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Sample records for astaxanthin chiral isomers

  1. Determination of astaxanthin and astaxanthin esters in the microalgae Haematococcus pluvialis by LC-(APCI)MS and characterization of predominant carotenoid isomers by NMR spectroscopy.

    PubMed

    Holtin, Karsten; Kuehnle, Maximilian; Rehbein, Jens; Schuler, Paul; Nicholson, Graeme; Albert, Klaus

    2009-11-01

    The oily product ZANTHIN consists of natural astaxanthin, which is manufactured from the microalgae Haematococcus pluvialis by supercritical CO(2) extraction. An HPLC method was developed to separate all of the components of the complex astaxanthin extract using a C(30) column. The separation resulted in different isomers of astaxanthin accompanied by two other carotenoids. The main component consisted of astaxanthin singly esterified with several different fatty acids. C18:3, C18:2, C18:1 and C16:0 were identified as the most commonly occurring fatty acids. Doubly esterified astaxanthin was also found, although in lower concentrations compared to singly esterified astaxanthin. After performing a detailed fatty acid analysis by GC-MS, the peaks from the extract were assigned via HPLC-MS. A trans to cis transmutation of the all-trans compound was performed by thermal treatment in order to obtain an enrichment of cis isomers as the basis for unambiguous identification via NMR experiments. The all-trans as well as the 9- and 13-cis isomers of astaxanthin were characterized in detail by UV/Vis, (1)H, and (1)H,(1)H COSY NMR spectroscopy. PMID:19466394

  2. Identification of geometrical isomers and comparison of different isomeric samples of astaxanthin.

    PubMed

    Qiu, Dan; Wu, Yue-Chan; Zhu, Wen-Li; Yin, Hong; Yi, Long-Tao

    2012-09-01

    A high-performance liquid chromatographic (HPLC) analysis system for isomeric astaxanthin was developed. The separation system consisted of a C(30) column and an elution system of methanol/MTBE/water/dichloromethane (77:13:8:2, v/v/v/v). Using the combination of HPLC diode array detector and HPLC atmospheric pressure chemical ionization mass spectrometry, 11 geometrical isomers and 4 epoxides of astaxanthin were successfully identified. Referred to crystal, only isomerization with different degrees was found for solvent dissolving and iodine catalysis, while melting of astaxanthin caused isomerization, slight oxidation, and more noticeable polymerization confirmed by gel permeation chromatography. Chemical changes in isomeric samples all caused a decrease in UV content. The vibrational spectra (infrared and Raman) showed that epoxide was the only new functional group generated for melting. Changes of several key bands and formations of new bands were found in iodine catalysis and melting samples because of isomerization. Practical Application:  Eleven geometrical isomers and 4 epoxides, which were normally generated for solvent dissolving, iodine catalysis, and melting of astaxanthin, have been identified by C(30) -HPLC-MS technology. Furthermore, different samples were measured by gel permeation chromatography, UV, infrared, and Raman, based on the analysis of messages, the effect of each processing was well understood. PMID:22900833

  3. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    SciTech Connect

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-15

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  4. Enumeration of chiral and positional isomers of substituted fullerene cages (C[sub 20]-C[sub 70])

    SciTech Connect

    Balasubramanian, K. )

    1993-07-08

    Enumeration of chiral isomers of substituted fullerene cages (C[sub 20]-C[sub 70]) is considered using the generalized character cycle index (GCCI) of the alternating representation of the point group of the parent cage. It is shown that there are no chiral isomers for the monsubstituted C[sub 20], C[sub 24], C[sub 28], C[sub 30], C[sub 36], and C[sub 60] fullerene cages but there are chiral isomers for other monosubstituted cages. All cages considered here possess chiral isomers for disubstituted cages. It is shown that the number of positional isomers can be obtained using the GCCI of the totally symmetric representation. We also enumerate the [sup 13]C NMR signals of all fullerene cages C[sub 20]-C[sub 70]. 30 refs., 4 figs., 6 tabs.

  5. Chiral separation of deprenyl-N-oxide isomers by capillary electrophoresis using various cyclodextrin derivatives.

    PubMed

    Tábi, Tamás; Halász, Attila Sándor; Pálfi, Melinda; Magyar, Kálmán; Szöko, Eva

    2004-01-01

    Chiral separation of deprenyl-N-oxide isomers is presented using capillary electrophoresis in the presence of various cyclodextrin (CD) derivatives. This recently identified metabolite of R-(-)-deprenyl may possess desirable pharmacological activities. The effect of the cavity size and the substituents of the CD are examined on the enantiomer resolution of the compound having an asymmetric center on a heteroatom. The importance of hydrophilic or hydrogen bonding interaction, as well as the position of the interacting groups is demonstrated. Outstanding selectivity and resolution values are achieved using the chargeable carboxymethyl-beta-CD. 2-Hydroxypropyl-beta-CD is also suitable for the enantiomer separation of the analyte. Native beta-CD and carboxyethyl-beta-CD provide only poor enantioselectivity, whereas heptakis-(2,6-di-O-methyl)-beta-CD is capable of separating only the diastereomers. No chiral resolution can be observed in the presence of gamma-CD. PMID:14965411

  6. Spectroscopic investigations of the chiral interactions of metolachlor and its (S)-isomer with lipase and phosphatase.

    PubMed

    Wen, Yue Z; Yuan, Yu L; Chen, Hui; Wang, He L; Liu, Hui J; Kang, Xiao D; Fu, Liu S

    2010-04-01

    Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] is a chiral acetanilide herbicide. We investigated its enantioselective interactions, and that of its (S)-isomer, with Penicillium expansum alkaline lipase and phosphatase. UV differential spectroscopy and fluorescence spectrophotometry studies were conducted in phosphate buffered solution at pH 7. Chiral differences in the UV absorption and fluorescence spectra of lipase and phosphatase with metolachlor and its (S)-isomer were detected. The results showed that the interactions of metolachlor and its (S)-isomer with lipase and phosphatase occur statically through complex formation, and enantioselectivity was clearly observed. In addition, both UV absorption and fluorescence spectrophotometry showed that the (S)-isomer interacted more strongly with lipase and phosphatase than metolachlor. PMID:20390958

  7. Effect of thermal processing on astaxanthin and astaxanthin esters in pacific white shrimp Litopenaeus vannamei.

    PubMed

    Yang, Shu; Zhou, Qingxin; Yang, Lu; Xue, Yong; Xu, Jie; Xue, Changhu

    2015-01-01

    The red color of processed shrimp, one of the most attractive attributes and an important criterion for consumers, is often limited by thermal processing (microwaving, boiling and frying), due to astaxanthin degradation. The effect of thermal processing on astaxanthin in Pacific white shrimp (Litopenaeus vannamei) were investigated. A High-performance liquid chromatographic - atmospheric pressure chemical ionization mass spectrometry (LC-(APCI)-MS/MS) method was used to identify and quantify all-trans- and cis-isomers of astaxanthin, and molecular species of astaxanthin esters in fresh and thermal processed shrimps. Total astaxanthin loss ranged from 7.99% to 52.01% in first 3 min under three thermal processing. All-trans-astaxanthin was most affected, with a reduction from 32.81 to 8.72 μg kg(-1), while 13-cis-astxanthin had a rise (from 2.38 to 4.58 μg kg(-1)). Esterified astaxanthin was shown to hydrolyze and degrade, furthermore astaxanthin diesters had a better thermostability compare to astaxanthin monoesters. Astaxanthin monoesters with eicosapntemacnioc acid (EPA, C20:5) and docosahexaenoic acid (DHA, C22:6), had a lower thermal stability than those with saturated fatty acids, however, it was the opposite of astaxanthin diesters. The findings suggested that the method of thermal processing should be carefully used in the manufacturing and domestic cooking of shrimps. The results also could be useful in calculating the dietary intake of astaxanthin and in assessing astaxanthin profiles and contents of shrimp containing products. PMID:25757428

  8. Chirality at metal and helical ligand folding in optical isomers of chiral bis(naphthaldiminato)nickel(II) complexes.

    PubMed

    Enamullah, Mohammed; Quddus, Mohammad Abdul; Hasan, Mohammad Rezabul; Pescitelli, Gennaro; Berardozzi, Roberto; Makhloufi, Gamall; Vasylyeva, Vera; Janiak, Christoph

    2016-01-14

    Enantiopure bis[{(R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldiminato-κ(2)N,O}]nickel(ii) complexes {Ar = C6H5 ( or ), p-OMeC6H4 ( or ), and p-BrC6H4 ( or )} are synthesized from the reactions between (R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldimine and nickel(ii) acetate. Circular-dichroism spectra and their density-functional theoretical simulation reveal the expected mirror image relationship between the enantiomeric pairs / and / in solution. CD spectra are dominated by the metal-centered Λ- or Δ-chirality of non-planar four-coordinated nickel, this latter being in turn dictated by the ligand chirality. Single crystal structure determination for and shows that there are two symmetry-independent molecules (A and B) in each asymmetric unit that give a Z' = 2 structure. Two asymmetric and chiral bidentate N^O-chelate Schiff base ligands coordinate to the nickel atom in a distorted square planar N2O2-coordination sphere. The conformational difference between the symmetry-independent molecules arises from the "up-or-down" folding of the naphthaldiminato ligand with respect to the coordination plane, which creates right- (P) or left-handed (M) helical conformations. Overall, the combination of ligand chirality, chirality at the metal and ligand folding gives rise to discrete metal helicates of preferred helicity in a selective way. Cyclic voltammograms (CV) show an oxidation wave at ca. 1.30 V for the [Ni(L)2]/[Ni(L)2](+) couple, and a reduction wave at ca. -0.35 V for the [Ni(L)2]/[Ni(L)2](-) couple in acetonitrile. PMID:26619269

  9. Perfluorooctane sulfonate: a review of human exposure, biomonitoring and the environmental forensics utility of its chirality and isomer distribution.

    PubMed

    Miralles-Marco, Ana; Harrad, Stuart

    2015-04-01

    Perfluorooctane sulfonate (PFOS) found extensive use for over 60 years up until its restriction in the early 2000s, culminating in its listing under the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2009. Efforts to minimise human body burdens are hindered by uncertainty over their precise origins. While diet appears the principal source for the majority of western populations (with other pathways like dust ingestion, drinking water and inhalation also important contributors); the role played by exposure to PFOS-precursor compounds followed by in vivo metabolism to PFOS as the ultimate highly stable end-product is unclear. Such PFOS-precursor compounds include perfluorooctane sulfonamide derivates, e.g., perfluorooctane sulfonamides (FOSAs) and sulfonamidoethanols (FOSEs). Understanding the indirect contribution of such precursors to human body burdens of PFOS is important as a significant contribution from this pathway would render the margin of safety between the current exposure limits and estimates of external exposure to PFOS alone, narrower than hitherto appreciated. Estimates derived from mathematical modelling studies, put the contribution of so-called "precursor exposure" at between 10% and 40% of total PFOS body burdens. However, there are substantial uncertainties associated with such approaches. This paper reviews current understanding of human exposure to PFOS, with particular reference to recent research highlighting the potential of environmental forensics approaches based on the relative abundance and chiral signatures of branched chain PFOS isomers to provide definitive insights into the role played by "precursor exposure". PMID:25728452

  10. Capillary electrophoretic enantioseparation of basic drugs using a new single-isomer cyclodextrin derivative and theoretical study of the chiral recognition mechanism.

    PubMed

    Liu, Yongjing; Deng, Miaoduo; Yu, Jia; Jiang, Zhen; Guo, Xingjie

    2016-05-01

    A novel single-isomer cyclodextrin derivative, heptakis {2,6-di-O-[3-(1,3-dicarboxyl propylamino)-2-hydroxypropyl]}-β-cyclodextrin (glutamic acid-β-cyclodextrin) was synthesized and used as a chiral selector in capillary electrophoresis for the enantioseparation of 12 basic drugs, including terbutaline, clorprenaline, tulobuterol, clenbuterol, procaterol, carvedilol, econazole, miconazole, homatropine methyl bromide, brompheniramine, chlorpheniramine and pheniramine. The primary factors affecting separation efficiency, which include the background electrolyte pH, the concentration of glutamic acid-β-cyclodextrin and phosphate buffer concentration, were investigated. Satisfactory enantioseparations were obtained using an uncoated fused-silica capillary of 50 cm (effective length 40 cm) × 50 μm id with 120 mM phosphate buffer (pH 2.5-4.0) containing 0.5-4.5 mM glutamic acid-β-cyclodextrin as background electrolyte. A voltage of 20 kV was applied and the capillary temperature was kept at 20°C. The results proved that glutamic acid-β-cyclodextrin was an effective chiral selector for studied 12 basic drugs. Moreover, the possible chiral recognition mechanism of brompheniramine, chlorpheniramine and pheniramine on glutamic acid-β-cyclodextrin was investigated using the semi-empirical Parametric Method 3. PMID:26935589

  11. Chromatographic, NMR and vibrational spectroscopic investigations of astaxanthin esters: application to "Astaxanthin-rich shrimp oil" obtained from processing of Nordic shrimps.

    PubMed

    Subramanian, B; Thibault, M-H; Djaoued, Y; Pelletier, C; Touaibia, M; Tchoukanova, N

    2015-11-01

    Astaxanthin (ASTX) is a keto carotenoid, which possesses a non-polar linear central conjugated chain and polar β-ionone rings with ketone and hydroxyl groups at the extreme ends. It is well known as a super anti-oxidant, and recent clinical studies have established its nutritional benefits. Although it occurs in several forms, including free molecule, crystalline, aggregates and various geometrical isomers, in nature it exists primarily in the form of esters. Marine animals accumulate ASTX from primary sources such as algae. Nordic shrimps (P. borealis), which are harvested widely in the Atlantic Ocean, form a major source of astaxanthin esters. "Astaxanthin-rich shrimp oil" was developed as a novel product in a shrimp processing plant in Eastern Canada. A compositional analysis of the shrimp oil was performed, with a view to possibly use it as a nutraceutical product for humans and animals. Astaxanthin-rich shrimp oil contains 50% MUFAs and 22% PUFAs, of which 20% are omega-3. In addition, the shrimp oil contains interesting amounts of EPA and DHA, with 10%/w and 8%/w, respectively. Astaxanthin concentrations varied between 400 and 1000 ppm, depending on the harvesting season of the shrimp. Astaxanthin and its esters were isolated from the oil and analysed by NMR, FTIR and Micro-Raman spectroscopy. Astaxanthin mono- and diesters were synthesized and used as standards for the analysis of astaxanthin-rich shrimp oil. NMR and vibrational spectroscopy techniques were successfully used for the rapid characterization of monoesters and diesters of astaxanthin. Raman spectroscopy provided important intermolecular interactions present in the esterified forms of astaxanthin molecules. Also discussed in this paper is the use of NMR, FTIR and Micro-Raman spectroscopy for the detection of astaxanthin esters in shrimp oil. PMID:26393239

  12. Chiral recognition of pinacidil and its 3-pyridyl isomer by canine cardiac and smooth muscle: Antagonism by sulfonylureas

    SciTech Connect

    Steinberg, M.I.; Wiest, S.A.; Zimmerman, K.M.; Ertel, P.J.; Bemis, K.G.; Robertson, D.W. )

    1991-01-01

    Pinacidil, a potassium channel opener (PCO), relaxes vascular smooth muscle by increasing potassium ion membrane conductance, thereby causing membrane hyperpolarization. PCOs also act on cardiac muscle to decrease action potential duration (APD) selectively. To examine the enantiomeric selectivity of pinacidil, the stereoisomers of pinacidil (a 4-pyridylcyanoguanidine) and its 3-pyridyl isomer (LY222675) were synthesized and studied in canine Purkinje fibers and cephalic veins. The (-)-enantiomers of both pinacidil and LY222675 were more potent in relaxing phenylephrine-contracted cephalic veins and decreasing APD than were their corresponding (+)-enantiomers. The EC50 values for (-)-pinacidil and (-)-LY222675 in relaxing cephalic veins were 0.44 and 0.09 microM, respectively. In decreasing APD, the EC50 values were 3.2 microM for (-)-pinacidil and 0.43 microM for (-)-LY222675. The eudismic ratio was greater for the 3-pyridyl isomer than for pinacidil in both cardiac (71 vs. 22) and vascular (53 vs. 17) tissues. (-)-LY222675 and (-)-pinacidil (0.1-30 microM) also increased 86Rb efflux from cephalic veins to a greater extent than did their respective optical antipodes. The antidiabetic sulfonylurea, glyburide (1-30 microM), shifted the vascular concentration-response curve of (-)-pinacidil to the right by a similar extent at each inhibitor concentration. Glipizide also antagonized the response to (-)-pinacidil, but was about 1/10 as potent with a maximal shift occurring at 10 and 30 microM. Glyburide antagonized the vascular relaxant effects of 0.3 microM (-)-LY222675 (EC50, 2.3 microM) and reversed the decrease in APD caused by 3 microM (-)-LY222675 (EC50, 1.9 microM). Nitroprusside did not alter 86Rb efflux, and vascular relaxation induced by sodium nitroprusside was unaffected by sulfonylureas.

  13. Preferential selection of isomer binding from chiral mixtures: alternate binding modes observed for the E and Z isomers of a series of 5-substituted 2,4-diaminofuro[2,3-d]pyrimidines as ternary complexes with NADPH and human dihydrofolate reductase

    SciTech Connect

    Cody, Vivian; Piraino, Jennifer; Pace, Jim; Li, Wei; Gangjee, Aleem

    2010-12-01

    The structures of six chirally mixed E/Z-isomers of 5-substituted 2,4-diaminofuro[2,3-d]pyrimidines reveals only one isomer is bound in the active site of human DHFR. The configuration of all but one C9-analogue is observed as the E-isomer. The crystal structures of six human dihydrofolate reductase (hDHFR) ternary complexes with NADPH and a series of mixed E/Z isomers of 5-substituted 5-[2-(2-methoxyphenyl)-prop-1-en-1-yl]furo[2,3-d]pyrimidine-2,4-diamines substituted at the C9 position with propyl, isopropyl, cyclopropyl, butyl, isobutyl and sec-butyl (E2–E7, Z3) were determined and the results were compared with the resolved E and Z isomers of the C9-methyl parent compound. The configuration of all of the inhibitors, save one, was observed as the E isomer, in which the binding of the furopyrimidine ring is flipped such that the 4-amino group binds in the 4-oxo site of folate. The Z3 isomer of the C9-isopropyl analog has the normal 2,4-diaminopyrimidine ring binding geometry, with the furo oxygen near Glu30 and the 4-amino group interacting near the cofactor nicotinamide ring. Electron-density maps for these structures revealed the binding of only one isomer to hDHFR, despite the fact that chiral mixtures (E:Z ratios of 2:1, 3:1 and 3:2) of the inhibitors were incubated with hDHFR prior to crystallization. Superposition of the hDHFR complexes with E2 and Z3 shows that the 2′-methoxyphenyl ring of E2 is perpendicular to that of Z3. The most potent inhibitor in this series is the isopropyl analog Z3 and the least potent is the isobutyl analog E6, consistent with data that show that the Z isomer makes the most favorable interactions with the active-site residues. The isobutyl moiety of E6 is observed in two orientations and the resultant steric crowding of the E6 analog is consistent with its weaker activity. The alternative binding modes observed for the furopyrimidine ring in these E/Z isomers suggest that new templates can be designed to probe these binding

  14. Synthesis of cationic single-isomer cyclodextrins for the chiral separation of amino acids and anionic pharmaceuticals.

    PubMed

    Tang, Weihua; Ng, Siu-Choon

    2007-01-01

    We describe a protocol for the synthesis of mono-6(A)-(1-butyl-3-imidazolium)-6(A)-deoxy-beta-cyclodextrin chloride (BIMCD), a cationic, water-soluble cyclodextrin used in the chiral separation of amino acids and anionic pharmaceuticals by capillary electrophoresis. Starting from commercially available chemicals, BIMCD is synthesized in five steps. The first step involves a nucleophilic substitution between p-toluenesulfonyl chloride and imidazole to afford 1-(p-toluenesulfonyl)imidazole (A). In the second step, a nucleophilic substitution between beta-cyclodextrin and A affords mono-6(A)-(p-toluenesulfonyl)-6(A)-deoxy-beta-cyclodextrin (B). In the third step, a nucleophilic substitution between 1-bromobutane and imidazole affords 1-butylimidazole (C). In the fourth step, a nucleophilic addition between A and C affords BIMCD tosylate. In the final step, anion exchange using an ion-exchange resin yields BIMCD as a highly water-soluble solid. Each step takes up to 2 d, including the time required for product purification. The overall protocol requires approximately 6 d. PMID:18079719

  15. Development and validation of a chiral high-performance liquid chromatography assay for rogletimide and rogletimide-N-oxide isomers in plasma.

    PubMed

    Etienne, M C; Oster, W; Milano, G

    1996-01-01

    The purpose of the present study was to develop and validate a stereo-specific high-performance liquid chromatography (HPLC) assay for rogletimide (Rog) and rogletimide-N-oxide (Nox) isomers in plasma. The assay was performed with a chiral cellulose-[4-methylbenzoate]ester column (Chiracel OJ). Optimal separation was achieved isocratically with a mobile phase consisting of n-hexane/anhydrous ethanol (65/35, v/v) at a flow rate of 0.9 ml/min, with the column being thermostated at +35 degrees C (UV detection at 257 nm). Under these conditions, retention times were approximately 17, 28, 31 and 76 min for R-Rog, S-Rog, R-Nox and S-Nox, respectively. S-aminoglutethimide (S-Ag) served as the internal standard (retention time 70 min). An extraction procedure from plasma samples was developed on Bond Elut RP8 500-mg cartridges; conditioning was performed with 5 ml methanol and 5 ml water, after which 1 ml plasma that had previously been spiked with 5 microM S-Ag was applied. Washing was done with 6 ml water and elution, with 4 ml methanol. After evaporation to dryness, residues were dissolved in 400 microliters anhydrous ethanol and 12-48 microliters was injected onto the HPLC system. Blank plasma from healthy donors showed the random presence of a small interference eluting at the retention time of R-Rog, precluding the accurate quantification of R-Rog concentrations below 2.5 microM. Reproducibility assays demonstrated the need to use an internal standard. Taking into account the internal standard, at 2.5 microM the intra- and inter-assay coefficients of variation were 10.5% and 21.0% for R-Rog 5.5% and 8.7% for S-Rog, 7.6% and 20.8% for R-Nox and 11.7% and 6.4% for S-Nox, respectively. The detection limit was 2.5 microM for R-Rog, 0.5 microM for S-Rog, 0.25 microM for R-Nox and 0.5 microM for S-Nox. Linearity was satisfactory at concentrations ranging from 2.5 to 10 microM for R-Rog, from 0.5 to 10 microM for S-Rog, from 0.25 to 2.5 microM for R-Nox and from 0.50 to 2

  16. Prediction of ROA and ECD Related to Conformational Changes of Astaxanthin Enantiomers.

    PubMed

    Zajac, Grzegorz; Kaczor, Agnieszka; Buda, Szymon; Młynarski, Jacek; Frelek, Jadwiga; Dobrowolski, Jan Cz; Baranska, Małgorzata

    2015-09-17

    ECD, ROA, and VCD were used to characterize astaxanthin conformers that differ in their arrangements of the β-ionone ring in respect to the chain. We obtained ECD spectra experimentally, and the ECD, ROA, and VCD spectra of both individual conformers and conformation-averaged mixtures were predicted using quantum-chemical calculations at the CAM-B3LYP level of theory using the PCM solvation model. The chiroptical methods employed (particularly ECD and ROA) were considerably more sensitive to conformational changes of astaxanthin compared to "mono-signed" conventional Raman spectroscopy. Strikingly, conformers that are the same optical isomers (e.g., of 3S,3'S-astxanthin), while geometrically nearly mirror images, exhibited sign-inversed ECD and ROA spectra. The conformational sensitivity of these chiroptical methods makes them a promising tool in the study of carotenoids in the natural environment (for instance, in de novo algal or yeast astaxanthin sources). PMID:26305416

  17. 21 CFR 73.35 - Astaxanthin.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Astaxanthin. 73.35 Section 73.35 Food and Drugs... ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.35 Astaxanthin. (a) Identity. (1) The color additive astaxanthin is 3, 3′-dihydroxy-β, β-carotene-4, 4′-dione. (2) Astaxanthin may be added to the fish feed...

  18. 21 CFR 73.35 - Astaxanthin.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Astaxanthin. 73.35 Section 73.35 Food and Drugs... ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.35 Astaxanthin. (a) Identity. (1) The color additive astaxanthin is 3, 3′-dihydroxy-β, β-carotene-4, 4′-dione. (2) Astaxanthin may be added to the fish feed...

  19. 21 CFR 73.35 - Astaxanthin.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Astaxanthin. 73.35 Section 73.35 Food and Drugs... ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.35 Astaxanthin. (a) Identity. (1) The color additive astaxanthin is 3, 3′-dihydroxy-β, β-carotene-4, 4′-dione. (2) Astaxanthin may be added to the fish feed...

  20. 21 CFR 73.35 - Astaxanthin.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Astaxanthin. 73.35 Section 73.35 Food and Drugs... ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.35 Astaxanthin. (a) Identity. (1) The color additive astaxanthin is 3, 3′-dihydroxy-β, β-carotene-4, 4′-dione. (2) Astaxanthin may be added to the fish feed...

  1. 21 CFR 73.35 - Astaxanthin.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Astaxanthin. 73.35 Section 73.35 Food and Drugs... ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.35 Astaxanthin. (a) Identity. (1) The color additive astaxanthin is 3, 3′-dihydroxy-β, β-carotene-4, 4′-dione. (2) Astaxanthin may be added to the fish feed...

  2. Fatty acids attached to all-trans-astaxanthin alter its cis-trans equilibrium, and consequently its stability, upon light-accelerated autoxidation.

    PubMed

    de Bruijn, Wouter J C; Weesepoel, Yannick; Vincken, Jean-Paul; Gruppen, Harry

    2016-03-01

    Fatty acid esterification, common in naturally occurring astaxanthin, has been suggested to influence both colour stability and degradation of all-trans-astaxanthin. Therefore, astaxanthin stability was studied as influenced by monoesterification and diesterification with palmitate. Increased esterification decelerated degradation of all-trans-astaxanthin (RP-UHPLC-PDA), whereas, it had no influence on colour loss over time (spectrophotometry). This difference might be explained by the observation that palmitate esterification influenced the cis-trans equilibrium. Free astaxanthin produced larger amounts of 9-cis isomer whereas monopalmitate esterification resulted in increased 13-cis isomerization. The molar ratios of 9-cis:13-cis after 60min were 1:1.7 (free), 1:4.8 (monopalmitate) and 1:2.6 (dipalmitate). The formation of 9-cis astaxanthin, with its higher molar extinction coefficient than that of all-trans-astaxanthin, might compensate for colour loss induced by conjugated double bond cleavage. As such, it was concluded that spectrophotometry is not an accurate measure of the degradation of the all-trans-astaxanthin molecule. PMID:26471660

  3. Chiral Drugs: An Overview

    PubMed Central

    Nguyen, Lien Ai; He, Hua; Pham-Huy, Chuong

    2006-01-01

    About more than half of the drugs currently in use are chiral compounds and near 90% of the last ones are marketed as racemates consisting of an equimolar mixture of two enantiomers. Although they have the same chemical structure, most isomers of chiral drugs exhibit marked differences in biological activities such as pharmacology, toxicology, pharmacokinetics, metabolism etc. Some mechanisms of these properties are also explained. Therefore, it is important to promote the chiral separation and analysis of racemic drugs in pharmaceutical industry as well as in clinic in order to eliminate the unwanted isomer from the preparation and to find an optimal treatment and a right therapeutic control for the patient. In this article, we review the nomenclature, pharmacology, toxicology, pharmacokinetics, metabolism etc of some usual chiral drugs as well as their mechanisms. Different techniques used for the chiral separation in pharmaceutical industry as well as in clinical analyses are also examined. PMID:23674971

  4. Potential Anti-Atherosclerotic Properties of Astaxanthin

    PubMed Central

    Kishimoto, Yoshimi; Yoshida, Hiroshi; Kondo, Kazuo

    2016-01-01

    Astaxanthin is a naturally occurring red carotenoid pigment classified as a xanthophyll, found in microalgae and seafood such as salmon, trout, and shrimp. This review focuses on astaxanthin as a bioactive compound and outlines the evidence associated with its potential role in the prevention of atherosclerosis. Astaxanthin has a unique molecular structure that is responsible for its powerful antioxidant activities by quenching singlet oxygen and scavenging free radicals. Astaxanthin has been reported to inhibit low-density lipoprotein (LDL) oxidation and to increase high-density lipoprotein (HDL)-cholesterol and adiponectin levels in clinical studies. Accumulating evidence suggests that astaxanthin could exert preventive actions against atherosclerotic cardiovascular disease (CVD) via its potential to improve oxidative stress, inflammation, lipid metabolism, and glucose metabolism. In addition to identifying mechanisms of astaxanthin bioactivity by basic research, much more epidemiological and clinical evidence linking reduced CVD risk with dietary astaxanthin intake is needed. PMID:26861359

  5. Potential Anti-Atherosclerotic Properties of Astaxanthin.

    PubMed

    Kishimoto, Yoshimi; Yoshida, Hiroshi; Kondo, Kazuo

    2016-02-01

    Astaxanthin is a naturally occurring red carotenoid pigment classified as a xanthophyll, found in microalgae and seafood such as salmon, trout, and shrimp. This review focuses on astaxanthin as a bioactive compound and outlines the evidence associated with its potential role in the prevention of atherosclerosis. Astaxanthin has a unique molecular structure that is responsible for its powerful antioxidant activities by quenching singlet oxygen and scavenging free radicals. Astaxanthin has been reported to inhibit low-density lipoprotein (LDL) oxidation and to increase high-density lipoprotein (HDL)-cholesterol and adiponectin levels in clinical studies. Accumulating evidence suggests that astaxanthin could exert preventive actions against atherosclerotic cardiovascular disease (CVD) via its potential to improve oxidative stress, inflammation, lipid metabolism, and glucose metabolism. In addition to identifying mechanisms of astaxanthin bioactivity by basic research, much more epidemiological and clinical evidence linking reduced CVD risk with dietary astaxanthin intake is needed. PMID:26861359

  6. A novel radio-tolerant astaxanthin-producing bacterium reveals a new astaxanthin derivative: astaxanthin dirhamnoside.

    PubMed

    Asker, Dalal; Awad, Tarek S; Beppu, Teruhiko; Ueda, Kenji

    2012-01-01

    Astaxanthin is a red ketocarotenoid that exhibits extraordinary health-promoting activities such as antioxidant, anti-inflammatory, antitumor, and immune booster. The recent discovery of the beneficial roles of astaxanthin against many degenerative diseases such as cancers, heart diseases, and exercise-induced fatigue has raised its market demand as a nutraceutical and medicinal ingredient in aquaculture, food, and pharmaceutical industries. To satisfy the growing demand for this high-value nutraceuticals ingredient and consumer interest in natural products, many research efforts are being made to discover novel microbial producers with effective biotechnological production of astaxanthin. Using a rapid screening method based on 16S rRNA gene, and effective HPLC-Diodearray-MS methods for carotenoids analysis, we succeeded to isolate a unique astaxanthin-producing bacterium (strain TDMA-17(T)) that belongs to the family Sphingomonadaceae (Asker et al., Appl Microbiol Biotechnol 77: 383-392, 2007). In this chapter, we provide a detailed description of effective HPLC-Diodearray-MS methods for rapid analysis and identification of the carotenoids produced by strain TDMA-17(T). We also describe the methods of isolation and identification for a novel bacterial carotenoid (astaxanthin derivative), a major carotenoid that is produced by strain TDMA-17(T). Finally, we describe the polyphasic taxonomic analysis of strain TDMA-17(T) and the description of a novel species belonging to genus Sphingomonas. PMID:22623297

  7. Interstellar isomers

    NASA Technical Reports Server (NTRS)

    Defrees, D.; Mclean, D.; Herbst, E.

    1986-01-01

    Both observational and theoretical studies of molecular clouds are hindered by many difficulties. One way to partially circumvent the difficulties of characterizing the chemistry within these objects is to study the relative abundances of isomers which are synthesized from a common set of precursors. Unfortunately, only one such system has been confirmed, the HCN/HNC pair of isomers. While the basic outlines of its chemistry have been known for some years, there are still many aspects of the chemistry which are unclear. Another potential pair of isomers is HCO+/HOC+; HCO+ is an abundant instellar molecule and a tentative identification of HOC+ has been made in Sgr B2. This identification is being challenged, however, based on theoretical and laboratory evidence that HOC+ reacts with H2. Another potential pair of interstellar isomers is methyl cyanide (CH3CN, acetonitrile) and methyl isocyanide (CH3NC). The cyanide is well known, however the isocyanide has yet to be observed despite theoretical predictions that appreciable quantities should be present.

  8. Characterization and storage stability of astaxanthin esters, fatty acid profile and α-tocopherol of lipid extract from shrimp (L. vannamei) waste with potential applications as food ingredient.

    PubMed

    Gómez-Estaca, J; Calvo, M M; Álvarez-Acero, I; Montero, P; Gómez-Guillén, M C

    2017-02-01

    In this work a lipid extract from shrimp waste was obtained and characterized. The most abundant fatty acids found were C16:0, C18:2n6c, C18:1n9c, C22:6n3, and C20:5n3. The extract contained all-trans-astaxanthin, two cis-astaxanthin isomers, 5 astaxanthin monoesters, and 10 astaxanthin diesters (7±1mg astaxanthin/g). C22:6n3 and C20:5n3 were the most frequent fatty acids in the esterified forms. Appreciable amounts of α-tocopherol and cholesterol were also found (126±11mg/g and 65±1mg/g, respectively). Little lipid oxidation was observed after 120days of storage at room temperature, revealed by a slight reduction of ω-3 fatty acids, but neither accumulation of TBARS nor formation of oxidized cholesterol forms was found. This is attributed to the antioxidant effect of astaxanthin and α-tocopherol, as their concentrations decreased as storage continued. The lipid extract obtained has interesting applications as food ingredient, owing to the coloring capacity and the presence of healthy components. PMID:27596389

  9. Astaxanthin dynamics in Baltic Sea mesozooplankton communities

    NASA Astrophysics Data System (ADS)

    Snoeijs, Pauline; Häubner, Norbert

    2014-01-01

    The red pigment astaxanthin is a powerful antioxidant, which occurs in eggs and body tissues of crustaceans and fish. It is produced by crustaceans from algal carotenoids. In a two-year field study we assessed natural concentrations and dynamics of astaxanthin in mesozooplankton communities in the brackish Baltic Sea area. Astaxanthin levels varied between 0.37 and 36 ng L- 1. They increased with salinity along the Baltic Sea gradient and were linked to zooplankton biomass and phytoplankton community composition. Astaxanthin concentrations showed typical seasonal patterns and varied from 0.2 to 5.1 ng ind- 1, 0.2 to 3.4 ng (μg C)- 1 and 6 to 100 ng mm- 3. These concentrations were inversely related to water temperature and strongly linked to zooplankton community composition. Communities dominated by the calanoid copepods Temora longicornis, Pseudocalanus acuspes and Eurytemora spp. generally held the highest concentrations. With increasing cladocerans:copepods biomass ratios community astaxanthin concentrations decreased and with higher relative biomass of Acartia spp. the proportion of astaxanthin diesters decreased. Diesters prevailed in the cold season and they are thought to improve the antioxidant protection of storage lipids during winter. Climate change causes higher temperature and lower salinity in the Baltic Sea proper. This modifies zooplankton community composition, but not necessarily into a community with lower concentrations of astaxanthin since T. longicornis (high concentrations) has been reported to increase with higher temperature. However, decreased astaxanthin production in the ecosystem is expected if a basin-wide increase in the cladocerans:copepods biomass ratios would occur with further climate change.

  10. Astaxanthin as a Potential Protector of Liver Function: A Review

    PubMed Central

    Chen, Jui-Tung; Kotani, Kazuhiko

    2016-01-01

    Protecting against liver damage, such as non-alcoholic fatty liver disease, is currently considered to be important for the prevention of adverse conditions, such as cardiovascular and cancerous diseases. Liver damage often occurs in relation to oxidative stress with metabolic disorders, including cellular lipid accumulation. Astaxanthin (3,3′-dihydroxy-β,β-carotene-4,4′dione), a xanthophyll carotenoid, is a candidate for liver protection. Here, we briefly review astaxanthin as a potential protector against liver damage. In particular, studies have reported antioxidative effects of astaxanthin in liver tissues. Astaxanthin treatment is also reported to improve hyperlipidemia, which indirectly induces the antioxidative effects of astaxanthin on liver pathologies. Furthermore, astaxanthin may alleviate liver damage independent of its antioxidative effects. Of note, there are still insufficient human data to observe the effect of astaxanthin treatment on liver function in clinical conditions. More studies investigating the relevance of astaxanthin on liver protection are necessary.

  11. Biotechnological production of astaxanthin with Phaffia rhodozyma/Xanthophyllomyces dendrorhous.

    PubMed

    Schmidt, Isabell; Schewe, Hendrik; Gassel, Sören; Jin, Chao; Buckingham, John; Hümbelin, Markus; Sandmann, Gerhard; Schrader, Jens

    2011-02-01

    The oxygenated β-carotene derivative astaxanthin exhibits outstanding colouring, antioxidative and health-promoting properties and is mainly found in the marine environment. To satisfy the growing demand for this ketocarotenoid in the feed, food and cosmetics industries, there are strong efforts to develop economically viable bioprocesses alternative to the current chemical synthesis. However, up to now, natural astaxanthin from Haematococcus pluvialis, Phaffia rhodozyma or Paracoccus carotinifaciens has not been cost competitive with chemically synthesized astaxanthin, thus only serving niche applications. This review illuminates recent advances made in elucidating astaxanthin biosynthesis in P. rhodozyma. It intensely focuses on strategies to increase astaxanthin titers in the heterobasidiomycetous yeast by genetic engineering of the astaxanthin pathway, random mutagenesis and optimization of fermentation processes. This review emphasizes the potential of P. rhodozyma for the biotechnological production of astaxanthin in comparison to other natural sources such as the microalga H. pluvialis, other fungi and transgenic plants and to chemical synthesis. PMID:21046372

  12. Excited-state dynamics of astaxanthin aggregates

    NASA Astrophysics Data System (ADS)

    Fuciman, Marcel; Durchan, Milan; Šlouf, Václav; Keşan, Gürkan; Polívka, Tomáš

    2013-05-01

    Astaxanthin forms three types of aggregates in hydrated dimethyl sulfoxide (DMSO). In DMSO/water ratio of 1:1, a red-shifted J-aggregate with maximum at 570 nm is generated, while a ratio of 1:9 produces blue-shifted H-aggregates with peaks at 386 nm (H1) and 460 nm (H2). Monomeric astaxanthin in DMSO has an S1 lifetime of 5.3 ps, but a long-lived (33 ps) S∗ signal was also identified. Aggregation changes the S1 lifetimes to 17 ps (H1), 30 ps (H2), and 14 ps (J). Triplet state of astaxanthin, most likely generated via singlet homofission, was observed in H1 and H2 aggregates.

  13. High-harmonic spectroscopy of molecular isomers

    SciTech Connect

    Wong, M. C. H.; Brichta, J.-P.; Bhardwaj, V. R.; Spanner, M.; Patchkovskii, S.

    2011-11-15

    We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greater than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).

  14. Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin.

    PubMed

    Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

    2016-01-01

    Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health. PMID:26784174

  15. Recovery of astaxanthin from seafood wastewater utilizing fish scales waste.

    PubMed

    Stepnowski, P; Olafsson, G; Helgason, H; Jastorff, B

    2004-01-01

    The paper presents basic data on astaxanthin adsorption from fisheries wastewater to fish scales. This process has been proposed to be applicable in fisheries and shrimp waste management [Helgason, Recovery of compounds using a natural adsorbent, Patent WO 01/77230, 2001]. The innovative feature of the method is the application of a solid waste (fish scales) as a natural adsorbent for a carotenoid pigment (astaxanthin) from the seafood industry wastewater. The model investigations were performed with pure synthetic carotenoids to exclude the role of matrix in which astaxanthin is present in the wastewater. Under the experimental conditions used, the maximum loading capacity of astaxanthin onto the scales is 360 mg kg(-1) dry wt. Studies of the thus formed value added product indicated that drying causes significant loss of astaxanthin activity. Due to the effective filtration characteristics of the studied sorption material, we suggest the scale/astaxanthin sorption process to be suitable for treatment of wastewater from different industries. PMID:14575754

  16. Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin

    PubMed Central

    Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

    2016-01-01

    Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health. PMID:26784174

  17. Astaxanthin binding protein in Atlantic salmon.

    PubMed

    Matthews, Sarah J; Ross, Neil W; Lall, Santosh P; Gill, Tom A

    2006-06-01

    The rubicund pigmentation in salmon and trout flesh is unique and is due to the deposition of dietary carotenoids, astaxanthin and canthaxanthin in the muscle. The present study was undertaken to determine which protein was responsible for pigment binding. Salmon muscle proteins were solubilized by sequential extractions with non-denaturing, low ionic strength aqueous solutions and segregated as such into six different fractions. Approximately 91% of the salmon myofibrillar proteins were solubilized under non-denaturing conditions using a protocol modified from a method described by Krishnamurthy et al. [Krishnamurthy, G., Chang, H.S., Hultin, H.O., Feng, Y., Srinivasan, S., Kelleher. S.D., 1996. Solubility of chicken breast muscle proteins in solutions of low ionic strength. J. Agric. Food Chem. 44: 408-415.] for the dissolution of avian muscle. To our knowledge, this is the first time this solubilization approach has been applied to the study of molecular interactions in myofibrillar proteins. Astaxanthin binding in each fraction was determined using an in vitro binding assay. In addition, SDS-PAGE and quantitative densitometry were used to separate and determine the relative amounts of each of the proteins in the six fractions. The results showed that alpha-actinin was the only myofibrillar protein correlating significantly (P<0.05) with astaxanthin binding. Alpha-actinin was positively identified using electrophoretic techniques and confirmed by tandem mass spectroscopy. Purified salmon alpha-actinin bound synthetic astaxanthin in a molar ratio of 1.11:1.00. The study was repeated using halibut alpha-actinin, which was found to have a molar binding ratio of astaxanthin to alpha-actinin of 0.893:1. These results suggest that the difference in pigmentation between white fish and Atlantic salmon is not due to binding capacity in the muscle, but rather differences in the metabolism or transport of pigment. PMID:16644255

  18. Xanthophyllomyces dendrorhous for the industrial production of astaxanthin.

    PubMed

    Rodríguez-Sáiz, Marta; de la Fuente, Juan Luis; Barredo, José Luis

    2010-10-01

    Astaxanthin is a red xanthophyll (oxygenated carotenoid) with large importance in the aquaculture, pharmaceutical, and food industries. The green alga Haematococcus pluvialis and the heterobasidiomycetous yeast Xanthophyllomyces dendrorhous are currently known as the main microorganisms useful for astaxanthin production at the industrial scale. The improvement of astaxanthin titer by microbial fermentation is a requirement to be competitive with the synthetic manufacture by chemical procedures, which at present is the major source in the market. In this review, we show how the isolation of new strains of X. dendrorhous from the environment, the selection of mutants by the classical methods of random mutation and screening, and the rational metabolic engineering, have provided improved strains with higher astaxanthin productivity. To reduce production costs and enhance competitiveness from an industrial point of view, low-cost raw materials from industrial and agricultural origin have been adopted to get the maximal astaxanthin productivity. Finally, fermentation parameters have been studied in depth, both at flask and fermenter scales, to get maximal astaxanthin titers of 4.7 mg/g dry cell matter (420 mg/l) when X. dendrorhous was fermented under continuous white light. The industrial scale-up of this biotechnological process will provide a cost-effective method, alternative to synthetic astaxanthin, for the commercial exploitation of the expensive astaxanthin (about $2,500 per kilogram of pure astaxanthin). PMID:20711573

  19. Chiral Graphene Quantum Dots.

    PubMed

    Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; Qu, Zhi-Bei; Kim, Kyoungwon; Jiang, Shuang; Baumeister, Elizabeth; Lee, Jaewook; Yeom, Bongjun; Bahng, Joong Hwan; Lee, Jaebeom; Violi, Angela; Kotov, Nicholas A

    2016-02-23

    Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the "crowded" edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210-220 and 250-265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210-220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250-265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to L/D-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than L-GQDs. Emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials. PMID:26743467

  20. Atroposelective Synthesis of Axially Chiral Thiohydantoin Derivatives.

    PubMed

    Sarigul, Sevgi; Dogan, Ilknur

    2016-07-15

    Nonracemic axially chiral thiohydantoins were synthesized atroposelectively by the reaction of o-aryl isothiocyanates with amino acid ester salts in the presence of triethylamine (TEA). The synthesis of the nonaxially chiral derivatives, however, gave thiohydantoins racemized at C-5 of the heterocyclic ring. The micropreparatively resolved enantiomers of the nonaxially chiral derivatives from the racemic products were found to be optically stable under neutral conditions. On formation of the 5-methyl-3-arylthiohydantoin ring, bulky o-aryl substituents at N3 were found to suppress the C-5 racemization and in this way enabled the transfer of chirality from the α-amino acid to the products. The corresponding 5-isopropylthiohydantoins turned out to be more prone to racemization at C-5 during the ring formation. The isomer compositions of the synthesized axially chiral thiohydantoins have been determined through HPLC analyses with chiral stationary phases. In most cases a high prevalence of the P isomers over the M isomers has been obtained. The barriers to rotation determined around the Nsp(2)-Caryl chiral axis were found to be dependent upon the size of the o-halo aryl substituents. PMID:27322739

  1. Influence of astaxanthin, emulsifier and organic phase concentration on physicochemical properties of astaxanthin nanodispersions

    PubMed Central

    2013-01-01

    Background The emulsification-evaporation method was used to prepare astaxanthin nanodispersions using a three-component emulsifier system composed of Tween 20, sodium caseinate and gum Arabic. Using Response-surface methodology (RSM), we studied the main and interaction effects of the major emulsion components, namely, astaxanthin concentration (0.02–0.38 wt %, x1), emulsifier concentration (0.2–3.8 wt %, x2) and organic phase (dichloromethane) concentration (2–38 wt %, x3) on nanodispersion characteristics. The physicochemical properties considered as response variables were: average particle size (Y1), PDI (Y2) and astaxanthin loss (Y3). Results The results indicated that the response-surface models were significantly (p < 0.05) fitted for all studied response variables. The fitted polynomial regression models for the prediction of variations in the response variables showed high coefficients of determination (R2 > 0.930) for all responses. The overall optimum region resulted in a desirable astaxanthin nanodispersions obtained with the concentrations of 0.08 wt % astaxanthin, 2.5 wt % emulsifier and 11.5 wt % organic phase. Conclusion No significant differences were found between the experimental and predicted values, thus certifying the adequacy of the Response-surface models developed for describing the changes in physicochemical properties as a function of main emulsion component concentrations. PMID:23875816

  2. Nonlinear optics of astaxanthin thin films

    NASA Astrophysics Data System (ADS)

    Esser, A.; Fisch, Herbert; Haas, Karl-Heinz; Haedicke, E.; Paust, J.; Schrof, Wolfgang; Ticktin, Anton

    1993-02-01

    Carotinoids exhibit large nonlinear optical properties due to their extended (pi) -electron system. Compared to other polyenes which show a broad distribution of conjugation lengths, carotinoids exhibit a well defined molecular structure, i.e. a well defined conjugation length. Therefore the carotinoid molecules can serve as model compounds to study the relationship between structure and nonlinear optical properties. In this paper the synthesis of four astaxanthins with C-numbers ranging from 30 to 60, their preparation into thin films, wavelength dispersive Third Harmonic Generation (THG) measurements and some molecular modelling calculations will be presented. Resonant (chi) (3) values reach 1.2(DOT)10-10 esu for C60 astaxanthin. In the nonresonant regime a figure of merit (chi) (3)/(alpha) of several 10-13 esu-cm is demonstrated.

  3. Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

    NASA Astrophysics Data System (ADS)

    Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

    2010-12-01

    We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

  4. Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

    NASA Astrophysics Data System (ADS)

    Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

    2011-08-01

    We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

  5. Asymmetric Synthesis of Overcrowded Alkenes by Transfer of Axial Single Bond Chirality to Axial Double Bond Chirality.

    PubMed

    Geertsema; Meetsma; Feringa

    1999-09-01

    Optically active overcrowded alkenes were synthesized by employing bis-beta-naphthol as a chiral template during an intramolecular coupling reaction. The major isomer 2 has a unique helical structure with twisted and folded structural moieties. Removal of the chiral template afforded overcrowded thioxanthylidene 3 with 96 % ee, which indicates that no racemization or isomerization of the enantiomers took place. PMID:10508366

  6. Stability and changes in astaxanthin ester composition from Haematococcus pluvialis during storage

    NASA Astrophysics Data System (ADS)

    Miao, Fengping; Geng, Yahong; Lu, Dayan; Zuo, Jincheng; Li, Yeguang

    2013-11-01

    In this paper, we investigated the effects of temperature, oxygen, antioxidants, and corn germ oil on the stability of astaxanthin from Haematococcus pluvialis under different storage conditions, and changes in the composition of astaxanthin esters during storage using high performance liquid chromatography and spectrophotometry. Oxygen and high temperatures (22-25°C) significantly reduced the stability of astaxanthin esters. Corn germ oil and antioxidants (ascorbic acid and vitamin E) failed to protect astaxanthin from oxidation, and actually significantly increased the instability of astaxanthin. A change in the relative composition of astaxanthin esters was observed after 96 weeks of long-term storage. During storage, the relative amounts of free astaxanthin and astaxanthin monoesters declined, while the relative amount of astaxanthin diesters increased. Thus, the ratio of astaxanthin diester to monoester increased, and this ratio could be used to indicate if astaxanthin esters have been properly preserved. If the ratio is greater than 0.2, it suggests that the decrease in astaxanthin content could be higher than 20%. Our results show that storing algal powder from H. pluvialis or other natural astaxanthin products under vacuum and in the dark below 4°C is the most economical and applicable storage method for the large-scale production of astaxanthin from H. pluvialis. This storage method can produce an astaxanthin preservation rate of at least 80% after 96 weeks of storage.

  7. Astaxanthin blocks preeclampsia progression by suppressing oxidative stress and inflammation.

    PubMed

    Xuan, Rong-Rong; Niu, Ting-Ting; Chen, Hai-Min

    2016-09-01

    To investigate the antioxidative effect of astaxanthin on Nω-nitro-L-arginine methyl ester (L-NAME)-induced preeclamptic rats. Cell survival, the level of reactive oxygen species (ROS) and the changes in mitochondrial membrane potential (MMP) were examined in astaxanthin and H2O2-treated human umbilical vein endothelial cells (HUVECs). The preeclamptic Sprague-Dawley (SD) rat model was established by injection of L‑NAME and treatment with astaxanthin. The activities of malondialdehyde (MDA), superoxide dismutase (SOD) and nitric oxide synthase (NOS) in serum were analyzed. Pathological changes were examined by hematoxylin and eosin (H&E) staining. The expression of nuclear factor (NF)‑κB, Rho‑associated protein kinase II (ROCK II), heme oxygenase‑1 (HO‑1) and caspase 3 in preeclamptic placentas were examined by immunohistochemistry. Astaxanthin significantly reduced H2O2‑induced HUVEC cell death, decreased ROS and increased MMP. Astaxanthin significantly reduced blood pressure and the content of MDA, but significantly increased the activity of SOD in preeclamptic rats. The urinary protein and the level of NO and NOS were also decreased. H&E staining revealed that the thickness of the basilar membrane was increased, while the content of trophoblast cells and spiral arteries were reduced following astaxanthin treatment. Immunohistochemistry results showed that the expression of NF‑κB, ROCK II and caspase 3 in preeclamptic placentas was significantly decreased after astaxanthin treatment, while HO‑1 expression was increased. In conclusion, astaxanthin inhibited H2O2‑induced oxidative stress in HUVECs. Astaxanthin treatment significantly improved L‑NAME‑induced preeclamptic symptoms and reduced the oxidative stress and inflammatory damages in preeclamptic placentas. Astaxanthin treatment may effectively prevent and treat preeclampsia. PMID:27484589

  8. Power optimization in logic isomers

    NASA Technical Reports Server (NTRS)

    Panwar, Ramesh; Rennels, David; Alkalaj, Leon

    1993-01-01

    Logic isomers are labeled, 2-isomorphic graphs that implement the same logic function. Logic isomers may have significantly different power requirements even though they have the same number of transistors in the implementation. The power requirements of the isomers depend on the transition activity of the input signals. The power requirements of isomorphic graph isomers of n-input NAND and NOR gates are shown. Choosing the less power-consuming isomer instead of the others can yield significant power savings. Experimental results on a ripple-carry adder are presented to show that the implementation using the least power-consuming isomers requires approximately 10 percent less power than the implementation using the most power-consuming isomers. Simulations of other random logic designs also confirm that designs using less power-consuming isomers can reduce the logic power demand by approximately 10 percent as compared to designs using more power-consuming isomers.

  9. Astaxanthin: A Potential Therapeutic Agent in Cardiovascular Disease

    PubMed Central

    Fassett, Robert G.; Coombes, Jeff S.

    2011-01-01

    Astaxanthin is a xanthophyll carotenoid present in microalgae, fungi, complex plants, seafood, flamingos and quail. It is an antioxidant with anti-inflammatory properties and as such has potential as a therapeutic agent in atherosclerotic cardiovascular disease. Synthetic forms of astaxanthin have been manufactured. The safety, bioavailability and effects of astaxanthin on oxidative stress and inflammation that have relevance to the pathophysiology of atherosclerotic cardiovascular disease, have been assessed in a small number of clinical studies. No adverse events have been reported and there is evidence of a reduction in biomarkers of oxidative stress and inflammation with astaxanthin administration. Experimental studies in several species using an ischaemia-reperfusion myocardial model demonstrated that astaxanthin protects the myocardium when administered both orally or intravenously prior to the induction of the ischaemic event. At this stage we do not know whether astaxanthin is of benefit when administered after a cardiovascular event and no clinical cardiovascular studies in humans have been completed and/or reported. Cardiovascular clinical trials are warranted based on the physicochemical and antioxidant properties, the safety profile and preliminary experimental cardiovascular studies of astaxanthin. PMID:21556169

  10. Accurate quantification of astaxanthin from Haematococcus crude extract spectrophotometrically

    NASA Astrophysics Data System (ADS)

    Li, Yeguang; Miao, Fengping; Geng, Yahong; Lu, Dayan; Zhang, Chengwu; Zeng, Mingtao

    2012-07-01

    The influence of alkali on astaxanthin and the optimal working wave length for measurement of astaxanthin from Haematococcus crude extract were investigated, and a spectrophotometric method for precise quantification of the astaxanthin based on the method of Boussiba et al. was established. According to Boussiba's method, alkali treatment destroys chlorophyll. However, we found that: 1) carotenoid content declined for about 25% in Haematococcus fresh cysts and up to 30% in dry powder of Haematococcus broken cysts after alkali treatment; and 2) dimethyl sulfoxide (DMSO)-extracted chlorophyll of green Haematococcus bares little absorption at 520-550 nm. Interestingly, a good linear relationship existed between absorbance at 530 nm and astaxanthin content, while an unknown interference at 540-550 nm was detected in our study. Therefore, with 530 nm as working wavelength, the alkali treatment to destroy chlorophyll was not necessary and the influence of chlorophyll, other carotenoids, and the unknown interference could be avoided. The astaxanthin contents of two samples were measured at 492 nm and 530 nm; the measured values at 530 nm were 2.617 g/100 g and 1.811 g/100 g. When compared with the measured values at 492 nm, the measured values at 530 nm decreased by 6.93% and 11.96%, respectively. The measured values at 530 nm are closer to the true astaxanthin contents in the samples. The data show that 530 nm is the most suitable wave length for spectrophotometric determination to the astaxanthin in Haematococcus crude extract.

  11. Atlas of Nuclear Isomers

    NASA Astrophysics Data System (ADS)

    Jain, Ashok Kumar; Maheshwari, Bhoomika; Garg, Swati; Patial, Monika; Singh, Balraj

    2015-09-01

    We present an atlas of nuclear isomers containing the experimental data for the isomers with a half-life ≥ 10 ns together with their various properties such as excitation-energy, half-life, decay mode(s), spin-parity, energies and multipolarities of emitted gamma transitions, etc. The ENSDF database complemented by the XUNDL database has been extensively used in extracting the relevant data. Recent literature from primary nuclear physics journals, and the NSR bibliographic database have been searched to ensure that the compiled data Table is as complete and current as possible. The data from NUBASE-12 have also been checked for completeness, but as far as possible original references have been cited. Many interesting systematic features of nuclear isomers emerge, some of them new; these are discussed and presented in various graphs and figures. The cutoff date for the extraction of data from the literature is August 15, 2015.

  12. Atlas of Nuclear Isomers

    SciTech Connect

    Jain, Ashok Kumar; Maheshwari, Bhoomika; Garg, Swati; Patial, Monika; Singh, Balraj

    2015-09-15

    We present an atlas of nuclear isomers containing the experimental data for the isomers with a half-life ≥ 10 ns together with their various properties such as excitation-energy, half-life, decay mode(s), spin-parity, energies and multipolarities of emitted gamma transitions, etc. The ENSDF database complemented by the XUNDL database has been extensively used in extracting the relevant data. Recent literature from primary nuclear physics journals, and the NSR bibliographic database have been searched to ensure that the compiled data Table is as complete and current as possible. The data from NUBASE-12 have also been checked for completeness, but as far as possible original references have been cited. Many interesting systematic features of nuclear isomers emerge, some of them new; these are discussed and presented in various graphs and figures. The cutoff date for the extraction of data from the literature is August 15, 2015.

  13. Structure investigations on assembled astaxanthin molecules

    NASA Astrophysics Data System (ADS)

    Köpsel, Christian; Möltgen, Holger; Schuch, Horst; Auweter, Helmut; Kleinermanns, Karl; Martin, Hans-Dieter; Bettermann, Hans

    2005-08-01

    The carotenoid r,r-astaxanthin (3R,3‧R-dihydroxy-4,4‧-diketo-β-carotene) forms different types of aggregates in acetone-water mixtures. H-type aggregates were found in mixtures with a high part of water (e.g. 1:9 acetone-water mixture) whereas two different types of J-aggregates were identified in mixtures with a lower part of water (3:7 acetone-water mixture). These aggregates were characterized by recording UV/vis-absorption spectra, CD-spectra and fluorescence emissions. The sizes of the molecular assemblies were determined by dynamic light scattering experiments. The hydrodynamic diameter of the assemblies amounts 40 nm in 1:9 acetone-water mixtures and exceeds up to 1 μm in 3:7 acetone-water mixtures. Scanning tunneling microscopy monitored astaxanthin aggregates on graphite surfaces. The structure of the H-aggregate was obtained by molecular modeling calculations. The structure was confirmed by calculating the electronic absorption spectrum and the CD-spectrum where the molecular modeling structure was used as input.

  14. Multispectral Imaging for Determination of Astaxanthin Concentration in Salmonids

    PubMed Central

    Dissing, Bjørn S.; Nielsen, Michael E.; Ersbøll, Bjarne K.; Frosch, Stina

    2011-01-01

    Multispectral imaging has been evaluated for characterization of the concentration of a specific cartenoid pigment; astaxanthin. 59 fillets of rainbow trout, Oncorhynchus mykiss, were filleted and imaged using a rapid multispectral imaging device for quantitative analysis. The multispectral imaging device captures reflection properties in 19 distinct wavelength bands, prior to determination of the true concentration of astaxanthin. The samples ranged from 0.20 to 4.34 g per g fish. A PLSR model was calibrated to predict astaxanthin concentration from novel images, and showed good results with a RMSEP of 0.27. For comparison a similar model were built for normal color images, which yielded a RMSEP of 0.45. The acquisition speed of the multispectral imaging system and the accuracy of the PLSR model obtained suggest this method as a promising technique for rapid in-line estimation of astaxanthin concentration in rainbow trout fillets. PMID:21573000

  15. Astaxanthin as a Potential Neuroprotective Agent for Neurological Diseases.

    PubMed

    Wu, Haijian; Niu, Huanjiang; Shao, Anwen; Wu, Cheng; Dixon, Brandon J; Zhang, Jianmin; Yang, Shuxu; Wang, Yirong

    2015-09-01

    Neurological diseases, which consist of acute injuries and chronic neurodegeneration, are the leading causes of human death and disability. However, the pathophysiology of these diseases have not been fully elucidated, and effective treatments are still lacking. Astaxanthin, a member of the xanthophyll group, is a red-orange carotenoid with unique cell membrane actions and diverse biological activities. More importantly, there is evidence demonstrating that astaxanthin confers neuroprotective effects in experimental models of acute injuries, chronic neurodegenerative disorders, and neurological diseases. The beneficial effects of astaxanthin are linked to its oxidative, anti-inflammatory, and anti-apoptotic characteristics. In this review, we will focus on the neuroprotective properties of astaxanthin and explore the underlying mechanisms in the setting of neurological diseases. PMID:26378548

  16. Astaxanthin as a Potential Neuroprotective Agent for Neurological Diseases

    PubMed Central

    Wu, Haijian; Niu, Huanjiang; Shao, Anwen; Wu, Cheng; Dixon, Brandon J.; Zhang, Jianmin; Yang, Shuxu; Wang, Yirong

    2015-01-01

    Neurological diseases, which consist of acute injuries and chronic neurodegeneration, are the leading causes of human death and disability. However, the pathophysiology of these diseases have not been fully elucidated, and effective treatments are still lacking. Astaxanthin, a member of the xanthophyll group, is a red-orange carotenoid with unique cell membrane actions and diverse biological activities. More importantly, there is evidence demonstrating that astaxanthin confers neuroprotective effects in experimental models of acute injuries, chronic neurodegenerative disorders, and neurological diseases. The beneficial effects of astaxanthin are linked to its oxidative, anti-inflammatory, and anti-apoptotic characteristics. In this review, we will focus on the neuroprotective properties of astaxanthin and explore the underlying mechanisms in the setting of neurological diseases. PMID:26378548

  17. Evaluation of hepatoprotective and antioxidant activity of astaxanthin and astaxanthin esters from microalga-Haematococcus pluvialis.

    PubMed

    Rao, A Ranga; Sarada, R; Shylaja, M D; Ravishankar, G A

    2015-10-01

    Effect of isolated astaxanthin (ASX) and astaxanthin esters (ASXEs) from green microalga-Haematococcus pluvialis on hepatotoxicity and antioxidant activity against carbon tetrachloride (CCl4) induced toxicity in rats was compared with synthetic astaxanthin (SASX). ASX, ASXEs, and SASX, all dissolved in olive oil, fed to rats with 100 and 250 μg/kg b.w for 14 days. They were evaluated for their hepatoprotective and antioxidant activity by measuring appropriate enzymes. Among the treated groups, the SGPT, SGOT and ALP levels were decreased by 2, 2.4, and 1.5 fold in ASXEs treated group at 250 μg/Kg b.w. when compared to toxin group. Further, antioxidant enzymes catalase, glutathione, superoxide dismutase and lipid peroxidase levels were estimated in treated groups, their levels were reduced by 30-50 % in the toxin group, however these levels restored by 136.95 and 238.48 % in ASXEs treated group at 250 μg/kg. The lipid peroxidation was restored by 5.2 and 2.8 fold in ASXEs and ASX treated groups at 250 μg/kg. The total protein, albumin and bilirubin contents were decreased in toxin group, whereas normalized in ASXEs treated group. These results indicates that ASX and ASXEs have better hepatoprotection and antioxidant activity, therefore can be used in pharmaceutical and nutraceutical applications and also extended to use as food colorant. PMID:26396419

  18. Astaxanthin intake attenuates muscle atrophy caused by immobilization in rats.

    PubMed

    Shibaguchi, Tsubasa; Yamaguchi, Yusuke; Miyaji, Nobuyuki; Yoshihara, Toshinori; Naito, Hisashi; Goto, Katsumasa; Ohmori, Daijiro; Yoshioka, Toshitada; Sugiura, Takao

    2016-08-01

    Astaxanthin is a carotenoid pigment and has been shown to be an effective inhibitor of oxidative damage. We tested the hypothesis that astaxanthin intake would attenuate immobilization-induced muscle atrophy in rats. Male Wistar rats (14-week old) were fed for 24 days with either astaxanthin or placebo diet. After 14 days of each experimental diet intake, the hindlimb muscles of one leg were immobilized in plantar flexion position using a plaster cast. Following 10 days of immobilization, both the atrophic and the contralateral plantaris muscles were removed and analyzed to determine the level of muscle atrophy along with measurement of the protein levels of CuZn-superoxide dismutase (CuZn-SOD) and selected proteases. Compared with placebo diet animals, the degree of muscle atrophy in response to immobilization was significantly reduced in astaxanthin diet animals. Further, astaxanthin supplementation significantly prevented the immobilization-induced increase in the expression of CuZn-SOD, cathepsin L, calpain, and ubiquitin in the atrophied muscle. These results support the postulate that dietary astaxanthin intake attenuates the rate of disuse muscle atrophy by inhibiting oxidative stress and proteolysis via three major proteolytic pathways. PMID:27482075

  19. Chiral squaring

    NASA Astrophysics Data System (ADS)

    Nagy, S.

    2016-07-01

    We construct the states and symmetries of N = 4 super-Yang-Mills by tensoring two N = 1 chiral multiplets and introducing two extra SUSY generators. This allows us to write the maximal N = 8 supergravity as four copies of the chiral multiplet. We extend this to higher dimensions and discuss applications to scattering amplitudes.

  20. Chiral superconductors.

    PubMed

    Kallin, Catherine; Berlinsky, John

    2016-05-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed. PMID:27088452

  1. Chiral superconductors

    NASA Astrophysics Data System (ADS)

    Kallin, Catherine; Berlinsky, John

    2016-05-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

  2. Complete Hexose Isomer Identification with Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nagy, Gabe; Pohl, Nicola L. B.

    2015-04-01

    The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.

