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Sample records for chiral separations based

  1. Chromatographic Studies of Protein-Based Chiral Separations

    Science.gov (United States)

    Bi, Cong; Zheng, Xiwei; Azaria, Shiden; Beeram, Sandya; Li, Zhao; Hage, David S.

    2016-01-01

    The development of separation methods for the analysis and resolution of chiral drugs and solutes has been an area of ongoing interest in pharmaceutical research. The use of proteins as chiral binding agents in high-performance liquid chromatography (HPLC) has been an approach that has received particular attention in such work. This report provides an overview of proteins that have been used as binding agents to create chiral stationary phases (CSPs) and in the use of chromatographic methods to study these materials and protein-based chiral separations. The supports and methods that have been employed to prepare protein-based CSPs will also be discussed and compared. Specific types of CSPs that are considered include those that employ serum transport proteins (e.g., human serum albumin, bovine serum albumin, and alpha1-acid glycoprotein), enzymes (e.g., penicillin G acylase, cellobiohydrolases, and α-chymotrypsin) or other types of proteins (e.g., ovomucoid, antibodies, and avidin or streptavidin). The properties and applications for each type of protein and CSP will also be discussed in terms of their use in chromatography and chiral separations.

  2. Separation of piracetam derivatives on polysaccharide-based chiral stationary phases.

    Science.gov (United States)

    Kažoka, H; Koliškina, O; Veinberg, G; Vorona, M

    2013-03-15

    High-performance liquid chromatography was used for the enantiomeric separation of two chiral piracetam derivatives. The suitability of six commercially available polysaccharide-based chiral stationary phases (CSPs) under normal phase mode for direct enantioseparation has been investigated. The influence of the CSPs as well the nature and content of an alcoholic modifier in the mobile phase on separation and elution order was studied. It was established that CSP Lux Amylose-2 shows high chiral recognition ability towards 4-phenylsubstituted piracetam derivatives.

  3. High-performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide-based chiral columns and polar organic mobile phases.

    Science.gov (United States)

    Matarashvili, Iza; Shvangiradze, Iamze; Chankvetadze, Lali; Sidamonidze, Shota; Takaishvili, Nino; Farkas, Tivadar; Chankvetadze, Bezhan

    2015-12-01

    The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide-based chiral columns in high-performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination.

  4. High-Throughput Genetic Analysis and Combinatorial Chiral Separations Based on Capillary Electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Wenwan Zhong

    2003-08-05

    Capillary electrophoresis (CE) offers many advantages over conventional analytical methods, such as speed, simplicity, high resolution, low cost, and small sample consumption, especially for the separation of enantiomers. However, chiral method developments still can be time consuming and tedious. They designed a comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral, and acidic compounds with a 96-capillary array system. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pKs and structures. Therefore, unknown compounds can be screened in this manner to identify optimal enantioselective conditions in just one rn. In addition to superior separation efficiency for small molecules, CE is also the most powerful technique for DNA separations. Using the same multiplexed capillary system with UV absorption detection, the sequence of a short DNA template can be acquired without any dye-labels. Two internal standards were utilized to adjust the migration time variations among capillaries, so that the four electropherograms for the A, T, C, G Sanger reactions can be aligned and base calling can be completed with a high level of confidence. the CE separation of DNA can be applied to study differential gene expression as well. Combined with pattern recognition techniques, small variations among electropherograms obtained by the separation of cDNA fragments produced from the total RNA samples of different human tissues can be revealed. These variations reflect the differences in total RNA expression among tissues. Thus, this Ce-based approach can serve as an alternative to the DNA array techniques in gene expression analysis.

  5. Zwitterionic chiral stationary phases based on cinchona and chiral sulfonic acids for the direct stereoselective separation of amino acids and other amphoteric compounds.

    Science.gov (United States)

    Zhang, Tong; Holder, Emilie; Franco, Pilar; Lindner, Wolfgang

    2014-06-01

    An extensive series of free amino acids and analogs were directly resolved into enantiomers (and stereoisomers where appropriate) by HPLC on zwitterionic chiral stationary phases (Chiralpak ZWIX(+) and Chiralpak ZWIX(-)). The interaction and chiral recognition mechanisms were based on the synergistic double ion-paring process between the analyte and the chiral selectors. The chiral separation and elution order were found to be predictable for primary α-amino acids with apolar aliphatic side chains. A systematic investigation was undertaken to gain an insight into the influence of the structural features on the enantiorecognition. The presence of polar and/or aromatic groups in the analyte structure is believed to tune the double ion-paring equilibrium by the involvement of the secondary interaction forces such as hydrogen bonding, Van der Waals forces and π-π stacking in concert with steric parameters. The ZWIX chiral columns were able to separate enantiomers and stereoisomers of various amphoteric compounds with no need for precolumn derivatization. Column switching between ZWIX(+) and ZWIX(-) is believed to be an instrumental tool to reverse or control the enantiomers elution order, due to the complementarity of the applied chiral selectors.

  6. Chiral separation of agricultural fungicides.

    Science.gov (United States)

    Pérez-Fernández, Virginia; García, Maria Ángeles; Marina, Maria Luisa

    2011-09-23

    Fungicides are very important and diverse environmental and agricultural concern species. Their determination in commercial formulations or environmental matrices, requires highly efficient, selective and sensitive methods. A significant number of these chemicals are chiral with the activity residing usually in one of the enantiomers. The different toxicological and degradation behavior observed in many cases for fungicide enantiomers, results in the need to investigate them separately. For this purpose, separation techniques such as GC, HPLC, supercritical fluid chromatography (SFC) and CE have widely been employed although, at present, HPLC still dominates chromatographic chiral analysis of fungicides. This review covers the literature concerning the enantiomeric separation of fungicides usually employed in agriculture grouping the chiral separation methodologies developed for their analysis in environmental, biological, and food samples.

  7. Silica-based polypeptide-monolithic stationary phase for hydrophilic chromatography and chiral separation.

    Science.gov (United States)

    Zhao, Licong; Yang, Limin; Wang, Qiuquan

    2016-05-13

    Glutathione (GSH)-, somatostatin acetate (ST)- and ovomucoid (OV)-functionalized silica-monolithic stationary phases were designed and synthesized for HILIC and chiral separation using capillary electrochromatography (CEC). GSH, ST and OV were covalently incorporated into the silica skeleton via the epoxy ring-opening reaction between their amino groups and the glycidyl moiety in γ-glycidoxypropyltrimethoxysilane (GPTMS) together with polycondensation and copolymerization of tetramethyloxysilane and GPTMS. Not only could the direction and electroosmotic flow magnitude on the prepared GSH-, ST- and OV-silica hybrid monolithic stationary phases be controlled by the pH of the mobile phase, but also a typical HILIC behavior was observed so that the nucleotides and HPLC peptide standard mixture could be baseline separated using an aqueous mobile phase without any acetonitrile during CEC. Moreover, the prepared monolithic columns had a chiral separation ability to separate dl-amino acids. The OV-silica hybrid monolithic column was most effective in chiral separation and could separate dl-glutamic acid (Glu) (the resolution R=1.07), dl-tyrosine (Tyr) (1.57) and dl-histidine (His) (1.06). Importantly, the chiral separation ability of the GSH-silica hybrid monolithic column could be remarkably enhanced when using gold nanoparticles (AuNPs) to fabricate an AuNP-mediated GSH-AuNP-GSH-silica hybrid monolithic column. The R of dl-Glu, dl-Tyr and dl-His reached 1.19, 1.60 and 2.03. This monolithic column was thus applied to separate drug enantiomers, and quantitative separation of all four R/S drug enantiomers were achieved with R ranging from 4.36 to 5.64. These peptide- and protein-silica monolithic stationary phases with typical HILIC separation behavior and chiral separation ability implied their promise for the analysis of not only the future metabolic studies, but also drug enantiomers recognition.

  8. [Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids].

    Science.gov (United States)

    Wu, Haixia; Wang, Dongqiang; Zhao, Jianchao; Ke, Yanxiong; Liang, Xinmiao

    2016-01-01

    A novel chiral stationary phase combining quinine and crown ether (QN-CR CSP) was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids, a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point (FACP), the adsorption isotherms of tryptophan (Trp) under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether, the equilibrium constant of complexing adsorption was found increased. The chiral separation ability was decreased. The adsorption isotherm improved the understanding of the retention behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase.

  9. [Chiral separation of drugs based on macrocyclic antibiotics using HPLC, supercritical fluid chromatography (SFC) and capillary electrochromatography (CEC)].

    Science.gov (United States)

    Dungelová, J; Lehotay, J; Rojkovicová, T; Cizmárik, J

    2003-05-01

    Separation of enantiomers by means of high-performance liquid chromatography (HPLC), supercritical fluid chromatography (SFC), and capillary electrochromatography (CEC) is of great importance in pharmaceutical analyses. In recent years, separation of various types of racemates employs most frequently chiral stationary phases based on macrocyclic antibiotics. This class of chiral selectors includes vancomycin, teikoplanin, ristocetin A, teikoplanin without saccharide components, avoparcin, etc. The review paper describes the properties of selected antibiotics, the effect of chromatographic conditions on enantioselectivity (effect of the composition of the mobile phase, effect of pH of the mobile phase, effect of temperature), and the study of possible mechanisms of interaction, which play an important role in the separation of enantiomers. Examples of the use of macrocyclic antibiotics in the separation of various compounds by means of the HPLC, SFC, and CEC methods follow.

  10. Chiral separation of novel diazenes on a polysaccharide-based stationary phase in the reversed-phase mode.

    Science.gov (United States)

    Vojtylová, Terézia; Hamplová, Věra; Galewski, Zbigniew; Korbecka, Izabela; Sýkora, David

    2017-01-31

    Chiral high-performance liquid chromatography separation of two recently synthesized liquid crystalline materials C1 and C2 was studied in the reversed-phase mode. Both materials have an azo-moiety and one chiral centre in their molecular structures. They were available in racemic and pure S forms. For the enantiomeric separations, a Chiralpak AY-RH stationary phase based on amylose tris(5-chloro-2-methylphenylcarbamate) coated on 5 μm silica was used. The compounds were analyzed in both of their possible forms, the more thermodynamically stable E form and the labile Z form. The conditions and time scale of the UV-induced E to Z transition were briefly evaluated. Under the optimized conditions, we were able to baseline separate S and R enantiomers of both of the studied materials not only in their E forms but also in their Z forms. In comparison to the separation in the normal-phase mode, which we have reported recently, the resolution in the reversed-phase mode is significantly better. Interestingly, peak reversal was noticed for the S and R enantiomers when the separation was carried out with E versus Z forms of both compounds. This article is protected by copyright. All rights reserved.

  11. Separation of Chiral Active Pharmaceutical Ingredients

    DEFF Research Database (Denmark)

    Chaaban, Joussef Hussein

    is regarded as a first step towards a fully continuous PC process. The current knowledge of the importance of crystallization processes in the pharmaceutical industry and the complex thermodynamic and kinetic phenomena accompanied with the separation of chiral compounds are addressed. The experimental work...

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

    Science.gov (United States)

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

    2016-07-12

    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.

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

    Science.gov (United States)

    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.

  14. Chiral Ionic Liquids in Chromatographic Separation and Spectroscopic Discrimination

    Science.gov (United States)

    Li, Min; Bwambok, David K.; Fakayode, Sayo O.; Warner, Isiah M.

    Chiral ionic liquids (CILs) are a subclass of ionic liquids (ILs) in which the cation, anion, or both may be chiral. The chirality can be central, axial, or planar. CILs possess a number of unique advantageous properties which are inherited from ionic liquids including negligible vapor pressure, wide liquidus temperature range, high thermal stability, and high tunability. Due to their dual functionalities as chiral selectors and chiral solvents simultaneously, CILs recently have been widely used both in enantiomeric chromatographic separation and in chiral spectroscopic discrimination. In this chapter, the various applications of CILs in chiral chromatographic separations such as GC, HPLC, CE, and MEKC are reviewed. The applications of CILs in enantiomeric spectroscopic discrimination using techniques such as NMR, fluorescence, and NIR are described. In addition, chiral recognition and separation mechanism using the CILs as chiral selectors or chiral solvents is also discussed.

  15. Chiral separation and twin-beam photonics

    Science.gov (United States)

    Bradshaw, David S.; Andrews, David L.

    2016-03-01

    It is well-known that, in a homogeneous fluid medium, most optical means that afford discrimination between molecules of opposite handedness are intrinsically weak effects. The reason is simple: the wide variety of origins for differential response commonly feature real or virtual electronic transitions that break a parity condition. Despite being electric dipole allowed, they manifest the chirality of the material in which they occur by breaking a selection rule that would otherwise preclude the simultaneous involvement of magnetic dipole or electric quadrupole forms of coupling. Although the latter are typically weaker than electric dipole effects by several orders of magnitude, it is the involvement of these weak forms of interaction that are responsible for chiral sensitivity. There have been a number of attempts to cleverly exploit novel optical configurations to enhance the relative magnitude - and hence potentially the efficiency - of chiral discrimination. The prospect of success in any such venture is enticing, because of the huge impact that such an advance might be expected to have in the health, food and medical sectors. Some of these proposals have utilized mirror reflection, and others surface plasmon coupling, or optical binding methods. Several recent works in the literature have drawn attention to a further possibility: the deployment of optical beam interference as a means to achieve chiral separations of sizeable extent. In this paper the underlying theory is fully developed to identify the true scope and limitations of such an approach.

  16. Emerging functional chiral microporous materials: synthetic strategies and enantioselective separations

    Directory of Open Access Journals (Sweden)

    Ming Xue

    2016-11-01

    Full Text Available In recent years, chiral microporous materials with open pores have attracted much attention because of their potential applications in enantioselective separation and catalysis. This review summarizes the recent advances on chiral microporous materials, such as metal-organic frameworks (MOFs, hydrogen-bonded organic frameworks (HOFs and covalent organic frameworks (COFs. We will introduce the synthetic strategies in detail and highlight the current status of chiral microporous materials on solid enantioselective adsorption, chiral chromatography resolution and membrane separation.

  17. Enantiomeric separation and simulation studies of pheniramine, oxybutynin, cetirizine, and brinzolamide chiral drugs on amylose-based columns.

    Science.gov (United States)

    Ali, Imran; Al-Othman, Zeid A; Al-Warthan, Abdulrahman; Alam, Syed Dilshad; Farooqi, Javed A

    2014-03-01

    Solid phase extraction (SPE)-chiral separation of the important drugs pheniramine, oxybutynin, cetirizine, and brinzolamide was achieved on the C18 cartridge and AmyCoat (150 x 46 mm) and Chiralpak AD (25 cm x 0.46 cm id) chiral columns in human plasma. Pheniramine, oxybutynin, cetirizine, and brinzolamide were resolved using n-hexane-2-PrOH-DEA (85:15:0.1, v/v), n-hexane-2-PrOH-DEA (80:20:0.1, v/v), n-hexane-2-PrOH-DEA (70:30:0.2, v/v), and n-hexane-2-propanol (90:10, v/v) as mobile phases. The separation was carried out at 25 ± 1 ºC temperature with detection at 225 nm for cetirizine and oxybutynin and 220 nm for pheniramine and brinzolamide. The flow rates of the mobile phases were 0.5 mL min(-1). The retention factors of pheniramine, oxybutynin, cetirizine and brinzolamide were 3.25 and 4.34, 4.76 and 5.64, 6.10 and 6.60, and 1.64 and 2.01, respectively. The separation factors of these drugs were 1.33, 1.18, 1.09 and 1.20 while their resolutions factors were 1.09, 1.45, 1.63 and 1.25, and 1.15, respectively. The absolute configurations of the eluted enantiomers of the reported drugs were determined by simulation studies. It was observed that the order of enantiomers elution of the reported drugs was S-pheniramine > R-pheniramine; R-oxybutynin > S-oxybutynin; S-cetirizine > R-cetirizine; and S-brinzolamide > R-brinzolamide. The mechanism of separation was also determined at the supramolecular level by considering interactions and modeling results. The reported SPE-chiral high-performance liquid chromatography (HPLC) methods are suitable for the enantiomeric analyses of these drugs in any biological sample. In addition, simulation studies may be used to determine the absolute configuration of the first and second eluted enantiomers.

  18. Chiral Separation of Erythromycin as a New Chiral Selector on CE

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Erythromycin as a new chiral selector was first used for chrial separation of four derivatives of biphenyldimethylester enantiomers on CE. The influence of pH, the chiral selector concentration and organic modifiers were preliminarily studied. Experiments show that the erythromycin as chiral selector is useful to CE.

  19. Chiral separation of pharmaceutical compounds using electrochemically modulated liquid chromatography (EMLC)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S. [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    This research explores the application of a new technique, termed electrochemically modulated liquid chromatography (EMLC), to the chiral separations of pharmaceutical compounds. The introduction section provides a literature review of the technique and its applications, as well as brief overview of the research described in each of the next two chapters. Chapter 2 investigates the EMLC-based enantiomeric separation of a group of chiral benzodiazepines with β-cyclodextrin as a chiral mobile phase additive. Chapter 3 demonstrates the effects of several experimental parameters on the separation efficiency of drug enantiomers. The author concludes with a general summary and possible directions for future studies. Chapters 2 and 3 are processed separately.

  20. Simultaneous Chiral SeparationUsing a Combinatorial Molecular Imprinting Phase

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Molecular imprinting chiral stationary phase against Cbz-L-Serine (Cbz-L-Ser) and Cbz-L-Alaine (Cbz-L-Ala) were prepared utilizing acrylamide + 2-vinylpyridine as combined basic functional monomers.Cross-selectivity was used to obtain simultaneous chiral separations of Cbz-DL-Ser and Cbz-DL-Ala by connecting two columns packed with Cbz-L-Ser and Cbz-L-Ala imprinted chiral stationary phase, respectively.

  1. Chiral Recognition Mechanisms in Enantiomers Separations: A General View

    Science.gov (United States)

    Berthod, Alain

    In 1858, Louis Pasteur, the first to accomplish the separation of two enantiomers wrote: “Most natural organic products, the essential products of life, are asymmetric and possess such asymmetry that they are not superimposable on their image. This establishes perhaps the only well-marked line of demarcation that can at present be drawn between the chemistry of dead matter and the chemistry of living matter.” Enantiomers have exactly the same properties in isotropic conditions. They behave differently only in anisotropic conditions. Chiral-chiral interactions are needed for enantiomeric separations. The fundamental mechanisms for chiral separations are listed along with the commercially available chiral selectors. Two chemometric examples are commented: one on quantitative structure enantioselectivity relationship and the second one on linear solvation energy relationships. It is shown that the solvents used in the mobile phase may play the most critical role in the chiral mechanism.

  2. A molecular propeller effect for chiral separation and analysis

    Science.gov (United States)

    Clemens, Jonathon B.; Kibar, Osman; Chachisvilis, Mirianas

    2015-07-01

    Enantiomers share nearly identical physical properties but have different chiral geometries, making their identification and separation difficult. Here we show that when exposed to a rotating electric field, the left- and right-handed chiral molecules rotate with the field and act as microscopic propellers; moreover, owing to their opposite handedness, they propel along the axis of field rotation in opposite directions. We introduce a new molecular parameter called hydrodynamic chirality to characterize the coupling of rotational motion of a chiral molecule into its translational motion and quantify the direction and velocity of such motion. We demonstrate >80% enrichment level of counterpart enantiomers in solution without using chiral selectors or circularly polarized light. We expect our results to have an impact on multiple applications in drug discovery, analytical and chiral chemistry, including determination of absolute configuration, as well as in influencing the understanding of artificial and natural molecular systems where rotational motion of the molecules is involved.

  3. Exploring chiral separation of 3-carboxamido-5-aryl isoxazole derivatives by supercritical fluid chromatography on amylose and cellulose tris dimethyl- and chloromethyl phenylcarbamate polysaccharide based stationary phases.

    Science.gov (United States)

    Zehani, Yasmine; Lemaire, Lucas; Ghinet, Alina; Millet, Régis; Chavatte, Philippe; Vaccher, Claude; Lipka, Emmanuelle

    2016-10-07

    Four polysaccharide based chiral stationary phases were chosen, two chlorinated: Lux™ Amylose-2 (tris-5-chloro-2-methylphenylcarbamate of amylose) and Lux™ Cellulose-2 (tris-3-chloro-4-methylphenylcarbamate of cellulose) and two methylated: Chiralpak(®) AD-H (tris-3,5-dimethylphenylcarbamate of amylose) and Chiralcel(®) OD-H (tris-3,5-dimethylphenylcarbamate of cellulose) to separate four 3-carboxamido-5-aryl isoxazole derivatives by supercritical fluid chromatography. The effect of chiral stationary phase, co-solvent nature (MeOH, EtOH, 2-PrOH and ACN) and percentage (10-20%), temperature (20-45°C) and chemical structure of the compounds on retention, resolution and elution order were thoroughly studied. In addition, thermodynamic parameters were determined from the linear portion of the Van't Hoff plots. For all the derivatives, the Lux™ Cellulose-2 and Chiralpak(®) AD-H provided excellent resolutions (Rs=9.78) in short run time (under 6min). The preparation of about 10mg of each of the eight enantiomers was achieved successfully on a Chiralpak(®) AD-H with various percentages of ethanol as a co-solvent. Lastly, the enantiomeric purity of each of the eight individual enantiomer generated was determined and found higher than 98%.

  4. Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging.

    Science.gov (United States)

    Yomogida, Yohei; Tanaka, Takeshi; Zhang, Minfang; Yudasaka, Masako; Wei, Xiaojun; Kataura, Hiromichi

    2016-06-28

    Single-chirality, single-wall carbon nanotubes are desired due to their inherent physical properties and performance characteristics. Here, we demonstrate a chromatographic separation method based on a newly discovered chirality-selective affinity between carbon nanotubes and a gel containing a mixture of the surfactants. In this system, two different selectivities are found: chiral-angle selectivity and diameter selectivity. Since the chirality of nanotubes is determined by the chiral angle and diameter, combining these independent selectivities leads to high-resolution single-chirality separation with milligram-scale throughput and high purity. Furthermore, we present efficient vascular imaging of mice using separated single-chirality (9,4) nanotubes. Due to efficient absorption and emission, blood vessels can be recognized even with the use of ∼100-fold lower injected dose than the reported value for pristine nanotubes. Thus, 1 day of separation provides material for up to 15,000 imaging experiments, which is acceptable for industrial use.

  5. Chiral separation of amides using supercritical fluid chromatography.

    Science.gov (United States)

    Xiang, Yanqiao; Dunetz, Joshua R; Lovdahl, Michael

    2013-06-07

    Nine amide derivatives bearing α-stereocenters as well as different substitutions on the amide nitrogen were synthesized via an n-propanephosphonic acid cyclic anhydride (T3P)-mediated coupling, and their enantiomeric pairs were separated using supercritical fluid chromatography (SFC). Five polysaccharide-based chiral stationary phases (CSPs), Chiralcel OD-H, and OJ-H, and Chiralpak AD-H, AS-H and IC columns were explored for the chiral separation of these compounds. None of the compounds could be resolved on all five columns, and no single column could separate all nine pairs of enantiomers. Comparatively, the IC and OD-H columns showed the best results for this group of amides, yielding baseline separations for eight of nine pairs. The type of polar functional group and aromatic substitution in the CSPs and the substitutions on the amide nitrogen had a significant impact on the enantiomeric resolution of the compounds in the interaction between the analyte and the stationary phases. The potential separation mechanism and the effect of substitutions in the CSPs and amide solutes on the separation are discussed. The effects of the organic modifiers, modifier composition, mobile phase additives, and temperature were investigated for the separation of these amides on the IC or the OD-H column. Baseline resolution was achieved under optimized chromatographic conditions using an IC or an OD-H column. Linearity, reproducibility, and limit of quantitation were also demonstrated for the compound 9. Approximately three-fold improvement in signal-to-noise was observed using a SFC system with better instrument design.

  6. Chiral quantum dot based materials

    Science.gov (United States)

    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.

  7. Enantiomeric separations of chiral pharmaceuticals using chirally modified tetrahexahedral Au nanoparticles

    Science.gov (United States)

    Shukla, N.; Yang, D.; Gellman, A. J.

    2016-06-01

    Tetrahexahedral (THH, 24-sided) Au nanoparticles modified with D- or L-cysteine (Cys) have been used as enantioselective separators of the chiral pharmaceutical propranolol (PLL) in solution phase. Polarimetry has been used to measure the rotation of linearly polarized light by solutions containing mixtures of PLL and Cys/THH-Au NPs with varying enantiomeric excesses of each. Polarimetry yields clear evidence of enantiospecific adsorption of PLL onto the Cys/THH-Au NPs. This extends prior work using propylene oxide as a test chiral probe, by using the crystalline THH Au NPs with well-defined facets to separate a real pharmaceutical. This work suggests that chiral nanoparticles, coupled with a density separation method such as centrifugation, could be used for enantiomeric purification of real pharmaceuticals. A simple robust model developed earlier has also been used to extract the enantiospecific equilibrium constants for R- and S-PLL adsorption onto the D- and L-Cys/THH-Au NPs.

  8. Separation of carbon nanotubes into chirally enriched fractions

    Science.gov (United States)

    Doorn, Stephen K [Los Alamos, NM; Niyogi, Sandip [Los Alamos, NM

    2012-04-10

    A mixture of single-walled carbon nanotubes ("SWNTs") is separated into fractions of enriched chirality by preparing an aqueous suspension of a mixture of SWNTs and a surfactant, injecting a portion of the suspension on a column of separation medium having a density gradient, and centrifuging the column. In some embodiments, salt is added prior to centrifugation. In other embodiments, the centrifugation is performed at a temperature below room temperature. Fractions separate as colored bands in the column. The diameter of the separated SWNTs decreases with increasing density along the gradient of the column. The colored bands can be withdrawn separately from the column.

  9. A validated chiral LC method for enantiomeric separation of nebivolol stereoisomers in bulk drugs and dosage forms on amylose-based stationary phase.

    Science.gov (United States)

    Visweswara Rao, Karri; Padmaja Reddy, Kesareddy; Haldar, Pranab

    2014-10-01

    A novel and reproducible isocratic normal phase liquid chromatographic method was developed for the quantitative determination of 10 stereoisomers of Nebivolol in pharmaceutical bulk drugs and dosage forms. The method was developed using an amylose-based chiral stationary phase, Chiralpak AD-3 (250 × 4.6 mm, 3 μm) column with mobile phase containing n-hexane-ethanol-isopropanol-diethanolamine in the ratio 42:45:13:0.1 (v/v/v/v). The eluted compounds were monitored at 280 nm. Ten stereoisomers of Nebivolol were well separated with resolution >2.0 for all pair of components. The developed method was validated as per International Conference on Harmonization (ICH) guidelines with respect to specificity, linearity (R(2) value >0.999), limit of detection, limit of quantification, accuracy (recovery range 95.8-103.2%), precision (relative standard deviation, RSD, <2.5%) and robustness. Nebivolol sample solutions were found to be stable when characterized over a period of 48 h. Forced degradation studies were also performed to demonstrate the stability-indicating power of the developed HPLC method. The method was found to be rugged and robust.

  10. Enantiomer Separation of α-Dimethyl Dicarboxylate Biphenyl and Related Biphenyl Compounds by Normal Phase HPLC on Polysaccharide Based Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    LIU,Yue-Qi(刘月启); HAN,Xiao-Qian(韩小茜); Qi,Bang-Feng(齐邦峰); LIU,Chun-Hui(柳春辉); LI,Yong-Min(李永民); CHEN,Li-Ren(陈立仁)

    2002-01-01

    Cellulose tris(4-methylphenylcarbamate), amylose tris(3,5-dimethylpphenylcarbamate) and amylose tris (phenylcarbamate)were prepared by the method reported by Okamoto and were coated onto an aminopropylated mesoporous spherical silica gel. These final products were used as chiral stationary phases of high performance liquid chromatography for the eighteen structurally related biphenyl conmpounds. The resolution was made using normal-phase methodology with a mobile phase consisting of n-hexane-alcohol (ethanol, 1-propanol, 2-propanol or 1-butanol). The effects of various aliphatic alcohols in the mobile phase were studied. The structural features of the solutes that influence their k'were discussed. A dominant effect of trifluoroaetic acid on chiral separation of aacidicdic solutes was noted.

  11. Separation of chiral particles in micro- or nanofluidic channels

    CERN Document Server

    Meinhardt, Sebastian; Eichhorn, Ralf; Schmid, Friederike

    2012-01-01

    We propose a method to separate enantiomers in microfluidic or nanofluidic channels. It requires flow profiles which break chiral symmetry and have regions with high local shear. Such profiles can be generated in channels confined by walls with different hydrodynamic boundary conditions (e.g. slip lengths). Due to a nonlinear hydrodynamic effect, particles with different chirality migrate at different speed and can be separated. The mechanism is demonstrated by computer simulations. We investigate the influence of thermal fluctuations (i.e. the P\\'eclet number) and show that the effect disappears in the linear response regime. The details of the microscopic flow are important and determine which volume forces are necessary to achieve separation.

  12. Velocity gap mode of capillary electrophoresis developed for high-resolution chiral separations.

    Science.gov (United States)

    Li, Xue; Li, Youxin; Zhao, Lumeng; Shen, Jianguo; Zhang, Yong; Bao, James J

    2014-10-01

    A new CE method based on velocity gap (VG) theory has been developed for high-resolution chiral separations. In VG, two consecutive electric fields are adopted to drive analytes passing through two capillaries, which are linked together through a joint. The joint is immersed inside another buffer vial which has conductivity communication with the buffer inside the capillary. By adjusting the field strengths onto the two capillaries, it is possible to observe different velocities of an analyte when it passes through those two capillaries and there would be a net velocity change (NVC) for the same analyte. Different analytes may have different NVC which may be specifically meaningful for enantioseparations because enantiomers are usually hard to resolve. By taking advantage of this NVC, it is possible to enhance the resolution of a chiral separation if a proper voltage program is applied. The feasibility of using NVC to enhance chiral separation was demonstrated in the separations of three pairs of enantiomers: terbutaline, chlorpheniramine, and promethazine. All separations started with partial separation in a conventional CE and were significantly improved under the same experimental conditions. The results indicated that VG has the potential to be used to improve the resolving power of CE in chiral separations.

  13. Reprint of: Enantiomeric separation of functionalized ethano-bridged Tröger bases using macrocyclic cyclofructan and cyclodextrin chiral selectors in high-performance liquid chromatography and capillary electrophoresis with application of principal component analysis.

    Science.gov (United States)

    Weatherly, Choyce A; Na, Yun-Cheol; Nanayakkara, Yasith S; Woods, Ross M; Sharma, Ankit; Lacour, Jérôme; Armstrong, Daniel W

    2014-10-01

    The enantiomeric separation of a series of racemic functionalized ethano-bridged Tröger base compounds was examined by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). Using HPLC and CE the entire set of 14 derivatives was separated by chiral stationary phases (CSPs) and chiral additives composed of cyclodextrin (native and derivatized) and cyclofructan (derivatized). Baseline separations (Rs ≥ 1.5) in HPLC were achieved for 13 of the 14 compounds with resolution values as high as 5.0. CE produced 2 baseline separations. The separations on the cyclodextrin CSPs showed optimum results in the reversed phase mode, and the LARIHC cyclofructan CSPs separations showed optimum results in the normal phase mode. HPLC separation data of the compounds was analyzed using principal component analysis (PCA). The PCA biplot analysis showed that retention is governed by the size of the R1 substituent in the case of derivatized cyclofructan and cyclodextrin CSPs, and enantiomeric resolution closely correlated with the size of the R2 group in the case of non-derivatized γ-cyclodextrin CSP. It is clearly shown that chromatographic retention is necessary but not sufficient for the enantiomeric separations of these compounds.

  14. Enantiomeric separation of functionalized ethano-bridged Tröger bases using macrocyclic cyclofructan and cyclodextrin chiral selectors in high-performance liquid chromatography and capillary electrophoresis with application of principal component analysis.

    Science.gov (United States)

    Weatherly, Choyce A; Na, Yun-Cheol; Nanayakkara, Yasith S; Woods, Ross M; Sharma, Ankit; Lacour, Jérôme; Armstrong, Daniel W

    2014-04-01

    The enantiomeric separation of a series of racemic functionalized ethano-bridged Tröger base compounds was examined by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). Using HPLC and CE the entire set of 14 derivatives was separated by chiral stationary phases (CSPs) and chiral additives composed of cyclodextrin (native and derivatized) and cyclofructan (derivatized). Baseline separations (Rs≥1.5) in HPLC were achieved for 13 of the 14 compounds with resolution values as high as 5.0. CE produced 2 baseline separations. The separations on the cyclodextrin CSPs showed optimum results in the reversed phase mode, and the LARIHC™ cyclofructan CSPs separations showed optimum results in the normal phase mode. HPLC separation data of the compounds was analyzed using principal component analysis (PCA). The PCA biplot analysis showed that retention is governed by the size of the R1 substituent in the case of derivatized cyclofructan and cyclodextrin CSPs, and enantiomeric resolution closely correlated with the size of the R2 group in the case of non-derivatized γ-cyclodextrin CSP. It is clearly shown that chromatographic retention is necessary but not sufficient for the enantiomeric separations of these compounds.

