal oxidation to alcohols, which are further oxidized by alcohol and aldehyde dehydrogenases, whose products can enter β-oxidation pathways. B. bassiana contains at least 83 genes coding for cytochrome P450s (CYP), a subset of which are involved in hydrocarbon oxidation, and several of which represent new CYP subfamilies/families. Expression data indicated differential induction by alkanes and insect lipids and four CYP proteins have been partially characterized after heterologous expression in yeast. Gene knockouts revealed a phenotype for only one (cyp52X1) out of six genes examined to date. CYP52X1 oxidizes long chain fatty acids and participates in the degradation of specific epicuticular lipid components needed for breaching the insect waxy layer. Examining the hydrocarbon oxidizing CYP repertoire of pathogens involved in insect epicuticle degradation can lead to the characterization of enzymes with novel substrate specificities. Pathogen targeting may also represent an important co-evolutionary process regarding insect cuticular hydrocarbon

Synthesis of All-carbon Chains and Nanoparticles by Chemical Transformation of Halogenated Hydrocarbons at Low Temperatures

Czech Academy of Sciences Publication Activity Database

Kavan, Ladislav

č. 196 (2001), s. 22-38 ISSN 0371-5345 R&D Projects: GA ČR GA203/98/1168; GA ČR GA203/99/1015; GA ČR GA203/00/0634 Institutional research plan: CEZ:AV0Z4040901 Keywords : halogenated hydrocarbon * electrochemical carbon * fullerenes Subject RIV: CG - Electrochemistry

Production of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Day, D T; Day, R E

1920-04-27

A process is disclosed of converting hydro-carbon oils having high boiling points to hydro-carbon oils having low boiling points, which process comprises adding the oil to be treated to a mass of hydro-carbon oil bearing shale, passing the shale with the oil through a conveyor retort and subjecting the material while in the retort to a heat treatment involving a temperature of at least 500/sup 0/F.

Synthesis of Ag nanocubes 18-32 nm in edge length: the effects of polyol on reduction kinetics, size control, and reproducibility.

Science.gov (United States)

Wang, Yi; Zheng, Yiqun; Huang, Cheng Zhi; Xia, Younan

2013-02-06

This article describes a robust method for the facile synthesis of small Ag nanocubes with edge lengths controlled in the range of 18-32 nm. The success of this new method relies on the substitution of ethylene glycol (EG)--the solvent most commonly used in a polyol synthesis--with diethylene glycol (DEG). Owing to the increase in hydrocarbon chain length, DEG possesses a higher viscosity and a lower reducing power relative to EG. As a result, we were able to achieve a nucleation burst in the early stage to generate a large number of seeds and a relatively slow growth rate thereafter; both factors were critical to the formation of Ag nanocubes with small sizes and in high purity (>95%). The edge length of the Ag nanocubes could be easily tailored in the range of 18-32 nm by quenching the reaction at different time points. For the first time, we were able to produce uniform sub-20 nm Ag nanocubes in a hydrophilic medium and on a scale of ∼20 mg per batch. It is also worth pointing out that the present protocol was remarkably robust, showing good reproducibility between different batches and even for DEGs obtained from different vendors. Our results suggest that the high sensitivity of synthesis outcomes to the trace amounts of impurities in a polyol, a major issue for reproducibility and scale up synthesis, did not exist in the present system.

Thermodynamics of Inozemtsev's elliptic spin chain

International Nuclear Information System (INIS)

Klabbers, Rob

2016-01-01

We study the thermodynamic behaviour of Inozemtsev's long-range elliptic spin chain using the Bethe ansatz equations describing the spectrum of the model in the infinite-length limit. We classify all solutions of these equations in that limit and argue which of these solutions determine the spectrum in the thermodynamic limit. Interestingly, some of the solutions are not selfconjugate, which puts the model in sharp contrast to one of the model's limiting cases, the Heisenberg XXX spin chain. Invoking the string hypothesis we derive the thermodynamic Bethe ansatz equations (TBA-equations) from which we determine the Helmholtz free energy in thermodynamic equilibrium and derive the associated Y-system. We corroborate our results by comparing numerical solutions of the TBA-equations to a direct computation of the free energy for the finite-length hamiltonian. In addition we confirm numerically the interesting conjecture put forward by Finkel and González-López that the original and supersymmetric versions of Inozemtsev's elliptic spin chain are equivalent in the thermodynamic limit.

Human beta 2 chain of laminin (formerly S chain): cDNA cloning, chromosomal localization, and expression in carcinomas

DEFF Research Database (Denmark)

Wewer, U M; Gerecke, D R; Durkin, M E

1994-01-01

or other known laminin genes. Immunostaining showed that the beta 2 chain is localized to the smooth muscle basement membranes of the arteries, while the homologous beta 1 chain is confined to the subendothelial basement membranes. The beta 2 chain was found in the basement membranes of ovarian carcinomas......Overlapping cDNA clones that encode the full-length human laminin beta 2 chain, formerly called the S chain, were isolated. The cDNA of 5680 nt contains a 5391-nt open reading frame encoding 1797 amino acids. At the amino terminus is a 32-amino-acid signal peptide that is followed by the mature...... beta 2 chain polypeptide of 1765 amino acids with a calculated molecular mass of 192,389 Da. The human beta 2 chain is predicted to have all of the seven structural domains typical of the beta chains of laminin, including the short cysteine-rich alpha region. The amino acid sequence of human beta 2...

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.