  3. Chiral plasmonic nanostructures on achiral nanopillars.

    PubMed

    Yeom, Bongjun; Zhang, Huanan; Zhang, Hui; Park, Jai Il; Kim, Kyoungwon; Govorov, Alexander O; Kotov, Nicholas A

    2013-11-13

    Chirality of plasmonic films can be strongly enhanced by three-dimensional (3D) out-of-plane geometries. The complexity of lithographic methods currently used to produce such structures and other methods utilizing chiral templates impose limitations on spectral windows of chiroptical effects, the size of substrates, and hence, further research on chiral plasmonics. Here we demonstrate 3D chiral plasmonic nanostructures (CPNs) with high optical activity in the visible spectral range based on initially achiral nanopillars from ZnO. We made asymmetric gold nanoshells on the nanopillars by vacuum evaporation at different inclination and rotation angles to achieve controlled symmetry breaking and obtained both left- and right-rotating isomers. The attribution of chiral optical effects to monolithic enantiomers made in this process was confirmed by theoretical calculations based on their geometry established from scanning electron microscope (SEM) images. The chirality of the nanoshells is retained upon the release from the substrate into a stable dispersion. Deviation of the incident angle of light from normal results in increase of polarization rotation and chiral g-factor as high as -0.3. This general approach for preparation of abiological nanoscale chiral materials can be extended to other out-of plane 3D nanostructures. The large area films made on achiral nanopillars are convenient for sensors, optical devices, and catalysis. PMID:24111695

  4. Electronic circular dichroism behavior of chiral Phthiobuzone

    PubMed Central

    Li, Li; Wang, Lin; Si, Yikang

    2014-01-01

    Phthiobuzone is a bis(thiosemicarbazone) derivative with a single chiral center which has been used as a racemate in the clinical treatment of herpes and trachoma diseases. In this study, its two enantiomers were prepared from chiral amino acids and their absolute configurations were investigated by electronic circular dichroism (ECD) combined with modern quantum-chemical calculations using time-dependent density functional theory. It was found that solvation changed both the conformational distribution and the ECD spectrum of each conformer. The theoretical ECD spectra of the two enantiomers were in good agreement with the experimentally determined spectra of the corresponding isomers in dimethyl sulfoxide. The ECD behavior of the bis(thiosemicarbazone) chromophore in a chiral environment is also discussed. Our results indicate that ECD spectroscopy may be a useful tool for the stereochemical evaluation of chiral drugs. PMID:26579380

  5. H-bond-driven supramolecular architectures of the syn and anti isomers of the dioxime of bicyclo[3.3.1]nonane-3,7-dione.

    PubMed

    Toşa, Nicoleta; Bende, Attila; Varga, Richard Attila; Terec, Anamaria; Bratu, Ioan; Grosu, Ion

    2009-05-15

    The formation and high stability of the H-bond-driven supramolecular architectures of the syn and anti isomers of the dioxime of bicyclo[3.3.1]nonane-3,7-dione were investigated by single crystal X-ray diffraction, NMR, FTIR, and molecular modeling. Self-assembly of the achiral syn isomer into a cyclic trimer (supramolecular wheel) and of the chiral anti isomer into homochiral cyclic dimers was observed. PMID:19371097

  6. Preparation of astaxanthin nanodispersions using gelatin-based stabilizer systems.

    PubMed

    Anarjan, Navideh; Nehdi, Imededdine Arbi; Sbihi, Hassen Mohamed; Al-Resayes, Saud Ibrahim; Malmiri, Hoda Jafarizadeh; Tan, Chin Ping

    2014-01-01

    The incorporation of lipophilic nutrients, such as astaxanthin (a fat soluble carotenoid) in nanodispersion systems can either increase the water solubility, stability and bioavailability or widen their applications in aqueous food and pharmaceutical formulations. In this research, gelatin and its combinations with sucrose oleate as a small molecular emulsifier, sodium caseinate (SC) as a protein and gum Arabic as a polysaccharide were used as stabilizer systems in the formation of astaxanthin nanodispersions via an emulsification-evaporation process. The results indicated that the addition of SC to gelatin in the stabilizer system could increase the chemical stability of astaxanthin nanodispersions significantly, while using a mixture of gelatin and sucrose oleate as a stabilizer led to production of nanodispersions with the smallest particle size (121.4±8.6 nm). It was also shown that a combination of gelatin and gum Arabic could produce optimal astaxanthin nanodispersions in terms of physical stability (minimum polydispersity index (PDI) and maximum zeta-potential). This study demonstrated that the mixture of surface active compounds showed higher emulsifying and stabilizing functionality compared to using them individually in the preparation of astaxanthin nanodispersions. PMID:25211006

  7. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  8. Molecular mechanisms of the coordination between astaxanthin and fatty acid biosynthesis in Haematococcus pluvialis (Chlorophyceae).

    PubMed

    Chen, Guanqun; Wang, Baobei; Han, Danxiang; Sommerfeld, Milton; Lu, Yinghua; Chen, Feng; Hu, Qiang

    2015-01-01

    Astaxanthin, a red ketocarotenoid with strong antioxidant activity and high commercial value, possesses important physiological functions in astaxanthin-producing microalgae. The green microalga Haematococcus pluvialis accumulates up to 4% fatty acid-esterified astaxanthin (by dry weight), and is used as a model species for exploring astaxanthin biosynthesis in unicellular photosynthetic organisms. Although coordination of astaxanthin and fatty acid biosynthesis in a stoichiometric fashion was observed in H. pluvialis, the interaction mechanism is unclear. Here we dissected the molecular mechanism underlying coordination between the two pathways in H. pluvialis. Our results eliminated possible coordination of this inter-dependence at the transcriptional level, and showed that this interaction was feedback-coordinated at the metabolite level. In vivo and in vitro experiments indicated that astaxanthin esterification drove the formation and accumulation of astaxanthin. We further showed that both free astaxanthin biosynthesis and esterification occurred in the endoplasmic reticulum, and that certain diacylglycerol acyltransferases may be the candidate enzymes catalyzing astaxanthin esterification. A model of astaxanthin biosynthesis in H. pluvialis was subsequently proposed. These findings provide further insights into astaxanthin biosynthesis in H. pluvialis. PMID:25353310

  9. Screening factors influencing the production of astaxanthin from freshwater and marine microalgae.

    PubMed

    Binti Ibnu Rasid, Elda Nurafnie; Mohamad, Shaza Eva; Jamaluddin, Haryati; Salleh, Madihah Md

    2014-02-01

    Astaxanthin, a carotenoid pigment found in several aquatic organisms, is responsible for the red colour of salmon, trout and crustaceans. In this study, astaxanthin production from freshwater microalga Chlorella sorokiniana and marine microalga Tetraselmis sp. was investigated. Cell growth and astaxanthin production were determined spectrophotometrically at 620 and 480 nm, respectively. Astaxanthin was extracted using acetone and measured subsequent to biomass removal. Aerated conditions favoured astaxanthin production in C. sorokiniana, whereas Tetraselmis sp. was best cultured under unaerated conditions. C. sorokiniana produced more astaxanthin with the highest yield reached at 7.83 mg/l in 6.0 mM in nitrate containing medium compared to Tetraselmis sp. which recorded the highest yield of only 1.96 mg/l in 1.5 mM nitrate containing medium. Production in C. sorokiniana started at the early exponential phase, indicating that astaxanthin may be a growth-associated product in this microalga. Further optimization of astaxanthin production was performed using C. sorokiniana through a 2(3) full factorial experimental design, and a yield of 8.39 mg/l was achieved. Overall, the study has shown that both microalgae are capable of producing astaxanthin. Additionally, this research has highlighted C. sorokiniana as a potential astaxanthin producer that could serve as a natural astaxanthin source in the current market. PMID:24338298

  10. Using One's Hands for Naming Optical Isomers and Other Stereochemical Positions.

    ERIC Educational Resources Information Center

    Mezl, Vasek A.

    1996-01-01

    Presents a method that allows students to use their hands to obtain the stereochemistry of chiral centers without redrawing the structure. Discusses the use of the model in: determining the configurations of amino acids, determining if sugars are D or L isomers, the sequence rule procedure, prochirality, naming the sides of trigonal carbons, and…

  11. Improving the Stability of Astaxanthin by Microencapsulation in Calcium Alginate Beads

    PubMed Central

    Lin, Shen-Fu; Chen, Ying-Chen; Chen, Ray-Neng; Chen, Ling-Chun; Ho, Hsiu-O; Tsung, Yu-Han; Sheu, Ming-Thau; Liu, Der-Zen

    2016-01-01

    There has been considerable interest in the biological functions of astaxanthin and its potential applications in the nutraceutical, cosmetics, food, and feed industries in recent years. However, the unstable structure of astaxanthin considerably limits its application. Therefore, this study reports the encapsulation of astaxanthin in calcium alginate beads using the extrusion method to improve its stability. This study also evaluates the stability of the encapsulated astaxanthin under different storage conditions. The evaluation of astaxanthin stability under various environmental factors reveals that temperature is the most influential environmental factor in astaxanthin degradation. Stability analysis shows that, regardless of the formulation used, the content of astaxanthin encapsulated in alginate beads remains above 90% of the original amount after 21 days of storage at 25°C. These results suggest that the proposed technique is a promising way to enhance the stability of other sensitive compounds. PMID:27093175

  12. The effective photoinduction of Haematococcus pluvialis for accumulating astaxanthin with attached cultivation.

    PubMed

    Wan, Minxi; Hou, Dongmei; Li, Yuanguang; Fan, Jianhua; Huang, Jianke; Liang, Songtao; Wang, Weiliang; Pan, Ronghua; Wang, Jun; Li, Shulan

    2014-07-01

    As the optimal source of astaxanthin, Haematococcus pluvialis was cultured for commercial production of astaxanthin through two continuous phases: cell growth and astaxanthin induction. In this study, the efficiency of an attached system for producing astaxanthin from H. pluvialis was investigated and compared to that of the suspended system (bubble column bioreactor) under various conditions. Results showed that this attached system is more suitable for photoinduction of H. pluvialis than the suspended bioreactor. Under the optimal conditions, the astaxanthin productivity of the attached system was 65.8 mg m(-2)d(-1) and 2.4-fold of that in the suspended system. This attached approach also offers other advantages over suspended systems, such as, producing astaxanthin under a wide range of light intensities and temperatures, saving water, ease to harvest cells, resisting contamination. Therefore, the attached approach can be considered an economical, environmentally friendly and highly-efficient technology for producing astaxanthin from H. pluvialis. PMID:24787315

  13. Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Mori, Keiji; Itakura, Tsubasa; Akiyama, Takahiko

    2016-09-12

    Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o-tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method. PMID:27491630

  14. Metabolic engineering of astaxanthin production in tobacco flowers.

    PubMed

    Mann, V; Harker, M; Pecker, I; Hirschberg, J

    2000-08-01

    Using metabolic engineering, we have modified the carotenoid biosynthesis pathway in tobacco (Nicotiana tabacum) to produce astaxanthin, a red pigment of considerable economic value. To alter the carotenoid pathway in chromoplasts of higher plants, the cDNA of the gene CrtO from the alga Haematococcus pluvialis, encoding beta-carotene ketolase, was transferred to tobacco under the regulation of the tomato Pds (phytoene desaturase) promoter. The transit peptide of PDS from tomato was used to target the CRTO polypeptide to the plastids. Chromoplasts in the nectary tissue of transgenic plants accumulated (3S,3'S) astaxanthin and other ketocarotenoids, changing the color of the nectary from yellow to red. This accomplishment demonstrates that plants can be used as a source of novel carotenoid pigments such as astaxanthin. The procedures described in this work can serve as a platform technology for future genetic manipulations of pigmentation of fruits and flowers of horticultural and floricultural importance. PMID:10932161

  15. Attached cultivation of Haematococcus pluvialis for astaxanthin production.

    PubMed

    Zhang, Wenduo; Wang, Junfeng; Wang, Jialin; Liu, Tianzhong

    2014-04-01

    Haematococcus pluvialis, the best natural source for astaxanthin, was cultivated with an immobilized biofilm method, viz. "attached cultivation", which was high in photosynthetic efficiency. A practical operational protocol for this "attached cultivation" method was investigated by studying the effects of inoculum density, light intensity, nitrogen quantity as well as medium volume on growth and astaxanthin accumulation. Results indicated the optimized inoculum density and light intensity were 10 g m(-2) and 100 μmol m(-2)s(-1), respectively. The optimized nitrogen supply strategy was circulating ca. 30 L of BG-11 medium with initial sodium nitrate concentration of ca. 1.8mM for 1m(2) of cultivation surface. With this strategy, the maximum astaxanthin productivity reached ca. 160 mg m(-2)d(-1) which is much higher than many other indoor researches. Both of the red and green cells were found in the biofilm with red cells on the top. PMID:24632411

  16. Effect of Astaxanthin on Human Sperm Capacitation

    PubMed Central

    Donà, Gabriella; Kožuh, Ivana; Brunati, Anna Maria; Andrisani, Alessandra; Ambrosini, Guido; Bonanni, Guglielmo; Ragazzi, Eugenio; Armanini, Decio; Clari, Giulio; Bordin, Luciana

    2013-01-01

    In order to be able to fertilize oocytes, human sperm must undergo a series of morphological and structural alterations, known as capacitation. It has been shown that the production of endogenous sperm reactive oxygen species (ROS) plays a key role in causing cells to undergo a massive acrosome reaction (AR). Astaxanthin (Asta), a photo-protective red pigment belonging to the carotenoid family, is recognized as having anti-oxidant, anti-cancer, anti-diabetic and anti-inflammatory properties and is present in many dietary supplements. This study evaluates the effect of Asta in a capacitating buffer which induces low ROS production and low percentages of acrosome-reacted cells (ARC). Sperm cells were incubated in the presence or absence of increasing concentrations of Asta or diamide (Diam) and analyzed for their ROS production, Tyr-phosphorylation (Tyr-P) pattern and percentages of ARC and non-viable cells (NVC). Results show that Asta ameliorated both sperm head Tyr-P and ARC values without affecting the ROS generation curve, whereas Diam succeeded in enhancing the Tyr-P level but only of the flagellum without increasing ARC values. It is suggested that Asta can be inserted in the membrane and therefore create capacitation-like membrane alteration which allow Tyr-P of the head. Once this has occurred, AR can take place and involves a higher numbers of cells. PMID:23736766

  17. Effect of astaxanthin on human sperm capacitation.

    PubMed

    Donà, Gabriella; Kožuh, Ivana; Brunati, Anna Maria; Andrisani, Alessandra; Ambrosini, Guido; Bonanni, Guglielmo; Ragazzi, Eugenio; Armanini, Decio; Clari, Giulio; Bordin, Luciana

    2013-06-01

    In order to be able to fertilize oocytes, human sperm must undergo a series of morphological and structural alterations, known as capacitation. It has been shown that the production of endogenous sperm reactive oxygen species (ROS) plays a key role in causing cells to undergo a massive acrosome reaction (AR). Astaxanthin (Asta), a photo-protective red pigment belonging to the carotenoid family, is recognized as having anti-oxidant, anti-cancer, anti-diabetic and anti-inflammatory properties and is present in many dietary supplements. This study evaluates the effect of Asta in a capacitating buffer which induces low ROS production and low percentages of acrosome-reacted cells (ARC). Sperm cells were incubated in the presence or absence of increasing concentrations of Asta or diamide (Diam) and analyzed for their ROS production, Tyr-phosphorylation (Tyr-P) pattern and percentages of ARC and non-viable cells (NVC). Results show that Asta ameliorated both sperm head Tyr-P and ARC values without affecting the ROS generation curve, whereas Diam succeeded in enhancing the Tyr-P level but only of the flagellum without increasing ARC values. It is suggested that Asta can be inserted in the membrane and therefore create capacitation-like membrane alteration which allow Tyr-P of the head. Once this has occurred, AR can take place and involves a higher numbers of cells. PMID:23736766

  18. Enantioselective separation of defined endocrine-disrupting nonylphenol isomers.

    PubMed

    Acir, Ismail-Hakki; Wüst, Matthias; Guenther, Klaus

    2016-08-01

    Nonylphenol is in the focus of worldwide endocrine-disrupter research and accounted for as a priority hazardous substance of the Water Framework Directive of the European Union. Technical nonylphenol consists of a very complex mixture of isomers and enantiomers. As estrogenic effect and degradation behavior in environmental processes of single nonylphenols are heavily dependent on the structure of the nonyl side chain, it is absolutely necessary to consider the nonylphenol problem from an isomer and enantiomer-specific viewpoint. In this study, an enantiomer-specific separation of eight defined synthesized nonylphenol isomers by five different special chiral cyclodextrin columns was performed underivatized and after methylation, silylation, and acylation. This work demonstrates that three columns out of the investigated five show an excellent separation behavior for the studied different nonylphenol isomers and can be used for the enantiomer-specific determination of nonylphenols in food, other biological matrices, and environmental samples in the future. Graphical abstract Enantiomeric pair of 4-NP170 (4-[1-ethyl-1,3,3-trimethylbutyl]phenol). PMID:27236316

  19. Chemical stability of astaxanthin nanodispersions in orange juice and skimmed milk as model food systems.

    PubMed

    Anarjan, Navideh; Tan, Chin Ping

    2013-08-15

    Solubilising astaxanthin in nanodispersion systems is a promising approach to incorporate astaxanthin into water-based food formulations. In this research, the chemical stabilities of astaxanthin nanodispersions diluted in orange juice and skimmed milk as model food systems and in deionised water as a control were evaluated. The nanodispersions displayed significantly (p<0.05) better stability in food systems compared to the control. The effects of stabilisers and dilution factor were also studied. In skimmed milk and deionised water, the type of stabiliser had a significant effect (p<0.05) on astaxanthin degradation during storage. In vitro cellular uptake of astaxanthin from diluted astaxanthin nanodispersions in selected food systems was also evaluated. The cellular uptake of astaxanthin nanodispersions in skimmed milk was significantly higher (p<0.05) than that of astaxanthin nanodispersions in orange juice and deionised water. High in vitro cellular uptake of astaxanthin from the prepared astaxanthin nanodispersions can be achieved via incorporation into protein-based foods such as milk. PMID:23561141

  20. Astaxanthin: Sources, Extraction, Stability, Biological Activities and Its Commercial Applications—A Review

    PubMed Central

    Ambati, Ranga Rao; Siew Moi, Phang; Ravi, Sarada; Aswathanarayana, Ravishankar Gokare

    2014-01-01

    There is currently much interest in biological active compounds derived from natural resources, especially compounds that can efficiently act on molecular targets, which are involved in various diseases. Astaxanthin (3,3′-dihydroxy-β, β′-carotene-4,4′-dione) is a xanthophyll carotenoid, contained in Haematococcus pluvialis, Chlorella zofingiensis, Chlorococcum, and Phaffia rhodozyma. It accumulates up to 3.8% on the dry weight basis in H. pluvialis. Our recent published data on astaxanthin extraction, analysis, stability studies, and its biological activities results were added to this review paper. Based on our results and current literature, astaxanthin showed potential biological activity in in vitro and in vivo models. These studies emphasize the influence of astaxanthin and its beneficial effects on the metabolism in animals and humans. Bioavailability of astaxanthin in animals was enhanced after feeding Haematococcus biomass as a source of astaxanthin. Astaxanthin, used as a nutritional supplement, antioxidant and anticancer agent, prevents diabetes, cardiovascular diseases, and neurodegenerative disorders, and also stimulates immunization. Astaxanthin products are used for commercial applications in the dosage forms as tablets, capsules, syrups, oils, soft gels, creams, biomass and granulated powders. Astaxanthin patent applications are available in food, feed and nutraceutical applications. The current review provides up-to-date information on astaxanthin sources, extraction, analysis, stability, biological activities, health benefits and special attention paid to its commercial applications. PMID:24402174

  1. The role of photorespiration during astaxanthin accumulation in Haematococcus pluvialis (Chlorophyceae).

    PubMed

    Zhang, Chunhui; Zhang, Litao; Liu, Jianguo

    2016-10-01

    Most previous studies on Haematococcus pluvialis have been focused on growth and astaxanthin accumulation. However, the relationships between photorespiration and astaxanthin accumulation have not been clarified. The purpose of this study was to examine the role of photorespiration during the process of astaxanthin accumulation in H. pluvialis. During astaxanthin accumulation, the astaxanthin content was reduced significantly when photorespiration was inhibited by its specific inhibitor, carboxymethoxylamine. The inhibition of photorespiration did not change the dry weight, chlorophyll content and OJIP transients during the incubation; however, the inhibition of photorespiration significantly decreased the photochemistry of photosystem II and total photosynthetic O2 evolution capacity. Moreover, the restriction in photorespiration was synchronized with a decrease of astaxanthin accumulation. These results suggest that the photorespiratory pathway in H. pluvialis can accelerate astaxanthin accumulation. We speculate that photorespiration can enhance astaxanthin accumulation in the following ways: (i) photorespiration directly affects the glycerate-3-phosphate (PGA) level, which is intrinsically related to the accumulation of astaxanthin in H. pluvialis; (ii) the photorespiratory pathway indirectly affects the PGA level by effecting the dark reactions of photosynthesis, which then results in the enhancement of astaxanthin accumulation in H. pluvialis. PMID:27258571

  2. Astaxanthin: sources, extraction, stability, biological activities and its commercial applications--a review.

    PubMed

    Ambati, Ranga Rao; Phang, Siew Moi; Ravi, Sarada; Aswathanarayana, Ravishankar Gokare

    2014-01-01

    There is currently much interest in biological active compounds derived from natural resources, especially compounds that can efficiently act on molecular targets, which are involved in various diseases. Astaxanthin (3,3'-dihydroxy-β, β'-carotene-4,4'-dione) is a xanthophyll carotenoid, contained in Haematococcus pluvialis, Chlorella zofingiensis, Chlorococcum, and Phaffia rhodozyma. It accumulates up to 3.8% on the dry weight basis in H. pluvialis. Our recent published data on astaxanthin extraction, analysis, stability studies, and its biological activities results were added to this review paper. Based on our results and current literature, astaxanthin showed potential biological activity in in vitro and in vivo models. These studies emphasize the influence of astaxanthin and its beneficial effects on the metabolism in animals and humans. Bioavailability of astaxanthin in animals was enhanced after feeding Haematococcus biomass as a source of astaxanthin. Astaxanthin, used as a nutritional supplement, antioxidant and anticancer agent, prevents diabetes, cardiovascular diseases, and neurodegenerative disorders, and also stimulates immunization. Astaxanthin products are used for commercial applications in the dosage forms as tablets, capsules, syrups, oils, soft gels, creams, biomass and granulated powders. Astaxanthin patent applications are available in food, feed and nutraceutical applications. The current review provides up-to-date information on astaxanthin sources, extraction, analysis, stability, biological activities, health benefits and special attention paid to its commercial applications. PMID:24402174

  3. Punctuated Chirality

    NASA Astrophysics Data System (ADS)

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life’s homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  4. Punctuated chirality.

    PubMed

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average. PMID:18841492

  5. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

    Bringing closer phospholipids each other on a bilayer of liposome, causes their rotation around their fatty acids axis, generating a force which brings closer the two sheets of the bilayer. In this theoretical study I show that for getting the greater cohesion of the liposome, by these forces, the serine in the hydrophilic head must have a L chirality. In the case where the hydrophilic head is absent amino acids with L chirality could contribute to this cohesion by taking the place of L-serine. Some coenzymes having a configuration similar to ethanolamine may also contribute. This is the case of pyridoxamine, thiamine and tetrahydrofolic acid. The grouping of amino acids of L chirality and pyridoxamine on the wall could initialize the prebiotic metabolism of these L amino acids only. This would explain the origin of the homo-chirality of amino acids in living world. Furthermore I show that in the hydrophilic head, the esterification of glycerol-phosphate by two fatty acids go through the positioning of dihydroxyacetone-phosphate and L-glyceraldehyde-3-phosphate, but not of D-glyceraldehyde-3-phosphate, prior their hydrogenation to glycerol-3- phosphate. The accumulation of D-glyceraldehyde-3-phosphate in the cytoplasm displace the thermodynamic equilibria towards the synthesis of D-dATP from D-glyceraldehyde-3-phosphate, acetaldehyde and prebiotic adenine, a reaction which does not require a coenzyme in the biotic metabolism. D-dATP and thiamine, more prebiotic metabolism of L-amino acids on the wall, would initialize D-pentoses phosphate and D-nucleotides pathways from the reaction of D-glyceraldehyde-3-phosphate + dihydroxyacetone-phosphate + prebiotic nucleic bases. The exhaustion of the prebiotic glyceraldehyde (racemic) and the nascent biotic metabolism dominated by D-glyceraldehyde-3-phosphate, would explain the origin of homo-chirality of sugars in living world. References: http://en.wikiversity.org/wiki/Prebiotic_chirality

  6. Electromagnetic propulsion and separation by chirality of nanoparticles in liquids.

    PubMed

    Kirkinis, E; Andreev, A V; Spivak, B

    2012-01-01

    We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope. PMID:22400671

  7. Electromagnetic propulsion and separation by chirality of nanoparticles in liquids

    NASA Astrophysics Data System (ADS)

    Kirkinis, E.; Andreev, A. V.; Spivak, B.

    2012-01-01

    We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope.

  8. The astaxanthin dideoxyglycoside biosynthesis pathway in Sphingomonas sp. PB304.

    PubMed

    Kim, Se Hyeuk; Kim, Jin Ho; Lee, Bun Yeol; Lee, Pyung Cheon

    2014-12-01

    A major carotenoid in Sphingomonas sp. PB304, originally isolated from a river in Daejon City, South Korea, was identified as astaxanthin dideoxyglycoside. Gene clusters encoding the astaxanthin dideoxyglycoside biosynthetic enzymes were identified by screening Sphingomonas sp. PB304 fosmid libraries using degenerate probes that harbor highly conserved sequences from the Sphigomonas elodea-derived crtI and Nostoc sp. PCC 7120-dervied crtW genes. Selected positive gene clusters were fully sequenced and annotated, revealing genes encoding six putative carotenogenic enzymes: phytoene synthase (CrtB), phytoene desaturase (CrtI), lycopene cyclase (CrtY), carotene hydroxylase (CrtZ), carotene ketolase (CrtW), and glycosyltransferase (CrtX). All of the carotenogenic enzymes, except for CrtX, were functional in the recombinant host Escherichia coli expressing synthetic carotenogenic modules from Pantoea agglomerans. CrtX did not take up UDP-glucose or GDP-fucose as sugar substrates during the in vitro reaction. Although no direct experimental evidence was obtained for the function of Sphingomonas sp. PB304 CrtX, it can be categorized as a putative deoxyglycosyltransferase based on the presence of astaxanthin dideoxyglycoside in Sphingomonas sp. PB304, a putative corresponding gene in the carotenoid biosynthetic gene cluster, and high amino acid sequence homology to the existing glycosyltransferases. Therefore, we propose that astaxanthin dideoxyglycoside can be synthesized in Sphingomonas sp. PB304 via sequential reactions of six pathway enzymes, including CrtX on the phytoene intermediate. PMID:25193422

  9. Kinetic model for astaxanthin aggregation in water-methanol mixtures

    NASA Astrophysics Data System (ADS)

    Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo

    2009-07-01

    The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

  10. A new paradigm for producing astaxanthin from the unicellular green alga Haematococcus pluvialis.

    PubMed

    Zhang, Zhen; Wang, Baobei; Hu, Qiang; Sommerfeld, Milton; Li, Yuanguang; Han, Danxiang

    2016-10-01

    The unicellular green alga Haematococcus pluvialis has been exploited as a cell factory to produce the high-value antioxidant astaxanthin for over two decades, due to its superior ability to synthesize astaxanthin under adverse culture conditions. However, slow vegetative growth under favorable culture conditions and cell deterioration or death under stress conditions (e.g., high light, nitrogen starvation) has limited the astaxanthin production. In this study, a new paradigm that integrated heterotrophic cultivation, acclimation of heterotrophically grown cells to specific light/nutrient regimes, followed by induction of astaxanthin accumulation under photoautotrophic conditions was developed. First, the environmental conditions such as pH, carbon source, nitrogen regime, and light intensity, were optimized to induce astaxanthin accumulation in the dark-grown cells. Although moderate astaxanthin content (e.g., 1% of dry weight) and astaxanthin productivity (2.5 mg L(-1)  day(-1) ) were obtained under the optimized conditions, a considerable number of cells died off when subjected to stress for astaxanthin induction. To minimize the susceptibility of dark-grown cells to light stress, the algal cells were acclimated, prior to light induction of astaxanthin biosynthesis, under moderate illumination in the presence of nitrogen. Introduction of this strategy significantly reduced the cell mortality rate under high-light and resulted in increased cellular astaxanthin content and astaxanthin productivity. The productivity of astaxanthin was further improved to 10.5 mg L(-1)  day(-1) by implementation of such a strategy in a bubbling column photobioreactor. Biochemical and physiological analyses suggested that rebuilding of photosynthetic apparatus including D1 protein and PsbO, and recovery of PSII activities, are essential for acclimation of dark-grown cells under photo-induction conditions. Biotechnol. Bioeng. 2016;113: 2088-2099. © 2016 The Authors

  11. Enhancement of astaxanthin production using Haematococcus pluvialis with novel LED wavelength shift strategy.

    PubMed

    Xi, Tianqi; Kim, Dae Geun; Roh, Seong Woon; Choi, Jong-Soon; Choi, Yoon-E

    2016-07-01

    Haematococcus pluvialis is a green microalga of particular interest, since it is considered the best potential natural source of astaxanthin, which is widely used as an additive for natural pigmentation. In addition, astaxanthin has recently garnered commercial interest as a nutraceutical, cosmetic, and pharmaceutical. However, producing astaxanthin from H. pluvialis necessitates separation with distinctive culture conditions, dividing between the microalgae growth and the astaxanthin production stages. Light-emitting diodes (LEDs) have emerged as a replacement for traditional light sources, and LED applications are now rapidly expanding to multiple areas in fields such as biotechnology. However, further detail application into microalgae biotechnology remains limited. In this study, we have attempted to establish new protocols based on the specific wavelength of LEDs for the cultivation and production of astaxanthin using H. pluvialis. Specifically, we applied red LEDs for microalgae cell growth and then switched to blue LEDs to induce astaxanthin biosynthesis. The result showed that astaxanthin productions based on a wavelength shift from red to blue were significantly increased, compared to those with continuous illumination using red LEDs. Furthermore, additional increase of astaxanthin production was achieved with simultaneous application of exogenous carbon with blue LED illumination. Our approach based on the proper manipulation of LED wavelengths upon H. pluvialis cell stages will enable the improvement of biomass and enhance astaxanthin production using H. pluvialis. PMID:26860938

  12. Chiral streamers

    SciTech Connect

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya

    2015-10-15

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  13. Chiral streamers

    NASA Astrophysics Data System (ADS)

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya Ken

    2015-10-01

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  14. Genome mining of astaxanthin biosynthetic genes from Sphingomonas sp. ATCC 55669 for heterologous overproduction in Escherichia coli.

    PubMed

    Ma, Tian; Zhou, Yuanjie; Li, Xiaowei; Zhu, Fayin; Cheng, Yongbo; Liu, Yi; Deng, Zixin; Liu, Tiangang

    2016-02-01

    As a highly valued keto-carotenoid, astaxanthin is widely used in nutritional supplements and pharmaceuticals. Therefore, the demand for biosynthetic astaxanthin and improved efficiency of astaxanthin biosynthesis has driven the investigation of metabolic engineering of native astaxanthin producers and heterologous hosts. However, microbial resources for astaxanthin are limited. In this study, we found that the α-Proteobacterium Sphingomonas sp. ATCC 55669 could produce astaxanthin naturally. We used whole-genome sequencing to identify the astaxanthin biosynthetic pathway using a combined PacBio-Illumina approach. The putative astaxanthin biosynthetic pathway in Sphingomonas sp. ATCC 55669 was predicted. For further confirmation, a high-efficiency targeted engineering carotenoid synthesis platform was constructed in E. coli for identifying the functional roles of candidate genes. All genes involved in astaxanthin biosynthesis showed discrete distributions on the chromosome. Moreover, the overexpression of exogenous E. coli idi in Sphingomonas sp. ATCC 55669 increased astaxanthin production by 5.4-fold. This study described a new astaxanthin producer and provided more biosynthesis components for bioengineering of astaxanthin in the future. PMID:26580858

  15. Quantification of astaxanthin in shrimp waste hydrolysate by HPLC.

    PubMed

    López-Cervantes, J; Sánchez-Machado, D I; Gutiérrez-Coronado, M A; Ríos-Vázquez, N J

    2006-10-01

    In the present study, a simple and rapid reversed-phase HPLC method for the determination of astaxanthin in shrimp waste hydrolysate has been developed and validated. The analytical procedure involves the direct extraction of astaxanthin from the lipid fraction with methanol. The analytical column, SS Exil ODS, was operated at 25C. The mobile phase consisted of a mixture of water:methanol:dichloromethane:acetonitrile (4.5:28:22:45.5 v/v/v/v) at a flow rate of 1.0 mL/min. Detection and identification were performed using a photodiode array detector (lambda(detection) = 476 nm). The proposed HPLC method showed adequate linearity, repeatability and accuracy. PMID:16802328

  16. Metabolic engineering of astaxanthin biosynthesis in maize endosperm and characterization of a prototype high oil hybrid.

    PubMed

    Farré, Gemma; Perez-Fons, Laura; Decourcelle, Mathilde; Breitenbach, Jürgen; Hem, Sonia; Zhu, Changfu; Capell, Teresa; Christou, Paul; Fraser, Paul D; Sandmann, Gerhard

    2016-08-01

    Maize was genetically engineered for the biosynthesis of the high value carotenoid astaxanthin in the kernel endosperm. Introduction of a β-carotene hydroxylase and a β-carotene ketolase into a white maize genetic background extended the carotenoid pathway to astaxanthin. Simultaneously, phytoene synthase, the controlling enzyme of carotenogenesis, was over-expressed for enhanced carotenoid production and lycopene ε-cyclase was knocked-down to direct more precursors into the β-branch of the extended ketocarotenoid pathway which ends with astaxanthin. This astaxanthin-accumulating transgenic line was crossed into a high oil- maize genotype in order to increase the storage capacity for lipophilic astaxanthin. The high oil astaxanthin hybrid was compared to its astaxanthin producing parent. We report an in depth metabolomic and proteomic analysis which revealed major up- or down- regulation of genes involved in primary metabolism. Specifically, amino acid biosynthesis and the citric acid cycle which compete with the synthesis or utilization of pyruvate and glyceraldehyde 3-phosphate, the precursors for carotenogenesis, were down-regulated. Nevertheless, principal component analysis demonstrated that this compositional change is within the range of the two wild type parents used to generate the high oil producing astaxanthin hybrid. PMID:26931320

  17. Astaxanthin stimulates cell-mediated and humoral immune responses in cats.

    PubMed

    Park, Jean Soon; Mathison, Bridget D; Hayek, Michael G; Massimino, Stefan; Reinhart, Gregory A; Chew, Boon P

    2011-12-15

    Astaxanthin is a potent antioxidant carotenoid and may play a role in modulating immune response in cats. Blood was taken from female domestic shorthair cats (8-9 mo old; 3.2 ± 0.04 kg body weight) fed 0, 1, 5 or 10mg astaxanthin daily for 12 wk to assess peripheral blood mononuclear cell (PBMC) proliferation response, leukocyte subpopulations, natural killer (NK) cell cytotoxic activity, and plasma IgG and IgM concentration. Cutaneous delayed-type hypersensitivity (DTH) response against concanavalin A and an attenuated polyvalent vaccine was assessed on wk 8 (prior to vaccination) and 12 (post-vaccination). There was a dose-related increase in plasma astaxanthin concentrations, with maximum concentrations observed on wk 12. Dietary astaxanthin enhanced DTH response to both the specific (vaccine) and nonspecific (concanavalin A) antigens. In addition, cats fed astaxanthin had heightened PBMC proliferation and NK cell cytotoxic activity. The population of CD3(+) total T and CD4(+) T helper cells were also higher in astaxanthin-fed cats; however, no treatment difference was found with the CD8(+) T cytotoxic and MHC II(+) activated lymphocyte cell populations. Dietary astaxanthin increased concentrations of plasma IgG and IgM. Therefore, dietary astaxanthin heightened cell-mediated and humoral immune responses in cats. PMID:21930306

  18. Astaxanthin Inhibits Proliferation of Human Gastric Cancer Cell Lines by Interrupting Cell Cycle Progression

    PubMed Central

    Kim, Jung Ha; Park, Jong-Jae; Lee, Beom Jae; Joo, Moon Kyung; Chun, Hoon Jai; Lee, Sang Woo; Bak, Young-Tae

    2016-01-01

    Background/Aims Astaxanthin is a carotenoid pigment that has antioxidant, antitumoral, and anti-inflammatory properties. In this in vitro study, we investigated the mechanism of anticancer effects of astaxanthin in gastric carcinoma cell lines. Methods The human gastric adenocarcinoma cell lines AGS, KATO-III, MKN-45, and SNU-1 were treated with various concentrations of astaxanthin. A cell viability test, cell cycle analysis, and immunoblotting were performed. Results The viability of each cancer cell line was suppressed by astaxanthin in a dose-dependent manner with significantly decreased proliferation in KATO-III and SNU-1 cells. Astaxanthin increased the number of cells in the G0/G1 phase but reduced the proportion of S phase KATO-III and SNU-1 cells. Phosphorylated extracellular signal-regulated kinase (ERK) was decreased in an inverse dose-dependent correlation with astaxanthin concentration, and the expression of p27kip-1 increased the KATO-III and SNU-1 cell lines in an astaxanthin dose-dependent manner. Conclusions Astaxanthin inhibits proliferation by interrupting cell cycle progression in KATO-III and SNU-1 gastric cancer cells. This may be caused by the inhibition of the phosphorylation of ERK and the enhanced expression of p27kip-1. PMID:26470770

  19. [Characterization and evaluation of an astaxanthin over-producing Phaffia rhodozyma].

    PubMed

    Ni, Hui; Hong, Qinglin; Xiao, Anfeng; Li, Lijun; Cai, Huinong; Su, Wenjin

    2011-07-01

    We evaluated an astaxanthin overproducing Phaffia rhodozyma JMU-MVP14, and developed astaxanthin high-yielding fermentation process. We analyzed several fermentation parameters, i.e., biomass, astaxanthin and total carotenoids content to compare the characteristics of P rhodozyma JMU-MVP14 and the original strain through flask fermentation experiments. We conducted batch and fed-batch fermentation experiments in 7 L fermentor to investigate the effects of pH controlling models and feeding medium compositions on the production of astaxanthin. We further evaluated the capability and practical value of P rhodozyma JMU-MVP14 by fed-batch cultivation in the 1 m3 fermentor. Flask fermentation experiments revealed that P. rhodozyma JMU-MVP14 produced high yield of astaxanthin and carotenoids with specific productivity of astaxanthin and specific productivity of total carotenoids of 6.01 mg/g and 10.38 mg/g. Results of batch culture experiments in the 7 L fermentor showed that controlling the pH by ammonia auto-feeding was better than discontinuously adjusting pH value at 6.0 with regard to the high productivities of biomasses and astaxanthin. This P. rhodozyma strain synthesized astaxanthin partially linked to the growth with the Ks and pmax of 0.20 h ' and 21.73 g/L, respectively. Results of batch-fed fermentations in 7 L fermentor indicated that the complex feeding medium consisted of 50% glucose, 0.5% yeast extract and 0.3% corn steep syrup had lower astaxanthin productivity than the simple feeding medium containing only 50% glucose, which produced biomass, volumetric productivity of astaxanthin, volumetric productivity of total carotenoids, specific productivity of astaxanthin and total carotenoids at 32.81 g/L, 155.99 mg/L, 4.94 mg/g, 399.99 mg/L and 12.19 mg/g, respectively. As fed-batch cultured in 1 m3 fermentor, P rhodozyma JMU-MVP14 yielded 85.11 g/L of biomass, 279.96 mg/L of volumetric productivity of astaxanthin, 618.01 mg/L of volumetric productivity of

  20. Nuclear isomers: stepping stones to the unknown

    SciTech Connect

    Walker, P. M.

    2006-03-13

    The utility of isomers for exploring the nuclear landscape is discussed, including their role in superheavy-element research, and the possibility of observing neutron radioactivity. Emphasis is given to K isomers in deformed nuclei. Transition rates are examined in the NpNn scheme for 2- and 3-quasiparticle K-isomer decays, and in connection with level densities for higher quasiparticle numbers.

  1. Aggregation-Induced Resonance Raman Optical Activity (AIRROA): A New Mechanism for Chirality Enhancement.

    PubMed

    Zajac, Grzegorz; Kaczor, Agnieszka; Pallares Zazo, Ana; Mlynarski, Jacek; Dudek, Monika; Baranska, Malgorzata

    2016-05-01

    Raman optical activity (ROA) spectroscopy is hampered by low sensitivity, with limited possibilities for enhancing the signal. In the present study, we report a new mechanism whereby chirality is enhanced using the resonance resulting from supramolecular aggregation. We have named this mechanism aggregation-induced resonance Raman optical activity (AIRROA). As an example, we study J-aggregates of astaxanthin (AXT), which show strong absorption of circularly polarized light in the range of ROA excitation. The implications of aggregation-induced signal enhancement for chiroptical spectroscopy are discussed. PMID:27057926

  2. Chiral mirrors

    SciTech Connect

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

    Mirrors are used in telescopes, microscopes, photo cameras, lasers, satellite dishes, and everywhere else, where redirection of electromagnetic radiation is required making them arguably the most important optical component. While conventional isotropic mirrors will reflect linear polarizations without change, the handedness of circularly polarized waves is reversed upon reflection. Here, we demonstrate a type of mirror reflecting one circular polarization without changing its handedness, while absorbing the other. The polarization-preserving mirror consists of a planar metasurface with a subwavelength pattern that cannot be superimposed with its mirror image without being lifted out of its plane, and a conventional mirror spaced by a fraction of the wavelength from the metasurface. Such mirrors enable circularly polarized lasers and Fabry-Pérot cavities with enhanced tunability, gyroscopic applications, polarization-sensitive detectors of electromagnetic waves, and can be used to enhance spectroscopies of chiral media.

  3. Chiral Hexahalogenated 4,4'-Bipyridines.

    PubMed

    Mamane, V; Peluso, P; Aubert, E; Cossu, S; Pale, P

    2016-06-01

    The preparation of 27 isomers of chiral hexahalogeno-4,4'-bipyridines by means of two complementary methods is described. The first one is convergent and based on the LDA-induced 4,4'-dimerization of trihalopyridines, whereas the second method is divergent and achieved through regioselective halogenation reactions of 4,4'-bipyridine-2,2'-diones. Iodine in 2,2'-positions of the 4,4'-bipyridines was introduced by a copper-catalyzed Finkelstein reaction (Buchwald procedure) performed on 2,2'-dibromo derivatives. Selected compounds of this new family of atropisomeric 4,4'-bipyridines were enantioseparated by high performance liquid chromatography on chiral stationary phases, and the absolute configurations of the separated enantiomers were assigned by using X-ray diffraction analysis. The latter revealed that various halogen bond types are responsible for crystal cohesion. PMID:27149320

  4. Inhibition of inflammation by astaxanthin alleviates cognition deficits in diabetic mice.

    PubMed

    Zhou, Xiaoyan; Zhang, Fang; Hu, Xiaotong; Chen, Jing; Wen, Xiangru; Sun, Ying; Liu, Yonghai; Tang, Renxian; Zheng, Kuiyang; Song, Yuanjian

    2015-11-01

    Neurons in the hippocampal and cortical functional regions are more susceptible to damage induced by hyperglycemia, which can result in severe spatial learning and memory impairment. Neuroprotection ameliorates cognitive impairment induced by hyperglycemia in diabetic encephalopathy (DE). Astaxanthin has been widely studied in diabetes mellitus and diabetic complications due to its hypoglycemic, antioxidant and anti-apoptotic effects. However, whether astaxanthin can alleviate cognition deficits induced by DE and its precise mechanisms remain undetermined. In this study, DE was induced by streptozotocin (STZ, 150 mg/kg) in ICR mice. We observed the effect of astaxanthin on cognition and investigated its potential mechanisms in DE mice. Results showed that astaxanthin treatment significantly decreased the latency and enhanced the distance and time spent in the target quadrant in the Morris water maze test. Furthermore, neuronal survival was significantly increased in the hippocampal CA3 region and the frontal cortex following treatment with astaxanthin. Meanwhile, immunoblotting was used to observe the nuclear translocation of nuclear factor-kappaB (NF-κB) p65 and the expression of tumor necrosis factor-α (TNF-α) in the hippocampus and frontal cortex. The results indicated that astaxanthin could inhibit NF-κB nuclear translocation and downregulate TNF-α expression in the hippocampus and frontal cortex. Overall, the present study implied that astaxanthin could improve cognition by protecting neurons against inflammation injury potentially through inhibiting the nuclear translocation of NF-κB and down-regulating TNF-α. PMID:26272354

  5. Assessment and comparison of in vitro immunoregulatory activity of three astaxanthin stereoisomers

    NASA Astrophysics Data System (ADS)

    Sun, Weihong; Xing, Lihong; Lin, Hong; Leng, Kailiang; Zhai, Yuxiu; Liu, Xiaofang

    2016-04-01

    In recent years, the immune-modulatory role of all- trans astaxanthin from different pigment sources has been studied. It was reported that all- trans astaxanthin might exist as three stereoisomers, and the composition of all- trans stereoisomers in natural materials differs from that of synthetic products. However, the different biological effects of various all- trans stereoisomers still remain unclear. In the present study, we evaluated the bioactivity of three astaxanthin stereoisomers, ( 3S, 3'S)- trans-, ( 3R,3'R)- trans-and meso-trans-astaxanthin, in regulating cell-mediated immune response using mice lymphocytes and peritoneal exudates cells (PECs) systems. After the treatment with three astaxanthin stereoisomers (20 μmol L-1), the lymphocyte proliferation capacity, neutral red phagocytosis of PECs and natural killer (NK) cell cytotoxic activity were comparatively assessed. The results showed that all three astaxanthin stereoisomers significantly promoted lymphocyte proliferation, phagocytic capacity of PECs, and cytotoxic activity of NK cells. Moreover, the ( 3S,3'S)-trans-astaxanthin exhibited a much higher response than others.

  6. Chlorella zofingiensis as an Alternative Microalgal Producer of Astaxanthin: Biology and Industrial Potential

    PubMed Central

    Liu, Jin; Sun, Zheng; Gerken, Henri; Liu, Zheng; Jiang, Yue; Chen, Feng

    2014-01-01

    Astaxanthin (3,3′-dihydroxy-β,β-carotene-4,4′-dione), a high-value ketocarotenoid with a broad range of applications in food, feed, nutraceutical, and pharmaceutical industries, has been gaining great attention from science and the public in recent years. The green microalgae Haematococcus pluvialis and Chlorella zofingiensis represent the most promising producers of natural astaxanthin. Although H. pluvialis possesses the highest intracellular astaxanthin content and is now believed to be a good producer of astaxanthin, it has intrinsic shortcomings such as slow growth rate, low biomass yield, and a high light requirement. In contrast, C. zofingiensis grows fast phototrophically, heterotrophically and mixtrophically, is easy to be cultured and scaled up both indoors and outdoors, and can achieve ultrahigh cell densities. These robust biotechnological traits provide C. zofingiensis with high potential to be a better organism than H. pluvialis for mass astaxanthin production. This review aims to provide an overview of the biology and industrial potential of C. zofingiensis as an alternative astaxanthin producer. The path forward for further expansion of the astaxanthin production from C. zofingiensis with respect to both challenges and opportunities is also discussed. PMID:24918452

  7. Ethanol induced astaxanthin accumulation and transcriptional expression of carotenogenic genes in Haematococcus pluvialis.

    PubMed

    Wen, Zewen; Liu, Zhiyong; Hou, Yuyong; Liu, Chenfeng; Gao, Feng; Zheng, Yubin; Chen, Fangjian

    2015-10-01

    Haematococcus pluvialis is one of the most promising natural sources of astaxanthin. However, inducing the accumulation process has become one of the primary obstacles in astaxanthin production. In this study, the effect of ethanol on astaxanthin accumulation was investigated. The results demonstrated that astaxanthin accumulation occurred with ethanol addition even under low-light conditions. The astaxanthin productivity could reach 11.26 mg L(-1) d(-1) at 3% (v/v) ethanol, which was 2.03 times of that of the control. The transcriptional expression patterns of eight carotenogenic genes were evaluated using real-time PCR. The results showed that ethanol greatly enhanced transcription of the isopentenyl diphosphate (IPP) isomerase genes (ipi-1 and ipi-2), which were responsible for isomerization reaction of IPP and dimethylallyl diphosphate (DMAPP). This finding suggests that ethanol induced astaxanthin biosynthesis was up-regulated mainly by ipi-1 and ipi-2 at transcriptional level, promoting isoprenoid synthesis and substrate supply to carotenoid formation. Thus ethanol has the potential to be used as an effective reagent to induce astaxanthin accumulation in H. pluvialis. PMID:26215339

  8. Recent breakthroughs in the biology of astaxanthin accumulation by microalgal cell.

    PubMed

    Solovchenko, Alexei E

    2015-09-01

    Massive accumulation of the secondary ketokarotenoid astaxanthin is a characteristic stress response of certain microalgal species with Haematococcus pluvialis as an illustrious example. The carotenogenic response confers these organisms a remarkable ability to survive in extremely unfavorable environments and makes them the richest source of natural astaxanthin. Exerting a plethora of beneficial effects on human and animal health, astaxanthin is among the most important bioproducts from microalgae. Though our understanding of astaxanthin biosynthesis, induction, and regulation is far from complete, this gap is filling rapidly with new knowledge generated predominantly by application of advanced "omics" approaches. This review focuses on the most recent progress in the biology of astaxanthin accumulation in microalgae including the genomic, proteomic, and metabolomics insights into the induction and regulation of secondary carotenogenesis and its role in stress tolerance of the photosynthetic microorganisms. Special attention is paid to the coupling of the carotenoid and lipid biosynthesis as well as deposition of astaxanthin in the algal cell. The place of the carotenogenic response among the stress tolerance mechanisms is revisited, and possible implications of the new findings for biotechnological production of astaxanthin from microalgae are considered. The potential use of the carotenogenic microalgae as a source not only of value-added carotenoids, but also of biofuel precursors is discussed. PMID:25975708

  9. Astaxanthin from Haematococcus pluvialis Prevents Oxidative Stress on Human Endothelial Cells without Toxicity.

    PubMed

    Régnier, Philippe; Bastias, Jorge; Rodriguez-Ruiz, Violeta; Caballero-Casero, Noelia; Caballo, Carmen; Sicilia, Dolores; Fuentes, Axelle; Maire, Murielle; Crepin, Michel; Letourneur, Didier; Gueguen, Virginie; Rubio, Soledad; Pavon-Djavid, Graciela

    2015-05-01

    Astaxanthin, a powerful antioxidant, is a good candidate for the prevention of intracellular oxidative stress. The aim of the study was to compare the antioxidant activity of astaxanthin present in two natural extracts from Haematococcus pluvialis, a microalgae strain, with that of synthetic astaxanthin. Natural extracts were obtained either by solvent or supercritical extraction methods. UV, HPLC-DAD and (HPLC-(atmospheric pressure chemical ionization (APCI)+)/ion trap-MS) characterizations of both natural extracts showed similar compositions of carotenoids, but different percentages in free astaxanthin and its ester derivatives. The Trolox equivalent antioxidant capacity (TEAC) assay showed that natural extracts containing esters displayed stronger antioxidant activities than free astaxanthin. Their antioxidant capacities to inhibit intracellular oxidative stress were then evaluated on HUVEC cells. The intracellular antioxidant activity in natural extracts was approximately 90-times higher than synthetic astaxanthin (5 µM). No modification, neither in the morphology nor in the viability, of vascular human cells was observed by in vitro biocompatibility study up to 10 µM astaxanthin concentrations. Therefore, these results revealed the therapeutic potential of the natural extracts in vascular human cell protection against oxidative stress without toxicity, which could be exploited in prevention and/or treatment of cardiovascular diseases. PMID:25962124

  10. Chlorella zofingiensis as an alternative microalgal producer of astaxanthin: biology and industrial potential.

    PubMed

    Liu, Jin; Sun, Zheng; Gerken, Henri; Liu, Zheng; Jiang, Yue; Chen, Feng

    2014-06-01

    Astaxanthin (3,3'-dihydroxy-β,β-carotene-4,4'-dione), a high-value ketocarotenoid with a broad range of applications in food, feed, nutraceutical, and pharmaceutical industries, has been gaining great attention from science and the public in recent years. The green microalgae Haematococcus pluvialis and Chlorella zofingiensis represent the most promising producers of natural astaxanthin. Although H. pluvialis possesses the highest intracellular astaxanthin content and is now believed to be a good producer of astaxanthin, it has intrinsic shortcomings such as slow growth rate, low biomass yield, and a high light requirement. In contrast, C. zofingiensis grows fast phototrophically, heterotrophically and mixtrophically, is easy to be cultured and scaled up both indoors and outdoors, and can achieve ultrahigh cell densities. These robust biotechnological traits provide C. zofingiensis with high potential to be a better organism than H. pluvialis for mass astaxanthin production. This review aims to provide an overview of the biology and industrial potential of C. zofingiensis as an alternative astaxanthin producer. The path forward for further expansion of the astaxanthin production from C. zofingiensis with respect to both challenges and opportunities is also discussed. PMID:24918452

  11. Astaxanthin from Haematococcus pluvialis Prevents Oxidative Stress on Human Endothelial Cells without Toxicity

    PubMed Central

    Régnier, Philippe; Bastias, Jorge; Rodriguez-Ruiz, Violeta; Caballero-Casero, Noelia; Caballo, Carmen; Sicilia, Dolores; Fuentes, Axelle; Maire, Murielle; Crepin, Michel; Letourneur, Didier; Gueguen, Virginie; Rubio, Soledad; Pavon-Djavid, Graciela

    2015-01-01

    Astaxanthin, a powerful antioxidant, is a good candidate for the prevention of intracellular oxidative stress. The aim of the study was to compare the antioxidant activity of astaxanthin present in two natural extracts from Haematococcus pluvialis, a microalgae strain, with that of synthetic astaxanthin. Natural extracts were obtained either by solvent or supercritical extraction methods. UV, HPLC-DAD and (HPLC-(atmospheric pressure chemical ionization (APCI)+)/ion trap-MS) characterizations of both natural extracts showed similar compositions of carotenoids, but different percentages in free astaxanthin and its ester derivatives. The Trolox equivalent antioxidant capacity (TEAC) assay showed that natural extracts containing esters displayed stronger antioxidant activities than free astaxanthin. Their antioxidant capacities to inhibit intracellular oxidative stress were then evaluated on HUVEC cells. The intracellular antioxidant activity in natural extracts was approximately 90-times higher than synthetic astaxanthin (5 µM). No modification, neither in the morphology nor in the viability, of vascular human cells was observed by in vitro biocompatibility study up to 10 µM astaxanthin concentrations. Therefore, these results revealed the therapeutic potential of the natural extracts in vascular human cell protection against oxidative stress without toxicity, which could be exploited in prevention and/or treatment of cardiovascular diseases. PMID:25962124

  12. Astaxanthin reduces isoflurane-induced neuroapoptosis via the PI3K/Akt pathway.

    PubMed

    Wang, Chun-Mei; Cai, Xiao-Lan; Wen, Qing-Ping

    2016-05-01

    Astaxanthin is an oxygen-containing derivative of carotenoids that effectively suppresses reactive oxygen and has nutritional and medicinal value. The mechanisms underlying the effects of astaxanthin on isoflurane‑induced neuroapoptosis remain to be fully understood. The present study was conducted to evaluate the protective effect of astaxanthin to reduce isoflurane‑induced neuroapoptosis and to investigate the underlying mechanisms. The results demonstrated that isoflurane induced brain damage, increased caspase‑3 activity and suppressed the phosphatidylinositol 3‑kinase (PI3K)/protein kinase B (Akt) signaling pathway in an in vivo model. However, treatment with astaxanthin significantly inhibited brain damage, suppressed caspase‑3 activity and upregulated the PI3K/Akt pathway in the isoflurane‑induced rats. Furthermore, isoflurane suppressed cell growth, induced cell apoptosis, enhanced caspase‑3 activity and downregulated the PI3K/Akt pathway in organotypic hippocampal slice culture. Administration of astaxanthin significantly promoted cell growth, reduced cell apoptosis and caspase‑3 activity, and upregulated the PI3K/Akt pathway and isoflurane‑induced neuroapoptosis. The present study demonstrated that downregulation of the PI3K/Akt pathway reduced the effect of astaxanthin to protect against isoflurane‑induced neuroapoptosis in the in vitro model. The results of the current study suggested that the protective effect of astaxanthin reduces the isoflurane-induced neuroapoptosis via activation of the PI3K/Akt signaling pathway. PMID:27035665

  13. Astaxanthin ameliorates aluminum chloride-induced spatial memory impairment and neuronal oxidative stress in mice.

    PubMed

    Al-Amin, Md Mamun; Reza, Hasan Mahmud; Saadi, Hasan Mahmud; Mahmud, Waich; Ibrahim, Abdirahman Adam; Alam, Musrura Mefta; Kabir, Nadia; Saifullah, A R M; Tropa, Sarjana Tarannum; Quddus, A H M Ruhul

    2016-04-15

    Aluminum chloride induces neurodegenerative disease in animal model. Evidence suggests that aluminum intake results in the activation of glial cells and generation of reactive oxygen species. By contrast, astaxanthin is an antioxidant having potential neuroprotective activity. In this study, we investigate the effect of astaxanthin on aluminum chloride-exposed behavioral brain function and neuronal oxidative stress (OS). Male Swiss albino mice (4 months old) were divided into 4 groups: (i) control (distilled water), (ii) aluminum chloride, (iii) astaxanthin+aluminum chloride, and (iv) astaxanthin. Two behavioral tests; radial arm maze and open field test were conducted, and OS markers were assayed from the brain and liver tissues following 42 days of treatment. Aluminum exposed group showed a significant reduction in spatial memory performance and anxiety-like behavior. Moreover, aluminum group exhibited a marked deterioration of oxidative markers; lipid peroxidation (MDA), nitric oxide (NO), glutathione (GSH) and advanced oxidation of protein products (AOPP) in the brain. To the contrary, co-administration of astaxanthin and aluminum has shown improved spatial memory, locomotor activity, and OS. These results indicate that astaxanthin improves aluminum-induced impaired memory performances presumably by the reduction of OS in the distinct brain regions. We suggest a future study to determine the underlying mechanism of astaxanthin in improving aluminum-exposed behavioral deficits. PMID:26927754

  14. Studies on the metabolism of astaxanthin in the rainbow trout (Salmo gairdneri)

    SciTech Connect

    Al-Khalifah, A.S.

    1986-01-01

    Racemic astaxanthin was fed to rainbow trout (Salmo gairdneri) for 2, 4, and 6 weeks. The fish showed a bright pink coloration of the skin and flesh; the highest amount of astaxanthin was found in the skin of fish fed the test diet for six weeks. Lutein, 3-epilutein, and zeaxanthin were also detected in the flesh and skin; it was concluded that astaxanthin was converted to zeaxanthin in the skin. The mean vitamin A content of the liver was determined; the ratio of vitamin A/sub 1/:vitamin A/sub 2/ was approximately 1:3. Retinol and 3,4-dehydroretinol were extracted from the intestine of rainbow trout low in vitamin A, after force feeding with astaxanthin using a feeding tube. Antibiotic-treated fish had no marked difference in vitamin A content compared with a control group that received no antibiotic. This proves that astaxanthin was converted to vitamin A in fish depleted of vitamin A, that microorganisms were not involved in the conversion, and that conversion occurred in the intestine. An in vitro study using /sup 3/H 3S, 3S'-astaxanthin incubated with duodenal and ileal segments of the intestine provided HLPC and radioisotope data, which showed that rainbow trout were able to bioconvert astaxanthin to vitamin A.

  15. Astaxanthin-Producing Green Microalga Haematococcus pluvialis: From Single Cell to High Value Commercial Products

    PubMed Central

    Shah, Md. Mahfuzur R.; Liang, Yuanmei; Cheng, Jay J.; Daroch, Maurycy

    2016-01-01

    Many species of microalgae have been used as source of nutrient rich food, feed, and health promoting compounds. Among the commercially important microalgae, Haematococcus pluvialis is the richest source of natural astaxanthin which is considered as “super anti-oxidant.” Natural astaxanthin produced by H. pluvialis has significantly greater antioxidant capacity than the synthetic one. Astaxanthin has important applications in the nutraceuticals, cosmetics, food, and aquaculture industries. It is now evident that, astaxanthin can significantly reduce free radicals and oxidative stress and help human body maintain a healthy state. With extraordinary potency and increase in demand, astaxanthin is one of the high-value microalgal products of the future.This comprehensive review summarizes the most important aspects of the biology, biochemical composition, biosynthesis, and astaxanthin accumulation in the cells of H. pluvialis and its wide range of applications for humans and animals. In this paper, important and recent developments ranging from cultivation, harvest and postharvest bio-processing technologies to metabolic control and genetic engineering are reviewed in detail, focusing on biomass and astaxanthin production from this biotechnologically important microalga. Simultaneously, critical bottlenecks and major challenges in commercial scale production; current and prospective global market of H. pluvialis derived astaxanthin are also presented in a critical manner. A new biorefinery concept for H. pluvialis has been also suggested to guide toward economically sustainable approach for microalgae cultivation and processing. This report could serve as a useful guide to present current status of knowledge in the field and highlight key areas for future development of H. pluvialis astaxanthin technology and its large scale commercial implementation. PMID:27200009

  16. Astaxanthin-Producing Green Microalga Haematococcus pluvialis: From Single Cell to High Value Commercial Products.

    PubMed

    Shah, Md Mahfuzur R; Liang, Yuanmei; Cheng, Jay J; Daroch, Maurycy

    2016-01-01

    Many species of microalgae have been used as source of nutrient rich food, feed, and health promoting compounds. Among the commercially important microalgae, Haematococcus pluvialis is the richest source of natural astaxanthin which is considered as "super anti-oxidant." Natural astaxanthin produced by H. pluvialis has significantly greater antioxidant capacity than the synthetic one. Astaxanthin has important applications in the nutraceuticals, cosmetics, food, and aquaculture industries. It is now evident that, astaxanthin can significantly reduce free radicals and oxidative stress and help human body maintain a healthy state. With extraordinary potency and increase in demand, astaxanthin is one of the high-value microalgal products of the future.This comprehensive review summarizes the most important aspects of the biology, biochemical composition, biosynthesis, and astaxanthin accumulation in the cells of H. pluvialis and its wide range of applications for humans and animals. In this paper, important and recent developments ranging from cultivation, harvest and postharvest bio-processing technologies to metabolic control and genetic engineering are reviewed in detail, focusing on biomass and astaxanthin production from this biotechnologically important microalga. Simultaneously, critical bottlenecks and major challenges in commercial scale production; current and prospective global market of H. pluvialis derived astaxanthin are also presented in a critical manner. A new biorefinery concept for H. pluvialis has been also suggested to guide toward economically sustainable approach for microalgae cultivation and processing. This report could serve as a useful guide to present current status of knowledge in the field and highlight key areas for future development of H. pluvialis astaxanthin technology and its large scale commercial implementation. PMID:27200009

  17. Astaxanthin production in marine pelagic copepods grazing on two different phytoplankton diets

    NASA Astrophysics Data System (ADS)

    Van Nieuwerburgh, Lies; Wänstrand, Ingrid; Liu, Jianguo; Snoeijs, Pauli

    2005-02-01

    The red carotenoid astaxanthin is a powerful natural antioxidant of great importance in aquatic food webs where it is abundant in eggs and body tissues of fish and crustaceans. Little is known about the impact of the phytoplankton diet on astaxanthin production in copepods, its major pelagic producers. We followed the transfer of carotenoids from phytoplankton to copepods in a mesocosm experiment on the northern Atlantic coast (Norway) and recorded the astaxanthin production in copepods. Wild copepods grazed on nutrient-manipulated phytoplankton blooms, which differed in community composition and nutrient status (nitrogen or silicate limitation). The copepod pigments consisted mainly of free astaxanthin and mono- and diesters of astaxanthin. We found no significant difference in astaxanthin production per copepod individual or per unit C depending on the phytoplankton community. However, in the mesocosms astaxanthin per unit C decreased compared with natural levels, probably through a lower demand for photoprotection by the copepods in the dense phytoplankton blooms. The total astaxanthin production per litre was higher in the silicate-limited mesocosms through increased copepod density. Pigment ratio comparisons suggested that the copepod diet here consisted more of diatoms than in the nitrogen-limited mesocosms. Silicate-saturated diatoms were less grazed, possibly because they could invest more in defence mechanisms against their predators. Our study suggests that the production of astaxanthin in aquatic systems can be affected by changes in nutrient dynamics mediated by phytoplankton community composition and copepod population growth. This bottom-up force may have implications for antioxidant protection at higher trophic levels in the food web.

  18. Effect of Diets Supplemented with Different Sources of Astaxanthin on the Gonad of the Sea Urchin Anthocidaris crassispina

    PubMed Central

    Peng, Juan; Yuan, Jian-Ping; Wang, Jiang-Hai

    2012-01-01

    The effect of the microalgae Haematococcus pluvialis and Chorella zofingiensis, and synthetic astaxanthin on the gonad of the sea urchin Anthocidaris crassispina was studied. The basal diet was supplemented with H. pluvialis, C. zofingiensis, or synthetic astaxanthin, at two levels of astaxanthin (approximately 400 mg/kg and 100 mg/kg), to obtain the experimental diets HP1, HP2, CZ1, CZ2, AST1, and AST2, respectively, for two months of feeding experiment. The results showed that the concentrations of astaxanthin in the gonads of the sea urchins fed these experimental diets ranged from 0.15 to 3.01 mg/kg dry gonad weight. The higher astaxanthin levels (>2.90 mg/kg) were found in the gonads of the sea urchins fed the diets HP1 (containing 380 mg/kg of astaxanthins, mostly mono- and diesters) and AST1 (containing 385 mg/kg of synthetic astaxanthin). The lowest astaxanthin level (0.15 mg/kg) was detected in the gonads of the sea urchins fed the diet CZ2 (containing 98 mg/kg of astaxanthins, mostly diesters). Furthermore, the highest canthaxanthin level (7.48 mg/kg) was found in the gonads of the sea urchins fed the diet CZ1 (containing 387 mg/kg of astaxanthins and 142 mg/kg of canthaxanthin), suggesting that astaxanthins, especially astaxanthin esters, might not be assimilated as easily as canthaxanthin by the sea urchins. Our results show that sea urchins fed diets containing astaxanthin pigments show higher incorporation of these known antioxidant constituents, with the resultant seafood products therefore being of potential higher nutritive value. PMID:23016124

  19. Chirality of Viral Capsids

    NASA Astrophysics Data System (ADS)

    Dharmavaram, Sanjay; Xie, Fangming; Bruinsma, Robijn; Klug, William; Rudnick, Joseph

    Most icosahedral viruses are classified by their T-number which identifies their capsid in terms of the number of capsomers and their relative arrangement. Certain T-numbers (T = 7 for instance) are inherently chiral (with no reflection planes) while others (e.g. T = 1) are achiral. We present a Landau-Brazovskii (LB) theory for weak crystallization in which a scalar order parameter that measures density of capsid proteins successfully predicts the various observed T-numbers and their respective chiralities. We find that chiral capsids gain stability by spontaneously breaking symmetry from an unstable chiral state. The inherently achiral LB-free energy does not preferentially select a particular chiral state from its mirror reflection. Based on the physical observation that proteins are inherently chiral molecules with directional interactions, we propose a new chiral term to the LB energy as a possible selection mechanism for chirality.

  20. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

    These lectures are an attempt to a pedagogical introduction into the elementary concepts of chiral symmetry in nuclear physics. Effective chiral models such as the linear and nonlinear sigma model will be discussed as well as the essential ideas of chiral perturbation theory. Some applications to the physics of ultrarelativistic heavy ion collisions will be presented.