  15. Recent Advances in Protein Extraction and Chiral Separation of Biomolecules

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Reverse micelles create unique environment in organic media. They are capable of solubilizing hydrophilic biomolecules (e.g., proteins, peptides, amino acids, and DNAs) in their aqueous interior. This feature brings about the practical use of biomaterials in organic media because reverse micelles solubilize them with the intrinsic activity. In this paper, we focus on recent two topics concerning protein extraction and chiral separation of biomolecules using liquid membranes. In the first topic, we present recent attempts to extract proteins from an aqueous solution into isooctane using reverse micelles, and some important operational parameters to achieve an efficient protein transfer are discussed. Furthermore, novel function of reverse micelles as a protein activation medium is introduced. In the reverse micellar phase, denatured proreins were completely reactivated in the reverse micellar solution. The reverse micellar technique is found to be a useful tool not only for protein separation but also for protein refolding. Furthermore, we found that a cyclic ligand carixarene has an extraction ability to set up optimum conditions for protein transfer. In the second topic, we have found that a supported liquid membrane (SLM) encapsulating enzymes shows high enantioselectivity (enantioselective excess value is over 96%) in the transport of racemic pharmaceutical compound ibuprofen. A different experiment also suggests that the α-chymotrypsin-catalyzed reactions droved the enantioselective transport of L-phenylalanine based on the enantioselectivity of the enzyme. The SLM encapsulating the surfactant-enzyme complex enabled the highly enantioselective separation of racemic mixtures. It can be envisioned that arrangement of appropriate enzymes in the SLM system will allow enantioselective separation of various useful organic compounds.

  16. Enantiomeric Separation of Four Chiral Compounds Using Immobilized Cellulose 3, 5-Dimethylphenylcarbamate as Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    Yong Fei MING; Liang ZHAO; Hong Li ZHANG; Yan Ping SHI; Yong Min LI; Li Ren CHEN

    2006-01-01

    A new chiral stationary phase of 3, 5-dimethylphenylcarbamates of cellulose,chemically bonded to 3-aminopropylsilica gel at the 6-positions of the glucose units, was prepared.The solvent versatility of the CSP was investigated for the enantioselective separation of four pairs of enantiomers using THF and chloroform as non-standard mobile phase eluent in HPLC. The influence of temperature on the resolution was investigated.

  17. On the chiral separation effect in a slab

    CERN Document Server

    Sitenko, Yu A

    2016-01-01

    We study an influence of boundaries on chiral effects in hot dense relativistic spinor matter in a strong magnetic field which is transverse to bounding planes. The most general set of boundary conditions ensuring the confinement of matter within the bounding planes is considered. We find that, in thermal equilibrium, the nondissipative axial current along the magnetic field is induced, depending on chemical potential and temperature, as well as on a choice of boundary conditions. As temperature increases from zero to large values, a stepwise behaviour of the axial current density as a function of chemical potential is changed to a smooth one; the choice of a boundary condition can facilitate either amplification or diminution of the chiral separation effect. This points at a significant role of boundaries for physical systems with hot dense magnetized relativistic spinor matter, e.g., compact stars, heavy-ion collisions, novel materials known as Dirac and Weyl semimetals.

  18. Quark Mass Correction to Chiral Separation Effect and Pseudoscalar Condensate

    CERN Document Server

    Guo, Er-dong

    2016-01-01

    We derived an analytic structure of the quark mass correction to chiral separation effect (CSE) in small mass regime. We confirmed this structure by a D3/D7 holographic model study in a finite density, finite magnetic field background. The quark mass correction to CSE can be related to correlators of pseudo-scalar condensate, quark number density and quark condensate in static limit. We found scaling relations of these correlators with spatial momentum in the small momentum regime. They characterize medium responses to electric field, inhomogeneous quark mass and chiral shift. Beyond the small momentum regime, we found existence of normalizable mode, which possibly leads to formation of spiral phase. The normalizable mode exists beyond a critical magnetic field, whose magnitude decreases with quark chemical potential.

  19. (-)/(+)-Sparteine induced chirally-active carbon nanoparticles for enantioselective separation of racemic mixtures.

    Science.gov (United States)

    Vulugundam, Gururaja; Misra, Santosh K; Ostadhossein, Fatemeh; Schwartz-Duval, Aaron S; Daza, Enrique A; Pan, Dipanjan

    2016-06-14

    Chiral carbon nanoparticles (CCNPs) were developed by surface passivation using the chiral ligand (-)-sparteine or (+)-sparteine (denoted (-)-SP/CNP and (+)-SP/CNP, respectively). The chirality of the prepared CCNPs was demonstrated by circular dichroism and polarimetry and employed as an enantioselective separation platform for representative racemic mixtures.

  20. Conventional Chiralpak ID vs. capillary Chiralpak ID-3 amylose tris-(3-chlorophenylcarbamate)-based chiral stationary phase columns for the enantioselective HPLC separation of pharmaceutical racemates.

    Science.gov (United States)

    Ahmed, Marwa; Gwairgi, Marina; Ghanem, Ashraf

    2014-11-01

    A comparative enantioselective analysis using immobilized amylose tris-(3-chlorophenylcarbamate) as chiral stationary phase in conventional high-performance liquid chromatography (HPLC) with Chiralpak ID (4.6 mm ID × 250 mm, 5 µm silica gel) and micro-HPLC with Chiralpak ID-3 (0.30 mm ID × 150 mm, 3 µm silica gel) was conducted. Pharmaceutical racemates of 12 pharmacological classes, namely, α- and β-blockers, anti-inflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs were screened under normal phase conditions. The effect of an organic modifier on the analyte retentions and enantiomer recognition was investigated. Baseline separation was achieved for 1-acenaphthenol, carprofen, celiprolol, cizolirtine carbinol, miconazole, tebuconazole, 4-hydroxy-3-methoxymandelic acid, 1-indanol, 1-(2-chlorophenyl)ethanol, 1-phenyl-2-propanol, flavanone, 6-hydroxyflavanone, 4-bromogluthethimide, and pentobarbital on the 4.6 mm ID packed with a 5 µm silica column using conventional HPLC. Nonetheless, baseline separation was achieved for aminoglutethimide, naftopidil, and thalidomide on the 0.3 mm ID packed with a 3 µm silica capillary column.

  1. [Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers].

    Science.gov (United States)

    Qi, Xiaoyue; Li, Xianjiang; Bai, Yu; Liu, Huwei

    2016-01-01

    Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.

  2. Separation and Structure of Chiral S-Malic Acid Hydrate

    Institute of Scientific and Technical Information of China (English)

    NIE,Jing-Jing(聂晶晶); XU,Duan-Jun(徐端钧); WU,Jing-Yun(吴景云); CHIANG,Michael Y.(蒋燕南)

    2002-01-01

    Crystals of the chiral malic acid hydrate ( C4H6O5@H2O ) were unexpectedly obtained from an ethanol ethanol/water solution containing racemic D,L-malic acid and L-asparagine. The crystal belongs to orthorhombic space group P21 21 21 with cell dimensions of a=0.5576(1), b=0.9818(2), c=1.1793(2) nm, V=0.9455(2) nm3, Z=4, μ(Mo Kα) =0.152 mm-1, F(000) =320, Dc= 1.565 g@cm-3, R =0.051, wR =0.136 for 657 observed reflections [I>2σ(I)]. The significant difference in bond distances for carboxyl groups suggests that the crystal consist of malate anion and protonized crystalline water. This is a report for direct separation of racemic mixture, i.e., without the formation of a molecular complex of raceme with a chiral separating reagent.

  3. Chiral Separation by Flows: The Role of Flow Symmetry and Dimensionality

    Science.gov (United States)

    Ro, Sunghan; Yi, Juyeon; Kim, Yong Woon

    2016-01-01

    Separation of enantiomers by flows is a promising chiral resolution method using cost-effective microfluidics. Notwithstanding a number of experimental and numerical studies, a fundamental understanding still remains elusive, and an important question as to whether it is possible to specify common physical properties of flows that induce separation has not been addressed. Here, we study the separation of rigid chiral objects of an arbitrary shape induced by a linear flow field at low Reynolds numbers. Based on a symmetry property under parity inversion, we show that the rate-of-strain field is essential to drift the objects in opposite directions according to chirality. From eigenmode analysis, we also derive an analytic expression for the separation conditions which shows that the flow field should be quasi-two-dimensional for the precise and efficient resolutions of microscopic enantiomers. We demonstrate this prediction by Langevin dynamics simulations with hydrodynamic interactions fully implemented. Finally, we discuss the practical feasibility of the linear flow analysis, considering separations by a vortex flow or an extensional flow under a confining potential. PMID:27739430

  4. Chiral Separation of Ibuprofen and Terbutaline by Nonaqueous Capillary Electrophoresis with Conductance Detection

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In the nonaqueous N,N-dimethylformamide medium, the chiral drugs ibuprofen and terbutaline were successfully separated with sulfonyl-β-cyclodextrin(s-β-CD) as the chiral selector by capillary electrophoresis with conductance detection. The comparison of the effects of three CDS(β-CD, diethylic-β-CD, sulfonyl-β-CD) on the chiral separation was made and the resolution mechanism was proposed.

  5. Chiral separation of racemic drugs using molecular imprinting

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Molecularly imprinted polymers (MIPs) of (S)-ketoprofen and (S)-naproxen are prepared using non-covalent imprinting in the presence of template molecules. The prepared MIPs are used as the chiral stationary phase to separate ramemic naproxen and ketoprofen. The results show that racemic naproxen and ketoprofen are efficiently resolved on MIPs. The effect of concentration of acetic acid in the mobile phase is studied, and the data are analyzed using the affinity chromatography model, and the close agreement is achieved between the simulated and experimental curves. The results suggest that the affinity chromatography mechanism controls the retention in this system. Moreover, the affinity chromatography equilibrium constants on (S)-naproxen and (S)-ketoprofen are estimated.

  6. Synthesis of chiral dopants based on carbohydrates.

    Science.gov (United States)

    Tsuruta, Toru; Koyama, Tetsuo; Yasutake, Mikio; Hatano, Ken; Matsuoka, Koji

    2014-07-01

    Chiral dopants based on carbohydrates for nematic liquid crystals were synthesized from D-glucose, and their helical twisting power (HTP) values were evaluated. The chiral dopants induced helices in the host nematic liquid crystals. An acetyl derivative having an ether-type glycosidic linkage between carbohydrate and a mesogenic moiety showed the highest HTP value of 10.4 μm(-1), while an acetyl derivative having an anomeric ester-type linkage did not show any HTP. It was surprising that this molecule had no HTP despite the presence of chirality in the molecule. A relationship between HTP and specific rotation was not observed in this study.

  7. Chiral Separation of Spiro-compounds and Determination Configuration

    Institute of Scientific and Technical Information of China (English)

    LIANG Ya; GUO Jing-jing; LIU Xiu-ming; WEI Rong-bao

    2008-01-01

    Chiral spirocyclic compounds have attracted the attention of scholars and scientists owing to their potential applications in the pharmaceutical industry as either active pharmaceutical ingredients,catalysts in synthesizing active enantiomers,or as surface modifiers on silica particles to resolve entantiomers,In this study,five spiro compounds of 3,9-diphenyl-2,4,8,10-tetraoxaspiro[5.5]-undecane(1),3,9-(4-methoxyphenyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane(2),3,9-(4-methylphenyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane(3),4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dibenzoie acid(4) and 3,9-di(4-formyl-phenyl)-2,4,8,10-tetraoxa-spiro[5.5]-undecane(5) were synthesized by grinding pentaerythritol with benzaldehyde,4-methoxybenzaldehyde,4-methylbenzaldehyde,4-carboxybenzaldehyde or terephthalaldehyde monoacetal in the presence of InBr3 under solvent-free conditions,A normal phase HPLC method was successfully developed to resolve entantiomers of compounds 1-5 on a chiral column,Specific optical rotation of R or S entantiomers(1) was determined and the corresponding configurations were proposed based on Lowe's rule.

  8. Chiral separation of the clinically important compounds fucose and pipecolic acid using CE: determination of the most effective chiral selector.

    Science.gov (United States)

    Hadjistasi, Christoforos A; Stavrou, Ioannis J; Stefan-Van Staden, Raluca-Ioana; Aboul-Enein, Hassan Y; Kapnissi-Christodoulou, Constantina P

    2013-09-01

    In this study, simple electrophoretic methods were developed for the chiral separation of the clinically important compounds fucose and pipecolic acid. In recent years, these analytes, and particularly their individual enantiomers, have attracted considerable attention due to their role in biological functions and disorders. The detectability and sensitivity of pipecolic acid and fucose were improved by reacting them with fluorenylmethyloxycarbonyl chloride (FMOC-Cl) and 5-amino-2-naphthalene-sulfonic acid (ANSA), respectively. The enantioseparation conditions were optimized by initially investigating the type of the chiral selector. Different chiral selectors, such as polymeric surfactants and cyclodextrins, were used and the most effective ones were determined with regard to resolution and analysis time. A 10-mM β-cyclodextrin was able to separate the enantiomers of ANSA-DL-fucose and the polymeric surfactant poly(sodium N-undecanoyl-LL-leucine-valinate) was able to separate the enantiomers of FMOC-DL-pipecolic acid, with resolution values of 3.45 and 2.78, respectively. Additional parameters, such as the concentration and the pH of the background electrolyte (BGE), the concentration of the chiral selector, and the addition of modifiers were examined in order to optimize the separations. The addition of the chiral ionic liquid D-alanine tert-butyl ester lactate into the BGE was also investigated, for the first time, in order to improve resolution of the enantiomers.

  9. Application of cinchona-sulfonate-based chiral zwitterionic ion exchangers for the separation of proline-containing dipeptide rotamers and determination of on-column isomerization parameters from dynamic elution profiles

    Energy Technology Data Exchange (ETDEWEB)

    Wernisch, Stefanie, E-mail: stefanie.wernisch@univie.ac.at [Institute for Analytical Chemistry, University of Vienna, Währinger Straße 38, A-1090 Vienna (Austria); Trapp, Oliver, E-mail: trapp@oci.uni-heidelberg.de [Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg (Germany); Lindner, Wolfgang, E-mail: wolfgang.lindner@univie.ac.at [Institute for Analytical Chemistry, University of Vienna, Währinger Straße 38, A-1090 Vienna (Austria)

    2013-09-17

    Graphical abstract: -- Highlights: •X-Pro peptides produce interconverting elution profiles on zwitterionic stationary phases. •The cis–trans isomerization rate in solution is lower than in the chromatographic system. •Cinchona-based zwitterionic selectors apparently lower the isomerization barrier. •Rotamer separation is feasible <0 °C, enantiomer separation above room temperature. -- Abstract: The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from −15 °C to +45 °C The cis–trans isomers could be separated below 0 °C and above 0–10 °C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics.

  10. Application of High Performance Liquid Chromatography to Separation of Novel Chiral Tetrahedral Heterometal Clusters

    Institute of Scientific and Technical Information of China (English)

    Xin Yi ZHU; Wei Qiang ZHANG; Yu Hua ZHANG; Li Ren CHEN; Yong Min LI

    2003-01-01

    A series of novel chiral tetrahedral heterometal clusters have firstly been separated oncellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high performance liquid chrom-atography, using hexane as the mobile phase with various alcohols as modifiers.

  11. Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

    Science.gov (United States)

    Peng, Yongwu; Gong, Tengfei; Zhang, Kang; Lin, Xiaochao; Liu, Yan; Jiang, Jianwen; Cui, Yong

    2014-07-01

    The separation of racemic molecules is of substantial significance not only for basic science but also for technical applications, such as fine chemicals and drug development. Here we report two isostructural chiral metal-organic frameworks decorated with chiral dihydroxy or -methoxy auxiliares from enantiopure tetracarboxylate-bridging ligands of 1,1‧-biphenol and a manganese carboxylate chain. The framework bearing dihydroxy groups functions as a solid-state host capable of adsorbing and separating mixtures of a range of chiral aromatic and aliphatic amines, with high enantioselectivity. The host material can be readily recycled and reused without any apparent loss of performance. The utility of the present adsorption separation is demonstrated in the large-scale resolution of racemic 1-phenylethylamine. Control experiments and molecular simulations suggest that the chiral recognition and separation are attributed to the different orientations and specific binding energies of the enantiomers in the microenvironment of the framework.

  12. Molecularly Imprinted Polymers for the Identification and Separation of Chiral Drugs and Biomolecules

    Directory of Open Access Journals (Sweden)

    Sha Yang

    2016-06-01

    Full Text Available Molecularly imprinting polymers (MIPs have been extensively applied in chromatography for the separation of chiral drugs. In this review, we mainly summarize recent developments of various MIPs used as chiral stationary phases (CSPs in high performance liquid chromatography (HPLC, capillary electrochromatography (CEC, and supercritical fluid chromatography (SFC. Among them, HPLC has the advantages of straightforward operation and high selectivity. However, the low separation efficiency, due to slow interaction kinetics and heavy peak broadening, is the main challenge for the application of MIPs in HPLC. On the other hand, CEC possesses both the high selectivity of HPLC and the high efficiency of capillary electrophoresis. In CEC, electroosmotic flow is formed across the entire column and reduces the heavy peak broadening observed in HPLC mode. SFC can modify the low interaction kinetics in HPLC when supercritical fluids are utilized as mobile phases. If SFC and MIP-based CSPs can be well combined, better separation performance can be achieved. Particles, monoliths and membrane are typical formats of MIPs. Traditional MIP particles produced by bulk polymerization have been replaced by MIP particles by surface imprinting technology, which are highly consistent in size and shape. Monolithic MIPs are prepared by in situ method in a column, greatly shortening the pre-preparation time. Some novel materials, such as magnetic nanoparticles, are integrated into the MIPs to enhance the controllability and efficiency of the polymerization. This review will be helpful to guide the preparation, development, and application of MIPs in chromatographic and electrophoretic enantioseparation.

  13. Preparation of Two New Diasteromeric Chiral Stationary Phases Based on (+-(18-Crown-6-2,3,11,12-tetracarboxylic Acid and (R- or (S-1-(1-Naphthylethylamine and Chiral Tethering Group Effect on the Chiral Recognition

    Directory of Open Access Journals (Sweden)

    Rajalingam Agneeswari

    2016-08-01

    Full Text Available Two new diastereomeric chiral stationary phases (CSPs based on (+-(18-crown-6-2,3,11,12-tetracarboxylic acid as a chiral tethering group and a Π-basic chiral unit such as (R-1-(1-naphthylethylamine (CSP 1 or (S-1-(1-naphthylethylamine (CSP 2 were prepared. The two CSPs were applied to the enantiomeric separation of N-(3,5-dinitrobenzoyl-1-phenylalkylamines and N-(3,5-dinitrobenzoyl-α-amino acid derivatives using 20% isopropyl alcohol in hexane as a normal mobile phase. To elucidate the effect of the two chiral units on the chiral recognition, the chiral recognition abilities of the two CSPs were compared with each other and with that of a CSP (CSP 3 based on (R-1-(1-naphthylethylamine. From the chromatographic chiral recognition results, (R-1-(1-naphthylethylamine and (+−(18-crown-6-2,3,11,12-tetracarboxylic acid constituting CSP 1 were concluded to show a cooperative (“matched” effect on the chiral recognition while (S-1-(1-naphthylethylamine and (+-(18-crown-6-2,3,11,12-tetracarboxylic acid constituting CSP 2 were concluded to show an uncooperative (“mismatched” effect on the chiral recognition. From these results, it was concluded that (+-(18-crown-6-2,3,11,12-tetracarboxylic acid can be successfully used as a chiral tethering group for the preparation of new CSPs.

  14. Preparation of Two New Diasteromeric Chiral Stationary Phases Based on (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic Acid and (R)- or (S)-1-(1-Naphthyl)ethylamine and Chiral Tethering Group Effect on the Chiral Recognition.

    Science.gov (United States)

    Agneeswari, Rajalingam; Sung, Ji Yeong; Jo, Eun Sol; Jeon, Hee Young; Tamilavan, Vellaiappillai; Hyun, Myung Ho

    2016-08-12

    Two new diastereomeric chiral stationary phases (CSPs) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid as a chiral tethering group and a Π-basic chiral unit such as (R)-1-(1-naphthyl)ethylamine (CSP 1) or (S)-1-(1-naphthyl)ethylamine (CSP 2) were prepared. The two CSPs were applied to the enantiomeric separation of N-(3,5-dinitrobenzoyl)-1-phenylalkylamines and N-(3,5-dinitrobenzoyl)-α-amino acid derivatives using 20% isopropyl alcohol in hexane as a normal mobile phase. To elucidate the effect of the two chiral units on the chiral recognition, the chiral recognition abilities of the two CSPs were compared with each other and with that of a CSP (CSP 3) based on (R)-1-(1-naphthyl)ethylamine. From the chromatographic chiral recognition results, (R)-1-(1-naphthyl)ethylamine and (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid constituting CSP 1 were concluded to show a cooperative ("matched") effect on the chiral recognition while (S)-1-(1-naphthyl)ethylamine and (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid constituting CSP 2 were concluded to show an uncooperative ("mismatched") effect on the chiral recognition. From these results, it was concluded that (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid can be successfully used as a chiral tethering group for the preparation of new CSPs.

  15. Two-dimensional liquid chromatography for direct chiral separations: a review.

    Science.gov (United States)

    León-González, María Eugenia; Rosales-Conrado, Noelia; Pérez-Arribas, Luis Vicente; Guillén-Casla, Vanesa

    2014-01-01

    Separation of enantiomers remains a challenge owing to their identical physical and chemical properties in an achiral environment, and research on specialized separation techniques such as multidimensional achiral-chiral liquid chromatography continues to resolve individual enantiomers in complex samples. Recent advances in application of multidimensional liquid chromatography applied to chiral analysis are reviewed. For this reason, benefits of achiral-chiral coupling are shown, with emphasis in applications on biological and pharmaceutical fields as well as pesticide analysis. A description of standard instrumental setup in both heart-cut and comprehensive multidimensional liquid chromatography is shown. The most broadly used chiral stationary phases for multidimensional liquid chromatography are summarized. An extensive overview of different interface designs applied to complex samples is presented.

  16. 信息动态%Preparation of Polysaccharide Derivatives-based Composite Chiral Stationary Phases and Their Chiral Recognition

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Two coated-type composite chiral stationary phases (CSPs) were prepared based on cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) and amylose tris (3,5-dimethylphenylcarbamate)(ADMPC) by coating the corresponding derivatives onto 3-aminopropyl silica gel separately and then mixing or by coating the mixed derivatives onto silica gel. The CSPs containing only CDMPC or ADMPC were also prepared for comparison. The mixing method does not significantly influence the enantioselectivities. The composite CSPs generally show chiral recognition abilities intermediate between those of the two individual phases, while some racemates were poorer and at the same time one was better resolved on the composite CSPs.

  17. Preparation and evaluation of a chiral stationary phase covalently bound with a chiral pseudo-18-crown-6 ether having a phenolic hydroxy group for enantiomer separation of amino compounds.

    Science.gov (United States)

    Yongzhu, Jin; Hirose, Keiji; Nakamura, Takashi; Nishioka, Ryota; Ueshige, Tetsuro; Tobe, Yoshito

    2006-10-06

    In order to develop a chiral stationary phase (CSP), which has even higher separation ability than the corresponding commercially available crown ether based CSP (OA-8000 having a pseudo-18-crown-6 ether with an OMe group as a selector), chemically bonded type CSP having a phenolic OH group on a crown ring was developed. Normal mobile phases with or without acid additive can be used with this OH type CSP in contrast to the conventional OMe type CSP which has a neutral chiral selector. Enantiomers of 25 out of 27 amino compounds, including 20 amino acids, 5 amino alcohols, and 2 lipophilic amines, were efficiently separated on a column with this CSP. Nine amino compounds out of 27 were separated with better separation factors than the corresponding OMe type CSP. It is noteworthy that the chromatography on this CSP exhibited excellent enantiomer-separations for amines and amino alcohols when triethyl amine was used as an additive in the mobile phase. Comparison of enantiomer separation ability on this OH type of CSP and on the OMe type of CSP and correlation between the enantioselectivity in chiral chromatography and that of the corresponding model compounds in solution imply that the chiral separation arose from chiral recognition in host guest interactions.

  18. Synthesis of Chiral Metal Complexes of Unsymmetrical Schiff Bases

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Recently, in asymmetric catalyst research the great developments of chiral Salen complexes have been made, but the report on unsymmetrical schiff bases is deficient. The unsymmetrical schiff bases complexes are an effective system in catalytically selective Olefin-epoxidations1. At the same time, unsymmetrical schiff bases was immobilized onto polymer supports for heterogenization2. The potential benefits of the catalyst include facilitation of catalyst separation from reagents, simplification of methods for catalyst recycle, and the possible adaptation of the immobilized catalyst to continuous-flow processes. A series of new unsymmetrical schiff bases was synthesized to study the relations between unsymmetry and enantioselectivity and select better catalyst. The following is the route:

  19. Chiral conducting polymers.

    Science.gov (United States)

    Kane-Maguire, Leon A P; Wallace, Gordon G

    2010-07-01

    This critical review describes the preparation and properties of a relatively new class of chiral macromolecules, namely chiral conducting polymers. It focuses in particular on examples based on polypyrrole, polythiophene and polyaniline. They possess remarkable properties, combining not only chirality with electrical conductivity but also the ability to undergo facile redox and pH switching. These unique properties have opened up a range of exciting new potential applications, including as chiral sensors, as novel stationary phases for chiral separations, and as chiral electrodes for electrochemical asymmetric synthesis (153 references).

  20. Test-set reduction in the screening step definition of a chiral separation strategy in polar organic solvents chromatography.

    Science.gov (United States)

    Ates, Hasret; Desmedt, Bart; Heyden, Yvan Vander

    2012-12-01

    The last decades, many efforts have been made to design and develop chiral separation strategies for different analytical techniques. To ensure that these strategies are broadly applicable rather large test-sets of molecules with very diverse molecules are used. The most enantioselective and complementary separation systems are then used as screening conditions in separation strategies. Potential changes in conditions e.g. implementation of new chiral selectors, requires screening of the entire set to retain the most enantioselective systems. A rational reduction of the test-sets may open new perspectives for developing and updating separation strategies. In the present work, it is investigated whether the screening step of an existing separation strategy in polar organic solvents chromatography can be reconstructed based on reduced test-set results Therefore, the structures of the 58 molecules of the test-set are digitally drawn and their optimal geometrical conformations calculated. From these conformations 3D-molecular descriptors are calculated. The test-set reduction is performed using the Kennard and Stone algorithm: compounds with the most diverse descriptors are selected. The test-sets are gradually reduced with 10% starting from 90% to 30% of the initial size. The results pointed out that with some reduced test-sets the same chromatographic systems are selected. A test-set reduction with 30% (41 remaining compounds) seems possible without losing information on the global enantioselectivity and complementarity of the tested chiral stationary phases.

  1. [Capillary electrochromatography for chiral separation and purity testing of pharmaceutical drug substances].

    Science.gov (United States)

    Gazdag, Mária; Takács, Tímea; Szóllósi, Eva

    2003-01-01

    Chiral separation of D,L-Norgestrel was successfully performed by cyclodextrin-modified capillary electrochromatographic (CEC) method. Optimized CEC conditions for purity testing were achieved: Hypersil C-18 packed capillary and 10 mM 2-[N-morpholino]-ethanesulfonic acid buffer (MES) and 40 v/v % methanol as background electrolyte containing 10 mM gamma-cyclodextrin at pH = 5.5. The resolution was found to be strongly dependent on the concentration of chiral selector gamma-cyclodextrin, applied voltage and temperature of the capillary. Our results represent a simple, fast and reproducible method for the separation of D,L-Norgestrel and purity testing of D-Norgestrel. It can be concluded that cyclodextrin modified HPLC, HPCE and CEC offer inexpensive, attractive and reliable chiral separation methods.

  2. Chiral Separation by Capillary Zone Electrophoresis Used Cyclodextrins and Their Derivatives as Chiral Selector

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Capillary zone electrophoresis (CZE) is a very pronising analytical technique for the optical isomer resolution of the compounds studied. The drawbacks of the techniques such as HPLC [1] were sophisticated stationary phases and/or the relatively high quantity of the chiral agent in the mobile phase, which do not exist in CZE. The capillary electrophoresis (CE) method can offer advantages on lower consumption of analyte and background electrolyte (BGE), shorter analysis time, and higher efficiencies [2-3

  3. Separation of chiral primary amino compounds by forming a sandwiched complex in reversed-phase high performance liquid chromatography.

    Science.gov (United States)

    Zhang, Chen; Huang, Wei X; Chen, Zhi; Rustum, Abu M

    2010-07-23

    Separation of chiral primary amino compounds was efficiently achieved under reversed-phase high performance liquid chromatography (RP-HPLC) conditions using a mixture of non-chiral crown ether (18-crown-6) and dimethyl-beta-cyclodextrin (DM-beta-CD) in the mobile phase. Under these conditions, the amino group of the chiral compound was protonated in a low pH mobile phase, and then interacted with 18-crown-6 and DM-beta-CD to form a sandwiched complex [18-crown-6+amine+CD]. Enantiomers of the compound in the sandwiched complex were separated with good enantioselectivity. Formation of the sandwiched complex among the chiral compound and additives in the mobile phase is a key step of the chiral separation. Four different chiral amino compounds namely, 1-aminoindan (AI), 1,2,3,4-tetrahydro-1-naphthylamine (THNA), tyrosine (Tyr), and phenylalanine (Phe), were selected to demonstrate the separation using the sandwiched complex mechanism in RP-HPLC.

  4. Chiral Separation by Capillary Zone Electrophoresis Used Cyclodextrins and Their Derivatives as Chiral Selector

    Institute of Scientific and Technical Information of China (English)

    HOU; JingGuo

    2001-01-01

    Capillary zone electrophoresis (CZE) is a very pronising analytical technique for the optical isomer resolution of the compounds studied. The drawbacks of the techniques such as HPLC [1] were sophisticated stationary phases and/or the relatively high quantity of the chiral agent in the mobile phase, which do not exist in CZE. The capillary electrophoresis (CE) method can offer advantages on lower consumption of analyte and background electrolyte (BGE), shorter analysis time, and higher efficiencies [2-3]  ……

  5. Enantiomeric Separations of Pyriproxyfen and its Six Chiral Metabolites by High-Performance Liquid Chromatography.

    Science.gov (United States)

    Zhang, Chuntao; Liu, Hui; Liu, Donghui; Wang, Liying; Gao, Jing; Zhou, Zhiqiang; Wang, Peng

    2016-03-01

    Pyriproxyfen is a chiral insecticide, and over 10 metabolites have been identified in the environment. In this work the separations of the enantiomers of pyriproxyfen and its six chiral metabolites were studied by high-performance liquid chromatography (HPLC). Both normal phase and reverse phase were applied using the chiral columns Chiralpak IA, Chiralpak IB, Chiralpak IC, Chiralcel OD, Chiralcel OD-RH, Chiralpak AY-H, Chiralpak AD-H, Chiracel OJ-H, (R,R)-Whelk-O 1, and Lux Cellulose-3. The effects of the chromatographic parameters such as mobile phase composition and temperature on the separations were investigated and the enantiomers were identified with an optical rotation detector. The enantiomers of these targets could obtain complete separations (resolution factor Rs > 1.5) on Chiralpak IA, Chiralpak IB, Chiralcel OD, Chiralpak AY-H, or Chiracel OJ-H under normal conditions. Chiralcel OJ-H showed the best chiral separation results with n-hexane as mobile phase and isopropanol (IPA) as modifier. The simultaneous enantiomeric separation of pyriproxyfen and four chiral metabolites was achieved on Chiralcel OJ-H under optimized condition: n-hexane/isopropanol = 80/20, 15°C, flow rate of 0.8 ml/min, and UV detection at 230 nm. The enantiomers of pyriproxyfen and the metabolites , , and obtained complete separations on Chiralpak IA, Chiralpak IC, and Lux Cellulose-3 under reverse phase using acetonitrile/water as the mobile phase. The retention factors (k) and selectivity factors (α) decreased with increasing temperature, and the separations were better under low temperature in most cases. The work is of significance for the investigation of the environmental behaviors of pyriproxyfen on an enantiomeric level.

  6. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    Directory of Open Access Journals (Sweden)

    Hironori Izawa

    2010-07-01

    Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

  7. Separation of flow from chiral magnetic effect in U+U collisions using spectator asymmetry

    CERN Document Server

    Chatterjee, Sandeep

    2014-01-01

    We demonstrate that the prolate shape of the Uranium nucleus generates anti-correlation between spectator asymmetry and initial state ellipticity of the collision zone, providing a way to constrain the initial event shape in U+U collisions. As an application, we show that this can be used to separate the background contribution due to flow from the signals of chiral magnetic effect.

  8. Factors That Control Successful Entropically Driven Chiral Separations in SFC and HPLC.

    Science.gov (United States)

    Stringham, R W; Blackwell, J A

    1997-04-01

    With temperature increases, selectivity of chiral separations decreases until enantiomers coelute at an isoelution temperature. Above this temperature, elution order should reverse and selectivity will increase with temperature. In this region, separation is termed "entropically driven". Entropically driven chiral separations hold the promise of being able to concurrently increase selectivity and column efficiency by means of increased temperature. The ability to achieve such separations is hindered by high isoelution temperatures. The isoelution temperature is determined by a balance of enthalpic and entropic contributions. A variety of mobile phase modifiers are evaluated for their ability to moderate these contributions. Results suggest that more use should be made of non-alcohol modifiers. The major barrier to entropically driven separations was found to be the nonspecific retention increase that is characteristic when the critical temperature is traversed. Use of hexane in place of CO(2) shifts the position of the retention increase away from the temperature range used in this study, and dramatically successful entropically driven chiral separations are obtained.