Bio-crude transcriptomics: Gene discovery and metabolic network reconstruction for the biosynthesis of the terpenome of the hydrocarbon oil-producing green alga, Botryococcus braunii race B (Showa*

Directory of Open Access Journals (Sweden)

Molnár István

2012-10-01

Full Text Available Abstract Background Microalgae hold promise for yielding a biofuel feedstock that is sustainable, carbon-neutral, distributed, and only minimally disruptive for the production of food and feed by traditional agriculture. Amongst oleaginous eukaryotic algae, the B race of Botryococcus braunii is unique in that it produces large amounts of liquid hydrocarbons of terpenoid origin. These are comparable to fossil crude oil, and are sequestered outside the cells in a communal extracellular polymeric matrix material. Biosynthetic engineering of terpenoid bio-crude production requires identification of genes and reconstruction of metabolic pathways responsible for production of both hydrocarbons and other metabolites of the alga that compete for photosynthetic carbon and energy. Results A de novo assembly of 1,334,609 next-generation pyrosequencing reads form the Showa strain of the B race of B. braunii yielded a transcriptomic database of 46,422 contigs with an average length of 756 bp. Contigs were annotated with pathway, ontology, and protein domain identifiers. Manual curation allowed the reconstruction of pathways that produce terpenoid liquid hydrocarbons from primary metabolites, and pathways that divert photosynthetic carbon into tetraterpenoid carotenoids, diterpenoids, and the prenyl chains of meroterpenoid quinones and chlorophyll. Inventories of machine-assembled contigs are also presented for reconstructed pathways for the biosynthesis of competing storage compounds including triacylglycerol and starch. Regeneration of S-adenosylmethionine, and the extracellular localization of the hydrocarbon oils by active transport and possibly autophagy are also investigated. Conclusions The construction of an annotated transcriptomic database, publicly available in a web-based data depository and annotation tool, provides a foundation for metabolic pathway and network reconstruction, and facilitates further omics studies in the absence of a genome

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: Concentrations, composition, and associated risks to protected sea otters

International Nuclear Information System (INIS)

Harris, Kate A.; Yunker, Mark B.; Dangerfield, Neil; Ross, Peter S.

2011-01-01

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills. - Highlights: → Sediment hydrocarbon signatures differed between remote and impacted coastal sites. → A natural background comprised terrestrial plant alkanes and petrogenic PAHs. → Impacted sites reflected a history of petrogenic and pyrogenic hydrocarbon inputs. → Hydrocarbons at some sites exceeded guidelines for the protection of aquatic life. → Protected sea otters may thus be at risk as they rely primarily on benthic prey. - Anthropogenically-derived hydrocarbons in coastal sediments in British Columbia may pose a risk to protected sea otters.

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.

Effect of surfactant excess on the stability of low-polarity ferrofluids probed by small-angle neutron scattering

Energy Technology Data Exchange (ETDEWEB)

Petrenko, V. I., E-mail: vip@nf.jinr.ru; Avdeev, M. V. [Joint Institute for Nuclear Research (Russian Federation); Bulavin, L. A. [Taras Shevchenko National University of Kyiv (Ukraine); Almasy, L. [Hungarian Academy of Science, Wigner Research Centre for Physics (Hungary); Grigoryeva, N. A. [St. Petersburg State University (Russian Federation); Aksenov, V. L. [National Research Centre “Kurchatov Institute”, Konstantinov Petersburg Nuclear Physics Institute (Russian Federation)

2016-01-15

The structures of ferrofluids (FFs) based on nonpolar solvent decahydronaphthalene, stabilized by saturated monocarboxylic acids with hydrocarbon chains of different lengths, C16 (palmitic acid) and ?12 (lauric acid), with an excess of acid molecules, have been studied by small-angle neutron scattering. It is found that the addition of acid to an initially stable system with optimal composition leads to more significant structural changes (related to aggregation) than those observed previously for this class of FFs. A comparison of the influence of monocarboxylic acids on the stability of nonpolar FFs suggests that the enhancement of aggregation is much more pronounced in the case of palmitic acid excess. This fact confirms the conclusion of previous studies, according to which an increase in the hydrocarbon chain length in a saturated acid reduces the efficiency of the corresponding FF stabilization.

Solubilization and mineralization of polycyclic aromatic hydrocarbons by Pseudomonas putida in the presence of surfactant

International Nuclear Information System (INIS)

Doong Rueyan; Lei Wengang

2003-01-01

The solubilization and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a soil system amended with different surfactants was examined. Mineralization experiments were conducted with the addition of [ 14 C]pyrene. An inoculum of the PAH-degrading microorganism, Pseudomonas putida, was investigated for its sensitivity towards four non-ionic and one anionic surfactants with different polyoxyethylene (POE) chain lengths. The addition of surfactant was found to enhance the bioavailability of naphthalene, phenanthrene and pyrene with efficiencies ranging from 21.1 to 60.6%, 33.3 to 62.8% and 26.8 to 70.9%, respectively. The enhanced efficiency followed the order of Brij 30, Triton X-100, Tween 80, and Brij 35, which is correlated with the polyoxyethylene chain of the surfactants. Brij 35 and Tween 80 inhibited the growth of P. putida. However, microorganisms can utilize Triton X-100 and Brij 30 as the sole carbon and energy sources at concentrations above CMC values. In the aqueous system without the addition of surfactants, microorganisms could mineralize [ 14 C]pyrene to 14 CO 2 which corresponds to 28% of mineralization. The addition of surfactants decreased the mineralization rate of pyrene. Also, the fraction of the micellar-phase pyrene that can be directly biodegraded decreased as the concentration of micelle increases. However, the mineralization rate can be enhanced by the amendment of Brij 30 when soil was applied to the cultures. This suggests that biodegradable surfactants can be applicable for increasing the bioavailability and mineralization of PAHs in soil systems

A matrix product solution for a nonequilibrium steady state of an XX chain

International Nuclear Information System (INIS)

Znidaric, Marko

2010-01-01

A one-dimensional XX spin chain of finite length coupled to reservoirs at both ends is solved exactly in terms of a matrix product state ansatz. An explicit representation of matrices of fixed dimension 4 independent of the chain length is found. Expectations of all observables are evaluated, showing that all connected correlations, apart from the nearest neighbor z-z, are zero.