  1. Cloning and selection of carotenoid ketolase genes for the engineering of high-yield astaxanthin in plants.

    PubMed

    Huang, Junchao; Zhong, Yujuan; Sandmann, Gerhard; Liu, Jin; Chen, Feng

    2012-08-01

    β-Carotene ketolase (BKT) catalyzes the rate-limiting steps for the biosynthesis of astaxanthin. Several bkt genes have been isolated and explored to modify plant carotenoids to astaxanthin with limited success. In this study, five algal BKT cDNAs were isolated and characterized for the engineering of high-yield astaxanthin in plants. The products of the cDNAs showed high similarity in sequence and enzymatic activity of converting β-carotene into canthaxanthin. However, the enzymes exhibited extremely different activities in converting zeaxanthin into astaxanthin. Chlamydomonas reinhardtii BKT showed the highest conversion rate (ca 85%), whereas, Neochloris wimmeri BKT exhibited very poor activity of ketolating zeaxanthin. Expression of C. reinhardtii BKT in tobacco led to a twofold increase of total carotenoids in the leaves with astaxanthin being the predominant. The bkt genes described here provide a valuable resource for metabolic engineering of plants as cell factories for astaxanthin production. PMID:22526507

  2. The effect of temperature on cell growth and astaxanthin accumulation of Haematococcus pluvialis during a light-dark cyclic cultivation.

    PubMed

    Wan, Minxi; Zhang, Jingkui; Hou, Dongmei; Fan, Jianhua; Li, Yuanguang; Huang, Jianke; Wang, Jun

    2014-09-01

    Haematococcus pluvialis is the best source of natural astaxanthin known as "the king of antioxidants". The mass outdoor culture is the most workable strategy for astaxanthin production, but the effects of daytime and night temperatures on the biomass concentration and astaxanthin content of H. pluvialis have received little attention. This study indicated that, raising the daytime or night temperature could stimulate night accumulation of astaxanthin until temperature up to 28°C; the night biomass loss increased firstly and then decreased along with the daytime temperature reducing; decreasing the night temperature can lessen night biomass loss; the daytime temperature of 28°C and the night temperature below 28°C were optimal for achieving high biomass and astaxanthin content. Subsequently, the outdoor culture strategy has been improved and can increase the net biomass and astaxanthin productivities by 5 and 2.9-fold as compared to the former strategy. PMID:24995877

  3. Review of genotoxicity and rat carcinogenicity investigations with astaxanthin.

    PubMed

    Edwards, James A; Bellion, Phillip; Beilstein, Paul; Rümbeli, Robert; Schierle, Joseph

    2016-03-01

    Synthetic astaxanthin has been extensively tested for safety. Genotoxicity studies including Ames and in vitro Micronucleus Tests show absence of genotoxic potential. Although a long-term mouse study showed no carcinogenicity potential, the rat carcinogenicity study with dietary dosages of 0 (control), 0 (placebo beadlet), 40, 200 and 1000 mg astaxanthin/kg bw/day showed an increased incidence of benign, hepatocellular adenoma in females only, at 200 mg/kg bw/day and above. There was no clear evidence of toxicity during the in-life phase. Discoloration of feces was observed and a reduction in body weight gain in all groups receiving beadlets, probably reflecting a nutritional influence. Blood sampling confirmed systemic exposure and some minor clinical chemistry differences in females at 200 and 1000 mg/kg bw/day. There was no effect on adjusted liver weight. Histopathological examination showed hepatic changes indicative of slight hepatotoxicity and hepatocyte regeneration in females at 200 and 1000 mg/kg bw/day, in addition to the adenoma. Taking into account this pathological background in the female rat, and a wide variety of other supporting information, it is concluded that the hepatocellular adenoma in female rats was secondary to hepatotoxicity and regeneration, and is most probably a species-specific phenomenon of doubtful human relevance. PMID:26713891

  4. Excited state dynamics of the astaxanthin radical cation

    NASA Astrophysics Data System (ADS)

    Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

    2010-07-01

    Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

  5. Interconversion of diborane(4) isomers

    NASA Technical Reports Server (NTRS)

    Stanton, John F.; Gauss, Juergen; Bartlett, Rodney J.; Helgaker, Trygve; Jorgensen, Poul; Jensen, Hans J. A.; Taylor, Peter R.

    1992-01-01

    Highly correlated electronic structure computations using many-body perturbation theory and coupled-cluster gradient techniques are used to study the reaction pathway that links the two forms (C2u and D2d) of diborane(4). The results obtained indicate that a low-energy pathway exists for interconversion of the two low-lying isomers of diborane(4). The proposed mechanism consists of a single concerted but nonsynchronous rotation of the BH2 groups. The pathway first follows an idealized reaction coordinate which preserves C2 symmetry, but then bifurcates at a branch point, leading to two equivalent transition states which lack nontrivial elements of symmetry.

  6. Enhancing Photon Utilization Efficiency for Astaxanthin Production from Haematococcus lacustris Using a Split-Column Photobioreactor.

    PubMed

    Kim, Z-Hun; Park, Hanwool; Lee, Ho-Sang; Lee, Choul-Gyun

    2016-07-28

    A split-column photobioreactor (SC-PBR), consisting of two bubble columns with different sizes, was developed to enhance the photon utilization efficiency in an astaxanthin production process from Haematococcus lacustris. Among the two columns, only the smaller column of SC-PBR was illuminated. Astaxanthin productivities and photon efficiencies of the SC-PBRs were compared with a standard bubble-column PBR (BC-PBR). Astaxanthin productivity of SC-PBR was improved by 28%, and the photon utilization efficiencies were 28-366% higher than the original BC-PBR. The results clearly show that the effective light regime of SC-PBR could enhance the production of astaxanthin. PMID:27056475

  7. Sequential Heterotrophy-Dilution-Photoinduction Cultivation of Haematococcus pluvialis for efficient production of astaxanthin.

    PubMed

    Wan, Minxi; Zhang, Zhen; Wang, Jun; Huang, Jianke; Fan, Jianhua; Yu, Anquan; Wang, Weiliang; Li, Yuanguang

    2015-12-01

    A novel cultivation strategy called "Sequential Heterotrophy-Dilution-Photoinduction" was successfully applied in the cultivation of Haematococcus pluvialis to produce astaxanthin effectively. Cells were first cultivated heterotrophically to achieve a high cell density, then were diluted to a suitable concentration and switched to a favorable environment for cells acclimation. Finally, the culture was transferred to high light environment for astaxanthin accumulation. By this strategy, the dry cell weight of 26 g/L and biomass productivity of 64.1mg/L/h were obtained in heterotrophy stage which surpassed ever before reported in literatures. Meanwhile, the cells could accumulate considerable astaxanthin up to 4.6% of dry cell weight after 10 days of photoinduction. Furthermore, the application prospects of the strategy were confirmed further by outdoor experiments. Therefore, this novel strategy provided a promising approach for high-efficient production of natural astaxanthin from H. pluvialis to meet the huge demand of this high value product. PMID:26433152

  8. High spin isomer beam line at RIKEN

    SciTech Connect

    Kishida, T.; Ideguchi, E.; Wu, H.Y.

    1996-12-31

    Nuclear high spin states have been the subject of extensive experimental and theoretical studies. For the production of high spin states, fusion reactions are usually used. The orbital angular momentum brought in the reaction is changed into the nuclear spin of the compound nucleus. However, the maximum induced angular momentum is limited in this mechanism by the maximum impact parameter of the fusion reaction and by the competition with fission reactions. It is, therefore, difficult to populate very high spin states, and as a result, large {gamma}-detector arrays have been developed in order to detect subtle signals from such very high spin states. The use of high spin isomers in the fusion reactions can break this limitation because the high spin isomers have their intrinsic angular momentum, which can bring the additional angular momentum without increasing the excitation energy. There are two methods to use the high spin isomers for secondary reactions: the use of the high spin isomers as a target and that as a beam. A high spin isomer target has already been developed and used for several experiments. But this method has an inevitable shortcoming that only {open_quotes}long-lived{close_quotes} isomers can be used for a target: {sup 178}Hf{sup m2} (16{sup +}) with a half-life of 31 years in the present case. By developing a high spin isomer beam, the authors can utilize various short-lived isomers with a short half-life around 1 {mu}s. The high spin isomer beam line of RIKEN Accelerator Facility is a unique apparatus in the world which provides a high spin isomer as a secondary beam. The combination of fusion-evaporation reaction and inverse kinematics are used to produce high spin isomer beams; in particular, the adoption of `inverse kinematics` is essential to use short-lived isomers as a beam.

  9. Friction-induced enhancement in the optical activity of interacting chiral molecules

    NASA Astrophysics Data System (ADS)

    Bargueño, Pedro; Peñate-Rodríguez, Helen C.; Gonzalo, Isabel; Sols, Fernando; Miret-Artés, Salvador

    2011-11-01

    The stability of chiral molecules described by a non-linear two-state system which accounts for mean-field interactions between different isomers, including any external chiral influence (in particular, the parity violating energy difference) is investigated. By introducing the population and phase difference of the chiral states as a pair of canonical variables, driving an analogy to a bosonic Josephson junction, our study to include dissipative effects in condensed phase described by a Caldeira-Leggett like Hamiltonian is extended using the Langevin formalism. Dissipative effects produce an enhancement in the population difference, not leading to racemization.

  10. Anti-inflammatory Effect of Astaxanthin on the Sickness Behavior Induced by Diabetes Mellitus.

    PubMed

    Ying, Chang-jiang; Zhang, Fang; Zhou, Xiao-yan; Hu, Xiao-tong; Chen, Jing; Wen, Xiang-ru; Sun, Ying; Zheng, Kui-yang; Tang, Ren-xian; Song, Yuan-jian

    2015-10-01

    Chronic inflammation appears to play a critical role in sickness behavior caused by diabetes mellitus. Astaxanthin has been used in treating diabetes mellitus and diabetic complications because of its neuroprotective and anti-inflammatory actions. However, whether astaxanthin can improve sickness behavior induced by diabetes and its potential mechanisms are still unknown. The aim of this study was to investigate the effects of astaxanthin on diabetes-elicited abnormal behavior in mice and its corresponding mechanisms. An experimental diabetic model was induced by streptozotocin (150 mg/kg) and astaxanthin (25 mg/kg/day) was provided orally for 10 weeks. Body weight and water consumption were measured, and the sickness behavior was evaluated by the open field test (OFT) and closed field test (CFT). The expression of glial fibrillary acidic protein (GFAP) was measured, and the frontal cortical cleaved caspase-3 positive cells, interleukin-6 (IL-6), and interleukin-1β (IL-1β) expression levels were also investigated. Furthermore, cystathionine β-synthase (CBS) in the frontal cortex was detected to determine whether the protective effect of astaxanthin on sickness behavior in diabetic mice is closely related to CBS. As expected, we observed that astaxanthin improved general symptoms and significantly increase horizontal distance and the number of crossings in the OFT and CFT. Furthermore, data showed that astaxanthin could decrease GFAP-positive cells in the brain and down-regulate the cleaved caspase-3, IL-6, and IL-1β, and up-regulate CBS in the frontal cortex. These results suggest that astaxanthin provides neuroprotection against diabetes-induced sickness behavior through inhibiting inflammation, and the protective effects may involve CBS expression in the brain. PMID:25971983

  11. Prediction of enantiomeric selectivity in chromatography. Application of conformation-dependent and conformation-independent descriptors of molecular chirality.

    PubMed

    Aires-de-Sousa, João; Gasteiger, Johann

    2002-03-01

    In order to process molecular chirality by computational methods and to obtain predictions for properties that are influenced by chirality, a fixed-length conformation-dependent chirality code is introduced. The code consists of a set of molecular descriptors representing the chirality of a 3D molecular structure. It includes information about molecular geometry and atomic properties, and can distinguish between enantiomers, even if chirality does not result from chiral centers. The new molecular transform was applied to two datasets of chiral compounds, each of them containing pairs of enantiomers that had been separated by chiral chromatography. The elution order within each pair of isomers was predicted by means of Kohonen neural networks (NN) using the chirality codes as input. A previously described conformation-independent chirality code was also applied and the results were compared. In both applications clustering of the two classes of enantiomers (first eluted and last eluted enantiomers) could be successfully achieved by NN and accurate predictions could be obtained for independent test sets. The chirality code described here has a potential for a broad range of applications from stereoselective reactions to analytical chemistry and to the study of biological activity of chiral compounds. PMID:11885960

  12. Astaxanthin prevents and reverses diet-induced insulin resistance and steatohepatitis in mice: A comparison with vitamin E

    PubMed Central

    Ni, Yinhua; Nagashimada, Mayumi; Zhuge, Fen; Zhan, Lili; Nagata, Naoto; Tsutsui, Akemi; Nakanuma, Yasuni; Kaneko, Shuichi; Ota, Tsuguhito

    2015-01-01

    Hepatic insulin resistance and nonalcoholic steatohepatitis (NASH) could be caused by excessive hepatic lipid accumulation and peroxidation. Vitamin E has become a standard treatment for NASH. However, astaxanthin, an antioxidant carotenoid, inhibits lipid peroxidation more potently than vitamin E. Here, we compared the effects of astaxanthin and vitamin E in NASH. We first demonstrated that astaxanthin ameliorated hepatic steatosis in both genetically (ob/ob) and high-fat-diet-induced obese mice. In a lipotoxic model of NASH: mice fed a high-cholesterol and high-fat diet, astaxanthin alleviated excessive hepatic lipid accumulation and peroxidation, increased the proportion of M1-type macrophages/Kupffer cells, and activated stellate cells to improve hepatic inflammation and fibrosis. Moreover, astaxanthin caused an M2-dominant shift in macrophages/Kupffer cells and a subsequent reduction in CD4+ and CD8+ T cell recruitment in the liver, which contributed to improved insulin resistance and hepatic inflammation. Importantly, astaxanthin reversed insulin resistance, as well as hepatic inflammation and fibrosis, in pre-existing NASH. Overall, astaxanthin was more effective at both preventing and treating NASH compared with vitamin E in mice. Furthermore, astaxanthin improved hepatic steatosis and tended to ameliorate the progression of NASH in biopsy-proven human subjects. These results suggest that astaxanthin might be a novel and promising treatment for NASH. PMID:26603489

  13. Effects of selected polysorbate and sucrose ester emulsifiers on the physicochemical properties of astaxanthin nanodispersions.

    PubMed

    Anarjan, Navideh; Tan, Chin Ping

    2013-01-01

    The effects of selected nonionic emulsifiers on the physicochemical characteristics of astaxanthin nanodispersions produced by an emulsification/evaporation technique were studied. The emulsifiers used were polysorbates (Polysorbate 20, Polysorbate 40, Polysorbate 60 and Polysorbate 80) and sucrose esters of fatty acids (sucrose laurate, palmitate, stearate and oleate). The mean particle diameters of the nanodispersions ranged from 70 nm to 150 nm, depending on the emulsifier used. In the prepared nanodispersions, the astaxanthin particle diameter decreased with increasing emulsifier hydrophilicity and decreasing carbon number of the fatty acid in the emulsifier structure. Astaxanthin nanodispersions with the smallest particle diameters were produced with Polysorbate 20 and sucrose laurate among the polysorbates and the sucrose esters, respectively. We also found that the Polysorbate 80- and sucrose oleate-stabilized nanodispersions had the highest astaxanthin losses (i.e., the lowest astaxanthin contents in the final products) among the nanodispersions. This work demonstrated the importance of emulsifier type in determining the physicochemical characteristics of astaxanthin nano-dispersions. PMID:23303336

  14. Determination of astaxanthin in Haematococcus pluvialis by first-order derivative spectrophotometry.

    PubMed

    Liu, Xiao Juan; Juan, Liu Xiao; Wu, Ying Hua; Hua, Wu Ying; Zhao, Li Chao; Chao, Zhao Li; Xiao, Su Yao; Yao, Xiao Su; Zhou, Ai Mei; Mei, Zhou Ai; Liu, Xin; Xin, Liu

    2011-01-01

    A highly selective, convenient, and precise method, first-order derivative spectrophotometry, was applied for the determination of astaxanthin in Haematococcus pluvialis. Ethyl acetate and ethanol (1:1, v/v) were found to be the best extraction solvent tested due to their high efficiency and low toxicity compared with nine other organic solvents. Astaxanthin coexisting with chlorophyll and beta-carotene was analyzed by first-order derivative spectrophotometry in order to optimize the conditions for the determination of astaxanthin. The results show that when detected at 432 nm, the interfering substances could be eliminated. The dynamic linear range was 2.0-8.0 microg/mL, with a correlation coefficient of 0.9916. The detection threshold was 0.41 microg/mL. The RSD for the determination of astaxanthin was in the range of 0.01-0.06%; the results of recovery test were 98.1-108.0%. The statistical analysis between first-order derivative spectrophotometry and HPLC by T-testing did not exceed their critical values, revealing no significant differences between these two methods. It was proved that first-order derivative spectrophotometry is a rapid and convenient method for the determination of astaxanthin in H. pluvialis that can eliminate the negative effect resulting from the coexistence of astaxanthin with chlorophyll and beta-carotene. PMID:22320081

  15. Chirality in nonlinear optics.

    PubMed

    Haupert, Levi M; Simpson, Garth J

    2009-01-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made approximately 50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity. PMID:19046125

  16. Chirality in Nonlinear Optics

    NASA Astrophysics Data System (ADS)

    Haupert, Levi M.; Simpson, Garth J.

    2009-05-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made ˜50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity.

  17. Enumeration of chiral and achiral edge and face substitutions of buckminsterfullerene

    NASA Astrophysics Data System (ADS)

    Balasubramanian, K.

    1995-05-01

    The edge and face groups of the buckminsterfullerene cluster are formulated. The generalized character cycle indices of all the irreducible representations of both edge and face groups are obtained. The generating functions computed from these groups yield the chiral and achiral isomers, and mappings that transform according to the specified irreducible representation for edge and face colorings of buckminsterfullerene.

  18. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

    These lectures concern the dynamics of fermions in strong interaction with gauge fields. Systems of fermions coupled by gauge forces have a very rich structure of global symmetries, which are called chiral symmetries. These lectures will focus on the realization of chiral symmetries and the causes and consequences of thier spontaneous breaking. A brief introduction to the basic formalism and concepts of chiral symmetry breaking is given, then some explicit calculations of chiral symmetry breaking in gauge theories are given, treating first parity-invariant and then chiral models. These calculations are meant to be illustrative rather than accurate; they make use of unjustified mathematical approximations which serve to make the physics more clear. Some formal constraints on chiral symmetry breaking are discussed which illuminate and extend the results of our more explicit analysis. Finally, a brief review of the phenomenological theory of chiral symmetry breaking is presented, and some applications of this theory to problems in weak-interaction physics are discussed. (WHK)

  19. Analytical chiral separation of the stereoisomers of a novel carbonic anhydrase inhibitor and its deethylated metabolite, and the assignment of absolute configuration of the human metabolite and chiral degradation products.

    PubMed

    Matuszewski, B K; Constanzer, M L; Kiganda, M

    1994-03-01

    Several approaches to the separation of four stereoisomers, 1-4, of a novel, topically active, carbonic anhydrase inhibitor, 1, with two chiral centers in the molecule and four isomers, 5-8, of its chiral metabolite, 5, were evaluated. These methods include nonchiral derivatization followed by separation on chiral stationary phases (CSPs) and chiral derivatization and separation on nonchiral columns and on CSPs. Baseline separation of stereoisomers 1-4 was achieved in less than 15 min after chiral derivatization with (S)-(+)-1-(1-naphthyl)ethyl isocyanate (NEIC) and chiral chromatography on a (R)-N-(3,5-dinitrobenzoyl)phenyl glycine (DNBPG) column under normal phase (NP) conditions. Similarly, isomers 5-8 were baseline separated in less than 20 min after derivatization with NEIC and chromatography on nonchiral (nitrophenyl) and chiral [(S)-(3,5-dinitrobenzoyl)leucine; DNBL] columns in series under the same NP chromatographic conditions. Only partial separation of the diastereomeric derivatives was observed on a variety of nonchiral columns. In addition, all other direct and indirect chiral separation approaches gave only partial separation of at least two stereoisomers within the group of 1-4 or 5-8. The details of chiral separations using various methods and separation (alpha) and capacity factors (k') of the derivatized isomers 1-8 on a series of chiral and nonchiral columns are presented. Using these methods, the absolute configuration of the human metabolite of 1 was established as S1S2 (5), and the heat (HD) and light (LD) degradation products of 1 as R1S2 (3) and S1S2 (5), respectively. PMID:8008715

  20. E/Z Isomers and Isomerization

    NASA Astrophysics Data System (ADS)

    Liaaen-Jensen, Synnøve; Lutnœes, Bjart Frode

    The natural occurrence of several carotenoid cis isomers and their biological significance were not anticipated in 1962, when the classical monograph on cis-trans isomeric carotenoids [1] was published. More recent research has demonstrated that various cis isomers occur naturally in bacteria plants, algae and invertebrate animals, and are present in human blood and tissues. The participation of cis isomers in the biosynthethic route to coloured carotenoids is well established (Volume 3, Chapter 2). Important biological functions of (15Z)-carotenoids in photosynthesis have been revealed [2]. In relation to health aspects of carotenoids, the bioavailability of cis isomers may be higher than that of the all-trans isomer [3], and accumulated evidence suggests that cis/trans isomerization may occur in biological tissues, particularly of lycopene (31) in human serum [4] (Volume 5, Chapter 7).

  1. High-performance liquid chromatographic resolution of reverse isomers of 1,2-diacyl-rac-glycerols as 3,5-dinitrophenylurethanes.

    PubMed

    Itabashi, Y; Myher, J J; Kuksis, A

    2000-10-01

    The resolution of reverse isomers remains a major unsolved problem in glycerolipid chromatography. We have investigated the separation of the reverse isomers of 1,2-diacyl-rac-glycerols under a variety of high-performance liquid chromatography (HPLC) conditions. The reverse isomers of diacylglycerols having various pairs of acyl groups including short and highly unsaturated chains, which were prepared by partial Grignard degradation of the corresponding triacylglycerols, were chromatographed as 3,5-dinitrophenylurethanes. Excellent resolution was achieved for the reverse isomers of very different pairs of acyl groups, such as acetate-palmitate and docosahexaenoate-palmitate, by chiral-phase HPLC on columns containing (R)- and (S)-1-(1-naphthyl)ethylamine polymeric phases, reversed-phase HPLC on a highly efficient C18 column (4 microm particle size) and silver ion HPLC on a silver loaded cation-exchange column. The chiral-phase HPLC also permitted complete enantiomer resolution for all the reverse isomers examined. No satisfactory resolution by any of the HPLC methods, however, was obtained for the reverse isomers possessing minor differences in chain lengths and degree of unsaturation, such as laurate-palmitate and oleate-linoleate. The limitations of resolution and characteristics of elution are described. PMID:11073297

  2. Separation and identification of cis and trans isomers of 2-butene-1,4-diol and lafutidine by HPLC and LC-MS*

    PubMed Central

    Pan, Chun-xiu; Xu, Xiu-zhu; He, Hong-mei; Cai, Xiao-jun; Zhang, Xue-jun

    2005-01-01

    The cis and trans isomers separation of 2-butene-1,4-diol and lafutidine were studied by HPLC on two kinds of chiral columns: (S,S)-Whelk-O 1 and ChiraSpher. The isomers of 2-butene-1,4-diol can be separated on both chiral columns while the isomers of lafutidine can only be resolved on ChiraSpher column. The influence of different type and amount of mobile phase modifier on the isomers separation was extensively studied. The resolution of cis and trans isomers of 2-butene-1,4-diol was 2.61 on (S,S)-Whelk-O 1 column with hexane-ethanol (97:3, v/v) as the mobile phase. The resolution of lafutidine was 1.89 on ChiraSpher column with hexane-ethanol-THF-diethylamine (92:3:5:0.1, v/v/v/v) as the mobile phase. LC-MS methods were developed to identify the isomer peaks. PMID:15593397

  3. Enantioselective and Synergetic Toxicity of Axial Chiral Herbicide Propisochlor to SP2/0 Myeloma Cells.

    PubMed

    Liu, Yao; Zhang, Xuan; Liu, Chunhong; Yang, Ruili; Xu, Zhenlin; Zhou, Lijun; Sun, Yuanming; Lei, Hongtao

    2015-09-16

    The axial chiral herbicide propisochlor is used to control weeds. Different enantiomers of a compound usually have different biological activities. It is unclear how the toxicities of the propisochlor enantiomers differ. Propisochlor enantiomers, separated by high-performance liquid chromatography, were tested on SP2/0 myeloma cells. Cytotoxicity and apoptosis were measured, and interactions between the enantiomers were evaluated. The rac-propisochlor, pure R-(+) isomer, and pure S-(-) isomer inhibited cell proliferation and induced apoptosis. The rac-propisochlor, R-(+) isomer, and S-(-) isomer half maximal effective concentration values after 24 h of incubation were 111 ± 0.15, 68 ± 0.09, and 99 ± 0.21 μM, respectively. R-(+) isomer induced the most apoptosis. R-(+) isomer was ∼1.63 times more cytotoxic than rac-propisochlor and ∼1.46 times more cytotoxic than S-(-) isomer. Antagonistic cytotoxic interactions were found between R-(+) and S-(-) isomers. This is the first time the toxicities of these enantiomers and antagonism between the enantiomers have been reported. The antagonism indicates that the ecotoxicological effects of the enantiomers should be investigated. PMID:26299567

  4. The effect of various antioxidants on the degradation of O/W microemulsions containing esterified astaxanthins from Haematococcus pluvialis.

    PubMed

    Zhou, Qingxin; Xu, Jie; Yang, Shu; Xue, Yong; Zhang, Ting; Wang, Jingfeng; Xue, Changhu

    2015-01-01

    Esterified astaxanthins are used as functional nutraceuticals and pigments in many food products. Unfortunately, the utilization is currently limited due to their chemical instability and poor water-solubility. In this study, esterified astaxanthins were quantified and purified from Haematococcus pluvialis using a novel and precise approach. By HPLC-(+)APCI-MS/MS, twenty esterified astaxanthin molecular species were identified, of which classified into eight monoester forms (approximately 85%, w/w) and twelve diester forms (approximately 15%, w/w), depending on the number of fatty acids that bind thereto. The MS data showed that the predominant fatty acids in astaxanthin esters of H. pluvialis are usually a long chain fatty acid with 16~18 carbon atoms, such as C18:1, C18:2, C18:3, C18:4, C16:0, C16:1. The purity of the esterified astaxanthins was determined to be 96.8±1.2% after purification. A well water-dispersible microemulsion was fabricated using high purity esterified astaxanthins, ethyl butyrate, Tween 80 and ethanol; and that emulsion exhibited a mean particle radius around 60 nm. The chemical degradation of esterified astaxanthins was monitored under accelerated stress storage conditions. After storage for 20 days, the results indicated that the degradation of esterified astaxanthins was effectively slowed by the addition of antioxidants to the microemulsions. By investigating the dependence of the chemical degradation of the esterified astaxanthins in O/W microemulsions on the concentration of the additives, it was concluded that the effectiveness of the additives at inhibiting the degradation of the esterified astaxanthins decreased in the following order: EDTA > ascorbic acid > vitamin E acetate. The utilization of antioxidants in combination was less effective than using them individually. These results provide information for designing effective delivery systems, thereby delaying the chemical degradation of esterified astaxanthins in foods

  5. Induction of molecular chirality by circularly polarized light in cyclic azobenzene with a photoswitchable benzene rotor.

    PubMed

    Hashim, P K; Thomas, Reji; Tamaoki, Nobuyuki

    2011-06-20

    New phototriggered molecular machines based on cyclic azobenzene were synthesized in which a 2,5-dimethoxy, 2,5-dimethyl, 2,5-difluorine or unsubstituted-1,4-dioxybenzene rotating unit and a photoisomerizable 3,3'-dioxyazobenzene moiety are bridged together by fixed bismethylene spacers. Depending upon substitution on the benzene moiety and on the E/Z conformation of the azobenzene unit, these molecules suffer various degrees of restriction on the free rotation of the benzene rotor. The rotation of the substituted benzene rotor within the cyclic azobenzene cavity imparts planar chirality to the molecules. Cyclic azobenzene 1, with methoxy groups at both the 2- and 5-positions of the benzene rotor, was so conformationally restricted that free rotation of the rotor was prevented in both the E and Z isomers and the respective planar chiral enantiomers were resolved. In contrast, compound 2, with 2,5-dimethylbenzene as the rotor, demonstrated the property of a light-controlled molecular brake, whereby rotation of the 2,5-dimethylbenzene moiety is completely stopped in the E isomer (brake ON, rotation OFF), while the rotation is allowed in the Z isomer (brake OFF, rotation ON). The cyclic azobenzene 3, with fluorine substitution on the benzene rotor, was in the brake OFF state regardless of E/Z photoisomerization of the azobenzene moiety. More interestingly, for the first time, we demonstrated the induction of molecular chirality in a simple monocyclic azobenzene by circular-polarized light. The key characteristics of cyclic azobenzene 2, that is, stability of the chiral structure in the E isomer, fast racemization in the Z isomer, and the circular dichroism of enantiomers of both E and Z isomers, resulted in a simple reversible enantio-differentiating photoisomerization directly between the E enantiomers. Upon exposure to r- or l-circularly polarized light at 488 nm, partial enrichment of the (S)- or (R)-enantiomers of 2 was observed. PMID:21567494

  6. Encapsulation of astaxanthin-rich Xanthophyllomyces dendrorhous for antioxidant delivery.

    PubMed

    Lee, Ji-Soo; Park, Sun-Ah; Chung, Donghwa; Lee, Hyeon Gyu

    2011-10-01

    Calcium alginate gel (CAG) beads were used to entrap the antioxidant astaxanthin-rich Xanthophyllomyces dendrorhous (ASX) by ionic gelation. ASX-CAG bead entrapment efficiency and release behavior, as influenced by alginate and CaCl(2) concentration and hardening time, were investigated. The optimized bead preparation conditions that gave rise to an efficient ASX release pattern were 1.5% alginate, 50mM CaCl(2), and a 5min hardening time. The antioxidant activity of non-encapsulated ASX was maintained for 4 days and then sharply decreased, whereas encapsulated ASX was maintained for 6 days. These results revealed that physical entrapment of ASX within CAG beads could be an effective technique for protecting the antioxidant activity of ASX from lipid peroxidation. PMID:21575657

  7. Mechanically selflocked chiral gemini-catenanes

    PubMed Central

    Li, Sheng-Hua; Zhang, Heng-Yi; Xu, Xiufang; Liu, Yu

    2015-01-01

    Mechanically interlocked and entangled molecular architectures represent one of the elaborate topological superstructures engineered at a molecular resolution. Here we report a methodology for fabricating mechanically selflocked molecules (MSMs) through highly efficient one-step amidation of a pseudorotaxane derived from dual functionalized pillar[5]arene (P[5]A) threaded by α,ω-diaminoalkane (DA-n; n=3–12). The monomeric and dimeric pseudo[1]catenanes thus obtained, which are inherently chiral due to the topology of P[5]A used, were isolated and fully characterized by NMR and circular dichroism spectroscopy, X-ray crystallography and DFT calculations. Of particular interest, the dimeric pseudo[1]catenane, named ‘gemini-catenane', contained stereoisomeric meso-erythro and dl-threo isomers, in which two P[5]A moieties are threaded by two DA-n chains in topologically different patterns. This access to chiral pseudo[1]catenanes and gemini-catenanes will greatly promote the practical use of such sophisticated chiral architectures in supramolecular and materials science and technology. PMID:26126502

  8. Astaxanthin reduces ischemic brain injury in adult rats

    PubMed Central

    Shen, Hui; Kuo, Chi-Chung; Chou, Jenny; Delvolve, Alice; Jackson, Shelley N.; Post, Jeremy; Woods, Amina S.; Hoffer, Barry J.; Wang, Yun; Harvey, Brandon K.

    2009-01-01

    Astaxanthin (ATX) is a dietary carotenoid of crustaceans and fish that contributes to their coloration. Dietary ATX is important for development and survival of salmonids and crustaceans and has been shown to reduce cardiac ischemic injury in rodents. The purpose of this study was to examine whether ATX can protect against ischemic injury in the mammalian brain. Adult rats were injected intracerebroventricularly with ATX or vehicle prior to a 60-min middle cerebral artery occlusion (MCAo). ATX was present in the infarction area at 70-75 min after onset of MCAo. Treatment with ATX, compared to vehicle, increased locomotor activity in stroke rats and reduced cerebral infarction at 2 d after MCAo. To evaluate the protective mechanisms of ATX against stroke, brain tissues were assayed for free radical damage, apoptosis, and excitoxicity. ATX antagonized ischemia-mediated loss of aconitase activity and reduced glutamate release, lipid peroxidation, translocation of cytochrome c, and TUNEL labeling in the ischemic cortex. ATX did not alter physiological parameters, such as body temperature, brain temperature, cerebral blood flow, blood gases, blood pressure, and pH. Collectively, our data suggest that ATX can reduce ischemia-related injury in brain tissue through the inhibition of oxidative stress, reduction of glutamate release, and antiapoptosis. ATX may be clinically useful for patients vulnerable or prone to ischemic events.—Shen, H., Kuo, C.-C., Chou, J., Delvolve, A., Jackson, S. N., Post, J., Woods, A. S., Hoffer, B. J., Wang, Y., Harvey, B. K. Astaxanthin reduces ischemic brain injury in adult rats. PMID:19218497

  9. Planar plasmonic chiral nanostructures.

    PubMed

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-21

    A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response. PMID:26818746

  10. Effects of iron electrovalence and species on growth and astaxanthin production of Haematococcus pluvialis

    NASA Astrophysics Data System (ADS)

    Cai, Minggang; Li, Zhe; Qi, Anxiang

    2009-05-01

    To increase the cell concentration and the accumulation of astaxanthin in the cultivation of Haematococcus pluvialis, effects of different iron electrovalencies (Fe2+-EDTA and Fe3+-EDTA) and species (Fe-EDTA, Fe(OH){x/32x} and FeC6H5O7) addition on cell growth and accumulation of astaxanthin were studied. Results show that different iron electrovalencies have various effects on cell growth and astaxanthin accumulation of H. pluvialis. Compared with Fe3+-EDTA, Fe2+-EDTA stimulate more effectively the formation of astaxanthin. The maximum astaxanthin content (30.70 mg/g biomass cell) was obtained under conditions of 18 μmol/L Fe2+-EDTA, despite the lower cell density (2.3×105 cell/ml) in such condition. Fe3+-EDTA is more effective than Fe2+-EDTA in improving the cell growth. Especially, the maximal steady-state cell density, 2.9×105 cell/ml was obtained at 18 μmol/L Fe3+-EDTA addition. On the other hand, all the various species of iron (EDTA-Fe, Fe(OH){x/32x}, FeC6H5O7) are capable to improve the growth of the algae and astaxanthin production. Among the three iron species, FeC6H5O7 performed the best. Under the condition of a higher concentration (36 μmol/L) of FeC6H5O7, the cell density and astaxanthin production is 2 and 7 times higher than those of iron-limited group, respectively. The present study demonstrates that the effects of the stimulation with different iron species increased in the order of FeC6H5O7, Fe(OH){x/32x} and EDTA-Fe.

  11. Axially chiral BODIPYs.

    PubMed

    Lerrick, Reinner I; Winstanley, Thomas P L; Haggerty, Karen; Wills, Corinne; Clegg, William; Harrington, Ross W; Bultinck, Patrick; Herrebout, Wouter; Benniston, Andrew C; Hall, Michael J

    2014-05-11

    The synthesis and resolution of a class of chiral organic fluorophores, axially chiral 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (Ax*-BODIPY), is described. Ax*-BODIPYs were prepared through a modular synthesis combined with a late stage Heck functionalisation. Resolution was achieved by preparative chiral HPLC. Absolute stereochemical assignment was performed by comparison of experimental ECD spectra with TD-DFT calculations. PMID:24676233

  12. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm–1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  13. Chiral atomically thin films.

    PubMed

    Kim, Cheol-Joo; Sánchez-Castillo, A; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm(-1)) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra. PMID:26900756

  14. Highly efficient biosynthesis of astaxanthin in Saccharomyces cerevisiae by integration and tuning of algal crtZ and bkt.

    PubMed

    Zhou, Pingping; Ye, Lidan; Xie, Wenping; Lv, Xiaomei; Yu, Hongwei

    2015-10-01

    Astaxanthin is a highly valued carotenoid with strong antioxidant activity and has wide applications in aquaculture, food, cosmetic, and pharmaceutical industries. The market demand for natural astaxanthin promotes research in metabolic engineering of heterologous hosts for astaxanthin production. In this study, an astaxanthin-producing Saccharomyces cerevisiae strain was created by successively introducing the Haematococcus pluvialis β-carotenoid hydroxylase (crtZ) and ketolase (bkt) genes into a previously constructed β-carotene hyperproducer. Further integration of strategies including codon optimization, gene copy number adjustment, and iron cofactor supplementation led to significant increase in the astaxanthin production, reaching up to 4.7 mg/g DCW in the shake-flask cultures which is the highest astaxanthin content in S. cerevisiae reported to date. Besides, the substrate specificity of H. pluvialis CrtZ and BKT and the probable formation route of astaxanthin from β-carotene in S. cerevisiae were figured out by expressing the genes separately and in combination. The yeast strains engineered in this work provide a basis for further improving biotechnological production of astaxanthin and might offer a useful general approach to the construction of heterologous biosynthetic pathways for other natural products. PMID:26156241

  15. Organization of astaxanthin within oil bodies of Haematococcus pluvialis studied with polarization-dependent harmonic generation microscopy.

    PubMed

    Tokarz, Danielle; Cisek, Richard; El-Ansari, Omar; Espie, George S; Fekl, Ulrich; Barzda, Virginijus

    2014-01-01

    Nonlinear optical microscopy was used to image the localization of astaxanthin accumulation in the green alga, Haematococcus pluvialis. Polarization-in, polarization-out (PIPO) second harmonic generation (SHG) and third harmonic generation (THG) microscopy was applied to study the crystalline organization of astaxanthin molecules in light-stressed H. pluvialis in vivo. Since astaxanthin readily forms H- and J-aggregates in aqueous solutions, PIPO THG studies of astaxanthin aggregates contained in red aplanospores were compared to PIPO THG of in vitro self-assembled H- and J-aggregates of astaxanthin. The PIPO THG data clearly showed an isotropic organization of astaxanthin in red aplanospores of H. pluvialis. This is in contrast to the highly anisotropic organization of astaxanthin in synthetic H- and J-aggregates, which showed to be uniaxial. Since carotenoids in vitro preferentially form H- and J-aggregates, but in vivo form a randomly organized structure, this implies that astaxanthin undergoes a different way of packing in biological organisms, which is either due to the unique physical environment of the alga or is controlled enzymatically. PMID:25215522

  16. Organization of Astaxanthin within Oil Bodies of Haematococcus pluvialis Studied with Polarization-Dependent Harmonic Generation Microscopy

    PubMed Central

    Tokarz, Danielle; Cisek, Richard; El-Ansari, Omar; Espie, George S.; Fekl, Ulrich; Barzda, Virginijus

    2014-01-01

    Nonlinear optical microscopy was used to image the localization of astaxanthin accumulation in the green alga, Haematococcus pluvialis. Polarization-in, polarization-out (PIPO) second harmonic generation (SHG) and third harmonic generation (THG) microscopy was applied to study the crystalline organization of astaxanthin molecules in light-stressed H. pluvialis in vivo. Since astaxanthin readily forms H- and J-aggregates in aqueous solutions, PIPO THG studies of astaxanthin aggregates contained in red aplanospores were compared to PIPO THG of in vitro self-assembled H- and J-aggregates of astaxanthin. The PIPO THG data clearly showed an isotropic organization of astaxanthin in red aplanospores of H. pluvialis. This is in contrast to the highly anisotropic organization of astaxanthin in synthetic H- and J-aggregates, which showed to be uniaxial. Since carotenoids in vitro preferentially form H- and J-aggregates, but in vivo form a randomly organized structure, this implies that astaxanthin undergoes a different way of packing in biological organisms, which is either due to the unique physical environment of the alga or is controlled enzymatically. PMID:25215522

  17. Metal-Organic Framework Isomers with Diamondoid Networks Constructed of a Semi-Rigid Tetrahedral Linker

    SciTech Connect

    Tian, Jian; Motkuri, Radha K.; Thallapally, Praveen K.; McGrail, B. Peter

    2010-10-19

    Solvothermal assembly of a semi-rigid tetrahedral carboxylate ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4X) with Cd(II) ion in different solvent systems yields three novel metal-organic framework isomers (1-3) based on different secondary building units (SBUs). Although all three frameworks have the same dia (diamondoid) topology, complex 1 and 3 are chiral and complex 2 is achiral. One of the networks, 3 shows cross-linked three-fold interpenetration of the single dia net and exhibits permanent porosities, as confirmed by BET and selective CO2 adsorption.

  18. Introduction of a single isomer beta agonist.

    PubMed

    Rau, J L

    2000-08-01

    The release of levalbuterol offers the first approved single-isomer beta agonist for oral inhalation. Data from in vitro studies support the concept that S albuterol is not inactive and may have properties antagonistic to bronchodilation. There is some variability in the results of clinical studies with the separate isomers of albuterol, which suggests the need for further study. The introduction of levalbuterol into general clinical use in managing asthma and chronic obstructive disease should begin to offer additional information on the effects of a single isomer beta agonist in comparison to previous racemic mixtures. PMID:10963321

  19. Anti-inflammatory effects of astaxanthin in the human gingival keratinocyte line NDUSD-1

    PubMed Central

    Miyachi, Masashiro; Matsuno, Tomonori; Asano, Kazunari; Mataga, Izumi

    2015-01-01

    Oral lichen planus is a chronic inflammatory disease that affects the mucous membrane of the oral cavity and can contribute to the development of other diseases. Inflammation in oral lichen planus is a T-cell-mediated autoimmune disease that acts through cytotoxic CD8+ T cells to trigger apoptosis of keratinocytes. However, the specific cause of oral lichen planus remains unknown and no effective medical treatment has yet been established. Astaxanthin is a carotenoid pigment with capacity for anti-inflammatory and anti-oxidant activities. In this study, we evaluated whether astaxanthin could be used to improve the pathology of oral lichen planus by reducing inflammation. In particular, the anti-inflammatory effects of astaxanthin on the chronic inflammation caused by lipopolysaccharide derived from Escherichia coli O55 in human gingival keratinocytes (NDUSD-1) were evaluated. Following astaxanthin treatment, localization of nuclear factor κB/p65 and the level of inflammatory cytokines (interleukin-6, tumor necrosis factor-α) tended to decrease, and cell proliferation significantly increased in vitro. These results suggest that astaxanthin could be useful for improving chronic inflammation such as that associated with oral lichen planus. PMID:26060346

  20. Safety assessment of [3S, 3'S]-astaxanthin--Subchronic toxicity study in rats.

    PubMed

    Buesen, R; Schulte, S; Strauss, V; Treumann, S; Becker, M; Gröters, S; Carvalho, S; van Ravenzwaay, B

    2015-07-01

    Astaxanthin, a naturally occurring xanthophyll, is commercially used as a coloring agent in salmon feed, but also marketed as a dietary supplement. The objective of this study was to investigate the subchronic toxicity of synthetic [3S, 3'S]-Astaxanthin in rats. A powder formulation containing approximately 20% [3S, 3'S]-Astaxanthin was administered via the diet to groups of 10 male and 10 female Wistar rats at concentrations of 5000, 15,000 and 50,000 ppm for a period of 13 weeks. A formulation of comparable composition but without [3S, 3'S]-Astaxanthin served as a placebo control. There were no effects observed on survival, clinical examinations, clinical pathology, estrous cycle as well as on sperm parameters. At terminal necropsy, a macroscopically visible brown-blue discoloration of the gastrointestinal contents was noted which was considered to be secondary to the violet-brown color of the test material. No other significant or dose-related abnormalities were found in the tissues collected at termination. Our observations support that ingestion of [3S, 3'S]-Astaxanthin of up to 700-920 mg/kg bw/day in rats in a gelatin/carbohydrate formulation is without adverse effects. PMID:25910834

  1. Transcriptome Analysis in Haematococcus pluvialis: Astaxanthin Induction by Salicylic Acid (SA) and Jasmonic Acid (JA)

    PubMed Central

    Wu, Guanxun; Li, Guoqiang; Sun, Haifeng; Deng, Suzhen; Shen, Yicheng; Chen, Guoqiang; Zhang, Ruihao; Meng, Chunxiao; Zhang, Xiaowen

    2015-01-01

    Haematococcus pluvialis is an astaxanthin-rich microalga that can increase its astaxanthin production by salicylic acid (SA) or jasmonic acid (JA) induction. The genetic transcriptome details of astaxanthin biosynthesis were analyzed by exposing the algal cells to 25 mg/L of SA and JA for 1, 6 and 24 hours, plus to the control (no stress). Based on the RNA-seq analysis, 56,077 unigenes (51.7%) were identified with functions in response to the hormone stress. The top five identified subcategories were cell, cellular process, intracellular, catalytic activity and cytoplasm, which possessed 5600 (~9.99%), 5302 (~9.45%), 5242 (~9.35%), 4407 (~7.86%) and 4195 (~7.48%) unigenes, respectively. Furthermore, 59 unigenes were identified and assigned to 26 putative transcription factors (TFs), including 12 plant-specific TFs. They were likely associated with astaxanthin biosynthesis in Haematococcus upon SA and JA stress. In comparison, the up-regulation of differential expressed genes occurred much earlier, with higher transcript levels in the JA treatment (about 6 h later) than in the SA treatment (beyond 24 h). These results provide valuable information for directing metabolic engineering efforts to improve astaxanthin biosynthesis in H. pluvialis. PMID:26484871

  2. Production of the Marine Carotenoid Astaxanthin by Metabolically Engineered Corynebacterium glutamicum.

    PubMed

    Henke, Nadja A; Heider, Sabine A E; Peters-Wendisch, Petra; Wendisch, Volker F

    2016-01-01

    Astaxanthin, a red C40 carotenoid, is one of the most abundant marine carotenoids. It is currently used as a food and feed additive in a hundred-ton scale and is furthermore an attractive component for pharmaceutical and cosmetic applications with antioxidant activities. Corynebacterium glutamicum, which naturally synthesizes the yellow C50 carotenoid decaprenoxanthin, is an industrially relevant microorganism used in the million-ton amino acid production. In this work, engineering of a genome-reduced C. glutamicum with optimized precursor supply for astaxanthin production is described. This involved expression of heterologous genes encoding for lycopene cyclase CrtY, β-carotene ketolase CrtW, and hydroxylase CrtZ. For balanced expression of crtW and crtZ their translation initiation rates were varied in a systematic approach using different ribosome binding sites, spacing, and translational start codons. Furthermore, β-carotene ketolases and hydroxylases from different marine bacteria were tested with regard to efficient astaxanthin production in C. glutamicum. In shaking flasks, the C. glutamicum strains developed here overproduced astaxanthin with volumetric productivities up to 0.4 mg·L(-1)·h(-1) which are competitive with current algae-based production. Since C. glutamicum can grow to high cell densities of up to 100 g cell dry weight (CDW)·L(-1), the recombinant strains developed here are a starting point for astaxanthin production by C. glutamicum. PMID:27376307

  3. Separation of astaxanthin from cells of Phaffia rhodozyma using colloidal gas aphrons in a flotation column.

    PubMed

    Dermiki, Maria; Bourquin, Anne Lise; Jauregi, Paula

    2010-01-01

    The aim of this study is to investigate the separation of astaxanthin from the cells of Phaffia rhodozyma using colloidal gas aphrons (CGA), which are surfactant stabilized microbubbles, in a flotation column. It was reported in previous studies that optimum recoveries are achieved at conditions that favor electrostatic interactions. Therefore, in this study, CGA generated from the cationic surfactant hexadecyl trimethyl ammonium bromide (CTAB) were applied to suspensions of cells pretreated with NaOH. The different operation modes (batch or continuous) and the effect of volumetric ratio of CGA to feed, initial concentration of feed, operating height, and flow rate of CGA on the separation of astaxanthin were investigated. The volumetric ratio was found to have a significant effect on the separation of astaxanthin for both batch and continuous experiments. Additionally, the effect of homogenization of the cells on the purity of the recovered fractions was investigated, showing that the homogenization resulted in increased purity. Moreover, different concentrations of surfactant were used for the generation of CGA for the recovery of astaxanthin on batch mode; it was found that recoveries up to 98% could be achieved using CGA generated from a CTAB solution 0.8 mM, which is below the CTAB critical micellar concentration (CMC). These results offer important information for the scale-up of the separation of astaxanthin from the cells of P. rhodozyma using CGA. PMID:19941328

  4. Transcriptome Analysis in Haematococcus pluvialis: Astaxanthin Induction by Salicylic Acid (SA) and Jasmonic Acid (JA).

    PubMed

    Gao, Zhengquan; Li, Yan; Wu, Guanxun; Li, Guoqiang; Sun, Haifeng; Deng, Suzhen; Shen, Yicheng; Chen, Guoqiang; Zhang, Ruihao; Meng, Chunxiao; Zhang, Xiaowen

    2015-01-01

    Haematococcus pluvialis is an astaxanthin-rich microalga that can increase its astaxanthin production by salicylic acid (SA) or jasmonic acid (JA) induction. The genetic transcriptome details of astaxanthin biosynthesis were analyzed by exposing the algal cells to 25 mg/L of SA and JA for 1, 6 and 24 hours, plus to the control (no stress). Based on the RNA-seq analysis, 56,077 unigenes (51.7%) were identified with functions in response to the hormone stress. The top five identified subcategories were cell, cellular process, intracellular, catalytic activity and cytoplasm, which possessed 5600 (~9.99%), 5302 (~9.45%), 5242 (~9.35%), 4407 (~7.86%) and 4195 (~7.48%) unigenes, respectively. Furthermore, 59 unigenes were identified and assigned to 26 putative transcription factors (TFs), including 12 plant-specific TFs. They were likely associated with astaxanthin biosynthesis in Haematococcus upon SA and JA stress. In comparison, the up-regulation of differential expressed genes occurred much earlier, with higher transcript levels in the JA treatment (about 6 h later) than in the SA treatment (beyond 24 h). These results provide valuable information for directing metabolic engineering efforts to improve astaxanthin biosynthesis in H. pluvialis. PMID:26484871

  5. Four different methods comparison for extraction of astaxanthin from green alga Haematococcus pluvialis.

    PubMed

    Dong, Shengzhao; Huang, Yi; Zhang, Rui; Wang, Shihui; Liu, Yun

    2014-01-01

    Haematococcus pluvialis is one of the potent organisms for production of astaxanthin. Up to now, no efficient method has been achieved due to its thick cell wall hindering solvent extraction of astaxanthin. In this study, four different methods, hydrochloric acid pretreatment followed by acetone extraction (HCl-ACE), hexane/isopropanol (6:4, v/v) mixture solvents extraction (HEX-IPA), methanol extraction followed by acetone extraction (MET-ACE, 2-step extraction), and soy-oil extraction, were intensively evaluated for extraction of astaxanthin from H. pluvialis. Results showed that HCl-ACE method could obtain the highest oil yield (33.3±1.1%) and astaxanthin content (19.8±1.1%). Quantitative NMR analysis provided the fatty acid chain profiles of total lipid extracts. In all cases, oleyl chains were predominant, and high amounts of polyunsaturated fatty acid chains were observed and the major fatty acid components were oleic acid (13-35%), linoleic acid (37-43%), linolenic acid (20-31%), and total saturated acid (17-28%). DPPH radical scavenging activity of extract obtained by HCl-ACE was 73.2±1.0%, which is the highest amongst the four methods. The reducing power of extract obtained by four extraction methods was also examined. It was concluded that the proposed extraction method of HCl-ACE in this work allowed efficient astaxanthin extractability with high antioxidant properties. PMID:24574909

  6. Four Different Methods Comparison for Extraction of Astaxanthin from Green Alga Haematococcus pluvialis

    PubMed Central

    Dong, Shengzhao; Huang, Yi; Zhang, Rui; Wang, Shihui; Liu, Yun

    2014-01-01

    Haematococcus pluvialis is one of the potent organisms for production of astaxanthin. Up to now, no efficient method has been achieved due to its thick cell wall hindering solvent extraction of astaxanthin. In this study, four different methods, hydrochloric acid pretreatment followed by acetone extraction (HCl-ACE), hexane/isopropanol (6 : 4, v/v) mixture solvents extraction (HEX-IPA), methanol extraction followed by acetone extraction (MET-ACE, 2-step extraction), and soy-oil extraction, were intensively evaluated for extraction of astaxanthin from H. pluvialis. Results showed that HCl-ACE method could obtain the highest oil yield (33.3 ± 1.1%) and astaxanthin content (19.8 ± 1.1%). Quantitative NMR analysis provided the fatty acid chain profiles of total lipid extracts. In all cases, oleyl chains were predominant, and high amounts of polyunsaturated fatty acid chains were observed and the major fatty acid components were oleic acid (13–35%), linoleic acid (37–43%), linolenic acid (20–31%), and total saturated acid (17–28%). DPPH radical scavenging activity of extract obtained by HCl-ACE was 73.2 ± 1.0%, which is the highest amongst the four methods. The reducing power of extract obtained by four extraction methods was also examined. It was concluded that the proposed extraction method of HCl-ACE in this work allowed efficient astaxanthin extractability with high antioxidant properties. PMID:24574909

  7. Milks pigmentation with astaxanthin and determination of colour stability during short period cold storage.

    PubMed

    Mezquita, Pedro Cerezal; Huerta, Blanca E Barragán; Ramírez, Jenifer C Palma; Hinojosa, Claudia P Ortíz

    2015-03-01

    Astaxanthin has been used as a colorant and antioxidant with excellent results, its application and stability in food matrices to human consumption has been little studied. The aim of this work was the incorporation of astaxanthin oleoresin to milks with different fat content, simulating the red-orange color that can impart apricot fruit. For astaxanthin determination by HPLC, a methodology was implemented for its extraction from the food matrix, followed by saponification with KOH. Milk samples were stored (5 ± 2 °C) and stability of color and astaxanthin content were determined by colorimetry and high performance liquid chromatography each 24 h for a week. Pigment degradation followed first-order kinetic with a constant degradation of 0.259 day(-1) and 0.104 day(-1), in whole and semi-skimmed milk, respectively. Chromaticity coordinates L*, a*, b* for different types of milk showed a low dispersion of their values during the storage time, indicating high stability of astaxanthin within the matrix. PMID:25745234

  8. Extraction of astaxanthin from Euphausia pacific using subcritical 1, 1, 1, 2-tetrafluoroethane

    NASA Astrophysics Data System (ADS)

    Han, Yuqian; Ma, Qinchuan; Wang, Lan; Xue, Changhu

    2012-12-01

    Euphausia pacific is an important source of natural astaxanthin. Studies were carried out to assess the extractability of astaxanthin from E. pacific using subcritical 1, 1, 1, 2-tetrafluoroethane (R134a). To examine the effects of multiple process variables on the extraction yield, astaxanthin was extracted under various conditions of pressure (30-150 bar), temperature (303-343 K), time (10-50 min), flow rate (2-10 g min-1), moisture content (5.5%-63.61%), and particle size (0.25-0.109 mm). The results showed that the extraction yield increased with temperature, pressure, time and flow rate, but decreased with moisture content and particle size. A maximum yield of 87.74% was obtained under conditions of 100 bar, 333 K, and 30 min with a flow rate of 6 g min-1 and a moisture content of 5.5%. The substantial astaxanthin yield obtained under low-pressure conditions demonstrates that subcritical R134a is a good alternative to CO2 for extraction of astaxanthin from E. pacific.

  9. Molasses-based growth and production of oil and astaxanthin by Chlorella zofingiensis.

    PubMed

    Liu, Jin; Huang, Junchao; Jiang, Yue; Chen, Feng

    2012-03-01

    The aim of this study is to evaluate the industrial waste cane molasses as a carbon source for cell growth, lipid and astaxanthin production of Chlorella zofingiensis. Pretreated with cation exchange resin to remove the metal ions, cane molasses provided better productivities of biomass, lipid, and astaxanthin (1.55, 0.71 g L(-1)day(-1) and 1.7 mg L(-1)day(-1), respectively) than glucose. Using a strategy of semi-continuous cultures coupled with feeding at a low concentration, molasses without pretreatment has the same effect as pretreated one on supporting the algal cell growth, lipid and astaxanthin production. The efficient metabolism of molasses triggered the up-regulation of genes involved in fatty acid and also astaxanthin biosynthesis, leading to the very high production of the two metabolites. This study highlights the possibility of using C. zofingiensis to deal with industrial wastes and to produce profitable biodiesel as well as the high-value astaxanthin. PMID:22221991

  10. Production of the Marine Carotenoid Astaxanthin by Metabolically Engineered Corynebacterium glutamicum

    PubMed Central

    Henke, Nadja A.; Heider, Sabine A. E.; Peters-Wendisch, Petra; Wendisch, Volker F.

    2016-01-01

    Astaxanthin, a red C40 carotenoid, is one of the most abundant marine carotenoids. It is currently used as a food and feed additive in a hundred-ton scale and is furthermore an attractive component for pharmaceutical and cosmetic applications with antioxidant activities. Corynebacterium glutamicum, which naturally synthesizes the yellow C50 carotenoid decaprenoxanthin, is an industrially relevant microorganism used in the million-ton amino acid production. In this work, engineering of a genome-reduced C. glutamicum with optimized precursor supply for astaxanthin production is described. This involved expression of heterologous genes encoding for lycopene cyclase CrtY, β-carotene ketolase CrtW, and hydroxylase CrtZ. For balanced expression of crtW and crtZ their translation initiation rates were varied in a systematic approach using different ribosome binding sites, spacing, and translational start codons. Furthermore, β-carotene ketolases and hydroxylases from different marine bacteria were tested with regard to efficient astaxanthin production in C. glutamicum. In shaking flasks, the C. glutamicum strains developed here overproduced astaxanthin with volumetric productivities up to 0.4 mg·L−1·h−1 which are competitive with current algae-based production. Since C. glutamicum can grow to high cell densities of up to 100 g cell dry weight (CDW)·L−1, the recombinant strains developed here are a starting point for astaxanthin production by C. glutamicum. PMID:27376307

  11. Improved Chiral Separation of Methamphetamine Enantiomers Using CSP-LC-MS-MS.

    PubMed

    Ward, Lauren F; Enders, Jeffrey R; Bell, David S; Cramer, Hugh M; Wallace, Frank N; McIntire, Gregory L

    2016-05-01

    To determine the true enantiomeric composition of methamphetamine urine drug testing results, chiral separation of dextro (d) and levo (l) enantiomers is necessary. While enantiomeric separation of methamphetamine has traditionally been accomplished using gas chromatography-mass spectrometry (GC-MS), chiral separation ofd- andl-methamphetamine by chiral stationary phase (CSP) liquid chromatography-mass spectrometry/mass spectrometry (LC-MS-MS) has proved more reliable. Chirally selective detection of methamphetamine by GC-MS is often performed usingl-N-trifluoroacetyl-prolyl chloride (TPC).l-TPC, a chiral compound, is known to have impurities that can affect the chiral composition percentages of the methamphetamine sample, potentially leading to inaccurate patient results. The comparative analysis of the samples run by GC and LC methods showed preferential bias of the GC method for producing error rates, consistent with previous research, of 8-19%. The CSP-LC-MS-MS method produces percent deviation errors of <2%. Additionally, the GC method failed to produce results that were 100%d- orl-isomer even for enantiomerically pure standards. A higher rate ofd- andl-methamphetamine isomer racemization is seen in samples when analyzed by GC-MS usingl-TPC-derivatizing agent. This racemization is not seen when these samples are tested with CSP-LC-MS-MS. Thus, a more accurate method of enantiomeric analysis is provided by CSP-LC-MS-MS. PMID:26869715

  12. Astaxanthin Normalizes Epigenetic Modifications of Bovine Somatic Cell Cloned Embryos and Decreases the Generation of Lipid Peroxidation.

    PubMed

    Li, R; Wu, H; Zhuo, W W; Mao, Q F; Lan, H; Zhang, Y; Hua, S

    2015-10-01

    Astaxanthin is an extremely common antioxidant scavenging reactive oxygen species (ROS) and blocking lipid peroxidation. This study was conducted to investigate the effects of astaxanthin supplementation on oocyte maturation, and development of bovine somatic cell nuclear transfer (SCNT) embryos. Cumulus-oocyte complexes were cultured in maturation medium with astaxanthin (0, 0.5, 1.0, or 1.5 mg/l), respectively. We found that 0.5 mg/l astaxanthin supplementation significantly increased the proportion of oocyte maturation. Oocytes cultured in 0.5 mg/l astaxanthin supplementation were used to construct SCNT embryos and further cultured with 0, 0.5, 1.0 or 1.5 mg/l astaxanthin. The results showed that the supplementation of 0.5 mg/l astaxanthin significantly improved the proportions of cleavage and blastulation, as well as the total cell number in blastocysts compared with the control group, yet this influence was not concentration dependent. Chromosomal analyses revealed that more blastomeres showed a normal chromosomal complement in 0.5 mg/l astaxanthin treatment group, which was similar to that in IVF embryos. The methylation levels located on the exon 1 of the imprinted gene H19 and IGF2, pluripotent gene OCT4 were normalized, and global DNA methylation, H3K9 and H4K12 acetylation were also improved significantly, which was comparable to that in vitro fertilization (IVF) embryos. Moreover, we also found that astaxanthin supplementation significantly decreased the level of lipid peroxidation. Our findings showed that the supplementation of 0.5 mg/l astaxanthin to oocyte maturation medium and embryo culture medium improved oocyte maturation, SCNT embryo development, increased chromosomal stability and normalized the epigenetic modifications, as well as inhibited overproduction of lipid peroxidation. PMID:26280670

  13. Astaxanthin enhances ATP-binding cassette transporter A1/G1 expressions and cholesterol efflux from macrophages.

    PubMed

    Iizuka, Maki; Ayaori, Makoto; Uto-Kondo, Harumi; Yakushiji, Emi; Takiguchi, Shunichi; Nakaya, Kazuhiro; Hisada, Tetsuya; Sasaki, Makoto; Komatsu, Tomohiro; Yogo, Makiko; Kishimoto, Yoshimi; Kondo, Kazuo; Ikewaki, Katsunori

    2012-01-01

    ATP-binding cassette transporters (ABC) A1 and G1 are key molecules in cholesterol efflux from macrophages, which is an initial step of reverse cholesterol transport (RCT), a major anti-atherogenic property of high-density lipoprotein (HDL). Astaxanthin is one of the naturally occurring carotenoids responsible for the pink-red pigmentation in a variety of living organisms. Although astaxanthin is known to be a strong antioxidant, it remains unclear through what mechanism of action it affects cholesterol homeostasis in macrophages. We therefore investigated the effects of astaxanthin on cholesterol efflux and ABCA1/G1 expressions in macrophages. Astaxanthin enhanced both apolipoprotein (apo) A-I- and HDL-mediated cholesterol efflux from RAW264.7 cells. In supporting these enhanced cholesterol efflux mechanisms, astaxanthin promoted ABCA1/G1 expression in various macrophages. In contrast, peroxisome proliferator-activated receptor γ, liver X receptor (LXR) α and LXRβ levels remained unchanged by astaxanthin. An experiment using actinomycin D demonstrated that astaxanthin transcriptionally induced ABCA1/G1 expression, and oxysterol depletion caused by overexpression of cholesterol sulfotransferase further revealed that these inductions in ABCA1/G1 were independent of LXR-mediated pathways. Finally, we performed luciferase assays using human ABCA1/G1 promoter-reporter constructs to reveal that astaxanthin activated both promoters irrespective of the presence or absence of LXR-responsive elements, indicating LXR-independence of these activations. In conclusion, astaxanthin increased ABCA1/G1 expression, thereby enhancing apoA-I/HDL-mediated cholesterol efflux from the macrophages in an LXR-independent manner. In addition to the anti-oxidative properties, the potential cardioprotective properties of astaxanthin might therefore be associated with an enhanced anti-atherogenic function of HDL. PMID:22790567

  14. Chiral geometry in multiple chiral doublet bands

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Chen, Qibo

    2016-02-01

    The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

  15. On the nature of non-covalent interactions in isomers of 2,5-dichloro-1,4-benzoquinone dimers - ground- and excited-state properties.

    PubMed

    Vijaya Pandiyan, B; Deepa, P; Kolandaivel, P

    2014-10-01

    The competition between non-covalent interactions (NCIs), such as C-H∙∙∙O, C-H∙∙∙Cl, C-Cl∙∙∙O, C-Cl∙∙∙Cl-C, C-O∙∙∙C, C-Cl∙∙∙C and C-O∙∙∙π, in the isomers of the 2,5-dichloro-1,4-benzoquinone (DCBQ) dimer were investigated by quantum chemical calculations to study the properties of the ground and excited states. All the interactions were identified through bond critical points (BCP) with an atoms in molecule (AIM) study. Isomer 1 (IH) and isomer 6 (IP) were surprisingly very stable, and the largest stabilization energies of 4.16 and 5.39 kcal mol(-1), respectively, were observed for the ground state and 5.67 and 6.07 kcal mol(-1), respectively, were observed for the excited state at the MP2/6-31++G(d,p) level of theory. The orientations of the excited-state isomers were similar to those of the ground-state except for isomer 5 (IX) and isomer 9 (IM), which disturbed the relative energy stability order. The calculated absorption spectra have shown two absorption splits for isomers 5, 7, 8 and 9 through the acute angle between the transition dipole moment of the monomers. The circular dichroism (CD) couplet of the CD spectrum and the value of optical rotation (OR) have indicated that isomers 1, 3, 5, 7, 8 and 9 have chiral characteristics. The study of the absorption and CD spectra has revealed the impact of intermolecular NCIs on chirality. PMID:25119497

  16. Subthreshold kaons would reveal density isomers

    SciTech Connect

    Hartnack, C.; Aichelin, J.; Stoecker, H.; Greiner, W. Gesellschaft fuer Schwerionenforschung, D-64220 Darmstadt Institut fuer Theoretische Physik, Universitaet Frankfurt, D-60065 Frankfurt )

    1994-06-13

    If density isomers exist they can be detected by measuring the excitation function of subthreshold kaon production. When the system reaches the density where the density isomer has influence on the equation of state (which depends on the beam energy and on the optical potential), we observe a jump in the cross section of the kaons whereas other observables change little. Above threshold [bar [Lambda

  17. Energetic and Structural Study of Diphenylpyridine Isomers

    NASA Astrophysics Data System (ADS)

    Rocha, Marisa A. A.; Gomes, Lígia R.; Low, John N.; Santos, Luís M. N. B. F.