  9. Molecular model for chirality phenomena.

    Science.gov (United States)

    Latinwo, Folarin; Stillinger, Frank H; Debenedetti, Pablo G

    2016-10-21

    Chirality is a hallmark feature for molecular recognition in biology and chemical physics. We present a three-dimensional continuum model for studying chirality phenomena in condensed phases using molecular simulations. Our model system is based upon a simple four-site molecule and incorporates non-trivial kinetic behavior, including the ability to switch chirality or racemize, as well as thermodynamics arising from an energetic preference for specific chiral interactions. In particular, we introduce a chiral renormalization parameter that can locally favor either homochiral or heterochiral configurations. Using this model, we explore a range of chirality-specific phenomena, including the kinetics of chiral inversion, the mechanism of spontaneous chiral symmetry breaking in the liquid, chirally driven liquid-liquid phase separation, and chiral crystal structures.

  10. Comparative Optical Separation of Racemic Ibuprofen by Using Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    Dalkeun; PARK; Joong; Kee; LEE; 等

    2002-01-01

    Ibprofen is widely used as a non-steroidal anti-inflammatory drug and poduced as racemic mixture.Its pharmacological activity resides only is S-(+)-enantiomer,and R-(-)-enantiomer is not only inactive but also has many side effects.Thus it is necessary to separate Renantiomer from racemic ibuprofen.We studied optical separation of racemic Ibuprofen with chiral high performance liquid chromatography(HPLC).,Out of three different chiral stationary phases,which were selected on the basis of structure and availability,two were found to be effective.There was optimum eluent composition for each stationary phase for good resolution in optical separation.Resolution decreased with increase of eluent flow rate,but effect of injection volume on resolution was insignificant at high eluent flow rate.

  11. Synthesis and Chiral Separation of Dinucleotide(TpAZT) Phosphoramidates

    Institute of Scientific and Technical Information of China (English)

    Chang Xue LIN; Hua FU; Guang Zhong TU; Yu Fen ZHAO

    2003-01-01

    Dinucleotide (TpAZT) phosphoramidates were synthesized by Todd reaction of dinucleoside H-phosphonates and amino acid methyl esters, and their diastereomers (Rp and Sp) were separated by crystallization, and the results showed that natural and cheap methyl esters of alanine and phenylalanine can be used for large-scale synthesis of dinucleotide analogs.

  12. The Role Seemingly of Amorphous Silica Gel Layers in Chiral Separations by Planar Chromatography

    Directory of Open Access Journals (Sweden)

    Teresa Kowalska

    2007-12-01

    Full Text Available In planar chromatography, silica gel appears as the most frequently used adsorbent. Its preference as planar chromatographic stationary phase is due to its high specific surface area (ca. 700 m2 g-1 and relatively simple active sites (silanol groups, Si-OH. The high specific surface area of silica gel and a high density of coverage of its surface with the silanol active sites contribute jointly to an excellent separation performance of this adsorbent. In our experiments on chiral separation of the enantiomer pairs by planar chromatography, contradictory behavior of the silica gel layers versus the chiral compounds was observed. The migration tracks of chiral compounds in the ascending planar chromatographic mode were not vertical but bent on either side being a function of analyte chirality. This deviation of the analyte’s migration track was noticed, when using the densitometric scanner to quantify the respective chromatograms. In order to confirm the hypothesis as to the microcrystalline nature of silica gel used in liquid chromatography, it was further investigated through circular dichroism (CD and the data thereof confirmed that the ‘chromatographic’ silica gels are not amorphous but microcrystalline, contributing to the (partial horizontal enantioseparation of the antimer pairs. This paper summarizes the results of our investigation on the microcrystalline nature of silica gels used in planar chromatography and their impact on enantioseparation of the selected pairs of antimers.

  13. Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

    Science.gov (United States)

    Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

    2016-02-24

    Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

  14. Synthesis of Chiral Metal Complexes of Unsymmetrical Schiff Bases

    Institute of Scientific and Technical Information of China (English)

    SONG; Bo

    2001-01-01

    Recently, in asymmetric catalyst research the great developments of chiral Salen complexes have been made, but the report on unsymmetrical schiff bases is deficient. The unsymmetrical schiff bases complexes are an effective system in catalytically selective Olefin-epoxidations1. At the same time, unsymmetrical schiff bases was immobilized onto polymer supports for heterogenization2. The potential benefits of the catalyst include facilitation of catalyst separation from reagents, simplification of methods for catalyst recycle, and the possible adaptation of the immobilized catalyst to continuous-flow processes. A series of new unsymmetrical schiff bases was synthesized to study the relations between unsymmetry and enantioselectivity and select better catalyst. The following is the route:  ……

  15. A Non—linear Non—ideal Model of Simulated Moving Bed Chromatography for Chiral Separations

    Institute of Scientific and Technical Information of China (English)

    卢建刚

    2003-01-01

    A non-linear non-ideal model,taking into account non-linear competitive isotherms,axial disperison,film mass transfer,intraparticle diffusion,and port periodic switching,was developed to simulate the dynamics of simulated moving bed chromatography(SMBC),The model equations were solved by a new efficient numerical technique of orthogonal collocation on finite elements with periodical movement of conceantration vector,The simulated SMBC performance is in accordance with the experimental results reported in the literature for separation of 1,1''''''''-bi-2-naphtol enantiomers using SMBC,This model is useful for design,operation ,optimization and scale-up of non-linear SMBC for chiral separations with significant non-ideal effects,especially for high solute concentration and small intraparticle diffusion coefficient or large chiral stationary phase particle.

  16. Comparison of chiral electrophoretic separation methods for phenethylamines and application on impurity analysis.

    Science.gov (United States)

    Borst, Claudia; Holzgrabe, Ulrike

    2010-12-15

    A chiral microemulsion electrokinetic chromatography method has been developed for the separation of the enantiomers of the phenethylamines ephedrine, N-methylephedrine, norephedrine, pseudoephedrine, adrenaline (epinephrine), 2-amino-1-phenylethanol, diethylnorephedrine, and 2-(dibutylamino)-1-phenyl-1-propanol, respectively. The separations were achieved using an oil-in-water microemulsion consisting of the oil-component ethyl acetate, the surfactant sodium dodecylsulfate, the cosurfactant 1-butanol, the organic modifier propan-2-ol and 20mM phosphate buffer pH 2.5 as aqueous phase. For enantioseparation sulfated beta-cyclodextrin was added. The method was compared to an already described CZE method, which made use of heptakis(2,3-di-O-diacetyl-6-O-sulfo)-beta-cyclodextrin (HDAS) as chiral selector. Additionally, the developed method was successfully applied to the related substances analysis of noradrenaline, adrenaline, dipivefrine, ephedrine and pseudoephedrine monographed in the European Pharmacopoeia 6.

  17. Synthesis of novel chiral compounds of purine and pyrimidine bases

    Institute of Scientific and Technical Information of China (English)

    汪毓海; 陈庆华

    1999-01-01

    The physiologically active groups such as purine and pyrimidine bases are introduced to the asymmetric ynthesis. The optically pure compounds bearing purine and pyrimidine bases (5a—5e) were prepared via the asymetric Michael addition reaction of purines and pyrimidines as Michael donators with the chiral source 5-(R)-[(1R, 2S, 5R)-menthyloxy]-2(5H)-furanone (3a), which was prepared from the natural chiral auxiliary (-)-menthol. The synthetic method was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]D20, IR, UV, 1H NMR, 13C NMR and MS. The absolute configuration of 5a was established by X-ray crystallography. The results provided an efficient synthetic route to chiral purines and pyrimidine analogues, and offered chiral sources for further research on the physiologically active compounds of chiral nucleotides.

  18. Chiral separation of a diketopiperazine pheromone from marine diatoms using supercritical fluid chromatography.

    Science.gov (United States)

    Frenkel, Johannes; Wess, Carsten; Vyverman, Wim; Pohnert, Georg

    2014-03-01

    The proline derived diketopiperazine has been identified in plants, insects and fungi with unknown function and was recently also reported as the first pheromone from a diatom. Nevertheless the stereochemistry and enantiomeric excess of this natural product remained inaccessible using direct analytical methods. Here we introduce a chiral separation of this metabolite using supercritical fluid chromatography/mass spectrometry. Several chromatographic methods for chiral analysis of the diketopiperazine from the diatom Seminavis robusta and synthetic enantiomers have been evaluated but neither gas chromatography nor high performance liquid chromatography on different chiral cyclodextrin phases were successful in separating the enantiomers. In contrast, supercritical fluid chromatography achieved baseline separation within four minutes of run time using amylose tris(3,5-dimethylphenylcarbamate) as stationary phase and 2-propanol/CO2 as mobile phase. This very rapid chromatographic method in combination with ESI mass spectrometry allowed the direct analysis of the cyclic dipeptide out of the complex sea water matrix after SPE enrichment. The method could be used to determine the enantiomeric excess of freshly released pheromone and to follow the rapid degradation observed in diatom cultures. Initially only trace amounts of c(d-Pro-d-Pro) were found besides the dominant c(l-Pro-l-Pro) in the medium. However the enantiomeric excess decreased upon pheromone degradation within few hours indicating that a preferential conversion and thus inactivation of the l-proline derived natural product takes place.

  19. Chiral Separation of Novel a-Aminophosphonates Containing a Benzothiazole Moiety by Liquid Chromatography Using an Amylose Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    LU Ping; ZHANG Yu-Ping; SONG Bao-An; YANG Song; BHADURY Shankar Pinaki; HU De-Yu; XUE Wei; CHEN Zhuo; JIN Lin-Hong

    2008-01-01

    The present report describes a chiral HPLC method for the enantiomeric separation of a-aminophosphonate derivatives using two new coated and immobilized amylose-based chiral stationary phases (CSP,Chiralpak IA and Chiralpak AD-H).The chromatographic parameters such as retention factor (k),separation factor (a),and resolution (Rs) of the solutes were investigated on these two CSPs.Reasonably good baseline separation for these compounds was achieved using Chiralpak IA column.The influences of temperature,content of ethanol modifier and the structure of analyte were also studied.THF,EtOAc and CH2Cl2 were used as ehients on analytical and semi-preparative columns.Highly enriched enantiomers with purities of up to 96.4%--100% (ee) and yields of 90.2%--95.5% were obtained,respectively.The proposed methods were found to be suitable and accurate for rapid separation and semi-preparation of enantiomeric a-aminophosphonate derivatives available.

  20. Hydroxypyridyl Imines: Enhancing Chromatographic Separation and Stereochemical Analysis of Chiral Amines via Circular Dichroism.

    Science.gov (United States)

    Joyce, Leo A; Regalado, Erik L; Welch, Christopher J

    2016-09-16

    Imine-bond formation between chiral amines and commercially available 3-hydroxypyridine-2-carboxaldehyde (HCA) was exploited for rapid determination of stereochemical composition. Chiral supercritical fluid chromatography (SFC) screening of the derivatized imine compounds led to the elucidation of multiple combinations of mobile and stationary phases that gave resolution of all members of a series of chiral amines. The first eluting enantiomer was generally the derivative of the (R)-amine enantiomer across the series that was studied, indicating that the imine formed from the (S)-amine has more favorable interaction with the chiral stationary phase of the column. These conditions were then applied to more challenging compounds, namely amino alcohols and diastereomers possessing more than one stereocenter. The approach was utilized to monitor stereoselective biocatalytic transamination and assign the absolute configuration of the enantiomeric products. Finally, hydrolysis of the imine bond of the derivative was shown to generate enantiopure amine starting materials without racemization. This further highlights the value of this approach for creating readily reversed derivatives that enhance chromatographic separation and aid in the determination of absolute configuration.

  1. Application of cinchona-sulfonate-based chiral zwitterionic ion exchangers for the separation of proline-containing dipeptide rotamers and determination of on-column isomerization parameters from dynamic elution profiles.

    Science.gov (United States)

    Wernisch, Stefanie; Trapp, Oliver; Lindner, Wolfgang

    2013-09-17

    The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from -15°C to +45°C The cis-trans isomers could be separated below 0°C and above 0-10°C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics.

  2. Hydrodynamics with chiral anomaly and charge separation in relativistic heavy ion collisions

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Yi, E-mail: yyin@bnl.gov [Physics Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Liao, Jinfeng, E-mail: liaoji@indiana.edu [Physics Department and Center for Exploration of Energy and Matter, Indiana University, 2401 N Milo B. Sampson Lane, Bloomington, IN 47408 (United States); RIKEN BNL Research Center, Bldg. 510A, Brookhaven National Laboratory, Upton, NY 11973 (United States)

    2016-05-10

    Matter with chiral fermions is microscopically described by theory with quantum anomaly and macroscopically described (at low energy) by anomalous hydrodynamics. For such systems in the presence of external magnetic field and chirality imbalance, a charge current is generated along the magnetic field direction — a phenomenon known as the Chiral Magnetic Effect (CME). The quark–gluon plasma created in relativistic heavy ion collisions provides an (approximate) example, for which the CME predicts a charge separation perpendicular to the collisional reaction plane. Charge correlation measurements designed for the search of such signal have been done at RHIC and the LHC for which the interpretations, however, remain unclear due to contamination by background effects that are collective flow driven, theoretically poorly constrained, and experimentally hard to separate. Using anomalous (and viscous) hydrodynamic simulations, we make a first attempt at quantifying contributions to observed charge correlations from both CME and background effects in one and same framework. The implications for the search of CME are discussed.

  3. Comparison of chiral separation of basic drugs in capillary electrophoresis and liquid chromatography using neutral and negatively charged cyclodextrins.

    Science.gov (United States)

    Kwaterczak, Arkadiusz; Duszczyk, Kazimiera; Bielejewska, Anna

    2009-07-10

    Liquid chromatography (LC) and capillary electrophoresis (CE) are very widely used as chiral separation methods. In this publication we try to find if the results obtained in CE and LC with the chiral selector added to the electrolyte and the mobile phase, respectively, can be used as tools for studying weak stereoselective interactions, and how this information can be useful for optimizing chiral separation processes. The manuscript presents a systematic comparison of chiral discrimination of model compounds in HPLC and CE using neutral and negatively charged cyclodextrins. The enantiomeric separation of basic chiral pharmaceuticals such as pheniramine, brompheniramine, metoxyphenamine, cyclopentolate, doxylamine and ketamine was investigated in capillary electrophoresis (CE) and liquid chromatography (HPLC) using negatively charged sulfated-beta-cyclodextrin (S-beta-CD) and neutral cyclodextrins (CDs). The apparent stability constants between the model compounds and cyclodextrins were estimated in both techniques. We discuss the influence of the stability constant and K1/K2 ratio of the investigated complexes on chiral separation obtained in both techniques.

  4. A numerical study of non-perturbative corrections to the Chiral Separation Effect in quenched finite-density QCD

    CERN Document Server

    Puhr, M

    2016-01-01

    We use exactly chiral overlap lattice fermions to investigate the Chiral Separation Effect in quenched QCD at finite density. We employ a recently developed numerical method which allows, for the first time, to address the transport properties of exactly chiral lattice fermions with non-zero chemical potential. Studying the axial current along the external magnetic field, we find a linear dependence consistent with the free fermion result for topologically trivial gauge field configurations. However, for configurations with nontrivial topology in the confinement regime the axial current is strongly suppressed due to contributions of topological modes of the Dirac operator, which suggests that non-perturbative corrections to the Chiral Separation Effect have topological origin.

  5. Separation of chiral drugs with β-CD phosphate by capillary electrophoresis

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    β -Cyclodextrin phosphate (β -CD-phosphate) was used as a selector for separating chiral drugs by capillary electrophoresis (CE). A solution comprising of 120 mmol/L Britton-Robinson buffer (BRB) containing 10 mmol/L β -CD phosphate with the pH adjusted to 7.0 was used as the background electrolyte (BGE), and a small amount of analyte was injected (600v/1s). Triethylamine, diethylamine, triethanolamine, diethanolamine, Tris added as modifier were compared. Isoprenaline, methoxamine, oxprenolol, practolol were successfully resolved.

  6. Indirect chiral separation of new recreational drugs by gas chromatography-mass spectrometry using trifluoroacetyl-L-prolyl chloride as chiral derivatization reagent.

    Science.gov (United States)

    Weiß, Jennifer A; Mohr, Stefan; Schmid, Martin G

    2015-03-01

    New recreational drugs such as amphetamine-, cathinone, and benzofury derivatives gained high popularity on the drug market in recent years. They can be purchased via the Internet from different providers and online portals. Most of these compounds are chiral, which makes the development of chiral separation methods necessary. Besides this, it is useful to find out if the compounds were sold as racemic mixtures. Also, it is important to check whether the new psychoactive compounds contain further ingredients or impurities. The aim of this research was the continuation of the application of a method for indirect chiral separation of 24 new psychoactive compounds recently purchased via the Internet. After derivatization with the chiral derivatization reagent trifluoroacetyl-L-prolyl chloride, chromatographic separation of diastereomers was achieved using a 30 m HP5-MS capillary column. As carrier gas, helium was used with a constant flow of 1.0 ml/min. Three different column temperature programs were tested. Under optimum conditions 13 out of 24 compounds were successfully resolved into their enantiomers obtaining Rs values up to 7.0. The use of a single quadrupole mass spectrometer as the detector allowed the identification of the compounds in multicomponent samples.

  7. Individual ((f,t) A)- and ((f,t) C)-Fullerene-Based Nickel(II) Glycinates: Protected Chiral Amino Acids Directly Linked to a Chiral π-Electron System.

    Science.gov (United States)

    Levitskiy, Oleg A; Grishin, Yuri K; Semivrazhskaya, Olesya O; Ambartsumyan, Asmik A; Kochetkov, Konstantin A; Magdesieva, Tatiana V

    2017-03-01

    Stereoselective electrosynthesis of the first individual ((f,t) A)- and ((f,t) C)-1,4-fullerene derivatives with a non-inherently chiral functionalization pattern is described, as well as the first example of an optically pure protected primary amino acid directly linked to the fullerene through only the chiral α-amino-acid carbon atom. An application of an auxiliary chiral nickel-Schiff base moiety as derivatizing agent allowed separation of ((f,t) A)- and ((f,t) C)-1,4-fullerene derivatives using an achiral stationary phase, a separation which has never been done before.

  8. 8种手性化合物在不同载体涂敷的纤维素-苯基氨基甲酸酯类手性固定相上的拆分及比较%Chiral separation of eight enantiomers on cellulose phenylcarbamate-based chiral stationary phases

    Institute of Scientific and Technical Information of China (English)

    仵佩佩; 韩小茜; 李文玲

    2016-01-01

    The cellulose phenylcarbamate derivatives were prepared and coated on SiO2 spheric parti-cles,aminopropylied SiO2 spheric particles,SBA-15 and aminopropylied SBA-15,respectively. The ob-tained chiral stationary phases (SBA-CDMPC,SBA-NH 2-CDMPC,SBA-CClPC,SiO2-NH 2-CClPC)were separated for eight enantiomers with n-hexane/alcohol as the mobile phases by high-performance liquid chromatography (HPLC). The results showed that chiral recognition ability of SBA-CDMPC was higher than SBA-NH 2-CDMPC,chiral recognition ability of SiO2-NH 2-CCLPC was higher than SBA-CCLPC,but partial enantioseparation of compounds 7 and 8 could be obtained on SBA-CCLPC.%将自行合成的纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)、纤维素-三(4-氯苯基氨基甲酸酯)(CClPC)分别涂敷在 SBA-15或氨丙基化的 SBA-15或氨丙基硅胶上,制得4种手性固定相(CSPs):SBA-CDMPC、SBA-NH 2-CDMPC、SBA-CClPC、SiO2-NH 2-CClPC。在正相条件下,采用8种手性化合物对自制 CSPs 进行了评价,并与 Chiralcel OD-H 上的拆分结果作比较。实验结果表明:SBA-CDMPC 的手性识别能力比 SBA-NH 2-CDMPC 的手性识别能力好;SiO2-NH 2-CCLPC 的手性识别能力比 SBA-CCLPC 的 手 性 识 别 能力好,但在 SiO2-NH 2-CCLPC 上未获拆分的化合物7和8在 SBA-CCLPC 上获得分离,SBA-15作为色谱填料基质的条件仍需不断的探索和发现。

  9. Chiral separation of cathinone and amphetamine derivatives by HPLC/UV using sulfated ß-cyclodextrin as chiral mobile phase additive.

    Science.gov (United States)

    Taschwer, Magdalena; Seidl, Yvonne; Mohr, Stefan; Schmid, Martin G

    2014-08-01

    In the last years the identification of new legal and illegal highs has become a huge challenge for the police and prosecution authorities. In an analytical context, only a few analytical methods are available to identify these new substances. Moreover, many of these recreational drugs are chiral and it is supposed that the enantiomers differ in their pharmacological potency. Since nonenantioselective synthesis is easier and cheaper, they are mainly sold as racemic mixtures. The goal of this research work was to develop an inexpensive method for the chiral separation of cathinones and amphetamines. This should help to discover if the substances are sold as racemic mixtures and give further information about their quality as well as their origin. Chiral separation of a set of 6 amphetamine and 25 cathinone derivatives, mainly purchased from various Internet shops, is presented. A LiChrospher 100 RP-18e, 250 x 4 mm, 5 µm served as the stationary phase. The chiral mobile phase consisted of methanol, water, and sulfated ß-cyclodextrin. Measurements were performed under isocratic conditions in reversed phase mode using UV detection. Four model compounds of the two substance classes were used to optimize the mobile phase. Under final conditions (methanol:water 2.5:97.5 + 2% sulfated ß-cyclodextrin) enantiomers of amphetamine and five derivatives were baseline separated within 23 min. In all, 17 cathinones were completely or partially chirally separated. However, as only 3 of 25 cathinones were baseline resolved, the application of this method is limited for cathinone analogs. Additionally, the results were compared with an RP-8e column.

  10. Chiral separation of bavachinin in Fructus Psoraleae and rat plasma by liquid chromatography using permethylated-b-CD as a chiral selector

    Institute of Scientific and Technical Information of China (English)

    Jing-Jing Liu; Juan Zhang; Zi-Lin Chen

    2013-01-01

    A simple, sensitive and selective method of high-performance liquid chromatography (HPLC) has been successfully developed for separation of bavachinin enantiomers in Fructus Psoraleae and rat plasma. The separation and detection conditions of HPLC were optimized. Chiral bavachinin were separated with the mobile phase of methanol and water (70:30, v/v) at a flow rate of 1.0 mL/min. The linear ranges were in the range of 20-1000 mg/mL. The detection limits were tested as 4 ng/mL and 6 ng/mL for (þ)-bavachinin and (À)-bavachinin, respectively. The method has been applied to analyze chiral bavachinin in rat plasma. HPLC-MS method was used to test the accuracy.

  11. Separation of Ofloxacin and Its Six Related Substances Enantiomers by Chiral Ligand-Exchange Chromatography.

    Science.gov (United States)

    Liang, Xinlei; Zhao, Longshan; Deng, Miaoduo; Liu, Lijie; Ma, Yongfu; Guo, Xingjie

    2015-11-01

    A chiral ligand-exchange high-performance liquid chromatography method was developed for the enantioseparation of ofloxacin and its six related substances termed impurities A, B, C, D, E, and F. The separation was performed on a conventional C18 column. Different organic modifiers, copper salts, amino acids, the ratio of Cu(2+) to amino acid, pH of aqueous phase, and column temperature were optimized. The optimal mobile phase conditions were methanol-water systems consisting of 5 mmol/L copper sulfate and 10 mmol/L L-isoleucine (L-Ile). Under such conditions, good enantioseparation of ofloxacin and impurities A, C, E, and F could be observed with resolutions (RS ) of 3.54, 1.97, 3.21, 3.50, and 2.12, respectively. On the relationship between the thermodynamic parameters and structures of analytes, the mechanism of chiral recognition was investigated. It was concluded that ofloxacin and impurities A, C, E, and F were all enthalpically driven enantioseparation and that low column temperature was beneficial to enantioseparation. Furthermore, the structure-separation relationship of these analytes is also discussed.

  12. Separation of mandelic acid and its derivatives with new immobilized cellulose chiral stationary phase

    Institute of Scientific and Technical Information of China (English)

    Jie ZHOU; Qian LIU; Guang-jun FU; Zhen-zhong ZHANG

    2013-01-01

    A new liquid chromatographic method has been developed for the chiral separation of the enantiomers of mandelic acid and their derivatives 2-chloromandelic acid,4-hydroxymandelic acid,4-methoxymandelic acid,and 3,4,5-trismethoxymandelic acid.The enantiomers were separated by a CHIRALPAK(R) IC (250 mm×4.6 mm,5 μm).Mandelic acid,4-methoxymandelic acid,and 3,4,5-trismethoxymandelic acid were baseline resolved (resolution factor (Rs)=2.21,Rs=2.14,and Rs=3.70,respectively).In contrast,the enantioselectivities between CHIRALPAK(R) IC and 2-chloromandelic acid and 4-hydroxymandelic acid investigated were low.By comparing the chromatographs of mandelic acid enantiomers and mandelic acid spiked with (R)-mandelic acid,it was determined that the first effluent was (R)-mandelic acid.

  13. Quality by design in the chiral separation strategy for the determination of enantiomeric impurities: development of a capillary electrophoresis method based on dual cyclodextrin systems for the analysis of levosulpiride.

    Science.gov (United States)

    Orlandini, S; Pasquini, B; Del Bubba, M; Pinzauti, S; Furlanetto, S

    2015-02-06

    Quality by design (QbD) concepts, in accordance with International Conference on Harmonisation Pharmaceutical Development guideline Q8(R2), represent an innovative strategy for the development of analytical methods. In this paper QbD principles have been comprehensively applied in the set-up of a capillary electrophoresis method aimed to quantify enantiomeric impurities. The test compound was the chiral drug substance levosulpiride (S-SUL) and the developed method was intended to be used for routine analysis of the pharmaceutical product. The target of analytical QbD approach is to establish a design space (DS) of critical process parameters (CPPs) where the critical quality attributes (CQAs) of the method have been assured to fulfil the desired requirements with a selected probability. QbD can improve the understanding of the enantioseparation process, including both the electrophoretic behavior of enantiomers and their separation, therefore enabling its control. The CQAs were represented by enantioresolution and analysis time. The scouting phase made it possible to select a separation system made by sulfated-β-cyclodextrin and a neutral cyclodextrin, operating in reverse polarity mode. The type of neutral cyclodextrin was included among other CPPs, both instrumental and related to background electrolyte composition, which were evaluated in a screening phase by an asymmetric screening matrix. Response surface methodology was carried out by a Doehlert design and allowed the contour plots to be drawn, highlighting significant interactions between some of the CPPs. DS was defined by applying Monte-Carlo simulations, and corresponded to the following intervals: sulfated-β-cyclodextrin concentration, 9-12 mM; methyl-β-cyclodextrin concentration, 29-38 mM; Britton-Robinson buffer pH, 3.24-3.50; voltage, 12-14 kV. Robustness of the method was examined by a Plackett-Burman matrix and the obtained results, together with system repeatability data, led to define a method

  14. Novel chiral stationary phases based on peptoid combining a quinine/quinidine moiety through a C9-position carbamate group.

    Science.gov (United States)

    Wu, Haibo; Wang, Dongqiang; Song, Guangjun; Ke, Yanxiong; Liang, Xinmiao

    2014-04-01

    By connecting a quinine or quinidine moiety to the peptoid chain through the C9-position carbamate group, we synthesized two new chiral selectors. After immobilizing them onto 3-mercaptopropyl-modified silica gel, two novel chiral stationary phases were prepared. With neutral, acid, and basic chiral compounds as analytes, we evaluated these two stationary phases and compared their chromatographic performance with chiral columns based on quinine tert-butyl carbamate and the previous peptoid. From the resolution of neutral and basic analytes under normal-phase mode, it was found that the new stationary phases exhibited much better enantioselectivity than the quinine tert-butyl carbamate column; the peptoid moiety played an important role in enantiorecognition, which controlled the elution orders of enantiomers; the assisting role of the cinchona alkaloid moieties was observed in some separations. Under acid polar organic phase mode, it was proved that cinchona alkaloid moieties introduced excellent enantiorecognitions for chiral acid compounds; in some separations, the peptoid moiety affected enantioseparations as well. Overall, chiral moieties with specific enantioselectivity were demonstrated to improve the performance of peptoid chiral stationary phase efficiently.

  15. Study of the correlation of charge separation of the chiral magnetic effect in Relativistic Heavy-ion Collisions

    CERN Document Server

    Feng, Sheng-Qin; Sun, Fei; Zhong, Yang; Yin, Zhong-Bao

    2016-01-01

    It was pointed out that the Chiral Magnetic Effect is a process of charge separation with respect to the reaction plane. There is one kind of phenomenon of gauge field configurations with nonzero topological charge, which can be a sphaleron in the QCD vacuum. At high temperatures, one expects that the sphaleron process is a dominant process. One finds that left-handed quarks will become right-handed quarks, and right-handed quarks will remain right-handed in a region with negative topological charge. The strong magnetic field produced in relativistic heavy-ion collisions interacts with the magnetic moment of the quarks and locates the spins of quarks with positive (negative) electric charge to be parallel (anti-parallel) to the field direction. The Chiral Separation Effect is a similar effect in which the occurrence of a vector charge, e.g. electric charge, causes a separation of chiralities. We calculate the chiral separation effects during RHIC and LHC energy regions by studying the detailed chiral charge s...

  16. Enantiomeric Separation of Epinephrine and Salbutamol by Micellar Electrokinetic Chromatography Using β-Cyclodextrin as Chiral Additive

    Institute of Scientific and Technical Information of China (English)

    ZHENG,Yan-Peng(郑妍鹏); MO,Jin-Yuan(莫金垣)

    2004-01-01

    Enantiomeric separations of epinephrine and salbutamol, by means of micellar electrokinetic chromatography (MEKC) employing β-cyclodextrin as chiral additive in ammonium chloride-ammonia solution were investigated.In this system, the analytes migrated with the micellar phase towards the anode and were detected by electrochemistry using gold microelectrode at +0.65 V vs. SCE. The success of the chiral separations is strongly dependent on the concentration of β-CD and SDS, and the optimal concentration is 8 mmol·L-1 and 15 mmol·L-1 respectively.The effects of detection potential, pH value of electrolyte and applied voltage were discussed also. Using the proposed method, baseline separation of the enantiomers could be accomplished in 6 min. Further, an attempt was made to elucidate the plausible mechanism of the chiral recognition.

  17. Molecular Modeling Study of Chiral Separation and Recognition Mechanism of β-Adrenergic Antagonists by Capillary Electrophoresis

    Directory of Open Access Journals (Sweden)

    Yifeng Chai

    2012-01-01

    Full Text Available Chiral separations of five β-adrenergic antagonists (propranolol, esmolol, atenolol, metoprolol, and bisoprolol were studied by capillary electrophoresis using six cyclodextrins (CDs as the chiral selectors. Carboxymethylated-β-cyclodextrin (CM-β-CD exhibited a higher enantioselectivity power compared to the other tested CDs. The influences of the concentration of CM-β-CD, buffer pH, buffer concentration, temperature, and applied voltage were investigated. The good chiral separation of five β-adrenergic antagonists was achieved using 50 mM Tris buffer at pH 4.0 containing 8 mM CM-β-CD with an applied voltage of 24 kV at 20 °C. In order to understand possible chiral recognition mechanisms of these racemates with CM-β-CD, host-guest binding procedures of CM-β-CD and these racemates were studied using the molecular docking software Autodock. The binding free energy was calculated using the Autodock semi-empirical binding free energy function. The results showed that the phenyl or naphthyl ring inserted in the hydrophobic cavity of CM-β-CD and the side chain was found to point out of the cyclodextrin rim. Hydrogen bonding between CM-β-CD and these racemates played an important role in the process of enantionseparation and a model of the hydrogen bonding interaction positions was constructed. The difference in hydrogen bonding formed with the –OH next to the chiral center of the analytes may help to increase chiral discrimination and gave rise to a bigger separation factor. In addition, the longer side chain in the hydrophobic phenyl ring of the enantiomer was not beneficial for enantioseparation and the chiral selectivity factor was found to correspond to the difference in binding free energy.

  18. Optical chiral metamaterial based on the resonant behaviour of nanodiscs

    Science.gov (United States)

    Kordi, Mahdi; Mojtaba Mirsalehi, Mir

    2016-08-01

    Circular dichorism and optical activity have been achieved by chiral metamaterials in the optical spectrum, but for the case of negative index of refraction, remarkable achievements have not been obtained in this region so far. We employ nanoparticles to shift the resonant frequency of a chiral metamaterial based on twisted cross wires to optical domain. Our proposed structure provides giant optical activity, strong circular dichorism and also negative refractive index in the optical wavelengths. Optical activity in our structure has a rotary power similar to a gyrotropic crystal of quartz, but in a thickness which is four orders of magnitude smaller. The foundation of our method for realizing such an optical chiral metamaterial is based on creating a different coupling between longitudinal modes of localized surface plasmons for right and left circularly polarized incident waves.