Fiber optic distributed chemical sensor for the real time detection of hydrocarbon fuel leaks

Science.gov (United States)

Mendoza, Edgar; Kempen, C.; Esterkin, Yan; Sun, Sunjian

2015-09-01

With the increase worldwide demand for hydrocarbon fuels and the vast development of new fuel production and delivery infrastructure installations around the world, there is a growing need for reliable hydrocarbon fuel leak detection technologies to provide safety and reduce environmental risks. Hydrocarbon leaks (gas or liquid) pose an extreme danger and need to be detected very quickly to avoid potential disasters. Gas leaks have the greatest potential for causing damage due to the explosion risk from the dispersion of gas clouds. This paper describes progress towards the development of a fast response, high sensitivity, distributed fiber optic fuel leak detection (HySense™) system based on the use of an optical fiber that uses a hydrocarbon sensitive fluorescent coating to detect the presence of fuel leaks present in close proximity along the length of the sensor fiber. The HySense™ system operates in two modes, leak detection and leak localization, and will trigger an alarm within seconds of exposure contact. The fast and accurate response of the sensor provides reliable fluid leak detection for pipelines, storage tanks, airports, pumps, and valves to detect and minimize any potential catastrophic damage.

Screened ion-ion interaction in mercury-chain compounds: Single chain

International Nuclear Information System (INIS)

Mohan, M.M.; Griffin, A.

1985-01-01

At room temperature, the mercury chains in Hg/sub 3-delta/AsF 6 exhibit phonons characteristic of a one-dimensional lattice. We calculate the screening of the Hg ion-ion interaction in a single chain by electrons moving in a cylindrical potential of finite radius, within the random-phase approximation. The resulting Bohm-Staver-type expression for the phonon velocity is (Z 2 mN/sub I//MN/sub e/)/sup 1/2/v/sub F/, where Z is the Hg ionic charge and N/sub I/ (N/sub e/) is the number of ions (electrons) per unit length. Use of the Tomonaga-Luttinger solution for the electronic response function (keeping only the small-momentum scattering processes) just renormalizes the Fermi velocity in this expression

Performance of a Throttle Cycle Refrigerator with Nitrogen-Hydrocarbon and Argon-Hydrocarbon Mixtures

Science.gov (United States)

Venkatarathnam, G.; Senthil Kumar, P.; Srinivasa Murthy, S.

2004-06-01

Throttle cycle refrigerators are a class of vapor compression refrigerators that can provide refrigeration at cryogenic temperatures and operate with refrigerant mixtures. The performance of our prototype refrigerators with nitrogen-hydrocarbon, nitrogen-hydrocarbon-helium and argon-hydrocarbon refrigerant mixtures is presented in this paper.

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in Hong Kong marine sediments

International Nuclear Information System (INIS)

Zheng, G.J.; Richardson, B.J.

1999-01-01

A total of 20 surficial sediment samples, obtained from Hong Kong coastal waters, were analysed for petroleum hydrocarbons (PHCs) and a suite of 15 polycyclic aromatic hydrocarbons (PAHs). The results indicate that Hong Kong coastal sediments are often seriously polluted with petroleum related hydrocarbons. This is especially so in heavily urbanised or industrialized localities, such as Kowloon Bay (Victoria Harbour), Tsing Yi North and Tolo Harbour. Petroleum hydrocarbon pollutants in marine sediments are believed to be mainly derived from the transportation of oil, shipping activities, spillages, and industrial, stormwater and waste wastewater discharge. The ratio of unresolved complex mixture (UCM) to n-alkanes, carbon preference index (CPI), and n-C 16 values indicate that the main contribution to petroleum hydrocarbon contamination is via oil and its products. Pollutant sources appear to be stable and continuing when compared with previous data. (author)

Purifying hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Demoulins, H D; Garner, F H

1923-02-07

Hydrocarbon distillates, including natural gases and vapors produced by cracking hydrocarbon oils, are desulfurized etc. by treating the vapor with an aqueous alkaline solution of an oxidizing agent. The hydrocarbons may be previously purified by sulfuric acid. In examples aqueous solutions of sodium or calcium hydrochlorite containing 1.5 to 5.0 grams per liter of available chlorine and sufficient alkali to give an excess of 0.1 percent in the spent reagent are preheated to the temperature of the vapor, and either sprayed or atomized into the vapors near the outlet of the dephlegmator or fractionating tower, or passed in countercurrent to the vapors through one or a series of scrubbers.

Evolution of topological features in finite antiferromagnetic Heisenberg chains

International Nuclear Information System (INIS)

Chen Changfeng

2003-01-01

We examine the behavior of nonlocal topological order in finite antiferromagnetic Heisenberg chains using the density matrix renormalization group techniques. We find that chains with even and odd site parity show very different behavior in the topological string order parameter, reflecting interesting interplay of the intrinsic magnetic correlation and the topological term in the chains. Analysis of the calculated string order parameter as a function of the chain length and the topological angle indicates that S=1/2 and S=1 chains show special behavior while all S>1 chains have similar topological structure. This result supports an earlier conjecture on the classification of quantum spin chains based on an analysis of their phase diagrams. Implications of the topological behavior in finite quantum spin chains are discussed

Synthesis of Ag Nanocubes 18–32 nm in Edge Length: The Effects of Polyol on Reduction Kinetics, Size Control, and Reproducibility

Science.gov (United States)

Wang, Yi; Zheng, Yiqun; Huang, Cheng Zhi; Xia, Younan

2013-01-01

This article describes a robust method for the facile synthesis of small Ag nanocubes with edge lengths controlled in the range of 18–32 nm. The success of this new method relies on the substitution of ethylene glycol (EG) -- the solvent most commonly used in a polyol synthesis -- with diethylene glycol (DEG). Owing to the increase in hydrocarbon chain length, DEG possesses a higher viscosity and a lower reducing power relative to EG. As a result, we were able to achieve a nucleation burst in the early stage to generate a large number of seeds and a relatively slow growth rate thereafter; both factors were critical to the formation of Ag nanocubes with small sizes and in high purity (>95%). The edge length of the Ag nanocubes could be easily tailored in the range of 18–32 nm by quenching the reaction at different time points. For the first time, we were able to produce uniform sub-20 nm Ag nanocubes in a hydrophilic medium and on a scale of ~20 mg per batch. It is also worth pointing out that the present protocol was remarkably robust, showing good reproducibility between different batches and even for DEGs obtained from different vendors. Our results suggest that the high sensitivity of synthesis outcomes to the trace amounts of impurities in a polyol, a major issue for reproducibility and scale up synthesis, did not exist in the present system. PMID:23317148

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

SCit: web tools for protein side chain conformation analysis.