    2009-09-01

    The energetic and structural study of three diphenylpyridine isomers is presented in detail. The three isomers, 2,6-, 2,5-, and 3,5-diphenylpyridines, were synthesized via Suzuki-Miyaura methodology based on palladium catalysis, and the crystal structures of the isomers were obtained by X-ray diffraction. The relative energetic stabilities in the condensed and gaseous phases as well as volatilities and structures of the three studied isomers were evaluated, regarding the position of the phenyl groups relative to the nitrogen atom of the pyridine ring. The temperature, standard molar enthalpies, and entropies of fusion were measured and derived by differential scanning calorimetry. The vapor pressures of the considered isomers were determined by a static apparatus based on a MKS capacitance diaphragm manometer. The standard molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived, and the phase diagram near the triple point coordinates were determined for all isomers. The standard (p° = 0.1 MPa) molar enthalpies of combustion of all crystalline isomers were determined, at T = 298.15 K, by static bomb combustion calorimetry. The standard molar enthalpies of formation, in the crystalline and gaseous phases, at T = 298.15 K, were derived. The experimental results for the energetics in the gaseous phase of the three compounds were compared and assessed with the values obtained by ab initio calculations at different levels of theory (DFT and MP2) showing that, at this level of theory, the computational methods underestimate the energetic stability, in the gaseous phase, for these molecules. In order to understand the aromaticity in the central ring of each isomer, calculations of NICS (B3LYP/6-311G++(d,p) level of theory) values on the pyridine ring were also performed.

  18. Optimization of the IPP Precursor Supply for the Production of Lycopene, Decaprenoxanthin and Astaxanthin by Corynebacterium glutamicum

    PubMed Central

    Heider, Sabine A. E.; Wolf, Natalie; Hofemeier, Arne; Peters-Wendisch, Petra; Wendisch, Volker F.

    2014-01-01

    The biotechnologically relevant bacterium Corynebacterium glutamicum, currently used for the million ton-scale production of amino acids for the food and feed industries, is pigmented due to synthesis of the rare cyclic C50 carotenoid decaprenoxanthin and its glucosides. The precursors of carotenoid biosynthesis, isopenthenyl pyrophosphate (IPP) and its isomer dimethylallyl pyrophosphate, are synthesized in this organism via the methylerythritol phosphate (MEP) or non-mevalonate pathway. Terminal pathway engineering in recombinant C. glutamicum permitted the production of various non-native C50 and C40 carotenoids. Here, the role of engineering isoprenoid precursor supply for lycopene production by C. glutamicum was characterized. Overexpression of dxs encoding the enzyme that catalyzes the first committed step of the MEP-pathway by chromosomal promoter exchange in a prophage-cured, genome-reduced C. glutamicum strain improved lycopene formation. Similarly, an increased IPP supply was achieved by chromosomal integration of two artificial operons comprising MEP pathway genes under the control of a constitutive promoter. Combined overexpression of dxs and the other six MEP pathways genes in C. glutamicum strain LYC3-MEP was not synergistic with respect to improving lycopene accumulation. Based on C. glutamicum strain LYC3-MEP, astaxanthin could be produced in the milligrams per gram cell dry weight range when the endogenous genes crtE, crtB, and crtI for conversion of geranylgeranyl pyrophosphate to lycopene were coexpressed with the genes for lycopene cyclase and β-carotene hydroxylase from Pantoea ananatis and carotene C(4) oxygenase from Brevundimonas aurantiaca. PMID:25191655

  19. Physico-chemical stability of astaxanthin nanodispersions prepared with polysaccharides as stabilizing agents.

    PubMed

    Anarjan, Navideh; Tan, Chin Ping

    2013-09-01

    The emulsification and stabilization ability of four selected polysaccharides, namely, gum Arabic, xanthan gum, pectin and methyl cellulose, in the preparation of water-dispersible astaxanthin nanoparticles using the emulsification-evaporation technique was investigated in this study. The chemical and molecular structure of polysaccharides had significant effects (p < 0.05) on the physicochemical properties of the prepared astaxanthin nanodispersions. Among all prepared nanodispersions, sample produced and stabilized using gum Arabic showed the smallest average particle size (295 nm) and highest physical stability. The observed considerable degradation of astaxanthin in the resulting nanodispersions during processing (24-70% w/w) and storage at 10 °C for 30 d (86-96% w/w) illustrated the limited chemical stability of polysaccharide-stabilized nanodispersions. PMID:23590613

  20. Cell-wall disruption and lipid/astaxanthin extraction from microalgae: Chlorella and Haematococcus.

    PubMed

    Kim, Dong-Yeon; Vijayan, Durairaj; Praveenkumar, Ramasamy; Han, Jong-In; Lee, Kyubock; Park, Ji-Yeon; Chang, Won-Seok; Lee, Jin-Suk; Oh, You-Kwan

    2016-01-01

    Recently, biofuels and nutraceuticals produced from microalgae have emerged as major interests, resulting in intensive research of the microalgal biorefinery process. In this paper, recent developments in cell-wall disruption and extraction methods are reviewed, focusing on lipid and astaxanthin production from the biotechnologically important microalgae Chlorella and Haematococcus, respectively. As a common, critical bottleneck for recovery of intracellular components such as lipid and astaxanthin from these microalgae, the composition and structure of rigid, thick cell-walls were analyzed. Various chemical, physical, physico-chemical, and biological methods applied for cell-wall breakage and lipid/astaxanthin extraction from Chlorella and Haematococcus are discussed in detail and compared based on efficiency, energy consumption, type and dosage of solvent, biomass concentration and status (wet/dried), toxicity, scalability, and synergistic combinations. This report could serve as a useful guide to the implementation of practical downstream processes for recovery of valuable products from microalgae including Chlorella and Haematococcus. PMID:26342788

  1. Effects of Astaxanthin from Litopenaeus Vannamei on Carrageenan-Induced Edema and Pain Behavior in Mice.

    PubMed

    Kuedo, Zulkiflee; Sangsuriyawong, Anantita; Klaypradit, Wanwimol; Tipmanee, Varomyalin; Chonpathompikunlert, Pennapa

    2016-01-01

    Carrageenan produces both inflammation and pain when injected in mouse paws via enhancement of reactive oxygen species formation. We have investigated an effect of astaxanthin extracted from Litopenaeus vannamei in carrageenan-induced mice paw edema and pain. The current study demonstrates interesting effects from astaxanthin treatment in mice: an inhibition of paw edema induced in hind paw, an increase in mechanical paw withdrawal threshold and thermal paw withdrawal latency, and a reduction in the amount of myeloperoxidase enzyme and lipid peroxidation products in the paw. Furthermore the effect was comparable to indomethacin, a standard treatment for inflammation symptoms. Due to adverse effects of indomethacin on cardiovascular and gastrointestinal systems, our study suggests promising prospect of astaxanthin extract as an anti-inflammatory alternative against carrageenan-induced paw edema and pain behavior. PMID:27007359

  2. Recovery of astaxanthin from discharged wastewater during the production of chitin

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolin; Yang, Shengfeng; Xing, Ronge; Yu, Huahua; Liu, Song; Li, Pengcheng

    2012-06-01

    In this paper, studies were carried out to extract astaxanthin from discharged wastewater during the production of chitin and to reveal the scavenging effect of the obtained pigment on 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radical. Different ratios of dichloromethane/methanol (V/V) were used to extract astaxanthin. When the ratio of dichloromethane/methanol was 2:8 and the ratio between the mixed organic solvent (dichloromethane/methanol, 2:8, V/V) and wastewater was 1:1, the highest yield of pigment was obtained (8.4 mg/50 mL). The concentration of free astaxanthin in the obtained pigment analyzed by HPLC was 30.02%. The obtained pigment possessed strong scavenging ability on DPPH radical and IC50 was 0.84mg/ml.

  3. Specific light uptake rates can enhance astaxanthin productivity in Haematococcus lacustris.

    PubMed

    Lee, Ho-Sang; Kim, Z-Hun; Park, Hanwool; Lee, Choul-Gyun

    2016-05-01

    Lumostatic operation was applied for efficient astaxanthin production in autotrophic Haematococcus lacustris cultures using 0.4-L bubble column photobioreactors. The lumostatic operation in this study was performed with three different specific light uptake rates (q(e)) based on cell concentration, cell projection area, and fresh weight as one-, two- and three-dimensional characteristics values, respectively. The q(e) value from the cell concentration (q(e1D)) obtained was 13.5 × 10⁻⁸ μE cell⁻¹ s⁻¹, and the maximum astaxanthin concentration was increased to 150 % compared to that of a control with constant light intensity. The other optimum q e values by cell projection area (q(e2D)) and fresh weight (q( e3D)) were determined to be 195 μE m⁻² s⁻¹ and 10.5 μE g⁻¹ s⁻¹ for astaxanthin production, respectively. The maximum astaxanthin production from the lumostatic cultures using the parameters controlled by cell projection area (2D) and fresh weight (3D) also increased by 36 and 22% over that of the controls, respectively. When comparing the optimal q e values among the three different types, the lumostatic cultures using q(e) based on fresh weight showed the highest astaxanthin productivity (22.8 mg L⁻¹ day⁻¹), which was a higher level than previously reported. The lumostatic operations reported here demonstrated that more efficient and effective astaxanthin production was obtained by H. lacustris than providing a constant light intensity, regardless of which parameter is used to calculate the specific light uptake rate. PMID:26873706

  4. One-solvent extraction of astaxanthin from lactic acid fermented shrimp wastes.

    PubMed

    Gimeno, Miquel; Ramírez-Hernández, Jessica Yesemite; Mártinez-Ibarra, César; Pacheco, Neith; García-Arrazola, Roeb; Bárzana, Eduardo; Shirai, Keiko

    2007-12-12

    Free astaxanthin one-solvent extractions with ethanol, acetone, and liquid 1,1,1,2-tetrafluoroethane from raw and lactic acid fermented (ensilaged) shrimp residues were investigated. The total carotenoid recovery from ensilaged shrimp wastes was higher than that from non-ensilaged ones as assessed by HPLC analyses. Acetone gave the highest extraction yields of free astaxanthin with up to 115 microg/g of material. Moreover, liquid tetrafluoroethane is reported for the first time in a successful one-solvent extraction of carotenoids from shrimp. PMID:18020413

  5. Chiral Perturbation Theory

    NASA Astrophysics Data System (ADS)

    Tiburzi, Brian C.

    The era of high-precision lattice QCD has led to synergy between lattice computations and phenomenological input from chiral perturbation theory. We provide an introduction to chiral perturbation theory with a bent towards understanding properties of the nucleon and other low-lying baryons. Four main topics are the basis for this chapter. We begin with a discussion of broken symmetries and the procedure to construct the chiral Lagrangian. The second topic concerns specialized applications of chiral perturbation theory tailored to lattice QCD, such as partial quenching, lattice discretization, and finite-volume effects. We describe inclusion of the nucleon in chiral perturbation theory using a heavy-fermion Euclidean action. Issues of convergence are taken up as our final topic. We consider expansions in powers of the strange-quark mass, and the appearance of unphysical singularities in the heavy-particle formulation. Our aim is to guide lattice practitioners in understanding the predictions chiral perturbation theory makes for baryons, and show how the lattice will play a role in testing the rigor of the chiral expansion at physical values of the quark masses.

  6. Applications of chiral symmetry

    SciTech Connect

    Pisarski, R.D.

    1995-03-01

    The author discusses several topics in the applications of chiral symmetry at nonzero temperature. First, where does the rho go? The answer: up. The restoration of chiral symmetry at a temperature T{sub {chi}} implies that the {rho} and a{sub 1} vector mesons are degenerate in mass. In a gauged linear sigma model the {rho} mass increases with temperature, m{sub {rho}}(T{sub {chi}}) > m{sub {rho}}(0). The author conjectures that at T{sub {chi}} the thermal {rho} - a{sub 1}, peak is relatively high, at about {approximately}1 GeV, with a width approximately that at zero temperature (up to standard kinematic factors). The {omega} meson also increases in mass, nearly degenerate with the {rho}, but its width grows dramatically with temperature, increasing to at least {approximately}100 MeV by T{sub {chi}}. The author also stresses how utterly remarkable the principle of vector meson dominance is, when viewed from the modern perspective of the renormalization group. Secondly, he discusses the possible appearance of disoriented chiral condensates from {open_quotes}quenched{close_quotes} heavy ion collisions. It appears difficult to obtain large domains of disoriented chiral condensates in the standard two flavor model. This leads to the last topic, which is the phase diagram for QCD with three flavors, and its proximity to the chiral critical point. QCD may be very near this chiral critical point, and one might thereby generated large domains of disoriented chiral condensates.

  7. Chirality control in oligothiophene through chiral wrapping.

    PubMed

    Sanji, Takanobu; Kato, Nobu; Tanaka, Masato

    2006-01-19

    [structure: see text] Mixing oligothiophenes and polysaccharides, such as amylose and schizophyllan, affords novel inclusion complexes, in which oligothiophene guests adopt twisted conformation in the chiral channel created by left- or right-handed helical wrapping with the polysaccharide host polymers, leading to optical activity. PMID:16408883

  8. Astaxanthin reduces ischemic brain injury in adult rats.

    PubMed

    Shen, Hui; Kuo, Chi-Chung; Chou, Jenny; Delvolve, Alice; Jackson, Shelley N; Post, Jeremy; Woods, Amina S; Hoffer, Barry J; Wang, Yun; Harvey, Brandon K

    2009-06-01

    Astaxanthin (ATX) is a dietary carotenoid of crustaceans and fish that contributes to their coloration. Dietary ATX is important for development and survival of salmonids and crustaceans and has been shown to reduce cardiac ischemic injury in rodents. The purpose of this study was to examine whether ATX can protect against ischemic injury in the mammalian brain. Adult rats were injected intracerebroventricularly with ATX or vehicle prior to a 60-min middle cerebral artery occlusion (MCAo). ATX was present in the infarction area at 70-75 min after onset of MCAo. Treatment with ATX, compared to vehicle, increased locomotor activity in stroke rats and reduced cerebral infarction at 2 d after MCAo. To evaluate the protective mechanisms of ATX against stroke, brain tissues were assayed for free radical damage, apoptosis, and excitoxicity. ATX antagonized ischemia-mediated loss of aconitase activity and reduced glutamate release, lipid peroxidation, translocation of cytochrome c, and TUNEL labeling in the ischemic cortex. ATX did not alter physiological parameters, such as body temperature, brain temperature, cerebral blood flow, blood gases, blood pressure, and pH. Collectively, our data suggest that ATX can reduce ischemia-related injury in brain tissue through the inhibition of oxidative stress, reduction of glutamate release, and antiapoptosis. ATX may be clinically useful for patients vulnerable or prone to ischemic events. PMID:19218497

  9. Multiple Mechanisms of Anti-Cancer Effects Exerted by Astaxanthin

    PubMed Central

    Zhang, Li; Wang, Handong

    2015-01-01

    Astaxanthin (ATX) is a xanthophyll carotenoid which has been approved by the United States Food and Drug Administration (USFDA) as food colorant in animal and fish feed. It is widely found in algae and aquatic animals and has powerful anti-oxidative activity. Previous studies have revealed that ATX, with its anti-oxidative property, is beneficial as a therapeutic agent for various diseases without any side effects or toxicity. In addition, ATX also shows preclinical anti-tumor efficacy both in vivo and in vitro in various cancer models. Several researches have deciphered that ATX exerts its anti-proliferative, anti-apoptosis and anti-invasion influence via different molecules and pathways including signal transducer and activator of transcription 3 (STAT3), nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) and peroxisome proliferator-activated receptor gamma (PPARγ). Hence, ATX shows great promise as chemotherapeutic agents in cancer. Here, we review the rapidly advancing field of ATX in cancer therapy as well as some molecular targets of ATX. PMID:26184238

  10. Synthesis of Chiral Cyclopentenones.

    PubMed

    Simeonov, Svilen P; Nunes, João P M; Guerra, Krassimira; Kurteva, Vanya B; Afonso, Carlos A M

    2016-05-25

    The cyclopentenone unit is a very powerful synthon for the synthesis of a variety of bioactive target molecules. This is due to the broad diversity of chemical modifications available for the enone structural motif. In particular, chiral cyclopentenones are important precursors in the asymmetric synthesis of target chiral molecules. This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetric functionalization of the existing cyclopentenone unit, and functionalization of chiral building blocks. PMID:27101336

  11. The covariant chiral ring

    NASA Astrophysics Data System (ADS)

    Bourget, Antoine; Troost, Jan

    2016-03-01

    We construct a covariant generating function for the spectrum of chiral primaries of symmetric orbifold conformal field theories with N = (4 , 4) supersymmetry in two dimensions. For seed target spaces K3 and T 4, the generating functions capture the SO(21) and SO(5) representation theoretic content of the chiral ring respectively. Via string dualities, we relate the transformation properties of the chiral ring under these isometries of the moduli space to the Lorentz covariance of perturbative string partition functions in flat space.

  12. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

    The analysis of the magnetic domain wall motion in a nanostructured magnetic system with strong spin-orbit coupling shows that the energy dissipation can be chiral when the inversion symmetry is broken. PMID:26906956

  13. Nonlinear chiral transport phenomena

    NASA Astrophysics Data System (ADS)

    Chen, Jiunn-Wei; Ishii, Takeaki; Pu, Shi; Yamamoto, Naoki

    2016-06-01

    We study the nonlinear responses of relativistic chiral matter to the external fields such as the electric field E , gradients of temperature and chemical potential, ∇T and ∇μ . Using the kinetic theory with Berry curvature corrections under the relaxation time approximation, we compute the transport coefficients of possible new electric currents that are forbidden in usual chirally symmetric matter but are allowed in chirally asymmetric matter by parity. In particular, we find a new type of electric current proportional to ∇μ ×E due to the interplay between the effects of the Berry curvature and collisions. We also derive an analog of the "Wiedemann-Franz" law specific for anomalous nonlinear transport in relativistic chiral matter.

  14. Metolachlor stereoisomers: Enantioseparation, identification and chiral stability.

    PubMed

    Xie, Jingqian; Zhang, Lijuan; Zhao, Lu; Tang, Qiaozhi; Liu, Kai; Liu, Weiping

    2016-09-01

    Metolachlor is a chiral herbicide consisting of four stereoisomers, which is typically used as a racemic mixture or is enriched with the herbicidally active 1'S-isomers. Because studies on the enantioselective behavior of phyto-biochemical processes and the environmental fate of metolachlor have become significant, a practical method for analyzing and separating metolachlor stereoisomers must be developed. In the present study, the enantiomeric separation of metolachlor was achieved using OD-H, AS-H, OJ-H and AY-H chiral columns. The effects of different organic modifiers in an n-hexane-based mobile phase were investigated, and various temperatures and flow rates, which may influence metolachlor separation, were also explored. The optimal resolution was obtained using an AY-H column with n-hexane/EtOH (96/4) as the mobile phase at a rate and temperature of 0.6mLmin(-1) and 25°C, respectively. The absolute configuration of the four stereoisomers was identified as αSS, αRS, αSR, αRR using computed and experimentally measured ECD and VCD spectra. Thermal interconversion and solvent stability experiments were also performed. Pure metolachlor stereoisomers in different organic solvents and water at 4°C or 30°C were stable. These results were used to establish a sound method for analyzing, preparing, characterizing, and preserving individual metolachlor stereoisomers in most natural environments. PMID:27544750

  15. Chiral plasma instabilities.

    PubMed

    Akamatsu, Yukinao; Yamamoto, Naoki

    2013-08-01

    We study the collective modes in relativistic electromagnetic or quark-gluon plasmas with an asymmetry between left- and right-handed chiral fermions, based on the recently formulated kinetic theory with Berry curvature corrections. We find that there exists an unstable mode, signaling the presence of a plasma instability. We argue the fate of this "chiral plasma instability" including the effect of collisions, and briefly discuss its relevance in heavy ion collisions and compact stars. PMID:23952387

  16. Capillary electrochromatographic fast enantioseparation based on a chiral metal-organic framework.

    PubMed

    Fei, Zhi-Xin; Zhang, Mei; Xie, Sheng-Ming; Yuan, Li-Ming

    2014-12-01

    Metal-organic frameworks (MOFs) have received great attention because of their unusual properties and fascinating structures in separation sciences. However, to the best of our knowledge, there has been no attempt to utilize chiral MOFs as stationary phases in packed-CEC. Here, a chiral MOF [In3 O(obb)3 (HCO2 )(H2 O)]·solvent (4,4'-oxybisbenzoic acid) was explored as the chiral stationary phase in packed-CEC for separation of chiral compounds and isomers. The fabricated [In3 O(obb)3 (HCO2 )(H2 O)]·solvent packed capillary columns gave fast enantioseparation of (±)-hydrobenzoin, (±)-1-phenyl-1,2-ethanediol, and clenbuterol within 3 min in CEC. Besides, the baseline separations of nitrophenol isomers within 6 min were also achieved. The RSDs for the retention time of run-to-run, day-to-day, and column-to-column reproducibility were 1.51-3.63, 1.83-3.98, and 3.42-5.66%, respectively. These results demonstrate that chiral MOFs are promising for enantioseparation in CEC. PMID:25223618

  17. Nuclear isomer suitable for gamma ray laser

    NASA Technical Reports Server (NTRS)

    Jha, S.

    1979-01-01

    The operation of gamma ray lasers (gasers) are studied. It is assumed that the nuclear isomers mentioned in previously published papers have inherent limitations. It is further assumed that the judicious use of Bormann effect or the application of the total external reflection of low energy gamma radiation at grazing angle of incidence may permit the use of a gaser crystal sufficiently long to achieve observable stimulated emission. It is suggested that a long lived 0(+) isomer decaying by low energy gamma ray emission to a short lived 2(+) excited nuclear state would be an attractive gaser candidate. It is also suggested that the nuclear isomer be incorporated in a matrix of refractory material having an electrostatic field gradient whose principal axis lies along the length of the medium. This results in the preferential transmission of electric quadrupole radiation along the length of the medium.

  18. K isomers as probes of nuclear structure

    SciTech Connect

    Tandel, S. K.

    2014-08-14

    K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

  19. Separation of cis and trans geometric isomers by Coulomb explosion imaging

    NASA Astrophysics Data System (ADS)

    Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Rudenko, A.; Rolles, D.; Bomme, C.; Savelyev, E.; Xiong, H.; Berrah, N.; Kilcoyne, D.

    2016-05-01

    Isomers, i.e. molecules with the same chemical formula but different chemical structure, play an important role in many biological processes. Recently, it was shown that it is possible to identify different isomers of a chiral molecule by Coulomb explosion imaging. Here, we show that by imaging the Coulomb explosion of C2 H2 Br2 molecules after inner-shell photoionization, we are able to separate a mixture of cis and trans structures using the momentum correlation between ionic fragments measured in coincidence. Furthermore, we used this capability to investigate the isomer-selective photoionization and fragmentation dynamics of C2 H2 Br2 after Br (3d) ionization. Coulomb explosion simulation results for momentum correlation as well as kinetic energies match closely the experimental results. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

  20. Origin of Kinetic Resolution of Hydroxy Esters through Catalytic Enantioselective Lactonization by Chiral Phosphoric Acids.

    PubMed

    Changotra, Avtar; Sunoj, Raghavan B

    2016-08-01

    Kinetic resolution is a widely used strategy for separation and enrichment of enantiomers. Using density functional theory computations, the origin of how a chiral BINOL-phosphoric acid catalyzes the selective lactonization of one of the enantiomers of α-methyl γ-hydroxy ester is identified. In a stepwise mechanism, the stereocontrolling transition state for the addition of the hydroxyl group to the si face of the ester carbonyl in the case of the S isomer exhibits a network of more effective noncovalent interactions between the substrate and the chiral catalyst. PMID:27463593

  1. Astaxanthin extraction from shrimp wastes and its stability in 2 model systems.

    PubMed

    Franco-Zavaleta, M E; Jiménez-Pichardo, R; Tomasini-Campocosio, A; Guerrero-Legarreta, I

    2010-06-01

    The objective of this work was to study the stability of astaxanthin, obtained from shrimp wastes, and incorporated to 2 model systems: egg albumin protein solution and sunflower oil. Shrimp wastes were ensiled by a treatment with formic/acetic acids (4%-4% v/w wastes) and stored at 4 degrees C for 24 h. The pigment was extracted with organic solvents (petroleum ether:acetone:water, 15 : 75 : 10) and concentrated. The storage parameters studied were: illumination (light/dark), temperature (4/20 degrees C), atmosphere (air/air-free), and storage time (0, 1, 2, 3, 4, 5 wk). Results showed that total xantophylls and astaxanthin were more stable in sunflower oil than in the protein system. Total xantophylls showed more stability than astaxanthin, possibly due to the presence of other, more stable carotenoids quantified together with xantophylls. Astaxanthin concentration was significantly affected by storage time; its degradation followed a first-order reaction rate under all the studied conditions. This pigment was stable only for 17 d, even when stored in air-free flasks, under refrigeration, and in the dark. PMID:20629858

  2. Response Surface Methodology for Ultrasound-Assisted Extraction of Astaxanthin from Haematococcus pluvialis

    PubMed Central

    Zou, Tang-Bin; Jia, Qing; Li, Hua-Wen; Wang, Chang-Xiu; Wu, Hong-Fu

    2013-01-01

    Astaxanthin is a novel carotenoid nutraceutical occurring in many crustaceans and red yeasts. It has exhibited various biological activities including prevention or amelioration of cardiovascular disease, gastric ulcer, hypertension, and diabetic nephropathy. In this study, ultrasound-assisted extraction was developed for the effective extraction of astaxanthin from Haematococcus pluvialis. Some parameters such as extraction solvent, liquid-to-solid ratio, extraction temperature, and extraction time were optimized by single-factor experiment and response surface methodology. The optimal extraction conditions were 48.0% ethanol in ethyl acetate, the liquid-to-solid ratio was 20:1 (mL/g), and extraction for 16.0 min at 41.1 °C under ultrasound irradiation of 200 W. Under optimal conditions, the yield of astaxanthin was 27.58 ± 0.40 mg/g. The results obtained are beneficial for the full utilization of Haematococcus pluvialis, which also indicated that ultrasound-assisted extraction is a very useful method for extracting astaxanthin from marine life. PMID:23697948

  3. Astaxanthin Protecting Membrane Integrity against Photosensitized Oxidation through Synergism with Other Carotenoids.

    PubMed

    Du, Hui-Hui; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2015-10-21

    Incorporation of astaxanthin or zeaxanthin in giant unilamellar vesicles (GUVs) of phosphatidylcholine resulted in a longer lag phase than incorporation of β-carotene or lycopene for the onset of budding induced by chlorophyll a photosensitization and quantified by a dimensionless entropy parameter using optical microscopy and digital image heterogeneity analysis. The lowest initial rate of GUV budding after the lag phase was seen for GUVs with astaxanthin as the least reducing carotenoid, while the lowest final level of entropy appeared for those with lycopene or β-carotene as a more reducing carotenoid. The combination of astaxanthin and lycopene gave optimal protection against budding with respect to both a longer lag phase and lower final level of entropy by combining good electron acceptance and good electron donation. Quenching of singlet oxygen by carotenoids close to chlorophyll a in the membrane interior in parallel with scavenging of superoxide radicals by astaxanthin anchored in the surface may explain the synergism between carotenoids involving both type I and type II photosensitization by chlorophyll a. PMID:26429551

  4. Gene expression profile analysis in astaxanthin-induced Haematococcus pluvialis using a cDNA microarray.

    PubMed

    Eom, Hyunsuk; Lee, Choul-Gyun; Jin, EonSeon

    2006-05-01

    The unicellular green alga Haematococcus pluvialis (Volvocales) is known for the ketocarotenoid astaxanthin (3, 3'-dihydroxy-beta, beta-carotene-4, 4'-dione) accumulation, which is induced under unfavorable culture conditions. In this work, we used cDNA microarray analysis to screen differentially expressed genes in H. pluvialis under astaxanthin-inductive culture conditions, such as combination of cell exposure to high irradiance and nutrient deprivation. Among the 965 genes in the cDNA array, there are 144 genes exhibiting differential expression (twofold changes) under these conditions. A significant decrease in the expression of photosynthesis-related genes was shown in astaxanthin-accumulating cells (red cells). Defense- or stress-related genes and signal transduction genes were also induced in the red cells. A comparison of microarray and real-time PCR analysis showed good correlation between the differentially expressed genes by the two methods. Our results indicate that the cDNA microarray approach, as employed in this work, can be relied upon and used to monitor gene expression profiles in H. pluvialis. In addition, the genes that were differentially expressed during astaxanthin induction are suitable candidates for further study and can be used as tools for dissecting the molecular mechanism of this unique pigment accumulation process in the green alga H. pluvialis. PMID:16320067

  5. Cholesterol oxidation and astaxanthin degradation in shrimp during sun drying and storage.

    PubMed

    Hernández Becerra, Josafat A; Ochoa Flores, Angélica A; Valerio-Alfaro, Gerardo; Soto-Rodriguez, Ida; Rodríguez-Estrada, María T; García, Hugo S

    2014-02-15

    Dried salted shrimps are made from raw shrimps, which are cooked and dried under direct sunlight. The preparation and storage include treatments and conditions that can promote oxidative changes in different components. The aim of this study was to monitor the formation of major cholesterol oxidation products and the changes in the astaxanthin content and fatty acid profile in dried salted shrimp during cooking, sun drying and storage. During sun drying, most of the astaxanthin (75%) was degraded in cooked shrimp, while cholesterol oxidation products (COPs) showed a dramatic increase (8.6-fold), reaching a total concentration of 372.9 ± 16.3 μg/g of lipids. Further storage favoured both astaxanthin degradation (83%) and COPs formation (886.6 ± 97.9 μg/g of lipids after 90 days of storage). The high degradation of astaxanthin and the elevated formation of COPs during sun drying and storage indicate the necessity to re-evaluate the processing and storage conditions of salted dried shrimp. PMID:24128553

  6. Astaxanthin induction in Microalga H. pluvialis with flat panel airlift photobioreactors under indoor and outdoor conditions.

    PubMed

    Poonkum, Woradej; Powtongsook, Sorawit; Pavasant, Prasert

    2015-01-01

    Astaxanthin was induced from Haematococcus pluvialis (NIES-144) under indoor and outdoor conditions using 17-, 50-, and 90-L flat-panel airlift photobioreactors (FP-APBRs). Preliminary experiments in 1.5-L bubble column photobioreactors (BC-PBRs) revealed that sterilized clean water with 3% CO2 aeration (1.47 cm(3) s(-1) CO2 loading) could best encourage astaxanthin accumulation at 18.21 g m(-3) (3.63% by weight). Operating 17-L FP-APBRs with these bubble column parameters under indoor conditions could further enhance astaxanthin to 26.63 g m(-3) (5.34% by weight). This was potentially due to the inherited up-lift force from the reactor that helped avoid cell precipitation by allowing the cells to be circulated within the reactor. In addition, the various sizes of FP-APBRs exhibited similar performance, implying a potential scale-up opportunity. However, similar operation under outdoor condition exhibited slightly poorer performance due to the light inhibition effect. The best outdoor performance was obtained with the FP-APBR covered with one layer of shading net, where 20.11 g m(-3) (4.47% by weight) of astaxanthin was resulted. PMID:25105532

  7. A Microreactor System for Cultivation of Haematococcus pluvialis and Astaxanthin Production.

    PubMed

    Kwak, Ho Seok; Kim, Jaoon Young Hwan; Sim, Sang Jun

    2015-02-01

    Development of efficient culture and monitoring system for cell growth and production of useful materials is required for practical utilization of microalgae. In the present study, we developed a PDMS-based microreactor system for efficient, rapid culture of microalgae and monitoring of cell growth, carotenoid content under diverse culture conditions. Due to advantages of PDMS, we optimized culture conditions (light intensity, pH, nitrate depletion, carbon dioxide concentration) for improving growth rate and astaxanthin productivity in considerably less time compared to conventional culture methods using flask or well plate. In addition, we found that there was a strong linear correlation between fluorescence intensity of astaxanthin stained by Nile red and the astaxanthin content, which can be utilized as a high-throughput screening tool in microfluidic systems. In this study, the growth rate of vegetative Haematococcus pluvialis was improved by 60% in microfluidic chamber than in flask and astaxanthin was produced up to 362 mg/L under the optimal conditions (300 µmol photon/m2/s of light, 7% CO2 (v/v), and pH 7.0) using designed microfluidic devices. This result shows that microfluidic system can provide effective means to address development of microalgal strains including H. pluvialis and bioprocess. PMID:26353702

  8. Elucidation of the pathway to astaxanthin in the flowers of Adonis aestivalis.

    PubMed

    Cunningham, Francis X; Gantt, Elisabeth

    2011-08-01

    A few species in the genus Adonis are the only land plants known to produce the valuable red ketocarotenoid astaxanthin in abundance. Here, we ascertain the pathway that leads from the β-rings of β-carotene, a carotenoid ubiquitous in plants, to the 3-hydroxy-4-keto-β-rings of astaxanthin (3,3'-dihydroxy-β,β-carotene-4,4'-dione) in the blood-red flowers of Adonis aestivalis, an ornamental and medicinal plant commonly known as summer pheasant's eye. Two gene products were found to catalyze three distinct reactions, with the first and third reactions of the pathway catalyzed by the same enzyme. The pathway commences with the activation of the number 4 carbon of a β-ring in a reaction catalyzed by a carotenoid β-ring 4-dehydrogenase (CBFD), continues with the further dehydrogenation of this carbon to yield a carbonyl in a reaction catalyzed by a carotenoid 4-hydroxy-β-ring 4-dehydrogenase, and concludes with the addition of an hydroxyl group at the number 3 carbon in a reaction catalyzed by the erstwhile CBFD enzyme. The A. aestivalis pathway is both portable and robust, functioning efficiently in a simple bacterial host. Our elucidation of the pathway to astaxanthin in A. aestivalis provides enabling technology for development of a biological production process and reveals the evolutionary origin of this unusual plant pathway, one unrelated to and distinctly different from those used by bacteria, green algae, and fungi to synthesize astaxanthin. PMID:21862704

  9. PCR-based method for the rapid identification of astaxanthin-accumulating yeasts (Phaffia spp.).

    PubMed

    Colabella, Fernando; Libkind, Diego

    2016-01-01

    It has been recently found that the natural distribution, habitat, and genetic diversity of astaxanthin-producing yeasts (i.e. Phaffia rhodozyma, synonym Xanthophyllomyces dendrorhous) is much greater than previously thought. P. rhodozyma is biotechnologically exploited due to its ability to produce the carotenoid pigment astaxanthin and thus, it is used as a natural source of this pigment for aquaculture. P. rhodozyma was also capable of synthesizing the potent UVB sunscreen mycosporine-glutaminol-glucoside (MGG). Therefore, further environmental studies are needed to elucidate its ecological aspects and detect new potential strains for the production of astaxanthin and MGG. However, obtaining new isolates of P. rhodozyma and related species is not always easy due to its low abundance and the presence of other sympatric and pigmented yeasts. In this work we report a successful development of a species-specific primer which has the ability to quickly and accurately detecting isolates representing all known lineages of the genus Phaffia (including novel species of the genus) and excluding closely related taxa. For this purpose, a primer of 20 nucleotides (called PhR) was designed to be used in combination with universal primers ITS3 and NL4 in a multiplex amplification. The proposed method has the sensitivity and specificity required for the precise detection of new isolates, and therefore represents an important tool for the environmental search for novel astaxanthin-producing yeasts. PMID:26922472

  10. A developmental toxicity study of 3S, 3'S-Astaxanthin in New Zealand white rabbits.

    PubMed

    Schneider, Steffen; Mellert, Werner; Schulte, Stefan; van Ravenzwaay, Bennard

    2016-04-01

    Astaxanthin, a naturally occurring pigment used to give the characteristic orange-pink colour to salmonid fish reared in aquaculture, is also marketed as a dietary supplement. Synthetic 3S, 3'S-Astaxanthin was tested for potential harmful effects on the in utero development of New Zealand white rabbits in a study according to international regulatory guidelines. There were two control groups, one being a placebo administration and three dose levels corresponding to 100, 200, and 400 mg of 3S, 3'S-Astaxanthin per kg body weight/day. The group sizes varied from 23 to 27 litters, providing approximately 200 fetuses per group for evaluation of developmental toxicity. There were no significant effects on the health of the does, nor on the size and viability of the litters. Malformations, both external and internal, were rare and occurred in all groups, including controls with no indication of a treatment relationship. Variations were much more common, being found in all litters. However, when examined by type and frequency, no pattern emerged indicating a relationship to administration of the test substance. It is concluded that administration of 3S, 3'S-Astaxanthin in a gelatin/carbohydrate powder formulation throughout pregnancy up to 400 mg/kg body weight/day is without harmful effects on reproduction or fetal development. PMID:26854919

  11. An Assessment of Nuclear Isomers as an Energy Storage Medium

    SciTech Connect

    Hartouni, Edward P.

    2009-03-16

    Nuclear Isomers have been suggested as a potential high energy density medium that might be used to store energy. This talk assesses the state of the science supporting key elements of using nuclear isomers in energy storage applications. The focus is on the nuclear isomer {sup 178m2}Hf which has been most widely suggested for energy storage applications. However, the science issues apply to all nuclear isomer. The assessment addresses the production of the nuclear isomer, and inducing the release of the isomer. Also discussed are novel speculations on photon and/or neutron chain reactions, both as a 'pure' material as well as mixed with other materials.

  12. An Assessment of Nuclear Isomers as an Energy Storage Medium

    SciTech Connect

    Hartouni, E P

    2008-12-08

    Nuclear Isomers have been suggested as a potential high energy density medium that might be used to store energy. This talk assesses the state of the science supporting key elements of using nuclear isomers in energy storage applications. The focus is on the nuclear isomer {sup 178m2}Hf which has been most widely suggested for energy storage applications. However, the science issues apply to all nuclear isomer. The assessment addresses the production of the nuclear isomer, and inducing the release of the isomer. Also discussed are novel speculations on photon and/or neutron chain reactions, both as a 'pure' material as well as mixed with other materials.

  13. New Millisecond Isomer Lifetime Measurements at LANSCE

    SciTech Connect

    Devlin, M. Nelson, R.O.; Fotiades, N.; O'Donnell, J.M.

    2014-06-15

    New half-life measurements have been made of the millisecond isomers {sup 71m}Ge, {sup 114m2}I, {sup 208m}Bi, {sup 88m1}Y, {sup 88m2}Y, and {sup 75m}As populated in neutron-induced reactions. These measurements were made using the unique time structure of the LANSCE/WNR neutron source, by observing the γ-ray decays of the isomers during the time between the LANSCE proton macropulses. Two different LANSCE proton beam time structures were used. The GEANIE array of HPGe detectors was used to detect the γ-ray decays.

  14. 'Melatonin isomer' in wine is not an isomer of the melatonin but tryptophan-ethylester.

    PubMed

    Gardana, Claudio; Iriti, Marcello; Stuknytė, Milda; De Noni, Ivano; Simonetti, Paolo

    2014-11-01

    Melatonin is a neurohormone, chronobiotic, and antioxidant compound found in wine and deriving directly from grapes and/or synthesized by yeast during alcoholic fermentation. In addition, a melatonin isomer has been detected in different foods, wine among them. The special interest for melatonin isomer related to the fact that it was found in greater quantities than melatonin and probably shares some of its biological properties. Despite this, its chemical structure has not yet been defined; although some researchers hypothesize, it could be melatonin with the ethylacetamide group shifted into position N1. Thus, the aim of our study was to identify the structures of the melatonin isomer. For this purpose, melatonin and melatonin isomer in Syrah wine were separated chromatographically by a sub-2 μm particle column and detected by tandem mass spectrometry. The sample was then purified and concentrated by solid-phase extraction, hydrolyzed with alkali or esterase, and substrates and products quantified by UPLC-MS/MS. Moreover, melatonin, melatonin isomer, and their product ions were evaluated by high-resolution mass spectrometry. The amount of melatonin isomer and melatonin in the wine was 84 ± 4 and 3 ± 0 ng/mL, respectively. In the solutions, containing diluted alkali or esterase, melatonin isomer was hydrolyzed in about 8 min. Correspondingly, tryptophan was detected, and its amount increased and reached the maximum concentration in about 8 min. Melatonin concentration was not affected by diluted alkali or esterase. The fragmentation pattern of melatonin isomer was different from that of melatonin but comparable to that of tryptophan-ethylester. Finally, the so-called melatonin isomer identity was verified by cochromatography with authentic standard of tryptophan-ethylester. PMID:25251161

  15. A sensitivity-enhanced field-effect chiral sensor

    NASA Astrophysics Data System (ADS)

    Torsi, Luisa; Farinola, Gianluca M.; Marinelli, Francesco; Tanese, M. Cristina; Omar, Omar Hassan; Valli, Ludovico; Babudri, Francesco; Palmisano, Francesco; Zambonin, P. Giorgio; Naso, Francesco

    2008-05-01

    Organic thin-film transistor sensors have been recently attracting the attention of the plastic electronics community for their potential exploitation in novel sensing platforms. Specificity and sensitivity are however still open issues: in this respect chiral discrimination-being a scientific and technological achievement in itself-is indeed one of the most challenging sensor bench-tests. So far, conducting-polymer solid-state chiral detection has been carried out at part-per-thousand concentration levels. Here, a novel chiral bilayer organic thin-film transistor gas sensor-comprising an outermost layer with built-in enantioselective properties-is demonstrated to show field-effect amplified sensitivity that enables differential detection of optical isomers in the tens-of-parts-per-million concentration range. The ad-hoc-designed organic semiconductor endowed with chiral side groups, the bilayer structure and the thin-film transistor transducer provide a significant step forward in the development of a high-performance and versatile sensing platform compatible with flexible organic electronic technologies.

  16. Chiral benzamidinate ligands in rare-earth-metal coordination chemistry.

    PubMed

    Benndorf, Paul; Kratsch, Jochen; Hartenstein, Larissa; Preuss, Corinna M; Roesky, Peter W

    2012-11-01

    The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln = Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3)Sm], bis(amidinate) complexes [{Ln(PEBA)(2)(μ-Cl)}(2)] (Ln = Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2)(thf)(n)] (Ln = Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound. PMID:23015310

  17. Astaxanthin down-regulates Rad51 expression via inactivation of AKT kinase to enhance mitomycin C-induced cytotoxicity in human non-small cell lung cancer cells.

    PubMed

    Ko, Jen-Chung; Chen, Jyh-Cheng; Wang, Tai-Jing; Zheng, Hao-Yu; Chen, Wen-Ching; Chang, Po-Yuan; Lin, Yun-Wei

    2016-04-01

    Astaxanthin has been demonstrated to exhibit a wide range of beneficial effects, including anti-inflammatory and anti-cancer properties. However, the molecular mechanism of astaxanthin-induced cytotoxicity in non-small cell lung cancer (NSCLC) cells has not been identified. Rad51 plays a central role in homologous recombination, and studies show that chemo-resistant carcinomas exhibit high levels of Rad51 expression. In this study, astaxanthin treatment inhibited cell viability and proliferation of two NSCLC cells, A549 and H1703. Astaxanthin treatment (2.5-20 μM) decreased Rad51 expression and phospho-AKT(Ser473) protein level in a time and dose-dependent manner. Furthermore, expression of constitutively active AKT (AKT-CA) vector rescued the decreased Rad51 mRNA and protein levels in astaxanthin-treated NSCLC cells. Combined treatment with phosphatidylinositol 3-kinase (PI3K) inhibitors (LY294002 or wortmannin) further decreased the Rad51 expression in astaxanthin-exposed A549 and H1703 cells. Knockdown of Rad51 expression by transfection with si-Rad51 RNA or cotreatment with LY294002 further enhanced the cytotoxicity and cell growth inhibition of astaxanthin. Additionally, mitomycin C (MMC) as an anti-tumor antibiotic is widely used in clinical NSCLC chemotherapy. Combination of MMC and astaxanthin synergistically resulted in cytotoxicity and cell growth inhibition in NSCLC cells, accompanied with reduced phospho-AKT(Ser473) level and Rad51 expression. Overexpression of AKT-CA or Flag-tagged Rad51 reversed the astaxanthin and MMC-induced synergistic cytotoxicity. In contrast, pretreatment with LY294002 further decreased the cell viability in astaxanthin and MMC co-treated cells. In conclusion, astaxanthin enhances MMC-induced cytotoxicity by decreasing Rad51 expression and AKT activation. These findings may provide rationale to combine astaxanthin with MMC for the treatment of NSCLC. PMID:26921637

  18. The effect of astaxanthin on vascular endothelial growth factor (VEGF) levels and peroxidation reactions in the aqueous humor.

    PubMed

    Hashimoto, Hirotaka; Arai, Kiyomi; Hayashi, Shimmin; Okamoto, Hiroyuki; Takahashi, Jiro; Chikuda, Makoto

    2016-07-01

    We explored the effect of astaxanthin on vascular endothelial growth factor in the aqueous humor, by measuring vascular endothelial growth factor levels and oxidation-related parameters, including O2 (•-) scavenging activity, H2O2 level, and total hydroperoxide level in the aqueous humor, obtained from 35 patients before and after astaxanthin administration. We evaluated the relationship between vascular endothelial growth factor and the oxidation-related parameters as well as the patient's diabetic status, age, and sex. Vascular endothelial growth factor levels did not change significantly but O2 (•-) scavenging activity and total hydroperoxide level significantly (p<0.05) increased and decreased, respectively. Both pre- and post- astaxanthin intake, vascular endothelial growth factor and total hydroperoxide levels were positively correlated (Pearson: r = 0.42, p<0.05; r = 0.55, p<0.01, respectively). Analysis of vascular endothelial growth factor levels and O2 (•-) scavenging activities gave a negative correlation but only pre-astaxanthin intake (r = -0.37, p<0.05). Differences in levels pre- and post-astaxanthin only showed association between vascular endothelial growth factor and total hydroperoxide (r = 0.49, p<0.01) analyzed by multiple linear regression. Using multivariate analysis, pre-astaxanthin vascular endothelial growth factor level was associated with two factors of total hydroperoxide and O2 (•-) scavenging activity (r = 0.49, p<0.05), and post-astaxanthin vascular endothelial growth factor level with two factors of total hydroperoxide and sex (r = 0.60, p<0.01). Astaxanthin intake may have affected vascular endothelial growth factor level through its antioxidant effects by increasing O2 (•-) scavenging activity and suppressing peroxide production. PMID:27499573

  19. The effect of astaxanthin on vascular endothelial growth factor (VEGF) levels and peroxidation reactions in the aqueous humor

    PubMed Central

    Hashimoto, Hirotaka; Arai, Kiyomi; Hayashi, Shimmin; Okamoto, Hiroyuki; Takahashi, Jiro; Chikuda, Makoto

    2016-01-01

    We explored the effect of astaxanthin on vascular endothelial growth factor in the aqueous humor, by measuring vascular endothelial growth factor levels and oxidation-related parameters, including O2•− scavenging activity, H2O2 level, and total hydroperoxide level in the aqueous humor, obtained from 35 patients before and after astaxanthin administration. We evaluated the relationship between vascular endothelial growth factor and the oxidation-related parameters as well as the patient’s diabetic status, age, and sex. Vascular endothelial growth factor levels did not change significantly but O2•− scavenging activity and total hydroperoxide level significantly (p<0.05) increased and decreased, respectively. Both pre- and post- astaxanthin intake, vascular endothelial growth factor and total hydroperoxide levels were positively correlated (Pearson: r = 0.42, p<0.05; r = 0.55, p<0.01, respectively). Analysis of vascular endothelial growth factor levels and O2•− scavenging activities gave a negative correlation but only pre-astaxanthin intake (r = −0.37, p<0.05). Differences in levels pre- and post-astaxanthin only showed association between vascular endothelial growth factor and total hydroperoxide (r = 0.49, p<0.01) analyzed by multiple linear regression. Using multivariate analysis, pre-astaxanthin vascular endothelial growth factor level was associated with two factors of total hydroperoxide and O2•− scavenging activity (r = 0.49, p<0.05), and post-astaxanthin vascular endothelial growth factor level with two factors of total hydroperoxide and sex (r = 0.60, p<0.01). Astaxanthin intake may have affected vascular endothelial growth factor level through its antioxidant effects by increasing O2•− scavenging activity and suppressing peroxide production. PMID:27499573

  20. Introduction of Branching Degrees of Octane Isomers.

    PubMed

    Perdih, Anton

    2016-01-01

    The concept of branching degrees is introduced. In the case of octane isomers it is derived from the values of a set of their physicochemical properties, calculating for each isomer the average of the normalized values and these averages are defined as branching degrees of octane isomers. The sequence of these branching degrees of octane isomers does not differ much from the »regular« one defined earlier. 2,2-Dimethylhexane appears to be less branched than 3,4-dimethylhexane and 3-ethyl, 2-methylpentane, whereas 2,3,4-trimethylpentane appears to be less branched than 3-ethyl, 3-methylpentane. While the increasing number of branches gives rise to increasing branching degrees, the peripheral position of branches and the separation between branches decreases the value of the branching degree. The central position of branches increases it. A bigger branch increases it more than a smaller one. The quantification of these structural features and their correlations with few indices is given as well. PMID:27333567

  1. Chiral quirkonium decays

    NASA Astrophysics Data System (ADS)

    Fok, R.; Kribs, Graham D.

    2011-08-01

    We calculate the two-body decay rates of quirkonium states formed from quirks that acquire mass solely through electroweak symmetry breaking. We consider SU(N)ic infracolor with two flavors of quirks transforming under the electroweak group (but not QCD) of the standard model. In one case, the quirks are in a chiral representation of the electroweak group, while in the other case, a vectorlike representation. The differences in the dominant decay channels between “chiral quirkonia” versus “vectorlike quirkonia” are striking. Several chiral quirkonia states can decay into the unique two-body resonance channels WH, ZH, tt¯, tb¯/bt¯, and γH, which never dominate for vectorlike quirkonia. Additionally, the channels WW, WZ, ZZ, and Wγ, are shared among both chiral and vectorlike quirkonia. Resonances of dileptons or light quarks (dijets) can dominate for some vectorlike quirkonia states throughout their mass range, while these modes never dominate for chiral quirkonia unless the decays into pairs of gauge or Higgs bosons are kinematically forbidden.

  2. Chiral Quirkonium Decays

    SciTech Connect

    Fok, R.; Kribs, Graham D.; /Fermilab

    2011-06-01

    We calculate the two-body decay rates of quirkonium states formed from quirks that acquire mass solely through electroweak symmetry breaking. We consider SU(N){sub ic} infracolor with two flavors of quirks transforming under the electroweak group (but not QCD) of the standard model. In one case, the quirks are in a chiral representation of the electroweak group, while in the other case, a vectorlike representation. The differences in the dominant decay channels between 'chiral quirkonia' versus 'vectorlike quirkonia' are striking. Several chiral quirkonia states can decay into the unique two-body resonance channels WH, ZH, t{bar t}, t{bar b}/b{bar t}, and {gamma}H, which never dominate for vectorlike quirkonia. Additionally, the channels WW, WZ, ZZ, and W{gamma}, are shared among both chiral and vectorlike quirkonia. Resonances of dileptons or light quarks (dijets) can dominate for some vectorlike quirkonia states throughout their mass range, while these modes never dominate for chiral quirkonia unless the decays into pairs of gauge or Higgs bosons are kinematically forbidden.

  3. Effects of homogenization process parameters on physicochemical properties of astaxanthin nanodispersions prepared using a solvent-diffusion technique

    PubMed Central

    Anarjan, Navideh; Jafarizadeh-Malmiri, Hoda; Nehdi, Imededdine Arbi; Sbihi, Hassen Mohamed; Al-Resayes, Saud Ibrahim; Tan, Chin Ping

    2015-01-01

    Nanodispersion systems allow incorporation of lipophilic bioactives, such as astaxanthin (a fat soluble carotenoid) into aqueous systems, which can improve their solubility, bioavailability, and stability, and widen their uses in water-based pharmaceutical and food products. In this study, response surface methodology was used to investigate the influences of homogenization time (0.5–20 minutes) and speed (1,000–9,000 rpm) in the formation of astaxanthin nanodispersions via the solvent-diffusion process. The product was characterized for particle size and astaxanthin concentration using laser diffraction particle size analysis and high performance liquid chromatography, respectively. Relatively high determination coefficients (ranging from 0.896 to 0.969) were obtained for all suggested polynomial regression models. The overall optimal homogenization conditions were determined by multiple response optimization analysis to be 6,000 rpm for 7 minutes. In vitro cellular uptake of astaxanthin from the suggested individual and multiple optimized astaxanthin nanodispersions was also evaluated. The cellular uptake of astaxanthin was found to be considerably increased (by more than five times) as it became incorporated into optimum nanodispersion systems. The lack of a significant difference between predicted and experimental values confirms the suitability of the regression equations connecting the response variables studied to the independent parameters. PMID:25709435

  4. The antioxidant effect of astaxanthin is higher in young mice than aged: a region specific study on brain.

    PubMed

    Al-Amin, Md Mamun; Akhter, Samiha; Hasan, Ahmed Tasdid; Alam, Tanzir; Nageeb Hasan, S M; Saifullah, A R M; Shohel, Mohammad

    2015-10-01

    Astaxanthin is a potential antioxidant which shows neuroprotective property. We aimed to investigate the age-dependent and region-specific antioxidant effects of astaxanthin in mice brain. Animals were divided into 4 groups; treatment young (3 months, n = 6) (AY), treatment old (16 months, n = 6) (AO), placebo young (3 months, n = 6) (PY) and placebo old (16 months, n = 6) (PO) groups. Treatment group was given astaxanthin (2 mg/kg/day, body weight), and placebo group was given 100 μl of 0.9% normal saline orally to the healthy Swiss albino mice for 4 weeks. The level of non-enzymatic oxidative markers namely malondialdehyde (MDA); nitric oxide (NO); advanced protein oxidation product (APOP); glutathione (GSH) and the activity of enzymatic antioxidants i.e.; catalase (CAT) and superoxide dismutase (SOD) were determined from the isolated brain regions. Treatment with astaxanthin significantly (p < 0.05) reduces the level of MDA, APOP, NO in the cortex, striatum, hypothalamus, hippocampus and cerebellum in both age groups. Astaxanthin markedly (p < 0.05) enhances the activity of CAT and SOD enzymes while improves the level of GSH in the brain. Overall, improvement of oxidative markers was significantly greater in the young group than the aged animal. In conclusion, we report that the activity of astaxanthin is age-dependent, higher in young in compared to the aged brain. PMID:26116165

  5. Astaxanthin present in the maturation medium reduces negative effects of heat shock on the developmental competence of porcine oocytes.

    PubMed

    Do, Lanh Thi Kim; Luu, Vien Viet; Morita, Yasuhiro; Taniguchi, Masayasu; Nii, Masahiro; Peter, Augustine T; Otoi, Takeshige

    2015-06-01

    Astaxanthin, one of the most common carotenoids, elicits antioxidant effects on cellular viability and embryonic development. This study was conducted to investigate the effects of astaxanthin on maturation, fertilization and development of porcine oocytes matured in vitro under heat stress conditions, and then fertilized and cultured under standard conditions. Porcine oocytes were cultured in maturation medium supplemented with different concentrations of astaxanthin (0, 0.25, 0.5 or 1 ppm) for 46 h at either 38.5 or 41 °C. In comparison to oocytes cultured at 38.5 °C, the exposure of porcine oocytes to 41.0 °C during in vitro maturation (IVM) significantly inhibited maturation and development of fertilized oocytes to the blastocyst stage. Supplementation of maturation medium with astaxanthin (0.5 ppm) significantly improved oocyte maturation, fertilization and development to the blastocysts stage in both oocyte groups. However, the total cell number and apoptosis index of blastocysts did not differ among groups. Moreover, astaxanthin (0.5 ppm) significantly increased the rate of oocytes that reached metaphase II and decreased proportion of apoptotic oocytes exposed to H2O2 (1.0mM) during IVM. In summary, we demonstrated that supplementation of maturation medium with astaxanthin (0.5 ppm) exerted antioxidative effects and improved the ability of maturation, fertilization, and development of porcine oocytes exposed to heat stress. PMID:26051456

  6. Dietary Carotenoids Regulate Astaxanthin Content of Copepods and Modulate Their Susceptibility to UV Light and Copper Toxicity

    PubMed Central

    Caramujo, Maria-José; de Carvalho, Carla C. C. R.; Silva, Soraya J.; Carman, Kevin R.

    2012-01-01

    High irradiation and the presence of xenobiotics favor the formation of reactive oxygen species in marine environments. Organisms have developed antioxidant defenses, including the accumulation of carotenoids that must be obtained from the diet. Astaxanthin is the main carotenoid in marine crustaceans where, among other functions, it scavenges free radicals thus protecting cell compounds against oxidation. Four diets with different carotenoid composition were used to culture the meiobenthic copepod Amphiascoides atopus to assess how its astaxanthin content modulates the response to prooxidant stressors. A. atopus had the highest astaxanthin content when the carotenoid was supplied as astaxanthin esters (i.e., Haematococcus meal). Exposure to short wavelength UV light elicited a 77% to 92% decrease of the astaxanthin content of the copepod depending on the culture diet. The LC50 values of A. atopus exposed to copper were directly related to the initial astaxanthin content. The accumulation of carotenoids may ascribe competitive advantages to certain species in areas subjected to pollution events by attenuating the detrimental effects of metals on survival, and possibly development and fecundity. Conversely, the loss of certain dietary items rich in carotenoids may be responsible for the amplification of the effects of metal exposure in consumers. PMID:22822352

  7. Construction of transplastomic lettuce (Lactuca sativa) dominantly producing astaxanthin fatty acid esters and detailed chemical analysis of generated carotenoids.

    PubMed

    Harada, Hisashi; Maoka, Takashi; Osawa, Ayako; Hattan, Jun-Ichiro; Kanamoto, Hirosuke; Shindo, Kazutoshi; Otomatsu, Toshihiko; Misawa, Norihiko

    2014-04-01

    The plastid genome of lettuce (Lactuca sativa L.) cv. Berkeley was site-specifically modified with the addition of three transgenes, which encoded β,β-carotenoid 3,3'-hydroxylase (CrtZ) and β,β-carotenoid 4,4'-ketolase (4,4'-oxygenase; CrtW) from a marine bacterium Brevundimonas sp. strain SD212, and isopentenyl diphosphate isomerase from a marine bacterium Paracoccus sp. strain N81106. Constructed transplastomic lettuce plants were able to grow on soil at a growth rate similar to that of non-transformed lettuce cv. Berkeley and generate flowers and seeds. The germination ratio of the lettuce transformants (T0) (98.8%) was higher than that of non-transformed lettuce (93.1 %). The transplastomic lettuce (T1) leaves produced the astaxanthin fatty acid (myristate or palmitate) diester (49.2% of total carotenoids), astaxanthin monoester (18.2%), and the free forms of astaxanthin (10.0%) and the other ketocarotenoids (17.5%), which indicated that artificial ketocarotenoids corresponded to 94.9% of total carotenoids (230 μg/g fresh weight). Native carotenoids were there lactucaxanthin (3.8%) and lutein (1.3 %) only. This is the first report to structurally identify the astaxanthin esters biosynthesized in transgenic or transplastomic plants producing astaxanthin. The singlet oxygen-quenching activity of the total carotenoids extracted from the transplastomic leaves was similar to that of astaxanthin (mostly esterified) from the green algae Haematococcus pluvialis. PMID:24287848

  8. [Astaxanthin inhibits proliferation and promotes apoptosis of A549 lung cancer cells via blocking JAK1/STAT3 pathway].

    PubMed

    Wu, Chuntao; Zhang, Jinji; Liu, Tienan; Jiao, Guimei; Li, Changzai; Hu, Baoshan

    2016-06-01

    Objective To investigate the anti-tumor effects of astaxanthin on A549 lung cancer cells and the related mechanisms. Methods A549 cells were cultured with various concentrations of astaxanthin (20, 40, 60, 80, 100 μmol/L), and DMSO at the same concentrations served as vehicle controls. The viability of A549 cells was detected by CCK-8 assay; cell cycle and apoptosis were observed by flow cytometry; and the expressions of B-cell lymphoma-2 (Bcl-2), Bcl-2 associated X protein (Bax), signal transducers and activators of transcription 3 (STAT3), and Janus kinase 1 (JAK1) were evaluated by Western blotting. Results CCK-8 assay showed that astaxanthin decreased the proliferation of A549 cells in a dose-dependent manner. Flow cytometry showed that astaxanthin increased the number of cells in the G0/G1 phase and induced apoptosis in A549 cells. Western blotting showed that astaxanthin up-regulated the expression of Bax and down-regulated the expressions of Bcl-2, STAT3 and JAK1. Conclusion Astaxanthin functions as a potent inhibitor of A549 lung cancer cell growth by targeting JAK1/STAT3 signaling pathway. PMID:27371847

  9. Simultaneous production of triacylglycerol and high-value carotenoids by the astaxanthin-producing oleaginous green microalga Chlorella zofingiensis.

    PubMed

    Liu, Jin; Mao, Xuemei; Zhou, Wenguang; Guarnieri, Michael T

    2016-08-01

    The production of lipids and astaxanthin, a high-value carotenoid, by Chlorella zofingiensis was investigated under different culture conditions. Comparative analysis revealed a good correlation between triacylglycerol (TAG) and astaxanthin accumulation in C. zofingiensis. Stress conditions promoted cell size and weight and induced the accumulation of neutral lipids, especially TAG and astaxanthin, with a concomitant decrease in membrane lipids. The highest contents of TAG and astaxanthin achieved were 387 and 4.89mgg(-1) dry weight, respectively. A semi-continuous culture strategy was developed to optimize the TAG and astaxanthin productivities, which reached 297 and 3.3mgL(-1)day(-1), respectively. Additionally, astaxanthin accumulation was enhanced by inhibiting de novo fatty acid biosynthesis. In summary, our study represents a pioneering work of utilizing Chlorella for the integrated production of lipids and high-value products and C. zofingiensis has great potential to be a promising production strain and serve as an emerging oleaginous model alga. PMID:27152772

  10. Chirality and Pinwheels

    ERIC Educational Resources Information Center

    Rodriguez-Fernandez, Emilio

    2013-01-01

    By using cardboard models that resemble propellers, the students of inorganic courses can easily visualizing the distinct rotation of optical isomers. These propellers rotate clockwise or counterclockwise when they are dropped from a certain height or in the presence of wind. (Contains 1 figure.)

  11. Spontaneous chirality in simple systems

    PubMed

    Pickett; Gross; Okuyama

    2000-10-23

    Two simple examples of spontaneous chiral symmetry breaking are presented. The first is close-packed cylindrically confined spheres. As the cylinder diameter is varied, one obtains a variety of chiral phases. The second example involves unconfined dipolar particles with an isotropic attraction, which also exhibits chiral ground states. We speculate that a dilute magnetorheological fluid film, with the addition of smaller particles to provide an attractive entropic interaction, will exhibit a chiral columnar ground state. PMID:11030973

  12. Excitation of nuclear isomers by X rays from laser plasma

    SciTech Connect

    Andreev, Aleksandr A; Karpeshin, F; Trzhaskovskaya, M B; Platonov, Konstantin Yu; Rozhdestvenskii, Yu V

    2010-06-23

    The possibility of obtaining isomer nuclei is studied by the example of the molybdenum isomer {sup 93}Mo upon irradiation of a niobium {sup 93}Nb target by {approx}50-J, 100-fs laser pulses. It is shown that the modern laser technique allows production of isomer nuclei by accelerated protons and radiative de-excitation of isomer nuclear states by thermal or line X-rays from laser plasma. (interaction of laser radiation with matter. laser plasma)

  13. Uptake and incorporation of labeled tryptophan isomers into IAA in the jsR sub 1 mutant of Lemna gibba

    SciTech Connect

    Baldi, B.G.; Maher, B.R.; Cohen, J.D. )

    1989-04-01

    Analyses of the IAA-overproducing mutant of Lemna have been initiated in order to study in vivo biosynthesis of IAA. Using radiolabelled tryptophan isomers prepared from commercial sources of {sup 14}C-D,L tryptophan by chiral separation kinetics of uptake of L and D tryptophan were determined for sterile cultures of individual jsR{sub 1} four-frond colonies. Over a 24 h period, about 50% of the radioactivity from {sup 14}C-L-TRP in media, or about 25% from {sup 14}C-D-TRP, was found in the plant tissue. Maximal rates of uptake were seen in the first six hors for both isomers. Endogenous levels of tryptophan determined in jsR{sub 1} as measures of pool sizes in vivo show 5 to 10 ug/g FW total tryptophan with less than 1% in the D isomer form. Information on uptake and endogenous pool sizes of tryptophan isomers is being used for feeding of stable isotope labeled tryptophan ({sup 13}C, {sup 14}N) to jsR{sub 1} at physiological levels. Analyses of incorporation of label into IAA using GC-MS and high resolution mass spectrometry are currently underway.

  14. Chiral molecules in the ISM: the best candidates

    NASA Astrophysics Data System (ADS)

    Pilme, J.; Marloie, G.; Lattelais, M.; Pauzat, F.; Ellinger, Y.

    2011-05-01

    In this report we address the question of whether some chiral molecules have a probability of being detected in the interstellar medium (ISM). It is a crucial question since life on Earth, as we know it today, is inseparable from homochirality. Under these conditions, the identification of any chiral species in the interstellar medium (ISM) would be a considerable breakthrough in the pursuit of the origin of life. To this end we rely on the Minimum Energy Principle that states that the most abundant isomer of a given generic formula should be that of lowest energy (Lattelais et al. 2009). We present here computations of the relative stability of complex organic molecules (COMs) believed to be potentially able to exist in the ISM under a chiral isomeric form. Such a search is submitted to a number of constraints. The molecules we are looking for should present precise characteristics, namely: i) have no improper axis of rotation Sn; possess at least one asymmetric center ; ii) satisfy the Minimum Energy Principle; iii) be small with a large enough dipole moment to be possibly identified through their radio millimeter rotational spectra. The energies and dipole moments are calculated by means of quantum simulations based on density functional theory (DFT). The result is that no chiral isomer in the C3H6O (acetone), C2H5ON, C3H7ON (amides), C2H5O2N, C3H7O2N (amino acid) families is the most stable species. This is also true of the C2(H2O)2 and C3(H2O)3 species when restricted to the sugar families, but another chiral molecule of the same chemical formula, i.e. lactic acid HOCH(CH3)COOH is found to be the most stable of all structures. Two other molecules with an NH2 group, namely, NH2CH(CH3)CN, the precursor of α-alanine and NH2CH(CH3)OH, the simplest chiral molecule (beyond halogen or isotopically substituted methane curiosities) are also the most stable species in their respective families. These three molecules satisfy the conditions for being detected according

  15. Baryon chiral perturbation theory

    NASA Astrophysics Data System (ADS)

    Scherer, S.

    2012-03-01

    We provide a short introduction to the one-nucleon sector of chiral perturbation theory and address the issue of power counting and renormalization. We discuss the infrared regularization and the extended on-mass-shell scheme. Both allow for the inclusion of further degrees of freedom beyond pions and nucleons and the application to higher-loop calculations. As applications we consider the chiral expansion of the nucleon mass to order Script O(q6) and the inclusion of vector and axial-vector mesons in the calculation of nucleon form factors. Finally, we address the complex-mass scheme for describing unstable particles in effective field theory.

  16. Functional characterization of various algal carotenoid ketolases reveals that ketolating zeaxanthin efficiently is essential for high production of astaxanthin in transgenic Arabidopsis.