  19. Comparison of the performance of chiral stationary phase for separation of fluoxetine enantiomers

    Institute of Scientific and Technical Information of China (English)

    ZHOU Jie; YANG Yi-wen; WEI Feng; WU Ping-dong

    2007-01-01

    Separation of fluoxetine enantiomers on five chiral stationary phases (chiralcel OD-H, chiralcel OJ-H, chiralpak AD-H, cyclobond I 2000 DM and kromasil CHI-TBB) was investigated. The optimal mobile phase compositions of fluoxetine separation on each column were hexane/isopropanol/diethyl amine (98/2/0.2, v/v/v), hexane/isopropanol/diethyl amine (99/1/0.1,v/v/v), hexane/isopropanol/diethyl amine (98/2/0.2, v/v/v), methanol/0.2% triethylamine acetic acid (TEAA) (25/75, v/v; pH 3.8)and hexane/isopropanol/diethyl amine (98/2/0.2, v/v/v), respectively. Experimental results demonstrated that baseline separation (RS>1.5) of fluoxetine enantiomers was obtained on chiralcel OD-H, chiralpak AD-H, and cyclobond I 2000 DM while the best separation was obtained on the last one. The eluate orders of fluoxetine enantiomers on the columns were determined. The first eluate by chiralcel OJ-H and kromasil CHI-TBB is the S-enantiomer, while by chiralpak AD-H and cyclobond I 2000 DM is the R-enantiomer.

  20. Solving multicomponent chiral separation challenges using a new SFC tandem column screening tool.

    Science.gov (United States)

    Welch, Christopher J; Biba, Mirlinda; Gouker, Joseph R; Kath, Gary; Augustine, Paul; Hosek, Paul

    2007-03-01

    A tool for improved tandem column chiral supercritical fluid chromatography (SFC) method development screening was prepared by modification of a commercial analytical SFC instrument with two different software-controllable, six position high-pressure column selection valves, each controlling a bank of five different columns and a pass through line. The resulting instrument, which has the ability to screen 10 different individual columns and 25 different tandem column arrangements, is a useful tool for facilitating the screening of tandem column SFC arrangements for separation of complex mixtures of stereoisomers or other multicomponent mixtures. Strategies for optimal use of the instrument are discussed, and several examples of the use of the instrument in developing tandem SFC methods for resolution of multicomponent mixtures are presented.

  1. Improved Chiral Separation of (R,S-Goitrin by SFC: An Application in Traditional Chinese Medicine

    Directory of Open Access Journals (Sweden)

    Lixing Nie

    2016-01-01

    Full Text Available Like chemical drugs, research and development of herbal medicine also have a need to resolve enantiomers. To help illustrating the antiviral bioactivity of Isatidis Radix, a widely used traditional Chinese medicine (TCM, supercritical fluid chromatography (SFC was used for analytical and preparative separation of (R,S-goitrin, which was reported as the active ingredient of the herbal. Improved resolution was achieved on Chiralpak IC column, using acetonitrile as the organic modifier, representing a tenfold increase in speed, compared to the previous normal phase HPLC (NPLC method. The newly developed chromatographic method was validated in terms of linearity, precision, limit of detection (LOD, and limit of quantitation (LOQ. Scale-up purification of (R-goitrin and (S-goitrin was performed on a preparative column with >90% total recovery. The absolute stereochemical assignment of the purified isomers was determined through optical rotation study. This attempt explored SFC’s application in chiral research of traditional Chinese medicine.

  2. Improved Chiral Separation of (R,S)-Goitrin by SFC: An Application in Traditional Chinese Medicine.

    Science.gov (United States)

    Nie, Lixing; Dai, Zhong; Ma, Shuangcheng

    2016-01-01

    Like chemical drugs, research and development of herbal medicine also have a need to resolve enantiomers. To help illustrating the antiviral bioactivity of Isatidis Radix, a widely used traditional Chinese medicine (TCM), supercritical fluid chromatography (SFC) was used for analytical and preparative separation of (R,S)-goitrin, which was reported as the active ingredient of the herbal. Improved resolution was achieved on Chiralpak IC column, using acetonitrile as the organic modifier, representing a tenfold increase in speed, compared to the previous normal phase HPLC (NPLC) method. The newly developed chromatographic method was validated in terms of linearity, precision, limit of detection (LOD), and limit of quantitation (LOQ). Scale-up purification of (R)-goitrin and (S)-goitrin was performed on a preparative column with >90% total recovery. The absolute stereochemical assignment of the purified isomers was determined through optical rotation study. This attempt explored SFC's application in chiral research of traditional Chinese medicine.

  3. 奎宁-冠醚组合型手性固定相直接拆分氨基酸的机理%Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids

    Institute of Scientific and Technical Information of China (English)

    吴海霞; 王东强; 赵见超; 柯燕雄; 梁鑫淼

    2016-01-01

    合成了一种新型奎宁-冠醚组合型手性固定相( QN-CR CSP)并用于氨基酸手性对映体的直接拆分,该固定相对12种氨基酸对映体有良好的手性拆分能力。基于氨基酸手性识别中离子交换和络合的协同作用,建立了一种新型的等温吸附模型。通过迎头特殊点洗脱法( FACP)测定色氨酸( Trp)在不同金属离子添加剂条件下的等温吸附线,验证了模型的合理性。流动相中的 Li+、Na+、K+等金属离子与氨基酸竞争固定相中的冠醚络合位点,随着金属离子与冠醚的络合作用力和络合吸附平衡常数增大,固定相对 Trp的手性拆分能力下降。该模型的建立对理解氨基酸在此类固定相中的手性保留行为以及固定相结构的进一步优化具有重要意义。%A novel chiral stationary phase combining quinine and crown ether( QN-CR CSP ) was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids,a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point( FACP),the adsorption isotherms of tryptophan( Trp)under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether,the equilibrium constant of complexing adsorption was found increased. The chiral sepa-ration ability was decreased. The adsorption isotherm improved the understanding of the reten-tion behavior of amino acids on QN-CR CSP,which was also benefit to optimize the structure of the stationary phase.

  4. Chiral HPLC analysis of milnacipran and its FMOC-derivative on cellulose-based stationary phases.

    Science.gov (United States)

    Patti, Angela; Pedotti, Sonia; Sanfilippo, Claudia

    2008-02-01

    The HPLC enantioseparation of the last generation antidepressive drug milnacipran (+/-)-1 was investigated on different cellulose-based chiral stationary phases (CSPs). On carbamate-type columns, Chiralcel OD and OD-H (+/-)-1 could be separated with alpha value about 1.20 but the resolution was quite low because of the tailing of the peaks. Direct determination of (+/-)-1 with high selectivity and resolution was obtained on Chiralcel OJ in normal phase mode elution. Precolumn derivatization of milnacipran with Fmoc-Cl gave compound (+/-)-2 which was enantioseparated on all the investigated CSPs and allowed enhanced UV or fluorimetric detection. The Chiralpak IB, that could be considered the immobilized version of Chiralcel OD-H, was found completely ineffective in the chiral recognition of (+/-)-1 and moderately efficient in the separation of (+/-)-2.

  5. Elastic properties of chiral, anti-chiral, and hierarchical honeycombs:A simple energy-based approach

    Institute of Scientific and Technical Information of China (English)

    Davood Mousanezhad; Babak Haghpanah; Ranajay Ghosh; Abdel Magid Hamouda; Hamid Nayeb-Hashemi; Ashkan Vaziri

    2016-01-01

    The effects of two geometric refinement strategies widespread in natural structures, chirality and self-similar hierarchy, on the in-plane elastic response of two-dimensional honeycombs were studied systematically. Simple closed-form expressions were derived for the elastic moduli of several chiral, anti-chiral, and hierarchical honeycombs with hexagon and square based networks. Finite element analysis was employed to validate the analytical estimates of the elastic moduli. The results were also compared with the numerical and experimental data available in the literature. We found that introducing a hier-archical refinement increases the Young’s modulus of hexagon based honeycombs while decreases their shear modulus. For square based honeycombs, hierarchy increases the shear modulus while decreasing their Young’s modulus. Introducing chirality was shown to always decrease the Young’s modulus and Poisson’s ratio of the structure. However, chirality remains the only route to auxeticity. In particular, we found that anti-tetra-chiral structures were capable of simultaneously exhibiting anisotropy, auxeticity, and remarkably low shear modulus as the magnitude of the chirality of the unit cell increases.

  6. Enantioselective and diastereoselective separation of synthetic pyrethroid insecticides on a novel chiral stationary phase by high-performance liquid chromatography.

    Science.gov (United States)

    Tan, Xulin; Hou, Shicong; Wang, Min

    2007-07-01

    A novel chiral packing material for high-performance liquid chromatography (HPLC) was prepared by connecting (R)-1-phenyl-2-(4-methylphenyl) ethylamine (PTE) amide derivative of (S)-isoleucine to aminopropyl silica gel through 2-amino-3,5-dinitro-1-carboxamido-benzene unit. This chiral stationary phase was applied to the enantioselective and diastereoselective separation of five pyrethroid insecticides by HPLC under normal phase condition. To achieve satisfactory baseline separation an optimization of the variables of mobile phase composition was required. The two enantiomers of fenpropathrin and four stereoisomers of fenvalerate were baseline separated using hexane-1,2-dichloroethane-2-propanol as mobile phase. The results show that the enantioselectivity of CSP is better than Pirkle type 1-A column for these compounds. Only partial separations for the cypermethrin and cyfluthrin stereoisomers were observed. Seven peaks and eight peaks were observed for cypermethrin and cyfluthrin, respectively. The elution orders were assigned by using different stereoisomer-enriched products.

  7. Enantiomeric separation of tolperisone and eperisone by reversed-phase HPLC with cellulose tris(3-chloro-4-methylphenylcarbamate)-coated chiral column.

    Science.gov (United States)

    Owada, Yuri; Takahashi, Mizuho; Iwasa, Sumiko; Ichiba, Hideaki; Sadamoto, Kiyomi; Fukushima, Takeshi

    2014-01-01

    Enantiomeric separations of centrally acting muscle relaxants, that is, tolperisone (TOL) and eperisone (EP), that are marketed as racemates were investigated by reversed-phase high-performance liquid chromatography (HPLC) on a polysaccharide-based chiral column. Both TOL and EP are basic drugs because they contain a tertiary amino group and have similar chemical structures with the exception of the p-methylphenyl and p-ethylphenyl groups in TOL and EP, respectively. A reversed-phase chiral column, that is, a Chiralcel OZ-RH column, which bears cellulose tris(3-chloro-4-methylphenylcarbamate) as the chiral moiety, was effective for the enantiomeric separation of TOL and EP enantiomers. The separation factor and resolution values obtained for TOL were 1.22 and 1.66, respectively, and those for EP were 1.21 and 2.24, respectively, using a 20 mm ammonium acetate in H2 O (pH 8.0 and 7.0, respectively)-CH3 CN (70:30) mobile phase. Using the proposed HPLC conditions, it was found that (R)-TOL eluted faster than (S)-TOL, as revealed by the optical rotation and circular dichroism spectroscopy. In contrast, EP was easily racemized under the experimental conditions, and hence, the elution order was not determined.

  8. Thermodynamic study of an unusual chiral separation. Propranolol enantiomers on an immobilized cellulase

    Energy Technology Data Exchange (ETDEWEB)

    Fornstedt, T.; Sajonz, P.; Guiochon, G. [Univ. of Tennessee, Knoxville, TN (United States)]|[Oak Ridge National Lab., TN (United States)

    1997-02-12

    The thermodynamics of interaction of (R)- and (S)-propranolol between an acetic acid buffer (pH = 4.7 and 5.5) and the protein cellobiohydrolase I immobilized on silica gel was studied between 5 and 45{degree}C. The equilibrium data were fitted to a biLangmuir adsorption isotherm with excellent agreement. One of the two Langmuir contributions is the same for both enantiomers and accounts for the nonspecific interactions between these compounds and most sites on the surfaces (type-I, nonselective sites). It has a large saturation capacity. The second contribution accounts for the chiral selective interactions (type-II sites). It has a lower monolayer capacity than the first. The interaction enthalpy and entropy on type-I sites are -1.1 kcal/mol and +0.1 cal/(mol K), respectively. For type-II sites, they are -1.9 kcal/mol and -2.6 cal/(mol K), respectively, for (R)-propranolol and +1.6 kcal/mol and +11.6 cal/(mol K), respectively, for (S)-propranolol at pH = 5.5. This explains why at this pH the retention time of the less-retained R enantiomer decreases with increasing temperature, while the retention time of the S enantiomer increases, causing a large increase of the separation factor when the temperature is raised from 5 to 45{degree}C. The saturation capacity of the chiral contributions depends strongly on the pH, and the retention times of both enantiomers decrease with increasing temperature at pH = 4.7. 46 refs., 6 figs., 5 tabs.

  9. Enantiomer separation of acidic chiral compounds on a quinine-silica/zirconia hybrid monolith by capillary electrochromatography.

    Science.gov (United States)

    Tran, Le Ngoc; Park, Jung Hag

    2015-05-29

    A weak anion-exchanger chiral selector, quinine-incorporated silica/zirconia hybrid monolithic (QUI-S/ZHM) capillary column was prepared by sol-gel technology. The performance of the QUI-S/ZHM column was investigated for enantioresolution of a set of acidic chiral drugs and dinitrobenzoyl (DNB)-amino acids by capillary electrochromatography in aqueous organic mobile phases composed of acetonitrile (ACN) and triethylammonium acetate (TEAA) buffer. Effects of several parameters including the ACN content, concentration and pH of the mobile phase on the chiral separation were examined. Baseline resolutions of all the compounds were obtained in the mobile phase consisting of 70:30 ACN/TEAA (10mM, pH 6) under applied voltage of -10kV at 25°C within 20min.

  10. Separation of positional CPP isomers by chiral HPLC-DAD of seized tablets.

    Science.gov (United States)

    Schürenkamp, Jennifer; Beike, Justus; Pfeiffer, Heidi; Köhler, Helga

    2011-01-01

    Meta-chlorophenylpiperazine, one of the synthetic piperazine-derived designer drugs, is to date controlled as an illicit substance in five European member states. Depending on the position of the chlorine atom, different positional isomers of CPP (ortho-, meta- and para-) are possible. Therefore, there is a need to develop an analytical method for the separation and identification of the three 1-chlorophenylpiperazines in tablets containing CPP. In this work, the position isomers o-, m- and p-CPP were separated by liquid chromatography (HPLC) on a reversed-phase chiral column. Different mobile phase compositions and pH ranges were systematically studied to find optimum chromatographic conditions. Best results were achieved with isocratic mobile phase of triethyl amine buffer and methanol (V/V = 70/30) at pH 9 with a flow rate of 0.8 ml/min. The method was validated in terms of selectivity, linearity, limit of detection and quantification and precision. At last, the developed method was successfully applied on seized ecstasy tablets.

  11. Synthesis of ino Acid Derived β-Cyclodextrins Used in Chiral Separation by Capillary Electrophoresis

    Institute of Scientific and Technical Information of China (English)

    戴荣继; 佟斌; 魏征; 顾峻岭; 邓玉林; 李明愉; 傅若农

    2004-01-01

    Six new kinds of ino acid derived β-cyclodextrins were synthesized to improve their water solubility and chiral separation properties. They are heptakis{2,6-di-O-[3-L-(1-isopropyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Val-β-CD), heptakis{2,6-di-O-[3-L-(1-benzyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Phe-β-CD), heptakis{2,6-di-O-[3-(D, L-1-benzyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. D,L-Phe-β-CD), heptakis{2,6-di-O-[3-(L-1-hydroxymethyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Ser-β-CD), heptakis{2,6-di-O-[3-(L-1-carboxylmethyl carboxyl methyl ino)- 2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Asp-β-CD), heptakis{2,6-di-O-[3-(L-2-carboxyl tetrethylene ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Pro-β-CD). Their chemical structures were certified using FTIR and 1H NMR. Except for L-Phe-β-CD and D,L-Phe-β-CD, that are in soluble in water, the other ino acid derived β-CDs all have good water solubility. D,L-tyrosine and promethazine were baselinely separated by L-Val-β-CD in capillary electrophoresis.

  12. Separation of basic drug enantiomers by capillary electrophoresis using chicken alpha1-acid glycoprotein: insight into chiral recognition mechanism.

    Science.gov (United States)

    Matsunaga, Hisami; Sadakane, Yutaka; Haginaka, Jun

    2003-08-01

    Recombinant chicken alpha(1)-acid glycoprotein (alpha(1)-AGP) was prepared by the Escherichia coli expression system and completely deglycosylated alpha(1)-AGP (cd-alpha(1)-AGP) was obtained by treatments of native alpha(1)-AGP with a mixture of endoglycosidase and N-glycosidase. The average molecular masses of chicken alpha(1)-AGP, cd-alpha(1)-AGP and recombinant alpha(1)-AGP were estimated to be about 29 200, 21 700 and 20 700, respectively, by matrix-assisted laser desorption-time of flight-mass spectrometry. We compared the chiral recognition ability of chicken alpha(1)-AGP, cd-alpha(1)-AGP and recombinant alpha(1)-AGP using them as chiral selectors in capillary electrophoresis. The chicken alpha(1)-AGP showed higher resolution for eperisone, pindolol and tolperisone than cd-alpha(1)-AGP or recombinant alpha(1)-AGP. Recombinant alpha(1)-AGP still showed chiral recognition for three basic drugs tested. By addition of propranolol as a competitor in the separation solution in CE, no enantioseparations of three basic drugs were observed with chicken alpha(1)-AGP, cd-alpha(1)-AGP or recombinant alpha(1)-AGP. These results reveal that the protein domain of the chicken alpha(1)-AGP is responsible for the chiral recognition ability, and that the chiral recognition site(s) for basic drugs exists on the protein domain.

  13. High performance liquid chromatographic separation of eight drugs collected in Chinese Pharmacopoeia 2010 on amylose ramification chiral stationary phase

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2012-10-01

    Full Text Available The enantiomers separation of eight pharmaceutical racemates collected in Chinese Pharmacopoeia 2010 (Ch.P2010, including nitrendipine, felodipine, omeprazole, praziquantel, sulpiride, clenbuterol hydrochloride, verapamil hydrochloride and chlorphenamine maleate, was performed on chiral stationary phase of amylose ramification by high performance liquid chromatography (HPLC on Chiralpak AD-H column and Chiralpak AS-H column with the mobile phase consisted of isopropanol and n-hexane. The detection wavelength and the flow rate were set at 254 nm and 0.7 mL/min, respectively. The effects of proportion of organic additives, alcohol displacer and temperature on the separation were investigated. The results indicated that eight chiral drugs were separated on chiral stationary phase of amylase ramification in normal phase chromatographic system. The chromatographic retention and resolution of enantiomers were adjusted by factors, including the changes of the concentration of alcohol displacer in mobile phase, organic alkaline modifier and column temperature. It was shown that the resolution was improved with reducing concentration of alcohol displacer. When the concentration of organic alkaline modifier was 0.2%, the resolution and the peak shape were fairly good. Most racemates mentioned above had the best resolution at column temperature of 25 °C. The best temperature should be kept unchanged in the process of separation so as to obtain stable separation results.

  14. Chiral stationary phases based on chitosan bis(methylphenylcarbamate)-(isobutyrylamide) for high-performance liquid chromatography.

    Science.gov (United States)

    Tang, Sheng; Bin, Qin; Chen, Wei; Bai, Zheng-Wu; Huang, Shao-Hua

    2016-04-01

    A series of chitosan bis(methylphenylcarbamate)-(isobutyrylamide) derivatives were synthesized by carbamylating chitosan isobutyrylamide with different methylphenyl isocyanates. Then the prepared chitosan derivatives were coated onto 3-aminopropyl silica particles, resulting in a series of new chiral stationary phases (CSPs) for high-performance liquid chromatography. It was observed that the chiral recognition abilities of these coated-type CSPs depended very much on the substituents on the phenyl moieties of the chitosan derivatives, the eluent composition, as well as the structure of racemates. As a typical example, the eluent tolerance of the prepared CSP with the best enantioseparation ability was investigated in detail, and the results revealed that the CSP exhibited extraordinary solvent tolerance and could still work without significant loss in enantioseparation capability after being flushed with chloroform (100%), ethyl acetate (100%) and even THF/n-hexane (70/30, v/v), while the traditional coated-type CSPs based on the cellulose and amylose derivatives, such as cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) and amylose tris(3,5-dimethylphenylcarbamate) (ADMPC), might be dissolved or highly swollen in these eluents. Therefore, the application of the resultant CSPs could address the problem of the dissolution and high swelling of traditional coated-type CSPs in some unusual eluents, broadening the possibility of eluent choice. In addition, a comparison of the prepared CSPs with the well known CDMPC- and ADMPC- based CSPs concerning the chiral recognition ability was also made. Separation performances achieved on the as-prepared CSPs in different eluents were found to be even superior to CDMPC- and ADMPC-based CSPs for the tested chiral compounds. In summary, we could safely draw the conclusion that the CSPs derived from chitosan isobutyrylamide derivatives were capable of excellent chiral recognition ability, and meanwhile possessed satisfactory

  15. Chiral separation of (d- and (l-enantiomers of doxylamine succinate in rat plasma

    Directory of Open Access Journals (Sweden)

    Tadiboyina Sirisha

    2015-12-01

    Full Text Available A selective chiral ultra fast liquid chromatography (UFLC-DAD method was developed and validated to separate and quantify the (d- and (l-enantiomers of doxylamine in rat plasma. After extraction of the plasma samples with acetonitrile, the separation of doxylamine succinate enantiomers and internal standard (I.S., diphenhydramine hydrochloride was achieved on a cellulose Tris (4-chloro,3-methylphenylcarbamate column with a mobile phase of 20 mM ammonium bicarbonate buffer–acetonitrile (65:35 v/v with 0.15% diethylamine in the buffer at a flow rate of 1.0 mL/min. The diode array (DAD detection wavelength was set at 220 nm. The peaks obtained were identified as (d and (l by injecting the pure (d form into the liquid chromatography and comparing the chromatograms. The effect of column oven temperature on the retention of doxylamine and mobile phase variables which have an effect on the enantiomers separation like ionic strength, type and concentration of organic modifier was studied. Linear calibration curves were obtained over the range of 100–1400 ng/mL in plasma for both enantiomers (R2 > 0.995. The mean extraction recoveries were 94.5–104.7% of rat plasma. The mean relative standard deviation (RSD% of accuracy and intra-day and inter-day precision for both enantiomers were ⩽10%. The method can be further applied to determine the pharmacokinetics of (d- and (l-enantiomers in rat plasma.

  16. The CGC enantiomer separation of 2-arylcarboxylic acid esters by using β-cyclodextrin derivatives as chiral stationary phases.

    Science.gov (United States)

    Shi, Xueyan; Liu, Feipeng; Mao, Jianyou

    2016-03-17

    Chiral 2-arylcarboxylic acid esters are important intermediates in preparation of enantioenriched 2-arylpropionic acids type Non-steroidal anti-inflammatory drugs (NSAIDs). Enantiomer separation of 2-arylcarboxylic acid esters is crucial for evaluation of the asymmetric synthesis efficiency and the enantiomer excess of chiral 2-arylcarboxylic acid derivatives. The capillary gas chromatography (CGC) enantiomer separation of 17 pairs of 2-arylcarboxylic acid esters enantiomers was conducted by using seven different β-cyclodextrin derivatives (CDs) as chiral stationary phases. It was found that for the 7 pairs of 2-phenylpropionates enantiomers, CDs with both alkyl and acyl substituents especially 2,6-di-O-pentyl-3-O-butyryl-β-cyclodextrin exhibited better enantiomer separation abilities than the other CDs examined. For the 7 pairs of 2-(4-substituted phenyl)propionates enantiomers, 2,3,6-tri-O-methyl-β-cyclodextrin possessed better enantiomer separation abilities than the other CDs. Among the 3 pairs of 2-phenylbutyrates enantiomers examined, only methyl 2-phenylbutyrate enantiomers could be separated by three CDs among the 7 CDs tested, while enantiomers of ethyl 2-phenylbutyrate and isopropyl 2-phenylbutyrate couldn't be separated by any of the 7 CDs tested. Besides the structures of CDs, the structures of 2-arylcarboxylic acid esters including different ester moieties, substituents of phenyl, and different carboxylic acids moieties in 2-arylcarboxylic acid esters also affected the enantiomer separation results greatly. The CGC enantiomer separation results of 2-arylcarboxylic acid esters on different CDs are useful for solving the enantiomer separation problem of 2-arylcarboxylic acid esters.

  17. Chiral Separation of G-type Chemical Warfare Nerve Agents via Analytical Seupercritical Fluid Chromatography

    Science.gov (United States)

    2014-01-01

    by HPLC have not been well characterized . Supercritical fluid chromatography (SFC) is a well- established chiral chromatography technology that offers...smoothed chromatograms. For presentation purposes only smoothed chromatograms are shown. Chromatographic Characterization Chromatography parameters were...under these conditions (data not shown). Various other polysaccharide -type chiral columns (Chiralpak AD-H, Chiralcel OJ-RH, Chiralpak IB) were tested

  18. Kinetic study on reactive extraction for chiral separation of phenylsuccinic acid enantiomers

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer solution(pH = 2.5) was selected as the chiral extractant.PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module.The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module.The different parameters affecting the extraction rate such as agitation speed,interfacial area,initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied.The experimental results demonstrate that the extraction reactions are fast.The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10-2 m6 mol-2 s-1 for R-PSA and 9.96 × 10?3 m6 mol-2 s-1 for S-PSA.These data will be useful in the design of extraction processes.

  19. A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

    Science.gov (United States)

    Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

    2013-12-14

    Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

  20. Enantiomeric separation of volatile organics by gas chromatography for the in situ analysis of extraterrestrial materials: kinetics and thermodynamics investigation of various chiral stationary phases.

    Science.gov (United States)

    Freissinet, C; Buch, A; Szopa, C; Sternberg, R

    2013-09-01

    The performances of several commercial chiral capillary columns have been evaluated with the aim of determining the one most suitable for enantiomeric separation in a gas chromatograph onboard a space probe. We compared the GC-MS response of three capillary columns coated with different chiral stationary phases (CSP) using volatile chiral organic molecules which are potential markers of a prebiotic organic chemistry. The three different chiral capillary columns are Chirasil-Val, with an amino acid derivative CSP, ChiralDex-β-PM, with a CSP composed of dissolved permethylated β-cyclodextrins in polysiloxane, and Chirasil-Dex, with a CSP made of modified cyclodextrins chemically bonded to the polysiloxane backbone. Both kinetics and thermodynamics studies have been carried out to evaluate the chiral recognition potential in these different types of columns. The thermodynamic parameters also allow a better understanding of the driving forces affecting the retention and separation of the enantiomers. The Chirasil-Dex-CSP displays the best characteristics for an optimal resolution of the chiral compounds, without preliminary derivatization. This CSP had been chosen to be the only chiral column in the Sample Analysis at Mars (SAM) experiment onboard the current Mars Science Laboratory (MSL) mission, and is also part of the Mars Organic Molecules Analyzer (MOMA) gas chromatograph onboard the next Martian mission ExoMars. The use of this column could also be extended to all space missions aimed at studying chirality in space.

  1. The vorticity induced chiral separation effect from the compactified D4-branes with smeared D0-brane charge

    CERN Document Server

    Wu, Chao; Huang, Mei

    2016-01-01

    By using the boundary derivative expansion formalism of fluid/gravity correspondence, we study the chiral vortical separation effect in a strongly coupled nonconformal relativistic fluid in the background of D0-D4 Sakai-Sugimoto model. The relativistic fluid of this model is nonconformal with a conserved axial vector current, and the presence of the chiral vortical separation effect is induced by the addition of a Chern-Simons term in the bulk action. Except the non-dissipative anomalous viscous coefficient and the sound speed, all other thermal and hydrodynamical quantities of first order depend on the temperature and the axial chemical potential. Stability analysis shows that this anomalous relativistic fluid is stable and the doping of smeared D0-brane will slow down the sound speed.

  2. Enantiomeric Separation of Epinephrine and Salbutamol by Micellar Electrokinetic Chromatography Using β-Cyclodextrin as Chiral Additive

    Institute of Scientific and Technical Information of China (English)

    Yan Peng ZHENG; Jin Yuan MO

    2004-01-01

    Enantiomeric separation of epinephrine and salbutamol was investigated by micellar electrokinetic chromatography employing β-cyclodextrin as chiral additive in ammonium chloride-ammonia solution. The analytes were detected by electrochemistry using gold microelectrode at +0.65 V versus SCE reference electrode. The effects of detection potential,concentration of β-cyclodextrin, concentration of sodium dodecyl sulfate, pH value of electrolyte and applied voltage were discussed.

  3. Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

    Science.gov (United States)

    Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

    2012-11-01

    A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

  4. Resolution and isolation of enantiomers of (±)-isoxsuprine using thin silica gel layers impregnated with L-glutamic acid, comparison of separation of its diastereomers prepared with chiral derivatizing reagents having L-amino acids as chiral auxiliaries.

    Science.gov (United States)

    Bhushan, Ravi; Nagar, Hariom

    2015-03-01

    Thin silica gel layers impregnated with optically pure l-glutamic acid were used for direct resolution of enantiomers of (±)-isoxsuprine in their native form. Three chiral derivatizing reagents, based on DFDNB moiety, were synthesized having l-alanine, l-valine and S-benzyl-l-cysteine as chiral auxiliaries. These were used to prepare diastereomers under microwave irradiation and conventional heating. The diastereomers were separated by reversed-phase high-performance liquid chromatography on a C18 column with detection at 340 nm using gradient elution with mobile phase containing aqueous trifluoroacetic acid and acetonitrile in different compositions and by thin-layer chromatography (TLC) on reversed phase (RP) C18 plates. Diastereomers prepared with enantiomerically pure (+)-isoxsuprine were used as standards for the determination of the elution order of diastereomers of (±)-isoxsuprine. The elution order in the experimental study of RP-TLC and RP-HPLC supported the developed optimized structures of diastereomers based on density functional theory. The limit of detection was 0.1-0.09 µg/mL in TLC while it was in the range of 22-23 pg/mL in HPLC and 11-13 ng/mL in RP-TLC for each enantiomer. The conditions of derivatization and chromatographic separation were optimized. The method was validated for accuracy, precision, limit of detection and limit of quantification.

  5. Separation of antifungal chiral drugs by SFC and HPLC: a comparative study.

    Science.gov (United States)

    Bernal, J L; Toribio, L; del Nozal, M J; Nieto, E M; Montequi, M I

    2002-12-31

    The enantiomeric separation of several compounds, including an antifungal drug and several of its precursors, using HPLC and SFC is described in this work. The columns employed were based on polysaccharide derivatives and the results show that most of the separations obtained by SFC are better, in terms of high resolution and short analysis time, than those obtained by HPLC. Only one compound could not be resolved using SFC but, in this case, HPLC provided baseline resolution.

  6. Chiral Separation and Identification of D,L-Histidine Based on Nanochannels Membrane Coupling with Surface Enhanced Raman Scattering Spectroscopy%基于纳米通道表面增强拉曼散射光谱分离检测组氨酸对映体的研究

    Institute of Scientific and Technical Information of China (English)

    钟桐生; 尹志芳; 柳悦; 黄杉生

    2015-01-01

    Gold nanochannels were prepared using Al2 O3 nanotubules membrane as the carrier and modified with chitosan by a classical N-(3-dimethylaminopropyl)-N-ethyl carbodiimide ( EDC)/N-hydroxysuccinimide ( NHS ) coupling reaction. The nanochannels were characterized by field emission scanning electron microscopy ( FESEM) , cyclic voltammetry and AC impedance method. The Au nanochannels modified with chitosan showed a chiral environment and can be used to separate histidine enantiomer. The effects of pore size and solution pH on the separation efficiency of histidine were investigated. To increase the detection sensitivity of D-, L-histidine, Ag nanoparticles were used to enhance the surface enhanced Raman scattering ( SERS) activity. The results showed that the chitosan-modified gold nanochannels can be used to separate chiral histidine based on this unique selective nanochannel membrane. L-Histidine and D-histidine were respectively detected by SERS at wavelengths of 1000 and 1590 cm-1 . The results showed that L-histidine and D-histidine were separated well in the mixture containing 200 μL of histidine, 100 μL of colloidal Ag and 100 μL of 80 mmol/L NaCl ( pH=7 . 59 ) with a separation efficiency of 4 . 91 .%以Al2 O3纳米通道膜为基体制备金纳米通道,以场发射扫描电镜、循环伏安、交流阻抗等方法对金纳米通道进行表征。采用EDC-NHS的交联反应,将壳聚糖自组装至金纳米通道孔壁上,形成表面具有手性位点选择性的功能化纳米通道膜,利用纳米通道优异的分离能力手性分离D-,L-组氨酸。考察了纳米通道孔径和溶液的pH值对分离效果的影响。采用银溶胶作为表面增强拉曼( SERS)测试的基底,增强对D-,L-组氨酸的SERS效应,提高检测该物质的选择性和灵敏度。分别在1000和1590 cm-1处测定L-组氨酸和D-组氨酸。在含200μL组氨酸、100μL银溶胶和100μL 80 mmol/L NaCl溶液(pH=7.59)中,D-组氨酸和L-组氨酸可得

  7. Enantioselective extraction of mandelic acid enantiomers based on chiral ligand exchange

    Institute of Scientific and Technical Information of China (English)

    TANG Ke-wen; HUANG Ke-long

    2005-01-01

    Based on the chiral ligand exchange, the distribution behavior of mandelic acid enantiomers, and the partition of Cu2+ at different pH values were studied in a water/alcohol two-phase system containing Cu2+ and N-n-dodecyl-L-proline(A). The influences of the solvent sort, the pH value, the concentrations of Cu2+ and chiral ligand on the partition coefficient(K) and separation factor(α) were discussed. The experimental results show that the A formed has more stable ternary complex with D-mandelic acid enantiomer than with L-mandelic acid enantiomer. There is an important influence of the pH value on K and α. When the pH values are less than 3.5, the formation of binary complexes is thermodynamically unfavourable. K and α become maximum when pH values are above 3.5 and the molar ratio of the chiral ligand to Cu2+ is 2:1.