Science.gov (United States)

Gautier, R; Camproux, A-C; Tufféry, P

2004-07-01

SCit is a web server providing services for protein side chain conformation analysis and side chain positioning. Specific services use the dependence of the side chain conformations on the local backbone conformation, which is described using a structural alphabet that describes the conformation of fragments of four-residue length in a limited library of structural prototypes. Based on this concept, SCit uses sets of rotameric conformations dependent on the local backbone conformation of each protein for side chain positioning and the identification of side chains with unlikely conformations. The SCit web server is accessible at http://bioserv.rpbs.jussieu.fr/SCit.

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.

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.

Cuticular hydrocarbons of Glossina austeni and Glossina pallidipes: Similarities between populations and activity as sex pheromones

International Nuclear Information System (INIS)

Carlson, D.A.; Bernier, U.R.; Sutton, B.D.

2000-01-01

Tsetse flies are a hazard to the health of humans and domestic animals because they spread trypanosomiasis, also known as nagana. Glossina austeni Newstead and Glossina pallidipes Austen are important vectors of this disease in East Africa. Sex pheromones were shown to be present in the surface or cuticular hydrocarbon waterproofing waxes of female of several species of the tsetse fly (Huyton et al. 1980). The pheromones identified in Glossina morsitans morsitans Westwood (Carlson et al. 1978) and G. pallidipes (Carlson et al. 1984, McDowell et al. 1985) have been shown to consist of species-specific, long-chain, high molecular weight hydrocarbons with several methyl branches, present with at least 20 other hydrocarbon compounds in the surface waxes (Nelson and Carlson 1986, Nelson et al. 1988, Sutton and Carlson 1997). The assignment of KI (Kovacx Index) narrows the range of possible methyl-branch configurations in cases of ambiguous or insufficient EI (electron impact) spectra (Carlson et al. 1998). We used gas chromatography/mass spectrometry to demonstrate that different populations of tsetse flies (Carlson et al. 1993) are closely related by investigating these patterns of surface hydrocarbons

Formation and structural phase transition in Co atomic chains on a Cu(775) surface

International Nuclear Information System (INIS)

Syromyatnikov, A. G.; Kabanov, N. S.; Saletsky, A. M.; Klavsyuk, A. L.

2017-01-01

The formation of Co atomic chains on a Cu(775) surface is investigated by the kinetic Monte Carlo method. It is found that the length of Co atomic chains formed as a result of self-organization during epitaxial growth is a random quantity and its mean value depends on the parameters of the experiment. The existence of two structural phases in atomic chains is detected using the density functional theory. In the first phase, the separations between an atom and its two nearest neighbors in a chain are 0.230 and 0.280 nm. In the second phase, an atomic chain has identical atomic spacings of 0.255 nm. It is shown that the temperature of the structural phase transition depends on the length of the atomic chain.

Formation and structural phase transition in Co atomic chains on a Cu(775) surface

Energy Technology Data Exchange (ETDEWEB)

Syromyatnikov, A. G.; Kabanov, N. S.; Saletsky, A. M.; Klavsyuk, A. L., E-mail: klavsyuk@physics.msu.ru [Moscow State University (Russian Federation)

2017-01-15

The formation of Co atomic chains on a Cu(775) surface is investigated by the kinetic Monte Carlo method. It is found that the length of Co atomic chains formed as a result of self-organization during epitaxial growth is a random quantity and its mean value depends on the parameters of the experiment. The existence of two structural phases in atomic chains is detected using the density functional theory. In the first phase, the separations between an atom and its two nearest neighbors in a chain are 0.230 and 0.280 nm. In the second phase, an atomic chain has identical atomic spacings of 0.255 nm. It is shown that the temperature of the structural phase transition depends on the length of the atomic chain.

Medium-chain fatty acids undergo elongation before β-oxidation in fibroblasts

International Nuclear Information System (INIS)

Jones, Patricia M.; Butt, Yasmeen; Messmer, Bette; Boriak, Richard; Bennett, Michael J.

2006-01-01

Although mitochondrial fatty acid β-oxidation (FAO) is considered to be well understood, further elucidation of the pathway continues through evaluation of patients with FAO defects. The FAO pathway can be examined by measuring the 3-hydroxy-fatty acid (3-OHFA) intermediates. We present a unique finding in the study of this pathway: the addition of medium-chain fatty acids to the culture media of fibroblasts results in generation of 3-OHFAs which are two carbons longer than the precursor substrate. Cultured skin fibroblasts from normal and LCHAD-deficient individuals were grown in media supplemented with various chain-length fatty acids. The cell-free medium was analyzed for 3-OHFAs by stable-isotope dilution gas-chromatography/mass-spectrometry. Our finding suggests that a novel carbon chain-length elongation process precedes the oxidation of medium-chain fatty acids. This previously undescribed metabolic step may have important implications for the metabolism of medium-chain triglycerides, components in the dietary treatment of a number of disorders

Gamma radiation-initiated polymerization of styrene at high pressure. II. Chain termination

International Nuclear Information System (INIS)

Moore, P.W.; Clouston, J.G.; Chaplin, R.P.