    PubMed

    Zhong, Yu-Juan; Huang, Jun-Chao; Liu, Jin; Li, Yin; Jiang, Yue; Xu, Zeng-Fu; Sandmann, Gerhard; Chen, Feng

    2011-06-01

    Extending the carotenoid pathway to astaxanthin in plants is of scientific and industrial interest. However, expression of a microbial β-carotene ketolase (BKT) that catalyses the formation of ketocarotenoids in transgenic plants typically results in low levels of astaxanthin. The low efficiency of BKTs in ketolating zeaxanthin to astaxanthin is proposed to be the major limitation for astaxanthin accumulation in engineered plants. To verify this hypothesis, several algal BKTs were functionally characterized using an Escherichia coli system and three BKTs were identified, with high (up to 85%), moderate (∼38%), and low (∼1%) conversion rate from zeaxanthin to astaxanthin from Chlamydomonas reinhardtii (CrBKT), Chlorella zofingiensis (CzBKT), and Haematococcus pluvialis (HpBKT3), respectively. Transgenic Arabidopsis thaliana expressing the CrBKT developed orange leaves which accumulated astaxanthin up to 2 mg g(-1) dry weight with a 1.8-fold increase in total carotenoids. In contrast, the expression of CzBKT resulted in much lower astaxanthin content (0.24 mg g(-1) dry weight), whereas HpBKT3 was unable to mediate synthesis of astaxanthin in A. thaliana. The none-native astaxanthin was found mostly in a free form integrated into the light-harvesting complexes of photosystem II in young leaves but in esterified forms in senescent leaves. The alteration of carotenoids did not affect chlorophyll content, plant growth, or development significantly. The astaxanthin-producing plants were more tolerant to high light as shown by reduced lipid peroxidation. This study advances a decisive step towards the utilization of plants for the production of high-value astaxanthin. PMID:21398427

  17. Contesting the paradigm of chirality

    NASA Astrophysics Data System (ADS)

    Efrati, Efi

    2012-02-01

    In 1893 Lord Kelvin coined the term chirality, and stated what is to become the elementary paradigm of chirality: 'I call any geometrical figure, or any group of points, chiral, and say it has chirality, if its image in a plane mirror , ideally realized cannot be brought to coincide with itself'. While the notion of chirality has greatly advanced our understanding of the structures of molecules and crystals, it has been shown to be inconsistent with every pseudo-scalar quantification. In this talk I will present a tabletop demonstration of a chiral structure which is constructed through the achiral summation of identical elementary units which are symmetric under reflection. The seeming contradiction to the definition of chirality is reconciled by proposing an alternative definition, relying on the physicist interpretation of the right hand rule.

  18. Enantiomeric separation of tapentadol by capillary electrophoresis--study of chiral selectivity manipulation by various types of cyclodextrins.

    PubMed

    Znaleziona, Joanna; Fejős, Ida; Ševčík, Juraj; Douša, Michal; Béni, Szabolcs; Maier, Vítězslav

    2015-02-01

    The chiral recognition of the centrally acting analgesic agent tapentadol and its isomers with various cyclodextrins (CDs) was studied by capillary electrophoresis, focusing on the migration order of four stereoisomers. In the case of non-charged hydroxypropylated CDs (2-hydroxypropyl-β-CD, 2-hydroxypropyl-γ-CD) the beta derivative was able to discriminate the S,R- and R,S-isomers in acidic background electrolyte, whereas the gamma allowed the separation of S,S- and R,R-tapentadol, respectively. Dual CD system containing both hosts was used to separate all of four isomers. Negatively charged sulfated-α-CD at 1.0% (w/v) concentration in 100mM sodium borate buffer (pH 9.5) was capable of separating the isomers with favorable enantiomer migration order and the optimized method was able to determine 0.15% of chiral impurities of tapentadol in the presence of the last migrating clinically important R,R-isomer. PMID:25527976

  19. Isomer Shifts in Solid State Chemistry

    NASA Astrophysics Data System (ADS)

    Wagner, F. E.; Stievano, L.

    The isomer shift of the Mössbauer resonance is a rather unique quantity that cannot be obtained by any of the other techniques used for measuring hyperfine interactions in solids, such as NMR or perturbed angular correlations (TDPAC). It shifts the resonance pattern as a whole without affecting the magnetic dipole and electric quadrupole hyperfine splittings. Methods that measure only these hyperfine splittings are insensitive to the isomer shift. The magnitude of the observed shift is proportional to the product of a nuclear parameter, the change Δ⟨r 2⟩ of the nuclear radius that goes along with the Mössbauer transition, and to an electronic property of the material, the electron density ρ(0) at the Mössbauer nucleus or, more precisely, to the difference Δρ(0) of the electron densities at the Mössbauer nuclei in the materials of which the source and the absorber are made. The electron density at the nucleus is due to s-electrons and, to a lesser extent and mainly in heavy nuclei, to relativistic p1 / 2-electrons. All the other electrons have a vanishing density inside the nucleus and do not contribute. Thus, to a very good accuracy, the Mössbauer isomer shift enables one to obtain information on the s-electron density at the Mössbauer nuclei in solids.

  20. Biodegradation of cresol isomers in anoxic aquifers.

    PubMed Central

    Smolenski, W J; Suflita, J M

    1987-01-01

    The biodegradation of o-, m-, and p-cresol was examined in material obtained from a shallow anaerobic alluvial sand aquifer. The cresol isomers were preferentially metabolized, with p-cresol being the most easily degraded. m-Cresol was more persistent than the para-isomer, and o-cresol persisted for over 90 days. Biodegradation of cresol isomers was favored under sulfate-reducing conditions (SRC) compared with that under methanogenic conditions (MC). Slurries that were acclimated to p-cresol metabolism transformed this substrate at 18 and 330 nmol/h per g (dry weight) for MC and SRC, respectively. Inhibition of electron flow to sulfate reduction with 2.0 mM molybdate reduced p-cresol metabolism in incubations containing sulfate. When methanogenesis was blocked with 5 mM bromoethanesulfonic acid in incubations lacking sulfate, p-cresol catabolism was retarded. Under SRC 3.4 mol of sulfate was consumed per mol of p-cresol metabolized. The addition of sulfate to methanogenic incubations stimulated p-cresol degradation. Simultaneous adaptation studies in combination with spectrophotometric and chromatographic analysis of metabolites indicated that p-cresol was oxidized under SRC to p-hydroxybenzoate via the corresponding alcohol and aldehyde. This series of reactions was inhibited under sulfate-limited or aerobic conditions. Therefore, the primary catabolic event for p-cresol decomposition under SRC appears to involve the hydroxylation of the aryl methyl group. PMID:3579279

  1. Effect of temperature on chitin and astaxanthin recoveries from shrimp waste using lactic acid bacteria.

    PubMed

    Pacheco, Neith; Garnica-González, Mónica; Ramírez-Hernández, Jessica Y; Flores-Albino, Belem; Gimeno, Miquel; Bárzana, Eduardo; Shirai, Keiko

    2009-06-01

    The chitin and astaxanthin recoveries by lactic acid fermentation of shrimp wastes (Litopenaeus sp) were conducted in bed-column reactors at 15, 20, 25, 30, 35, 40 and 45 degrees C. The response surface methodology showed that the fermentations carried out in the 27-36 degrees C temperature range with lactic acid above 0.319 mmol/g resulted in the highest demineralization. The maximal deproteinizations were attained from 30 to 40 degrees C. The extraction of free-astaxanthin did not present significant differences between 20 and 35 degrees C and the proportion of cis-stereoisomer forms increased with temperature. The growth rates of Lactobacillus plantarum were estimated in the 15-45 degrees C range and analyzed by Arrhenius and square root models. The cardinal values were 3.94 and 51.7 degrees C for minimum and maximum temperatures, respectively, with activation energy of 43.38 Jmol(-1). PMID:19230657

  2. Enhanced production of fatty acids and astaxanthin in Aurantiochytrium sp. by the expression of Vitreoscilla hemoglobin.

    PubMed

    Suen, Yung Lee; Tang, Hongmei; Huang, Junchao; Chen, Feng

    2014-12-24

    Dissolved oxygen is a critical factor for heterotrophic cell growth and metabolite production. The aim of this study was to investigate the effects of an oxygen-involved protein on cell growth and fatty acid and astaxanthin production in the biologically important thraustochytrid Aurantiochytrium sp. The hemoglobin of the Vitreoscilla stercoraria (VHb) gene was fused upstream with a zeocin resistance gene (ble) and driven by the Aurantiochytrium tubulin promoter. The expression construct was introduced into two strains of Aurantiochytrium sp. by electroporation. Transgenic Aurantiochytrium sp. strains MP4 and SK4 expressing the heterologous VHb achieved significantly higher maximum biomass than their corresponding controls in microaerobic conditions. Furthermore, the transformants of Aurantiochytrium sp. SK4 produced 44% higher total fatty acid and 9-fold higher astaxanthin contents than the wild type control in aerobic conditions. The present study highlights the biotechnological application of VHb in high-cell density fermentation for enhanced biomass production as well as high-value metabolites. PMID:25420960

  3. Astaxanthin preparation by lipase-catalyzed hydrolysis of its esters from Haematococcus pluvialis algal extracts.

    PubMed

    Zhao, Yingying; Guan, Feifei; Wang, Guili; Miao, Lili; Ding, Jing; Guan, Guohua; Li, Ying; Hui, Bodi

    2011-05-01

    Five of 8 fungal lipases screened were found to effectively hydrolyze astaxanthin esters from Haematococcus pluvialis algal cell extracts. Among these, an alkaline lipase from Penicillium cyclopium, expressed in Pichia pastoris, had the highest enzymolysis efficiency. Tween80 was shown to be an effective emulsifier in this lipase hydrolysis system for the 1st time. A series of experiments were performed to find optimal conditions for hydrolysis (pH, temperature, reaction time, lipase dosage). In the optimal reaction system, Tween80 and H. pluvialis extracts (mass ratio 1:1) were emulsified and added to the above lipase at a dosage of 4.6 U/μg (relative to total carotenoids), in phosphate buffer (0.1 M, pH 7.0), and incubated at 28 °C for 7 h, with agitation at 180 rpm. The free astaxanthin recovery ratio under these conditions was 63.2%. PMID:22417348

  4. On the bathochromic shift of the absorption by astaxanthin in crustacyanin: a quantum chemical study

    NASA Astrophysics Data System (ADS)

    Durbeej, Bo; Eriksson, Leif A.

    2003-06-01

    The structural origin of the bathochromic shift assumed by the electronic absorption spectrum of protein-bound astaxanthin, the carotenoid that upon binding to crustacyanin is responsible for the blue colouration of lobster shell, is investigated by means of quantum chemical methods. The calculations suggest that the bathochromic shift is largely due to one of the astaxanthin C4 keto groups being hydrogen-bonded to a histidine residue of the surrounding protein, and that the effect of this histidine is directly dependent on its protonation state. Out of the different methodologies (CIS, TD-DFT, and ZINDO/S) employed to calculate wavelengths of maximum absorption, the best agreement with experimental data is obtained using the semiempirical ZINDO/S method.

  5. Photo-stimulated phase and anchoring transitions of chiral azo-dye doped nematic liquid crystals.

    PubMed

    Kundu, Sudarshan; Kang, Shin-Woong

    2013-12-16

    We report concurring phase and anchoring transitions of chiral azo-dye doped nematic liquid crystals. The transitions are induced by photo-stimulation and stable against light and thermal treatments. Photochromic trans- to cis-isomerization of azo-dye induces an augmented dipole moment and strong dipole-dipole interaction of the cis-isomers, resulting in the formation of nano-sized dye-aggregates. Consequent phase separation of the aggregates of a chiral azo-dye induces phase transition from a chiral to nonchiral nematic phase. In addition, the deposition of dye-aggregates at the surfaces brings about anchoring transition of LC molecules. The stability and irreversibility of the transition, together with no need of pretreatments for LC alignment, provide fascinating opportunity for liquid crystal device applications. PMID:24514707

  6. Astaxanthin alleviates oxidative stress insults-related derangements in human vascular endothelial cells exposed to glucose fluctuations.

    PubMed

    Abdelzaher, Lobna A; Imaizumi, Takahiro; Suzuki, Tokiko; Tomita, Kengo; Takashina, Michinori; Hattori, Yuichi

    2016-04-01

    Glycemic fluctuations may play a critical role in the pathogenesis of diabetic complications, such as cardiovascular disease. We investigated whether the oxycarotenoid astaxanthin can reduce the detrimental effects of fluctuating glucose on vascular endothelial cells. Human umbilical venous endothelial cells were incubated for 3 days in media containing 5.5mM glucose, 22 mM glucose, or 5.5mM glucose alternating with 22 mM glucose in the absence or presence of astaxanthin or N-acetyl-L-cysteine (NAC). Constant high glucose increased reactive oxygen species (ROS) generation, but such an effect was more pronounced in fluctuating glucose. This was associated with up-regulated p22(phox) expression and down-regulated peroxisome proliferator activated receptor-γ coactivator (PGC-1α) expression. Astaxanthin inhibited ROS generation, p22(phox) up-regulation, and PGC-1α down-regulation by the stimuli of glucose fluctuation. Fluctuating glucose, but not constant high glucose, significantly decreased the endothelial nitric oxide synthase (eNOS) phosphorylation level at Ser-1177 without affecting total eNOS expression, which was prevented by astaxanthin as well as by the anti-oxidant NAC. Transferase-mediated dUTP nick end labeling (TUNEL) showed increased cell apoptosis in fluctuating glucose. Glucose fluctuation also resulted in up-regulating gene expression of pro-inflammatory mediators, interleukin-6 and intercellular adhesion molecule-1. These adverse changes were subdued by astaxanthin. The phosphorylation levels of c-Jun N-terminal kinase (JNK) and p38 were significantly increased by glucose fluctuations, and astaxanthin significantly inhibited the increase in JNK and p38 phosphorylation. Taken together, our results suggest that astaxanthin can protect vascular endothelial cells against glucose fluctuation by reducing ROS generation. PMID:26924495

  7. Elucidation of the Pathway to Astaxanthin in the Flowers of Adonis aestivalis[C][W

    PubMed Central

    Cunningham, Francis X.; Gantt, Elisabeth

    2011-01-01

    A few species in the genus Adonis are the only land plants known to produce the valuable red ketocarotenoid astaxanthin in abundance. Here, we ascertain the pathway that leads from the β-rings of β-carotene, a carotenoid ubiquitous in plants, to the 3-hydroxy-4-keto-β-rings of astaxanthin (3,3′-dihydroxy-β,β-carotene-4,4’-dione) in the blood-red flowers of Adonis aestivalis, an ornamental and medicinal plant commonly known as summer pheasant’s eye. Two gene products were found to catalyze three distinct reactions, with the first and third reactions of the pathway catalyzed by the same enzyme. The pathway commences with the activation of the number 4 carbon of a β-ring in a reaction catalyzed by a carotenoid β-ring 4-dehydrogenase (CBFD), continues with the further dehydrogenation of this carbon to yield a carbonyl in a reaction catalyzed by a carotenoid 4-hydroxy-β-ring 4-dehydrogenase, and concludes with the addition of an hydroxyl group at the number 3 carbon in a reaction catalyzed by the erstwhile CBFD enzyme. The A. aestivalis pathway is both portable and robust, functioning efficiently in a simple bacterial host. Our elucidation of the pathway to astaxanthin in A. aestivalis provides enabling technology for development of a biological production process and reveals the evolutionary origin of this unusual plant pathway, one unrelated to and distinctly different from those used by bacteria, green algae, and fungi to synthesize astaxanthin. PMID:21862704

  8. Stereochemical control of nonamphiphilic lyotropic liquid crystals: chiral nematic phase of assemblies separated by six nanometers of aqueous solvents.

    PubMed

    Yang, Sijie; Wang, Bing; Cui, Dawei; Kerwood, Deborah; Wilkens, Stephan; Han, Junjie; Luk, Yan-Yeung

    2013-06-13

    Unlike conventional thermotropic and lyotropic liquid crystals, nonamphiphilic lyotropic liquid crystals consist of hydrated assemblies of nonamphiphilic molecules that are aligned with a separation of about 6 nm between assemblies in an aqueous environment. This separation raises the question of how chirality, either from chiral mesogens or chiral dopants, would impact the phase as the assemblies that need to interact with each other are about 6 nm apart. Here, we report the synthesis of three stereoisomers of disodium chromonyl carboxylate, 5'DSCG-diviol, and the correlation between the molecular structure, bulk assembly, and liquid crystal formation. We observed that the chiral isomers (enantiomers 5'DSCG-(R,R)-diviol and 5'DSCG-(S,S)-diviol) formed liquid crystals while the achiral isomer 5'DSCG-meso-diviol did not. Circular dichroism indicated a chiral conformation with bisignate cotton effect. The nuclear Overhauser effect in proton NMR spectroscopy revealed conformations that are responsible for liquid crystal formation. Cryogenic transmission electron microscopy showed that chiral 5'DSCG-diviols form assemblies with crossings. Interestingly, only planar alignment of the chiral nematic phase was observed in liquid crystal cells with thin spacers. The homeotropic alignment that permitted a fingerprint texture was obtained only when the thickness of the liquid crystal cell was increase to above ~500 μm. These studies suggest that hydrated assemblies of chiral 5'DSCG-diviol can interact with each other across a 6 nm separation in an aqueous environment by having a twist angle of about 0.22° throughout the sample between the neighboring assemblies. PMID:23688325

  9. Quantitative detection of astaxanthin and cantaxanthin in Atlantic salmon by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner

    2006-02-01

    Two major carotenoids species found in salmonids muscle tissues are astaxanthin and cantaxanthin. They are taken up from fish food and are responsible for the attractive red-orange color of salmon filet. Since carotenoids are powerful antioxidants and biomarkers of nutrient consumption, they are thought to indicate fish health and resistance to diseases in fish farm environments. Therefore, a rapid, accurate, quantitative optical technique for measuring carotenoid content in salmon tissues is of economic interest. We demonstrate the possibility of using fast, selective, quantitative detection of astaxanthin and cantaxanthin in salmon muscle tissues, employing resonance Raman spectroscopy. Analyzing strong Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue laser excitation, we are able to characterize quantitatively the concentrations of carotenoids in salmon muscle tissue. To validate the technique, we compared Raman data with absorption measurements of carotenoid extracts in acetone. A close correspondence was observed in absorption spectra for tissue extract in acetone and a pure astaxanthin solution. Raman results show a linear dependence between Raman and absorption data. The proposed technique holds promise as a method of rapid screening of carotenoid levels in fish muscle tissues and may be attractive for the fish farm industry to assess the dietary status of salmon, risk for infective diseases, and product quality control.

  10. Metabolomic and network analysis of astaxanthin-producing Haematococcus pluvialis under various stress conditions.

    PubMed

    Su, Yingxue; Wang, Jiangxin; Shi, Mengliang; Niu, Xiangfeng; Yu, Xinheng; Gao, Lianju; Zhang, Xiaoqing; Chen, Lei; Zhang, Weiwen

    2014-10-01

    Various combinations of acetate (Ac), Fe(2+) and high light (HL) stress conditions were evaluated to maximize astaxanthin accumulation and biomass production in Haematococcus pluvialis, and then GC-MS and LC-MS based metabolomics were applied to determine molecular mechanisms responsible for enhancing astaxanthin accumulation under the stress conditions. With the optimized analytical protocols, the GC-MS and LC-MS analyses allowed identification of 93 stable and 24 unstable intracellular metabolites from H. pluvialis, respectively. In addition, a metabolic network was constructed based on GC-MS metabolomic datasets using a weighted correlation network analysis (WGCNA) approach. The network analysis uncovered 2, 1 and 1 distinguished metabolic modules highly associated with HL, Fe(2+) & HL, and Ac & Fe(2+) & HL conditions, respectively. Finally, LC-MS analysis found that AKG, Glu and R5P may be metabolites associated with the Fe(2+) & HL condition. The study provided the first metabolomic view of cell growth and astaxanthin accumulation in H. pluvialis. PMID:25164345

  11. Kinetic models for astaxanthin production by high cell density mixotrophic culture of the microalga Haematococcus pluvialis.

    PubMed

    Zhang, X W; Gong, X D; Chen, F

    1999-07-01

    High cell density cultivation of Haematococcus pluvialis for astaxanthin production was carried out in batch and fed-batch modes in 3.7-L bioreactors with stepwise increased light intensity control mode. A high cell density of 2.65 g x L(-1) (batch culture) or 2.74 g x L(-1) (fed-batch culture) was obtained, and total astaxanthin production in the fed-batch culture (64.36 mg x L(-1)) was about 20.5% higher than in the batch culture (53.43 mg x L(-1)). An unstructured kinetic model to describe the microalga culture system including cell growth, astaxanthin formation, as well as sodium acetate consumption was proposed. Good agreement was found between the model predictions and experimental data. The models demonstrated that the optimal light intensity for mixotrophic growth of H. pluvialis in batch or fed-batch cultures in a 3.7-L bioreactor was 90-360 micromol x m(-2) x s(-1), and that the stepwise increased light intensity mode could be replaced by a constant light intensity mode. PMID:10455503

  12. Influence of Oxygen and Glucose on Primary Metabolism and Astaxanthin Production by Phaffia rhodozyma in Batch and Fed-Batch Cultures: Kinetic and Stoichiometric Analysis

    PubMed Central

    Yamane, Y.; Higashida, K.; Nakashimada, Y.; Kakizono, T.; Nishio, N.

    1997-01-01

    The influence of the oxygen and glucose supply on primary metabolism (fermentation, respiration, and anabolism) and astaxanthin production in the yeast Phaffia rhodozyma was investigated. When P. rhodozyma grew under fermentative conditions with limited oxygen or high concentrations of glucose, the astaxanthin production rate decreased remarkably. On the other hand, when the yeast grew under aerobic conditions, the astaxanthin production rate increased with increasing oxygen uptake. A kinetic analysis showed that the respiration rate correlated positively with the astaxanthin production rate, whereas there was a negative correlation with the ethanol production rate. The influence of glucose concentration at a fixed nitrogen concentration with a high level of oxygen was then investigated. The results showed that astaxanthin production was enhanced by an initial high carbon/nitrogen ratio (C/N ratio) present in the medium, but cell growth was inhibited by a high glucose concentration. A stoichiometric analysis suggested that astaxanthin production was enhanced by decreasing the amount of NADPH required for anabolism, which could be achieved by the repression of protein biosynthesis with a high C/N ratio. Based on these results, we performed a two-stage fed-batch culture, in which cell growth was enhanced by a low C/N ratio in the first stage and astaxanthin production was enhanced by a high C/N ratio in the second stage. In this culture system, the highest astaxanthin production, 16.0 mg per liter, was obtained. PMID:16535733

  13. Genetic engineering of the complete carotenoid pathway towards enhanced astaxanthin formation in Xanthophyllomyces dendrorhous starting from a high-yield mutant.

    PubMed

    Gassel, Sören; Breitenbach, Jürgen; Sandmann, Gerhard

    2014-01-01

    The yeast Xanthophyllomyces dendrorhous is one of the rare organisms which can synthesize the commercially interesting carotenoid astaxanthin. However, astaxanthin yield in wild-type and also in classical mutants is still too low for an attractive bioprocess. Therefore, we combined classical mutagenesis with genetic engineering of the complete pathway covering improved precursor supply for carotenogenesis, enhanced metabolite flow into the pathway, and efficient conversion of intermediates into the desired end product astaxanthin. We also constructed new transformation plasmids for the stepwise expression of the genes of 3-hydroxymethyl-3-glutaryl coenzyme A reductase, geranylgeranyl pyrophosphate synthase, phytoene synthase/lycopene cyclase, and astaxanthin synthase. Starting from two mutants with a 15-fold higher astaxanthin, we obtained transformants with an additional 6-fold increase in the final step of pathway engineering. Thus, a maximum astaxanthin content of almost 9 mg per g dry weight was reached in shaking cultures. Under optimized fermenter conditions, astaxanthin production with these engineered transformants should be comparable to Haematococcus pluvialis, the leading commercial producer of natural astaxanthin. PMID:24241897

  14. Chiral electron-chiral target scattering

    SciTech Connect

    Trantham, K.W.; Gay, T.J. Johnston, M.E.

    1996-05-01

    It is possible to have an electronic counterpart to the well known effect of optical circular dichroism: electron circular dichroism (ECD) is the preferential scattering of longitudinally polarized electrons by a chiral target. Resulting essentially from a difference in total scattering cross section for different incident electron helicities, this {open_quotes}parity-violating{close_quotes} effect is allowed by symmetry because the scattering target is handed. The authors have searched for ECD in camphor by measuring the transmitted intensity of electrons with positive (negative) helicity I{sub +({minus})} through a gas cell containing stereoisomers of camphor vapor and constructing the asymmetry A = (I{sub +} {minus} I{sub {minus}}). Within their sensitivity (2x10{sup {minus}4}) the authors were not able to detect ECD at the energies investigated (10 eV). Prospects for future investigations, particularly in light of the recent positive results measured in Muenster, will be discussed.

  15. Isomer-specific comparisons of the hydrolysis of synthetic pyrethroids and their fluorogenic analogues by esterases from the cotton bollworm Helicoverpa armigera.

    PubMed

    Yuan, G; Li, Y; Farnsworth, C A; Coppin, C W; Devonshire, A L; Scott, C; Russell, R J; Wu, Y; Oakeshott, J G

    2015-06-01

    The low aqueous solubility and chiral complexity of synthetic pyrethroids, together with large differences between isomers in their insecticidal potency, have hindered the development of meaningful assays of their metabolism and metabolic resistance to them. To overcome these problems, Shan and Hammock (2001) [7] therefore developed fluorogenic and more water-soluble analogues of all the individual isomers of the commonly used Type 2 pyrethroids, cypermethrin and fenvalerate. The analogues have now been used in several studies of esterase-based metabolism and metabolic resistance. Here we test the validity of these analogues by quantitatively comparing their hydrolysis by a battery of 22 heterologously expressed insect esterases with the hydrolysis of the corresponding pyrethroid isomers by these esterases in an HPLC assay recently developed by Teese et al. (2013) [14]. We find a strong, albeit not complete, correlation (r = 0.7) between rates for the two sets of substrates. The three most potent isomers tested were all relatively slowly degraded in both sets of data but three esterases previously associated with pyrethroid resistance in Helicoverpa armigera did not show higher activities for these isomers than did allelic enzymes derived from susceptible H. armigera. Given their amenability to continuous assays at low substrate concentrations in microplate format, and ready detection of product, we endorse the ongoing utility of the analogues in many metabolic studies of pyrethroids. PMID:26047117

  16. Carotenoid genes transcriptional regulation for astaxanthin accumulation in fresh water unicellular alga Haematococcus pluvialis by gibberellin A3 (GA3).

    PubMed

    Gao, Zhengquan; Meng, Chunxiao; Gao, Hongzheng; Li, Yan; Zhang, Xiaowen; Xu, Dong; Zhou, Shitan; Liu, Banghui; Su, Yuanfeng; Ye, Naihao

    2013-12-01

    The fresh water unicellular alga Haematococcus pluvialis is a promising natural source of astaxanthin. The present study investigated the transcriptional expression of carotenoid genes for astaxanthin accumulation in H. pluvialis using real-time fluorescence quantitative PCR (qRT-PCR). With treatments of 20 and 40 mg/L of gibberllin A3 (GA3), five genes ipi-1, ipi-2, psy, pds and bkt2 were up-regulated with different expression profiles. GA20 (20 mg/L of GA3) treatment had a greater effect on transcriptional expression of bkt2 than on ipi-1 ipi-2, psy and pds (> 4-fold up-regulation). However, GA40 (40 mg/L of GA3) induced more transcriptional expression of ipi-2, psy and bkt2 than both ipi-1 and pds. The expression of lyc, crtR-B and crtO for astaxanthin biosynthesis was not affected by GA3 in H. piuvialis. In the presence of GA3, astaxanthin biosynthesis genes of ipi-1, pds and bkt2 were up-regulated at transcriptional level, psy at post-transcriptional level, whereas ipi-2 was up-regulated at both levels. The study could potentially lead to a scale application of exogenous GA3 in astaxanthin production with H. pluvialis just like GAs perform in increasing crops production and it would provide new insight about the multifunctional roles of carotenogenesis in response to GA3. PMID:24772980

  17. Enhanced autotrophic astaxanthin production from Haematococcus pluvialis under high temperature via heat stress-driven Haber-Weiss reaction.

    PubMed

    Hong, Min-Eui; Hwang, Sung Kwan; Chang, Won Seok; Kim, Byung Woo; Lee, Jeewon; Sim, Sang Jun

    2015-06-01

    High temperatures (30-36 °C) inhibited astaxanthin accumulation in Haematococcus pluvialis under photoautotrophic conditions. The depression of carotenogenesis was primarily attributed to excess intracellular less reactive oxygen species (LROS; O2 (-) and H2O2) levels generated under high temperature conditions. Here, we show that the heat stress-driven inefficient astaxanthin production was improved by accelerating the iron-catalyzed Haber-Weiss reaction to convert LROS into more reactive oxygen species (MROS; O2 and OH·), thereby facilitating lipid peroxidation. As a result, during 18 days of photoautotrophic induction, the astaxanthin concentration of cells cultured in high temperatures in the presence of iron (450 μM) was dramatically increased by 75 % (30 °C) and 133 % (36 °C) compared to that of cells exposed to heat stress alone. The heat stress-driven Haber-Weiss reaction will be useful for economically producing astaxanthin by reducing energy cost and enhancing photoautotrophic astaxanthin production, particularly outdoors utilizing natural solar radiation including heat and light for photo-induction of H. pluvialis. PMID:25683663

  18. Astaxanthin, a Carotenoid, Stimulates Immune Responses by Enhancing IFN-γ and IL-2 Secretion in Primary Cultured Lymphocytes in Vitro and ex Vivo

    PubMed Central

    Lin, Kuan-Hung; Lin, Kao-Chang; Lu, Wan-Jung; Thomas, Philip-Aloysius; Jayakumar, Thanasekaran; Sheu, Joen-Rong

    2015-01-01

    Astaxanthin, a potent antioxidant carotenoid, plays a major role in modulating the immune response. In this study, we examined the immunomodulatory effects of astaxanthin on cytokine production in primary cultured lymphocytes both in vitro and ex vivo. Direct administration of astaxanthin (70–300 nM) did not produce cytotoxicity in lipopolysaccharide (LPS, 100 µg/ mL)- or concanavalin A (Con A, 10 µg/ mL)-activated lymphocytes, whereas astaxanthin alone at 300 nM induced proliferation of splenic lymphocytes (p < 0.05) in vitro. Although astaxanthin, alone or with Con A, had no apparent effect on interferon (INF-γ) and interleukin (IL-2) production in primary cultured lymphocytes, it enhanced LPS-induced INF-γ production. In an ex vivo experiment, oral administration of astaxanthin (0.28, 1.4 and 7 mg/kg/day) for 14 days did not cause alterations in the body or spleen weights of mice and also was not toxic to lymphocyte cells derived from the mice. Moreover, treatment with astaxanthin significantly increased LPS-induced lymphocyte proliferation ex vivo but not Con A-stimulated lymphocyte proliferation ex vivo. Enzyme linked immunosorbent assay (ELISA) analysis revealed that administration of astaxanthin significantly enhanced INF-γ production in response to both LPS and Con A stimulation, whereas IL-2 production increased only in response to Con A stimulation. Also, astaxanthin treatment alone significantly increased IL-2 production in lymphocytes derived from mice, but did not significantly change production of INF-γ. These findings suggest that astaxanthin modulates lymphocytic immune responses in vitro, and that it partly exerts its ex vivo immunomodulatory effects by increasing INF-γ and IL-2 production without inducing cytotoxicity. PMID:26729100

  19. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    The chirality of organic molecules with the asymmetric location of group radicals was discovered in 1848 by Louis Pasteur during his investigations of the rotation of the plane of polarization of light by crystals of sodium ammonium paratartrate. It is well established that the amino acids in proteins are exclusively Levorotary (L-aminos) and the sugars in DNA and RNA are Dextrorotary (D-sugars). This phenomenon of homochirality of biological polymers is a fundamental property of all life known on Earth. Furthermore, abiotic production mechanisms typically yield recemic mixtures (i.e. equal amounts of the two enantiomers). When amino acids were first detected in carbonaceous meteorites, it was concluded that they were racemates. This conclusion was taken as evidence that they were extraterrestrial and produced by abiologically. Subsequent studies by numerous researchers have revealed that many of the amino acids in carbonaceous meteorites exhibit a significant L-excess. The observed chirality is much greater than that produced by any currently known abiotic processes (e.g. Linearly polarized light from neutron stars; Circularly polarized ultraviolet light from faint stars; optically active quartz powders; inclusion polymerization in clay minerals; Vester-Ulbricht hypothesis of parity violations, etc.). This paper compares the measured chirality detected in the amino acids of carbonaceous meteorites with the effect of these diverse abiotic processes. IT is concluded that the levels observed are inconsistent with post-arrival biological contamination or with any of the currently known abiotic production mechanisms. However, they are consistent with ancient biological processes on the meteorite parent body. This paper will consider these chiral biomarkers in view of the detection of possible microfossils found in the Orgueil and Murchison carbonaceous meteorites. Energy dispersive x-ray spectroscopy (EDS) data obtained on these morphological biomarkers will be

  20. A Chiral Granular Gas

    NASA Astrophysics Data System (ADS)

    Tsai, J.-C.; Ye, Fangfu; Rodriguez, Juan; Gollub, J. P.; Lubensky, T. C.

    2005-05-01

    Inspired by rattleback toys, we created small chiral wires that rotate in a preferred direction on a vertically oscillating platform and quantified their motion with experiment and simulation. We demonstrate experimentally that angular momentum of rotation about particle centers of mass is converted to collective angular momentum of center-of-mass motion in a granular gas of these wires, and we introduce a continuum model that explains our observations.

  1. A chiral granular gas.

    PubMed

    Tsai, J-C; Ye, Fangfu; Rodriguez, Juan; Gollub, J P; Lubensky, T C

    2005-06-01

    Inspired by rattleback toys, we created small chiral wires that rotate in a preferred direction on a vertically oscillating platform and quantified their motion with experiment and simulation. We demonstrate experimentally that angular momentum of rotation about particle centers of mass is converted to collective angular momentum of center-of-mass motion in a granular gas of these wires, and we introduce a continuum model that explains our observations. PMID:16090323

  2. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

    Ahmed, Mohammad W.; Gao, Haiyan; Weller, Henry R.; Holstein, Barry

    2007-10-01

    pt. A. Plenary session. Opening remarks: experimental tests of chiral symmetry breaking / A. M. Bernstein. [Double pie symbols] scattering / H. Leutwyler. Chiral effective field theory in a [Triangle]-resonance region / V. Pascalutsa. Some recent developments in chiral perturbation theory / Ulf-G. Mei ner. Chiral extrapolation and nucleon structure from the lattice / R.D. Young. Recent results from HAPPEX / R. Michaels. Chiral symmetries and low energy searches for new physics / M.J. Ramsey-Musolf. Kaon physics: recent experimental progress / M. Moulson. Status of the Cabibbo angle / V. Cirigliano. Lattice QCD and nucleon spin structure / J.W. Negele. Spin sum rules and polarizabilities: results from Jefferson lab / J-P Chen. Compton scattering and nucleon polarisabilities / Judith A. McGovern. Virtual compton scattering at MIT-bates / R. Miskimen. Physics results from the BLAST detector at the BATES accelerator / R.P. Redwine. The [Pie sympbol]NN system, recent progress / C. Hanhart. Application of chiral nuclear forces to light nuclei / A. Nogga. New results on few-body experiments at low energy / Y. Nagai. Few-body lattice calculations / M.J. Savage. Research opportunities at the upgraded HI?S facility / H.R. Weller -- pt. B. Goldstone boson dynamics. Working group summary: Goldstone Boson dynamics / G. Colangelo and S. Giovannella. Recent results on radiative Kaon decays from NA48 and NA48/2 / S.G. López. Cusps in K-->3 [Pie symbol] decays / B. Kubis. Recent KTeV results on radiative Kaon decays / M.C. Ronquest. The [Double pie symbols] scattering amplitude / J.R. Peláez. Determination of the Regge parameters in the [Double pie symbols] scattering amplitude / I. Caprini. e+e- Hadronic cross section measurement at DA[symbol]NE with the KLOE detector / P. Beltrame. Measurement of the form factors of e+e- -->2([Pie symbol]+[Pie symbol]-), pp and the resonant parameters of the heavy charmonia at BES / H. Hu. Measurement of e+e- multihadronic cross section below 4

  3. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

    Spontaneous chiral symmetry breaking, mesons and baryons are illustrated in the language of the Dirac theory. Various forces acting between quarks inside baryons are discussed. I explain why the naive quark models typically overestimate pentaquark masses by some 500 MeV and why in the fully relativistic approach to baryons pentaquarks turn out to be light. I discuss briefly why it can be easier to produce pentaquarks at low than at high energies.

  4. Chirality and protein folding

    NASA Astrophysics Data System (ADS)

    Kwiecinska, Joanna I.; Cieplak, Marek

    2005-05-01

    There are several simple criteria of folding to a native state in model proteins. One of them involves crossing of a threshold value of the root mean square deviation distance away from the native state. Another checks whether all native contacts are established, i.e. whether the interacting amino acids come closer than some characteristic distance. We use Go-like models of proteins and show that such simple criteria may prompt one to declare folding even though fragments of the resulting conformations have a wrong sense of chirality. We propose that a better condition of folding should augment the simple criteria with the requirement that most of the local values of the chirality should be nearly native. The kinetic discrepancy between the simple and compound criteria can be substantially reduced in the Go-like models by providing the Hamiltonian with a term which favours native values of the local chirality. We study the effects of this term as a function of its amplitude and compare it to other models such as ones with side groups and ones with angle-dependent potentials.

  5. Chirality and equilibrium biopolymer bundles.

    PubMed

    Grason, Gregory M; Bruinsma, Robijn F

    2007-08-31

    We use continuum theory to show that chirality is a key thermodynamic control parameter for the aggregation of biopolymers: chirality produces a stable disperse phase of hexagonal bundles under moderately poor solvent conditions, as has been observed in in vitro studies of F actin [O. Pelletier et al., Phys. Rev. Lett. 91, 148102 (2003)]. The large characteristic radius of these chiral bundles is not determined by a mysterious long-range molecular interaction but by in-plane shear elastic stresses generated by the interplay between a chiral torque and an unusual, but universal, nonlinear gauge term in the strain tensor of ordered chains that is imposed by rotational invariance. PMID:17931038

  6. The interstellar chemistry of H2C3O isomers

    NASA Astrophysics Data System (ADS)

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-03-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

  7. The interstellar chemistry of H2C3O isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-01-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects. PMID:27013768

  8. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

    We provide a holographic evaluation of novel contributions to the drag force acting on a heavy quark moving through strongly interacting plasma. The new contributions are chiral in the sense that they act in opposite directions in plasmas containing an excess of left- or right-handed quarks. The new contributions are proportional to the coefficient of the axial anomaly, and in this sense also are chiral. These new contributions to the drag force act either parallel to or antiparallel to an external magnetic field or to the vorticity of the fluid plasma. In all these respects, these contributions to the drag force felt by a heavy quark are analogous to the chiral magnetic effect (CME) on light quarks. However, the new contribution to the drag force is independent of the electric charge of the heavy quark and is the same for heavy quarks and antiquarks, meaning that these novel effects do not in fact contribute to the CME current. We show that although the chiral drag force can be non-vanishing for heavy quarks that are at rest in the local fluid rest frame, it does vanish for heavy quarks that are at rest in a suitably chosen frame. In this frame, the heavy quark at rest sees counterpropagating momentum and charge currents, both proportional to the axial anomaly coefficient, but feels no drag force. This provides strong concrete evidence for the absence of dissipation in chiral transport, something that has been predicted previously via consideration of symmetries. Along the way to our principal results, we provide a general calculation of the corrections to the drag force due to the presence of gradients in the flowing fluid in the presence of a nonzero chemical potential. We close with a consequence of our result that is at least in principle observable in heavy ion collisions, namely an anticorrelation between the direction of the CME current for light quarks in a given event and the direction of the kick given to the momentum of all the heavy quarks and

  9. Rhodium-Catalyzed Synthesis of Chiral Spiro-9-silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters.

    PubMed

    Murai, Masahito; Takeuchi, Yutaro; Yamauchi, Kanae; Kuninobu, Yoichiro; Takai, Kazuhiko

    2016-04-18

    Mechanistic insight into the construction of quaternary silicon chiral centers by rhodium-catalyzed synthesis of spiro-9-silabifluorenes through dehydrogenative silylation is reported. The C2 -symmetric bisphosphine ligand, BINAP, was effective in controlling enantioselectivity, and axially chiral spiro-9-silabifluorenes were obtained in excellent yields with high enantiomeric excess. Monitoring of the reaction revealed the presence of a monohydrosilane intermediate as a mixture of two constitutional isomers. The reaction proceeded through two consecutive dehydrogenative silylations, and the absolute configuration was determined in the first silylative cyclization. Competitive reactions with electron-rich and electron-deficient dihydrosilanes indicated that the rate of silylative cyclization increased with decreasing electron density on the silicon atom of the starting dihydrosilane. Further investigation disclosed a rare interconversion between the two constitutional isomers of the monohydrosilane intermediate with retention of the absolute configuration. PMID:26970095

  10. Astaxanthin hyperproduction by Phaffia rhodozyma (now Xanthophyllomyces dendrorhous) with raw coconut milk as sole source of energy.

    PubMed

    Domíguez-Bocanegra, A R; Torres-Muñoz, J A

    2004-12-01

    Natural carbon sources, such as those present in cane sugar molasses and grape juice, promote the synthesis of astaxanthin in different Phaffia rhodozyma yeasts. One of these, coconut milk, has a very rich nutrient composition. The aim of this work was to investigate the utility of coconut milk as sole source of energy for astaxanthin pigment production by P. rhodozyma strains. Currently, coconut pulp is widely used in industrial processes in Mexico for the production of shampoos, candies, food, etc. However, coconut milk is a waste product. We show that coconut milk enhances astaxanthin production. The fermentation yielded 850 microg/g yeast with the NRRL-10921 wild-type strain and 1850 microg/g yeast with the mutated R1 strain. Production was better than reported results employing other natural carbon sources. PMID:15290135

  11. Enhanced astaxanthin production from microalga, Haematococcus pluvialis by two-stage perfusion culture with stepwise light irradiation.

    PubMed

    Park, Joon Chul; Choi, Seung Phill; Hong, Min-Eui; Sim, Sang Jun

    2014-10-01

    For efficient astaxanthin production from the culture of green microalga, Haematococcus pluvialis, a two-stage mixotrophic culture system was established with stepwise increased light irradiance. By perfusion process, high density biomass (2.47 g/L) was achieved during the vegetative stage due to no detrimental effect of inhibitory metabolites, which was 3.09 and 1.67 times higher than batch and fed-batch processes, respectively. During the induction stage, biomass and astaxanthin were subsequently produced to the very high level 12.3 g/L and 602 mg/L, under stepwise increased light irradiance (150-450 μE/m(2)/s), respectively. These results indicate that the combinatorial approach of perfusion culture during the vegetative stage and stepwise light irradiation during the induction stage is a promising strategy for the simultaneous production of high concentration of biomass and astaxanthin in microalgae including H. pluvialis. PMID:24700132

  12. Separation and purification of astaxanthin from Phaffia rhodozyma by preparative high-speed counter-current chromatography.

    PubMed

    Du, Xiping; Dong, Congcong; Wang, Kai; Jiang, Zedong; Chen, Yanhong; Yang, Yuanfan; Chen, Feng; Ni, Hui

    2016-09-01

    An effective high-speed counter-current chromatography (HSCCC) method was established for the preparative isolation and purification of astaxanthin from Phaffia rhodozyma. With a two-phase solvent system composed of n-hexane-acetone-ethanol-water (1:1:1:1, v/v/v/v), 100mg crude extract of P. rhodozyma was separated to yield 20.6mg of astaxanthin at 92.0% purity. By further one step silica gel column chromatography, the purity reached 99.0%. The chemical structure of astaxanthin was confirmed by thin layer chromatography (TLC), UV spectroscopy scanning, high performance liquid chromatography with a ZORBAX SB-C18 column and a Waters Nova-pak C18 column, and ESI/MS/MS. PMID:27433984

  13. Separation of steroid isomers by ion mobility mass spectrometry.

    PubMed

    Ahonen, Linda; Fasciotti, Maíra; Gennäs, Gustav Boije Af; Kotiaho, Tapio; Daroda, Romeu J; Eberlin, Marcos; Kostiainen, Risto

    2013-10-01

    Ion mobility mass spectrometry performed in a compact traveling wave cell (TWIM-MS) is shown to provide a reliable, fast and repeatable method to separate derivatized steroid isomers. Three steroid isomer pairs were analyzed in their native form and as their p-toluenesulfonyl isocyanate derivatives. The native steroids were separated from each other, but no separation could be attained for the isomers. The derivatized steroid isomers were, however, properly separated by TWIM-MS with peak-to-peak resolutions close to or as high as baseline resolution (Rp-p=0.77-1.08). PMID:23992881

  14. Astaxanthin improves behavioral disorder and oxidative stress in prenatal valproic acid-induced mice model of autism.

    PubMed

    Al-Amin, Md Mamun; Rahman, Md Mahbubur; Khan, Fazlur Rahman; Zaman, Fahmida; Mahmud Reza, Hasan

    2015-06-01

    Prenatal exposure to valproic acid on gestational day 12.5 may lead to the impaired behavior in the offspring, which is similar to the human autistic symptoms. To the contrary, astaxanthin shows neuroprotective effect by its antioxidant mechanism. We aimed to (i) develop mice model of autism and (ii) investigate the effect of astaxanthin on such model animals. Valproic acid (600 mg/kg) was administered intraperitoneally to the pregnant mice on gestational day 12.5. Prenatal valproic acid-exposed mice were divided into 2 groups on postnatal day 25 and astaxanthin (2mg/kg) was given to the experimental group (VPA_AST, n=10) while saline was given to the control group (VPA, n=10) for 4 weeks. Behavioral test including social interaction, open field and hot-plate were conducted on postnatal day 25 and oxidative stress markers such as lipid peroxidation, advanced protein oxidation product, nitric oxide, glutathione, and activity of superoxide dismutase and catalase were estimated on postnatal day 26 to confirm mice model of autism and on postnatal day 56 to assess the effect of astaxanthin. On postnatal day 25, prenatal valproic acid-exposed mice exhibited (i) delayed eye opening (ii) longer latency to respond painful stimuli, (iii) poor sociability and social novelty and (iv) high level of anxiety. In addition, an increased level of oxidative stress was found by determining different oxidative stress markers. Treatment with astaxanthin significantly (p<0.05) improved the behavioral disorder and reduced the oxidative stress in brain and liver. In conclusion, prenatal exposure to valproic day in pregnant mice leads to the development of autism-like features. Astaxanthin improves the impaired behavior in animal model of autism presumably by its antioxidant activity. PMID:25732953

  15. The effect of gamma irradiation on astaxanthin synthetase encoding gene in two mutant strains of Phaffia rhodozyma

    PubMed Central

    Najafi, Naeimeh; Hosseini, Ramin; Ahmadi, Ali-Reza

    2013-01-01

    Background and Objectives Astaxanthin, an orange-red carotenoid pigment, acts as a protective agent against oxidative damage to cells in vivo. The astaxanthin synthetase gene (crtS) size consists of 3995 bp. This gene has been suggested to catalyse β-carotene to astaxanthin in Phaffia rhodozyma. The aim of this research was to find any possible changes in this gene in two mutant strains, Gam1 and Gam2 (with high astaxanthin pigment production), previously created by gamma irradiation. Materials and Methods The astaxanthin synthetase gene sequence of Phaffia rhodozyma in the NCBI Gene bank was used to design primer. In Gam1, this gene was amplified using primers Asta F1, Asta R2, Asta F3, Asta R4. In Gam2, primers asta F1, asta R4 were used to amplify the gene. The amplified fragments were 8 sequenced using primers Asta F1, Asta R1, Asta F2, Asta R2, Asta F3, Asta R3 and Asta F4, Asta R4. Astaxanthin synthetase gene from two mutant strains, Gam1 and Gam2 were amplified using PCR. The amplified products were sequenced and aligned using the ClustalW software. Conclusion The comparison of this gene showed 98% and 99% similarities between the reference sequence and Gam1 and Gam2 mutant strains, respectively, whereas the comparison of this gene in Gam1 and Gam2 mutant strains showed 97% similarity. However, the deduced proteins showed 78% and 83% between the reference protein obtained from the wild type and Gam1 and Gam2, respectively. This similarity was 75% between the mutant strains. PMID:24475339

  16. Enantiomer Identification in Chiral Mixtures with Broadband Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Shubert, V. Alvin; Schmitz, David; Medcraft, Chris; Patterson, David; Doyle, John M.; Schnell, Melanie

    2014-06-01

    In nature and as products of chemical syntheses, chiral molecules often exist in mixtures with other chiral molecules. The analysis of these complex mixtures to identify the components, determine which enantiomers are present, and to measure the enantiomeric excesses (ee) is still one of the challenging but very important tasks of analytical chemistry. These analyses are required at every step of modern drug development, from candidate searches to production and regulation. We present here a new method of identifying individual enantiomers in mixtures of chiral molecules in the gas phase. It is based on broadband rotational spectroscopy and employs a sum or difference frequency generation three-wave mixing process that involves a closed cycle of three rotational transitions. The phase of the acquired signal bares the signature of the enantiomer (see figure), as it depends upon the combined quantity, μaμbμc, which is of opposite sign between members of an enantiomeric pair. Furthermore, because the signal amplitude is proportional to the ee, this technique allows for both determining which enantiomer is in excess and by how much. The high resolution of our technique allows us to perform molecule specific measurements of mixtures of chiral molecules with μaμbμc ≠ 0, even when the molecules are very similar (e.g. conformational isomers). We introduce the technique and present results on the analysis of mixtures of the terpenes, carvone, menthone, and carvomenthenol. D. Patterson, M. Schnell, J. M. Doyle, Nature. 497, 475-477, 2013 V. A. Shubert, D. Schmitz, D. Patterson, J. M. Doyle, M. Schnell, Ang. Chem. Int. Ed. 53, 1152-1155,2014

  17. On the viability of achieving chiral separation through the optical manipulation of molecules

    NASA Astrophysics Data System (ADS)

    Andrews, David L.; Bradshaw, David S.

    2015-03-01

    Several different optical methods have recently been proposed for the potential separation of chiral molecules according to their intrinsic handedness. Applying fundamental symmetry and electrodynamical principles provides a perspective that casts doubt over the viability of some of the more extravagant claims. However there is a genuine basis for achieving chiral separation by using circularly polarized light to deliver chirally sensitive optical forces. The mechanism comes into play when molecules (or nanoscale particles) are optically trapped in a laser beam by forward Rayleigh scattering, as a result of trapping forces that depend on positioning within the beam profile. In such a setup, chiral molecules experience subtle additional forces associated with a combination of electric and magnetic transition dipoles; when circularly polarized light is used for the trapping, a discriminatory response can be identified that has the capacity to separate left- and righthanded molecular isomers. Here, clear differences can be observed between the behavior of isotropic liquids and poled solutions or liquid crystals. Detailed analysis provides an objective basis to assess new prospects for the recognition and differentiation of molecules with opposite chiral form, identifying and paving the way for future commercial applications.

  18. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

    Koby, Lawrence; Ningappa, Jyothi B.; Dakesssian, Maria; Cuccia, Louis A.

    2005-01-01

    The optimal conditions for the crystallization of achiral ethylenediamine sulfate into large chiral crystals that are ideal for polarimetry studies and observation using Polaroid sheets are presented. This experiment is an ideal undergraduate experiment, which clearly demonstrates the chiral crystallization of an achiral molecule.

  19. CHIRAL POLLUTANTS: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    This task involves process research to determine the environmental occurrence and fate of enantiomers of selected chiral pesticides, PCBs and other chiral pollutants with an emphasis on currently-used modern pesticides expected to have short to intermediate environmental half-liv...

  20. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

  1. Stereospecificity of mushroom tyrosinase immobilized on a chiral and a nonchiral support.

    PubMed

    Marín-Zamora, María Elisa; Rojas-Melgarejo, Francisco; García-Canovas, Francisco; García-Ruiz, Pedro Antonio

    2007-05-30

    Mushroom tyrosinase was immobilized from an extract onto glass beads covered with the cross-linked totally cinnamoylated derivates of d-sorbitol (sorbitol cinnamate) and glycerine (glycerine cinnamate). The enzyme was immobilized onto the support by direct adsorption, and the quantity of immobilized tyrosinase was higher for sorbitol cinnamate, the support with the higher number of esterified hydroxyls per unit of monosacharide, than for glycerine cinnamate. The results obtained from the stereospecificity study of the monophenolase and diphenolase activity of immobilized mushroom tyrosinase are reported. The enantiomers L-tyrosine, DL-tyrosine, D-tyrosine, L-dopa, DL-dopa, D-dopa, L-alpha-methyldopa, DL-alpha-methyldopa, L-isoprenaline, DL-isoprenaline, L-adrenaline, DL-adrenaline, L-noradrenaline, and D-noradrenaline were assayed with tyrosinase immobilized on a chiral support (sorbitol cinnamate), whereas L-tyrosine, DL-tyrosine, D-tyrosine, L-dopa, DL-dopa, D-dopa, L-alpha-methyldopa, and DL-alpha-methyldopa were assayed with tyrosinase immobilized on a nonchiral support (glycerine cinnamate). The same Vmax(app) values for each series of enantiomers were obtained. However, the Km(app) values were different, the l isomers showing lower values than the dl isomers, whereas the highest Km(app) value was obtained with d isomers. No difference was observed in the stereospecificity of tyrosinase immobilized on a chiral (sorbitol cinnamate) or nonchiral (glycerine cinnamate) support. PMID:17488091

  2. Cloning of the cytochrome p450 reductase (crtR) gene and its involvement in the astaxanthin biosynthesis of Xanthophyllomyces dendrorhous

    PubMed Central

    Alcaíno, Jennifer; Barahona, Salvador; Carmona, Marisela; Lozano, Carla; Marcoleta, Andrés; Niklitschek, Mauricio; Sepúlveda, Dionisia; Baeza, Marcelo; Cifuentes, Víctor

    2008-01-01

    Background The yeast Xanthophyllomyces dendrorhous synthesizes astaxanthin, a carotenoid with high commercial interest. The proposed biosynthetic route in this organism is isopentenyl-pyrophosphate (IPP) → geranyleranyl pyrophosphate (GGPP) → phytoene → lycopene → β-carotene → astaxanthin. Recently, it has been published that the conversion of β-carotene into astaxanthin requires only one enzyme, astaxanthin synthase or CrtS, encoded by crtS gene. This enzyme belongs to the cytochrome P450 protein family. Results In this work, a crtR gene was isolated from X. dendrorhous yeast, which encodes a cytochrome P450 reductase (CPR) that provides CrtS with the necessary electrons for substrate oxygenation. We determined the structural organization of the crtR gene and its location in the yeast electrophoretic karyotype. Two transformants, CBSTr and T13, were obtained by deleting the crtR gene and inserting a hygromycin B resistance cassette. The carotenoid composition of the transformants was altered in relation to the wild type strain. CBSTr forms yellow colonies because it is unable to produce astaxanthin, hence accumulating β-carotene. T13 forms pale colonies because its astaxanthin content is reduced and its β-carotene content is increased. Conclusion In addition to the crtS gene, X. dendrorhous requires a novel gene, crtR, for the conversion of β-carotene to astaxanthin. PMID:18837978

  3. Astaxanthin Inhibits JAK/STAT-3 Signaling to Abrogate Cell Proliferation, Invasion and Angiogenesis in a Hamster Model of Oral Cancer

    PubMed Central

    Kowshik, J.; Baba, Abdul Basit; Giri, Hemant; Deepak Reddy, G.; Dixit, Madhulika; Nagini, Siddavaram

    2014-01-01

    Identifying agents that inhibit STAT-3, a cytosolic transcription factor involved in the activation of various genes implicated in tumour progression is a promising strategy for cancer chemoprevention. In the present study, we investigated the effect of dietary astaxanthin on JAK-2/STAT-3 signaling in the 7,12-dimethylbenz[a]anthracene (DMBA)-induced hamster buccal pouch (HBP) carcinogenesis model by examining the mRNA and protein expression of JAK/STAT-3 and its target genes. Quantitative RT-PCR, immunoblotting and immunohistochemical analyses revealed that astaxanthin supplementation inhibits key events in JAK/STAT signaling especially STAT-3 phosphorylation and subsequent nuclear translocation of STAT-3. Furthermore, astaxanthin downregulated the expression of STAT-3 target genes involved in cell proliferation, invasion and angiogenesis, and reduced microvascular density, thereby preventing tumour progression. Molecular docking analysis confirmed inhibitory effects of astaxanthin on STAT signaling and angiogenesis. Cell culture experiments with the endothelial cell line ECV304 substantiated the role of astaxanthin in suppressing angiogenesis. Taken together, our data provide substantial evidence that dietary astaxanthin prevents the development and progression of HBP carcinomas through the inhibition of JAK-2/STAT-3 signaling and its downstream events. Thus, astaxanthin that functions as a potent inhibitor of tumour development and progression by targeting JAK/STAT signaling may be an ideal candidate for cancer chemoprevention. PMID:25296162

  4. Astaxanthin inhibits JAK/STAT-3 signaling to abrogate cell proliferation, invasion and angiogenesis in a hamster model of oral cancer.

    PubMed

    Kowshik, J; Baba, Abdul Basit; Giri, Hemant; Deepak Reddy, G; Dixit, Madhulika; Nagini, Siddavaram

    2014-01-01

    Identifying agents that inhibit STAT-3, a cytosolic transcription factor involved in the activation of various genes implicated in tumour progression is a promising strategy for cancer chemoprevention. In the present study, we investigated the effect of dietary astaxanthin on JAK-2/STAT-3 signaling in the 7,12-dimethylbenz[a]anthracene (DMBA)-induced hamster buccal pouch (HBP) carcinogenesis model by examining the mRNA and protein expression of JAK/STAT-3 and its target genes. Quantitative RT-PCR, immunoblotting and immunohistochemical analyses revealed that astaxanthin supplementation inhibits key events in JAK/STAT signaling especially STAT-3 phosphorylation and subsequent nuclear translocation of STAT-3. Furthermore, astaxanthin downregulated the expression of STAT-3 target genes involved in cell proliferation, invasion and angiogenesis, and reduced microvascular density, thereby preventing tumour progression. Molecular docking analysis confirmed inhibitory effects of astaxanthin on STAT signaling and angiogenesis. Cell culture experiments with the endothelial cell line ECV304 substantiated the role of astaxanthin in suppressing angiogenesis. Taken together, our data provide substantial evidence that dietary astaxanthin prevents the development and progression of HBP carcinomas through the inhibition of JAK-2/STAT-3 signaling and its downstream events. Thus, astaxanthin that functions as a potent inhibitor of tumour development and progression by targeting JAK/STAT signaling may be an ideal candidate for cancer chemoprevention. PMID:25296162

  5. Mass-Selective Chiral Analysis.

    PubMed

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-12

    Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here. PMID:27070181

  6. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

    Damasceno, Pablo F.; Karas, Andrew S.; Schultz, Benjamin A.; Engel, Michael; Glotzer, Sharon C.

    2015-10-01

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

  7. Mass-Selective Chiral Analysis

    NASA Astrophysics Data System (ADS)

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-01

    Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

  8. Controlling Chirality of Entropic Crystals.

    PubMed

    Damasceno, Pablo F; Karas, Andrew S; Schultz, Benjamin A; Engel, Michael; Glotzer, Sharon C

    2015-10-01

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. PMID:26550757

  9. Improved aqueous solubility of crystalline astaxanthin (3,3'-dihydroxy-beta, beta-carotene-4,4'-dione) by Captisol (sulfobutyl ether beta-cyclodextrin).

    PubMed

    Lockwood, Samuel F; O'Malley, Sean; Mosher, Gerold L

    2003-04-01

    Carotenoids are the most widely distributed natural pigments, with over 600 individual compounds identified and characterized from natural sources. A few are commercially important molecules, having found utility as additions to animal feed in the aquaculture, poultry, and swine feed industries. The majority are lipophilic molecules with near zero inherent aqueous solubility. Many different methods have been developed to make the carotenoids "water dispersible," as true water solubility has not been described. Astaxanthin (3,3'-dihydroxy-beta, beta-carotene-4,4'-dione) is a commercially important oxygenated carotenoid that has gained wide acceptance as a feed additive in the $50 billion salmon and trout aquaculture industry. Recently, interest in the human health applications of astaxanthin has increased, with astaxanthin receiving approval as a dietary supplement in several countries, including the United States. Moving astaxanthin into a pharmaceutical application will require a chemical delivery system that overcomes the problems with parenteral administration of a highly lipophilic, low molecular weight compound. In the current study, the ability of sulfobutyl ether beta-cyclodextrin (sodium), as the Captisol(R) brand, to increase the aqueous water solubility of crystalline astaxanthin was evaluated. Complexation of crystalline astaxanthin with Captisol increased the apparent water solubility of crystalline astaxanthin approximately 71-fold, to a concentration in the 2 microg/mL range. It is unlikely that this increase in solubility will result in a pharmaceutically acceptable chemical delivery system for humans. However, the increased aqueous solubility of crystalline astaxanthin to the range achieved in the current study will likely find utility in the introduction of crystalline astaxanthin into mammalian cell culture systems that have previously been dependent upon liposomes, or toxic organic solvents, for the introduction of carotenoids into aqueous

  10. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  11. Stereospecific Synthesis of the Geometrical Isomers of a Natural Product

    ERIC Educational Resources Information Center

    Grove, T.; DiLella, D.; Volker, E.

    2006-01-01

    Stereospecific synthesis of a geometrical isomer is not a common topic for the introductory organic chemistry laboratory. We have developed and tested an experiment for the synthesis of (Z) and (E) isomers that has been performed successfully by undergraduate students. The experiment is presented to the students as a puzzle in which they must…

  12. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  13. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  14. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  15. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  16. Pseudo-discontinuities in the isomer shift near magnetic transitions

    NASA Astrophysics Data System (ADS)

    Kolk, B.; Hall, D. B.; Zheng, Y.; Lumetta, J. T.

    1983-12-01

    It is shown that a relatively small non-linear behavior of the velocity drive system used in Mössbauer effect studies yields pseudo-discontinuities in the isomer shift near the critical temperature T c of a magnetic-paramagnetic transition. The anomaly of the57Fe isomer shift in iron is attributed to this effect.

  17. Remotely Controlled Isomer Selective Molecular Switching.

    PubMed

    Schendel, Verena; Borca, Bogdana; Pentegov, Ivan; Michnowicz, Tomasz; Kraft, Ulrike; Klauk, Hagen; Wahl, Peter; Schlickum, Uta; Kern, Klaus

    2016-01-13

    Nonlocal addressing-the "remote control"-of molecular switches promises more efficient processing for information technology, where fast speed of switching is essential. The surface state of the (111) facets of noble metals, a confined two-dimensional electron gas, provides a medium that enables transport of signals over large distances and hence can be used to address an entire ensemble of molecules simultaneously with a single stimulus. In this study we employ this characteristic to trigger a conformational switch in anthradithiophene (ADT) molecules by injection of hot carriers from a scanning tunneling microscope (STM) tip into the surface state of Cu(111). The carriers propagate laterally and trigger the switch in molecules at distances as far as 100 nm from the tip location. The switching process is shown to be long-ranged, fully reversible, and isomer selective, discriminating between cis and trans diastereomers, enabling maximum control. PMID:26619213

  18. Isomer ratio calculations using modeled discrete levels

    SciTech Connect

    Gardner, M.A.; Gardner, D.G.; Hoff, R.W.

    1984-10-16

    Isomer ratio calculations were made for the reactions: /sup 175/Lu(n,..gamma..)/sup 176m,g/Lu, /sup 175/Lu(n,2n)/sup 174m,g/Lu, /sup 237/Np(n,2n)/sup 236m,g/Np, /sup 241/Am(n,..gamma..)/sup 242m,g/Am, and /sup 243/Am(n,..gamma..)/sup 244m,g/Am using modeled level structures in the deformed, odd-odd product nuclei. The hundreds of discrete levels and their gamma-ray branching ratios provided by the modeling are necessary to achieve agreement with experiment. Many rotational bands must be included in order to obtain a sufficiently representative selection of K quantum numbers. The levels of each band must be extended to appropriately high values of angular momentum.

  19. Laboratory detection of the elusive HSCO+ isomer.

    PubMed

    McCarthy, M C; Thaddeus, P

    2007-12-14

    The rotational spectrum of protonated carbonyl sulfide, HSCO(+), has now been detected in the centimeter-wave band in a molecular beam by Fourier transform microwave spectroscopy. Rotational and centrifugal distortion constants have been determined from transitions in the K(a)=0 ladder of the normal isotopic species, and DSCO(+) and H(34)SCO(+). HSCO(+) is systematically more abundant by a factor of three than HOCS(+), the isomer obtained by attaching the H(+) to the other end of the molecule, which ab initio calculations long predicted to be higher in energy by 4-5 kcalmol. Because HSCO(+) is comparable in polarity to HOCS(+) and is apparently more stable and because OCS is widely distributed in astronomical sources, HSCO(+) is a good candidate for detection with radio telescopes. PMID:18081381

  20. Solvent-induced helical assembly and reversible chiroptical switching of chiral cyclic-dipeptide-functionalized naphthalenediimides.

    PubMed

    Manchineella, Shivaprasad; Prathyusha, V; Priyakumar, U Deva; Govindaraju, T

    2013-12-01

    Understanding the roles of various parameters in orchestrating the preferential chiral molecular organization in supramolecular self-assembly processes is of great significance in designing novel molecular functional systems. Cyclic dipeptide (CDP) chiral auxiliary-functionalized naphthalenediimides (NCDPs 1-6) have been prepared and their chiral self-assembly properties have been investigated. Detailed photophysical and circular dichroism (CD) studies have unveiled the crucial role of the solvent in the chiral aggregation of these NCDPs. NCDPs 1-3 form supramolecular helical assemblies and exhibit remarkable chiroptical switching behaviour (M- to P-type) depending on the solvent composition of HFIP and DMSO. The strong influence of solvent composition on the supramolecular chirality of NCDPs has been further corroborated by concentration and solid-state thin-film CD studies. The chiroptical switching between supramolecular aggregates of opposite helicity (M and P) has been found to be reversible, and can be achieved through cycles of solvent removal and redissolution in solvent mixtures of specific composition. The control molecular systems (NCDPs 4-6), with an achiral or D-isomer second amino acid in the CDP auxiliary, did not show chiral aggregation properties. The substantial roles of hydrogen bonding and π-π interactions in the assembly of the NCDPs have been validated through nuclear magnetic resonance (NMR), photophysical, and computational studies. Quantum chemical calculations at the ab initio, semiempirical, and density functional theory levels have been performed on model systems to understand the stabilities of the right (P-) and left (M-) handed helical supramolecular assemblies and the nature of the intermolecular interactions. This study emphasizes the role of CDP chiral auxiliaries on the solvent-induced helical assembly and reversible chiroptical switching of naphthalenediimides. PMID:24281809

  1. Nuclear structure and depletion of nuclear isomers using electron linacs

    SciTech Connect

    Carroll, J. J.; Litz, M. S.; Henriquez, S. L.; Burns, D. A.; Netherton, K. A.; Pereira, N. R.; Karamian, S. A.