  8. Large scale chiral chromatography for the separation of an enantiomer to accelerate drug development.

    Science.gov (United States)

    Hsu, Leo C; Kim, Hyunjung; Yang, Xiqin; Ross, David

    2011-04-01

    There are several approaches to produce enantiomerically pure drug substances, such as recrystallization, catalytic process (ligand and enzyme), indirect chromatographic resolution, and direct chromatographic resolution. However, the use of preparative chromatography with chiral stationary phases seems to be most effective for early phase projects, where the time and resources on the developments need to be minimized to get the drug candidates into the clinical studies. We showed that by following a well-defined process, chiral chromatography can be easily scaled up from an analytical system to a pilot plant system. We also used the results from a multicolumn continuous chromatography (MCC) study to conclude that MCC can be a cost-effective production method for chiral manufacturing.

  9. Tailoring the chirality of light emission with spherical Si-based antennas.

    Science.gov (United States)

    Zambrana-Puyalto, Xavier; Bonod, Nicolas

    2016-05-21

    Chirality of light is of fundamental importance in several enabling technologies with growing applications in life sciences, chemistry and photodetection. Recently, some attention has been focused on chiral quantum emitters. Consequently, optical antennas which are able to tailor the chirality of light emission are needed. Spherical nanoresonators such as colloids are of particular interest to design optical antennas since they can be synthesized at a large scale and they exhibit good optical properties. Here, we show that these colloids can be used to tailor the chirality of a chiral emitter. To this purpose, we derive an analytic formalism to model the interaction between a chiral emitter and a spherical resonator. We then compare the performances of metallic and dielectric spherical antennas to tailor the chirality of light emission. It is seen that, due to their strong electric dipolar response, metallic spherical nanoparticles spoil the chirality of light emission by yielding achiral fields. In contrast, thanks to the combined excitation of electric and magnetic modes, dielectric Si-based particles feature the ability to inhibit or to boost the chirality of light emission. Finally, it is shown that dual modes in dielectric antennas preserve the chirality of light emission.

  10. Proline Based Chiral Ionic Liquids for Enantioselective Michael Reaction

    Directory of Open Access Journals (Sweden)

    Kaoru Nobuoka

    2014-01-01

    Full Text Available Chiral ionic liquids, starting from (S-proline, have been prepared and evaluated the ability of a chiral catalyst. In Michael reaction of trans-β-nitrostyrene and cyclohexanone, all the reactions were carried out under homogeneous conditions without any solvent except for excess cyclohexanone. The chiral ionic liquid catalyst with the positive charge delocalized bulky pyrrolidinium cation shows excellent yields (up to 92%, diastereoselectivities (syn/anti = 96/4, and enantioselectivities (up to 95% ee and could be reused at least three times without any loss of its catalytic activity. Such results demonstrated a promising new approach for green and economic chiral synthesis by using the chiral ionic liquids as a chiral catalyst and a chiral medium.

  11. Preparation and evaluation of novel chiral stationary phases based on quinine derivatives comprising crown ether moieties.

    Science.gov (United States)

    Wang, Dongqiang; Zhao, Jianchao; Wu, Haixia; Wu, Haibo; Cai, Jianfeng; Ke, Yanxiong; Liang, Xinmiao

    2015-01-01

    The C9-position of quinine was modified by meta- or para-substituted benzo-18-crown-6, and immobilized on 3-mercaptopropyl-modified silica gel through the radical thiol-ene addition reaction. These two chiral stationary phases were evaluated by chiral acids, amino acids, and chiral primary amines. The crown ether moiety on the quinine anion exchanger provided a ligand-exchange site for primary amino groups, which played an important role in the retention and enantioselectivity for chiral compounds containing primary amine groups. These two stationary phases showed good selectivity for some amino acids. The complex interaction between crown ether and protonated primary amino group was investigated by the addition of inorganic salts such as LiCl, NH4Cl, NaCl, and KCl to the mobile phase. The resolution results showed that the simultaneous interactions between two function moieties (quinine and crown ether) and amino acids were important for the chiral separation.

  12. Non-ionic surfactant modified ligand exchange chromatography using copper (II) complex of N,N-dimethyl-L-phenylalanine as the chiral additive for enantioselective amino acids separation

    Energy Technology Data Exchange (ETDEWEB)

    Dimitrova, Pepa [TU Kaiserslautern, Institut fuer Thermische Verfahrenstechnik, P.O. Box 3049, Gottlieb-Daimler-Str. 44, 67653 Kaiserslautern (Germany); Bart, Hans-Joerg, E-mail: bart@mv.uni-kl.de [TU Kaiserslautern, Institut fuer Thermische Verfahrenstechnik, P.O. Box 3049, Gottlieb-Daimler-Str. 44, 67653 Kaiserslautern (Germany)

    2010-03-17

    The influence of non-ionic surfactants on the selectivity and retention in the ligand exchange chromatography for the enantioselective separation of racemic mixtures of the amino acids DL-methionine, DL-leucine, DL-valine and DL-tyrosine applying chiral mobile phases was investigated, whereas five different surfactants were tested as modifiers. The experiments were carried out using a commercially available non-chiral RP-C8 column and the copper (II) complex of N,N-dimethyl-L-phenylalanine as the chiral additive. Varying the surfactant concentrations the retention factors and the selectivity could be controlled and in general no negative influence on the separation (due to surfactant adsorption on the non-chiral stationary phase) occurred. Changing the temperature the van't Hoff plots were obtained and the thermodynamic parameters calculated. Temperature had influence on the selectivity for each surfactant and lowered the retention times as expected.

  13. Non-ionic surfactant modified ligand exchange chromatography using copper (II) complex of N,N-dimethyl-L-phenylalanine as the chiral additive for enantioselective amino acids separation.

    Science.gov (United States)

    Dimitrova, Pepa; Bart, Hans-Jörg

    2010-03-17

    The influence of non-ionic surfactants on the selectivity and retention in the ligand exchange chromatography for the enantioselective separation of racemic mixtures of the amino acids dl-methionine, dl-leucine, dl-valine and dl-tyrosine applying chiral mobile phases was investigated, whereas five different surfactants were tested as modifiers. The experiments were carried out using a commercially available non-chiral RP-C8 column and the copper (II) complex of N,N-dimethyl-l-phenylalanine as the chiral additive. Varying the surfactant concentrations the retention factors and the selectivity could be controlled and in general no negative influence on the separation (due to surfactant adsorption on the non-chiral stationary phase) occurred. Changing the temperature the van't Hoff plots were obtained and the thermodynamic parameters calculated. Temperature had influence on the selectivity for each surfactant and lowered the retention times as expected.

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

    Science.gov (United States)

    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.

  15. Enantiomeric separation of chiral polychlorinated biphenyls on B-cyclodextrin capillary columns by means of heart-cut multidimensional gas chromatography and comprehensive two-dimensional gas chromatography. Application to food samples

    NARCIS (Netherlands)

    Bordajandi, L.R.; Korytar, P.; Boer, de J.; Gonzalez, M.J.

    2005-01-01

    Three commercially available chiral capillary columns, Chirasil-Dex, BGB-176SE. and BGB-172, have been evaluated for the separation into enantiomers of the 19 chiral polychlorinated biphenyls (PCB) congeners stable at room temperature. The enantiomers of 15 chiral PCBs were, at least to some extent,

  16. Impact of the nature and composition of the mobile phase on the mass transfer mechanism in chiral reversed phase liquid chromatography. Application to the minimization of the solvent cost in chiral separations.

    Science.gov (United States)

    Gritti, Fabrice; Guiochon, Georges

    2014-01-31

    The mechanism of mass transfer was studied on a cellulose-based chiral stationary phase (CSP, Lux Cellulose-1) using aqueous mixtures of acetonitrile (50/50-90/10, v/v) or methanol (90/10 and 100/0, v/v) as the mobile phase. An experimental protocol validated in RPLC and HILIC chromatography and recently extended to chiral RPLC was applied. The five mass-transfer contributions (longitudinal diffusion, short-range and long-range eddy dispersion, solid-liquid mass transfer resistances due to finite intra-particle diffusivity and slow adsorption-desorption) to the reduced height equivalent to a theoretical plate (HETP) were measured. The experimental results show that the adsorption rate constants kads of trans-stilbene enantiomers onto the CSP are three times larger with acetonitrile than with methanol as the organic modifier. This is correlated to the decrease of enantioselectivity from 1.4 (in methanol) to only 1.1 (in acetonitrile). The amount of solvent needed to achieve a separation factor of exactly 2.0 was determined. This showed that analysis cost could be reduced seven times by selecting pure methanol as the eluent for a 5cm long column rather than an acetonitrile-water mixture for a longer (20-45cm) column.

  17. Synthesis and chromatographic evaluation of new polymeric chiral stationary phases based on three (1S,2S)-(-)-1,2-diphenylethylenediamine derivatives in HPLC and SFC.

    Science.gov (United States)

    Payagala, Tharanga; Wanigasekara, Eranda; Armstrong, Daniel W

    2011-03-01

    Three new polymeric chiral stationary phases were synthesized based on (1S,2S)-1,2-bis(2,4,6-trimethylphenyl)ethylenediamine, (1S,2S)-1,2-bis(2-chlorophenyl)ethylenediamine, and (1S,2S)-1,2-di-1-naphthylethylenediamine via a simple free-radical-initiated polymerization in solution. These monomers are structurally related to (1S,2S)-1,2-diphenylethylenediamine which is the chiral monomer used for the commercial P-CAP-DP polymeric chiral stationary phase (CSP). The performance of these three new chiral stationary phases were evaluated in normal phase high-performance liquid chromatography (HPLC) and supercritical fluid chromatography and the results were compared with those of the P-CAP-DP column. All three new phases showed enantioselectivity for a large number of racemates with a variety of functional groups, including amines, amides, alcohols, amino acids, esters, imines, thiols, and sulfoxides. In normal phase, 68 compounds were separated with 28 baseline separations (Rs ≥ 1.5) and in SFC, 65 compounds were separated with 24 baseline separations. In total 72 out of 100 racemates were separated by these CSPs with 37 baseline separations. Complimentary separation capabilities were observed for many analytes. The new polymeric CSPs showed similar or better enantioselectivities compared with the commercial column in both HPLC and SFC. However, faster separations were achieved on the new stationary phases. Also, it was shown that these polymeric stationary phases have good sample loading capacities while maintaining enantioselectivity.

  18. High efficiency, narrow particle size distribution, sub-2 μm based macrocyclic glycopeptide chiral stationary phases in HPLC and SFC.

    Science.gov (United States)

    Barhate, Chandan L; Wahab, M Farooq; Breitbach, Zachary S; Bell, David S; Armstrong, Daniel W

    2015-10-22

    State of the art chiral chromatography still employs 3-5 μm bonded or immobilized chiral selectors in 10-25 cm columns. With the availability of 1.9 μm narrow particle size distribution (NPSD) silica, it is now possible to make ever shorter, high efficiency columns practical for sub-minute chiral separations. Three macrocyclic glycopeptides (teicoplanin, teicoplanin aglycone, and vancomycin) were bonded onto 1.9 μm NPSD particles. Such packed columns had ∼80% lower backpressure as compared to polydisperse (PD) 1.7 μm silica materials when using the same mobile phase. The decreased backpressure allowed for diminution of frictional heating and allowed for the use of the 1.9 μm NPSD particle based columns at high flow rates. The 1.9 μm NPSD particle based columns showed up to 190,000 plates m(-1) for chiral molecules and 210,000 plates m(-1) for achiral probes. Representative enantiomeric separations are shown for wide classes of compounds, including different types of amino acids, β-blockers, and pharmaceutically important heterocyclic compounds such as oxazolidinones. Applications in three liquid chromatography modes, namely, reversed phase, polar organic mode and normal phase chiral separations were shown with resolution values ranging from 1.5 to 5.7. Additionally, the same columns were used with supercritical fluid chromatography (SFC) for ultrafast separations.

  19. Chiral separation of benzoporphyrin derivative mono- and diacids by laser induced fluorescence-capillary electrophoresis.

    Science.gov (United States)

    Peng, Xuejun; Sternberg, Ethan; Dolphin, David

    2002-01-01

    A method for the separation of benzoporphyrin derivative mono- and diacid (BPDMA, BPDDA) enantiomers by laser induced fluorescence-capillary electrophoresis (LIF-CE) has been developed. By using 300 mM borate buffer, pH 9.2, 25 mM sodium cholate and 10% acetronitrile as electrolyte, +10 kV electrokinetic sampling injection of 2 s and an applied +20 kV voltage across the ends of a 37 cm capillary (30 cm to the detector, 50 microm ID), all six BPD stereoisomers were baseline-separated within 20 min. Formation constants, free electrophoretic and complexation mobilities with borate and cholate were determined based on dynamic complexation capillary electrophoresis theory. The BPD enantiomers can be quantitatively determined in the range of 10(-2)-10(-5) mg mL(-1). The correlation coefficients (r2) of the least-squares linear regression analysis of the BPD enantiomers are in the range of 0.9914-0.9997. Their limits of detection are 2.18-3.5 x 10(-3) mg mL(-1). The relative standard deviations for the separation were 2.90-4.64% (n = 10). In comparison with high-performance liquid chromatography (HPLC), CE has better resolution and efficiency. This separation method was successfully applied to the BPD enantiomers obtained from a matrix of bovine serum and from liposomally formulated material as well as from studies with rat, dog and human microsomes.

  20. Novel Composite Materials for Chiral Separation from Cellulose and Barium Sulfate

    Directory of Open Access Journals (Sweden)

    Wei Chen

    2013-01-01

    Full Text Available Cellulose was dissolved in an aqueous solution of sodium hydroxide (NaOH and urea followed by the addition of barium sulfate (BaSO4 to yield the BaSO4/cellulose composite particles. The morphology, particle size, and BaSO4 content of the composite particles were adjusted by controlling the feed ratio of cellulose and BaSO4. The cellulose within the composite particles then reacted with 3,5-dimethylphenyl isocyanate. The resulting materials were utilized as the chiral stationary phases (CSPs whose enantioseparation capabilities were evaluated by various chiral analytes. Due to the mechanical enhancement effect of BaSO4, the composite particles could be applied to the chromatographic packing materials.

  1. Chiral separation by (S)-naproxen imprinted monolithic column with mixed functional monomers

    Institute of Scientific and Technical Information of China (English)

    Zhen Ying Li; Zhao Sheng Liu; Qing Wei Zhang; Hong Quan Duan

    2007-01-01

    Molecularly imprinted polymers (MIPs), using (S)-naproxen as template and the combination of butyl methacrylate (BMA) and column was evaluated in HPLC mode. The result showed that the monolithic MIPs with the combination of two monomers produced better chiral resolution of rac-naproxen (Rs = 1.55) and column efficiencies of imprinted molecules (N = 2860 plates/m)than that with pure MAA.

  2. Comparison of chiral recognition capabilities of cyclodextrins for the separation of basic drugs in capillary zone electrophoresis.

    Science.gov (United States)

    Jin, L J; Li, S F

    1998-04-24

    The enantiomeric separation of some racemic anti-histamines and anti-malarials, namely (+/-)-pheniramine, (+/-)-brompheniramine, (+/-)-chlorpheniramine, (+/-)-doxylamine, and (+/-)-chloroquine, was investigated by capillary zone electrophoresis. The enantiomeric separation of five compounds was obtained by addition of approximately 7 mM (1%, w/v) sulfated-beta-cyclodextrin into the buffer as a chiral selector. The effects of sulfated-beta-cyclodextrin concentration and buffer pH on migration and resolution are discussed. Two other cyclodextrins, carboxyethylated-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin were also investigated. Four of the racemic compounds were resolved using 14 mM (2%, w/v) carboxyethylated-beta-cyclodextrin while 28 mM (4%, w/v) hydroxypropyl-beta-cyclodextrin resolved only two of them. It was found that the type of substituent and the degree of substitution on the rim of the CD structure played an important role in enhancing the chiral recognition. Cyclodextrins with negatively charged substituents and higher degree of substitution on the rim of the structure proved to give better resolution to the cationic racemic compounds compared with cyclodextrin with neutral substituents. This is due to the countercurrent mobility of the negatively charged cyclodextrin relative to the cationic analytes thus allowing for a smaller difference in interaction constants to achieve a successful resolution of enantiomers. Furthermore, lower concentrations of negatively charged cyclodextrins were necessary to achieve the equivalent resolutions as compared with the neutral ones.

  3. Novel carbohydrate-based chiral ammonium ionic liquids derived from isomannide

    DEFF Research Database (Denmark)

    Kumar, Vineet; Pei, Cao; Olsen, Carl E.

    2008-01-01

    This report describes the synthesis and characterization of novel carbohydrate-based chiral ammonium ionic liquids using isomannide as a biorenewable substrate. The diastereomeric interactions of these chiral ammonium ionic liquids with racemic Mosher's acid salt have been studied using NMR, whic...

  4. High-performance liquid chromatographic separation of rolipram, bupivacaine and omeprazole using a tartardiamide-based stationary phase influence of flow rate and temperature on the enantioseparation.

    Science.gov (United States)

    da Silva Junior, Ivanildo José; Sartor, João Paulo; Rosa, Paulo César Pires; de Veredas, Vinícius; Barreto Júnior, Amaro Gomes; Santana, Cesar Costapinto

    2007-08-24

    Chromatographic separation of the chiral drugs rolipram, bupivacaine and omeprazole on a tartardiamide-based stationary phase commercially named Kromasil CHI-TBB is shown in this work. The effect of temperature on the chromatographic separation of the chiral drugs using the Kromasil CHI-TBB stationary phase was determined quantitatively so as to contribute toward the design for the racemic mixtures of the named compound by using chiral columns. A decrease in the retention and selectivity factors was observed, when the column temperature increased. Van't Hoff plots provided the thermodynamic data. The variation of the thermodynamic parameters enthalpy and entropy are clearly negative meaning that the separation is enthalpy controlled.

  5. Chiral Nanoscience and Nanotechnology

    Directory of Open Access Journals (Sweden)

    Dibyendu S. Bag

    2008-09-01

    Full Text Available The paper reviews nanoscale science and technology of chiral molecules/macromolecules-under twosubtopics-chiral nanotechnology and nano-chiral technology. Chiral nanotechnology discusses thenanotechnology, where molecular chirality plays a role in the properties of materials, including molecularswitches, molecular motors, and other molecular devices; chiral supramolecules and self-assembled nanotubesand their functions are also highlighted. Nano-chiral technology  describes the nanoscale approaches to chiraltechnology such as asymmetric synthesis and catalysis, chiral separation and detection, and enantiomericanalysis. Chiral sensors have also been included. The state-of-the-art chiral research at DMSRDE,Kanpur isalso presented.Defence Science Journal, 2008, 58(5, pp.626-635, DOI:http://dx.doi.org/10.14429/dsj.58.1685

  6. Application of Countercurrent Chromatography on Chiral Separation%逆流色谱技术在手性分离方面的应用

    Institute of Scientific and Technical Information of China (English)

    吕迎春; 樊竹青

    2014-01-01

    Countercurrent chromatography is a liquid -liquid partition chromatography,without the use of support body or carrier.It is of advantage for chiral separation.In this paper its recent application in chiral separation is reviewed.%逆流色谱是一种不用固态支撑体或载体的液液分配色谱技术,其分离原理具有手性制备性分离的优势。以近年采用逆流色谱技术对手性化合物分离的应用进行了综述。

  7. Enantioselective Recognition of Chiral Carboxylic Acids by a β-Amino Acid and 1,10-Phenanthroline Based Chiral Fluorescent Sensor.

    Science.gov (United States)

    Zhang, Yonghong; Hu, Fangzhi; Wang, Bin; Zhang, Xiaomei; Liu, Chenjiang

    2015-05-06

    A novel chiral 1,10-phenanthroline-based fluorescent sensor was designed and synthesized from optical active β-amino acids. It used 1,10-phenanthroline moiety as a fluorescent signaling site and binding site, with optically active β-amino acids as a chiral barrier site. Notably, the optically active β-amino acids were obtained by a Lewis base catalyzed hydrosilylation of β-enamino esters according to our former work. The chiral sensor has been used to conduct the enantioselective recognition of chiral mono and dicarboxylic acids derivatives. Using this fluorescent sensor, a moderate "turn-off" fluorescence-diminishment response towards enantiomer of tartaric acids, and proline was observed. It found that l-enantiomers quench the chiral fluorescence sensor more efficiently than d-enantiomers due to the absolute configuration of the β-amino acid.

  8. Chiral Separation of Ephedrine and Pseudoephedrine by Capillary Electrophoresis%毛细管电泳技术分离麻黄碱和伪麻黄碱

    Institute of Scientific and Technical Information of China (English)

    高冲; 王明召

    2015-01-01

    设计了一篇反映现代化学内容的高中化学教学材料。通过用氧化石墨烯修饰毛细管柱分离麻黄碱和伪麻黄碱的研究实例,介绍毛细管电泳技术分离手性对映体的基本原理,内容涉及分子的手性、分子间作用力、氢键等高中化学知识,供一线高中化学教师用于教学实践。%Based on high school chemistry knowledge such as chiral molecules,intermolecu-lar forces and hydrogen bond,an instructional material about the basic principles of chiral separa-tions of the ephedrine-pseudoephedrine (E-PE)isomers by GO-coated capillary electrophoresis was designed,in order to extend high school chemistry.

  9. Separators - Technology review: Ceramic based separators for secondary batteries

    Science.gov (United States)

    Nestler, Tina; Schmid, Robert; Münchgesang, Wolfram; Bazhenov, Vasilii; Schilm, Jochen; Leisegang, Tilmann; Meyer, Dirk C.

    2014-06-01

    Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ("Energiewende") was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membrane - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators

  10. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi

    2007-01-01

    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  11. Enantioselective Diels-Alder reactions of carboxylic ester dienophiles catalysed by titanium-based chiral Lewis acid

    Directory of Open Access Journals (Sweden)

    Yogesh K. Choughule

    2016-05-01

    Full Text Available A new titanium-based chiral Lewis acid 1 has been developed using (1R,2R-1,2-bis-(2-methoxyphenyl-ethane-1,2-diol as a chiral vicinal diol ligand. This chiral catalyst was found to exhibit uniformly high enantioselectivity towards carboxylic ester dienophiles in Diels-Alder reactions. The chiral vicinal ligand (1R,2R-1,2-bis-(2-methoxyphenyl-ethane-1,2-diol is inexpensive and is easily accessible.

  12. Chiral Edge States and Fractional Charge Separation in a System of Interacting Bosons on a Kagome Lattice

    Science.gov (United States)

    Zhang, Xue-Feng; Eggert, Sebastian

    2013-10-01

    We consider the extended hard-core Bose-Hubbard model on a kagome lattice with boundary conditions on two edges. We find that the sharp edges lift the degeneracy and freeze the system into a striped order at 1/3 and 2/3 filling for zero hopping. At small hopping strengths, holes spontaneously appear and separate into fractional charges which move to the edges of the system. This leads to a novel edge liquid phase, which is characterized by fractional charges near the edges and a finite edge compressibility but no superfluid density. The compressibility is due to excitations on the edge which display a chiral symmetry breaking that is reminiscent of the quantum Hall effect and topological insulators. Large scale Monte Carlo simulations confirm the analytical considerations.

  13. Carboxymethyl-β-cyclodextrin for Chiral Separation of Amino Acids Derivatized with Fluorescene-5-isothiocyanate by Capillary Electrophoresis and Laser-induced Fluorescence Detection

    Institute of Scientific and Technical Information of China (English)

    Yu Yun CHEN; Wei WANG; Wei Ping YANG; Zhu Jun ZHANG

    2004-01-01

    A method using carboxymethyl-β-cyclodextrin(CM-β-CD) as selector for chiral separation of amino acids by capillary electrophoresis and laser-induced fluorescence detection was studied. Resolution was better than that obtained byβ-CD or HP-β-CD.

  14. Chiral separation of neonicotinoid insecticides by polysaccharide-type stationary phases using high-performance liquid chromatography and supercritical fluid chromatography.

    Science.gov (United States)

    Zhang, Cheng; Jin, Lixia; Zhou, Shanshan; Zhang, Yifan; Feng, Shuoli; Zhou, Qinyan

    2011-03-01

    The enantiomeric separations of three neonicotinoid insecticides (identified as compounds 1, 2, and 3) were performed on three polysaccharide-type chiral columns, that is, Chiralcel OD-H, Chiralpak AD-H, and Chiralpak IB, by high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). Effects of the modifier percentage and column temperature on chiral recognitions of chiral stationary phases were also studied. Both 1 and 2 could be resolved on all three columns selected, with the highest R(s) values obtained on Chiralpak AD-H and Chiralcel OD-H, respectively. However, satisfactory separation of the four stereoisomers of 3 was only achieved on Chiralcel OD-H. Considering the effects of ethanol on the values of k, α, and R(s), we concluded that hydrogen bonding, π-π, and/or dipole-dipole interactions might be all responsible for the chiral separation. In comparison to HPLC, a shorter run time was achieved for 1 and 2 by SFC. However, 3 could not be stereoselectively resolved using SFC. On the basis of the calculated thermodynamic parameters, we found that the separation processes of enantiomers of 1 and 2 were entropy controlled and enthalpy controlled, respectively.

  15. Modelling of conditions for the enantiomeric separation of beta(2)-adrenergic sympathicomimetics by capillary electrophoresis using cyclodextrins as chiral selectors in a polyethylene glycol gel

    NARCIS (Netherlands)

    de Boer, Theo; Bijma, R; Ensing, K

    1999-01-01

    A two-factor central composite design was used to determine a mathematical model for prediction of the optimal conditions for the separation of the enantiomers of some widely used beta(2)-sympathicomimetic drugs (beta(2)-agonists) by capillary electrophoresis using cyclodextrins (CD) as a chiral sel

  16. Bulky melamine-based Zn-porphyrin tweezer as a CD probe of molecular chirality.

    Science.gov (United States)

    Petrovic, Ana G; Vantomme, Ghislaine; Negrón-Abril, Yashira L; Lubian, Elisa; Saielli, Giacomo; Menegazzo, Ileana; Cordero, Roselynn; Proni, Gloria; Nakanishi, Koji; Carofiglio, Tommaso; Berova, Nina

    2011-10-01

    The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers.

  17. Development of Amylose- and β-Cyclodextrin-Based Chiral Fluorescent Sensors Bearing Terthienyl Pendants

    Directory of Open Access Journals (Sweden)

    Tomoyuki Ikai

    2016-11-01

    Full Text Available Phenylcarbamate derivatives of amylose and β-cyclodextrin show excellent chiral recognition when used as chiral stationary phases (CSPs for high-performance liquid chromatography. To open up new possibilities of carbohydrate-based materials, we developed chiral fluorescent sensors based on amylose and β-cyclodextrin (Am-1b and CyD-1b, respectively by attaching fluorescent π-conjugated units on their side chains. Their recognition abilities toward chiral analytes containing a nitrophenyl unit were evaluated by measuring the enantioselective fluorescence quenching behavior. Both sensors showed the same degree of enantioselective fluorescence response for various aromatic nitro compounds. However, in some cases, their enantioselectivities were different depending on the analytes. The difference in the chiral recognition abilities between Am-1b and CyD-1b seems to be based on the structural difference of their inherent backbones, that is, the one-handed helical structure and cyclic structure, respectively. The study on the resolution ability of the Am-1b-based CSP revealed that the terthienyl-based pendant of Am-1b provides not only a fluorescent functionality but also a different chiral recognition site from that of amylose tris(phenylcarbamate.

  18. Chiral Separation of Ibuprofen by Supercritical Fluid Chromatography%超临界流体色谱手性分离布洛芬

    Institute of Scientific and Technical Information of China (English)

    HAN Soonkoo; ROW Kyungho

    2005-01-01

    The separation method using chiral stationary phase (CSP) for the preparation of enantioselective compound was widely used. In this work, supercritical fluid chromatography(SFC) was proposed to resolve the chiral mixtures. To determine the optimum operating conditions for the chiral separation of the racemic ibuprofen,the retention factors and resolutions with the change in pressure, temperature and the content of IPA (%, by volume)in supercritical CO2 were investigated. Experiments showed that the retention factor decreased with the increase of pressure and decrease in temperature. The retention factor was also influenced by the content of IPA in mobile phase, as the content of IPA in the supercritical fluid increased, the retention factor decreased. The resolution of the enantiomers became worse with the increase of IPA in the supercritical fluid. Through optimizing the experimental conditions, a SFC procedure with 13MPa, 311.15K and 4% IPA in CO2 was obtained. The peak shape of the enantiomers was symmetric with supercritical fluid chromatography when compared to the asymmetric peak shape obtained by the conventional liquid chromatography. This work demonstrated that the developed supercritical fluid chromatography procedure was suitable for the chiral separation of ibuprofen enantiomers.

  19. Chiral EFT based nuclear forces: Achievements and challenges

    CERN Document Server

    Machleidt, R

    2016-01-01

    During the past two decades, chiral effective field theory has become a popular tool to derive nuclear forces from first principles. Two-nucleon interactions have been worked out up to sixth order of chiral perturbation theory and three-nucleon forces up to fifth order. Applications of some of these forces have been conducted in nuclear few- and many-body systems---with a certain degree of success. But in spite of these achievements, we are still faced with great challenges. Among them is the issue of a proper uncertainty quantification of predictions obtained when applying these forces in {\\it ab initio} calculations of nuclear structure and reactions. A related problem is the order by order convergence of the chiral expansion. We start this review with a pedagogical introduction and then present the current status of the field of chiral nuclear forces. This is followed by a discussion of representative examples for the application of chiral two- and three-body forces in the nuclear many-body system includin...

  20. Investigation on enantiomeric separations of fluorenylmethoxycarbonyl amino acids and peptides by high-performance liquid chromatography using native cyclodextrins as chiral stationary phases.

    Science.gov (United States)

    Tang, Y; Zukowski, J; Armstrong, D W

    1996-09-06

    A systematic study was carried out to investigate enantiomeric separations of fluorenylmethoxycarbonyl (FMOC) amino acids and their peptides. Twenty amino acids were derivatized by 9-fluorenylmethyl chloroformate (FMOC-Cl) and its analogues, FMOC-glycyl-Cl and FMOC-beta-alanyl-Cl. All derivatives were chromatographed on native beta- and gamma-cyclodextrin columns using acetonitrile as the main mobile phase component. The results indicated that glycyl and beta-alanyl groups between FMOC and amino acid moieties enhanced chiral selectivities of amino acid derivatives. The addition of modifiers, triethylamine, acetic acid and methanol, into the mobile phase caused alterations in retention, enantiorecognition and elution order. The structures of amino acids and the type of chiral stationary phase employed exhibited significant impacts on chiral resolutions. It is also found that the number and position of glycyl moieties affect the retentions and enantioselectivities of FMOC derivatized glycyl containing peptides.

  1. Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

    Science.gov (United States)

    Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

    2014-11-01

    L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

  2. Facile Synthesis of Chiral Conjugated Polymer Based on BINOL Skeleton

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A new type of chiral conjugated polymers 6a-d has been synthesized by the reaction of (R)-2,2'-dihydroxy-1,1'-binaphthyl-6,6'-dicarbaldehyde 5 with corresponding diamine in the presence of acetic acid.

  3. Rapid chiral separation of atenolol, metoprolol, propranolol and the zwitterionic metoprolol acid using supercritical fluid chromatography-tandem mass spectrometry - Application to wetland microcosms.

    Science.gov (United States)

    Svan, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Jasper, Justin T; Sedlak, David L; Pettersson, Curt E

    2015-08-28

    A method for enantiomeric separation of the three β-blocking agents atenolol, metoprolol, propranolol and the zwitterionic metoprolol acid, a major metabolite of both metoprolol and in environmental matrices also atenolol, has been developed. By use of supercritical fluid chromatography and the polysaccharide-based Chiralpak(®) IB-3, all four compounds were simultaneously enantiomerically separated (Rs>1.5) within 8min. Detection was performed using tandem mass spectrometry, and to avoid isobaric interference between the co-eluting metoprolol and metoprolol acid, the achiral column Acquity(®) UPC(2) BEH 2-EP was attached ahead of to the chiral column. Carbon dioxide with 18% methanol containing 0.5% (v/v) of the additives trifluoroacetic acid and ammonia in a 2:1 molar ratio were used as mobile phase. A post column make-up flow (0.3mL/min) of methanol containing 0.1% (v/v) formic acid was used to enhance the positive electrospray ionization. Detection was carried out using a triple quadrupole mass spectrometer operating in the selected reaction monitoring mode, using one transition per analyte and internal standard. The method was successfully applied for monitoring the enantiomeric fraction change over time in a laboratory scale wetland degradation study. It showed good precision, recovery, sensitivity and low effect of the sample matrix.