1981-01-01

The pressure dependence of the termination rate constant k/sub t/ for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although k/sub t/ is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in k/sub t/ at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, k/sub t/is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible

One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

Science.gov (United States)

Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

2017-01-25

For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

Bioremediation of coastal areas 5 years after the Nakhodka oil spill in the Sea of Japan: isolation and characterization of hydrocarbon-degrading bacteria

International Nuclear Information System (INIS)

Chaerun, S. Khodijah; Tazaki, Kazue; Asada, Ryuji; Kogure, Kazuhiro

2004-01-01

Five years after the 1997 Nakhodka oil spill in the Sea of Japan, seven bacterial strains capable of utilizing the heavy oil spilled from the Nakhodka Russian oil tanker were isolated from three coastal areas (namely Katano Seashore of Fukui Prefecture, Osawa and Atake seashores of Ishikawa Prefecture) and the Nakhodka Russian oil tanker after a 5-year bioremediation process. All bacterial strains isolated could utilize long-chain-length alkanes efficiently, but not aromatic, and all of them were able to grow well on heavy oil. Using 16S rDNA sequencing, most of the strains were affiliated to Pseudomonas aeruginosa. Comparing between the year 1997 (at the beginning of bioremediation process) and the year 2001 (after 5 years of bioremediation), there was no significant change in morphology and size of hydrocarbon-degrading bacteria during the 5-year bioremediation. Scanning and transmission electron microscopic observations revealed that a large number of hydrocarbon- degrading bacteria still existed in the sites consisting of a variety of morphological forms of bacteria, such as coccus (Streptococcus and Staphylococcus) and bacillus (Streptobacillus). On the application of bioremediation processes on the laboratory-scale, laboratory microcosm experiments (containing seawater, beach sand, and heavy oil) under aerobic condition by two different treatments (i.e., placed inside the building and outside the building) were established for bioremediation of heavy oil to investigate the significance of the role of hydrocarbon-degrading bacteria on them. There was no significant bacterial activity differentiation in the two treatments, and removal of heavy oil by hydrocarbon degrading bacteria in the outside building was slightly greater than that in the inside building. The values of pH, Eh, EC, and dissolved oxygen (DO) in two treatments indicated that the bioremediation process took place under aerobic conditions (DO: 1-6 mg/l; Eh: 12-300 mV) and neutral

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

Hydrocarbon contamination of coastal sediments from the Sfax area (Tunisia), Mediterranean Sea.

Science.gov (United States)

Louati, A; Elleuch, B; Kallel, M; Saliot, A; Dagaut, J; Oudot, J

2001-06-01

The coastal area off the city of Sfax (730,000 inhabitants), well-known for fisheries and industrial activities, receives high inputs of organic matter mostly anthropogenic. Eighteen stations were selected in the vicinity of the direct discharge of industrial sewage effluents in the sea in order to study the spatial distribution of the organic contamination. Surface sediments sampled in the shallow shelf were analysed for hydrocarbons by Fourier transform infrared spectroscopy, gas chromatography and gas chromatography/mass spectrometry. Total hydrocarbon distributions revealed high contamination as compared to other coastal Mediterranean sites, with an average concentration of 1865 ppm/dry weight sediment. Gas chromatographic distribution patterns, values of unresolved mixture/n-alkane ratio and distributions of steranes and hopanes confirmed a petroleum contamination of the Arabian light crude oil type. Biogenic compounds were also identified with a series of short-chain carbon-numbered n-alkenes in the carbon range 16-24.

SCit: web tools for protein side chain conformation analysis

OpenAIRE

Gautier, R.; Camproux, A.-C.; Tufféry, P.

2004-01-01

SCit is a web server providing services for protein side chain conformation analysis and side chain positioning. Specific services use the dependence of the side chain conformations on the local backbone conformation, which is described using a structural alphabet that describes the conformation of fragments of four-residue length in a limited library of structural prototypes. Based on this concept, SCit uses sets of rotameric conformations dependent on the local backbone conformation of each...

Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Energy Technology Data Exchange (ETDEWEB)

Lall-Ramnarine, Sharon I.; Zhao, Man; Rodriguez, Chanele; Fernandez, Rahonel; Zmich, Nicole; Fernandez, Eddie D.; Dhiman, Surajdevprakash B.; Castner, Edward W.; Wishart, James F.

2017-01-01

X-ray diffraction and molecular dynamics simulations were used to probe the structures of two families of ionic liquids containing oligoether tails on the cations. Imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)amide ILs with side chains ranging from 4 to 10 atoms in length, including both linear alkyl and oligo-ethylene oxide tails, were prepared. Their physical properties, such as viscosity, conductivity and thermal profile, were measured and compared for systematic trends. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase in the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. To complement the experimentally determined properties, molecular dynamics simulations were run on the two ILs with the longest ether chains. The results point to specific aspects that could be useful for researchers designing ILs for specific applications.

Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface.

Science.gov (United States)

Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

2015-07-07

The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

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

cDNA cloning and characterization of Type I procollagen alpha1 chain in the skate Raja kenojei.

Science.gov (United States)

Hwang, Jae-Ho; Yokoyama, Yoshihiro; Mizuta, Shoshi; Yoshinaka, Reiji

2006-05-01

A full-length cDNA of the Type I procollagen alpha1 [pro-alpha1(I)] chain (4388 bp), coding for 1463 amino acid residues in the total length, was determined by RACE PCR using a cDNA library constructed from 4-week embryo of the skate Raja kenojei. The helical region of the skate pro-alpha1(I) chain consisted of 1014 amino acid residues - the same as other fibrillar collagen alpha chains from higher vertebrates. Comparison on denaturation temperatures of Type I collagens from the skate, rainbow trout (Oncorhynchus mykiss) and rat (Rattus norvegicus) revealed that the number of Gly-Pro-Pro and Gly-Gly in the alpha1(I) chains could be directly related to the thermal stability of the helix. The expression property of the skate pro-alpha1(I) chain mRNA and phylogenetic analysis with other vertebrate pro-alpha1(I) chains suggested that skate pro-alpha1(I) chain could be a precursor form of the skate Type I collagen alpha1 chain. The present study is the first evidence for the primary structure of full-length pro-alpha1(I) chain in an elasmobranch.