    2013-04-19

    Long-lived nuclear excited states (isomers) have proven important to understanding nuclear structure. With some isomers having half-lives of decades or longer, and intrinsic energy densities reaching 10{sup 12} J/kg, they have also been suggested for a wide range of applications. The ability to effectively transfer a population of nuclei from an isomer to shorter-lived levels will determine the feasibility of any applications. Here is described a first demonstration of the induced depletion of a population of the 438 year isomer of {sup 108}Ag to its 2.38 min ground state, using 6 MeV bremsstrahlung from a modified medical electron linac. The experiment suggests refinements to be implemented in the future and how a similar approach might be applied to study induced depletion of the 1200 year isomer of {sup 166}Ho.

  2. Quality evaluation of terpinen-4-ol-type Australian tea tree oils and commercial products: an integrated approach using conventional and chiral GC/MS combined with chemometrics.

    PubMed

    Wang, Mei; Zhao, Jianping; Avula, Bharathi; Wang, Yan-Hong; Chittiboyina, Amar G; Parcher, Jon F; Khan, Ikhlas A

    2015-03-18

    GC/MS, chiral GC/MS, and chemometric techniques were used to evaluate a large set (n=104) of tea tree oils (TTO) and commercial products purported to contain TTO. Twenty terpenoids were determined in each sample and compared with the standards specified by ISO-4730-2004. Several of the oil samples that were ISO compliant when distilled did not meet the ISO standards in this study primarily due to the presence of excessive p-cymene and/or depletion of terpinenes. Forty-nine percent of the commercial products did not meet the ISO specifications. Four terpenes, viz., α-pinene, limonene, terpinen-4-ol, and α-terpineol, present in TTOs with the (+)-isomer predominant were measured by chiral GC/MS. The results clearly indicated that 28 commercial products contained excessive (+)-isomer or contained the (+)-isomer in concentrations below the norm. Of the 28 outliers, 7 met the ISO standards. There was a substantial subset of commercial products that met ISO standards but displayed unusual enantiomeric+/-ratios. A class predictive model based on the oils that met ISO standards was constructed. The outliers identified by the class predictive model coincided with the samples that displayed an abnormal chiral ratio. Thus, chiral and chemometric analyses could be used to confirm the identification of abnormal commercial products including those that met all of the ISO standards. PMID:25727364

  3. Chiral fiber optical isolator

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Zhang, Guoyin; Zhang, Sheng; Genack, Azriel Z.; Neugroschl, Dan

    2009-02-01

    We propose an in-fiber chiral optical isolator based on chiral fiber polarizer technology and calculate its performance by incorporating the magnetic field into the scattering matrix. The design will be implemented in a special preform, which is passed through a miniature heat zone as it is drawn and twisted. The birefringence of the fiber is controlled by adjusted the diameter of a dual-core optical fiber. By adjusting the twist, the fiber can convert linear to circular polarization and reject one component of circular polarization. In the novel central portion of the isolator, the fiber diameter is large. The effective birefringence of the circular central core with high Verdet constant embedded in an outer core of slightly smaller index of refraction is small. The central potion is a non-reciprocal polarization converter which passes forward traveling left circularly polarized (LCP) light as LCP, while converting backward propagating LCP to right circularly polarized (RCP) light. Both polarizations of light traveling backwards are scattered out of the isolator. Since it is an all-glass structure, we anticipate that the isolator will be able to handle several watts of power and will be environmentally robust.

  4. PBPK modeling of the cis- and trans-permethrin isomers and their major urinary metabolites in rats.

    PubMed

    Willemin, Marie-Emilie; Desmots, Sophie; Le Grand, Rozenn; Lestremau, François; Zeman, Florence A; Leclerc, Eric; Moesch, Christian; Brochot, Céline

    2016-03-01

    Permethrin, a pyrethroid insecticide, is suspected to induce neuronal and hormonal disturbances in humans. The widespread exposure of the populations has been confirmed by the detection of the urinary metabolites of permethrin in biomonitoring studies. Permethrin is a chiral molecule presenting two forms, the cis and the trans isomers. Because in vitro studies indicated a metabolic interaction between the trans and cis isomers of permethrin, we adapted and calibrated a PBPK model for trans- and cis-permethrin separately in rats. The model also describes the toxicokinetics of three urinary metabolites, cis- and trans-3-(2,2 dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid (cis- and trans-DCCA), 3-phenoxybenzoic acid (3-PBA) and 4'OH-phenoxybenzoic acid (4'-OH-PBA). In vivo experiments performed in Sprague-Dawley rats were used to calibrate the PBPK model in a Bayesian framework. The model captured well the toxicokinetics of permethrin isomers and their metabolites including the rapid absorption, the accumulation in fat, the extensive metabolism of the parent compounds, and the rapid elimination of metabolites in urine. Average hepatic clearances in rats were estimated to be 2.4 and 5.7 L/h/kg for cis- and trans-permethrin, respectively. High concentrations of the metabolite 4'-OH-PBA were measured in urine compared to cis- and trans-DCCA and 3-PBA. The confidence in the extended PBPK model was then confirmed by good predictions of published experimental data obtained using the isomers mixture. The extended PBPK model could be extrapolated to humans to predict the internal dose of exposure to permethrin from biomonitoring data in urine. PMID:26802525

  5. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

    Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

    2014-05-01

    Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

  6. Chiral perturbation theory with nucleons

    SciTech Connect

    Meissner, U.G.

    1991-09-01

    I review the constraints posed on the interactions of pions, nucleons and photons by the spontaneously broken chiral symmetry of QCD. The framework to perform these calculations, chiral perturbation theory, is briefly discussed in the meson sector. The method is a simultaneous expansion of the Greens functions in powers of external moments and quark masses around the massless case, the chiral limit. To perform this expansion, use is made of a phenomenological Lagrangian which encodes the Ward-identities and pertinent symmetries of QCD. The concept of chiral power counting is introduced. The main part of the lectures of consists in describing how to include baryons (nucleons) and how the chiral structure is modified by the fact that the nucleon mass in the chiral limit does not vanish. Particular emphasis is put on working out applications to show the strengths and limitations of the methods. Some processes which are discussed are threshold photopion production, low-energy compton scattering off nucleons, {pi}N scattering and the {sigma}-term. The implications of the broken chiral symmetry on the nuclear forces are briefly described. An alternative approach, in which the baryons are treated as very heavy fields, is touched upon.

  7. Self-assembly and energy transfer in artificial light-harvesting complexes of bacteriochlorophyll c with astaxanthin.

    PubMed

    Alster, J; Polívka, T; Arellano, J B; Hříbek, P; Vácha, F; Hála, J; Pšenčík, J

    2012-03-01

    Chlorosomes, the light-harvesting antennae of green photosynthetic bacteria, are based on large aggregates of bacteriochlorophyll molecules. Aggregates with similar properties to those in chlorosomes can also be prepared in vitro. Several agents were shown to induce aggregation of bacteriochlorophyll c in aqueous environments, including certain lipids, carotenes, and quinones. A key distinguishing feature of bacteriochlorophyll c aggregates, both in vitro and in chlorosomes, is a large (>60 nm) red shift of their Q(y) absorption band compared with that of the monomers. In this study, we investigate the self-assembly of bacteriochlorophyll c with the xanthophyll astaxanthin, which leads to the formation of a new type of complexes. Our results indicate that, due to its specific structure, astaxanthin molecules competes with bacteriochlorophylls for the bonds involved in the aggregation, thus preventing the formation of any significant red shift compared with pure bacteriochlorophyll c in aqueous buffer. A strong interaction between both the types of pigments in the developed assemblies, is manifested by a rather efficient (~40%) excitation energy transfer from astaxanthin to bacteriochlorophyll c, as revealed by fluorescence excitation spectroscopy. Results of transient absorption spectroscopy show that the energy transfer is very fast (<500 fs) and proceeds through the S(2) state of astaxanthin. PMID:21833799

  8. Supplementation of laying-hen feed with palm tocos and algae astaxanthin for egg yolk nutrient enrichment.

    PubMed

    Walker, Laurie A; Wang, Tong; Xin, Hongwei; Dolde, David

    2012-02-29

    Adding supplements to hen feed can increase egg nutritional value. Astaxanthin, tocotrienols, and tocopherols are potent antioxidants that provide health benefits to humans. We hypothesized that the addition of these nutrients to hen feed would result in an increased nutrient content in egg yolk with minimum changes in functional properties. Laying hens (Hy-Line W-36 breed) were fed four diets with different supplementation levels of palm toco concentrate and algae biomass containing astaxanthin for 8 weeks. Egg yolks were analyzed for physical, chemical, and functional properties. The feed with the highest nutrient concentration was also studied for stability of these antioxidants using the Arrhenius approach. No significant differences were observed in functional properties except for emulsification capacity and sensory characteristics among eggs from different diet treatments. Changes in egg yolk color reached the maximum values at day 8. Incorporation of tocopherols and tocotrienols increased until day 8, astaxanthin incorporation increased until day 10, and all decreased thereafter. Feed nutrients resulted in a dose-response relationship of these compounds in the egg yolk. The transfer efficiency ranged from 0 to 9.9% for tocotrienols and tocopherols and from 7.6 to 14.9% for astaxanthin at their peak values. Results of the Arrhenius accelerated stability study showed significant differences in the shelf life of various nutrients, and these results can be used to properly formulate and store the feed materials. PMID:22276647

  9. Accumulation of astaxanthin by a new Haematococcus pluvialis strain BM1 from the white sea coastal rocks (Russia).

    PubMed

    Chekanov, Konstantin; Lobakova, Elena; Selyakh, Irina; Semenova, Larisa; Sidorov, Roman; Solovchenko, Alexei

    2014-08-01

    We report on a novel arctic strain BM1 of a carotenogenic chlorophyte from a coastal habitat with harsh environmental conditions (wide variations in solar irradiance, temperature, salinity and nutrient availability) identified as Haematococcus pluvialis Flotow. Increased (25‰) salinity exerted no adverse effect on the growth of the green BM1 cells. Under stressful conditions (high light, nitrogen and phosphorus deprivation), green vegetative cells of H. pluvialis BM1 grown in BG11 medium formed non-motile palmelloid cells and, eventually, hematocysts capable of a massive accumulation of the keto-carotenoid astaxanthin with a high nutraceutical and therapeutic potential. Routinely, astaxanthin was accumulated at the level of 4% of the cell dry weight (DW), reaching, under prolonged stress, 5.5% DW. Astaxanthin was predominantly accumulated in the form of mono- and diesters of fatty acids from C16 and C18 families. The palmelloids and hematocysts were characterized by the formation of red-colored cytoplasmic lipid droplets, increasingly large in size and number. The lipid droplets tended to merge and occupied almost the entire volume of the cell at the advanced stages of stress-induced carotenogenesis. The potential application of the new strain for the production of astaxanthin is discussed in comparison with the H. pluvialis strains currently employed in microalgal biotechnology. PMID:25196836

  10. Accumulation of Astaxanthin by a New Haematococcus pluvialis Strain BM1 from the White Sea Coastal Rocks (Russia)

    PubMed Central

    Chekanov, Konstantin; Lobakova, Elena; Selyakh, Irina; Semenova, Larisa; Sidorov, Roman; Solovchenko, Alexei

    2014-01-01

    We report on a novel arctic strain BM1 of a carotenogenic chlorophyte from a coastal habitat with harsh environmental conditions (wide variations in solar irradiance, temperature, salinity and nutrient availability) identified as Haematococcus pluvialis Flotow. Increased (25‰) salinity exerted no adverse effect on the growth of the green BM1 cells. Under stressful conditions (high light, nitrogen and phosphorus deprivation), green vegetative cells of H. pluvialis BM1 grown in BG11 medium formed non-motile palmelloid cells and, eventually, hematocysts capable of a massive accumulation of the keto-carotenoid astaxanthin with a high nutraceutical and therapeutic potential. Routinely, astaxanthin was accumulated at the level of 4% of the cell dry weight (DW), reaching, under prolonged stress, 5.5% DW. Astaxanthin was predominantly accumulated in the form of mono- and diesters of fatty acids from C16 and C18 families. The palmelloids and hematocysts were characterized by the formation of red-colored cytoplasmic lipid droplets, increasingly large in size and number. The lipid droplets tended to merge and occupied almost the entire volume of the cell at the advanced stages of stress-induced carotenogenesis. The potential application of the new strain for the production of astaxanthin is discussed in comparison with the H. pluvialis strains currently employed in microalgal biotechnology. PMID:25196836

  11. Study on the interaction of β-carotene and astaxanthin with trypsin and pepsin by spectroscopic techniques.

    PubMed

    Li, Xiangrong; Li, Peihong

    2016-05-01

    β-Carotene and astaxanthin are two carotenoids with powerful antioxidant properties, but the binding mechanisms of β-carotene/astaxanthin to proteases remain unclear. In this study, the interaction of these two carotenoids with trypsin and pepsin was investigated using steady-state and time-resolved fluorescence measurements, synchronous fluorescence spectroscopy, UV-vis absorption spectroscopy and circular dichroism (CD) spectroscopy. The experimental results indicated that the quenching mechanisms of trypsin/pepsin by the two carotenoids are static processes. The binding constants of trypsin and pepsin with these two carotenoids are in the following order: astaxanthin-trypsin > astaxanthin-pepsin > β-carotene-trypsin > β-carotene-pepsin, respectively. Thermodynamic investigations revealed that the interaction between the two carotenoids and trypsin/pepsin is synergistically driven by enthalpy and entropy, and hydrophobic forces and electrostatic attraction have a significant role in the reactions. In addition, as shown by synchronous fluorescence spectroscopy, UV-vis absorption spectroscopy and CD, the two carotenoids may induce conformational and microenvironmental changes in trypsin/pepsin. The study provides an accurate and full basic data for clarifying the binding mechanisms of the two carotenoids with trypsin/pepsin and is helpful in understanding their effect on protein function and their biological activity in vivo. PMID:26358735

  12. Production of astaxanthin from corn fiber as a value-added co-product of fuel ethanol fermentation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Five strains of the yeast Phaffia rhodozyma, NRRL Y-17268, NRRL Y-17270, ATCC 96594 (CBS 6938), ATCC 24202 (UCD 67-210), and ATCC 74219 (UBV-AX2) were tested for astaxanthin production using the major sugars derived from corn fiber, a byproduct from the wet milling of corn kernels that contains prim...

  13. Conformational arm-wrestling: battles for stereochemical control in benzamides bearing matched and mismatched chiral 2- and 6-substituents.

    PubMed

    Clayden, Jonathan; Foricher, Yann J Y; Helliwell, Madeleine; Johnson, Paul; Mitjans, David; Vinader, Victoria

    2006-02-01

    The orientation of a tertiary amide group adjacent to an aromatic ring may be governed by the stereochemistry of an adjacent chiral substituent. With a chiral substituent in both ortho positions, matched/mismatched pairs of isomers result. Evidence for matched stereochemistry is provided by the clean NMR spectra of single conformers, while mismatching gives poor or unexpected selectivities in the formation of chiral substituents, or mixtures of amide conformers. Attempts to use the match-mismatch effect to select for racemic pairs of enantiomeric substituents, and hence develop a "racemate-sequestering" reagent, are described, along with the use of "matching" to scavenge a single enantiomer of a diamine from material of incomplete enantiomeric purity. PMID:16446801

  14. Cationic permethylated 6-monoamino-6-monodeoxy-β-cyclodextrin as chiral selector of dansylated amino acids in capillary electrophoresis.

    PubMed

    Németh, Krisztina; Domonkos, Celesztina; Sarnyai, Virág; Szemán, Julianna; Jicsinszky, László; Szente, Lajos; Visy, Júlia

    2014-10-01

    The resolution power of permethylated 6-monoamino-6-monodeoxy-βCD (PMMABCD) - a single isomer, cationic CD derivative - developed previously for chiral analyses in capillary electrophoresis was further studied here. Dansylated amino acids (Dns-AA) were chosen as amphoteric chiral model compounds. Changes in the resolutions of Dns-AAs by varying pH and selector concentrations were investigated and correlated with their structures and chemical properties (isoelectric point and lipophilicity). Maximal resolutions could be achieved at pH 6 or pH 4. The separations improved with increasing concentration of the selector. Baseline or substantially better resolution for 8 pairs of these Dns-AAs could be achieved. Low CD concentration was enough for the separation of the most apolar Dns-AAs. Chiral discrimination ability of PMMABCD was demonstrated by the separation of an artificial mixture of 8 Dns-AA pairs. PMID:25044151

  15. The effect of astaxanthin on resistance of juvenile prawns Macrobrachium nipponense (Decapoda: Palaemonidae) to physical and chemical stress.

    PubMed

    Tizkar, Babak; Seidavi, Alireza; Ponce-Palafox, Jesús Trinidad; Pourashoori, Parastoo

    2014-12-01

    In recent years, the use of new scientific techniques has effectively improved aquaculture production processes. Astaxanthin has various properties in aquaculture and its antioxidant benefits have been closely related to stress resistance; besides, it is an essential factor for growth in many crustaceans and fish. The objective of this study was to evaluate the resistance of prawn (Macrobrachium nipponense) fed diets containing different amounts of astaxanthin (AX) to the shock and stress of different physicochemical environments. A 70-day trial was conducted to evaluate the effect of supplementation of a source of astaxanthin (Carophyll Pink, 10% astaxanthin, w/w, Hoffman-La Roche, Switzerland) at various levels in the diet of M. nipponense juveniles. Four dry diets were prepared: AX0 without astaxanthin, AX50 with 50 mg/kg, AX100 with 100 mg/kg, and AX150 with 150 mg/kg astaxanthin. The feeding trial was conducted in a recirculation water system consisting of 12 fiberglass tanks (1000L) used for holding prawns. Three replicate aquaria were initially stocked with 36 org/m2 per tank. During the trial, prawns were maintained on a 12:12-h light:dark photoperiod with an ordinary incandescent lamp, and the water quality parameters were maintained as follows: water temperature, 25-26°C; salinity, 1 g/L; pH, 8.5-8.8; dissolved oxygen, 6.0-6.5 mg/L; and ammonia-nitrogen, 0.05 mg/L. Incorporation of AX, production output, and physiological condition were recorded after 10 weeks of feeding. At the end of the growing period, the prawns were exposed to thermal shock (0°C), ammonia (0.75 mg/L), and reduced oxygen (0.5 mg/L). The time to lethargy and the time to complete death of the prawns were recorded. The results showed that control prawns had the shortest time to lethargy and death compared with prawns subjected to the other treatments. The results of this study have shown that the amount of muscle tissue and gill carotenoids in prawn fed with an AX150 diet showed

  16. Effects of astaxanthin and emodin on the growth, stress resistance and disease resistance of yellow catfish (Pelteobagrus fulvidraco).

    PubMed

    Liu, Fei; Shi, Hong-zhuan; Guo, Qiao-sheng; Yu, Ye-bing; Wang, Ai-ming; Lv, Fu; Shen, Wen-biao

    2016-04-01

    Yellow catfish (Pelteobagrus fulvidraco) has become a commercially important fish species in China and eastern Asia. High-density aquaculture has led to congestion and excessive stress and contributed to bacterial infection outbreaks that have caused high mortality. We investigated the effects of dietary supplementation with astaxanthin and emodin alone and in combination on the growth and stress resistance of yellow catfish. After 60 days of feeding, each group of fish (control, astaxanthin, emodin, and astaxanthin plus emodin (combination) groups) was exposed to acute crowding stress for 24 h, and a subsample of fish from the four groups was challenged with the bacterial septicemia pathogen Proteus mirabilis after the end of the crowding stress experiment. Compared with the control, the astaxanthin and emodin groups showed increases in serum total protein (TP), hepatic superoxide dismutase (SOD) activity and hepatic heat shock proteins 70 (HSP70) mRNA levels at 12 and 24 h after the initiation of crowding stress. The combination group exhibited increases in alanine aminotransferase (ALT) activity, aspartate aminotransferase (AST) activity, serum TP, hepatic SOD activity and hepatic HSP70 mRNA levels within 24 h after the initiation of crowding stress. However, decreases relative to the control were observed in the serum cortisol and glucose contents in the three treatment groups at 12 and 24 h after the initiation of crowding stress, in ALT and AST activity in the astaxanthin and emodin group at 24 h after the initiation of crowding stress, and in the serum lysozyme activity, serum alkaline phosphatase (ALP) activity, and hepatic catalase (CAT) and malondialdehyde (MDA) activity in the combination group at 24 h after the initiation of crowding stress. Additionally, the cumulative mortality after P. mirabilis infection was lower in all three treatment groups (57.00%-70.33%) than in the control (77.67%). Dietary supplementation with astaxanthin and emodin decreased

  17. Adsorption of hexane isomers on ion-exchanged mordenite

    SciTech Connect

    Huddersman, K.

    1996-10-01

    To remove lead from petrol and thereby promote a cleaner environment, other means must be found to keep the octane number or anti-knock qualities of the petrol high. It is found that this can be accomplished by increasing the proportion of highly branched chain hydrocarbon isomers in the fuel. This in turn promotes processes for the separation of the hydrocarbon isomers and in the case of hexane, it is an easy matter to separate out n-hexane from the more substituted isomers but it is difficult to separate out the mono- from the di-branched isomers. This work addresses itself to such challenging separations using modified zeolites as the separating agent, and by studying the heats of sorption of these isomers on zeolites using gas chromatographic techniques to find a trend in the potential abilities of these modified zeolites to effect a good separation. In this work mordenite zeolite was modified by a range of double cation exchanges and the resulting modified zeolites were investigated for their ability to sorb the hexane isomers 3-methylpentane and 2,3-dimethylbutane. These two isomers are closely related in size as they both have the same kinetic diameter of 0.56 nm. In this work only heats of sorption have been investigated and measurement of the diffusion coefficients, which also affect the ability of the modified zeolites to act as good separating agents, is currently under investigation.

  18. Comparison of the repeated dose toxicity of isomers of dinitrotoluene.

    PubMed

    Lent, Emily May; Crouse, Lee C B; Quinn, Michael J; Wallace, Shannon M

    2012-03-01

    Dinitrotoluene (DNT) is a nitroaromatic explosive used in propellant mixtures and in the production of plastics. Isomers of DNT were administered daily via oral gavage to male Sprague-Dawley rats for 14 days to determine the subacute toxicity of individual isomers of DNT. The 3,5-DNT isomer was the most toxic isomer, inducing weight loss and mortality within 3 days. Cyanosis and anemia were observed for all isomers. Exposure to 2,4-, 2,6-, and 3,5-DNT resulted in decreased testes mass and degenerative histopathological changes. Increased splenic mass was observed for 2,4-, 2,6-, and 2,5-DNT. Extramedullary hematopoiesis of the spleen was noted for all isomers, while lymphoid hyperplasia of the spleen was noted for all isomers except 2,5-DNT. Increased liver mass was observed for 2,3-DNT and 3,4-DNT. Hepatocellular lesions were observed for 2,6-DNT and 2,4-DNT. Neurotoxic effects were noted for 3,4-DNT, 2,4-DNT, and 3,5-DNT. PMID:22422434

  19. Novel Cholesteric Glassy Liquid Crystals Comprising Benzene Functionalized with Hybrid Chiral-Nematic Mesogens

    SciTech Connect

    Kim, C; Marshall, K L; Wallace, J U; Ou, J J; Chen, S H

    2010-03-12

    With 4-cyanobiphenyl-4-yl benzoate nematogens chemically bonded to a benzene core via enantiomeric 2-methylpropyl spacers, a new series of cholesteric glassy liquid crystals has been synthesized for an investigation of structure-property relationships. Glass-forming ability, phase-transition temperatures, and stability against crystallization are affected by both the number and the position of substituent groups on the benzene ring with 1,3,5-trisubstituted system possessing the most favorable set of properties, Tg at 73 °C and Tc at 295 °C. With (S)-3-bromo-2-methylpropanol as the chiral precursor, left-handed helical stacking was observed for all the cholesteric GLCs reported herein. Films of the 1,3,5-trisubstituted and meta-disubstituted systems show a selective reflection wavelength, λR, at 413 and 422 nm, respectively, whereas that of the ortho-isomer exhibits a λR at 860 nm. Replacing one of the hybrid chiral-nematic mesogen in the 1,3,5-trisubstituted system by a nematogen loosens the helical pitch to yield a λR at 630 nm, still shorter than that of the ortho-isomer despite the dilution by a nematogen. This observation suggests the importance of regioisomerism to helical twisting. The difference in λR was interpreted in terms of molecular packing involving chiral spacers through computational chemistry. The susceptibility of cholesteric GLCs to photoalignment was tested using the ortho-isomer. The degree of photoalignment improves with an increasing rotational mobility of pendant coumarin monomers to an extent comparable to mechanical alignment on conventional rubbed polyimide films.

  20. Amino Acids and Chirality

    NASA Technical Reports Server (NTRS)

    Cook, Jamie E.

    2012-01-01

    Amino acids are among the most heavily studied organic compound class in carbonaceous chondrites. The abundance, distributions, enantiomeric compositions, and stable isotopic ratios of amino acids have been determined in carbonaceous chondrites fi'om a range of classes and petrographic types, with interesting correlations observed between these properties and the class and typc of the chondritcs. In particular, isomeric distributions appear to correlate with parent bodies (chondrite class). In addition, certain chiral amino acids are found in enantiomeric excess in some chondrites. The delivery of these enantiomeric excesses to the early Earth may have contributed to the origin of the homochirality that is central to life on Earth today. This talk will explore the amino acids in carbonaceous chondritcs and their relevance to the origin of life.

  1. Effects of dietary supplementation with astaxanthin and β-carotene on the semen quality of goldfish (Carassius auratus).

    PubMed

    Tizkar, B; Kazemi, R; Alipour, A; Seidavi, A; Naseralavi, G; Ponce-Palafox, J T

    2015-10-15

    This study was conducted to investigate the effects of two carotenoids (astaxanthin and β-carotene) on the sperm quality of goldfish Carassius auratus (Linnaeus, 1758). For this purpose, six diets containing concentrations of 50, 100, and 150 mg/kg of synthetic astaxanthin and β-carotene were added to a basic carp diet. One group of fish was also fed with a control diet (no added carotenoids). Osmolality, spermatocrit value, and sperm concentration significantly increased in the treatment supplemented with 150 mg/kg of astaxanthin (296.6 ± 1.1 mOsm/kg; 29.2 ± 0.6%; 17.2 ± 0.4 × 10(9) cells/mL, respectively) and β-carotene (295.2 ± 2.1 mOsm/kg; 32.5 ± 1.6%; 17.9 ± 0.5 × 10(9) cells/mL, respectively). The highest concentration of astaxanthin (10.4 ± 1.4 mg/kg) was recorded in the treatment of A150 (P < 0.05) and did not differ between β-carotene treatments. The highest motility was observed in the A150 and B150 treatments, and the lowest was observed in the control group (P < 0.05). The artificial fertilization of the treated males with the similar females (fed with the control diet) showed that the fertilization rate in the A150 treatments was higher than in the other treatments (P < 0.05). In conclusion, dietary supplementation with 150 mg/kg of astaxanthin improves osmolality, motility, fertilization rate, and sperm concentration. PMID:26166170

  2. Chiral Bosonization of Superconformal Ghosts

    NASA Technical Reports Server (NTRS)

    Shi, Deheng; Shen, Yang; Liu, Jinling; Xiong, Yongjian

    1996-01-01

    We explain the difference of the Hilbert space of the superconformal ghosts (beta,gamma) system from that of its bosonized fields phi and chi. We calculate the chiral correlation functions of phi, chi fields by inserting appropriate projectors.

  3. Life's chirality from prebiotic environments

    NASA Astrophysics Data System (ADS)

    Gleiser, Marcelo; Walker, Sara Imari

    2012-10-01

    A key open question in the study of life is the origin of biomolecular homochirality: almost every life-form on Earth has exclusively levorotary amino acids and dextrorotary sugars. Will the same handedness be preferred if life is found elsewhere? We review some of the pertinent literature and discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events. In one scenario, autocatalytic prebiotic reactions undergo stochastic fluctuations due to environmental disturbances, in a mechanism reminiscent of evolutionary punctuated equilibrium: short-lived destructive events may lead to long-term enantiomeric excess. In another, chiral-selective polymerization reaction rates influenced by environmental effects lead to substantial chiral excess even in the absence of autocatalysis. Applying these arguments to other potentially life-bearing platforms has implications to the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic (chirally neutral) on average.

  4. High-spin torus isomers and their precession motions

    NASA Astrophysics Data System (ADS)

    Ichikawa, T.; Matsuyanagi, K.; Maruhn, J. A.; Itagaki, N.

    2014-09-01

    Background: In our previous study, we found that an exotic isomer with a torus shape may exist in the high-spin, highly excited states of Ca40. The z component of the total angular momentum, Jz=60ℏ, of this torus isomer is constructed by totally aligning 12 single-particle angular momenta in the direction of the symmetry axis of the density distribution. The torus isomer executes precession motion with the rigid-body moments of inertia about an axis perpendicular to the symmetry axis. The investigation, however, has been focused only on Ca40. Purpose: We systematically investigate the existence of exotic torus isomers and their precession motions for a series of N =Z even-even nuclei from Si28 to Ni56. We analyze the microscopic shell structure of the torus isomer and discuss why the torus shape is generated beyond the limit of large oblate deformation. Method: We use the cranked three-dimensional Hartree-Fock method with various Skyrme interactions in a systematic search for high-spin torus isomers. We use the three-dimensional time-dependent Hartree-Fock method for describing the precession motion of the torus isomer. Results: We obtain high-spin torus isomers in Ar36,Ca40,Ti44,Cr48, and Fe52. The emergence of the torus isomers is associated with the alignments of single-particle angular momenta, which is the same mechanism as found in Ca40. It is found that all the obtained torus isomers execute the precession motion at least two rotational periods. The moment of inertia about a perpendicular axis, which characterizes the precession motion, is found to be close to the classical rigid-body value. Conclusions: The high-spin torus isomer of Ca40 is not an exceptional case. Similar torus isomers exist widely in nuclei from Ar36 to Fe52 and they execute the precession motion. The torus shape is generated beyond the limit of large oblate deformation by eliminating the 0s components from all the deformed single-particle wave functions to maximize their mutual

  5. Raman spectroscopic analysis of isomers of biliverdin dimethyl ester.

    PubMed

    Matysik, J; Hildebrandt, P; Smit, K; Mark, F; Gärtner, W; Braslavsky, S E; Schaffner, K; Schrader, B

    1997-06-01

    The constitutional isomers of biliverdin dimethyl ester, IX alpha and XIII alpha, were studied by resonance Raman spectroscopy. The far-reaching spectral similarities suggest that despite the different substitution patterns, the compositions of the normal modes are closely related. This conclusion does not hold only for the parent state (ZZZ, sss configuration) but also for the configurational isomers which were obtained upon double-bond photoisomerization. Based on a comparison of the resonance Raman spectra, a EZZ configuration is proposed for one of the two photoisomers of biliverdin dimethyl ester IX alpha, while a ZZE, ssa configuration has been assigned previously to the second isomer. PMID:9226559

  6. Separation and identification of indene–C70 bisadduct isomers

    PubMed Central

    Zhang, Bolong; Subbiah, Jegadesan; Jones, David J

    2016-01-01

    Summary Following an initial work on the isolation of a single geometric isomer from an indene–C70 bisadduct (IC70BA) mixture, we report the full fractionation and identification of the bisadduct species in the material. Eleven fractions of IC70BA isomers were separated by high-performance liquid chromatography. A number of fractions contained relatively pure isomer species and their configuration were deduced using a variety of analytical techniques including 1H and 13C NMR and UV–vis spectroscopy. The electrochemical properties and the organic solar cell device performance were investigated for fractions where a reasonable quantity of sample could be isolated. PMID:27340480

  7. Detection of Actinides via Nuclear Isomer De-Excitation

    SciTech Connect

    Francy, Christopher J.

    2009-07-01

    This dissertation discusses a data collection experiment within the Actinide Isomer Identification project (AID). The AID project is the investigation of an active interrogation technique that utilizes nuclear isomer production, with the goal of assisting in the interdiction of illicit nuclear materials. In an attempt to find and characterize isomers belonging to 235U and its fission fragments, a 232Th target was bombarded with a monoenergetic 6Li ion beam, operating at 45 MeV.

  8. Asymmetric Hydrogenation of Isoxazolium Triflates with a Chiral Iridium Catalyst.

    PubMed

    Ikeda, Ryuhei; Kuwano, Ryoichi

    2016-06-13

    The iridium catalyst [IrCl(cod)]2 -phosphine-I2 (cod=1,5-cyclooctadiene) selectively reduced isoxazolium triflates to isoxazolines or isoxazolidines in the presence of H2 . The iridium-catalyzed hydrogenation proceeded in high-to-good enantioselectivity when an optically active phosphine-oxazoline ligand was used. The 3-substituted 5-arylisoxazolium salts were transformed into 4-isoxazolines with up to 95:5 enantiomeric ratio (e.r.). Chiral cis-isoxazolidines were obtained in up to 89:11 e.r., with no formation of their trans isomers, when the substrates had a primary alkyl substituent at the 5-position. The mechanistic studies indicate that the hydridoiridium(III) species prefers to deliver its hydride to the C5 atom of the isoxazole ring. The hydride attack leads to the formation of the chiral isoxazolidine via a 3-isoxazoline intermediate. Meanwhile, in the selective formation of 4-isoxazolines, hydride attack at the C5 atom may be obstructed by steric hindrance from the 5-aryl substituent. PMID:27105605

  9. Chiral recognition in adrenergic receptor binding mimics prepared by molecular imprinting.

    PubMed

    Ramström, O; Yu, C; Mosbach, K

    1996-01-01

    Molecularly imprinted polymers were prepared against the adrenomimetic agents ephedrine and pseudoephedrine. These compounds each incorporate two chiral centres. The polymers were evaluated with respect to enantiodiscrimination of various adrenergic ligands. The selectivity of the polymeric binding sites for the imprinted molecules was very high, and it was found that binding of both the enantiomeric and diastereomeric isomers of the imprint species were effectively obstructed, it was found that these polymers could selectively recognize the enantiomers of the endogenous adrenergic ligand epinephrine as well as several beta-adrenergic blockers. These observations suggest that these polymers effectively mimic the recognition patterns exhibited by natural adrenergic receptors. PMID:9174958

  10. Chirality effects at each amino acid position on tripeptide self-assembly into hydrogel biomaterials

    NASA Astrophysics Data System (ADS)

    Marchesan, S.; Easton, C. D.; Styan, K. E.; Waddington, L. J.; Kushkaki, F.; Goodall, L.; McLean, K. M.; Forsythe, J. S.; Hartley, P. G.

    2014-04-01

    Hydrogels formed by ultrashort peptides are emerging as cost-effective materials for cell culture. However, l-peptides are labile to proteases, while their d-isomers are thought to not support cell growth as well. In contrast, the self-assembly behaviour and biological performance of heterochiral peptides (i.e., made of both d and l amino acids) are largely unknown. In this study, we evaluate the effects of amino acid chirality on tripeptide self-assembly and hydrogelation at physiological pH, and cytocompatibility in fibroblast cell culture. A series of uncapped hydrophobic tripeptides with all combinations of d, l amino acids was prepared, tested for self-assembly under physiological conditions, and analysed by circular dichroism, FT-IR, cryo-TEM, AFM, and Thioflavin T fluorescence imaging. Amino acid chirality has a profound effect on the peptides' supramolecular behaviour. Only selected isomers form hydrogels, and of amyloid structure, as confirmed by rheology and XRD. Importantly, they are able to maintain the viability and proliferation of fibroblasts in vitro. This study identifies two heterochiral gels that perform well in cell culture and will assist in the design of innovative and cost-effective peptide gel biomaterials.Hydrogels formed by ultrashort peptides are emerging as cost-effective materials for cell culture. However, l-peptides are labile to proteases, while their d-isomers are thought to not support cell growth as well. In contrast, the self-assembly behaviour and biological performance of heterochiral peptides (i.e., made of both d and l amino acids) are largely unknown. In this study, we evaluate the effects of amino acid chirality on tripeptide self-assembly and hydrogelation at physiological pH, and cytocompatibility in fibroblast cell culture. A series of uncapped hydrophobic tripeptides with all combinations of d, l amino acids was prepared, tested for self-assembly under physiological conditions, and analysed by circular dichroism, FT

  11. Chiral Phosphinate Degradation by the Fusarium Species: Scope and Limitation of the Process

    PubMed Central

    Brzezińska-Rodak, Małgorzata

    2013-01-01

    Biodegradable capacities of fungal strains of Fusarium oxysporum (DSMZ 2018) and Fusarium culmorum (DSMZ 1094) were tested towards racemic mixture of chiral 2-hydroxy-2-(ethoxyphenylphosphinyl) acetic acid—a compound with two stereogenic centres. The effectiveness of decomposition was dependent on external factors such as temperature and time of the process. Optimal conditions of complete mineralization were established. Both Fusarium species were able to biodegrade every isomer of tested compound at 30°C, but F. culmorum required 10 days and F. oxysporum 11 days to accomplish the process, which was continuously monitored using the 31P NMR technique. PMID:24324893

  12. Critical dimensions for chiral bosons

    SciTech Connect

    Mezincescu, L.; Nepomechie, R.I.

    1988-05-15

    We give the Lagrangian formulation of a Bose model in 1+1 dimensions which describes a free chiral Lie-algebra-valued current. This model is a non-Abelian generalization of the chiral scalar model of Siegel. Both the Abelian and non-Abelian actions have a gauge invariance, which becomes anomalous when the models are quantized. The condition that this anomaly be canceled coincides with the string no-ghost condition.

  13. Astaxanthin Inhibits Acetaldehyde-Induced Cytotoxicity in SH-SY5Y Cells by Modulating Akt/CREB and p38MAPK/ERK Signaling Pathways

    PubMed Central

    Yan, Tingting; Zhao, Yan; Zhang, Xia; Lin, Xiaotong

    2016-01-01

    Excessive alcohol consumption can lead to brain tissue damage and cognitive dysfunction. Acetaldehyde, the most toxic metabolite of ethanol, mediates the brain tissue damage and cognitive dysfunction induced by chronic excessive alcohol consumption. In this study, the effect of astaxanthin, a marine bioactive compound, on acetaldehyde-induced cytotoxicity was investigated in SH-SY5Y cells. It was found that astaxanthin protected cells from apoptosis by ameliorating the effect of acetaldehyde on the expression of Bcl-2 family proteins, preventing the reduction of anti-apoptotic protein Bcl-2 and the increase of pro-apoptotic protein Bak induced by acetaldehyde. Further analyses showed that astaxanthin treatment inhibited acetaldehyde-induced reduction of the levels of activated Akt and cyclic AMP-responsive element binding protein (CREB). Astaxanthin treatment also prevented acetaldehyde-induced increase of the level of activated p38 mitogen-activated protein kinase (MAPK) and decrease of the level of activated extracellular signal-regulated kinases (ERKs). Activation of Akt/CREB pathway promotes cell survival and is involved in the upregulation of Bcl-2 gene. P38MAPK plays a critical role in apoptotic events while ERKs mediates the inhibition of apoptosis. Thus, astaxanthin may inhibit acetaldehyde-induced apoptosis through promoting the activation of Akt/CREB and ERKs and blocking the activation of p38MAPK. In addition, astaxanthin treatment suppressed the oxidative stress induced by acetaldehyde and restored the antioxidative capacity of SH-SY5Y cells. Therefore, astaxanthin may protect cells against acetaldehyde-induced cytotoxicity through maintaining redox balance and modulating apoptotic and survival signals. The results suggest that astaxanthin treatment may be beneficial for preventing neurotoxicity associated with acetaldehyde and excessive alcohol consumption. PMID:26978376

  14. Astaxanthin Inhibits Acetaldehyde-Induced Cytotoxicity in SH-SY5Y Cells by Modulating Akt/CREB and p38MAPK/ERK Signaling Pathways.

    PubMed

    Yan, Tingting; Zhao, Yan; Zhang, Xia; Lin, Xiaotong

    2016-03-01

    Excessive alcohol consumption can lead to brain tissue damage and cognitive dysfunction. Acetaldehyde, the most toxic metabolite of ethanol, mediates the brain tissue damage and cognitive dysfunction induced by chronic excessive alcohol consumption. In this study, the effect of astaxanthin, a marine bioactive compound, on acetaldehyde-induced cytotoxicity was investigated in SH-SY5Y cells. It was found that astaxanthin protected cells from apoptosis by ameliorating the effect of acetaldehyde on the expression of Bcl-2 family proteins, preventing the reduction of anti-apoptotic protein Bcl-2 and the increase of pro-apoptotic protein Bak induced by acetaldehyde. Further analyses showed that astaxanthin treatment inhibited acetaldehyde-induced reduction of the levels of activated Akt and cyclic AMP-responsive element binding protein (CREB). Astaxanthin treatment also prevented acetaldehyde-induced increase of the level of activated p38 mitogen-activated protein kinase (MAPK) and decrease of the level of activated extracellular signal-regulated kinases (ERKs). Activation of Akt/CREB pathway promotes cell survival and is involved in the upregulation of Bcl-2 gene. P38MAPK plays a critical role in apoptotic events while ERKs mediates the inhibition of apoptosis. Thus, astaxanthin may inhibit acetaldehyde-induced apoptosis through promoting the activation of Akt/CREB and ERKs and blocking the activation of p38MAPK. In addition, astaxanthin treatment suppressed the oxidative stress induced by acetaldehyde and restored the antioxidative capacity of SH-SY5Y cells. Therefore, astaxanthin may protect cells against acetaldehyde-induced cytotoxicity through maintaining redox balance and modulating apoptotic and survival signals. The results suggest that astaxanthin treatment may be beneficial for preventing neurotoxicity associated with acetaldehyde and excessive alcohol consumption. PMID:26978376

  15. Geometric enantiomerism in cyclic compounds: chiral dibrominated 1,3-dioxanes.

    PubMed

    Cismaş, Crina; Vanthuyne, Nicolas; Rispaud, Hélène; Varga, Richard Attila; Bogdan, Elena; Roussel, Christian; Grosu, Ion

    2011-02-01

    The first geometric enantiomers in the cyclic compounds series are reported. The investigated compounds are 2,2-disubstituted-5-methyl-1,3-dioxane derivatives in which the substituents at position 2 bear chiral centers with identical substituents but with opposite configurations. The structure of the unlike isomers was determined from the solid state molecular structure of the compounds obtained by single crystal X-ray diffractometry and the enantiomers of these diastereoisomers were observed by chiral column HPLC base-line separation. The investigated compounds were obtained by a diastereoselective bromination reaction of the corresponding 2,2-dialkyl and 2,2-dibenzyl-5-methyl-1,3-dioxanes. PMID:20872855

  16. Introducing Chirality into Nonionic Dendritic Amphiphiles and Studying Their Supramolecular Assembly.

    PubMed

    Kumar, Sumit; Ludwig, Kai; Schade, Boris; von Berlepsch, Hans; Papp, Ilona; Tyagi, Rahul; Gulia, Monika; Haag, Rainer; Böttcher, Christoph

    2016-04-11

    Chiral head groups have been introduced into water-soluble hydroxyl-terminated nonionic amphiphiles and the impact of the head group stereochemistry on the supramolecular ultrastructures has been studied. Enantiomeric isomers were compared with the achiral meso form and the racemic mixture by means of cryogenic transmission electron microscopy and circular dichroism spectroscopy. Structurally, all amphiphiles are composed of the first-generation hydrophilic polyglycerol head group coupled to a single hydrophobic hexadecyl chain through an amide linkage and diaromatic spacer. The enantiomers aggregate to form twisted ribbons with uniform handedness, whereas the meso stereoisomer and racemic mixture produce elongated assemblies, namely, tubules and platelets, but without a chiral ultrastructure. Simulations on the molecular packing geometries of the stereoisomers indicate different preferential assembly routes that explain the individual supramolecular aggregation behavior. PMID:26961861

  17. Isomer spectroscopy of {sup 127}Cd

    SciTech Connect

    Naqvi, F.; Gorska, M.; Grawe, H.; Beck, T.; Doornenbal, P.; Geissel, H.; Gerl, J.; Kojouharov, I.; Kurz, N.; Montes, F.; Prokopowicz, W.; Schaffner, H.; Tashenov, S.; Wollersheim, H. J.; Caceres, L.; Jungclaus, A.; Pfuetzner, M.; Werner-Malento, E.; Nowacki, F.; Sieja, K.

    2010-09-15

    The spin and configurational structure of excited states of {sup 127}Cd, the two-proton and three-neutron hole neighbor of {sup 132}Sn, has been studied. An isomeric state with a half-life of 17.5(3) {mu}s was populated in the fragmentation of a {sup 136}Xe beam on a {sup 9}Be target at a beam energy of 750 MeV/u. Time distributions of the delayed {gamma} transitions and {gamma}{gamma} coincidence relations were exploited to construct a decay scheme. The observed yrast (19/2){sup +} isomer is proposed to have dominant configurations of {nu}(h{sub 11/2}{sup -3}){pi}(g{sub 9/2}{sup -1},p{sub 1/2}{sup -1}), {nu}(h{sub 11/2}{sup -2}d{sub 3/2}{sup -1}){pi}(g{sub 9/2}{sup -2}), and {nu}(h{sub 11/2}{sup -2},s{sub 1/2}{sup -1}){pi}(g{sub 9/2}{sup -2}) and to decay by two competing stretched M2 and E3 transitions. Experimental results are compared with the isotone {sup 129}Sn. The new information provides input for the proton-neutron interaction and the evolution of neutron hole energies in nuclei around the doubly magic {sup 132}Sn core.

  18. Diastereomeric Ellagitannin Isomers from Penthorum chinense.

    PubMed

    Era, Manami; Matsuo, Yosuke; Shii, Takuya; Saito, Yoshinori; Tanaka, Takashi; Jiang, Zhi-Hong

    2015-08-28

    From the dried stem of Penthorum chinense (Penthoraceae), 1-O-galloyl-4,6-(R)-hexahydroxydiphenoyl (HHDP)-β-D-glucose and 2',4',6'-trihydroxyacetophenone 4'-O-[4,6-(R)-HHDP]-β-D-glucoside were isolated together with their (S)-HHDP isomers. Ellagitannins with a 4,6-(S)-HHDP-glucose moiety are widely distributed in the plant kingdom; however, 4,6-(R)-HHDP glucoses are extremely rare. Lowest-energy conformers of 1-O-galloyl-(S)- and (R)-HHDP-glucopyranoses were derived by density functional theory calculations, and the calculated (1)H and (13)C NMR chemical shifts and the (1)H-(1)H coupling constants were in agreement with the experimental values. The results revealed a conformational difference of the diastereomeric macrocyclic ester rings. In addition, a new compound, 1',3',5'-trihydroxybenzene 1'-O-[4,6-(S)-HHDP]-β-D-glucoside, was also isolated. PMID:26218585

  19. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    PubMed

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-01

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps. PMID:26575242

  20. Protective Effects of Astaxanthin on ConA-Induced Autoimmune Hepatitis by the JNK/p-JNK Pathway-Mediated Inhibition of Autophagy and Apoptosis

    PubMed Central

    Liu, Tong; Wang, Junshan; Dai, Weiqi; Wang, Fan; Zheng, Yuanyuan; Chen, Kan; Li, Sainan; Abudumijiti, Huerxidan; Zhou, Zheng; Wang, Jianrong; Lu, Wenxia; Zhu, Rong; Yang, Jing; Zhang, Huawei; Yin, Qin; Wang, Chengfen; Zhou, Yuqing; Lu, Jie; Zhou, Yingqun; Guo, Chuanyong

    2015-01-01

    Objective Astaxanthin, a potent antioxidant, exhibits a wide range of biological activities, including antioxidant, atherosclerosis and antitumor activities. However, its effect on concanavalin A (ConA)-induced autoimmune hepatitis remains unclear. The aim of this study was to investigate the protective effects of astaxanthin on ConA-induced hepatitis in mice, and to elucidate the mechanisms of regulation. Materials and Methods Autoimmune hepatitis was induced in in Balb/C mice using ConA (25 mg/kg), and astaxanthin was orally administered daily at two doses (20 mg/kg and 40 mg/kg) for 14 days before ConA injection. Levels of serum liver enzymes and the histopathology of inflammatory cytokines and other maker proteins were determined at three time points (2, 8 and 24 h). Primary hepatocytes were pretreated with astaxanthin (80 μM) in vitro 24 h before stimulation with TNF-α (10 ng/ml). The apoptosis rate and related protein expression were determined 24 h after the administration of TNF-α. Results Astaxanthin attenuated serum liver enzymes and pathological damage by reducing the release of inflammatory factors. It performed anti-apoptotic effects via the descending phosphorylation of Bcl-2 through the down-regulation of the JNK/p-JNK pathway. Conclusion This research firstly expounded that astaxanthin reduced immune liver injury in ConA-induced autoimmune hepatitis. The mode of action appears to be downregulation of JNK/p-JNK-mediated apoptosis and autophagy. PMID:25761053

  1. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation

    PubMed Central

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-01-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application. PMID:27401541

  2. Correlation between structures of chiral polymers and their efficiency for chiral resolution by crystallization.

    PubMed

    Menahem, Tali; Pravda, Martin; Mastai, Yitzhak

    2009-10-01

    In this work, we describe the correlation between chiral polymer structures, particularly alpha-helical and random coil conformations, and their efficiency as chiral resolving agents in crystallization processes. A set of chiral block copolymers based on polyethylene oxide with chiral glutamic acid oligopeptide segments (PEG(113)-b-(+)-(S)-Glu(20)) were synthesized and employed as additives in the crystallization of rac-threonine. CD spectroscopy demonstrates that structures of chiral polymers could be switched between a helical and a disordered random coil by pH. The effect of these polymers at different conformations on the crystallization kinetics, crystal morphology, and chiral resolution of rac-threonine is reported. Our study demonstrates that only chiral polymers with alpha-helical conformations of the chiral segment are effective as additives for chiral resolution throughout crystallization. Overall, our results provide useful guidelines for the selection and design of chiral polymer additives that will act efficiently for chiral resolution by crystallization. PMID:19455618

  3. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation

    NASA Astrophysics Data System (ADS)

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-07-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.

  4. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation.

    PubMed

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-01-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application. PMID:27401541

  5. Simple Nuclear Structure in Cd-129111 from Atomic Isomer Shifts

    NASA Astrophysics Data System (ADS)

    Yordanov, D. T.; Balabanski, D. L.; Bissell, M. L.; Blaum, K.; Budinčević, I.; Cheal, B.; Flanagan, K.; Frömmgen, N.; Georgiev, G.; Geppert, Ch.; Hammen, M.; Kowalska, M.; Kreim, K.; Krieger, A.; Meng, J.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Rajabali, M. M.; Papuga, J.; Schmidt, S.; Zhao, P. W.

    2016-01-01

    Isomer shifts have been determined in 111-129>Cd by high-resolution laser spectroscopy at CERN-ISOLDE. The corresponding mean square charge-radii changes, from the 1 /2+ and the 3 /2+ ground states to the 11 /2- isomers, have been found to follow a distinct parabolic dependence as a function of the atomic mass number. Since the isomers have been previously associated with simplicity due to the linear mass dependence of their quadrupole moments, the regularity of the isomer shifts suggests a higher order of symmetry affecting the ground states in addition. A comprehensive description assuming nuclear deformation is found to accurately reproduce the radii differences in conjunction with the known quadrupole moments. This intuitive interpretation is supported by covariant density functional theory.

  6. Molecular structure of uranium carbides: Isomers of UC3

    NASA Astrophysics Data System (ADS)

    Zalazar, M. Fernanda; Rayón, Víctor M.; Largo, Antonio

    2013-03-01

    In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C3 unit. Both, a rhombic and a ring CU(C2) structures are found about 104-125 kJ/mol higher in energy. Other possible isomers including linear geometries are located even higher. For each structure, we provide predictions for those molecular properties (vibrational frequencies, IR intensities, dipole moments) that could eventually help in their experimental detection. We also discuss the possible routes for the formation of the different UC3 isomers as well as the bonding situation by means of a topological analysis of the electron density.

  7. ORAL TOXICOLOGY STUDIES WITH XYLENE ISOMERS AND MIXED XYLENES

    EPA Science Inventory

    Xylene isomers and mixed xylenes were administered to male and female Sprague-Dawley rats to evaluate their effects on standard toxicological parameters rnhich included body and organ weights, hematology, serum chemistries, urinalysis and histopathological examination. n the init...

  8. Molecular structure of uranium carbides: isomers of UC3.

    PubMed

    Zalazar, M Fernanda; Rayón, Víctor M; Largo, Antonio

    2013-03-21

    In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C3 unit. Both, a rhombic and a ring CU(C2) structures are found about 104-125 kJ/mol higher in energy. Other possible isomers including linear geometries are located even higher. For each structure, we provide predictions for those molecular properties (vibrational frequencies, IR intensities, dipole moments) that could eventually help in their experimental detection. We also discuss the possible routes for the formation of the different UC3 isomers as well as the bonding situation by means of a topological analysis of the electron density. PMID:23534639

  9. Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Lee, Y. G.; Frazier, D. O.

    1986-01-01

    Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

  10. Synthesis of dibenzylamino-1-methylcyclohexanol and dibenzylamino-1-trifluoromethylcyclohexanol isomers.

    PubMed

    Jones, D Heulyn; Bresciani, Stefano; Tellam, James P; Wojno, Justyna; Cooper, Anthony W J; Kennedy, Alan R; Tomkinson, Nicholas C O

    2016-01-01

    The isomers of dibenzylamino-1-methylcyclohexan-1-ol and dibenzylamino-1-trifluoromethylcyclohexan-1-ol have been prepared. The stereochemistry of these compounds was unequivocally assigned through a combination of NMR spectroscopy and single crystal X-ray analysis. The cis-isomer of 3-N,N-dibenzylamino-1-trifluoromethylcyclohexanol and its derivatives display an unusual conformational behaviour in both solution-phase and the solid-state, where the amino group usually adopts an axial conformation. PMID:26468867

  11. Differential Degradation of Nonylphenol Isomers by Sphingomonas xenophaga Bayram

    PubMed Central

    Gabriel, Frédéric L. P.; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E.

    2005-01-01

    Sphingomonas xenophaga Bayram, isolated from the activated sludge of a municipal wastewater treatment plant, was able to utilize 4-(1-ethyl-1,4-dimethylpentyl)phenol, one of the main isomers of technical nonylphenol mixtures, as a sole carbon and energy source. The isolate degraded 1 mg of 4-(1-ethyl-1,4-dimethylpentyl)phenol/ml in minimal medium within 1 week. Growth experiments with five nonylphenol isomers showed that the three isomers with quaternary benzylic carbon atoms [(1,1,2,4-tetramethylpentyl)phenol, 4-(1-ethyl-1,4-dimethylpentyl)phenol, and 4-(1,1-dimethylheptyl)phenol] served as growth substrates, whereas the isomers containing one or two hydrogen atoms in the benzylic position [4-(1-methyloctyl)phenol and 4-n-nonylphenol] did not. However, when the isomers were incubated as a mixture, all were degraded to a certain degree. Differential degradation was clearly evident, as isomers with more highly branched alkyl side chains were degraded much faster than the others. Furthermore, the C9 alcohols 2,3,5-trimethylhexan-2-ol, 3,6-dimethylheptan-3-ol, and 2-methyloctan-2-ol, derived from the three nonylphenol isomers with quaternary benzylic carbon atoms, were detected in the culture fluid by gas chromatography-mass spectrometry, but no analogous metabolites could be found originating from 4-(1-methyloctyl)phenol and 4-n-nonylphenol. We propose that 4-(1-methyloctyl)phenol and 4-n-nonylphenol were cometabolically transformed in the growth experiments with the mixture but that, unlike the other isomers, they did not participate in the reactions leading to the detachment of the alkyl moiety. This hypothesis was corroborated by the observed accumulation in the culture fluid of an as yet unidentified metabolite derived from 4-(1-methyloctyl)phenol. PMID:15746308

  12. Existence of Exotic Torus Isomer States and Their Precession Motions

    NASA Astrophysics Data System (ADS)

    Ichikawa, Takatoshi; Matsuyanagi, Kenichi; Maruhn, Joachim A.; Itagaki, Naoyuki

    We systematically investigate the existence of exotic high-spin torus isomers and their precession motions for a series of N = Z even-even nuclei from 28Si to 56Ni. For this purpose, we use the cranked three-dimensional Hatree-Fock (HF) method in a systematic search for high-spin torus isomers and the three-dimensional time-dependent Hatree-Fock (TDHF) method for describing the precession motion of the torus isomer. We obtain high-spin torus isomers in 36Ar, 40Ca, 44Ti, 48Cr, and 52Fe. The emergence of the torus isomers is associated with the alignments of single-particle angular momenta, which is the same mechanism as found in 40Ca. We find that all the obtained torus isomers execute the precession motion at least two rotational periods. The moment of inertia about a perpendicular axis, which characterizes the precession motion, is found to be close to the classical rigid-body value.

  13. Chiral symmetry in rotating systems

    NASA Astrophysics Data System (ADS)

    Malik, Sham S.

    2015-08-01

    The triaxial rotating system at critical angular momentum I ≥Iband exhibits two enatiomeric (the left- and right-handed) forms. These enatiomers are related to each other through dynamical chiral symmetry. The chiral symmetry in rotating system is defined by an operator χ ˆ =Rˆy (π) T ˆ, which involves the product of two distinct symmetries, namely, continuous and discrete. Therefore, new guidelines are required for testing its commutation with the system Hamiltonian. One of the primary objectives of this study is to lay down these guidelines. Further, the possible impact of chiral symmetry on the geometrical arrangement of angular momentum vectors and investigation of observables unique to nuclear chiral-twins is carried out. In our model, the angular momentum components (J1, J2, J3) occupy three mutually perpendicular axes of triaxial shape and represent a non-planar configuration. At certain threshold energy, the equation of motion in angular momentum develops a second order phase transition and as a result two distinct frames (i.e., the left- and right-handed) are formed. These left- and right-handed states correspond to a double well system and are related to each other through chiral operator. At this critical angular momentum, the centrifugal and Coriolis interactions lower the barrier in the double well system. The tunneling through the double well starts, which subsequently lifts the degeneracy among the rotational states. A detailed analysis of the behavior of rotational energies, spin-staggering, and the electromagnetic transition probabilities of the resulting twin-rotational bands is presented. The ensuing model results exhibit similarities with many observed features of the chiral-twins. An advantage of our formalism is that it is quite simple and it allows us to pinpoint the understanding of physical phenomenon which lead to chiral-twins in rotating systems.

  14. Chromatographic resolution of closely related species in pharmaceutical chemistry: dehalogenation impurities and mixtures of halogen isomers.

    PubMed

    Regalado, Erik L; Zhuang, Ping; Chen, Yadan; Makarov, Alexey A; Schafer, Wes A; McGachy, Neil; Welch, Christopher J

    2014-01-01

    In recent years, the use of halogen-containing molecules has proliferated in the pharmaceutical industry, where the incorporation of halogens, especially fluorine, has become vitally important for blocking metabolism and enhancing the biological activity of pharmaceuticals. The chromatographic separation of halogen-containing pharmaceuticals from associated isomers or dehalogenation impurities can sometimes be quite difficult. In an attempt to identify the best current tools available for addressing this important problem, a survey of the suitability of four chromatographic method development platforms (ultra high-performance liquid chromatography (UHPLC), core shell HPLC, achiral supercritical fluid chromatography (SFC) and chiral SFC) for separating closely related mixtures of halogen-containing pharmaceuticals and their dehalogenated isosteres is described. Of the 132 column and mobile phase combinations examined for each mixture, a small subset of conditions were found to afford the best overall performance, with a single UHPLC method (2.1 × 50 mm, 1.9 μm Hypersil Gold PFP, acetonitrile/methanol based aqueous eluents containing either phosphoric or perchloric acid with 150 mM sodium perchlorate) affording excellent separation for all samples. Similarly, a survey of several families of closely related halogen-containing small molecules representing the diversity of impurities that can sometimes be found in purchased starting materials for synthesis revealed chiral SFC (Chiralcel OJ-3 and Chiralpak IB, isopropanol or ethanol with 25 mM isobutylamine/carbon dioxide) as well as the UHPLC (2.1 × 50 mm, 1.8 μm ZORBAX RRHD Eclipse Plus C18 and the Gold PFP, acetonitrile/methanol based aqueous eluents containing phosphoric acid) as preferred methods. PMID:24359254

  15. The combustion kinetics of octane isomers

    SciTech Connect

    Burcat, A.; Pitz, W.J.; Westbrook, C.K.

    1990-03-29

    Shock tube experiments provide conditions for testing kinetic models that are unique, since this is the only common environment in which initiation reactions, primarily the unimolecular decompositions of the fuel, play an important role. At least two factors are known to be very important, the fuel molecule size and its precise structure. Iso-octane has an octane number of 100, which reflects the relative difficulty with which iso-octanes/air mixtures ignite. Conversely, C{sub 8}H{sub 18}, the straight chain n-octane, ignites very easily, with an octane number of approximately zero. The present work addresses the importance of fuel structure for large hydrocarbon fuels, by comparing the ignition of isomers of octane under shock tube conditions. Ignition delay times were performed with n-octane, a linear chain molecular with only primary and secondary C-H bonds, 2-3-4-trimethyl-pentane has a highly branched molecule and contains only primary and tertiary C-H bonds, and iso-octane a molecule which includes a mixture of primary, secondary, and tertiary C-H bonds. Also 1-octene, a simple straight chain alkene was included. The experiments were run in a single pulse stainless steel shock tube. 475 shocks were performed. They were spread as follows: (1) 164 experiments with 1-octene (C{sub 8}H{sub 16}). (2) 137 experiments with 2,2,4 tri-methyl pentane. (3) 30 experiments with 2,3,4 tri-methyl pentane. (4) 144 experiments with n-octane. 3 refs.

  16. Lipid profile and glucose changes after supplementation with astaxanthin: a systematic review and meta-analysis of randomized controlled trials

    PubMed Central

    Ursoniu, Sorin; Sahebkar, Amirhossein; Banach, Maciej

    2015-01-01

    Introduction Many studies have shown that oral supplementation with astaxanthin may be a novel potential treatment for inflammation and oxidative stress in cardiovascular diseases, but evidence of the effects on lipid profile and glucose is still inconclusive. Therefore, we performed a meta-analysis to evaluate the efficacy of astaxanthin supplementation on plasma lipid and glucose concentrations. Material and methods The search included PubMed, Cochrane Library, Scopus, and EMBASE (up to November 27, 2014) to identify randomized controlled trials (RCTs) investigating the effects of astaxanthin supplementation on lipid profile and glucose levels. Two independent reviewers extracted data on study characteristics, methods and outcomes. Results Seven studies meeting inclusion criteria with 280 participants were selected for this meta-analysis; 163 participants were allocated to the astaxanthin supplementation group and 117 to the control group. A random-effect meta-analysis of data from 7 RCTs (10 treatment arms) did not show any significant effect of supplementation with astaxanthin on plasma concentrations of total cholesterol (weighted mean difference (WMD): –1.52 mg/dl, 95% CI: –8.69 to –5.66, p = 0.679), LDL-C (WMD: +1.25 mg/dl, 95% CI: –6.70 to +9.21, p = 0.758), HDL-C (WMD: +1.75 mg/dl, 95% CI: –0.92 to +4.42, p = 0.199), triglycerides (WMD: –4.76 mg/dl, 95% CI: –21.52 to +12.00, p = 0.578), or glucose (WMD: –2.65 mg/dl, 95% CI: –5.84 to +0.54, p = 0.103). All these effect sizes were robust, and omission of any of the included studies did not significantly change the overall estimate. Conclusions This meta-analysis of data from 10 RCT arms did not indicate a significant effect of supplementation with astaxanthin on plasma lipid profile, but a slight glucose-lowering effect was observed. Further, well-designed trials are necessary to validate these results. PMID:25995739

  17. In Vivo Effects of Free Form Astaxanthin Powder on Anti-Oxidation and Lipid Metabolism with High-Cholesterol Diet

    PubMed Central

    Chen, Yung-Yi; Lee, Pei-Chi; Wu, Yi-Long; Liu, Li-Yun

    2015-01-01

    Astaxanthin extracted from Pomacea canaliculata eggs was made into free-form astaxanthin powder (FFAP) and its effects on lipid metabolism, liver function, antioxidants activities and astaxanthin absorption rate were investigated. 45 hamsters were split into 5 groups and fed with normal diet, high-cholesterol control (0.2% cholesterol), 1.6FFAP (control+1.6% FFAP), 3.2FFAP (control+3.2% FFAP) and 8.0FFAP (control+8.0% FFAP), respectively, for 6 weeks. FFAP diets significantly decreased the liver total cholesterol, triglyceride levels and increased liver fatty acids (C20:5n3; C22:6n3) compositions. It decreased plasma alanine aminotransferase and aspartate aminotransferase. In terms of anti-oxidative activities, we found 8.0 FFAP diet significantly decreased plasma and liver malonaldehyde (4.96±1.96 μg TEP eq./mL and 1.56±0.38 μg TEP eq./g liver) and liver 8-isoprostane levels (41.48±13.69 μg 8-ISOP/g liver). On the other hand, it significantly increased liver catalase activity (149.10±10.76 μmol/min/g liver), Vitamin C (2082.97±142.23 μg/g liver), Vitamin E (411.32±81.67 μg/g liver) contents, and glutathione levels (2.13±0.42 mg GSH eq./g liver). Furthermore, 80% of astaxanthin absorption rates in all FFAP diet groups suggest FFAP is an effective form in astaxanthin absorption. Finally, astaxanthin was found to re-distribute to the liver and eyes in a dose dependent manner. Taken together, our results suggested that the appropriate addition of FFAP into high cholesterol diets increases liver anti-oxidative activity and reduces the concentration of lipid peroxidase and therefore, it may be beneficial as a material in developing healthy food. PMID:26262684

  18. Can a Non-Chiral Object Be Made of Two Identical Chiral Moieties?

    ERIC Educational Resources Information Center

    LeMarechal, Jean Francois

    2008-01-01

    Several pedagogical objects can be used to discuss chirality. Here, we use the cut of an apple to show that the association of identical chiral moieties can form a non-chiral object. Octahedral chirality is used to find situations equivalent to the cut of the apple. (Contains 5 figures.)

  19. Chiral Chlordane Components in Environmental Matrices

    EPA Science Inventory

    Chlordane, a persistent, bioaccumulative and toxic organochlorine pesticide, has been studied for many years. Since the advent of chiral analysis for environmental samples, over 2,400 measurements have been made of various chiral chlordane components. Chlordane enantiomer fractio...