  4. Comparing the selectivity and chiral separation of d- and l- fluorenylmethyloxycarbonyl chloride protected amino acids in analytical high performance liquid chromatography and supercritical fluid chromatography; evaluating throughput, economic and environmental impact.

    Science.gov (United States)

    Vera, C M; Shock, D; Dennis, G R; Farrell, W; Shalliker, R A

    2017-04-14

    The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO2, there is a reduction in organic solvent consumption, which minimises the economic and environmental costs.

  5. High resolution of racemic phenylalanine with dication imidazolium-based chiral ionic liquids in a solid-liquid two-phase system.

    Science.gov (United States)

    Huang, Xiaoxia; Wu, Haoran; Wang, Zhixia; Luo, Yingjie; Song, Hang

    2017-01-06

    A novel solid-liquid two-phase system was developed for the chiral separation of racemic phenylalanine with new dication imidazolium-based chiral ionic liquids. Preliminary experiments showed distinct enantioselectivity in amino acid extraction with the novel solid-liquid two-phase system, more L-enantiomer of amino acid cooperatively interacted with ionic liquids and copper ions to be the solid phase. Various factors, including the alkyl chain length of cations of ionic liquids, the amount of copper acetate, the ratio of n(ILs)/n(Cu(2+)), the amount of water and racemic phenylalanine, the resolution time together with the resolution temperature, were systematically investigated for their influence on resolution efficiency. The results showed that, under a certain condition, the enantiomeric excess value and the yield of phenylalanine in liquid phase (mainly containing D-enantiomer) were 67.8% and 96.5%, the enantiomeric excess value and the yield of phenylalanine in solid phase (mainly containing L-enantiomer) were 99.2% and 85.2%. Finally, 2D NMR technology, infrared spectroscopy and molecular simulation method were used to study the interaction mechanism. The results indicated that L-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+). The novel system has characteristics of free-organic solvent, simple operation, fast separation process and very high resolution efficiency for racemic phenylalanine. This work could provide a new and alternative resolution approach for other chiral separations.

  6. Direct enantioseparation of underivatized aliphatic 3-hydroxyalkanoic acids with a quinine-based zwitterionic chiral stationary phase.

    Science.gov (United States)

    Ianni, Federica; Pataj, Zoltán; Gross, Harald; Sardella, Roccaldo; Natalini, Benedetto; Lindner, Wolfgang; Lämmerhofer, Michael

    2014-10-10

    While aliphatic 2-hydroxyalkanoic acids have been more or less successfully enantioseparated with various chiral stationary phases by HPLC and GC, analogous applications on underivatized aliphatic 3-hydroxyalkanoic acids are completely absent in the scientific literature. With the aim of closing this gap, the enantioseparation of 3-hydroxybutyric acid, 3-hydroxydecanoic acid and 3-hydroxymyristic acid has been performed with two ion-exchange type chiral stationary phases (CSPs): one containing the anion-exchange type tert-butyl carbamoyl quinine chiral selector motif (Chiralpak QN-AX), and the other carrying the new zwitterionic variant based on trans-(S,S)-2-aminocyclohexanesulfonic acid-derivatized quinine carbamate (Chiralpak ZWIX(+)) as the chiral selector and enantiodiscriminating element, respectively. The zwitterionic enantiorecognition material provided better results in terms of enantioselectivity and resolution compared to the anion-exchanger CSP at reduced retention times due to the intramolecular counterion effect imposed by the sulfonic acid moiety and its competition with the 3-hydroxyalkanoic acid analyte for ionic interaction at the quininium-anion exchanger site. It is thus recommended as the CSP of first choice for enantioseparations of the class of aliphatic 3-hydroxyalkanoic acids. With use of polar organic eluent composed of ACN/MeOH/AcOH - 95/5/0.05 (v/v/v), a good compromise in terms of analysis time and enantioresolution quality was accomplished. The major experimental variables have been investigated for optimization of the resolution and allowed to derive information on the enantiorecognition mechanism. Corresponding Chiralpak ZWIX(-), based on pseudo-enantiomeric selector derived from quinidine and trans-(R,R)-2-aminocyclohexanesulfonic acid with opposite configurations provided reversed enantiomer elution orders. It has further to be stressed that these separations can be obtained with mass spectrometry compatible mobile phases.

  7. Enantiomeric separations of amino alcohols by packed-column SFC on Hypercarb with L-(+)-tartaric acid as chiral selector.

    Science.gov (United States)

    Gyllenhaal, Olle; Karlsson, Anders

    2002-12-31

    The use of L-(+)-tartaric acid as a chiral mobile phase additive (CMPA) has been investigated in a packed-column SFC system. The CMPA, carbon dioxide, and methanol, containing a high concentration of aliphatic amine additive, were used as the mobile phase and Hypercarb as support [Gyllenhaal O., Karlsson A., SFC of metoprolol and other amino alcohols on Hypercarb (in preparation)]. Good enantioselectivities were obtained for tertiary amine homologues of 2-amino alcohols, used as beta-adrenoreceptor-blocking drugs. Moderate selectivities were observed for aromatic compounds having a second substituent in the ortho-position. The overall retention was influenced by the aromaticity of the analytes as well as the presence of free electron pairs in the molecule. Increased concentrations of CMPA gave higher retention and also increased the enantioselectivity. The practical utility of this present enantioselective system was demonstrated on one batch of (S)-metoprolol that was N-methylated with methyl iodide. The enantiomeric separation was accomplished within 10 min.

  8. Mandelic acid chiral separation utilizing a two-phase partitioning bioreactor built by polysulfone microspheres and immobilized enzymes.

    Science.gov (United States)

    Wang, Xinyu; Cui, Yanjun; Chen, Xia; Zhu, Hao; Zhu, Weiwei; Li, Yanfeng

    2015-03-01

    A novel two-phase partitioning bioreactor (TPPB) modified by polysulfone (PSF) microspheres and immobilized enzyme (novozym-435) was formed, and the resulting TPPB was applied into mandelic acid chiral separation. The PSF microspheres containing n-hexanol (named PSF/hexanol microspheres) was prepared by using the phase inversion method, which was used as the organic phase. Meanwhile, the immobilized enzyme novozym-435 was used as a biocatalyst. The water phase was composed of the phosphate buffer solution (PBS). (R, S)-Methyl mandelate was selected as the substrate to study enzymatic properties. Different reaction factors have been researched, such as pH, reaction time, temperature and the quantity of biocatalyst and PSF/hexanol microspheres added in. Finally, (S)-mandelic acid was obtained with an 80 % optical purity after 24 h in the two-phase partitioning bioreactor. The enantiomeric excess (eep) values were very low in the water phase, in which the highest eep value was only 46 %. The eep of the two-phase partitioning bioreactor had been enhanced more obviously than that catalyzed in the water phase.

  9. Chiral Separation of Calcium (-)-2(S)-2-Benzyl-4-oxo-4-(cis-hexahydro-2-isoindolinyl)butyrate Enantiomers by High-performance Liquid Chromatography

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhefeng; YANG Gengliang; GAO Wenhui; CHEN yia

    2009-01-01

    A chiral high-performance liquid chromatographic method was developed for the enantioseparation of a new insulinotropic drug of the glinide class with rapid onset. The chiral separation was performed on a Sumichiral OA-3300 column (250 mm×4.6 mm, 5μm) with methanol containing 0.05 mol/L ammonium acetate as the opti-mized mobile phase at detection wavelengh 210 nm. Baseline separation of the two enantiomers was obtained in 22 (r=0.9997) for S-enantiomer and y=1.15 ×103x-1.78 (γ=0.9998) for R-enantiomer, respectively. The limits of detection obtained by S/N=3 were 0.15 ng for S-and 0.10 ng for R-enantiomer, respectively. RSD of the method was below 1.0% (n=5).

  10. Chiral separation of benzothiazole derivatives of amino acids using capillary zone electrophoresis.

    Science.gov (United States)

    Nováková, Zuzana; Pejchal, Vladimír; Fischer, Jan; Česla, Petr

    2017-02-01

    A method for the separation of enantiomers of leucine and phenylalanine benzothiazole derivatives as potential antimicrobial agents was developed using capillary zone electrophoresis with a dual cyclodextrin (CD) system. The best resolution of enantiomers was achieved in 100 mmol/L phosphate background electrolyte (pH 3.5) with the dual CD system consisting of 10 mmol/L of β-CD with 10 mmol/L of 2-hydroxypropyl-β-cyclodextrin for leucine derivative and 10 mmol/L of 2-hydroxypropyl-γ-cyclodextrin for phenylalanine derivative, respectively. Under the optimal conditions, the highest enantioresolution of 1.25 was achieved in a noncoated-fused silica capillary at 17°C and 24 kV applied voltage.

  11. Optical diode based on the chirality of guided photons

    CERN Document Server

    Sayrin, C; Mitsch, R; Albrecht, B; O'Shea, D; Schneeweiss, P; Volz, J; Rauschenbeutel, A

    2015-01-01

    Photons are nonchiral particles: their handedness can be both left and right. However, when light is transversely confined, it can locally exhibit a transverse spin whose orientation is fixed by the propagation direction of the photons. Confined photons thus have chiral character. Here, we employ this to demonstrate nonreciprocal transmission of light at the single-photon level through a silica nanofibre in two experimental schemes. We either use an ensemble of spin-polarised atoms that is weakly coupled to the nanofibre-guided mode or a single spin-polarised atom strongly coupled to the nanofibre via a whispering-gallery-mode resonator. We simultaneously achieve high optical isolation and high forward transmission. Both are controlled by the internal atomic state. The resulting optical diode is the first example of a new class of nonreciprocal nanophotonic devices which exploit the chirality of confined photons and which are, in principle, suitable for quantum information processing and future quantum optica...

  12. A Novel Two-Step Liquid-Liquid Extraction Procedure Combined with Stationary Phase Immobilized Human Serum Albumin for the Chiral Separation of Cetirizine Enantiomers along with M and P Parabens

    Directory of Open Access Journals (Sweden)

    Aleksandra Chmielewska

    2016-12-01

    Full Text Available The research into the separation of drug enantiomers is closely related to the safety and efficiency of the drugs. The aim of this study was to develop a simple and validated HPLC method to analyze cetirizine enantiomers. In the case of liquid dosage forms, besides the active substance in large amounts there are usually also inactive ingredients such as methyl- and propylparaben. Unfortunately, these compounds can interfere with the analyte, inter alia during chiral separation of the analyte enantiomers. The proposed innovative two-step liquid-liquid extraction procedure allowed for the determination of cetirizine enantiomers (along with M and P parabens also in liquid dosage forms. The main focus of this study was the chromatographic activity of cetirizine dihydrochloride on the proteinate-based chiral stationary phase. The chromatographic separation of cetirizine enantiomers was performed on an immobilized human serum albumin (HSA column for the first time. Measurements were performed at a wavelength of 227 nm. Under optimal conditions, baseline separation of two enantiomers was obtained with 1.43 enantioseparation factor (α and 1.82 resolution (Rs. Finally, the proposed method was successfully applied to the selected pharmaceutical formulations.

  13. Experimental implementation of automatic 'cycle to cycle' control to a nonlinear chiral simulated moving bed separation.

    Science.gov (United States)

    Grossmann, Cristian; Langel, Christian; Mazzotti, Marco; Morari, Manfred; Morbidelli, Massimo

    2010-03-26

    In order to better exploit the economic potential of the simulated moving bed chromatography a 'cycle to cycle' controller which only requires the information about the linear adsorption behavior and the overall average porosity of the columns has been proposed. Recently, an automated on-line HPLC monitoring system which determines the concentrations in the two product streams averaged over one cycle, and returns them as feedback information to the controller was implemented. The new system allows for an accurate determination of the average concentration of the product streams even if the plant is operated at high concentrations. This paper presents the experimental implementation of the 'cycle to cycle' control concept to the separation of guaifenesin enantiomers under nonlinear chromatographic conditions, i.e. at high feed concentrations. Different case studies have been carried out to challenge the controller under realistic operation conditions, e.g. introducing pump disturbances and changing the feed concentration during the operation. The experimental results clearly demonstrate that the controller can indeed deliver the specified purities and improve the process performance.

  14. Consistency tests of Ampcalculator and chiral amplitudes in SU(3) Chiral Perturbation Theory: A tutorial-based approach

    Science.gov (United States)

    Ananthanarayan, B.; Das, Diganta; Sentitemsu Imsong, I.

    2012-10-01

    Ampcalculator (AMPC) is a Mathematica © based program that was made publicly available some time ago by Unterdorfer and Ecker. It enables the user to compute several processes at one loop (upto O( p 4) in SU(3) chiral perturbation theory. They include computing matrix elements and form factors for strong and non-leptonic weak processes with at most six external states. It was used to compute some novel processes and was tested against well-known results by the original authors. Here we present the results of several thorough checks of the package. Exhaustive checks performed by the original authors are not publicly available, and hence the present effort. Some new results are obtained from the software especially in the kaon odd-intrinsic parity non-leptonic decay sector involving the coupling G 27. Another illustrative set of amplitudes at tree level we provide is in the context of τ-decays with several mesons including quark mass effects, of use to the BELLE experiment. All eight meson-meson scattering amplitudes have been checked. The Kaon-Compton amplitude has been checked and a minor error in the published results has been pointed out. This exercise is a tutorial-based one, wherein several input and output notebooks are also being made available as ancillary files on the arXiv. Some of the additional notebooks we provide contain explicit expressions that we have used for comparison with established results. The purpose is to encourage users to apply the software to suit their specific needs. An automatic amplitude generator of this type can provide error-free outputs that could be used as inputs for further simplification, and in varied scenarios such as applications of chiral perturbation theory at finite temperature, density and volume. This can also be used by students as a learning aid in low-energy hadron dynamics.

  15. Consistency tests of Ampcalculator and chiral amplitudes in SU(3) Chiral Perturbation Theory: A tutorial-based approach

    Energy Technology Data Exchange (ETDEWEB)

    Ananthanarayan, B.; Sentitemsu Imsong, I. [Indian Institute of Science, Centre for High Energy Physics, Bangalore (India); Das, Diganta [The Institute of Mathematical Sciences Taramani, Chennai (India)

    2012-10-15

    Ampcalculator (AMPC) is a Mathematica {sup copyright} based program that was made publicly available some time ago by Unterdorfer and Ecker. It enables the user to compute several processes at one loop (upto O(p {sup 4})) in SU(3) chiral perturbation theory. They include computing matrix elements and form factors for strong and non-leptonic weak processes with at most six external states. It was used to compute some novel processes and was tested against well-known results by the original authors. Here we present the results of several thorough checks of the package. Exhaustive checks performed by the original authors are not publicly available, and hence the present effort. Some new results are obtained from the software especially in the kaon odd-intrinsic parity non-leptonic decay sector involving the coupling G{sub 27}. Another illustrative set of amplitudes at tree level we provide is in the context of {tau}-decays with several mesons including quark mass effects, of use to the BELLE experiment. All eight meson-meson scattering amplitudes have been checked. The Kaon-Compton amplitude has been checked and a minor error in the published results has been pointed out. This exercise is a tutorial-based one, wherein several input and output notebooks are also being made available as ancillary files on the arXiv. Some of the additional notebooks we provide contain explicit expressions that we have used for comparison with established results. The purpose is to encourage users to apply the software to suit their specific needs. An automatic amplitude generator of this type can provide error-free outputs that could be used as inputs for further simplification, and in varied scenarios such as applications of chiral perturbation theory at finite temperature, density and volume. This can also be used by students as a learning aid in low-energy hadron dynamics. (orig.)

  16. Composite separators and redox flow batteries based on porous separators

    Science.gov (United States)

    Li, Bin; Wei, Xiaoliang; Luo, Qingtao; Nie, Zimin; Wang, Wei; Sprenkle, Vincent L.

    2016-01-12

    Composite separators having a porous structure and including acid-stable, hydrophilic, inorganic particles enmeshed in a substantially fully fluorinated polyolefin matrix can be utilized in a number of applications. The inorganic particles can provide hydrophilic characteristics. The pores of the separator result in good selectivity and electrical conductivity. The fluorinated polymeric backbone can result in high chemical stability. Accordingly, one application of the composite separators is in redox flow batteries as low cost membranes. In such applications, the composite separator can also enable additional property-enhancing features compared to ion-exchange membranes. For example, simple capacity control can be achieved through hydraulic pressure by balancing the volumes of electrolyte on each side of the separator. While a porous separator can also allow for volume and pressure regulation, in RFBs that utilize corrosive and/or oxidizing compounds, the composite separators described herein are preferable for their robustness in the presence of such compounds.

  17. Direct enantioseparation of nitrogen-heterocyclic pesticides on cellulose-based chiral column by high-performance liquid chromatography.

    Science.gov (United States)

    Chai, Tingting; Yang, Wenwen; Qiu, Jing; Hou, Shicong

    2015-01-01

    The enantiomeric separation of eight pesticides including bitertanol (), diclobutrazol (), fenbuconazole (), triticonazole (), imazalil (), triapenthenol (), ancymidol (), and carfentrazone-ethyl () was achieved, using normal-phase high-performance liquid chromatography on two cellulosed-based chiral columns. The effects of isopropanol composition from 2% to 30% in the mobile phase and column temperature from 5 to 40 °C were investigated. Satisfactory resolutions were obtained for bitertanol (), triticonazole (), imazalil () with the (+)-enantiomer eluted first and fenbuconazole () with the (-)-enantiomer eluted first on Lux Cellulose-2 and Lux Cellulose-3. (+)-Enantiomers of diclobutrazol () and triapenthenol () were first eluted on Lux Cellulose-2. (-)-Carfentrazone-ethyl () were eluted first on Lux Cellulose-2 and Lux Cellulose-3 with incomplete separation. Reversed elution orders were obtained for ancymidol (7). (+)-Ancymidol was first eluted on Lux Cellulose-2 while on Lux Cellulose-3 (-)-ancymidol was first eluted. The results of the elution order at different column temperatures suggested that column temperature did not affect the optical signals of the enantiomers. These results will be helpful to prepare and analyze individual enantiomers of chiral pesticides.

  18. Direct Separation of Pregabalin Enantiomers Using a Zwitterionic Chiral Selector by High Performance Liquid Chromatography Coupled to Mass Spectrometry and Ultraviolet Detection

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Chennuru

    2016-11-01

    Full Text Available The chromatographic resolution of pregabalin enantiomers has been often achieved by derivatization of the molecule, in order to reach enough sensitivity at low concentrations of the minor enantiomer present in the active principle. In the present article, the development and optimization of two liquid chromatographic methods are presented for the direct resolution of pregabalin enantiomers on a chiral stationary phase (CSP containing a zwitterionic selector derived from cinchona alkaloid and sulfonic acid (CHIRALPAK ZWIX. The key parameters for the separation as well as the compatibility of chromatographic conditions with different detection modes (ultraviolet and mass spectrometry were investigated. The resulting methods were found to be selective, of high performance and low limits of detection (2 µg/mL by UV and 1 ng/mL by MS, respectively and quantification (6 µg/mL by UV and 5 ng/mL by MS, respectively for the minor enantiomer which is considered as a chiral impurity.

  19. Single-walled carbon nanotube-based polymer monoliths for the enantioselective nano-liquid chromatographic separation of racemic pharmaceuticals.

    Science.gov (United States)

    Ahmed, Marwa; Yajadda, Mir Massoud Aghili; Han, Zhao Jun; Su, Dawei; Wang, Guoxiu; Ostrikov, Kostya Ken; Ghanem, Ashraf

    2014-09-19

    Single-walled carbon nanotubes were encapsulated into different polymer-based monolithic backbones. The polymer monoliths were prepared via the copolymerization of 20% monomers, glycidyl methacrylate, 20% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) or 16.4% monomers (16% butyl methacrylate, 0.4% sulfopropyl methacrylate), 23.6% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) along with 6% single-walled carbon nanotubes aqueous suspension. The effect of single-walled carbon nanotubes on the chiral separation of twelve classes of pharmaceutical racemates namely; α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs and antiarrhythmic drugs was investigated. The enantioselective separation was carried out under multimodal elution to explore the chiral recognition capabilities of single-walled carbon nanotubes using reversed phase, polar organic and normal phase chromatographic conditions using nano-liquid chromatography. Baseline separation was achieved for celiprolol, chlorpheniramine, etozoline, nomifensine and sulconazole under multimodal elution conditions. Satisfactory repeatability was achieved through run-to-run, column-to-column and batch-to-batch investigations. Our findings demonstrate that single-walled carbon nanotubes represent a promising stationary phase for the chiral separation and may open the field for a new class of chiral selectors.

  20. Role of substituents in cyclodextrin derivatives for enantioselective gas chromatographic separation of chiral terpenoids in the essential oils of Mentha spicata.

    Science.gov (United States)

    Pragadheesh, V S; Yadav, Anju; Chanotiya, Chandan Singh

    2015-10-01

    Enantioselective GC-FID and enantioselective GC-MS have been utilized under temperature gradient mode with differently substituted heptakis- and octakis-cyclodextrins to achieve the resolution of chiral terpenoids in the essential oil of indigenously grown cultivars of Mentha spicata. Modified cyclodextrins were derivatized in GC column for the separation of chiral terpenoids. A 2,3-diethyl-6-tert-butyldimethylsilyl-β-cyclodextrin doped into 14% cyanopropylphenyl/86%dimethylpolysiloxane (TBDE-β-CD) showed good enantioselectivity for all the studied chiral compounds excluding carvone. Carvone enantiomers were well resolved in 2,3-diacetoxy-6-tert-butyldimethylsilyl-β-cyclodextrin column (TBDA-β-CD) with enantioseparation (Es) of 1.006. A TBDE-β-CD provides maximum enantiomeric separation for β-pinene (Es 1.038), sabinene (Es 1.051), limonene (Es 1.045), isomenthone (Es 1.029) and α-terpineol (Es 1.014). Furthermore, enantiomer elution order reversal was observed for sabinene, menthone, terpinen-4-ol and menthol while changing from β- to γ-cyclodextrin phase. Carvone exhibits enantiomer elution order reversal by changing substituents i.e., methyl to acetyl at 2- & 3- position of the cyclodextrin derivative. Chiral constituents such as (+)-isomenthone, (-)-menthone, (1R,2S,5R)-(-)-menthol and (4S)-(+)-piperitone exist as a single enantiomer with >99% excess. Existence of (R)-(+)-limonene and (S)-(+)-carvone enantiomers has been proven first time in M. spicata essential oils and can be used as the marker for Indian origin.

  1. Chiral induction in phenanthroline-derived oligoamide foldamers: an acid- and base-controllable switch in helical molecular strands.

    Science.gov (United States)

    Hu, Hai-Yu; Xiang, Jun-Feng; Yang, Yong; Chen, Chuan-Feng

    2008-03-20

    A series of phenanthroline-derived oligoamides bearing a chiral (R)-phenethylamino end group were synthesized that displayed chiral helical induction and subsequently formed one-hand helical foldamers in solution. Moreover, an acid- and base-controllable switch in the helical molecular strands was observed, which has been demonstrated by NMR, UV-vis, and circular dichroism spectroscopy.

  2. Chiral Fluorescent Receptors Based on (R)-1,1'-Binaphthylene-2,2'-bisthiourea: Synthesis and Chiral Recognition

    Institute of Scientific and Technical Information of China (English)

    隗兰华; 何永炳; 徐括喜; 刘顺英; 孟令芝

    2005-01-01

    Two chiral fluorescent receptors 1 and 2 based on (R)-1,1'-binaphthylene-2,2'-bisthiourea were synthesized, and their chiral recognition properties for enantiomeric mandelate anions were studied by fluorescence spectra and molecular modeling. Addition of the L- and D-mandelate anions caused considerable fluorescent increases in the fluorescent intensity of the host solution. The L-enantiomer can enhance the fluorescence intensity of 1 much more than the D-enantiomer can do, and 1 shows a better enantioselective recognition ability than 2.

  3. Asymmetric Michael Reaction of Malononitrile Catalyzed by Chiral Ru(Ⅱ) Complex and Achiral Base

    Institute of Scientific and Technical Information of China (English)

    MA Ya-Ping; XING Zhi-Kui; ZHU Jin; CUI Xin; CUN Lin-Feng; DENG Jin-Gen

    2003-01-01

    @@ Michael addition reactions represent one of the most important carbon-carbon bond forming reactions in modern synthetic organic chemistry. [1 ~3] We achieved catalytic enantioselective Michael addition reactions of malononitrile with chiral vicinal diamine-Ru(Ⅱ) complex in the presence of achiral base. High yields and moderate ee were observed.

  4. Optimization of chiral lattice based metastructures for broadband vibration suppression using genetic algorithms

    Science.gov (United States)

    Abdeljaber, Osama; Avci, Onur; Inman, Daniel J.

    2016-05-01

    One of the major challenges in civil, mechanical, and aerospace engineering is to develop vibration suppression systems with high efficiency and low cost. Recent studies have shown that high damping performance at broadband frequencies can be achieved by incorporating periodic inserts with tunable dynamic properties as internal resonators in structural systems. Structures featuring these kinds of inserts are referred to as metamaterials inspired structures or metastructures. Chiral lattice inserts exhibit unique characteristics such as frequency bandgaps which can be tuned by varying the parameters that define the lattice topology. Recent analytical and experimental investigations have shown that broadband vibration attenuation can be achieved by including chiral lattices as internal resonators in beam-like structures. However, these studies have suggested that the performance of chiral lattice inserts can be maximized by utilizing an efficient optimization technique to obtain the optimal topology of the inserted lattice. In this study, an automated optimization procedure based on a genetic algorithm is applied to obtain the optimal set of parameters that will result in chiral lattice inserts tuned properly to reduce the global vibration levels of a finite-sized beam. Genetic algorithms are considered in this study due to their capability of dealing with complex and insufficiently understood optimization problems. In the optimization process, the basic parameters that govern the geometry of periodic chiral lattices including the number of circular nodes, the thickness of the ligaments, and the characteristic angle are considered. Additionally, a new set of parameters is introduced to enable the optimization process to explore non-periodic chiral designs. Numerical simulations are carried out to demonstrate the efficiency of the optimization process.

  5. K- nuclear potentials based on chiral meson-baryon amplitudes

    Science.gov (United States)

    Mareš, J.; Cieplý, A.; Gazda, D.; Friedman, E.; Gal, A.

    2012-09-01

    K- nuclear optical potentials are constructed from in-medium subthreshold K¯N scattering amplitudes within a chirally motivated coupled-channel model. We demonstrate how the strong energy and density dependence of the scattering amplitudes at and below threshold leads to a deep K- nuclear potential VK- for kaonic atoms and K- nuclear quasibound states. Selfconsistent evaluations yield K- potential depths -ReVK- (ρ0) of order 100 MeV. Allowing for K- NN absorption, better agreement with K- atoms data is achieved, leading to increased potential depths, -ReVK- (ρ0) ˜ 175 MeV, in accord with density dependent potentials obtained in purely phenomenological fits. Self consistent dynamical calculations of K- nuclear quasibound states are reported and discussed, as well.

  6. Geometrical approach to central molecular chirality: a chirality selection rule

    OpenAIRE

    Capozziello, S.; Lattanzi, A

    2004-01-01

    Chirality is of primary importance in many areas of chemistry and has been extensively investigated since its discovery. We introduce here the description of central chirality for tetrahedral molecules using a geometrical approach based on complex numbers. According to this representation, for a molecule having n chiral centres, it is possible to define an index of chirality. Consequently a chirality selection rule has been derived which allows the characterization of a molecule as achiral, e...

  7. Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

    Science.gov (United States)

    Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

    2012-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

  8. (S)-1-(4-Dimethylaminophenylcarbonyl)-3-aminopyrrolidine: a derivatization reagent for enantiomeric separation and sensitive detection of chiral carboxylic acids by LC/ESI-MS/MS.

    Science.gov (United States)

    Ogawa, Shoujiro; Tadokoro, Hiroaki; Sato, Maho; Hanawa, Takehisa; Higashi, Tatsuya

    2013-12-01

    A novel derivatization reagent, (S)-1-(4-dimethylaminophenylcarbonyl)-3-aminopyrrolidine (1-DAPAP), was developed for increasing the detection sensitivity and enantiomeric separation of chiral carboxylic acids by liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). 1-DAPAP reacted with carboxylic acids at room temperature within 5min in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride. The epimerization (racemization) during the derivatization reaction was negligible. The resulting derivatives were highly responsive during the ESI-MS operating in the positive-ion mode and gave a characteristic product ion during the MS/MS, which enabled the sensitive detection using selected reaction monitoring; the detection responses of the 1-DAPAP-derivatives were increased by 10-1100-fold over the intact carboxylic acids and the limits of detection ranged from 0.97 and 5.2fmol on the column. The 1-DAPAP-derivatization was also effective for the enantiomeric separation of chiral carboxylic acids; the resolution values were 1.2-4.3 for the evaluated carboxylic acids. The derivatization procedure was successfully applied to biological sample analyses; the derivatization followed by LC/ESI-MS/MS enabled the separation and detection of trace amounts of ibuprofen and naproxen in human saliva with a simple pretreatment and small sample volume.

  9. Selective Synthesis of [2+2] Macrocyclic Schiff Bases from Chiral 1,4-Diamines

    Institute of Scientific and Technical Information of China (English)

    ZHU Hai-Bin; HU Da-Hua; DONG Hua-Ze; LI Gen-Xi; GOU Shao-Hua

    2007-01-01

    [2+2] macrocyclic Schiff bases of three kinds have been synthesized from chiral 1,4-diamines by use of different methods. Macrocyclic Schiff bases 1a-1c have been selectively obtained based on a non-templated dilution method from chiral 1,4-diamines a-c and dialdehyde DA1, whereas macrocycles 2a-2c have been selectively produced from reaction of diamines a-c and dialdehyde DA2 in the presence of boric acid as templates. Macrocyclic Schiff bases 3a-3c have been afforded in high selectivity from diamines a-c and dialdehyde DA3 by means of sodium-template. All the titled compounds have been confirmed by 1H NMR and ESI-MS analyses.

  10. Chiral separation of six tetralone derivative enantiomers using immobilized cellulose chiral stationary phase%纤维素键合手性固定相拆分6种萘满酮衍生物对映体

    Institute of Scientific and Technical Information of China (English)

    赵允凤; 宋佳新; 孙嘉仪; 袁晓薇; 郭兴杰

    2014-01-01

    A high performance liquid chromatographic method( HPLC)was developed for the chiral separation of six α-aryl tetralone derivatives using a Chiralpak IC column. The factors influencing the chiral separation including the type and concentration of organic modifier,col-umn temperature and flow rate were investigated. The results showed that high enantiomeric separation can be obtained with isopropanol as modifier for the six compounds. The thermody-namic study indicated that the enantioseparation was enthalpically driven and showed that low column temperature was beneficial to separation. Complete separation of compound Ⅰ was achieved with a binary solvent mixture of n-hexane-isopropanol(90 : 10,v / v)as the recom-mended mobile phase. The compounds Ⅱ,Ⅲ and Ⅳ were separated with the mobile phase of the mixture of n-hexane-isopropanol(99 :1,v / v)and the compound Ⅴ was separated with the mixture of n-hexane-isopropanol(85 :15,v / v). The compound Ⅵ was separated with the mix-ture of n-hexane-isopropanol(80 :20,v / v). The column temperature was 25 ℃ ,and the flow rate was 1. 0 mL / min. The six tetralone derivative enantiomers were separated on a chiral sta-tionary phase of Chiralpak IC by HPLC. The column has high enantiomeric selectivity to the six tetralone derivative enantiomers.%使用 Chiralpak IC(纤维素-三(3,5-二氯苯基氨基甲酸酯)共价键合硅胶)手性柱,建立了采用手性固定相高效液相色谱拆分6种α-芳基萘满酮类衍生物对映体的方法。考察了流动相中有机改性剂的种类和比例、柱温和流速对对映体分离的影响。结果显示6种化合物在异丙醇为改性剂的条件下均可获得较高的对映体分离度。热力学研究表明6种化合物对映体的手性拆分过程均受焓驱动影响,且低温有利于对映体分离。最终推荐分离化合物Ⅰ对映体的流动相是正己烷-异丙醇(90:10,v / v);分离化合物Ⅱ、Ⅲ、Ⅳ对映体

  11. CMAC Based Color Separation in Printing Images

    Institute of Scientific and Technical Information of China (English)

    WANG Yong-gang; YANG Jie; DING Yong-sheng

    2005-01-01

    To over come the drawbacks existing in current measurement methods for detecting and controlling colors in printing process, a new model for color separation and dot recognition is proposed from a view of digital image processing and patter recognition. In this model, firstly data samples are collected from some color patches by the Fuzzy C-Means (FCM)method; then a classifier based on the Cerebellar Model Articulation Controller (CMAC) is constructed which is used to recognize color pattern of each pixel in a microscopic halftone image. The principle of color separation and the algorithm model are introduced and the experiments show the effectiveness of the CMAC-based classifier as opposed to the BP network.

  12. Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chiral Brønsted Acid Cooperative Catalysis

    OpenAIRE

    2013-01-01

    The development of a binary catalyst system for bromocycloetherification, consisting of an achiral Lewis base and a chiral Brønsted acid, is described in detail. The results of preliminary kinetic studies are also presented.