Plant-bacteria partnership: phytoremediation of hydrocarbons contaminated soil and expression of catabolic genes

Directory of Open Access Journals (Sweden)

Hamna Saleem

2016-01-01

Full Text Available Petroleum hydrocarbons are harmful to living organisms when they are exposed in natural environment. Once they come in contact, it is not an easy to remove them because many of their constituents are persistent in nature. To achieve this target, different approaches have been exploited by using plants, bacteria, and plant-bacteria together. Among them, combined use of plants and bacteria has gained tremendous attention as bacteria possess set of catabolic genes which produce catabolic enzymes to decontaminate hydrocarbons. In return, plant ooze out root exudates containing nutrients and necessary metabolites which facilitate the microbial colonization in plant rhizosphere. This results into high gene abundance and gene expression in the rhizosphere and, thus, leads to enhanced degradation. Moreover, high proportions of beneficial bacteria helps plant to gain more biomass due to their plant growth promoting activities and production of phytohromones. This review focuses functioning and mechanisms of catabolic genes responsible for degradation of straight chain and aromatic hydrocarbons with their potential of degradation in bioremediation. With the understanding of expression mechanisms, rate of degradation can be enhanced by adjusting environmental factors and acclimatizing plant associated bacteria in plant rhizosphere.

Electronic properties of linear carbon chains: Resolving the controversy

International Nuclear Information System (INIS)

Al-Backri, Amaal; Zólyomi, Viktor; Lambert, Colin J.

2014-01-01

Literature values for the energy gap of long one-dimensional carbon chains vary from as little as 0.2 eV to more than 4 eV. To resolve this discrepancy, we use the GW many-body approach to calculate the band gap E g of an infinite carbon chain. We also compute the energy dependence of the attenuation coefficient β governing the decay with chain length of the electrical conductance of long chains and compare this with recent experimental measurements of the single-molecule conductance of end-capped carbon chains. For long chains, we find E g = 2.16 eV and an upper bound for β of 0.21 Å −1

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.

Shark Ig light chain junctions are as diverse as in heavy chains.

Science.gov (United States)

Fleurant, Marshall; Changchien, Lily; Chen, Chin-Tung; Flajnik, Martin F; Hsu, Ellen

2004-11-01

We have characterized a small family of four genes encoding one of the three nurse shark Ig L chain isotypes, called NS5. All NS5 cDNA sequences are encoded by three loci, of which two are organized as conventional clusters, each consisting of a V and J gene segment that can recombine and one C region exon; the third contains a germline-joined VJ in-frame and the fourth locus is a pseudogene. This is the second nurse shark L chain type where both germline-joined and split V-J organizations have been found. Since there are only two rearranging Ig loci, it was possible for the first time to examine junctional diversity in defined fish Ig genes, comparing productive vs nonproductive rearrangements. N region addition was found to be considerably more extensive in length and in frequency than any other vertebrate L chain so far reported and rivals that in H chain. We put forth the speculation that the unprecedented efficiency of N region addition (87-93% of NS5 sequences) may be a result not only of simultaneous H and L chain rearrangement in the shark but also of processing events that afford greater accessibility of the V or J gene coding ends to terminal deoxynucleotidyltransferase.

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min

2017-01-01

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured

Many-body formation and dissociation of a dipolar chain crystal

International Nuclear Information System (INIS)

You, Jhih-Shih; Wang, Daw-Wei

2014-01-01

We propose an experimental scheme to effectively assemble chains of dipolar gases with a uniform length in a multi-layer system. The obtained dipolar chains can form a chain crystal with the system temperature easily controlled by the initial lattice potential and the external field strength during processing. When the density of chains increases, we further observe a second order quantum phase transition for the chain crystal to be dissociated toward layers of 2D crystal, where the quantum fluctuation dominates the classical energy and the compressibility diverges at the phase boundary. The experimental implication of such a dipolar chain crystal and its quantum phase transition is also discussed. (paper)

Neutron diffraction on polymorphic phases of phospholipids

International Nuclear Information System (INIS)

Adachi, Tomohiro; Furusaka, Michihiro; Otomo, Toshiya; Hatta, Ichiro

2001-01-01

Small angle neutron diffraction experiments were performed in DPPC and DPPC/cholesterol systems. We investigated the DPPC-d62 bilayers without cholesterol and the DPPC-d75 bilayers with 5 and 15 mol% cholesterol. For DPPC-d62 systems, in the gel and fluid phase, the reflections up to third order from lamellar structure were observed. Scattering length density profiles of these systems were generated. They show that the packing density of hydrocarbon chain in gel phase is higher than in fluid phase. We show that the neutron diffraction experiment is effective on observing the packing and the scattering length density of the hydrocarbon chain. On the other hand, for DPPC-d75/cholesterol systems, only the reflection from the ripple structure was observed. It shows that cholesterol is periodically localized in accordance with ripple structure forming a periodic bandlike structure parallel to a ridge of the ripple structure. (author)

Compound- and position-specific carbon isotopic signatures of abiogenic hydrocarbons from on-land serpentinite-hosted Hakuba Happo hot spring in Japan

Science.gov (United States)