  20. Anaerobic biodegradability of phthalic acid isomers and related compounds.

    PubMed

    Kleerebezem, R; Pol, L W; Lettinga, G

    1999-02-01

    All three phthalic acid isomers (ortho, meta and para benzene dicarboxylic acid) are produced in massive amounts, and used in the chemical industry as plasticizers or for the production of polyester. Wastestreams generated during the production of phthalate isomers generally contain high concentrations of aromatic acids. To study the potential biodegradability of these primarily anthropogenic compounds in anaerobic bioreactors, biodegradability studies were performed. Compounds tested were benzoate, ortho-phthalate, isophthalate, terephthalate, dimethyl phthalate, dimethyl terephthalate, para-toluate and para-xylene. Seed materials tested were two types of granular sludge and digested sewage sludge. It was found that all phthalate isomers and their corresponding dimethyl-esters, could be completely mineralized by all seed materials studied. Lag phases required for 50% degradation of these compounds, ranged from 17 to 156 days. The observed degradation curves could be explained by growth of an initially small amount of organisms in the inoculum with the specific ability to degrade one phthalate isomer. The observed order in the length of the lag phases for the phthalate isomers is: phthalate < terephthalate < isophthalate. This order appears to be related to the environmental abundancy of the different phthalate isomers. The initial step in the degradation pathway of both dimethyl phthalate esters was hydrolysis of the ester sidechain, resulting in the formation of the corresponding mono-methyl-phthalate isomer and phthalate isomer. The rate limiting step in mineralization of both dimethyl phthalate and dimethyl terephthalate was found to be fermentation of the phthalate isomer. Para-toluate was degraded only by digested sewage sludge after a lag phase of 425 days. The observed degradation rates of this compound were very low. No mineralization of para-xylene was observed. In general, the differences in the lag phases between different seed materials were relatively

  1. Mode of Action Studies on a Chiral Diphenyl Ether Peroxidizing Herbicide

    PubMed Central

    Hallahan, Beverly J.; Camilleri, Patrick; Smith, Alison; Bowyer, John R.

    1992-01-01

    The nitrodiphenyl ether herbicide 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitroacetophenone oxime-O-(acetic acid, methyl ester) (DPEI) induced an abnormal accumulation of protoporphyrin IX in darkness in the green alga Chlamydomonas reinhardtii, as determined by high-performance liquid chromatography and spectrofluorimetry. It also inhibited the increase in cell density of the alga in light-grown cultures with an I50 (concentration required to decrease cell density increase to 50% of the noninhibited control value) of 0.16 μm. The relative ability of four peroxidizing diphenyl ether herbicides to cause tetrapyrrole accumulation in C. reinhardtii correlated qualitatively with their ability to inhibit the increase in cell density in light-grown cultures. The purified S(−) enantiomer of the optically active phthalide DPE 5-[2-chloro-4-(trifluoromethyl)phenoxy]-3-methylphthalide (DPEIII), which has greater herbicidal activity than the R(+) isomer, induces a 4- to 5-fold greater tetrapyrrole accumulation than the R(+) isomer. The I50 for inhibition of increase in cell density in light-grown cultures of C. reinhardtii by the S(−) isomer (0.019 μm) is less than 25% of that for the R(+) isomer. DPEIII inhibits protoporphyrinogen IX oxidase activity in pea (Pisum sativum) etioplast lysates, with the S(−) enantiomer showing considerably greater potency than the R(+) isomer and the racemic mixture showing a potency intermediate between the two. The results indicate that the site at which DPEs inhibit protoporphyrinogen IX oxidase shows chiral discrimination and provide further evidence for the link between inhibition of this enzyme, protoporphyrin IX accumulation, and the phytotoxicity of DPE herbicides. PMID:16653107

  2. Effects of chirality and surface stresses on the bending and buckling of chiral nanowires

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Shan; Shimada, Takahiro; Wang, Gang-Feng; Kitamura, Takayuki

    2014-01-01

    Due to their superior optical, elastic and electrical properties, chiral nanowires have many applications as sensors, probes, and building blocks of nanoelectromechanical systems. In this paper, we develop a refined Euler-Bernoulli beam model for chiral nanowires with surface effects and material chirality incorporated. This refined model is employed to investigate the bending and buckling of chiral nanowires. It is found that surface effects and material chirality significantly affect the elastic behaviour of chiral nanowires. This study is helpful not only for understanding the size-dependent behaviour of chiral nanowires, but also for characterizing their mechanical properties.

  3. Hydrogen-Regulated Chiral Nanoplasmonics.

    PubMed

    Duan, Xiaoyang; Kamin, Simon; Sterl, Florian; Giessen, Harald; Liu, Na

    2016-02-10

    Chirality is a highly important topic in modern chemistry, given the dramatically different pharmacological effects that enantiomers can have on the body. Chirality of natural molecules can be controlled by reconfiguration of molecular structures through external stimuli. Despite the rapid progress in plasmonics, active regulation of plasmonic chirality, particularly in the visible spectral range, still faces significant challenges. In this Letter, we demonstrate a new class of hybrid plasmonic metamolecules composed of magnesium and gold nanoparticles. The plasmonic chirality from such plasmonic metamolecules can be dynamically controlled by hydrogen in real time without introducing macroscopic structural reconfiguration. We experimentally investigate the switching dynamics of the hydrogen-regulated chiroptical response in the visible spectral range using circular dichroism spectroscopy. In addition, energy dispersive X-ray spectroscopy is used to examine the morphology changes of the magnesium particles through hydrogenation and dehydrogenation processes. Our study can enable plasmonic chiral platforms for a variety of gas detection schemes by exploiting the high sensitivity of circular dichroism spectroscopy. PMID:26745446

  4. Tactoids of chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Palacio-Betancur, Viviana; Villada-Gil, Stiven; Zhou, Ye; Armas-Pérez, Julio C.; de Pablo, Juan José; Hernández-Ortiz, Juan Pablo

    The phase diagram of chiral liquid crystals confined in ellipsoids is obtained, by following a theoretically informed Monte Carlo relaxation of the tensor alignment field Q. The free energy of the system is described by a functional in the framework of the Landau-de Gennes formalism. This study also includes the effect of anchoring strength, curvature, and chirality of the system. In the low chirality region of the phase diagram we found the twist bipolar (BS) phase and some cholesteric phases such as the radial spherical structure (RSS), twist cylinder (TC) and double twist cylinder (DTC) whose axis of rotation is not necessarily aligned with the major axis of the geometry. For high chirality scenarios, the disclination lines are twisted or bent near the surface preventing the formation of symmetric networks of defects, although an hexagonal pattern is formed on the surface which might serve as open sites for collocation of colloids. By analyzing the free energies of isochoric systems, prolate geometries tend to be more favorable for high chirality and low anchoring conditions. Universidad Nacional de Colombia Ph.D. grant and COLCIENCIAS under the Contract No. 110-165-843-748. CONACYT for Postdoctoral Fellowships Nos. 186166 and 203840.

  5. Chiral Thirring–Wess model

    SciTech Connect

    Rahaman, Anisur

    2015-10-15

    The vector type of interaction of the Thirring–Wess model was replaced by the chiral type and a new model was presented which was termed as chiral Thirring–Wess model in Rahaman (2015). The model was studied there with a Faddeevian class of regularization. Few ambiguity parameters were allowed there with the apprehension that unitarity might be threatened like the chiral generation of the Schwinger model. In the present work it has been shown that no counter term containing the regularization ambiguity is needed for this model to be physically sensible. So the chiral Thirring–Wess model is studied here without the presence of any ambiguity parameter and it has been found that the model not only remains exactly solvable but also does not lose the unitarity like the chiral generation of the Schwinger model. The phase space structure and the theoretical spectrum of this new model have been determined in the present scenario. The theoretical spectrum is found to contain a massive boson with ambiguity free mass and a massless boson.

  6. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

    Damasceno, Pablo; Karas, Andrew; Schultz, Benjamin; Engel, Michael; Glotzer, Sharon

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. Work supported by the National Science Foundation, Division of Materials Research Award No. DMR 1120923, U.S. Army Research Office under Grant Award No. W911NF-10-1-0518, and also by the DOD/ASD (R&E) under Award No. N00244-09-1-0062.

  7. Extraction and purification of high-value metabolites from microalgae: essential lipids, astaxanthin and phycobiliproteins.

    PubMed

    Cuellar-Bermudez, Sara P; Aguilar-Hernandez, Iris; Cardenas-Chavez, Diana L; Ornelas-Soto, Nancy; Romero-Ogawa, Miguel A; Parra-Saldivar, Roberto

    2015-03-01

    The marked trend and consumers growing interest in natural and healthy products have forced researches and industry to develop novel products with functional ingredients. Microalgae have been recognized as source of functional ingredients with positive health effects since these microorganisms produce polyunsaturated fatty acids, polysaccharides, natural pigments, essential minerals, vitamins, enzymes and bioactive peptides. For this reason, the manuscript reviews two of the main high-value metabolites which can be obtained from microalgae: pigments and essential lipids. Therefore, the extraction and purification methods for polyunsaturated fatty acids, astaxanthin, phycoerythrin and phycocyanin are described. Also, the effect that environmental growth conditions have in the production of these metabolites is described. This review summarizes the existing methods to extract and purify such metabolites in order to develop a feasible and sustainable algae industry. PMID:25223877

  8. Astaxanthin Inhibits Proliferation and Induces Apoptosis and Cell Cycle Arrest of Mice H22 Hepatoma Cells

    PubMed Central

    Shao, Yiye; Ni, Yanbo; Yang, Jing; Lin, Xutao; Li, Jun; Zhang, Lixia

    2016-01-01

    Background It is widely recognized that astaxanthin (ASX), a member of the carotenoid family, has strong biological activities including antioxidant, anti-inflammation, and immune-modulation activities. Previous studies have confirmed that ASX can effectively inhibit hepatoma cells in vitro. Material/Methods MTT was used to assay proliferation of mice H22 cells, and flow cytometry was used to determine apoptosis and cell cycle arrest of H22 cells in vitro and in vivo. Moreover, anti-tumor activity of ASX was observed in mice. Results ASX inhibited the proliferation of H22 cells, promoted cell necrosis, and induced cell cycle arrest in G2 phase in vitro and in vivo. Conclusions This study indicated that ASX can inhibit proliferation and induce apoptosis and cell cycle arrest in mice H22 hepatoma cells in vitro and in vivo. PMID:27333866

  9. Extraction and purification of high-value metabolites from microalgae: essential lipids, astaxanthin and phycobiliproteins

    PubMed Central

    Cuellar-Bermudez, Sara P; Aguilar-Hernandez, Iris; Cardenas-Chavez, Diana L; Ornelas-Soto, Nancy; Romero-Ogawa, Miguel A; Parra-Saldivar, Roberto

    2015-01-01

    The marked trend and consumers growing interest in natural and healthy products have forced researches and industry to develop novel products with functional ingredients. Microalgae have been recognized as source of functional ingredients with positive health effects since these microorganisms produce polyunsaturated fatty acids, polysaccharides, natural pigments, essential minerals, vitamins, enzymes and bioactive peptides. For this reason, the manuscript reviews two of the main high-value metabolites which can be obtained from microalgae: pigments and essential lipids. Therefore, the extraction and purification methods for polyunsaturated fatty acids, astaxanthin, phycoerythrin and phycocyanin are described. Also, the effect that environmental growth conditions have in the production of these metabolites is described. This review summarizes the existing methods to extract and purify such metabolites in order to develop a feasible and sustainable algae industry. PMID:25223877

  10. Bistable aggregate of all-trans-astaxanthin in an aqueous solution

    NASA Astrophysics Data System (ADS)

    Mori, Yuso; Yamano, Kuniko; Hashimoto, Hideki

    1996-05-01

    The temperature dependence of the optical absorption spectra for astaxanthin aggregate has been studied between 2 and 32°C. Red-shifted absorption bands as compared to the monomer absorption band are found above 21°C in addition to the blue-shifted band of the aggregate. The spectra suggest that the molecular arrangement in the aggregate is a bistable one consisting of head-to-tail and card-packed arrangements. A diagram describing the bistability together with the monomer state is proposed in the space defined by the free energy and the quantity of Σi = 1 N< θ12 + < σθ12 for the ith molecule in the N-molecule aggregate.

  11. Astaxanthin Inhibits Proliferation and Induces Apoptosis and Cell Cycle Arrest of Mice H22 Hepatoma Cells.

    PubMed

    Shao, Yiye; Ni, Yanbo; Yang, Jing; Lin, Xutao; Li, Jun; Zhang, Lixia

    2016-01-01

    BACKGROUND It is widely recognized that astaxanthin (ASX), a member of the carotenoid family, has strong biological activities including antioxidant, anti-inflammation, and immune-modulation activities. Previous studies have confirmed that ASX can effectively inhibit hepatoma cells in vitro. MATERIAL AND METHODS MTT was used to assay proliferation of mice H22 cells, and flow cytometry was used to determine apoptosis and cell cycle arrest of H22 cells in vitro and in vivo. Moreover, anti-tumor activity of ASX was observed in mice. RESULTS ASX inhibited the proliferation of H22 cells, promoted cell necrosis, and induced cell cycle arrest in G2 phase in vitro and in vivo. CONCLUSIONS This study indicated that ASX can inhibit proliferation and induce apoptosis and cell cycle arrest in mice H22 hepatoma cells in vitro and in vivo. PMID:27333866

  12. Crystallisation of alpha-crustacyanin, the lobster carapace astaxanthin-protein: results from EURECA

    NASA Astrophysics Data System (ADS)

    Zagalsky, P. F.; Wright, C. E.; Parsons, M.

    1995-08-01

    Crystallisation of alpha-crustacyanin, the lobster carapace astaxanthin-protein was attempted under microgravity conditions in EURECA satellite using liquid-liquid diffusion with polyethyleneglycol (PEG) as precipitant; in a second reaction chamber phenol and dioxan were used as additives to prevent composite crystal growth. Crystals of alpha-crustacyanin grown under microgravity from PEG were larger than those grown terrestrially in the same apparatus under otherwise identical conditions. On retrieval, the crystals from PEG were shown to be composite and gave a powder diffraction pattern. The second reaction chamber showed leakage on retrieval and had also been subjected to rapid temperature variation during flight. Crystal fragments were nevertheless recovered but showed a powder diffraction pattern. It is concluded, certainly for liquid-liquid diffusion using PEG alone, that, for crustacyanin, although microgravity conditions resulted in an increase in dimensions of crystals, a measurable improvement in molecular ordering was not achieved.

  13. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    NASA Astrophysics Data System (ADS)

    Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef

    2010-07-01

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  14. Excited states and electrochromism of radical cation of the carotenoid astaxanthin

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-09-01

    Radical cations of the carotenoid astaxanthin were generated by chemical oxidation with Fe(Cl) 3, and their absorption and electroabsorption (Stark) spectra at temperatures about 150 K were recorded in the spectral range from 5900 to 26000 cm -1 (380 to 1700 nm), covering two absorptive electronic transitions from D 0 (ground) to D 1 and D 2 excited states. The changes in static polarizability are negative and equal -40±10 A 3 for D 0→D 1 and -105±15 A 3 for D 0→D 2, pointing that dominant contribution to polarizabilities results from the coupling of D 1 and D 2 with the ground state. An approximate localization of the next excited state with ground-state parity is estimated based on arguments from perturbation theory.

  15. Field induced spin chirality and chirality switching in magnetic multilayers

    NASA Astrophysics Data System (ADS)

    Tartakovskaya, Elena V.

    2015-05-01

    The physical origin of the field-induced spin chirality experimentally observed in rare earth multilayers is determined. It is shown that the effect is possible due to the interplay between solid-state exchange interactions (the Ruderman-Kittel-Kasuya-Yosida and the Dsyaloshinsky-Moriya interactions), the external magnetic field and a special confinement of magnetic constituents. The presented model describes a certain temperature dependence of the chirality factor in agreement with experimental data and opens a new way to design nanostructured objects with predicted handedness.

  16. Chiral lattice fermions with correct vacuum polarization and chiral anomaly

    SciTech Connect

    Pryor, C. )

    1991-04-15

    An action for chiral lattice fermions is proposed, which avoids the Nielsen-Ninomiya theorem by virtue of its nonlocality and nonbilinearity. The action is constructed by eliminating the extra fermion modes with a gauge-violating Majorana-type Wilson mass, which is then rendered invariant by an integration over gauge transformations. The free propagator is calculated, and the one-loop vacuum polarization is shown to be identical to that for Wilson fermions, even at nonzero lattice spacing. Also the chiral anomaly is shown to be the same as for Wilson fermions in the continuum limit.

  17. Repulsive Casimir force in chiral metamaterials.

    PubMed

    Zhao, R; Zhou, J; Koschny, Th; Economou, E N; Soukoulis, C M

    2009-09-01

    We demonstrate theoretically that one can obtain repulsive Casimir forces and stable nanolevitations by using chiral metamaterials. By extending the Lifshitz theory to treat chiral metamaterials, we find that a repulsive force and a minimum of the interaction energy possibly exist for strong chirality, under realistic frequency dependencies and correct limiting values (for zero and infinite frequencies) of the permittivity, permeability, and chiral coefficients. PMID:19792309

  18. Effect of dietary astaxanthin against Aeromonas hydrophila infection in common carp, Cyprinus carpio.

    PubMed

    Jagruthi, Chandrasekar; Yogeshwari, Govintharaj; Anbazahan, Sannasi Muthu; Mari, Lourthu Samy Shanthi; Arockiaraj, Jesu; Mariappan, Pitchaimuthu; Sudhakar, Gunamoni Rajam Learnal; Balasundaram, Chellam; Harikrishnan, Ramasamy

    2014-12-01

    The effect of astaxanthin at 0, 25, 50, and 100 mg kg(-1) incorporated in basal feed on immune response and disease resistance in Cyprinus carpio against Aeromonas hydrophila was investigated. When fed with 25 mg kg(-1) diet, the cumulative mortality was 35% whereas it was 10% and 20% with 50 and 100 mg kg(-1) diets. With all enriched diets the growth rate increased significantly from week 1 to 4 when compared with control. However, the specific growth rate (SGR), feed conversion ratio (FCR), and protein efficiency ratio (PER) did not vary significantly from that of the control except with 50 mg kg(-1) diet. When fed with 50 and 100 mg kg(-1) diets the red blood cells, white blood cells, hemoglobin, and hematocrit values significantly increased. However, the serum total protein, albumin, and globulin contents significantly increased only when fed with 50 and 100 mg kg(-1) diets. The phagocytic ratio also significantly raised with 50 and 100 mg kg(-1) diets on week 2 and 4 whereas the phagocytic index significantly increased with all groups only on fourth week. The respiratory burst activity significantly increased in 25 mg kg(-1) diet group on first week whereas in 50 and 100 mg kg(-1) diet groups the activity increased on weeks 2 and 4; a similar trend was observed in the anti-protease activity only on weeks 2 and 4. The serum lysozyme activity and bactericidal activity registered a significant increase with all enriched diets. This study suggests that supplementation of astaxanthin at 50 and 100 mg kg(-1) with the basal diet significantly promotes the growth restores hematology and modulates the immune system in C. carpio against A. hydrophila. PMID:25462460

  19. Inhibition of chemically-induced neoplastic transformation by a novel tetrasodium diphosphate astaxanthin derivative.

    PubMed

    Hix, Laura M; Frey, Dean A; McLaws, Mark D; Østerlie, Marianne; Lockwood, Samuel F; Bertram, John S

    2005-09-01

    Carotenoids have been implicated in numerous epidemiological studies as being protective against cancer at many sites, and their chemopreventive properties have been confirmed in laboratory studies. Astaxanthin (AST), primarily a carotenoid of marine origin, responsible for the pink coloration of salmon, shrimp and lobster, has received relatively little attention. As with other carotenoids, its highly lipophilic properties complicate delivery to model systems. To overcome this issue we have synthesized a novel tetrasodium diphosphate astaxanthin (pAST) derivative with aqueous dispersibility of 25.21 mg/ml. pAST was delivered to C3H/10T1/2 cells in an aqueous/ethanol solution and compared with non-esterified AST dissolved in tetrahydrofuran. We show pAST to (i) upregulate connexin 43 (Cx43) protein expression; (ii) increase the formation of Cx43 immunoreactive plaques; (iii) upregulate gap junctional intercellular communication (GJIC); and (iv) cause 100% inhibition of methylcholanthrene-induced neoplastic transformation at 10(-6) M. In all these assays, pAST was superior to non-esterified AST itself; in fact, pAST exceeded the potency of all other previously tested carotenoids in this model system. Cleavage of pAST to non-esterified (free) AST and uptake into cells was also verified by HPLC; however, levels of free AST were approximately 100-fold lower than in cells treated with AST itself, suggesting that pAST possesses intrinsic activity. The dual properties of water dispersibility (enabling parenteral administration in vivo) and increased potency should prove extremely useful in the future development of cancer chemopreventive agents. PMID:15888493

  20. Genotoxicity and subacute toxicity studies of a new astaxanthin-containing Phaffia rhodozyma extract.

    PubMed

    Tago, Yoshiyuki; Fujii, Toshihide; Wada, Jutaro; Kato, Masanori; Wei, Min; Wanibuchi, Hideki; Kitano, Mitsuaki

    2014-06-01

    Experimental and clinical studies demonstrate that astaxanthin (AXN), a xanthophyll carotenoid, has protective effects against oxidative damage. Because most of these studies assessed AXN derived from Haematococcus pluvialis that were cultivated at industrial scales, few studies have examined the toxicity of AXN derived from Phaffia rhodozyma. To evaluate the safety of astaxanthin-containing P. rhodozymaextract (AXN-PRE), genotoxicity was assessed in bacterial reverse mutation test and mouse bone marrow micronucleus test, and general toxicity was assessed in 4-week repeated oral toxicity study in rats. AXN-PRE did not induce reverse mutations in the Salmonella typhimurium strains TA98 or TA100 at concentrations of 5,000 µg/plate with or without S9 mix, and no chromosome damage was observed at a dose of 2,000 mg/kg in mouse micronucleus test. In the subacute toxicity study, male and female Sprague-Dawley rats were given AXN-PRE at doses of 0, 500, and 1,000 mg/kg by gavage for 4 weeks. Body weights, urinalysis, hematology, serum biochemistry, organ weights, or histopathological lesions indicated no distinct toxicity. In conclusion, AXN-PRE had no effect in bacterial reverse mutation test and mouse bone marrow micronucleus test. The no-observed-adverse-effect level for AXN-PRE in 4-week repeated oral toxicity study in rats was determined to be greater than 1,000 mg/kg (corresponding to dose of 50 mg/kg AXN) regardless of gender. PMID:24849672

  1. Characterization of the Azirinyl Cation and Its Isomers.

    PubMed

    Kokkila Schumacher, Sara I L; Bera, Partha P; Lee, Timothy J

    2016-03-01

    The azirinyl cation (C2H2N(+)) and its geometrical isomers could be present in the interstellar medium. The C2H2N(+) isomers are, however, difficult to identify in interstellar chemistry because of the lack of high-resolution spectroscopic data from laboratory experiments. Ab initio quantum chemical methods were used to characterize the structures, relative energies, and spectroscopic and physical properties of the low energy isomers of the azirinyl cation. We have employed second-order Møller-Plesset perturbation theory (MP2), second-order Z-averaged perturbation theory (ZAPT2), and coupled cluster theory with singles and doubles with perturbative triples CCSD(T) methods along with large correlation consistent basis sets such as cc-pVTZ, cc-pCVTZ, cc-pVQZ, cc-pCVQZ, and cc-pV5Z. Harmonic vibrational frequencies, dipole moments, rotational constants, and proton affinities for the lowest energy isomers were calculated using the CCSD(T) method. Azirinyl cation, a cyclic isomer, is lowest in energy at all levels of theory employed. Azirinyl cation is followed by the cyanomethyl cation (H2CCN)(+), isocyanomethyl cation (H2CNC)(+), and a quasilinear HCCNH(+) cation, which are 13.8, 17.3, and 21.5 kcal mol(-1) above the cyclic isomer, respectively, at the CCSD(T)/cc-pV5Z level of theory. The lowest three isomers all have C2v symmetry and (1)A1 ground electronic states. The quasilinear HCCNH(+) cation has a Cs symmetry planar structure, and a (3)A″ electronic ground state, unlike what some previous work suggested. PMID:26840658

  2. Computations of 36 tautomer/isomer equilibria of different lactams.

    PubMed

    Galstyan, Gegham; Knapp, Ernst-Walter

    2012-06-28

    Gas-phase energies of 36 tautomer/isomer pairs of 18 six-membered N-heterocyclic compounds were computed quantum chemically. Among the considered B3LYP, BH&HLYP, BH&HLYP(G), and PW6B95 DFT functionals, the latter two provide accurate tautomer/isomer pair energies with root-mean-square deviations (rmsd) relative to experiments of 0.2 and 0.3 kcal/mol, respectively. Since only few (namely five) experimental data are available, 15 tautomer/isomer pair energies were computed with the very precise QCISD(T)(quadruple-ζ) method serving as reference. Relative to this reference the PW6B95 DFT functional is slightly superior to the BH&HLYP(G) functional, yielding an rmsd of 0.7 and 0.8 kcal/mol, respectively. In contrast to BH&HLYP(G), the PW6B95 DFT functional yields also accurate tautomer/isomer pair energies if zwitterionic structures are involved. The tautomer/isomer pair states possess different amounts of aromaticity. This is characterized by nucleus-independent chemical shift (NICS) values. The tautomer/isomer pair reference energies, from which the energies computed with PW6B95 are subtracted, correlate linearly with the corresponding differences in the NICS values. This correlation is used to construct a correction term for the pair energies computed with PW6B95, yielding tautomer/isomer pair energies with rmsd of 0.3 kcal/mol with respect to the more CPU time demanding QCISD(T)(quadruple-ζ) method. PMID:22646903

  3. Chiral Sensor for Enantiodiscrimination of Varied Acids.

    PubMed

    Huang, Huayin; Bian, Guangling; Zong, Hua; Wang, Yabai; Yang, Shiwei; Yue, Huifeng; Song, Ling; Fan, Hongjun

    2016-06-01

    A chiral thiophosphoroamide 4 derived from (1R,2R)-1,2-diaminocyclohexane is used as a highly effective chiral sensor for the chiral recognition of varied acids via ion-pairing and hydrogen-bonding interactions using (1)H, (19)F and (31)P NMR. PMID:27192021

  4. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

    In this review, parity-violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long-range spin-dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short-range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity-violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented. PMID:25919812

  5. Gradient domestication of Haematococcus pluvialis mutant with 15% CO2 to promote biomass growth and astaxanthin yield.

    PubMed

    Cheng, Jun; Li, Ke; Yang, Zongbo; Lu, Hongxiang; Zhou, Junhu; Cen, Kefa

    2016-09-01

    In order to increase biomass yield and reduce culture cost of Haematococcus pluvialis with flue gas from coal-fired power plants, a screened mutant by nuclear irradiation was gradually domesticated with 15% CO2 to promote biomass dry weight and astaxanthin yield. The biomass yield of mutant after 10 generations of 15% CO2 domestication increased to 1.3 times as that with air. With the optimization of nitrogen and phosphorus concentration, the biomass dry weight was further increased by 62%. The astaxanthin yield induced with 15% CO2 and high light of 135 μmol photons m(-2) s(-1) increased to 87.4mg/L, which was 6 times higher than that induced with high light in air. PMID:27259189

  6. Effects of temperature on the astaxanthin productivity and light harvesting characteristics of the green alga Haematococcus pluvialis.

    PubMed

    Giannelli, Luca; Yamada, Hiroyuki; Katsuda, Tomohisa; Yamaji, Hideki

    2015-03-01

    The green alga Haematococcus pluvialis, which accumulates astaxanthin at an optimal temperature of 20°C, was cultivated under temperatures of 20°C, 23.5°C, 27°C, and 30.5°C, in order to assess the effects on algal metabolism during the growth phase. The culture growth rate declined with above-optimal increases in temperature, and the final maximum cell concentration at 30.5°C reached only 35% of that attained at 20°C. On the contrary, the biomass productivity was increased under all the high-temperature conditions, probably reflecting the metabolism switch from cell duplication to energy accumulation that is typically observed in algal cultures subjected to environmental stress. Moreover, an increase in the light-harvesting capability of the alga was observed by means of the total pigment balance and the photosynthesis-intensity (PI) curve measured under the different cultivation conditions. Cultures kept at higher temperatures were able to better harvest and utilize the impinging light due to photo-acclimation. Finally, the differences in the astaxanthin metabolism were elucidated by subjecting the cultures to nitrogen starvation at 20°C and 27°C. In the culture at 27°C, a 1.4-fold increase in the astaxanthin productivity was observed when compared to that at 20°C, and the latter required almost two-fold more energy for the astaxanthin production compared with the 27°C culture. PMID:25441445

  7. Microwave propagation in chiral metamaterials

    NASA Astrophysics Data System (ADS)

    Prybylski, Aida; Yon, Luis; Noginova, Natalia

    Chiral hyperbolic metamaterials are predicted to show interesting properties associated with possible topological photonic states in these materials, which present new opportunities for light control and manipulation. As prototypes, we consider two metal-dielectric systems designed for microwave range: a twisted wires array, where chirality is associated with shape of metal inclusions, and a rotated layer system, with parallel wires in each layer, and direction of the wires orientation rotated from layer to layer. Systems with different content of metal and layer-to-layer distance were fabricated and studied in the free space propagation experiment. The results were discussed in terms of effective media consideration.

  8. Collisions in Chiral Kinetic Theory.

    PubMed

    Chen, Jing-Yuan; Son, Dam T; Stephanov, Mikhail A

    2015-07-10

    Using a covariant formalism, we construct a chiral kinetic theory Lorentz invariant to order O(ℏ), which includes collisions. We find a new contribution to the particle number current due to the side jumps required by the conservation of angular momentum during collisions. We also find a conserved symmetric stress-energy tensor as well as the H function obeying Boltzmann's H theorem. We demonstrate their use by finding a general equilibrium solution and the values of the anomalous transport coefficients characterizing the chiral vortical effect. PMID:26207458

  9. Lipase-catalyzed fractionation of conjugated linoleic acid isomers.

    PubMed

    Haas, M J; Kramer, J K; McNeill, G; Scott, K; Foglia, T A; Sehat, N; Fritsche, J; Mossoba, M M; Yurawecz, M P

    1999-09-01

    The abilities of lipases produced by the fungus Geotrichum candidum to selectively fractionate mixtures of conjugated linoleic acid (CLA) isomers during esterification of mixed CLA free fatty acids and during hydrolysis of mixed CLA methyl esters were examined. The enzymes were highly selective for cis-9,trans-11-18:2. A commercial CLA methyl ester preparation, containing at least 12 species representing four positional CLA isomers, was incubated in aqueous solution with either a commercial G. candidum lipase preparation (Amano GC-4) or lipase produced from a cloned high-selectivity G. candidum lipase B gene. In both instances selective hydrolysis of the cis-9,trans-11-18:2 methyl ester occurred, with negligible hydrolysis of other CLA isomers. The content of cis-9, trans-11-18:2 in the resulting free fatty acid fraction was between 94 (lipase B reaction) and 77% (GC-4 reaction). The commercial CLA mixture contained only trace amounts of trans-9,cis-11-18:2, and there was no evidence that this isomer was hydrolyzed by the enzyme. Analogous results were obtained with these enzymes in the esterification in organic solvent of a commercial preparation of CLA free fatty acids containing at least 12 CLA isomers. In this case, G. candidum lipase B generated a methyl ester fraction that contained >98% cis-9,trans-11-18:2. Geotrichum candidum lipases B and GC-4 also demonstrated high selectivity in the esterification of CLA with ethanol, generating ethyl ester fractions containing 96 and 80%, respectively, of the cis-9,trans-11 isomer. In a second set of experiments, CLA synthesized from pure linoleic acid, composed essentially of two isomers, cis-9,trans-11 and trans-10,cis-12, was utilized. This was subjected to esterification with octanol in an aqueous reaction system using Amano GC-4 lipase as catalyst. The resulting ester fraction contained up to 97% of the cis-9,trans-11 isomer. After adjustment of the reaction conditions, a concentration of 85% trans-10,cis-12

  10. LC-MS-MS Analysis of Brodifacoum Isomers in Rat Tissue.

    PubMed

    Hauck, Zane Z; Feinstein, Douglas L; van Breemen, Richard B

    2016-05-01

    Brodifacoum (BDF) is a second-generation anticoagulant rodenticide structurally related to warfarin but containing two chiral centers. Highly stable, BDF can contaminate food and water supplies causing accidental poisoning of humans and nontarget animals. To determine the distribution of BDF isomers in serum and tissues, a quantitative method was developed and validated according to FDA guidelines based on high-performance liquid chromatography-tandem mass spectrometry. A single liquid-liquid extraction step provided recoveries exceeding 93%. Reversed-phase chromatographic separations required <6 min, and quantitative analysis utilized a triple-quadrupole mass spectrometer equipped with negative ion electrospray and selected reaction monitoring. The standard curve had a linear regression coefficient of 0.999 and intra- and inter-assay variations of <10%. The chromatographic method enabled the resolution and measurement of pairs of BDF diastereomers in commercial materials as well as in rat tissues. This method is suitable for measuring BDF exposure as well as basic science studies of the distribution and elimination of BDF diastereomers to various tissues. PMID:26912564

  11. Mechanical chirality: A chiral catalyst with a ring to it

    NASA Astrophysics Data System (ADS)

    Goldup, Stephen M.

    2016-05-01

    A chiral [2]rotaxane in which the asymmetry is derived from the way in which the two components are mechanically interlocked -- rather than being encoded in the covalent connectivity of the components themselves -- has been shown to act as an enantioselective organocatalyst.

  12. A new high-spin isomer in 195Bi

    NASA Astrophysics Data System (ADS)

    Roy, T.; Mukherjee, G.; Madhavan, N.; Rana, T. K.; Bhattacharya, Soumik; Asgar, Md. A.; Bala, I.; Basu, K.; Bhattacharjee, S. S.; Bhattacharya, C.; Bhattacharya, S.; Bhattacharyya, S.; Gehlot, J.; Ghugre, S. S.; Gurjar, R. K.; Jhingan, A.; Kumar, R.; Muralithar, S.; Nath, S.; Pai, H.; Palit, R.; Raut, R.; Singh, R. P.; Sinha, A. K.; Varughese, T.

    2015-11-01

    A new high-spin isomer has been identified in 195Bi at the focal plane of the HYbrid Recoil mass Analyser (HYRA) used in the gas-filled mode. The fusion evaporation reactions 169Tm (30Si, x n) 193, 195Bi were used with the beam energies on targets of 168 and 146MeV for 6n and 4n channels, respectively. The evaporation residues, separated from the fission fragments, and their decays were detected at the focal plane of HYRA using MWPC, Si-Pad and clover HPGe detectors. The half-life of the new isomer in 195Bi has been measured to be 1.6(1)μs. The configuration of the new isomer has been proposed and compared with the other isomers in this region. The Total Routhian Surface (TRS) calculations for the three-quasiparticle configurations corresponding to the new isomer suggest an oblate deformation for this isomeric state. The same calculations for different configurations in 195Bi and for the even-even 194Pb core indicate that the proton i 13/2 orbital has a large shape driving effect towards oblate shape in these nuclei.

  13. Electrochemical impedance based chiral analysis of anti-ascorbutic drug: l-Ascorbic acid and d-ascorbic acid using C-dots decorated conductive polymer nano-composite electrode.

    PubMed

    Pandey, Indu; Kant, Rama

    2016-03-15

    Clinical manifestations owing to l-ascorbic acid for scurvy as comparison to d-ascorbic acid and challenges of chiral purity are overcome by using chiral selective conductive polymer nanocomposite which mimics antibodies and enzymes. A novel chiral selective imprinted polyaniline-ferrocene-sulfonic acid film has been electrochemically fabricated on C-dots modified pencil graphite electrode. The performance of the obtained l-ascorbic acid or d-ascorbic acid chiral selective sensor was investigated by electrochemical impedance spectroscopy, cyclic and differential pulse voltammetry. The surface characteristics of the C-dots, chiral sensor before and after the de-doping of chiral d- and l-ascorbic acid were characterized by scanning electron microscopy, Raman spectroscopy and X-ray diffraction spectroscopy. Excellent recognition results were obtained by difference in electron transfer resistance. The proposed chiral sensor is capable of measuring d-ascorbic acid or l-ascorbic acid in aqueous as well as in real and commercial samples within the range of 0.020-0.187 nM and 0.003-0.232 nM with detection limit of 0.00073 nM and 0.00016 nM, respectively. The proposed method has also been examined for the chiral selective recognition of ascorbic acid isomers (d- and l-) quantitatively, in complicated matrices of real samples. PMID:26499067

  14. Astaxanthin and papilioerythrinone in the skin of birds: a chromatic convergence of two metabolic routes with different precursors?

    NASA Astrophysics Data System (ADS)

    García-de Blas, Esther; Mateo, Rafael; Guzmán Bernardo, Francisco Javier; Rodríguez Martín-Doimeadios, Rosa Carmen; Alonso-Alvarez, Carlos

    2014-05-01

    Carotenoids are organic pigments involved in several important physiological functions and may serve as indicators of individual quality in animals. These pigments are only obtained by animals from the diet, but they can be later transformed into other carotenoids by specific enzymatic reactions. The diet of farm-reared and probably wild red-legged partridges ( Alectoris rufa) is mainly based on cereals that contain high levels of lutein and zeaxanthin. These two carotenoids are also predominant in internal tissues and blood of red-legged partridges. However, in their integuments, astaxanthin and papilioerythrinone (the last one identified in this work) are mainly present in their free form and esterified with fatty acids. According to available literature about carotenoid metabolism in animals, we propose that astaxanthin ( λ max = 478 nm) and papilioerythrinone ( λ max = 452-478 nm) are the result of a chromatic convergence of the transformation of dietary zeaxanthin and lutein, respectively. Moreover, the results obtained in this work provide the first identification by liquid chromatography coupled to accurate mass quadrupole time-of-flight mass spectrometer system of papilioerythrinone ( m/z 581.3989 [M + H]+) in the skin (i.e., not feathers) of a vertebrate. Astaxanthin and papilioerythrinone are very close in terms of chemical structure and coloration, and the combination of these two keto-carotenoids is responsible for the red color of the ornaments in red-legged partridges.

  15. Effect of dietary astaxanthin on free radical scavenging capacity and nitrite stress tolerance of postlarvae shrimp, Pleoticus muelleri.

    PubMed

    Díaz, Ana Cristina; Velurtas, Susana María; Espino, María Laura; Fenucci, Jorge Lino

    2014-12-24

    The aim of this study was to investigate the effect of astaxanthin feed supplementation and environmental nitrite stress in postlarvae of Pleoticus muelleri (15 ± 0.004 mg initial weight) under culture conditions. Diets containing three levels of astaxanthin, 0 mg kg(-1) of diet (C0), 100 mg kg(-1) of diet (C(100)), and 300 mg kg(-1) of diet (C(300)), were used. Postlarvae fed with each diet were exposed to different concentrations of nitrite (NO(2)Na) (0-200 mg L(-1)). The 96 h median lethal concentration (LC50) values of nitrite N were 76.3, 89.7, and 157 mg L(-1) for shrimps fed to C0, C(100), and C(300). The scavenging properties were evaluated against the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical by electron resonance spectroscopy (EPR). For all feed treatments, the extracts exhibited strong DPPH scavenging activity; however, shrimp fed with C(100) and C(300) showed the greatest activity to quench DPPH (62 and 59%, respectively) with respect to C0 (43%). It can be concluded that astaxanthin acts as a protector of nitrite stress in P. muelleri. PMID:25427235

  16. Coherent perfect absorption in chiral metamaterials.

    PubMed

    Ye, Yuqian; Hay, Darrick; Shi, Zhimin

    2016-07-15

    We study the coherent perfect absorption (CPA) of a chiral structure and derive analytically the CPA condition for transversely isotropic chiral structures in circular polarization bases. The coherent absorption of such a chiral system is generally polarization dependent and can be tuned by the relative phase between the coherent input beams. To demonstrate our theoretical predictions, a chiral metamaterial absorber operating in the terahertz frequency range is optimized. We numerically demonstrate that a coherent absorption of 99.5% can be achieved. Moreover, we show that an optimized CPA chiral structure can be used as an interferometric control of polarization state of the output beams with constant output intensity. PMID:27420535

  17. Scaling laws in chiral hydrodynamic turbulence

    NASA Astrophysics Data System (ADS)

    Yamamoto, Naoki

    2016-06-01

    We study the turbulent regime of chiral (magneto)hydrodynamics for charged and neutral matter with chirality imbalance. We find that the chiral magnetohydrodynamics for charged plasmas possesses a unique scaling symmetry, only without fluid helicity under the local charge neutrality. We also find a different type of unique scaling symmetry in the chiral hydrodynamics for neutral matter with fluid helicity in the inertial range. We show that these symmetries dictate the self-similar inverse cascade of the magnetic and kinetic energies. Our results imply the possible inverse energy cascade in core-collapse supernovae due to the chiral transport of neutrinos.

  18. Chiral xenobiotics bioaccumulations and environmental health prospectives.

    PubMed

    Hussain, Iqbal; ALOthman, Zeid A; Alwarthan, Abdulrahman A; Sanagi, Mohd Marsin; Ali, Imran

    2015-08-01

    The chiral xenobiotics are very dangerous for all of us due to the different enantioselective toxicities of the enantiomers. Besides, these have different enantioselective bioaccumulations and behaviors in our body and other organisms. It is of urgent need to understand the enantioselective bioaccumulations, toxicities, and the health hazards of the chiral xenobiotics. The present article describes the classification, sources of contamination, distribution, enantioselective bioaccumulation, and the toxicities of the chiral xenobiotics. Besides, the efforts are also made to discuss the prevention and remedial measures of the havoc of the chiral xenobiotics. The challenges of the chiral xenobiotics have also been highlighted. Finally, future prospectives are also discussed. PMID:26148690

  19. Atropisomeric determination of chiral hydroxylated metabolites of polychlorinated biphenyls using HPLC-MS

    PubMed Central

    2013-01-01

    Background Polychlorinated biphenyls (PCBs) are a group of environmental persistent organic pollutants, which can be metabolized into a series of metabolites, including hydroxylated metabolites (OH-PCBs) in biota. Nineteen of 209 PCB congeners can form chiral stable isomers. However, atropisomeric determination of the hydroxylated metabolites of these chiral PCBs has never been reported by LC methods. In this work, a novel HPLC-MS method was developed to detect five chiral OH-PCBs (4OH-PCB91, 5OH-PCB91, 4OH-PCB95, 5OH-PCB95 and 5OH-PCB149) using HPLC-MS without a derivatization step. Results The influences of column-type, column temperature, flow rate and ratio of the mobile phase on the atropisomeric separation were investigated in detail. In the final method, calibration curves, based on peak areas against concentration, were linear in a range of 1–100 ng mL-1 of five chiral OH-PCBs with correlation coefficients ranging from 0.9996 to 0.9999 for all atropisomers of OH-PCBs. The relative standard deviations measured at the 10.0 ng mL-1 level for atropisomers of five chiral OH-PCBs were in the range of 0.60-7.55% (n = 5). Calculated detection limits (S/N = 3) of five chiral OH-PCBs were between 0.31 and 0.60 ng mL-1 for all OH-PCB atropisomers. Conclusion This HPLC-MS method was developed to detect chiral OH-PCBs and further successfully applied to measure OH-PCB atropisomer levels and enantiomeric fractions (EFs) in rat liver microsomal samples. The results from LC-MS method were highly consistent with those from GC-ECD method. It is the first time to report these OH-PCB atropisomers detected in microsomes by HPLC-MS. The proposed method might be applied also to detect chiral OH-PCBs in environmental samples and for metabolites of PCBs in vivo. PMID:24360245

  20. Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

    NASA Technical Reports Server (NTRS)

    Jackson, T. A.

    1971-01-01

    Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

  1. Helical motion of chiral liquid crystal droplets

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takaki; Sano, Masaki

    Artificial swimmers have been intensively studied to understand the mechanism of the locomotion and collective behaviors of cells and microorganisms. Among them, most of the artificial swimmers are designed to move along the straight path. However, in biological systems, chiral dynamics such as circular and helical motion are quite common because of the chirality of their bodies, which are made of chiral biomolecules. To understand the role of the chirality in the physics of microswimmers, we designed chiral artificial swimmers and the theoretical model for the chiral motion. We found that chiral liquid crystal droplets, when dispersed in surfactant solutions, swim in the helical path induced by the Marangoni effect. We will discuss the mechanism of the helical motion with our phenomenological model. This work is supported by Grant-in-Aid for JSPS Fellows (Grant No. 26.9814), and MEXT KAKENHI Grant No. 25103004.

  2. Chirality effect in disordered graphene ribbon junctions

    NASA Astrophysics Data System (ADS)

    Long, Wen

    2012-05-01

    We investigate the influence of edge chirality on the electronic transport in clean or disordered graphene ribbon junctions. By using the tight-binding model and the Landauer-Büttiker formalism, the junction conductance is obtained. In the clean sample, the zero-magnetic-field junction conductance is strongly chirality-dependent in both unipolar and bipolar ribbons, whereas the high-magnetic-field conductance is either chirality-independent in the unipolar or chirality-dependent in the bipolar ribbon. Furthermore, we study the disordered sample in the presence of magnetic field and find that the junction conductance is always chirality-insensitive for both unipolar and bipolar ribbons with adequate disorders. In addition, the disorder-induced conductance plateaus can exist in all chiral bipolar ribbons provided the disorder strength is moderate. These results suggest that we can neglect the effect of edge chirality in fabricating electronic devices based on the magnetotransport in a disordered graphene ribbon.

  3. On the tensorial nature of chirality

    NASA Astrophysics Data System (ADS)

    Efrati, Efi; Irvine, William

    2013-03-01

    Chirality occupies a central role in fields ranging from biological self assembly to the design of optical meta-materials. The definition of chirality, as given by lord Kelvin in 1893, associates handedness with the lack of mirror symmetry. However, the quantification of chirality based on this definition has proven to be an elusive task. The difficulty in quantifying chirality is contrasted by the ease with which one determines the handedness of objects with a well defined axis such as screws and helices. In this talk I will present table-top demonstrations that show that a single object can simultaneously be left handed and right handed when considered from different directions. The orientation dependence of handedness motivates a tensorial quantification of chirality relating directions to rotations. I will give an explicit example of such a tensorial measure of chirality for embedded surfaces, and show how the tensorial nature of chirality can be probed in experiments and exploited as a design principle.

  4. Micropatterning of cells reveals chiral morphogenesis

    PubMed Central

    2013-01-01

    Invariant left-right (LR) patterning or chirality is critical for embryonic development. The loss or reversal of LR asymmetry is often associated with malformations and disease. Although several theories have been proposed, the exact mechanism of the initiation of the LR symmetry has not yet been fully elucidated. Recently, chirality has been detected within single cells as well as multicellular structures using several in vitro approaches. These studies demonstrated the universality of cell chirality, its dependence on cell phenotype, and the role of physical boundaries. In this review, we discuss the theories for developmental LR asymmetry, compare various in vitro cell chirality model systems, and highlight possible roles of cell chirality in stem cell differentiation. We emphasize that the in vitro cell chirality systems have great promise for helping unveil the nature of chiral morphogenesis in development. PMID:23672821

  5. Separation of branched hexane isomers using zeolite molecular sieves

    SciTech Connect

    Huddersman, K.; Klimczyk, M.

    1996-02-01

    A range of small, medium and large pore zeolite, and their modified forms are studied for their ability to separate di- from monobranched isomers of hexane. The separation studies are carried out using high-temperature (250--350 C) gas chromatography. Beta(H,Ba) is found to be the most effective separator of 2,3-dimethylbutane and 3-methyl-pentane and is therefore studied for its sorption capacities toward the two hexane isomers. This work is directed to the improvement of the quality of petrol by separating hydrocarbon mixtures using zeolites. Since maximum hydrocarbon branching is desirable in petrol (hydrocarbons with a branching structure burn more efficiently and thus have a higher octane rating), catalytic isomerization is used to isomerize straight-chain hydrocarbons to their mono- or dibranched isomers.

  6. Separation of glyceride positional isomers by silver ion chromatography.

    PubMed

    Févrie, P; Bine, A; Dufossé, L; Grée, R; Yvergnaux, F

    2001-07-20

    Separation of triglyceride and diglyceride positional isomers by silver ion high-performance liquid chromatography coupled with an evaporative light-scattering detector is described. The triglyceride isomers had a fatty acid composition of CLC and CCL, where C and L were caprylic acid and linoleic acid, respectively. Diglyceride isomers, 1,2(2,3)-diglyceride and 1,3-diglyceride, which contained caprylic acid were separated too. A solvent system based on n-hexane, 2-propanol, ethyl acetate, and acetonitrile with a flow-rate of 0.8 ml/min was developed. Calibration curves of CLC and CCL were achieved with triolein as internal standard. Using this method, the incorporation of linoleic acid onto specific a position of glycerol backbone can be monitored. PMID:11510559

  7. Identification of the isomers using principal component analysis (PCA) method

    NASA Astrophysics Data System (ADS)

    Kepceoǧlu, Abdullah; Gündoǧdu, Yasemin; Ledingham, Kenneth William David; Kilic, Hamdi Sukur

    2016-03-01

    In this work, we have carried out a detailed statistical analysis for experimental data of mass spectra from xylene isomers. Principle Component Analysis (PCA) was used to identify the isomers which cannot be distinguished using conventional statistical methods for interpretation of their mass spectra. Experiments have been carried out using a linear TOF-MS coupled to a femtosecond laser system as an energy source for the ionisation processes. We have performed experiments and collected data which has been analysed and interpreted using PCA as a multivariate analysis of these spectra. This demonstrates the strength of the method to get an insight for distinguishing the isomers which cannot be identified using conventional mass analysis obtained through dissociative ionisation processes on these molecules. The PCA results dependending on the laser pulse energy and the background pressure in the spectrometers have been presented in this work.

  8. Metastable isomers - A new class of interstellar molecules

    NASA Technical Reports Server (NTRS)

    Green, S.; Herbst, E.

    1979-01-01

    The abundances of a variety of metastable isomers of small organic molecules, analogous to HNC/HCN, in dense interstellar clouds are considered. These metastable species, some of which are thought to exist as intermediates in laboratory organic chemical reactions, are of considerable interest to chemists. Current ideas of gas-phase, ion-molecule chemistry are utilized to demonstrate that such metastable species should often be present in dense clouds in sufficient abundance to be observed. Unfortunately, the spectral constants of metastable isomers have rarely been determined in the laboratory, and quantum chemical calculations of a varying degree of accuracy must be utilized; results are included of some new quantum chemical calculations. The interstellar chemistry and expected microwave spectra of a representative sample of possibly important interstellar metastable isomers are discussed.

  9. FY2010 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Miller, Erin A.; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for Special Nuclear Materials (SNM). Future work will include a follow-up measurement scheduled for December 2010 at LBNL. Lessons learned from the July 2010 measurements will be incorporated into these new measurements. Analysis of both the July and December experiments will be completed in a few months. A research paper to be submitted to a peer-reviewed journal will be drafted if the conclusions from the measurements warrant publication.

  10. Spectroscopy of {sup 144}Ho using recoil-isomer tagging

    SciTech Connect

    Mason, P. J. R; Cullen, D. M.; Scholey, C.; Greenlees, P. T.; Jakobsson, U.; Jones, P. M.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Nyman, M.; Peura, P.; Puurunen, A.; Rahkila, P.; Ruotsalainen, P.; Sorri, J.; Saren, J.; Uusitalo, J.; Xu, F. R.

    2010-02-15

    Excited states in the proton-unbound odd-odd nucleus {sup 144}Ho have been populated using the {sup 92}Mo({sup 54}Fe,pn){sup 144}Ho reaction and studied using the recoil-isomer-tagging technique. The alignment properties and signature splitting of the rotational band above the I{sup p}i=(8{sup +}){sup 144m}Ho isomer have been analyzed and the isomer confirmed to have a pih{sub 11/2} x nuh{sub 11/2} two-quasiparticle configuration. The configuration-constrained blocking method has been used to calculate the shapes of the ground and isomeric states, which are both predicted to have triaxial nuclear shapes with |gamma|approx =24 deg.

  11. Determining the number of isomers in X-, XY-, XYZ-, and XYZU-substituted D2 d allenes: Additive schemes for calculating enthalpies of vaporization

    NASA Astrophysics Data System (ADS)

    Nilov, D. Yu.; Smolyakov, V. M.

    2015-02-01

    Using Pólya's theorem, cycle indices are derived that identify the chiral and achiral substitution isomers of an allene (1,2-propadiene). Equations of symmetry that allow us to determine the number of isomers in a series and arrange the isomers according to families, depending on the number of substitution sites, are obtained. Eight- and nine-constant additive schemes based on the similarity between subgraphs in the molecular graphs (MGs) of a series of 120 molecules of X-, XY-, XYZ-, and XYZU-substituted allenes and the expansion of polygonal numbers (triangular, tetrahedral, and others) of a Pascal triangle are devised. Enthalpies of vaporization L NBP are calculated for 21 XY- and 120 XYZU-substituted allenes, respectively, not yet studied experimentally. It is shown that each coefficient of the scheme (the number of ways for superpositioning subgraphs with lengths i 1, i 2, ⋯ on molecular graphs of allene) is a result of partitioning triangular, tetrahedral, or four-dimensional tetrahedral numbers of a Pascal triangle.

  12. Baryon and chiral symmetry breaking

    SciTech Connect

    Gorsky, A.; Krikun, A.

    2014-07-23

    We briefly review the generalized Skyrmion model for the baryon recently suggested by us. It takes into account the tower of vector and axial mesons as well as the chiral symmetry breaking. The generalized Skyrmion model provides the qualitative explanation of the Ioffe’s formula for the baryon mass.

  13. Chiral phosphines in nucleophilic organocatalysis

    PubMed Central

    Xiao, Yumei; Sun, Zhanhu

    2014-01-01

    Summary This review discusses the tertiary phosphines possessing various chiral skeletons that have been used in asymmetric nucleophilic organocatalytic reactions, including annulations of allenes, alkynes, and Morita–Baylis–Hillman (MBH) acetates, carbonates, and ketenes with activated alkenes and imines, allylic substitutions of MBH acetates and carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. PMID:25246969

  14. Dynamics of the chiral transition

    SciTech Connect

    Gavin, S.

    1994-07-01

    Measurements of disoriented chiral condensates (DCC) in heavy ion collisions at RHIC can yield fundamental information on the nature of the QCD phase transition. I review theoretical efforts to understand DCC formation and present work in progress on possible experimental ramifications.

  15. Dynamics of the chiral transition

    SciTech Connect

    Gavin, S.

    1995-07-10

    Measurements of disoriented chiral condensates (DCC) in heavy ion collisions at RHIC can yield fundamental information on the nature of the QCD phase transition. I review theoretical efforts to understand DCC formation and present work in progress on their possible experimental ramifications. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  16. Effect of red cyst cell inoculation and iron(II) supplementation on autotrophic astaxanthin production by Haematococcus pluvialis under outdoor summer conditions.

    PubMed

    Hong, Min-Eui; Choi, Yoon Young; Sim, Sang Jun

    2016-01-20

    The negative effect of heat stress on the autotrophic astaxanthin production by Haematococcus pluvialis has been observed during outdoor culture in summer. Under the summer conditions, the proliferation of vegetative cells was highly halted in the green stage and the inducibility in the biosynthesis of astaxanthin was partly hindered in the red stage. Herein, under outdoor summer conditions in which variations of the diurnal temperature occur, heat-stress-driven inefficient vegetative growth of H. pluvialis was highly improved by inoculating the red cyst cells; thereby, maintaining relatively moderate intracellular carotenoid levels in the green stage. Subsequently, a remarkably enhanced astaxanthin titer was successfully obtained by supplementing 50 μM iron(II) to induce the heat stress-driven Haber-Weiss reaction in the red stage. As a result, the productivity of astaxanthin in the cells cultured under summer temperature conditions (23.4-33.5 °C) using the two methods of red cell (cyst) inoculation and the iron(Fe(2+)) supplementation was increased by 147% up to 5.53 mg/L day compared with that of the cells cultured under spring temperature conditions (17.5-27.3 °C). Our technical solutions will definitely improve the annual natural astaxanthin productivity in H. pluvialis in locations confronted by hot summer weather, particularly in large-scale closed photobioreactor systems. PMID:26630998

  17. Evidence for the effect of sorption enantioselectivity on the availability of chiral pesticide enantiomers in soil.

    PubMed

    Gámiz, Beatriz; Facenda, Gracia; Celis, Rafael

    2016-06-01

    Although enantioselective sorption to soil particles has been proposed as a mechanism that can potentially influence the availability of individual chiral pesticide enantiomers in the environment, environmental fate studies generally overlook this possibility and assume that only biotic processes can be enantioselective, whereas abiotic processes, such as sorption, are non-enantioselective. In this work, we present direct evidence for the effect of the enantioselective sorption of a chiral pesticide in a natural soil on the availability of the single pesticide enantiomers for transport. Batch sorption experiments, with direct determination of the sorbed amounts, combined with column leaching tests confirmed previous observations that from non-racemic aqueous solutions the sorption of the chiral fungicide metalaxyl on the soil appeared to be enantioselective, and further demonstrated that the enantiomer that was sorbed to a greater extent (R-metalaxyl, Kd = 1.73 L/kg) exhibited retarded leaching compared to its optical isomer (S-metalaxyl, Kd = 1.15 L/kg). Interconversion and degradation of the pesticide enantiomers, which are potential experimental artifacts that can lead to erroneous estimates of sorption and its enantioselectivity, were discarded as possible causes of the observed enantioselective behavior. The results presented here may have very important implications for a correct assessment of the environmental fate of chiral pesticides that are incorporated into the environment as non-racemic mixtures, and also of aged chiral pesticide residues that have been transformed from racemic to non-racemic by biologically-mediated processes. PMID:27060281

  18. Chiral conducting surfaces via electrochemical oxidation of L-leucine-oligothiophenes.

    PubMed

    McTiernan, Christopher D; Omri, Karim; Chahma, M'hamed

    2010-09-17

    Polythiophenes bearing a specific chiral center such as L-leucine have been prepared via the electrochemical oxidation of a series of L-leucine functionalized oligothiophenes (monothiophenes and terthiophenes). These oligothiophenes have been prepared through the condensation of L-leucine methyl ester and the corresponding thiophene monomers in the presence of hydroxybenzotriazole (HOBt) and N,N'-dicyclohexylcarbodiimide (DCC) followed by hydrolysis of the esters. The electroactive polymers are electrochemically stable and exhibit excellent adhesive properties on electrode surfaces (platinum, gold, and glassy carbon) as well as interesting optical properties in both doped and undoped states. Hydrogen bonds between a free amino acid (L-leucine, D-leucine, L-alanine, D-alanine, and D/L-alanine) and the L-leucine based polythiophenes (chiral conducting surface) were probed using cyclic voltammetry. Preliminary results show that the capacitive current of a modified L-leucine-polythiophene electrode decreases as a result of the formation of a hydrogen bond barrier on the surface of the chiral conducting surface accompanied with a shift of the oxidation potential. Cyclic voltammetry responses resulting from the interaction of the chiral conducting surface with L and Dfree amino acid isomers are similar. The formation of hydrogen bonds between the chiral conducting surfaces and the free amino acids was characterized by (1)H NMR. A chemical shift was observed for the N-H group in monomer 6 as a result of the hydrogen bond formation between the L-leucine methyl ester (D-leucine methyl ester, D/L-leucine methyl ester) and monomer 6. PMID:20718451

  19. Role of chirality in peptide-induced formation of cholesterol-rich domains

    PubMed Central

    2005-01-01

    The chiral specificity of the interactions of peptides that induce the formation of cholesterol-rich domains has not been extensively investigated. Both the peptide and most lipids are chiral, so there is a possibility that interactions between peptide and lipid could require chiral recognition. On the other hand, in our models with small peptides, the extent of folding of the peptide to form a specific binding pocket is limited. We have determined that replacing cholesterol with its enantiomer, ent-cholesterol, alters the modulation of lipid organization by peptides. The phase-transition properties of SOPC (1-stearoyl-2-oleoylphosphatidylcholine):cholesterol [in a 6:4 ratio with 0.2 mol% PtdIns(4,5)P2] are not significantly altered when ent-cholesterol replaces cholesterol. However, in the presence of 10 mol% of a 19-amino-acid, N-terminally myristoylated fragment (myristoyl-GGKLSKKKKGYNVNDEKAK-amide) of the protein NAP-22 (neuronal axonal membrane protein), the lipid mixture containing cholesterol undergoes separation into cholesterol-rich and cholesterol-depleted domains. This does not occur when ent-cholesterol replaces cholesterol. In another example, when N-acetyl-Leu-Trp-Tyr-Ile-Lys-amide (N-acetyl-LWYIK-amide) is added to SOPC:cholesterol (7:3 ratio), there is a marked increase in the transition enthalpy of the phospholipid, indicating separation of a cholesterol-depleted domain of SOPC. This phenomenon completely disappears when ent-cholesterol replaces cholesterol. The all-D-isomer of N-acetyl-LWYIK-amide also induces the formation of cholesterol-rich domains with natural cholesterol, but does so to a lesser extent with ent-cholesterol. Thus specific peptide chirality is not required for interaction with cholesterol-containing membranes. However, a specific chirality of membrane lipids is required for peptide-induced formation of cholesterol-rich domains. PMID:15929726

  20. Anaerobic degradation of phthalate isomers by methanogenic consortia

    SciTech Connect

    Kleerebezem, R.; Pol, L.W.H.; Lettinga, G.

    1999-03-01

    Three methanogenic enrichment cultures, grown on ortho-phthalate, iso-phthalate, or terephthalate were obtained from digested sewage sludge or methanogenic granular sludge. Cultures grown on one of the phthalate isomers were not capable of degrading the other phthalate isomers. All three cultures had the ability to degrade benzoate. Maximum specific growth rates ({mu}{sub S}{sup max}) and biomass yields (Y{sub X{sub tot}S}) of the mixed cultures were determined by using both the phthalate isomers and benzoate as substrates. Comparable values for these parameters were found for all three cultures. Values for {mu}{sub X}{sup max} and Y{sub X{sub tot}S} were higher for growth on benzoate compared to the phthalate isomers. Based on measured and estimated values for the microbial yield of the methanogens in the mixed culture, specific yields for the phthalate and benzoate fermenting organisms were calculated. A kinetic model, involving three microbial species, was developed to predict intermediate acetate and hydrogen accumulation and the final production of methane. Values for the ratio of the concentrations of methanogenic organisms, versus the phthalate isomer and benzoate fermenting organisms, and apparent half-saturation constants (K{sub S}) for the methanogens were calculated. By using this combination of measured and estimated parameter values, a reasonable description of intermediate accumulation and methane formation was obtained, with the initial concentration of phthalate fermenting organisms being the only variable. The energetic efficiency for growth of the fermenting organisms on the phthalate isomers was calculated to be significantly smaller than for growth on benzoate.

  1. Computation of Mössbauer isomer shifts from first principles

    NASA Astrophysics Data System (ADS)

    Zwanziger, J. W.

    2009-05-01

    Computation of the observables of a Mössbauer spectrum, primarily the isomer shift, from a first-principles approach is described. The framework used is density functional theory using the projector augmented wave formalism (DFT PAW), which enables efficient computation even of many-electron solids such as SnCl2. The proper PAW version of the isomer shift is derived and shown to be correct through comparison of computed shifts and experiment in a variety of compounds based on tin, germanium and zinc. The effects of pressure are considered as well as motional effects including the Lamb-Mössbauer factor and the second-order Doppler shift.

  2. Isomer Triggering via Nuclear Excitation by Electron Capture

    SciTech Connect

    Palffy, Adriana; Evers, Joerg; Keitel, Christoph H.

    2007-10-26

    Triggering of long-lived nuclear isomeric states via coupling to the atomic shells in the process of nuclear excitation by electron capture (NEEC) is studied. NEEC occurring in highly charged ions can excite the isomeric state to a triggering level that subsequently decays to the ground state. We present total cross sections for NEEC isomer triggering considering experimentally confirmed low-lying triggering levels and reaction rates based on realistic experimental parameters in ion storage rings. A comparison with other isomer triggering mechanisms shows that, among these, NEEC is the most efficient.

  3. Synthesis and characterization of tetrakis-silylated C60 isomers.

    PubMed

    Maeda, Yutaka; Rahman, G M Aminur; Wakahara, Takatsugu; Kako, Masahiro; Okamura, Mutsuo; Sato, Soichi; Akasaka, Takeshi; Kobayashi, Kaoru; Nagase, Shigeru

    2003-08-22

    A photochemical reaction of C(60) with disilane in a 2:3 ratio affords the isomer mixture of the tetrakis-adduct of C(60)((t)BuPh(2)Si)(4) as the major product. The use of a three-stage HPLC separation system isolated three of their isomers. Their structural assignments were based on FAB mass, UV-vis, NMR, and cyclic voltammetry (CV) measurements. The CV analysis showed that the terakis-adduct has lower oxidation and higher reduction potentials than the bis-adduct C(60)((t)BuPh(2)Si)(2) and the parent C(60). PMID:12919050

  4. New high spin isomers obtained in thermal fission

    SciTech Connect

    Fogelberg, B.; Mach, H.; Gausemel, H.; Omtvedt, J. P.; Mezilev, K. A.

    1998-10-26

    The product nuclei following fission often are initially highly excited and have high angular momenta. As a consequence, there is a substantial probability for the population of isomeric yrast traps in the vicinity of closed shells. The excitation energies and decay properties of such isomers give important formation regarding the shell structure and interaction energies. Recent experiments at the OSIRIS mass separator have revealed a number of isomers in the {sup 132}Sn region having angular momenta exceeding 10 units. A brief presentation is given of some experimental results and their interpretation.

  5. Differentiation of optical isomers through enhanced weak-field interactions

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.

    1980-01-01

    The influence of weak field interaction terms due to the cooperative effects which arise from a macroscopic assemblage of interacting sites is studied. Differential adsorption of optical isomers onto an achiral surface is predicted to occur if the surface was continuous and sufficiently large. However, the quantity of discontinuous crystal surfaces did not enhance the percentage of differentiation and thus the procedure of using large quantities of small particles was not a viable technique for obtaining a detectable differentiation of optical isomers on an achiral surface.