  13. Unusual dileptions at RHIC a field theoretic approach based on a non-equilibrium chiral phase transition

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, F. [Los Alamos National Labs., NM (United States)

    1997-09-22

    This paper contains viewgraphs on unusual dileptons at Brookhaven RHIC. A field theory approach is used based on a non-equilibrium chiral phase transformation utilizing the schroedinger and Heisenberg picture.

  14. 色谱技术在手性药物拆分中的应用进展%Application of chromatography in chiral drugs’ separation

    Institute of Scientific and Technical Information of China (English)

    吕志祥

    2012-01-01

    According to the literatures, this paper reviews the main classification, the methods , the advantages, disadvantages and application of chromatography in chiral drugs’ separation. Results and conclusion is that direct and indirect methods are available. The main methods include TLC、HPLC、GC、SFC、CE、TLC. With the improvement of in-depth research in variety of separation principles, methods, chromatography technology, chromatography in the split in chiral drugs will play an increasingly important role.%根据文献,综述了色谱法拆分手性药物的主要分类、方法、优缺点及其应用。结果与结论色谱法拆分药物对映体一般分为直接法和间接法。主要方法包括薄层色谱(TLC)、高效液相色谱(HPLC)、气相色谱(GC)、超临界流体色谱(SFC)和毛细管电泳(CE)法等。随着各种分离原理、方法的深入研究以及色谱联用技术的不断完善,色谱法在手性药物拆分中将会发挥越来越重要的作用。

  15. Chiral N-phosphonyl imine chemistry:asymmetric additions of glycine enolate to diphenyl diamine-based phosphonyl imines

    Institute of Scientific and Technical Information of China (English)

    PINDI; Suresh; KATTAMURI; Padmanabha; V.

    2010-01-01

    Diphenyl diamine-based phosphonyl imines attached by the N-isopropyl group in the auxiliary have been synthesized in good yields under convenient reaction conditions.These new chiral N-phosphonyl imines can react with glycine enolate smoothly to give chiral α-β diamino esters in good yields(72%-90%) and up to excellent diastereoselectivity(>99:1 dr).By treatment with HBr,the chiral auxiliary can be readily removed.The absolute structure has been unambiguously determined by converting a product to a known sample.

  16. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    Science.gov (United States)

    Werber, Liora; Preiss, Laura C; Landfester, Katharina; Muñoz-Espí, Rafael; Mastai, Yitzhak

    2015-09-01

    Chiral polymeric nanoparticles are of prime importance, mainly due to their enantioselective potential, for many applications such as catalysis and chiral separation in chromatography. In this article we report on the preparation of chiral polymeric nanoparticles by miniemulsion polymerization. In addition, we describe the use of isothermal titration calorimetry (ITC) to measure the chiral interactions and the energetics of the adsorption of enantiomers from aqueous solutions onto chiral polymeric nanoparticles. The characterization of chirality in nano-systems is a very challenging task; here, we demonstrate that ITC can be used to accurately determine the thermodynamic parameters associated with the chiral interactions of nanoparticles. The use of ITC to measure the energetics of chiral interactions and recognition at the surfaces of chiral nanoparticles can be applied to other nanoscale chiral systems and can provide further insight into the chiral discrimination processes of nanomaterials.

  17. Tunable multi-band chiral metamaterials based on double-layered asymmetric split ring resonators

    Science.gov (United States)

    Jia, Xiuli; Wang, Xiaoou; Meng, Qingxin; Zhou, Zhongxiang

    2016-07-01

    We have numerically demonstrated chiral metamaterials based on double-layered asymmetric Au film with hollow out design of split ring resonators on either side of the polyimide. Multiple electric dipoles and magnetic dipoles resulted from parallel and antiparallel currents between the eight split ring resonators. Multi-band circular dichroism is found in the visible frequency regime by studying the transmission properties. Huge optical activity and the induced multi-band negative refractive index are obtained at resonance by calculating the optical activity and ellipticity of the transmitted E-fields. Chirality parameter and effective refractive index are retrieved to illustrate the tunable optical properties of the metamaterials. The underlying mechanisms for the observed circular dichroism are analyzed. These metamaterials would offer flexible electromagnetic applications in the infrared and visible regime.

  18. Antibacterial adhesion of borneol-based polymer via surface chiral stereochemistry.

    Science.gov (United States)

    Luo, Lingqiong; Li, Guofeng; Luan, Di; Yuan, Qipeng; Wei, Yen; Wang, Xing

    2014-01-01

    During its adhesion on external surfaces, a cell exhibits obvious inclination to different molecular chirality, which encourages us to develop a new type of antibacterial material catering to the "chiral taste" of bacteria. On the basis of the natural product borneol (a camphane-type bicyclic monoterpene), a series of borneol-based polymer, polyborneolacrylate (PBA), was successfully prepared and showed superior antibacterial adhesion properties resulting from the borneol isomers on material surface. The results of this study reveal that bacteria simply dislike this type of stubborn surface of PBA, and the PBA surface stereochemistry contributes to the interfacial antibacterial activities. The PBA polymers were evaluated as noncytotoxic and can be simply synthesized, demonstrating their great potential for biomedical applications.

  19. Catalytic Enantioselective Aryl Transfer to Aldehydes Using Chiral 2,2’-Bispyrrolidine-Based Salan Ligands

    Directory of Open Access Journals (Sweden)

    Yixiang Cheng

    2011-04-01

    Full Text Available Chiral C2-symmetric diamines have emerged as versatile auxiliaries or ligands in numerous asymmetric transformations. Chiral 2,2’-bispyrrolidine-based salan ligands were prepared and applied to the asymmetric aryl transfer to aldehydes with arylboronic acids as the source of transferable aryl groups. The corresponding diarylmethanols were obtained in high yields with moderate to good enantioselectivitives of up to 83% ee.

  20. Molecular chirality and chiral capsule-type dimer formation of cyclic triamides via hydrogen-bonding interactions.

    Science.gov (United States)

    Fujimoto, Noriko; Matsumura, Mio; Azumaya, Isao; Nishiyama, Shizuka; Masu, Hyuma; Kagechika, Hiroyuki; Tanatani, Aya

    2012-05-18

    Chiral properties of bowl-shaped cyclic triamides bearing functional groups with hydrogen-bonding ability were examined. Chiral induction of cyclic triamide 3a was observed by addition of chiral amine in solution, and chiral separation was achieved by simple crystallization to afford chiral capsule-type dimer structure of 4a.

  1. Ceria Based Composite Membranes for Oxygen Separation

    DEFF Research Database (Denmark)

    Gurauskis, Jonas; Ovtar, Simona; Kaiser, Andreas;

    2014-01-01

    Mixed ionic-electronic conducting membranes for oxygen gas separation are attracting a lot of interest due to their promising potential for the pure oxygen and the syngas production. Apart from the need for a sufficiently high oxygen permeation fluxes, the prolonged stability of these membranes...... under the large oxygen potential gradients at elevated temperatures is decisive for the future applications. The gadolinium doped cerium oxide (CGO) based composite membranes are considered as promising candidates due to inherent stability of CGO phase. The CGO matrix is a main oxygen ion transporter......; meanwhile the primary role of a secondary phase in this membrane is to compensate the low electronic conductivity of matrix at intended functioning conditions. In this work thin film (15-20 μm) composite membranes based on CGO matrix and LSF electronic conducting phase were fabricated and evaluated...

  2. A new chiral derivatizing agent for the HPLC separation of α-amino acids on a standard reverse-phase column.

    Science.gov (United States)

    Kotthaus, A F; Altenbach, H-J

    2011-02-01

    A new chiral derivatizing agent for α-amino acids is described which leads to diastereomers that can be separated by reverse-phase HPLC with direct detection by a diode array detector. The main advantage of the presented procedure is the fact that an excess of the derivatizing reagent can be employed as the product exhibits an absorption maximum at 360 nm, while the reagent has its absorption maximum at 260 nm. Therefore, it is possible to suppress the reagent signal by a detection wavelength of 400 nm leading to an easy and general method for the enantioseparation of a mixture of DL-amino acids and the determination of the enantiomeric purity of α-amino acid as exemplified by 16 different α-amino acids.

  3. Efficient C2-Symmetric Chiral Schiff Bases for Lanthanide-catalyzed Asymmetric Hydrogenation of Acetophenone

    Institute of Scientific and Technical Information of China (English)

    Peng Fei YAN; Wen Bin SUN; Guang Ming LI; Chun Hong NIE; Zheng Yu YUE

    2006-01-01

    An array of C2-symmetric chiral Schiff bases of substituted salicylaldehyde (1R, 2R)-1,2-cyclohexanediamine and (R)-(+)-2, 2'-diamino-1, 1'-binaphthalene, incorporated with lanthanide complexes, have been applied as catalysts for asymmetric hydrogenation of acetophenone for the first time. Highly enantioselective product with 90% enantiomeric excess (e.e.) was obtained when the catalyst, hybridized by the bulky electron-donating 3, 5-di-tert-butyl substituted Schiff base (2) and SmCl3·4THF, was employed.

  4. Estudio de un absorbedor basado en metamaterial quiral Study of absorber based on chiral metamaterial

    Directory of Open Access Journals (Sweden)

    Perla Espinosa Diaz

    2011-06-01

    Full Text Available El presente trabajo estudia el comportamiento electromagnético de un dispositivo absorbedor con estructura metamaterial quiral. El dispositivo propuesto consiste en una estructura de planos paralelos, con rosetas metálicas implantadas, físicamente separadas por capas dieléctricas. Para demostrar el efecto absorbedor de tal estructura, se ejecuta una simulación básica, en la cual se hace incidir un haz gaussiano sobre el metamaterial quiral. Los resultados muestran que, para efectos prácticos, ocurre absorción total. Este comportamiento hace que la estructura propuesta se comporte como un "agujero negro espacial".The electromagnetic behavior of an absorber device with chiral metamaterial structure is studied. The proposed device is a structure formed by parallel planes with implanted metallic rosettes, physically separated by dielectric layers. In order to show the absorbing properties of such structure, a basic simulation is run, in which a gaussian beam is fed incident to the chiral metamaterial. Results show that there is, for practical purposes, full absorption. This behavior makes the proposed structure behave as a "spatial black hole".

  5. Synthesis and characterization of sugar based low molecular weight gelators and the preparation of chiral sulfinamides

    Science.gov (United States)

    Mangunuru, Hari Prasad Reddy

    Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications. Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D-glucosamine. D-glucosamine is the versatile starting material to make different peptoids and triazoles. Several series of compounds were synthesized using compounds 1-3 as starting material and studied the gelation behavior all the compounds. We have studied the self-assembling properties of a new class of tripeptoids, synthesized by one-pot Ugi reaction from simple starting materials. Among the focused library of tripeptoids synthesized, we found that several efficient low molecular weight organogelators were obtained for aqueous DMSO and ethanol mixtures. We have also synthesized and characterized a series of monosaccharide triazole derivatives. These compounds were synthesized from N-acetyl glucosamine and D-glucose via a Cu(I) catalyzed azide/alkyne cycloaddition reaction (CuAAc). The compounds have been screened for their gelation properties and several efficient low molecular weight organo/hydro gelators were obtained, among these compounds, five per-acetyl glucosamine derivatives and one peracetyl glucose derivative were able to form gels in water. These new molecules are expected to be useful in drug delivery and tissue engineering.*. Asymmetric synthesis of chiral amines is a challenging in synthetic organic chemistry. The development of new catalysts for asymmetric organic

  6. Transition state models for probing stereoinduction in Evans chiral auxiliary-based asymmetric aldol reactions.

    Science.gov (United States)

    Shinisha, C B; Sunoj, Raghavan B

    2010-09-08

    The use of chiral auxiliaries is one of the most fundamental protocols employed in asymmetric synthesis. In the present study, stereoselectivity-determining factors in a chiral auxiliary-based asymmetric aldol reaction promoted by TiCl(4) are investigated by using density functional theory methods. The aldol reaction between chiral titanium enolate [derived from Evans propionyl oxazolidinone (1a) and its variants oxazolidinethione (1b) and thiazolidinethione (1c)] and benzaldehyde is examined by using transition-state modeling. Different stereochemical possibilities for the addition of titanium enolates to aldehyde are compared. On the basis of the coordination of the carbonyl/thiocarbonyl group of the chiral auxiliary with titanium, both pathways involving nonchelated and chelated transition states (TSs) are considered. The computed relative energies of the stereoselectivity-determining C-C bond formation TSs in the nonchelated pathway, for both 1a and 1c, indicate a preference toward Evans syn aldol product. The presence of a ring carbonyl or thiocarbonyl group in the chiral auxiliary renders the formation of neutral TiCl(3)-enolate, which otherwise is energetically less favored as compared to the anionic TiCl(4)-enolate. Hence, under suitable conditions, the reaction between titanium enolate and aldehyde is expected to be viable through chelated TSs leading to the selective formation of non-Evans syn aldol product. Experimentally known high stereoselectivity toward Evans syn aldol product is effectively rationalized by using the larger energy differences between the corresponding diastereomeric TSs. In both chelated and nonchelated pathways, the attack by the less hindered face of the enolate on aldehyde through a chair-like TS with an equatorial disposition of the aldehydic substituent is identified as the preferred mode. The steric hindrance offered by the isopropyl group and the possible chelation are identified as the key reasons behind the interesting

  7. Chiral atomically thin films

    Science.gov (United States)

    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.

  8. A Sensitive DNAzyme-Based Chiral Sensor for Lead Detection

    Directory of Open Access Journals (Sweden)

    Chuanlai Xu

    2013-11-01

    Full Text Available A DNAzyme-based sensor for the determination and quantification of lead ions (Pb2+ has been established, which combines the recognition and catalysis of DNAzyme with the optical properties of nanomaterials. Circular dichroism (CD signals were obtained by a DNAzyme-based assembly of asymmetric silver nanoparticle (AgNPs dimers. A good linear relationship between CD signals and Pb2+ concentration was obtained ranging from 0.05 ng∙mL−1 to 10 ng∙mL−1 with a limit of detection (LOD of 0.02 ng∙mL−1. The specificity of this sensor in lead ion detection was excellent, and a satisfactory recovery was obtained in the analysis of tap water samples. The proposed technique possesses both high sensitivity and good specificity, giving it great potential for the analysis of Pb2+ in water.

  9. Design and synthesis of novel chiral molecular tweezers based on deoxycholic acid

    Institute of Scientific and Technical Information of China (English)

    Zhi Gang Zhao; Xing Li Liu; Yi Zhong

    2008-01-01

    A novel type of chiral molecular tweezers has been designed and synthesized by using deoxycholic acid as backbone and ethanoyl and the chiral unsymmetrical urea unit as arms. Their structures were characterized by 1H NMR, IR, MS spectra and elemental analysis. These molecular tweezers showed good binding ability for neutral molecules and chiral molecules.

  10. Chiral Synthons in Pesticide Syntheses

    NARCIS (Netherlands)

    Feringa, Bernard

    1988-01-01

    The use of chiral synthons in the preparation of enantiomerically pure pesticides is described in this chapter. Several routes to chiral synthons based on asymmetric synthesis or on natural products are illustrated. Important sources of chiral building blocks are reviewed. Furthermore the implicatio

  11. Applications of chiral symmetry

    CERN Document Server

    Pisarski, R D

    1995-01-01

    I discuss several topics in the applications of chiral symmetry at nonzero temperature, including: where the rho goes, disoriented chiral condensates, and the phase diagram for QCD with 2+1 flavors. (Based upon talks presented at the "Workshop on Finite Temperature QCD", Wuhan, P.R.C., April, 1994.)

  12. A chiral photochromic Schiff base: (R-4-methoxy-2-[(1-phenylethyliminomethyl]phenol

    Directory of Open Access Journals (Sweden)

    Yukie Miura

    2009-10-01

    Full Text Available The title chiral photochromic Schiff base compound, C16H17NO2, was synthesized from (R-1-phenylethylamine and 5-methoxysalicylaldehyde. The molecule of the title compound exists in the phenol–imine tautomeric form. The dihedral angle between the two aromatic rings is 62.61 (11°. An intramolecular O—H...N hydrogen bond with an O...N distance of 2.589 (2 Å is observed. The crystal packing is stabilized by C—H...π interactions involving the aromatic ring.

  13. Circular dichroism sensor based on cadmium sulfide quantum dots for chiral identification and detection of penicillamine

    Energy Technology Data Exchange (ETDEWEB)

    Ngamdee, Kessarin [Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, 40002 (Thailand); Puangmali, Theerapong [Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen, 40002 (Thailand); Tuntulani, Thawatchai [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330 (Thailand); Ngeontae, Wittaya, E-mail: wittayange@kku.ac.th [Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, 40002 (Thailand)

    2015-10-22

    A new chemical sensor based on the measuring of circular dichroism signal (CD) was fabricated from cysteamine capped cadmium sulfide quantum dots (Cys-CdS QDs). The chiral-thiol molecules, D-penicillamine (DPA) and L-penicillamine (LPA), were used to evaluate potentials of this sensor. Basically, DPA and LPA provide very low CD signals. However, the CD signals of DPA and LPA can be enhanced in the presence of Cys-CdS QDs. The CD spectra of DPA and LPA exhibited a mirror image profile. Parameters affecting the determination of DPA and LPA were thoroughly investigated in details. Under the optimized condition, the CD signals of DPA and LPA displayed a linear relationship with the concentrations of both enantiomers, ranging from 1 to 35 μM. Detection limits of this sensor were 0.49 and 0.74 μM for DPA and LPA, respectively. To demonstrate a potential application of this sensor, the proposed sensor was used to determine DPA and LPA in real urine samples. It was confirmed that the proposed detection technique was reliable and could be utilized in a broad range of applications. - Highlights: • This paper demonstrates a new CD sensor based on cadmium sulfide quantum dots. • Achiral quantum dots are used for the detection and chiral identification of thiol-chiral containing compounds. • The sensor show highest selectivity towards penicillamine. • The detection limits of the sensor less than 1 μM. • The sensor can potentially be used in physiological urine samples.

  14. A general model for membrane-based separation processes

    DEFF Research Database (Denmark)

    Soni, Vipasha; Abildskov, Jens; Jonsson, Gunnar Eigil;

    2009-01-01

    behaviour will play an important role. In this paper, modelling of membrane-based processes for separation of gas and liquid mixtures are considered. Two general models, one for membrane-based liquid separation processes (with phase change) and another for membrane-based gas separation are presented...

  15. Electronic and optoelectronic devices based on chirality-enriched wafer-scale single-wall carbon nanotube thin films

    Science.gov (United States)

    Gao, Weilu; He, Xiaowei; Xie, Lijuan; Zhang, Qi; Haroz, Erik; Doorn, Stephen K.; Kono, Junichiro

    2015-03-01

    The unique and rich material properties of single-wall carbon nanotubes (SWCNTs) make them attractive for nano-electronic and optoelectronic applications. Slight changes in tube diameter and wrapping angle, defined by the chirality indices (n, m), can dramatically modify the bandstructure, which can be utilized for designing devices with tailored properties. However, it remains to be a challenge to fabricate macroscopic, single-chirality devices. Here, we introduce a simple way of producing chirality-enriched wafer-scale SWCNT films by combining recently developed solution-based polymer-modified sorting method and vacuum filtration. The produced thin films can be easily transferred onto any substrate to have a CMOS compatible wafer. We fabricated a transistor of (6,5)-enriched SWCNTs with an on/off ratio >103. Large-scale photothermoelectric-effect-based and photovoltaic-effect-based photodetectors made of (6,6)- and (6,5)-enriched films, respectively, will also be discussed.

  16. Modeling Textural Processes during Self-Assembly of Plant-Based Chiral-Nematic Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Yogesh K. Murugesan

    2010-12-01

    Full Text Available Biological liquid crystalline polymers are found in cellulosic, chitin, and DNA based natural materials. Chiral nematic liquid crystalline orientational order is observed frozen-in in the solid state in plant cell walls and is known as a liquid crystal analogue characterized by a helicoidal plywood architecture. The emergence of the plywood architecture by directed chiral nematic liquid crystalline self assembly has been postulated as the mechanism that leads to optimal cellulose fibril organization. In natural systems, tissue growth and development takes place in the presence of inclusions and secondary phases leaving behind characteristic defects and textures, which provide a unique testing ground for the validity of the liquid crystal self-assembly postulate. In this work, a mathematical model, based on the Landau-de Gennes theory of liquid crystals, is used to simulate defect textures arising in the domain of self assembly, due to presence of secondary phases representing plant cells, lumens and pit canals. It is shown that the obtained defect patterns observed in some plant cell walls are those expected from a truly liquid crystalline phase. The analysis reveals the nature and magnitude of the viscoelastic material parameters that lead to observed patterns in plant-based helicoids through directed self-assembly. In addition, the results provide new guidance to develop biomimetic plywoods for structural and functional applications.

  17. Nanocellulose 3, 5-Dimethylphenylcarbamate Derivative Coated Chiral Stationary Phase: Preparation and Enantioseparation Performance.

    Science.gov (United States)

    Zhang, Xiaoli; Wang, Litao; Dong, Shuqing; Zhang, Xia; Wu, Qi; Zhao, Liang; Shi, Yanping

    2016-05-01

    Nanocrystalline cellulose (NCC) with high surface area and high ordered crystalline structure was prepared from microcrystalline cellulose (MCC) under the hydrolysis of sodium hypochlorite. NCC was further reacted with 3,5-dimethylphenyl isocyanate to obtain the nanocellulose derivative, and then coated successfully on the surface of silica gel to a prepared NCC-coated chiral stationary phase (CSP) as a new kind of chiral separation material. Similarly, MCC derivative-coated CSP was also prepared as contrast. The chiral separation performance of NCC-based CSP was evaluated and compared with MCC-based CSP by high-performance liquid chromatography. Moreover, the effects of the alcohol modifiers, mobile phase additives, and flow rates on chiral separations were investigated in detail. The results showed that 10 chiral compounds were separated on NCC-based CSP with better peak shape and higher column efficiency than MCC-based CSP, which confirmed that NCC-based CSP was a promising packing material for the resolution of chiral compounds.Chirality 28:376-381, 2016. © 2016 Wiley Periodicals, Inc.

  18. Development and validation of an enantioselective SFC-MS/MS method for simultaneous separation and quantification of oxcarbazepine and its chiral metabolites in beagle dog plasma.

    Science.gov (United States)

    Yang, Zhichao; Xu, Xueyu; Sun, Lingxia; Zhao, Xue; Wang, Hao; Fawcett, John Paul; Yang, Yan; Gu, Jingkai

    2016-05-01

    A rapid and sensitive assay based on supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) has been developed and validated for the determination of oxcarbazepine (OXC) and its chiral metabolite licarbazine (Lic) in beagle dog plasma using carbamazepine as internal standard. Chiral analysis in a run time of only 3 min was performed on an ACQUITY UPC(2) ™ Trefoil™ CEL2 column (3.0 × 150 mm, 2.5 μm) at 50 °C by isocratic elution with a mobile phase of supercritical carbon dioxide (purity ≥ 99.99%) and methanol (60:40, v/v) at a flow rate of 2.3 mL/min. The assay was linear over the concentration ranges 5-1000 ng/mL for OXC and 0.5-100 ng/mL for the enantiomers of Lic with corresponding lower limits of quantitation of 5 ng/mL and 0.5 ng/mL. Intra- and inter-day precisions were in the range 0.78-14.14% with accuracies in the range -10.80% to 0.42%. The method was successfully applied to a pharmacokinetic study involving a single oral administration of 16 mg/kg OXC as Trileptal(@) tablets to beagle dogs.

  19. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions.

    Science.gov (United States)

    Hayashi, Masahiko

    2016-12-01

    In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals.

  20. Comparative Optical Separation of Racemic Ibuprofen by Using Chiral Stationary Phase%运用手性固定相研究外消旋布洛芬的光学分离

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Ibuprofen is widely used as a non-steroidal anti-inflammatory drug and produced as racemic mixture. Its pharmacological activity resides only in S-(+)-enantiomer, and R-(-)-enantiomer is not only inactive but also has many side effects. Thus it is necessary to separate Renanfiomer from racemic ibuprofen. We studied optical separation of racemic Ibuprofen with chiral high performance liquid chromatography (HPLC). Out of three different chiral stationary phases, which were selected on the basis of structure and availability, two were found to be effective. There was optimum eluent composition for each stationary phase for good resolution in optical separation. Resolution decreased with increase of eluent flow rate, but effect of injection volume on resolution was insignificant at high eluent flow rate.

  1. Synthesis and characterization of a tetranuclear copper(Ⅱ) complex with a chiral Schiff base ligand

    Institute of Scientific and Technical Information of China (English)

    Hua Xiang; Long Jiang; Huan-Yong Li; Xiao-Dan Zheng; YU Li

    2013-01-01

    The title complex l-[CuⅡ4(Hvap)2(vap)2(MeOH)2](ClO4)2 1 has been synthesized and characterized by EA,IR,TGA,solid-state CD spectra and X-ray single-crystal analyses (I-H2vap:a Schiff base ligand derived from the condensation of o-vanillin and 1-2-amino-3-phenyl-1-propanol).Complex 1 crystallizes in monoclinic system,chiral space group P21 with a=10.4257(18),b=21.695(4),c=15.721(3) (A),β =94.443(3)°,V=3545.1 (11) (A)3,Z =2,Cu4C7oH78N4O22Cl2,Mr =1652.42,Dc =1.548 g/cm3,F(0 0 0) =1704 and μ(MoKα) =1.338 mm-1.The final R =0.0682 and wR =0.1420 for 6170 observed reflections with I > 2σ(Ⅰ) and R =0.1775 and wR =0.1830 for all data.The structure of complex 1 contains a boat-shaped {Cu4O4} motif.The solid-state CD spectra confirm the chiral nature of complex 1.

  2. Enantiomer separation by ultrafiltration of enantioselective micelles in multistage systems

    NARCIS (Netherlands)

    Overdevest, P.E.M.

    2000-01-01

    The Food and Bioprocess Engineering Group of Wageningen University, The Netherlands, is developing a new enantiomer separation system that is based on ultrafiltration (UF) of enantioselective micelles containing chiral selector molecules. Enantiomer molecules are optical isomers (mirror images), and

  3. CHIRAL CONJUGATED OLIGOMER BASED ON 1,1'-BINOL WITH 3,3'-ACETYLENE-PHENYLENE-ACETYLENE SPACER

    Institute of Scientific and Technical Information of China (English)

    Tian-jun Liu; Ke-shen Zhang; Yong-jun Chen; Dong Wang; Chao-jun Li

    2001-01-01

    The 1,1'-binaphthol based oligomers 3 and 7 with 3,3'-acetylene-phenylene-acetylene spacer were prepared from BINOL 1. The high optical rotation value and CD spectra demonstrated the main chain chirality of the oligomer molecule. The UV-VIS and fluorescent spectra evidence the characteristics of conjugated structure. In comparison with oligomer 2 bearing 3,3'-acetylene spacer, the oligomers 3 and 7 have longer efficient conjugation segment, and their fluorescent quantum yields (φ) increased (0.60-0.65 versus 0.14). Extending the effective conjugation segment would improve the photophysical properties of chiral conjugated polymers.``

  4. Hyperpolarizabilities of Chiral Molecules Based on Three-Coupled-Oscillator Model

    Institute of Scientific and Technical Information of China (English)

    WANG Xiao-Ou; LI Jun-Qing; LI Chun-Fei

    2004-01-01

    @@ A chiral molecular model of three coupled oscillators is established. A set of coupling equations and hyperpolarizabilities for the chiral molecules with the tripod structure are presented. The expression of second-order nonlinear susceptibility is derived for an isotropic molecular system. The calculated hyperpolarizabilities of NPAN and NPP chiral molecules are consistent with the experimental results and the applicability of this model is validated.

  5. Asymmetric Cyclopropanation Catalyzed by Four Stereoisomers of a Copper-(Schiff-base) Complex with Double Chiral Centers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Four stereoisomers of a copper-(Schiff-base) complex with double chiral centers were applied to catalyze the asymmetric cyclopropanation. Two of the stereoisomers were also efficient catalysts affording high enantiomeric excess of up to 91.8%. A mechanism that predicts the observed results accurately was proposed.

  6. Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

    Science.gov (United States)

    Qiang, Gen-Rong; Shen, Tian-Hua; Zhou, Xiao-Cong; An, Xiao-Xia; Song, Qing-Bao

    2014-12-01

    A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

  7. Helical Ordering in Chiral Block Copolymers

    Science.gov (United States)

    Zhao, Wei; Hong, Sung Woo; Chen, Dian; Grason, Gregory; Russell, Thomas

    2012-02-01

    Introducing molecular chirality into the segments of block copolymers can influence the nature of the resultant morphology. Such an effect was found for poly(styrene-b-L-lactide) (PS-b-PLLA) diblock copolymers where hexagonally packed PLLA helical microdomains (H* phase) form in a PS matrix. However, molecular ordering of PLLA within the helical microdomains and the transfer of chirality from the segmental level to the mesoscale is still not well understood. We developed a field theoretic model to describe the interactions between segments of chiral blocks, which have the tendency to form a ``cholesteric'' texture. Based on the model, we calculated the bulk morphologies of chiral AB diblock copolymers using self-consistent field theory (SCFT). Experiments show that the H* phase only forms when microphase separation between PS and PLLA block happens first and crystallization of PLLA block is suppressed or happens within confined microdomain. Hence, crystalline ordering is not necessary for H* phase formation. The SCFT offers the chance to explore the range of thermodynamic stability of helical structures in the phase diagram of chiral block copolymer melts, by tuning parameters not only like the block segregation strength and composition, but also new parameters such as the ratio between preferred helical pitch to the radius of gyration and the Frank elastic constant for inter-segment distortions.

  8. Development of a Validated LC Method for Separation of Process-Related Impurities Including the R-Enantiomer of S-Pramipexole on Polysaccharide Chiral Stationary Phases.

    Science.gov (United States)

    Ramisetti, Nageswara Rao; Kuntamukkala, Ramakrishna; Arnipalli, Manikanta Swamy

    2015-07-01

    Despite the availability of a few methods for individual separation of S-pramipexole from its process-related impurities, no common liquid chromatography (LC) method is reported so far in the literature. The present article describes the development of a single-run LC method for simultaneous determination of S-pramipexole and its enantiomeric and process-related impurities on a Chiralpak AD-H (150 x 4.6 mm, 5μm) column using n-hexane/ethanol/n-butylamine (75:25:0.1 v/v/v) as a mobile phase in an isocratic mode of elution at a flow rate of 1.2 ml/min at 30°C. The chromatographic eluents were monitored at a wavelength of 260 nm using a photodiode array detector. Excellent enantioseparation with good resolutions (Rs ≥ 2.88) and peak shapes (As ≤ 1.21) for all analytes was achieved. The proposed method was validated according to International Conference Harmonization (ICH) guidelines in terms of accuracy, precision, sensitivity, and linearity. Limits of quantification of impurities (0.25-0.55 μg/ml) indicate the highest sensitivity achievable by the proposed method. The method has an advantage of selectivity and suitability for routine determination of not only chiral impurity but also all possible related substances in active pharmaceutical ingredients of S-pramipexole.

  9. Highly sensitive trivalent copper chelate–luminol chemiluminescence system for capillary electrophoresis chiral separation and determination of ofloxacin enantiomers in urine samples

    Directory of Open Access Journals (Sweden)

    Hao-Yue Xie

    2014-12-01

    Full Text Available A simple, fast and sensitive capillary electrophoresis (CE strategy combined with chemiluminescence (CL detection for analysis of ofloxacin (OF enantiomers was established in the present work. Sulfonated β-cyclodextrin (β-CD was used as the chiral additive being added into the running buffer of luminol–diperiodatocuprate (III (K5[Cu(HIO62], DPC chemiluminescence system. Under the optimum conditions, the proposed method was successfully applied to separation and analysis of OF enantiomers with the detection limits (S/N=3 of 8.0 nM and 7.0 nM for levofloxacin and dextrofloxacin, respectively. The linear ranges were both 0.010–100 μM. The method was utilized for analyzing OF in urine; the results obtained were satisfactory and recoveries were 89.5–110.8%, which demonstrated the reliability of this method. This approach can also be further extended to analyze different commercial OF medicines.

  10. Discrete nanocubes as plasmonic reporters of molecular chirality.

    Science.gov (United States)

    Lu, Fang; Tian, Ye; Liu, Mingzhao; Su, Dong; Zhang, Hui; Govorov, Alexander O; Gang, Oleg

    2013-07-10

    One of the most intriguing structural properties, chirality, is often exhibited by organic and bio-organic molecular constructs. Chiral spectral signatures, typically appearing in the UV range for organic materials and known as circular dichroism (CD), are widely used to probe a molecular stereometry. Such probing has an increasingly broad importance for biomedical and pharmacological fields due to synthesis/separation/detection of homochiral species, biological role of chiral organization, and structural response to environmental conditions and enantiomeric drugs. Recent theoretical and experimental works demonstrated that the CD signal from chiral organic molecules could appear in the plasmonic (typically, visible) band when they coupled with plasmonic particles. However, the magnitude of this CD signal, induced by discrete nonchiral plasmonic particles, and its native molecular analog were found to be comparable. Here we show that shaped nonchiral nanoparticles, namely, gold/silver core/shell nanocubes, can act as plasmonic reporters of chirality for attached molecules by providing a giant, 2 orders of magnitude CD enhancement in a near-visible region. Through the experimental and theoretical comparison with nanoparticles of other shapes and materials, we demonstrate a uniqueness of silver nanocube geometry for the CD enhancement. The discovered phenomenon opens novel opportunities in ultrasensitive probing of chiral molecules and for novel optical nanomaterials based on the chiral elements.