Suda, Konomi; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Ueno, Yuichiro

2017-06-01

It has been proposed that serpentinite-hosted hydrothermal/hot spring systems played a significant role in the origin and early evolution of life on early Earth because abiogenic synthesis of organic compounds may accompany serpentinization. However, production mechanisms for apparently abiogenic hydrocarbons that have been observed in the ongoing serpentinizing systems are still poorly constrained. We report a new geochemical study of hydrocarbons in an on-land serpentinite-hosted hot spring in Hakuba Happo, Japan. We have conducted both compound-specific and position-specific carbon isotopic analyses of the observed C1 to C5 hydrocarbons. A positive linear relationship between the δ13C values and the inverse carbon number is found in C1 to C5 straight-chain alkanes in the Happo sample. This isotopic trend is consistent with a simple polymerization model developed in this study. Our model assumes that, for any particular alkane, all of the subsequently added carbons have the same isotopic composition, and those are depleted in 13C with respect to the first carbon in the growing carbon chain. The fit of this model suggests that Happo alkanes can be produced via polymerization from methane with a constant kinetic isotopic fractionation of -8.9 ± 1.0‰. A similar carbon isotopic relationship among alkanes has been observed in some serpentinite-hosted seafloor hydrothermal systems, indicating that the same process is responsible for the abiological hydrocarbon in general serpentinization fields, not only in the Hakuba Happo hot spring. Moreover, our model is also applicable to other potentially abiogenic natural gases and experimentally synthesized hydrocarbon products. For the first time, the intramolecular 13C composition of propane from a natural sample derived from a serpentinite-hosted system was determined. The intramolecular 13C distribution in propane shows the important potential to identify different polymerization mechanisms that cannot be discriminated

Sampling rare fluctuations of discrete-time Markov chains

Science.gov (United States)

Whitelam, Stephen

2018-03-01

We describe a simple method that can be used to sample the rare fluctuations of discrete-time Markov chains. We focus on the case of Markov chains with well-defined steady-state measures, and derive expressions for the large-deviation rate functions (and upper bounds on such functions) for dynamical quantities extensive in the length of the Markov chain. We illustrate the method using a series of simple examples, and use it to study the fluctuations of a lattice-based model of active matter that can undergo motility-induced phase separation.

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 ...

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

OpenAIRE

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-01-01

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction wi...

Hydrocarbon Source Signatures in Houston, Texas: Influence of the Petrochemical Industry

Energy Technology Data Exchange (ETDEWEB)

Jobson, B Tom T; Berkowitz, Carl M; Kuster, W C; Goldan, P D; Williams, E J; Fesenfeld, F; Apel, Eric; Karl, Thomas G; Lonneman, William A; Riemer, D

2004-12-22

Observations of C1-C10 hydrocarbon mixing ratios measured by in-situ instrumentation at the La Porte super site during the TexAQS 2000 field experiment are reported. The La Porte data were compared to a roadway vehicle exhaust signature obtained from canister samples collected in the Houston Washburn tunnel during the same summer to better understand the impact of petrochemical emissions of hydrocarbons at the site. It is shown that the abundance of ethene, propene, 1-butene, C2-C4 alkanes, hexane, cyclohexane, methylcyclohexane, isopropylbenzene, and styrene at La Porte were systematically impacted by petrochemical industry emissions. Coherent power law relationships between frequency distribution widths of hydrocarbon mixing ratios and their local lifetimes clearly identify two major source groups, roadway vehicle emissions and industrial emissions. Distributions of most aromatics and long chain alkanes were consistent with roadway vehicle emissions as the dominant source. Airmass reactivity was generally dominated by C1-C3 aldehydes. Propene and ethene sometimes dominated air mass reactivity with HO loss frequencies often greater than 10 s-1. Ozone mixing ratios near 200 ppbv were observed on two separate occasions and these air masses appear to have been impacted by industrial emissions of alkenes from the Houston Ship Channel. The La Porte data provide evidence of the importance of industrial emissions of ethene and propene on air masses reactivity and ozone formation in Houston.

Hydrocarbons and air pollution

International Nuclear Information System (INIS)

Herz, O.

1992-01-01

This paper shows the influence of hydrocarbons vapors, emitted by transports or by volatile solvents using, on air pollution. Hydrocarbons are the principal precursors of photochemical pollution. After a brief introduction on atmospheric chemistry and photochemical reactions, the author describes the french prevention program against hydrocarbons emissions. In the last chapter, informations on international or european community programs for photochemical pollution study are given. 5 figs., 10 tabs

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.

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.

Non-local spatial frequency response of photopolymer materials containing chain transfer agents: I. Theoretical modelling

International Nuclear Information System (INIS)

Guo, Jinxin; Gleeson, Michael R; Liu, Shui; Sheridan, John T

2011-01-01

The non-local photopolymerization driven diffusion (NPDD) model predicts that a reduction in the non-local response length within a photopolymer material will improve its high spatial frequency response. The introduction of a chain transfer agent reduces the average molecular weight of polymer chains formed during free radical polymerization. Therefore a chain transfer agent (CTA) provides a practical method to reduce the non-local response length. An extended NPDD model is presented, which includes the chain transfer reaction and most major photochemical processes. The addition of a chain transfer agent into an acrylamide/polyvinyl alcohol photopolymer material is simulated and the predictions of the model are examined. The predictions of the model are experimentally examined in part II of this paper

On energetics of hydrocarbon chemical reactions by ionizing irradiation

International Nuclear Information System (INIS)

Zaykin, Yu.A.; Zaykina, R.F.; Mirkin, G.

2002-01-01

Complete text of publication follows. The present global energy crisis requires the industry to look for technologies that are more effective and, particularly, less energy consuming. The hydrocarbon processing technology based on the electron radiation-induced thermal chemical conversion has a great potential. Comparing the presently predominant thermocatalytic processing, it is much more energy efficient, because chemical conversions go at a minimal processing temperature and pressure. To compare energy consumption by electron irradiation with thermal and thermocatalytic technologies of hydrocarbon processing one must see major differences between them. While traditional thermocatalytic processes are equilibrium and their energetics can be evaluated based on principles of classic thermodynamics, HEET processing is non-equilibrium and this evaluation approach is not valid for it. However, a theoretical description of radiation-chemical conversion using reaction rate constants determined in thermally equilibrium systems is approximately adequate to radiation processes by substituting equilibrium concentrations of reacting particles as their non-equilibrium concentrations under irradiation. In particular, description of radical reactions initiated by radiation requires substitution of thermally equilibrium radical concentration by much higher concentration defined by the dynamic equilibrium of radical radiation generation and their recombination. The paper presents the comparative analysis of energy consumption in different stages of hydrocarbon processing using classic thermal cracking by heating versus radiation induced cracking. It is shown that in the most energy-consuming stage of processing - the chain reaction initiation necessary for concentration of active radicals, irradiation processing has the great advantage compared to thermal cracking by heating and allows cutting down the total energy consumption by approximately 40%

Effect of including decay chains on predictions of equilibrium-type terrestrial food chain models

International Nuclear Information System (INIS)

Kirchner, G.