  6. Nuclear chiral dynamics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Holt, Jeremy W.; Kaiser, Norbert; Weise, Wolfram

    2013-11-01

    This presentation reviews an approach to nuclear many-body systems based on the spontaneously broken chiral symmetry of low-energy QCD. In the low-energy limit, for energies and momenta small compared to a characteristic symmetry breaking scale of order 1 GeV, QCD is realized as an effective field theory of Goldstone bosons (pions) coupled to heavy fermionic sources (nucleons). Nuclear forces at long and intermediate distance scales result from a systematic hierarchy of one- and two-pion exchange processes in combination with Pauli blocking effects in the nuclear medium. Short distance dynamics, not resolved at the wavelengths corresponding to typical nuclear Fermi momenta, are introduced as contact interactions between nucleons. Apart from a set of low-energy constants associated with these contact terms, the parameters of this theory are entirely determined by pion properties and low-energy pion-nucleon scattering observables. This framework (in-medium chiral perturbation theory) can provide a realistic description of both isospin-symmetric nuclear matter and neutron matter, with emphasis on the isospin-dependence determined by the underlying chiral NN interaction. The importance of three-body forces is emphasized, and the role of explicit Δ(1232)-isobar degrees of freedom is investigated in detail. Nuclear chiral thermodynamics is developed and a calculation of the nuclear phase diagram is performed. This includes a successful description of the first-order phase transition from a nuclear Fermi liquid to an interacting Fermi gas and the coexistence of these phases below a critical temperature Tc. Density functional methods for finite nuclei based on this approach are also discussed. Effective interactions, their density dependence and connections to Landau Fermi liquid theory are outlined. Finally, the density and temperature dependences of the chiral (quark) condensate are investigated.

  7. Application of Roof-Shape Amines as Chiral Solvating Agents for Discrimination of Optically Active Acids by NMR Spectroscopy: Study of Match-Mismatch Effect and Crystal Structure of the Diastereomeric Salts.

    PubMed

    Gupta, Riddhi; Gonnade, Rajesh G; Bedekar, Ashutosh V

    2016-09-01

    Optically active roof-shape amines were prepared and scanned as chiral solvating agents to study molecular recognition of acids by NMR analysis. Three types of amines were studied to establish a match-mismatch effect for structurally diverse acid analytes. Single-crystal X-ray diffraction analysis was performed on the diastereomeric salts of roof-shape amines and both isomers of mandelic acid to establish molecular conformation and correlate the absolute configuration with the observed NMR shift. The present system also recognizes the two isomers of weakly acidic BINOL and its derivatives. PMID:27484455

  8. DNA-decorated carbon nanotube-based FETs as ultrasensitive chemical sensors: Discrimination of homologues, structural isomers, and optical isomers

    NASA Astrophysics Data System (ADS)

    Khamis, S. M.; Jones, R. A.; Johnson, A. T. C.; Preti, G.; Kwak, J.; Gelperin, A.

    2012-06-01

    We have explored the abilities of all-electronic DNA-carbon nanotube (DNA-NT) vapor sensors to discriminate very similar classes of molecules. We screened hundreds of DNA-NT devices against a panel of compounds chosen because of their similarities. We demonstrated that DNA-NT vapor sensors readily discriminate between series of chemical homologues that differ by single methyl groups. DNA-NT devices also discriminate among structural isomers and optical isomers, a trait common in biological olfactory systems, but only recently demonstrated for electronic FET based chemical sensors.

  9. Chiral sensing by nonchiral tetrapyrroles.

    PubMed

    Labuta, Jan; Hill, Jonathan P; Ishihara, Shinsuke; Hanyková, Lenka; Ariga, Katsuhiko

    2015-03-17

    Enantiomeric excess (ee) is a measure of the purity of an enantiomer of a chiral compound with respect to the presence of the complementary enantiomer. It is an important aspect of chemistry, especially in the fields of pharmaceuticals and asymmetric catalysis. Existing methods for determination of enantiomeric excesses using nuclear magnetic resonance (NMR) spectroscopy mostly rely on special chiral reagents (auxiliaries) that form two or more diastereomeric complexes with a chiral compound. As a result of this, the NMR spectrum of each enantiomer is different, allowing the determination of enantiomeric excess. In this Account, we describe a molecular design process that has allowed us to prepare prochiral solvating agents for NMR determination of ee of a wide variety of analyte types. At the outset of this work, we initially encountered the phenomenon of NMR peak splitting in the oxoporphyrinogen (OxP) host component of a supramolecular host-guest complex, where the extent of the splitting is apparently proportional to the guests' ee. Upon closer examination of the mechanism of action, it was found that several complicating factors, including prototropic tautomerism, macrocyclic inversion (ring-flipping), and 1:2 host-guest stoichiometry, obstruct potential applications of OxP as a chiral solvating agent. By considering the molecular conformation of the OxP host, a saddle-shaped calix[4]pyrrole, we moved to study the tetraphenylporphyrin (TPP) dication since it has a similar form, and it was found that it could also be used to probe ee. However, although TPP does not suffer from disadvantageous tautomeric processes, it is still subject to macrocyclic inversion and has the additional serious disadvantage of operating for ee sensing only at depressed temperatures. The intrinsic disadvantages of the OxP and TPP systems were finally overcome by covalently modifying the OxP chromophore by regioselective N-alkylation at one face of the molecule. This procedure yields a

  10. Sphingomonas lacus sp. nov., an astaxanthin-dideoxyglycoside-producing species isolated from soil near a pond.

    PubMed

    Kim, Jin Ho; Kim, Se Hyeuk; Kim, Kyong Ho; Lee, Pyung Cheon

    2015-09-01

    Taxonomic studies were performed on an astaxanthin-dideoxyglycoside-producing strain, designated PB304(T), isolated from soil near a pond in Daejeon city, South Korea. Cells of strain PB304(T) were Gram-staining-negative, strictly aerobic, orange-coloured and motile, and occurred as single or paired short chains. PB304(T) did not contain bacteriochlorophyll a. 16S rRNA gene sequence analysis revealed that strain PB304(T) was closely related to 'Sphingomonas humi' KCTC 12341 (98.7%), Sphingomonas kaistensis KCTC 12344(T)(97.9%), Sphingomonas astaxanthinifaciens DSM 22298(T) (97.6%) and Sphingomonas ginsengisoli KCTC 12630(T) (97.5%). Analysis of pufLM gene sequences revealed strain PB304(T) to be closely related to 'S. humi' KCTC 12341 (88.1%). The major cellular fatty acids were C16 : 0, summed feature 4 (comprising iso-C15 : 0 2-OH and/or C16 : 1ω7c), and summed feature 7 (comprising C18  : 1ω7c/ω9t/ω12t). Ubiquinone 10 (Q-10) was the sole quinone identified, and the major pigment was astaxanthin dideoxyglycoside. The major polar lipids were sphingoglycolipid, phosphatidylcholine, phosphatidylglycerol, diphosphatidylglycerol and phosphatidylethanolamine. The polyamine was spermidine. The DNA-DNA relatedness values of strain PB304(T) with respect to its closest phylogenetic neighbours were 57.1% for 'S. humi' KCTC 12341, 51.2% for Sphingomonas kaistensis KCTC 12334T, 50.6% for Sphingomonas astaxanthinifaciens DSM 22298(T) and 50.2% for Sphingomonas ginsengisoli KCTC 12630(T). The DNA G+C content of strain PB304(T) was 66.6 mol%. On the basis of the phenotypic, chemotaxonomic and phylogenetic data, strain PB304T is concluded to represent a novel species of the genus Sphingomonas, for which the name Sphingomonas lacus is proposed. The type strain is PB304(T) ( = KCTC 32458(T) = CECT 8383(T)). PMID:25985832

  11. Chiral logarithms in quenched QCD

    SciTech Connect

    Y. Chen; S. J. Dong; T. Draper; I. Horvath; F. X. Lee; K. F. Liu; N. Mathur; and J. B. Zhang

    2004-08-01

    The quenched chiral logarithms are examined on a 163x28 lattice with Iwasaki gauge action and overlap fermions. The pion decay constant fpi is used to set the lattice spacing, a = 0.200(3) fm. With pion mass as low as {approx}180 MeV, we see the quenched chiral logarithms clearly in mpi2/m and fP, the pseudoscalar decay constant. The authors analyze the data to determine how low the pion mass needs to be in order for the quenched one-loop chiral perturbation theory (chiPT) to apply. With the constrained curve-fitting method, they are able to extract the quenched chiral logarithmic parameter delta together with other low-energy parameters. Only for mpi<=300 MeV do we obtain a consistent and stable fit with a constant delta which they determine to be 0.24(3)(4) (at the chiral scale Lambdachi = 0.8 GeV). By comparing to the 123x28 lattice, they estimate the finite volume effect to be about 2.7% for the smallest pion mass. They also fitted the pion mass to the form for the re-summed cactus diagrams and found that its applicable region is extended farther than the range for the one-loop formula, perhaps up to mpi {approx}500-600 MeV. The scale independent delta is determined to be 0.20(3) in this case. The authors study the quenched non-analytic terms in the nucleon mass and find that the coefficient C1/2 in the nucleon mass is consistent with the prediction of one-loop chiPT. They also obtain the low energy constant L5 from fpi. They conclude from this study that it is imperative to cover only the range of data with the pion mass less than {approx}300 MeV in order to examine the chiral behavior of the hadron masses and decay constants in quenched QCD and match them with quenched one-loop chiPT.

  12. Flexible metal–organic supramolecular isomers for gas separation

    SciTech Connect

    Motkuri, Radha K.; Tian, Jian; Thallapally, Praveen K.; Fernandez, Carlos A.; Dalgarno, Scott J.; Warren, John E.; McGrail, B. Peter; Atwood, Jerry L.

    2010-01-01

    Here in we report three porous metal-organic supramolecular isomers (PtS, Diamondoid and Lonsdaleite networks) generated from a single building block (tetrakis[4-(carboxyphenyl)oxamethyl]methane, 1), with the differences in solid-state packing, amount of gas uptake and selectivity towards other gases and so on

  13. Identification of position isomers by energy-resolved mass spectrometry.

    PubMed

    Menachery, Sunil Paul M; Laprévote, Olivier; Nguyen, Thao P; Aravind, Usha K; Gopinathan, Pramod; Aravindakumar, Charuvila T

    2015-07-01

    This study reports an energy-resolved mass spectrometric (ERMS) strategy for the characterization of position isomers derived from the reaction of hydroxyl radicals ((●)OH) with diphenhydramine (DPH) that are usually hard to differentiate by other methods. The isomer analogues formed by (●)OH attack on the side chain of DPH are identified with the help of a specific fragment ion peak (m/z 88) in the collision-induced dissociation (CID) spectrum of the protonated molecule. In the negative ion mode, the breakdown curves of the deprotonated molecules show an order of stability (supported by density functional theory (DFT) calculations) ortho > meta > para of the positional isomers formed by the hydroxylation of the aromatic ring. The gas phase stability of the deprotonated molecules [M - H](-) towards the benzylic cleavage depends mainly on the formation of intramolecular hydrogen bonds and of the mesomeric effect of the phenol hydroxyl. The [M - H](-) molecules of ortho and meta isomers result a peak at m/z 183 with notably different intensities because of the presence/absence of an intramolecular hydrogen bonding between the OH group and C9 protons. The ERMS approach discussed in this report might be an effective replacement for the conventional methods that requires very costly and time-consuming separation/purification methods along with the use of multi-spectroscopic methods. PMID:26349650

  14. Short-lived isomers in 192Po and 194Po

    NASA Astrophysics Data System (ADS)

    Andel, B.; Andreyev, A. N.; Antalic, S.; Heßberger, F. P.; Ackermann, D.; Hofmann, S.; Huyse, M.; Kalaninová, Z.; Kindler, B.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Nishio, K.; Page, R. D.; Sulignano, B.; Van Duppen, P.

    2016-06-01

    Isomeric states in 194Po and 192Po were studied at the velocity filter SHIP. The isotopes were produced in the fusion-evaporation reactions 141Pr(56Fe, p 2 n )194Po and 144Sm(51V, p 2 n )192Po . Several new γ -ray transitions were attributed to the isomers and γ -γ coincidences for both isomers were studied for the first time. The 459-keV transition earlier, tentatively proposed as de-exciting the isomeric level in 194Po, was replaced by a new 248-keV transition, and the spin of this isomer was reassigned from (11-) to (10-). The de-excitation of the (11-) isomeric level in 192Po by the 154-keV transition was confirmed and a parallel de-excitation by a 733-keV (E 3 ) transition to (8+) level of the ground-state band was suggested. Moreover, side feeding to the (4+) level of the ground-state band was proposed. The paper also discusses strengths of transitions de-exciting 11- isomers in neighboring Po and Pb isotopes.

  15. Conjugated Linoleic Acids and Inflammation: Isomer and Tissue Specific Responses

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conjugated linoleic acids (CLAs) are a series of geometric and positional isomers of linoleic acid that have been studied for their effects against diabetes, cancer, and atherosclerosis, all conditions with an inflammatory component. Despite the continued interest in CLA, there are many controversi...

  16. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Lozovoy, Vadim; Levine, Benjamin; Dantus, Marcos

    2014-05-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  17. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Levine, Benjamin; Lozovoy, Vadim; Dantus, Marcos

    2014-03-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  18. Identification of a shape isomer in 235U.

    PubMed

    Oberstedt, A; Oberstedt, S; Gawrys, M; Kornilov, N

    2007-07-27

    The shape isomer in 235U has been searched for in a neutron-induced fission experiment on 234U, which was performed at the isomer spectrometer NEPTUNE of the EC-JRC IRMM. A neutron source, with a tunable pulse frequency in the Hz to kHz range and its individually adjustable neutron pulse width in connection with an appropriate detector system turned out to be the ideal instrument to perform an isomer search, when decay half-lives above 100 micros are expected. From the delayed fission events observed for two different NEPTUNE settings and at mean incident neutron energies En=0.95 and 1.27 MeV the isomeric fission half-life could be determined to be T1/2=(3.6+/-1.8) ms. The corresponding cross section was determined to sigmaif=(10+/-8) microb. With these results an experimental confirmation for the existence of a superdeformed shape isomer in odd-uranium isotopes is given for the first time. PMID:17678355

  19. Isomer-Specific Distribution of Perfluoroalkyl Substances in Blood.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Jiang, Weiwei; Zhu, Lingyan; Martin, Jonathan W

    2016-07-19

    Perfluoroalkyl substances (PFASs) such as perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and PFOS-precursors are routinely measured in human plasma and serum, but their relative abundance in the blood cell fraction has not been carefully examined, particularly at the isomer-specific level. Human plasma and whole blood were collected and partitioning behaviors of PFASs and their isomers between plasma and blood cells were investigated. In human samples, mass fraction in plasma (Fp) for PFASs increased among perfluoroalkyl carboxylates as the carbon chain length increased from C6 (mean 0.24) to C11 (0.87), indicating preference for the plasma fraction with increasing chain length. However, among perfluoroalkyl sulfonates, PFHxS (mean 0.87) had a slightly higher Fp than PFOS (0.85). In vitro assays with spiked Sprague-Dawley rat blood were also conducted, and the results showed that PFOS-precursors had lower Fp values than perfluoroalkyl acids, with perfluoroctanesulfonamide having the lowest Fp (mean 0.24). Consistently, linear isomers of PFOS and PFOS-precursors had lower mean Fp than their corresponding total branched isomers. Multiplying by a factor of 2 is not a reasonable method to convert from whole blood to plasma PFAS concentrations, and current ratios could be used as more accurate conversion factors. PMID:27295125

  20. Synthesis and conformational studies of chiral macrocyclic [1.1.1]metacyclophanes containing benzofuran rings.

    PubMed

    Islam, Md Monarul; Tomiyasu, Hirotsugu; Matsumoto, Taisuke; Tanaka, Junji; Rahman, Shofiur; Georghiou, Paris E; Redshaw, Carl; Yamato, Takehiko

    2015-09-14

    Macrocyclic [1.1.1]metacyclophanes (MCPs) containing benzene and benzofuran rings linked by methylene bridges and which can be viewed as calixarene analogues, have been synthesized by demethylation of [3.3.1]MCP-diones with trimethylsilyl iodide (TMSI) in MeCN. The [3.3.1]MCP-diones are synthesized by using (p-tolylsulfonyl)methyl isocyanide (TosMIC) as the cyclization reagent in N,N-dimethylformamide (DMF) with an excess of sodium hydride. (1)H NMR spectroscopy revealed that the remaining hydroxyl group on the phenyl ring is involved in intramolecular hydrogen bonding with the oxygen of one of the benzofuran rings. O-Methylation at the lower rim of monohydroxy[1.1.1]MCP in the presence of K2CO3 in acetone afforded a novel and inherently chiral calixarene analogue, namely the macrocyclic [1.1.1]MCP, possessing C1 symmetry. The inherent chirality of the two conformers was characterized by (1)H NMR spectroscopy by addition of an excess of Pirkle's chiral shift reagent, which caused a splitting of the corresponding methylene protons to AB patterns. Single crystal X-ray analysis revealed the adoptation of a hemisphere-shaped cone isomer. DFT calculations were carried out to investigate the energy-minimized structures and the hydrogen bonds of the synthesized MCPs. PMID:26220058

  1. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal isomers and 4% aromatic...

  2. Computational Docking of the Isomers of Nonylphenol to the Ligand Binding Domain of the Estrogen Receptor

    EPA Science Inventory

    Nonylphenols are environmentally persistent endocrine disrupting chemicals. They exist in the environment as complex mixtures containing many nonylphenol isomers. Environmental mixtures of nonylphenols, along with a few single isomers have been tested for their capacity to inte...

  3. FY2011 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-10-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured [Ressler 2010]. The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 {mu}s. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  4. Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

    NASA Astrophysics Data System (ADS)

    Katsuno, Hiroyasu; Uwaha, Makio

    2016-01-01

    By grinding crystals in a solution, the chirality of crystal structure (and the molecular chirality for the case of chiral molecules as well) can be converted, and the cause of the phenomenon is attributed to crystal growth with chiral clusters. We show that the recently found chirality conversion with a periodic change of temperature can also be explained by crystal growth with chiral clusters. With the use of a generalized Becker-Döring model, which includes enantio-selective incorporation of small chiral clusters to large solid clusters, the change of cluster distribution and the mass flow between clusters are studied. The chiral clusters act as a reservoir to pump out the minority species to the majority, and the exponential amplification of the enantiomeric excess found in the experiment is reproduced in the numerical calculation.

  5. Isomer-specific combustion chemistry in allene and propyne flames

    SciTech Connect

    Hansen, Nils; Miller, James A.; Westmoreland, Phillip R.; Kasper, Tina; Kohse-Hoeinghaus, Katharina; Wang, Juan; Cool, Terrill A.

    2009-11-15

    A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C{sub 3}H{sub 4} isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O{sub 2}/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C{sub 6} aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C{sub 3}H{sub 5} potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007) 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction. (author)

  6. Production of long-lived hafnium isomers in reactor irradiations

    NASA Astrophysics Data System (ADS)

    Karamian, S. A.; Carroll, J. J.; Adam, J.; Kulagin, E. N.; Shabalin, E. P.

    2006-06-01

    Experiments on production of long-lived Hf178m isomer in reactor irradiations are described. Properties of this nuclide are promising for its potential application as a relatively safe power source characterized by high density of accumulated energy. Metal natHf samples were activated in the Dubna IBR-2 reactor at positions corresponding to different neutron fluxes. Samples were bare or shielded by Cd and B 4C layers. The gamma activity of the samples was analyzed with Ge gamma spectrometers during a two-year period following their irradiation. In the presence of dominant activation products 175Hf and 181Hf, the high-spin isomers Hf178m and Hf179m were also detected despite relatively low levels. The isomer-to-ground state ratios and cross-sections were determined from the measured yields. For Hf178m, the cross-section for burnup (destruction) by neutron capture after its production was also estimated, clarifying the results from earlier experiments. In the context of suggestions for use of Hf178m for applications, the results confirm that large-scale production of this isomer by reactor irradiations is not feasible. In contrast, the efficiency of production of Hf179m is much higher and an amount of about 10 16 atoms may be produced in standard reactor irradiations. For Hf178m, more productive methods are known, in particular fast neutron irradiations at E n ≥ 14 MeV and spallation reactions at intermediate energies. Neutron cross-sections for isomers may also be significant in astrophysics.

  7. Cyclodextrin and its complexation for resolution of isomers using diffusion ordered spectroscopy

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin R.; Srinivasa; Suryaprakash, N.

    2013-02-01

    Diffusion ordered spectroscopy (DOSY) generally fails to separate the peaks pertaining to isomeric species possessing identical molecular weights and similar hydrodynamic radii. The present study demonstrates the resolution of isomers using α/β-cyclodextrin as a co-solute by Matrix Assisted Diffusion Ordered Spectroscopy. The resolution of isomers has been achieved by measuring the significant differences in the diffusion rates between the positional isomers of aminobenzoic acids, benzenedicarboxylic acids and between the cis, trans isomers, fumaric acid and maleic acid.

  8. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-01-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes. PMID:24548992

  9. Asymmetric synthesis using chiral-encoded metal

    PubMed Central

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  10. Molecular chirality: language, history, and significance.

    PubMed

    Gal, Joseph

    2013-01-01

    In this chapter some background material concerning molecular chirality and enantiomerism is presented. First some basic chemical-molecular aspects of chirality are reviewed, after which certain relevant terminology whose use in the literature has been problematic is discussed. Then an overview is provided of some of the early discoveries that laid the foundations of the science of molecular chirality in chemistry and biology, including the discovery of the phenomenon of molecular chirality by L. Pasteur, the proposals for the asymmetric carbon atom by J.H. van 't Hoff and J.A. Lebel, Pasteur's discovery of biological enantioselectivity, the discovery of enantioselectivity at biological receptors by A. Piutti, the studies of enzymatic stereoselectivity by E. Fischer, and the work on enantioselectivity in pharmacology by A. Cushny. Finally, the role of molecular chirality in pharmacotherapy and new-drug development, arguably one of the main driving forces for the current intense interest in the phenomenon of molecular chirality, is discussed. PMID:23666078

  11. Stable Pentaquarks from Strange Chiral Multiplets

    SciTech Connect

    Silas Beane

    2004-12-01

    The assumption of strong diquark correlations in the QCD spectrum suggests flavor multiplets of hadrons that are degenerate in the chiral limit. Generally it would be unnatural for there to be degeneracy in the hadron spectrum that is not protected by a QCD symmetry. Here we show--for pentaquarks constructed from diquarks--that these degeneracies can be naturally protected by the full chiral symmetry of QCD. The resulting chiral multiplet structure recovers the ideally-mixed pentaquark mass spectrum of the diquark model, and interestingly, requires that the axial couplings of the pentaquarks to states outside the degenerate multiplets vanish in the chiral limit. This result suggests that if these hadrons exist, they are stable in the chiral limit and therefore have widths that scale as the fourth power of the kaon mass over the chiral symmetry breaking scale. Natural-size widths are of order a few MeV.

  12. Anomalous Maxwell equations for inhomogeneous chiral plasma

    NASA Astrophysics Data System (ADS)

    Gorbar, E. V.; Shovkovy, I. A.; Vilchinskii, S.; Rudenok, I.; Boyarsky, A.; Ruchayskiy, O.

    2016-05-01

    Using the chiral kinetic theory we derive the electric and chiral current densities in inhomogeneous relativistic plasma. We also derive equations for the electric and chiral chemical potentials that close the Maxwell equations in such a plasma. The analysis is done in the regimes with and without a drift of the plasma as a whole. In addition to the currents present in the homogeneous plasma (Hall current, chiral magnetic, chiral separation, and chiral electric separation effects, as well as Ohm's current) we derive several new terms associated with inhomogeneities of the plasma. Apart from various diffusionlike terms, we find also new dissipationless terms that are independent of relaxation time. Their origin can be traced to the Berry curvature modifications of the kinetic theory.

  13. Asymmetric synthesis using chiral-encoded metal.

    PubMed

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  14. Chiral description of massive gravity

    NASA Astrophysics Data System (ADS)

    Alexandrov, Sergei; Krasnov, Kirill; Speziale, Simone

    2013-06-01

    We propose and study a new first order version of the ghost-free massive gravity. Instead of metrics or tetrads, it uses a connection together with Plebanski's chiral 2-forms as fundamental variables, rendering the phase space structure similar to that of SU(2) gauge theories. The chiral description simplifies computations of the constraint algebra, and allows us to perform the complete canonical analysis of the system. In particular, we explicitly compute the secondary constraint and carry out the stabilization procedure, thus proving that in general the theory propagates 7 degrees of freedom, consistently with previous claims. Finally, we point out that the description in terms of 2-forms opens the door to an infinite class of ghost-free massive bi-gravity actions. Our results apply directly to Euclidean signature. The reality conditions to be imposed in the Lorentzian signature appear to be more complicated than in the usual gravity case and are left as an open issue.

  15. Bootstrapping N=2 chiral correlators

    NASA Astrophysics Data System (ADS)

    Lemos, Madalena; Liendo, Pedro

    2016-01-01

    We apply the numerical bootstrap program to chiral operators in four-dimensional N=2 SCFTs. In the first part of this work we study four-point functions in which all fields have the same conformal dimension. We give special emphasis to bootstrapping a specific theory: the simplest Argyres-Douglas fixed point with no flavor symmetry. In the second part we generalize our setup and consider correlators of fields with unequal dimension. This is an example of a mixed correlator and allows us to probe new regions in the parameter space of N=2 SCFTs. In particular, our results put constraints on relations in the Coulomb branch chiral ring and on the curvature of the Zamolodchikov metric.

  16. On chirality of slime mould.

    PubMed

    Dimonte, Alice; Adamatzky, Andrew; Erokhin, Victor; Levin, Michael

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown. PMID:26747637

  17. Microfluidic Separation of Chiral Particles

    NASA Astrophysics Data System (ADS)

    Marcos; Fu, Henry; Powers, Thomas; Stocker, Roman

    2008-11-01

    We present a combined theoretical and experimental investigation of the fluid mechanics of a helix exposed to a shear flow. In addition to classic Jeffery orbits, Resistive Force Theory predicts a drift of the helix across streamlines, perpendicular to the shear plane. The direction of the drift is determined by the direction of the shear and the chirality of the helix. We verify this prediction experimentally using microfluidics, by exposing Leptospira biflexa, a non-motile strain of helical-shaped bacteria, to a plane parabolic flow. As the shear in the top and bottom halves of the microchannel has opposite sign, we predict and observe the bacteria in these two regions to drift in opposite directions. The magnitude of the separation is in good quantitative agreement with theory. This setup can be used to separate microscale chiral objects.

  18. On lattice chiral gauge theories

    NASA Technical Reports Server (NTRS)

    Maiani, L.; Rossi, G. C.; Testa, M.

    1991-01-01

    The Smit-Swift-Aoki formulation of a lattice chiral gauge theory is presented. In this formulation the Wilson and other non invariant terms in the action are made gauge invariant by the coupling with a nonlinear auxilary scalar field, omega. It is shown that omega decouples from the physical states only if appropriate parameters are tuned so as to satisfy a set of BRST identities. In addition, explicit ghost fields are necessary to ensure decoupling. These theories can give rise to the correct continuum limit. Similar considerations apply to schemes with mirror fermions. Simpler cases with a global chiral symmetry are discussed and it is shown that the theory becomes free at decoupling. Recent numerical simulations agree with those considerations.

  19. ENANTIOMERIC RATIOS OF CHIRAL PCB ATROPISOMERS IN RADIODATED SEDIMENT CORES

    EPA Science Inventory

    Enantiomeric ratios (ERs)) of chiral polychlorinated biphenyl (PCB) atropisomers were quantified in radiodated sediment cores of Lake Hartwell SC, a reservoir heavily impacted by PCBS, to study spatial and temporal changes in chirality. A chiral analysis of cores showed accumulat...

  20. Anomalies and Discrete Chiral Symmetries

    SciTech Connect

    Creutz, M.

    2009-09-07

    The quantum anomaly that breaks the U(1) axial symmetry of massless multi-flavored QCD leaves behind a discrete flavor-singlet chiral invariance. With massive quarks, this residual symmetry has a close connection with the strong CP-violating parameter theta. One result is that if the lightest quarks are degenerate, then a first order transition will occur when theta passes through pi. The resulting framework helps clarify when the rooting prescription for extrapolating in the number of flavors is valid.

  1. Chiral particle separation by a nonchiral microlattice.

    PubMed

    Bogunovic, Lukas; Fliedner, Marc; Eichhorn, Ralf; Wegener, Sonja; Regtmeier, Jan; Anselmetti, Dario; Reimann, Peter

    2012-09-01

    We conceived a model experiment for a continuous separation strategy of chiral molecules (enantiomers) without the need of any chiral selector structure or derivatization agents: Microparticles that only differ by their chirality are shown to migrate along different directions when driven by a steady fluid flow through a square lattice of cylindrical posts. In accordance with our numerical predictions, the transport directions of the enantiomers depend very sensitively on the orientation of the lattice relative to the fluid flow. PMID:23005274

  2. Chiral Particle Separation by a Nonchiral Microlattice

    NASA Astrophysics Data System (ADS)

    Bogunovic, Lukas; Fliedner, Marc; Eichhorn, Ralf; Wegener, Sonja; Regtmeier, Jan; Anselmetti, Dario; Reimann, Peter

    2012-09-01

    We conceived a model experiment for a continuous separation strategy of chiral molecules (enantiomers) without the need of any chiral selector structure or derivatization agents: Microparticles that only differ by their chirality are shown to migrate along different directions when driven by a steady fluid flow through a square lattice of cylindrical posts. In accordance with our numerical predictions, the transport directions of the enantiomers depend very sensitively on the orientation of the lattice relative to the fluid flow.

  3. Chiral anomaly, bosonization, and fractional charge

    SciTech Connect

    Mignaco, J.A.; Monteiro, M.A.R.

    1985-06-15

    We present a method to evaluate the Jacobian of chiral rotations, regulating determinants through the proper-time method and using Seeley's asymptotic expansion. With this method we compute easily the chiral anomaly for ..nu.. = 4,6 dimensions, discuss bosonization of some massless two-dimensional models, and handle the problem of charge fractionization. In addition, we comment on the general validity of Fujikawa's approach to regulate the Jacobian of chiral rotations with non-Hermitian operators.

  4. Isomer-specific biodegradation of nonylphenol in an activated sludge bioreactor and structure-biodegradability relationship.

    PubMed

    Lu, Zhijiang; Reif, Rubén; Gan, Jay

    2015-01-01

    Nonylphenol (NP), one of the priority hazardous substances, is in fact a mixture of numerous isomers. It is inconclusive whether or not biodegradation during wastewater treatment process is isomer-specific, leading to the environmental release of NP in different isomer profiles. In this study, we evaluated the isomer selectivity of 19 NP isomers in a laboratory-scale continuous flow conventional activated sludge bioreactor under various operational conditions. The removal efficiency of NP isomers ranged from 90 to 99%, depending on the operational conditions and isomer structures. Isomer selective biodegradation resulted in the increase of composition of recalcitrant isomers, such as, NP₁₉₃a/b, NP₁₁₀a and NP₁₉₄ in the effluent. Moreover, biodegradability was related to the bulkiness of α-substituents and followed α-dimethyl > α-ethyl-α-methyl > α-methyl-α-n-propyl > α-iso-propyl-α-methyl. Steric effect index, a quantitative descriptor of steric hindrance, was linearly correlated with residues of NP isomers in the effluent (R² = 0.76). Decrease of temperature to 10 °C decreased the overall biodegradability and also enhanced the relative enrichment of recalcitrant isomers. These findings suggest that isomer compositions of NP entering the environment may be different from those in technical mixtures and that isomeric selectivity should be taken into account to better understand the occurrence, fate, and ecological risks of NP. PMID:25462736

  5. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Cypermethrin and an isomer zeta... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances for... (±))(cis-trans 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate and its inactive R-isomers in...

  6. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Cypermethrin and an isomer zeta... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances for... (±))(cis-trans 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate and its inactive R-isomers in...

  7. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  8. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  9. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Cypermethrin and an isomer zeta... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances for... (±))(cis-trans 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate and its inactive R-isomers in...

  10. Objects of Maximum Electromagnetic Chirality

    NASA Astrophysics Data System (ADS)

    Fernandez-Corbaton, Ivan; Fruhnert, Martin; Rockstuhl, Carsten

    2016-07-01

    We introduce a definition of the electromagnetic chirality of an object and show that it has an upper bound. Reciprocal objects attain the upper bound if and only if they are transparent for all the fields of one polarization handedness (helicity). Additionally, electromagnetic duality symmetry, i.e., helicity preservation upon interaction, turns out to be a necessary condition for reciprocal objects to attain the upper bound. We use these results to provide requirements for the design of such extremal objects. The requirements can be formulated as constraints on the polarizability tensors for dipolar objects or on the material constitutive relations for continuous media. We also outline two applications for objects of maximum electromagnetic chirality: a twofold resonantly enhanced and background-free circular dichroism measurement setup, and angle-independent helicity filtering glasses. Finally, we use the theoretically obtained requirements to guide the design of a specific structure, which we then analyze numerically and discuss its performance with respect to maximal electromagnetic chirality.

  11. Chiral plasmons without magnetic field.

    PubMed

    Song, Justin C W; Rudner, Mark S

    2016-04-26

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons-chiral Berry plasmons (CBPs)-for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron-electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands. PMID:27071090

  12. Chiral plasmons without magnetic field

    NASA Astrophysics Data System (ADS)

    Song, Justin C. W.

    2016-04-01

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons—chiral Berry plasmons (CBPs)—for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron–electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands.

  13. Sperm Trajectories Form Chiral Ribbons

    PubMed Central

    Su, Ting-Wei; Choi, Inkyum; Feng, Jiawen; Huang, Kalvin; McLeod, Euan; Ozcan, Aydogan

    2013-01-01

    We report the discovery of an entirely new three-dimensional (3D) swimming pattern observed in human and horse sperms. This motion is in the form of ‘chiral ribbons’, where the planar swing of the sperm head occurs on an osculating plane creating in some cases a helical ribbon and in some others a twisted ribbon. The latter, i.e., the twisted ribbon trajectory, also defines a minimal surface, exhibiting zero mean curvature for all the points on its surface. These chiral ribbon swimming patterns cannot be represented or understood by already known patterns of sperms or other micro-swimmers. The discovery of these unique patterns is enabled by holographic on-chip imaging of >33,700 sperm trajectories at >90–140 frames/sec, which revealed that only ~1.7% of human sperms exhibit chiral ribbons, whereas it increases to ~27.3% for horse sperms. These results might shed more light onto the statistics and biophysics of various micro-swimmers' 3D motion. PMID:23588811

  14. Distinction of tris(diimine)ruthenium(II) enantiomers chiral by virtue of helical chirality: temperature-dependent deuterium NMR spectroscopy in partially oriented phases.

    PubMed

    Szalontai, Gábor; Kovács, Margit

    2006-11-01

    2H NMR spectra of perdeuterated tris(diimine)ruthenium(II) complexes have been recorded in lyotropic liquid crystalline phase formed by the chiral polypeptide, poly-gamma-benzyl-L-glutamate (PBLG) and co-solvents. It is demonstrated that the left- and right-rotation isomers of these octahedral metal complexes with D3 symmetry can be distinguished. The effects of temperature and ligand size on spectral resolution were also studied. Although in the case of free bipyridine ligands excellent optical resolution could be obtained at room temperature in the complexes studied, the increase in ligand size has a detrimental effect on the resolution. This can be compensated to some extent by elevating the sample temperature and decreasing the deuterium relaxation rates, but the available temperature range and therefore the applicability of the technique are limited. PMID:16958156

  15. Chiral Ruthenium(II) Polypyridyl Complexes: Stabilization of G-Quadruplex DNA, Inhibition of Telomerase Activity and Cellular Uptake

    PubMed Central

    Yu, Qianqian; Liu, Yanan; Wang, Chuan; Sun, Dongdong; Yang, Xingcheng; Liu, Yanyu; Liu, Jie

    2012-01-01

    Two ruthenium(II) complexes, Λ-[Ru(phen)2(p-HPIP)]2+ and Δ-[Ru(phen)2(p-HPIP)]2+, were synthesized and characterized via proton nuclear magnetic resonance spectroscopy, electrospray ionization-mass spectrometry, and circular dichroism spectroscopy. This study aims to clarify the anticancer effect of metal complexes as novel and potent telomerase inhibitors and cellular nucleus target drug. First, the chiral selectivity of the compounds and their ability to stabilize quadruplex DNA were studied via absorption and emission analyses, circular dichroism spectroscopy, fluorescence-resonance energy transfer melting assay, electrophoretic mobility shift assay, and polymerase chain reaction stop assay. The two chiral compounds selectively induced and stabilized the G-quadruplex of telomeric DNA with or without metal cations. These results provide new insights into the development of chiral anticancer agents for G-quadruplex DNA targeting. Telomerase repeat amplification protocol reveals the higher inhibitory activity of Λ-[Ru(phen)2(p-HPIP)]2+ against telomerase, suggesting that Λ-[Ru(phen)2(p-HPIP)]2+ may be a potential telomerase inhibitor for cancer chemotherapy. MTT assay results show that these chiral complexes have significant antitumor activities in HepG2 cells. More interestingly, cellular uptake and laser-scanning confocal microscopic studies reveal the efficient uptake of Λ-[Ru(phen)2(p-HPIP)]2+ by HepG2 cells. This complex then enters the cytoplasm and tends to accumulate in the nucleus. This nuclear penetration of the ruthenium complexes and their subsequent accumulation are associated with the chirality of the isomers as well as with the subtle environment of the ruthenium complexes. Therefore, the nucleus can be the cellular target of chiral ruthenium complexes for anticancer therapy. PMID:23236402

  16. Mechanism of Different Stereoisomeric Astaxanthin in Resistance to Oxidative Stress in Caenorhabditis elegans.

    PubMed

    Liu, Xiaojuan; Luo, Qingxin; Cao, Yong; Goulette, Timothy; Liu, Xin; Xiao, Hang

    2016-09-01

    As a potent antioxidant in human diet, astaxanthin (AST) may play important roles in alleviating oxidative stress-driven adverse physiological effects. This study examined the effects of different stereoisomers of AST in protecting Caenorhabditis elegans from chemically induced oxidative stress. Three stereoisomers of AST investigated herein included 3S,3´S (S) AST, 3R,3´R (R) AST, and a statistical mixture (S: meso: R = 1:2:1) (M) AST. Under paraquat-induced oxidative conditions, all three types of AST significantly enhanced survival rate of C. elegans. The accumulation levels of ROS in the worms were reduced by 40.12%, 30.05%, and 22.04% by S, R, and M AST, respectively (P < 0.05). Compared with R and M AST, S significantly enhanced the expression levels of SOD-3. The results of RNA-Seq analysis demonstrated that AST protected C. elegans from oxidative damage potentially by modulating genes involved in the insulin/insulin-like growth factor (IGF) signaling (IIS) pathway and the oxidoreductase system. It is noteworthy that different stereoisomers of AST showed different effects on the expression levels of various genes related with oxidative stress. This study revealed important information on the in vivo antioxidative effects of AST stereoisomers, which might provide useful information for better utilization of AST. PMID:27527357

  17. Astaxanthin from psychrotrophic Sphingomonas faeni exhibits antagonism against food-spoilage bacteria at low temperatures.

    PubMed

    Mageswari, Anbazhagan; Subramanian, Parthiban; Srinivasan, Ramachandran; Karthikeyan, Sivashanmugam; Gothandam, Kodiveri Muthukaliannan

    2015-10-01

    Food production and processing industry holds a perpetual relationship with microorganisms and their by-products. In the present study, we aimed to identify beneficial cold-adapted bacteria devoid of any food spoilage properties and study their antagonism against common food-borne pathogens at low temperature conditions. Ten isolates were obtained on selective isolation at 5 °C, which were spread across genera Pseudomonas, Sphingomonas, Psychrobacter, Leuconostoc, Rhodococcus, and Arthrobacter. Methanol extracts of strains were found to contain several bioactive metabolites. Among the studied isolates, methanol extracts of S. faeni ISY and Rhodococcus fascians CS4 were found to show antagonism against growth of Escherichia coli, Proteus mirabilis, Enterobacter aerogenes, Listeria monocytogenes and Vibrio fischeri at refrigeration temperatures. Characterization of the abundant yellow pigment in methanol extracts of S. faeni ISY through UV-Vis spectrophotometry, high performance liquid chromatography (HPLC) and mass spectrometry (LC-MS) revealed the presence of astaxanthin, which, owing to its presence in very large amounts and evidenced to be responsible for antagonistic activity of the solvent extract. PMID:26411893

  18. Protective effects of astaxanthin against ischemia/reperfusion induced renal injury in mice.

    PubMed

    Qiu, Xuefeng; Fu, Kai; Zhao, Xiaozhi; Zhang, Yanting; Yuan, Yimin; Zhang, Shiwei; Gu, Xiaoping; Guo, Hongqian

    2015-01-01

    Astaxanthin (ATX) is a powerful antioxidant that occurs naturally in a wide variety of living organisms. Previous studies have shown that ATX has effects of eliminating oxygen free radicals and can protect organs from ischemia/reperfusion (IR) induced injury. The present study was designed to further investigate the protective effects of ATX on oxidative stress induced toxicity in tubular epithelial cells and on IR induced renal injury in mice. ATX, at a concentration of 250 nM, attenuated 100 μM H2O2-inudced viability decrease of tubular epithelial cells. In vivo, ATX preserved renal function 12 h or 24 h post IR. Pretreatment of ATX via oral gavage for 14 consecutive days prior to IR dramatically prevented IR induced histological damage 24 h post IR. Histological results showed that the pathohistological score, number of apoptotic cells, and the expression of α-smooth muscle actin were significantly decreased by pretreatment of ATX. In addition, oxidative stress and inflammation in kidney samples were significantly reduced by ATX 24 h post IR. Taken together, the current study suggests that pretreatment of ATX is effective in preserving renal function and histology via antioxidant activity. PMID:25623758

  19. Astaxanthin protects steroidogenesis from hydrogen peroxide-induced oxidative stress in mouse Leydig cells.

    PubMed

    Wang, Jyun-Yuan; Lee, Yue-Jia; Chou, Mei-Chia; Chang, Renin; Chiu, Chih-Hsien; Liang, Yao-Jen; Wu, Leang-Shin

    2015-03-01

    Androgens, especially testosterone produced in Leydig cells, play an essential role in development of the male reproductive phenotype and fertility. However, testicular oxidative stress may cause a decline in testosterone production. Many antioxidants have been used as reactive oxygen species (ROS) scavengers to eliminate oxidative stress to protect steroidogenesis. Astaxanthin (AST), a natural extract from algae and plants ubiquitous in the marine environment, has been shown to have antioxidant activity in many previous studies. In this study, we treated primary mouse Leydig cells or MA-10 cells with hydrogen peroxide (H2O2) to cause oxidative stress. Testosterone and progesterone production was suppressed and the expression of the mature (30 kDa) form of StAR protein was down-regulated in MA-10 cells by H2O2 and cAMP co-treatment. However, progesterone production and expression of mature StAR protein were restored in MA-10 cells by a one-hour pretreatment with AST. AST also reduced ROS levels in cells so that they were lower than the levels in untreated controls. These results provide additional evidence of the potential health benefits of AST as a potential food additive to ease oxidative stress. PMID:25786065

  20. Regenerative Astaxanthin Extraction from a Single Microalgal (Haematococcus pluvialis) Cell Using a Gold Nano-Scalpel.

    PubMed

    Praveenkumar, Ramasamy; Gwak, Raekeun; Kang, Mijeong; Shim, Tae Soup; Cho, Soojeong; Lee, Jiye; Oh, You-Kwan; Lee, Kyubock; Kim, Bongsoo

    2015-10-14

    Milking of microalgae, the process of reusing the biomass for continuous production of target compounds, can strikingly overcome the time and cost constraints associated with biorefinery. This process can significantly improve production efficiency of highly valuable chemicals, for example, astaxanthin (AXT) from Haematococcus pluvialis. Detailed understanding of the biological process of cell survival and AXT reaccumulation after extraction would be of great help for successful milking. Here we report extraction of AXT from a single cell of H. pluvialis through incision of the cell wall by a gold nanoscalpel (Au-NS), which allows single-cell analysis of wound healing and reaccumulation of AXT. Interestingly, upon the Au-NS incision, the cell could reaccumulate AXT at a rate two times faster than the control cells. Efficient extraction as well as minimal cellular damage, keeping cells alive, could be achieved with the optimized shape and dimensions of Au-NS: a well-defined sharp tip, thickness under 300 nm, and 1-3 μm of width. The demonstration of regenerative extraction of AXT at a single cell level hints toward the potential of a milking process for continuous recovery of target compounds from microalgae while keeping the cells alive. PMID:26397314

  1. Astaxanthin Inhibits Expression of Retinal Oxidative Stress and Inflammatory Mediators in Streptozotocin-Induced Diabetic Rats

    PubMed Central

    Yeh, Po-Ting; Huang, Hsin-Wei; Yang, Chung-May; Yang, Wei-Shiung; Yang, Chang-Hao

    2016-01-01

    Purpose We evaluated whether orally administered astaxanthin (AST) protects against oxidative damage in the ocular tissues of streptozotocin (STZ)-induced diabetic rats. Methods and Results Fifty 6-week-old female Wistar rats were randomly assigned to receive an injection of STZ to induce diabetes (n = 40) or to remain uninduced (n = 10). The diabetic rats were randomly selected into four groups and they were separately administered normal saline, 0.6 mg/kg AST, 3 mg/kg AST, or 0.5 mg/kg lutein daily for eight weeks. Retinal functions of each group were evaluated by electroretinography. The expression of oxidative stress and inflammatory mediators in the ocular tissues was then assessed by immunohistochemistry, western blot analysis, ELISA, RT-PCR, and electrophoretic mobility shift assay (EMSA). Retinal functions were preserved by AST and lutein in different levels. Ocular tissues from AST- and lutein-treated rats had significantly reduced levels of oxidative stress mediators (8-hydroxy-2'-deoxyguanosine, nitrotyrosine, and acrolein) and inflammatory mediators (intercellular adhesion molecule-1, monocyte chemoattractant protein-1, and fractalkine), increased levels of antioxidant enzymes (heme oxygenase-1 and peroxiredoxin), and reduced activity of the transcription factor nuclear factor-kappaB (NF-κB). Conclusion The xanthophyll carotenoids AST and lutein have neuroprotective effects and reduce ocular oxidative stress, and inflammation in the STZ diabetic rat model, which may be mediated by downregulation of NF-κB activity. PMID:26765843

  2. Repeated cultivation: non-cell disruption extraction of astaxanthin for Haematococcus pluvialis.

    PubMed

    Sun, Han; Guan, Bin; Kong, Qing; Geng, Zhaoyan; Wang, Ni

    2016-01-01

    The operation of cell disruption is indispensable but cost much in microalgae industry. To be simplified, two different reaction mechanisms await in the cell to respond to moderated or stressed environment. The physical and chemical changes of enzyme and turgor pressure of cell in this conversion play an important role in the enhancement of biomass and metabolites. Repeated turgor pressure (based on the structure and mechanics of cell wall) and converted enzyme system (based on photosynthesis) were used to loosen cell wall and then repeated cultivation of Haematococcus pluvialis for astaxanthin extraction was proposed. There was no significant difference of extraction yield between the broken cell (94.75 ± 3.13%) and non-broken cell (92.32 ± 3.24%) treated by the repeated cultivation. Meanwhile, fed-batch culture according to the relationship among pH and nutrient concentration was used to enhance the biomass of Haematococcus pluvialis with the dry cell weight of 1.63 ± 0.07 g/L. PMID:26838183

  3. Repeated cultivation: non-cell disruption extraction of astaxanthin for Haematococcus pluvialis

    PubMed Central

    Sun, Han; Guan, Bin; Kong, Qing; Geng, Zhaoyan; Wang, Ni

    2016-01-01

    The operation of cell disruption is indispensable but cost much in microalgae industry. To be simplified, two different reaction mechanisms await in the cell to respond to moderated or stressed environment. The physical and chemical changes of enzyme and turgor pressure of cell in this conversion play an important role in the enhancement of biomass and metabolites. Repeated turgor pressure (based on the structure and mechanics of cell wall) and converted enzyme system (based on photosynthesis) were used to loosen cell wall and then repeated cultivation of Haematococcus pluvialis for astaxanthin extraction was proposed. There was no significant difference of extraction yield between the broken cell (94.75 ± 3.13%) and non-broken cell (92.32 ± 3.24%) treated by the repeated cultivation. Meanwhile, fed-batch culture according to the relationship among pH and nutrient concentration was used to enhance the biomass of Haematococcus pluvialis with the dry cell weight of 1.63 ± 0.07 g/L. PMID:26838183

  4. Astaxanthin preparation by fermentation of esters from Haematococcus pluvialis algal extracts with Stenotrophomonas species.

    PubMed

    Dong, Hao; Li, Xuemin; Xue, Changhu; Mao, Xiangzhao

    2016-05-01

    Natural astaxanthin (Ax) is an additive that is widely used because of its beneficial biochemical functions. However, the methods used to produce free Ax have drawbacks. Chemical saponification methods produce several by-products, and lipase-catalyzed hydrolysis methods are not cost effective. In this study, a bacterial strain of Stenotrophomonas sp. was selected to enzymatically catalyze the saponification of Ax esters to produce free all-trans-Ax. Through single-factor experiments and a Box-Behnken design, the optimal fermentation conditions were determined as follows: a seed culture age of 37.79 h, an inoculum concentration of 5.92%, and an initial broth pH of 6.80. Under these conditions, a fermentation curve was drawn, and the optimal fermentation time was shown to be 60 h. At 60 h, the degradation rate of the Ax esters was 98.08%, and the yield of free all-trans-Ax was 50.130 μg/mL. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:649-656, 2016. PMID:26949202

  5. Astaxanthin Protects Steroidogenesis from Hydrogen Peroxide-Induced Oxidative Stress in Mouse Leydig Cells

    PubMed Central

    Wang, Jyun-Yuan; Lee, Yue-Jia; Chou, Mei-Chia; Chang, Renin; Chiu, Chih-Hsien; Liang, Yao-Jen; Wu, Leang-Shin

    2015-01-01

    Androgens, especially testosterone produced in Leydig cells, play an essential role in development of the male reproductive phenotype and fertility. However, testicular oxidative stress may cause a decline in testosterone production. Many antioxidants have been used as reactive oxygen species (ROS) scavengers to eliminate oxidative stress to protect steroidogenesis. Astaxanthin (AST), a natural extract from algae and plants ubiquitous in the marine environment, has been shown to have antioxidant activity in many previous studies. In this study, we treated primary mouse Leydig cells or MA-10 cells with hydrogen peroxide (H2O2) to cause oxidative stress. Testosterone and progesterone production was suppressed and the expression of the mature (30 kDa) form of StAR protein was down-regulated in MA-10 cells by H2O2 and cAMP co-treatment. However, progesterone production and expression of mature StAR protein were restored in MA-10 cells by a one-hour pretreatment with AST. AST also reduced ROS levels in cells so that they were lower than the levels in untreated controls. These results provide additional evidence of the potential health benefits of AST as a potential food additive to ease oxidative stress. PMID:25786065

  6. Astaxanthin prevents and reverses the activation of mouse primary hepatic stellate cells.

    PubMed

    Yang, Yue; Bae, Minkyung; Kim, Bohkyung; Park, Young-Ki; Koo, Sung I; Lee, Ji-Young

    2016-03-01

    Activation of hepatic stellate cells (HSCs) is a critical step that leads to the development of liver fibrosis. We showed that astaxanthin (ASTX), a xanthophyll carotenoid, displays antifibrogenic effects in LX-2 cells, a human HSC cell line. In this study, we further determined the effect of ASTX on HSC activation and inactivation using primary HSCs from C57BL/6J mice. Quiescent and activated HSCs were incubated with ASTX (25μM) at different stages of activation. ASTX prevented the activation of quiescent HSCs, as evidenced by the presence of intracellular lipid droplets and reduction of α-smooth muscle actin, an HSC activation marker. Also, ASTX reverted activated HSCs to a quiescent phenotype with the reappearance of lipid droplets with a concomitant increase in lecithin retinol acyltransferase mRNA. Cellular accumulation of reactive oxygen species was significantly reduced by ASTX, which was attributable to a decrease in NADPH oxidase 2 expression. The antifibrogenic effect of ASTX was independent of nuclear erythroid 2-related factor 2 as it was observed in HSCs from wild-type and Nrf2(-/-) mice. In conclusion, ASTX inhibits HSC activation and reverts activated HSCs to a quiescent state. Further investigation is warranted to determine if ASTX effectively prevents the development of liver fibrosis. PMID:26895661

  7. Combined effect of astaxanthin and squalene on oxidative stress in vivo.

    PubMed

    Ravi Kumar, Sangeetha; Narayan, Bhaskar; Sawada, Yuki; Hosokawa, Masashi; Miyashita, Kazuo

    2016-06-01

    Obesity and diabetes, risk factors for metabolic syndrome, are characterized by oxidative stress and inflammatory responses. Marine biofunctionals, astaxanthin (Ax) and squalene (SQ), were evaluated for their combined effect. Groups of male KK-A (y) mice were fed high fat/sucrose diet for 4 weeks, supplemented with either 0.1 %Ax, 2 %SQ or 0.1 %Ax + 2 %SQ. In comparison to control, Sod was elevated in only Ax + SQ. However, Gpx was highest in Ax + SQ, indicating the combined antioxidant effect of Ax and SQ. This was supported by elevated mRNA expression of Sod1 and Gpx1. Except adiponectin (elevated in Ax and Ax + SQ), expression of other inflammatory markers was not altered. Blood glucose levels were decreased in SQ and Ax + SQ while liver triglycerides decreased in SQ group. This is the first in vivo study demonstrating combined effects of Ax and SQ resulting in antioxidant effects and modulation of glucose/triglyceride levels. This study highlights the benefit of utilizing Ax and SQ together for management of obesity/diabetes. PMID:27188184

  8. Nephroprotective effect of astaxanthin against trivalent inorganic arsenic-induced renal injury in wistar rats

    PubMed Central

    Wang, Xiaona; Zhao, Haiyuan; Shao, Yilan; Wang, Pei; Wei, Yanru; Zhang, Weiqian; Jiang, Jing; Chen, Yan

    2014-01-01

    Inorganic arsenic (iAs) is a toxic metalloid found ubiquitously in the environment. In humans, exposure to iAs can result in toxicity and cause toxicological manifestations. Arsenic trioxide (As2O3) has been used in the treatment for acute promyelocytic leukemia. The kidney is the critical target organ of trivalent inorganic As (iAsIII) toxicity. We examine if oral administration of astaxanthin (AST) has protective effects on nephrotoxicity and oxidative stress induced by As2O3 exposure (via intraperitoneal injection) in rats. Markers of renal function, histopathological changes, Na+-K+ ATPase, sulfydryl, oxidative stress, and As accumulation in kidneys were evaluated as indicators of As2O3 exposure. AST showed a significant protective effect against As2O3-induced nephrotoxicity. These results suggest that the mechanisms of action, by which AST reduces nephrotoxicity, may include antioxidant protection against oxidative injury and reduction of As accumulation. These findings might be of therapeutic benefit in humans or animals suffering from exposure to iAsIII from natural sources or cancer therapy. PMID:24611105

  9. In Situ Assembly of Octahedral Fe(II) Complexes for the Enantiomeric Excess Determination of Chiral Amines Using CD spectroscopy

    PubMed Central

    Dragna, Justin; Pescitelli, Gennaro; Tran, Lee; Lynch, Vincent M.; Anslyn, Eric V.; Di Bari, Lorenzo

    2012-01-01

    A method for discriminating between α-chiral primary amine enantiomers is reported. The method utilizes circular dichroism spectroscopy and a sensing ensemble composed of 2-formyl-3-hydroxyl pyridine (4) and Fe(II)(TfO)2. Aldehyde 4 reacts rapidly with chiral amines to form chiral imines, which complex Fe(II) to form a series of diastereomeric octahedral complexes that are CD active in both the UV and visible spectrum. NMR studies showed that, for enantiomerically pure imine complexes, the Δ-fac isomer is preferred. A statistical analysis of the distribution of stereoisomers accurately models the calibration curves for enantiomeric excess. CD signals appearing in the UV region were bisignate, and the null of the CD signals were coincident with maxima in the UV spectrum, consistent with exciton coupling. TTDFT and semi-empirical calculations confirmed that the CD signals in the UV region arise from coupling of the π-π* transitions in the imine chromophores, and can be used to accurately describe the sign and magnitudes of the curves. The CD signals in the visible region arise from metal-to-ligand charge transfer bands, and these signals can be used to determine the ee values of chiral amines with an average absolute error of ±5%. Overall, the strategy presented herein represents a facile in situ assembly that uses commercially available simple reagents to create large optical signals indicative of ee values. PMID:22272943

  10. Chiral selection on inorganic crystalline surfaces

    NASA Technical Reports Server (NTRS)

    Hazen, Robert M.; Sholl, David S.

    2003-01-01

    From synthetic drugs to biodegradable plastics to the origin of life, the chiral selection of molecules presents both daunting challenges and significant opportunities in materials science. Among the most promising, yet little explored, avenues for chiral molecular discrimination is adsorption on chiral crystalline surfaces - periodic environments that can select, concentrate and possibly even organize molecules into polymers and other macromolecular structures. Here we review experimental and theoretical approaches to chiral selection on inorganic crystalline surfaces - research that is poised to open this new frontier in understanding and exploiting surface-molecule interactions.

  11. Lateral chirality-sorting optical forces

    PubMed Central

    Hayat, Amaury; Mueller, J. P. Balthasar; Capasso, Federico

    2015-01-01

    The transverse component of the spin angular momentum of evanescent waves gives rise to lateral optical forces on chiral particles, which have the unusual property of acting in a direction in which there is neither a field gradient nor wave propagation. Because their direction and strength depends on the chiral polarizability of the particle, they act as chirality-sorting and may offer a mechanism for passive chirality spectroscopy. The absolute strength of the forces also substantially exceeds that of other recently predicted sideways optical forces. PMID:26453555

  12. Chiral Magnetic Effect in Hydrodynamic Approximation

    NASA Astrophysics Data System (ADS)

    Zakharov, Valentin I.

    We review derivations of the chiral magnetic effect (ChME) in hydrodynamic approximation. The reader is assumed to be familiar with the basics of the effect. The main challenge now is to account for the strong interactions between the constituents of the fluid. The main result is that the ChME is not renormalized: in the hydrodynamic approximation it remains the same as for non-interacting chiral fermions moving in an external magnetic field. The key ingredients in the proof are general laws of thermodynamics and the Adler-Bardeen theorem for the chiral anomaly in external electromagnetic fields. The chiral magnetic effect in hydrodynamics represents a macroscopic manifestation of a quantum phenomenon (chiral anomaly). Moreover, one can argue that the current induced by the magnetic field is dissipation free and talk about a kind of "chiral superconductivity". More precise description is a quantum ballistic transport along magnetic field taking place in equilibrium and in absence of a driving force. The basic limitation is the exact chiral limit while temperature—excitingly enough—does not seemingly matter. What is still lacking, is a detailed quantum microscopic picture for the ChME in hydrodynamics. Probably, the chiral currents propagate through lower-dimensional defects, like vortices in superfluid. In case of superfluid, the prediction for the chiral magnetic effect remains unmodified although the emerging dynamical picture differs from the standard one.

  13. Chiral mass-gap in curved space.

    PubMed

    Flachi, Antonino; Fukushima, Kenji

    2014-08-29

    We discuss a new type of QCD phenomenon induced in curved space. In the QCD vacuum, a mass-gap of Dirac fermions is attributed to the spontaneous breaking of chiral symmetry. If the curvature is positive large, the chiral condensate melts but a chiral invariant mass-gap can still remain, which we name the chiral gap effect in curved space. This leads to decoupling of quark deconfinement which implies a view of black holes surrounded by a first-order QCD phase transition. PMID:25215970

  14. Generation of a Chiral Giant Micelle.

    PubMed

    Ito, Thiago H; Salles, Airton G; Priebe, Jacks P; Miranda, Paulo C M L; Morgon, Nelson H; Danino, Dganit; Mancini, Giovanna; Sabadini, Edvaldo

    2016-08-23

    Over the past few years, chiral supramolecular assemblies have been successfully used for recognition, sensing and enantioselective transformations. Several approaches are available to control chirality of discrete assemblies (e.g., cages and capsules), but few are efficient in assuring chirality for micellar aggregates. Optically active amino acid-derived surfactants are commonly used to generate chiral spherical micelles. To circumvent this limitation, we benefited from the uniaxial growth of spherical micelles into long cylindrical micelles usually called wormlike or giant micelles, upon the addition of cosolutes. This paper describes the unprecedented formation of chiral giant micelles in aqueous solutions of cetyltrimethylammonium bromide (CTAB) upon increasing addition of enantiopure sodium salt of 1,1'-bi-2-naphthol (Na-binaphtholate) as a cosolute. Depending on the concentrations of CTAB and Na-binaphtholate, chiral gel-like systems are obtained. The transition from spherical to giant micellar structures was probed using rheology, cryo-transmission electron microscopy, polarimetry, and electronic circular dichroism (CD). CD can be effectively used to monitor the incorporation of Na-binaphtholate into the micelle palisade as well as to determine its transition to giant micellar structures. Our approach expands the scope for chirality induction in micellar aggregates bringing the possibility to generate "smart" chiral systems and an alternative asymmetric chiral environment to perform enantioselective transformations. PMID:27499127

  15. Inherently Chiral Spider-Like Oligothiophenes.

    PubMed

    Sannicolò, Francesco; Mussini, Patrizia R; Benincori, Tiziana; Martinazzo, Rocco; Arnaboldi, Serena; Appoloni, Giulio; Panigati, Monica; Quartapelle Procopio, Elsa; Marino, Valentina; Cirilli, Roberto; Casolo, Simone; Kutner, Wlodzimierz; Noworyta, Krzysztof; Pietrzyk-Le, Agnieszka; Iskierko, Zofia; Bartold, Katarzyna

    2016-07-25

    The racemate of an inherently chiral "spider-like" octathiophene monomer T83 , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T83 racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross-linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer-based chemosensor selective for a thymine-adenine oligonucleotide. PMID:27321902

  16. Chiral pattern formation in compact microbial colonies

    NASA Astrophysics Data System (ADS)

    Korolev, Kirill; Bino George, Ashish

    Chirality is ubiquitous in biology from single molecules to entire populations. Yet, we are still lacking a detailed understanding of how chiral patterns emerge from cell competition and growth, even in simple microbial colonies. Although many microbes grow as dense colonies with no apparent chirality, recent experiments with Escherichia coli have demonstrated that internal dynamics in such populations can be in fact chiral. We show that there is a unique way to extend the commonly-used reaction-diffusion models of colony growth to account for the emergent chirality. This new model connects microscopic and macroscopic chirality and explains the origin of logarithmic spirals separating different sub-populations in a colony. We also show that chirality is substantially enhanced by the cooperation among the cells at the expansion frontier. In heterogeneous populations composed of strains with different chiralities and growth rates, our model predicts a very rich set of possible dynamics. For example, different chiralities can result in either sharp boundaries between the strains or promote their intermixing depending on the preferred twisting directions of the strains.

  17. Effect of Multiple Dietary Supplement Containing Lutein, 
Astaxanthin, Cyanidin-3-Glucoside, and DHA on Accommodative Ability

    PubMed Central

    Kono, Keiko; Shimizu, Yoshiki; Takahashi, Satomi; Matsuoka, Sayuri; Yui, Kei

    2014-01-01

    Objective The study aimed to verify that ingestion of multiple dietary supplement containing lutein, astaxanthin, cyanidin-3-glucoside and docosahexaenoic acid (DHA) would improve accommodative ability of aged and older subjects who were aware of eye strain on a daily basis. Methods A randomized double-blind placebo-controlled parallel group comparison study was conducted for 48 participants aged 45 to 64 years who complained of eye strain. The subjects took multiple dietary supplement containing 10 mg of lutein, 20 mg of bilberry extract and 26.5 mg of black soybean hull extract (a total of 2.3 mg of cyanidin-3-glucoside in both extracts), 4 mg of astaxanthin, and 50 mg of DHA (test supplement) or placebo for four consecutive weeks. Near-point accommodation (NPA) and subjective symptoms were evaluated both before and after four weeks’ intake. Results The variation of the NPA of both eyes from baseline to 4 weeks’ post-intake in the test supplement group was significantly higher than in the placebo group (1.321±0.394 diopter (D) in the test supplement group and 0.108±0.336 D in the placebo group, p=0.023). The multiple dietary supplement group showed improvement in the NPA. Regarding subjective symptoms, significant improvement of “stiff shoulders or neck” and “blurred vision” was also found in the test supplement group compared to the placebo group (p<0.05). There were no safety concerns in this study. Conclusion This study shows that multiple dietary supplement containing lutein, astaxanthin, cyanidin-3-glucoside, and DHA has effect to improve accommodative ability and subjective symptoms related to eye fatigue.

  18. Inherently Chiral Calixarenes: Synthesis, Optical Resolution, Chiral Recognition and Asymmetric Catalysis

    PubMed Central

    Li, Shao-Yong; Xu, Yao-Wei; Liu, Jun-Min; Su, Cheng-Yong

    2011-01-01

    Inherently chiral calixarenes, whose chirality is based on the absence of a planar symmetry or an inversion center in the molecules as a whole through the asymmetric array of several achiral groups upon the three-dimensional calix-skeletons, are challenging and attractive chiral molecules, because of their potential in supramolecular chemistry. The synthesis and optical resolution of all varieties of inherently chiral calixarenes are systematically discussed and classified, and their applications in chiral recognition and asymmetric catalysis are thoroughly illustrated in this review. PMID:21339996

  19. Chirally-modified metal surfaces: energetics of interaction with chiral molecules.

    PubMed

    Dementyev, Petr; Peter, Matthias; Adamovsky, Sergey; Schauermann, Swetlana

    2015-09-21

    Imparting chirality to non-chiral metal surfaces by adsorption of chiral modifiers is a highly promising route to create effective heterogeneously catalyzed processes for the production of enantiopure pharmaceuticals. One of the major current challenges in heterogeneous chiral catalysis is the fundamental-level understanding of how such chirally-modified surfaces interact with chiral and prochiral molecules to induce their enantioselective transformations. Herein we report the first direct calorimetric measurement of the adsorption energy of chiral molecules onto well-defined chirally-modified surfaces. Two model modifiers 1-(1-naphthyl)ethylamine and 2-methylbutanoic acid were used to impart chirality to Pt(111) and their interaction with propylene oxide was investigated by means of single-crystal adsorption calorimetry. Differential adsorption energies and absolute surface uptakes were obtained for the R- and S-enantiomers of propylene oxide under clean ultrahigh vacuum conditions. Two types of adsorption behavior were observed for different chiral modifiers, pointing to different mechanisms of imparting chirality to metal surfaces. The results are analyzed and discussed in view of previously reported stereoselectivity of adsorption processes. PMID:26256836

  20. Hydrodynamics of Liquids of Chiral Molecules and Suspensions Containing Chiral Particles

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Son, D. T.; Spivak, B.

    2010-05-01

    We obtain hydrodynamic equations describing a fluid consisting of chiral molecules or a suspension of chiral particles in a Newtonian fluid. The hydrodynamic velocity and stresses arising in a flowing chiral liquid have components that are forbidden by symmetry in a Newtonian liquid. For example, a chiral liquid in a Poiseuille flow between parallel plates exerts forces on the plates, which are perpendicular to the flow. A generic flow results in spatial separation of particles of different chirality. Thus even a racemic suspension will exhibit chiral properties in a generic flow. A suspension of particles of random shape in a Newtonian liquid is described by equations which are similar to those describing a racemic mixture of chiral particles in a liquid.