1990-01-01

Equilibrium-type food chain models are commonly used for assessing the radiological impact to man from environmental releases of radionuclides. Usually these do not take into account build-up of radioactive decay products during environmental transport. This may be a potential source of underprediction. For estimating consequences of this simplification, the equations of an internationally recognised terrestrial food chain model have been extended to include decay chains of variable length. Example calculations show that for releases from light water reactors as expected both during routine operation and in the case of severe accidents, the build-up of decay products during environmental transport is generally of minor importance. However, a considerable number of radionuclides of potential radiological significance have been identified which show marked contributions of decay products to calculated contamination of human food and resulting radiation dose rates. (author)

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.

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.

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.

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.

Detection of hydrocarbons in irradiated foods

International Nuclear Information System (INIS)

Miyahara, Makoto; Maitani, Tamio; Saito, Akiko; Kamimura, Tomomi; Nagasawa, Taeko; Kobayashi, Yasuo; Ito, Hitoshi

2003-01-01

The hydrocarbon method for the detection of irradiated foods is now recognized as the international technique. This method is based on radiolysis of fatty acids in food to give hydrocarbons. In order to expand this technique's application, ten foods (butter, cheese, chicken, pork, beef, tuna, dry shrimp, avocado, papaya, and mango) were irradiated in the range from 0.5 to 10 kGy and the hydrocarbons in them were detected. Recoveries of the hydrocarbons from most foods were acceptable (38-128%). Some hydrocarbons were found in non-irradiated foods, particularly, in butter, cheese, tuna, and shrimp. Seven irradiated foods, butter, cheese, chicken, beef, pork, tuna, dry shrimp, and avocado were detectable at their practical doses by measuring the appropriate marker hydrocarbons. In most case, marker hydrocarbon will be 1,7-hexadecadiene. However, the marker hydrocarbons produced only in irradiated foods varied from food to food; therefore, it is necessary to check a specific irradiated food for marker hydrocarbons. On the other hand, two irradiated foods (papaya and mango which were irradiated at their practical doses) were difficult to distinguish from non-irradiated foods using this method. (author)

Detection of hydrocarbons in irradiated foods

Energy Technology Data Exchange (ETDEWEB)

Miyahara, Makoto; Maitani, Tamio [National Inst. of Health Sciences, Tokyo (Japan); Saito, Akiko; Kamimura, Tomomi; Nagasawa, Taeko [Kitasato Univ., Sagamihara, Kanagawa (Japan). School of Allied Health Sciences; Kobayashi, Yasuo; Ito, Hitoshi [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Establishment

2003-06-01

The hydrocarbon method for the detection of irradiated foods is now recognized as the international technique. This method is based on radiolysis of fatty acids in food to give hydrocarbons. In order to expand this technique's application, ten foods (butter, cheese, chicken, pork, beef, tuna, dry shrimp, avocado, papaya, and mango) were irradiated in the range from 0.5 to 10 kGy and the hydrocarbons in them were detected. Recoveries of the hydrocarbons from most foods were acceptable (38-128%). Some hydrocarbons were found in non-irradiated foods, particularly, in butter, cheese, tuna, and shrimp. Seven irradiated foods, butter, cheese, chicken, beef, pork, tuna, dry shrimp, and avocado were detectable at their practical doses by measuring the appropriate marker hydrocarbons. In most case, marker hydrocarbon will be 1,7-hexadecadiene. However, the marker hydrocarbons produced only in irradiated foods varied from food to food; therefore, it is necessary to check a specific irradiated food for marker hydrocarbons. On the other hand, two irradiated foods (papaya and mango which were irradiated at their practical doses) were difficult to distinguish from non-irradiated foods using this method. (author)

Tolerance of Antarctic soil fungi to hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Hughes, Kevin A.; Bridge, Paul; Clark, Melody S. [British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge CB3 0ET (United Kingdom)

2007-01-01

Little is known about the effects of hydrocarbons and fuel oil on Antarctic filamentous fungi in the terrestrial Antarctic environment. Growth of fungi and bacteria from soils around Rothera Research Station (Adelaide Island, Antarctic Peninsula) was assessed in the presence of ten separate aromatic and aliphatic hydrocarbons [marine gas oil (MGO), dodecane, hexadecane, benzoic acid, p-hydroxybenzoic acid, toluene, phenol, biphenyl, naphthalene and m- and p-xylenes with ethylbenzene]. Aromatic hydrocarbons inhibited soil microbial growth more than aliphatic hydrocarbons. Soil microorganisms from a moss patch, where little previous impact or hydrocarbon contamination had occurred, were less tolerant of hydrocarbons than those from high impact sites. Fungal growth rates of Mollisia sp., Penicillium commune, Mortierella sp., Trichoderma koningii, Trichoderma sp. and Phoma herbarum were assessed in the presence of hydrocarbons. Generally, aromatic hydrocarbons inhibited or stopped hyphal extension, though growth rates increased with some aliphatic hydrocarbons. Hyphal dry weight measurements suggested that Mortierella sp. may be able to use dodecane as sole carbon and energy source. Hydrocarbon-degrading Antarctic fungi may have use in future hydrocarbon spill bioremediation. (author)

Excitation Chains at the Glass Transition