  11. Construction of KbarN potential and structure of Lambda(1405) based on chiral unitary approach

    CERN Document Server

    Miyahara, Kenta

    2015-01-01

    Based on chiral unitary approach, we construct the realistic KbarN local potential, which is useful for the quantitative calculation of Kbar-nuclei. Since the resonance pole structure of the KbarN system seems important for the Kbar-nuclei and the spacial structure of Lambda(1405), we establish the construction procedure of the local potential paying attention to the scattering amplitude in the complex energy plane. Furthermore, for the quantitative study of the Kbar-nuclei, we consider the constraint from the recent experimental data measured by SIDDHARTA, which significantly reduces the uncertainty of the KbarN amplitude. With this new local potential, we estimate the spacial structure of Lambda(1405) and obtain the result indicating the meson-baryon molecular state of Lambda(1405).

  12. Ring-shaped Racetrack memory based on spin orbit torque driven chiral domain wall motions

    Science.gov (United States)

    Zhang, Yue; Zhang, Xueying; Hu, Jingtong; Nan, Jiang; Zheng, Zhenyi; Zhang, Zhizhong; Zhang, Youguang; Vernier, Nicolas; Ravelosona, Dafine; Zhao, Weisheng

    2016-10-01

    Racetrack memory (RM) has sparked enormous interest thanks to its outstanding potential for low-power, high-density and high-speed data storage. However, since it requires bi-directional domain wall (DW) shifting process for outputting data, the mainstream stripe-shaped concept certainly suffers from the data overflow issue. This geometrical restriction leads to increasing complexity of peripheral circuits or programming as well as undesirable reliability issue. In this work, we propose and study ring-shaped RM, which is based on an alternative mechanism, spin orbit torque (SOT) driven chiral DW motions. Micromagnetic simulations have been carried out to validate its functionality and exhibit its performance advantages. The current flowing through the heavy metal instead of ferromagnetic layer realizes the “end to end” circulation of storage data, which remains all the data in the device even if they are shifted. It blazes a promising path for application of RM in practical memory and logic.

  13. Design and Synthesis of Chiral Molecular Tweezers Based on Deoxycholic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A series of new chiral molecular tweezers have been designed and synthesized by using deoxycholic acid as spacer and aromatic amines as arms.Instead of using toxic phosgene,the triphosgene was employed in synthesis of the molecular tweezers receptors.These chiral molecular tweezers showed good enantioselectivity for D-amino acid methyl esters.

  14. Bringing chiral optical forces to dominance with optical nanofibers

    CERN Document Server

    Alizadeh, M H

    2016-01-01

    Transverse spin angular momentum (SAM) of light and associated transverse chiral optical forces have received tremendous attention recently as the latter may lead to an optical separation of chiral biomolecules. Previous schemes to generate chiral forces are plagued by the fact that the chiral optical forces are orders of magnitude smaller than conventional gradient and scattering forces. The relative magnitude of chiral and non-chiral forces represents a fundamental challenge for the implementation of chiral separation schemes. In this work we demonstrate that, by spatially separating the maxima of transverse spin density from the gradient of field intensity, in the vicinity of optical nanofibers and nanowires, chiral optical forces can emerge that are stronger than gradient and scattering forces. This finding has important implications for the design of improved optical separation schemes for chiral biomolecules.

  15. Optimal separable bases and molecular collisions

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, L W [Univ. of California, Berkeley, CA (United States)

    1997-12-01

    A new methodology is proposed for the efficient determination of Green`s functions and eigenstates for quantum systems of two or more dimensions. For a given Hamiltonian, the best possible separable approximation is obtained from the set of all Hilbert space operators. It is shown that this determination itself, as well as the solution of the resultant approximation, are problems of reduced dimensionality for most systems of physical interest. Moreover, the approximate eigenstates constitute the optimal separable basis, in the sense of self-consistent field theory. These distorted waves give rise to a Born series with optimized convergence properties. Analytical results are presented for an application of the method to the two-dimensional shifted harmonic oscillator system. The primary interest however, is quantum reactive scattering in molecular systems. For numerical calculations, the use of distorted waves corresponds to numerical preconditioning. The new methodology therefore gives rise to an optimized preconditioning scheme for the efficient calculation of reactive and inelastic scattering amplitudes, especially at intermediate energies. This scheme is particularly suited to discrete variable representations (DVR`s) and iterative sparse matrix methods commonly employed in such calculations. State to state and cumulative reactive scattering results obtained via the optimized preconditioner are presented for the two-dimensional collinear H + H{sub 2} {yields} H{sub 2} + H system. Computational time and memory requirements for this system are drastically reduced in comparison with other methods, and results are obtained for previously prohibitive energy regimes.

  16. Optimal separable bases and molecular collisions

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, Lionel W. [Univ. of California, Berkeley, CA (United States)

    1997-12-01

    A new methodology is proposed for the efficient determination of Green`s functions and eigenstates for quantum systems of two or more dimensions. For a given Hamiltonian, the best possible separable approximation is obtained from the set of all Hilbert space operators. It is shown that this determination itself, as well as the solution of the resultant approximation, are problems of reduced dimensionality for most systems of physical interest. Moreover, the approximate eigenstates constitute the optimal separable basis, in the sense of self-consistent field theory. These distorted waves give rise to a Born series with optimized convergence properties. Analytical results are presented for an application of the method to the two-dimensional shifted harmonic oscillator system. The primary interest however, is quantum reactive scattering in molecular systems. For numerical calculations, the use of distorted waves corresponds to numerical preconditioning. The new methodology therefore gives rise to an optimized preconditioning scheme for the efficient calculation of reactive and inelastic scattering amplitudes, especially at intermediate energies. This scheme is particularly suited to discrete variable representations (DVR`s) and iterative sparse matrix methods commonly employed in such calculations. State to state and cumulative reactive scattering results obtained via the optimized preconditioner are presented for the two-dimensional collinear H + H2 → H2 + H system. Computational time and memory requirements for this system are drastically reduced in comparison with other methods, and results are obtained for previously prohibitive energy regimes.

  17. Broadband angle- and permittivity-insensitive nondispersive optical activity based on chiral metamaterials

    CERN Document Server

    Song, Kun; Su, Zhaoxian; Ding, Changlin; Liu, Yahong; Luo, Chunrong; Zhao, Xiaopeng; Bhattarai, Khagendra; Zhou, Jiangfeng

    2016-01-01

    Because of the strong inherent resonances, the giant optical activity obtained via chiral metamaterials generally suffers from high dispersion, which has been a big stumbling block to broadband applications. In this paper, we propose a type of chiral metamaterial consisting of interconnected metal helix structures with four-fold symmetry, which exhibits nonresonant Drude-like response and can therefore avoid the highly dispersive optical activity resulting from resonances. It shows that the well-designed chiral metamaterial can achieve nondispersive and pure optical activity with high transmittance in a broadband frequency range. And the optical activity of multi-layer chiral metamaterials is proportional to the layer numbers of single-layer chiral metamaterial. Most remarkably, the broadband behaviors of nondispersive optical activity and high transmission are insensitive to the incident angles of electromagnetic waves and permittivity of dielectric substrate, thereby enabling more flexibility in polarizatio...

  18. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

    Direct Asymmetric Photochemistry with Circularly Polarized Light, H. RauCoherent Laser Control of the Handedness of Chiral Molecules, P. Brumer and M. ShapiroMagnetochiral Anisotropy in Asymmetric Photochemistry, G.L.J.A.RikkenEnantiodifferentiating Photosensitized Reactions, Y. InoueDiastereodifferentiating Photoreactions, N. Hoffmann and J.-P. PeteChirality in Photochromism, Y. Yokoyama and M. SaitoChiral Photochemistry with Transition Metal Complexes, S. Sakaki and T. HamadaTemplate-Induced Enantioselective Photochemical Reactions in S

  19. Electrodynamics of chiral matter

    Science.gov (United States)

    Qiu, Zebin; Cao, Gaoqing; Huang, Xu-Guang

    2017-02-01

    Many-body systems with chiral fermions can exhibit novel transport phenomena that violate parity and time-reversal symmetries, such as the chiral magnetic effect, the anomalous Hall effect, and the anomalous generation of charge. Based on the Maxwell-Chern-Simons electrodynamics, we examine some electromagnetic and optical properties of such systems including the electrostatics, the magnetostatics, the propagation of electromagnetic waves, the novel optical effects, etc.

  20. Dispersing and Separating Carbon Nanotubes with Novel Surfactant Formulations

    Science.gov (United States)

    2010-08-01

    regions in the outer region of the complex. Following DGU, the buoyant density of the separated SWNTs is measured directly, and the SWNT chirality ...bioimaging, and drug delivery. Results and Discussion DGU-based separations of arc discharge grown SWNTs were performed with Pluronic block...17 Specific Chiralities Using Helical Assemblies of Flavin Mononucleotide. Nature Nanotech. 2008, 3, 356-362. 23. Green, A. A.; Hersam, M. C

  1. Enantiomeric Separation and Determination of the Enantiomeric Impurity of Armodafinil by Capillary Electrophoresis with Sulfobutyl Ether-β-cyclodextrin as Chiral Selector

    OpenAIRE

    Bingren Xiang; Yibing Ji; Suyun Xiang; Xiaojuan Zhou; Wei Wang

    2011-01-01

    A selective capillary electrophoresis method using sulfobutyl ether-β-cyclodextrin as a chiral selector was developed and validated for the determination of the enantiomeric impurity of (R)-modafinil, i.e., armodafinil. Several parameters were optimized for a satisfactory enantioresolution, including the type and concentration of chiral selector and organic modifier, pH of background electrolyte (BGE), capillary temperature. The finally adopted condition was: 20 mmol/L phosphate buffer at pH ...

  2. Synthesis, X-ray, and Spectroscopic Study of Dissymmetric Tetrahedral Zinc(II) Complexes from Chiral Schiff Base Naphthaldiminate Ligands with Apparent Exception to the ECD Exciton Chirality.

    Science.gov (United States)

    Enamullah, Mohammed; Makhloufi, Gamall; Ahmed, Rifat; Joy, Baitul Alif; Islam, Mohammad Ariful; Padula, Daniele; Hunter, Howard; Pescitelli, Gennaro; Janiak, Christoph

    2016-07-01

    Bidentate enantiopure Schiff base ligands, (R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldiminate (R- or S-N^O), diastereoselectively provide Λ- or Δ-chiral-at-metal four-coordinated Zn(R- or S-N^O)2 {Ar = C6H5; Zn-1R or Zn-1S and p-C6H4OMe; Zn-2R or Zn-2S}. Two R- or S-N^O-chelate ligands coordinate to the zinc(II) in a tetrahedral mode and induce Λ- or Δ-configuration at the zinc metal center. In the solid state, the R- or S-ligand diastereoselectively gives Λ- or Δ-Zn configuration, respectively, and forms enantiopure crystals. Single crystal structure determinations show two symmetry-independent molecules (A and B) in each asymmetric unit to give Z' = 2 structures. Electronic circular dichroism (ECD) spectra show the expected mirror image relationship resulting from diastereomeric excess toward the Λ-Zn for R-ligands and Δ-Zn for S-ligands in solution. ECD spectra are well reproduced by TDDFT calculations, while the application of the exciton chirality method, in the common point-dipole approximation, predicts the wrong sign for the long-wavelength couplet. A dynamic diastereomeric equilibrium (Λ vs Δ) prevails for both R- and S-ligand-metal complexes in solution, respectively, evidenced by (1)H NMR spectroscopy. Variable temperature (1)H NMR spectra show a temperature-dependent shift of the diastereomeric equilibrium and confirm Δ-Zn configuration (for S-ligand) to be the most stable one and favored at low temperature. DSC analyses provide quantitative diastereomeric excess in the solid state for Zn-2R and Zn-2S, which is comparable to the results of solution studies.

  3. Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

    CERN Document Server

    Kharzeev, Dmitri; Meyer, Rene

    2016-01-01

    We describe a new type of the Chiral Magnetic Effect (CME) that should occur in Weyl semimetals with an asymmetry in the dispersion relations of the left- and right-handed chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source generates a non-vanishing chiral chemical potential. This is due to the different capacities of the left- and right-handed (LH and RH) chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation f...

  4. Temperature-induced inversion of elution order in the chromatographic enantioseparation of 1,1'-bi-2-naphthol on an immobilized polysaccharide-based chiral stationary phase.

    Science.gov (United States)

    Yao, Bixia; Zhan, Fengping; Yu, Guangyan; Chen, Zhifen; Fan, Wenjing; Zeng, Xiongping; Zeng, Qingle; Weng, Wen

    2009-07-10

    In this work, the enantioseparations of 1,1'-bi-2-naphthol (BINOL) and its three derivatives were performed on an immobilized polysaccharide-based chiral stationary phase, Chiralpak IA, under normal-phase mode. The effects of the content of polar modifier in the mobile phase and the column temperature on the retention and enantioseparation were investigated in detail. Temperature-induced inversion of elution order for BINOL was observed directly when n-hexane/2-propanol (92/8, v/v) was used as mobile phase. The isoenantioselective temperature (T(iso)) was calculated to be 31.4 degrees C. When n-hexane/2-propanol/THF (93/2/5, v/v/v) was used as mobile phase, the T(iso) value decreased to -8.2 degrees C. Entropically driven enantioseparation which had practical application was obtained successfully (separation factor being 1.189 and 1.332 at 25 degrees C and 50 degrees C, respectively). The corresponding thermodynamic parameters for other three binaphthyl compounds were compared with that for BINOL. Some inferences about chiral recognition mechanism were stressed.

  5. Influence of steric hindrance on enantioseparation of Dns-amino acids and pesticides on terguride based chiral selectors in capillary electrophoresis.

    Science.gov (United States)

    Honzátko, Ales; Cvak, Jan; Vaingátová, Silvie; Flieger, Miroslav

    2005-05-01

    Three urea derivatives of ergoline-based chiral selectors (CSs), differing in the size of the urea side chain, i.e. dimethyl- (CSI), diethyl- (CSII), and diisopropylurea (CSIII), were used to study the effect of steric hindrance on the enantioseparation of dansyl amino acids (Dns-AAs), pesticides, and mandelic acid under condition of capillary electrophoresis (CE) in linear polyacrylamide coated capillaries. A mixture of organic modifiers (MeOH/THF, 4:1 v/v) in a BGE consisting of 100 mM beta-alanine-acetate was used to increase the solubility of CSs up to 25 mM. The capillary was filled with CS (high UV absorption), and the inlet and outlet vials contained buffer solutions only. The best enantioseparation of Dns-AAs was achieved on CSI. Increased steric hindrance of the chiral binding site led to reduction of both enantioselectivity and resolution. The opposite pattern was observed for the separation of mandelic acid enantiomers, where the best enantioseparation and resolution was obtained with CSIII. Most of the pesticides studied reached maximum selectivity on the diethylurea ergoline derivative (CSII). Enantioseparation of fenoxaprop was found to be independent of steric hindrance.

  6. Chiral superconductors.

    Science.gov (United States)

    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.

  7. Conceptual design of distillation-based hybrid separation processes.

    Science.gov (United States)

    Skiborowski, Mirko; Harwardt, Andreas; Marquardt, Wolfgang

    2013-01-01

    Hybrid separation processes combine different separation principles and constitute a promising design option for the separation of complex mixtures. Particularly, the integration of distillation with other unit operations can significantly improve the separation of close-boiling or azeotropic mixtures. Although the design of single-unit operations is well understood and supported by computational methods, the optimal design of flowsheets of hybrid separation processes is still a challenging task. The large number of operational and design degrees of freedom requires a systematic and optimization-based design approach. To this end, a structured approach, the so-called process synthesis framework, is proposed. This article reviews available computational methods for the conceptual design of distillation-based hybrid processes for the separation of liquid mixtures. Open problems are identified that must be addressed to finally establish a structured process synthesis framework for such processes.

  8. The synthesis and characterization of novel brush-type chiral stationary phase based on terpenoid selector for resolution of chiral drugs

    OpenAIRE

    Wang Dao-Cai; Luo Jia; Yao Shun; Song Hang

    2016-01-01

    In the light of the chiral resolution mechanism and structures of brush-type CSP, a new chiral selector 4′-carboxyl-1′-ursolic methyl ester-3β-yl-benzoate has been prepared. Then the terpenoid chiral selector was covalently linked to 3-aminopropyl silica gel. Its structure identification data are provided by 1H NMR, MS and elementary analysis. The enantiodiscriminating capability of the brush-type CSP was evaluated by static adsorption experiment with methyl mandelate, aniline derivative of m...

  9. One-Pot Click Access to a Cyclodextrin Dimer-Based Novel Aggregation Induced Emission Sensor and Monomer-Based Chiral Stationary Phase

    Directory of Open Access Journals (Sweden)

    Xiaoli Li

    2016-11-01

    Full Text Available A ‘two birds, one stone’ strategy was developed via a one-pot click reaction to simultaneously prepare a novel cyclodextrin (CD dimer based aggregation induced emission (AIE sensor (AIE-DCD and a monomer based chiral stationary phase (CSP-MCD for chiral high performance liquid chromatography (CHPLC. AIE-DCD was found to afford satisfactory AIE response for specific detection of Zn2+ with a detection limit of 50 nM. CSP-MCD exhibits excellent enantioseparation ability toward dansyl amino acids, where the resolution of dansyl amino leucine reaches 5.43.

  10. Synthesis of Three Novel Chiral Binuclear Mn(Ⅲ)-Schiff-base Complexes and the Application in Asymmetric Epoxidation of trans-Stilbene

    Institute of Scientific and Technical Information of China (English)

    Yang SUN; Ning TANG; Xin Wen LIU; Wei Sheng LIU

    2004-01-01

    Three novel chiral binuclear Mn(Ⅲ)-Schiff-base complexes have been synthesized and the application of these complexes in the asymmetric epoxidation of trans-stilbene is described, catalytic mechanism is also discussed briefly.

  11. Towards the chiral metabolomics: Liquid chromatography-mass spectrometry based DL-amino acid analysis after labeling with a new chiral reagent, (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidine-2-carboxylate, and the application to saliva of healthy volunteers.

    Science.gov (United States)

    Mochizuki, Toshiki; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

    2015-05-22

    A novel triazine-type chiral derivatization reagent, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu), was developed for the highly sensitive and selective detection of chiral amines and amino acids by UPLC-MS/MS analysis. The enantiomers of amino acids were easily labeled with the reagents at room temperature within 40 min in an alkaline medium containing triethylamine. The diastereomers derived from proteolytic amino acids, except serine, were well separated under isocratic elution conditions by reversed-phase chromatography using an ODS column (Rs=1.2-9.0). DL-Serine was separated by use of an ADME column which has relatively higher polar surface than the conventional ODS column. The characteristic product ions, i.e., m/z 195.3 and m/z 209.3, were detected from all the diastereomers by the collision-induced dissociation of the protonated molecule. A highly sensitive detection on the amol-fmol level was obtained from the selected reaction monitoring (SRM) chromatogram. The chiral amines (e.g., adrenaline and noradrenaline) labeled with DMT-(S)-Pro-OSu were also well separated and sensitively detected by the present procedure. The method using DMT-(S)-Pro-OSu was used for the determination of DL-amino acids in the human saliva from healthy volunteers. Various L-amino acids were identified in the saliva. Furthermore, D-alanine (D-Ala) and D-proline (D-Pro) were also detected in relatively high concentrations (>5%). The ratio was higher in male saliva than in female saliva. However, the difference in the ratio of D-Ala for one day was not very high and the effect of foods and beverage seemed to be negligible. Based on the results using L-Ala-d3, the D-Ala in saliva seemed to be produced due to the racemization with some enzymes such as racemase. The racemization reaction was reversible, i.e., D-Ala-d3 was also racemized to L-Ala-d3 in saliva. Thus, care should be taken during the analysis of DL

  12. Synthesis and characterization of mesoporous silica modified with chiral auxiliaries for their potential application as chiral stationary phase.

    Science.gov (United States)

    Mayani, Vishal J; Abdi, S H R; Kureshy, R I; Khan, N H; Agrawal, Santosh; Jasra, R V

    2008-05-16

    Novel chiral stationary phase (CSP) based on chiral aminoalcohol immobilized on ordered mesoporous silica SBA-15 1a and standard silica 1b and their copper complexes 1a' and 1b', respectively, was synthesized as potential material for chiral ligand exchange chromatography (CLEC). Microanalysis, inductively coupled plasma spectroscopy (ICP), thermo-gravimetric analysis (TGA), cross polarized magic angle spinning (CP-MAS) (13)C NMR, Powder X-ray diffraction (PXRD), FTIR, N(2) adsorption isotherm, scanning electron microscopy (SEM), transmitted electron microscope (TEM) and solid reflectance UV-vis spectroscopy were used to characterize these materials. All the chiral stationary phases thus synthesized were used for the separation of different racemic compounds such as mandelic acid, 2,2'-dihydroxy-1,1'-binaphthalene BINOL) and diethyl tartrate by simple medium-pressure column chromatography. Successful enantio-separation of racemic mandelic acid was achieved with all the stationary phases but 1a and 1b gave slightly better resolution than their copper complexes 1a' and 1b'. Remarkably these materials are stable under the given experimental conditions and can be used repeatedly for several cycles of enantioresolution. It was observed that the porosity and surface area of the stationary phase play an important role in the chiral separation.

  13. Proliferation-resistant stable isotope separation based on optical pumping

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Cheol-Jung; Park, Hyunmin; Ko, Kwang-Hoon; Lim, Gwon; Kim, Taek-Soo; Rho, Sipyo; Cha, Yong-Ho; Han, Jamin; Jeong, Do-Young [Korea Atomic Energy Research Institute, Deajeon (Korea, Republic of). Quantum Optics Division

    2008-07-01

    Korea Atomic Energy Research Institute (KAERI) has developed the laser stable isotope separation based on optical pumping which can be applied to isotopes with small isotopic shift, provides high enrichment, is economical owing to high efficiency, and is proliferation-resistant. KAERI's laser isotope separation is based on isotope-selective optical pumping by very narrow bandwidth continuous wave laser followed by efficient infrared photo-ionization. KAERI demonstrated the pilot production of Tl-203 enriching over 97 % and separating 100 mg/hr. KAERI also demonstrated the separation of Yb-168 over 30 % and Yb- 176 over 97 % with tens of mg/hr. KAERI plans to scale up the production of Tl-203 up to 500 mg/hr and apply it to separation of Zn-67, Zn-70, Ba-130 and Ca-48 which are very important in medical industry and basic sciences. (author)

  14. A Separated Domain-Based Kernel Model for Trusted Computing

    Institute of Scientific and Technical Information of China (English)

    FANG Yanxiang; SHEN Changxiang; XU Jingdong; WU Gongyi

    2006-01-01

    This paper fist gives an investigation on trusted computing on mainstream operation system (OS). Based on the observations, it is pointed out that Trusted Computing cannot be achieved due to the lack of separation mechanism of the components in mainstream OS. In order to provide a kind of separation mechanism, this paper proposes a separated domain-based kernel model (SDBKM), and this model is verified by non-interference theory. By monitoring and simplifying the trust dependence between domains, this model can solve problems in trust measurement such as deny of service (DoS) attack, Host security, and reduce the overhead of measurement.

  15. Common screening approaches for efficient analytical method development in LC and SFC on columns packed with immobilized polysaccharide-derived chiral stationary phases.

    Science.gov (United States)

    Franco, Pilar; Zhang, Tong

    2013-01-01

    Owing to their remarkable enantioselectivity, versatility, and stability, immobilized polysaccharide-based chiral stationary phases (CSPs) have been successfully integrated into the tool box of many research and industry groups for the separation of enantiomers or stereoisomers by liquid and supercritical fluid chromatography. Due to the structurally diverse range of compounds available, efficient method development for chiral separations utilizing such CSPs is a challenging subject. In this chapter, we will discuss simplified screening protocols and straightforward approaches to achieve chiral separations in HPLC and SFC using the column series CHIRALPAK™ IA, IB, IC, and ID in reasonable time frame and with limited experimental work and a high success rate.

  16. 冠醚固定相的制备及手性拆分%Crown ether stationary phase for chiral separation

    Institute of Scientific and Technical Information of China (English)

    伍鹏; 汤波; 路振宇; 孔娇; 袁黎明

    2015-01-01

    以 R‐联萘酚为原料合成了 R‐(1,1′‐二萘基)‐20‐冠‐6,并将其涂敷于 C18硅胶(平均粒径5μm ,孔径120 nm)上制成了可用于高效液相色谱手性拆分的 R‐(1,1′‐二萘基)‐20‐冠‐6冠醚固定相(CSP).在以 pH =2的高氯酸溶液为流动相,流速为0.1 mL ・min‐1,柱温为25℃的条件下,研究了 CSP 对9种α‐氨基酸对映体的拆分能力.实验结果表明,有5种手性氨基酸(缬氨酸、苯甘氨酸、对羟基苯甘氨酸、谷氨酸、色氨酸)得到不同程度的拆分,说明 CSP 能对手性氨基酸进行一定的拆分.%In this paper ,R‐(1 ,1′‐ binaphthyl)‐20‐crown‐6 was synthesized and coated on C18 silica gel ,which was used as the chiral stationary phase with pH = 2 perchloric acid solution as mobile phase in high performance liquid chromatography .Five α‐amino acid enantiomers (valine ,phenylglycine ,hydroxyphenylglycine ,glutamate and tryptophan) had been separated . The results showed that the R‐(1 ,1′‐ binaphthyl)‐20‐crown‐6 crown ether stationary phase (CSP) possesses a good enantioselectivity for α‐ amino acid enantiomers .

  17. Free-standing chiral plasmonics

    Science.gov (United States)

    Leong, Eunice Sok Ping; Deng, Jie; Wu, Siji; Khoo, Eng Huat; Liu, Yan Jun

    2014-11-01

    Chiral plasmonic nanostructures offer the ability to achieve strong optical circular dichroism (CD) activity over a broad spectral range, which has been challenging for chiral molecules. Chiral plasmonic nanostructures have been extensively studied based on top-down and bottom-up fabrication techniques. Particularly, in the top-down electron-beam lithography, 3D plasmonic nanostructure fabrication involves layer-by-layer patterning and complex alignment, which is time-consuming and causes many defects in the structures. Here, we present a free-standing 3D chiral plamonic nanostructures using the electron-beam lithography technique with much simplified fabrication processes. The 3D chiral plasmonic nanostructures consist of a free-standing ultrathin silicon nitride membrane with well-aligned L-shape metal nanostructures on one side and disk-shape ones on the other side. The free-standing membrane provides an ultra-smooth metal/dielectric interface and uniformly defines the gap between the upper and lower layers in an array of chiral nanostructures. Such free-standing chiral plasmonic nanostructures exhibit strong CD at optical frequencies, which can be engineered by simply changing the disk size on one side of the membrane. Experimental results are in good agreement with the finite-difference time-domain simulations. Such free-standing chiral plasmonics holds great potential for chirality analysis of biomolecules, drugs, and chemicals.

  18. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)

    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.

  19. Orientation-dependent handedness and chiral design

    OpenAIRE

    Efrati, Efi; Irvine, William T. M.

    2013-01-01

    Chirality occupies a central role in fields ranging from biological self-assembly to the design of optical metamaterials. The definition of chirality, as given by Lord Kelvin, associates chirality with the lack of mirror symmetry: the inability to superpose an object on its mirror image. While this definition has guided the classification of chiral objects for over a century, the quantification of handed phenomena based on this definition has proven elusive, if not impossible, as manifest in ...

  20. Metal-organic frameworks for membrane-based separations

    Science.gov (United States)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  1. [[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

    Science.gov (United States)

    Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

    2014-09-01

    Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

  2. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    Directory of Open Access Journals (Sweden)

    Marina Rubina

    2014-07-01

    Full Text Available A novel class of chiral phosphanyl-oxazoline (PHOX ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands.

  3. Preparation of novel chiral stationary phase based on click chemistry for ligand exchange chromatography

    Institute of Scientific and Technical Information of China (English)

    Chun Mei Fu; Hong Yu Shi; Guang Sheng Qian; Zhang Wan Li

    2009-01-01

    Click chemistry was applied to immobilize L-proline derivative onto azide-modified silica gel to give a novel chiral stationary phase (denoted as click-CSP) for ligand exchange chromatography. The developed protocol combines the benefits of operational simplicity, exceptionally mild conditions and high surface loadings. The enantioselectivity α of some DE-amino acids on the click-CSP were found to be in the range from 1.13 to 3.46. The chromatographic resolutions of some DL-amino acids and the stability study firmly illustrate the potential of click chemistry for preparation chiral stationary phase for ligand exchange chromatography.

  4. Non-reciprocal few-photon devices based on chiral waveguide-emitter couplings

    CERN Document Server

    Gonzalez-Ballestero, C; Vidal, F J Garcia; Gonzalez-Tudela, A

    2016-01-01

    We demonstrate the possibility of designing efficient, non reciprocal few-photon devices by exploiting the chiral coupling between two waveguide modes and a single quantum emitter. We show how this system can induce non-reciprocal photon transport at the single-photon level and act as an optical diode. Afterwards, we also show how the same system shows a transistor-like behaviour for a two-photon input. The efficiency in both cases is shown to be large for feasible experimental implementations. Our results illustrate the potential of chiral waveguide-emitter couplings for applications in quantum circuitry.

  5. Chiral Graphene Quantum Dots.

    Science.gov (United States)

    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.

  6. Quinine-Based Zwitterionic Chiral Stationary Phase as a Complementary Tool for Peptide Analysis: Mobile Phase Effects on Enantio- and Stereoselectivity of Underivatized Oligopeptides.

    Science.gov (United States)

    Ianni, Federica; Sardella, Roccaldo; Carotti, Andrea; Natalini, Benedetto; Lindner, Wolfgang; Lämmerhofer, Michael

    2016-01-01

    Peptide stereoisomer analysis is of importance for quality control of therapeutic peptides, the analysis of stereochemical integrity of bioactive peptides in food, and the elucidation of the stereochemistry of peptides from a natural chiral pool which often contains one or more D-amino acid residues. In this work, a series of model peptide stereoisomers (enantiomers and diastereomers) were analyzed on a zwitterionic ion-exchanger chiral stationary phase (Chiralpak ZWIX(+) 5 µm), in order to investigate the retention and separation performance for such compounds on this chiral stationary phase and elucidate its utility for this purpose. The goal of the study focused on 1) investigations of the effects of the sample matrix used to dissolve the peptide samples; 2) optimization of the mobile phase (enabling deriving information on factors of relevance for retention and separation); and 3) derivation of structure-selectivity relationships. It turned out that small di- and tripeptides can be well resolved under optimized conditions, typically with resolutions larger than 1.5. The optimized mobile phase often consisted of methanol-tetrahydrofuran-water (49:49:2; v/v/v) with 25 mM formic acid and 12.5 mM diethylamine. This work proposes some guidance on which mobile phases can be most efficiently used for peptide stereoisomer separations on Chiralpak ZWIX. Chirality 28:5-16, 2016. © 2015 Wiley Periodicals, Inc.

  7. Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Thacker, Nathan C.; Lin, Zekai; McIsaac, Alexandra R.; Lin, Wenbin (UC)

    2016-05-06

    We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions.

  8. [Enantioseparation behavior of chiral stationary phases AD, AS and OD].

    Science.gov (United States)

    Li, Liqun; Fan, Jun; Zhang, Jing; Chen, Xiaodong; Wang, Tai; He, Jianfeng; Zhang, Weiguang

    2016-01-01

    Over the past decades, HPLC enantioseparation with chiral stationary phases (CSPs) has been widely applied in chiral analysis and preparation of new pharmaceuticals, pesticides, food, etc. Herein, enantioseparation of 20 chiral compounds have been carried out on three polysaccharide-based CSPs (EnantioPak AD, AS and OD) with normal phases by HPLC, separately. The influences of skeletal structure and the kinds of derivative groups on separation behaviors of these CSPs have been studied in detail. As results indicated, except for compound 13, the other compounds were baseline separated on EnantioPak AD, with most of resolution over 2. 0; in addition, better separation for acidic or basic compounds was achieved through adding acidic/basic additives into the mobile phase of hexane-alcohol. For four aromatic alcohols (compounds 13-16), their retention in the EnantioPak AD column showed a weakening tendency with increase of carbon number in side chain group, and the reverse trend of their resolution was observed. Furthermore, EnantioPak AD showed much better separation performance for eight compounds (13-20) than the others. In short, these results have provided some references for further investigation of separation behavior and applications of polysaccharide-based CSPs.

  9. Calixarene based chiral solvating agents for α-hydroxy carboxylic acids

    Science.gov (United States)

    Bozkurt, Selahattin

    2013-09-01

    Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine derivative with N-Phthaloyl-L-phenylalanine or (2S)-2-((benzyloxy)carbonyl)amino)-3-hydroxypropanoic acid or (2S,3R)-2-((benzyloxy)carbonyl)amino-3-hydroxybutanoic acid in 63-81% yield. The structures of these receptors were characterized by FTIR, 1H, 13C and 2D COSY NMR spectroscopy. The enantioselective recognition of these receptors towards the enantiomers of racemic carboxylic acids was studied by 1H NMR spectroscopy. The molar ratios of the chiral compounds with each of the enantiomers of guests were determined by using Job plots. The Job plots indicate that the hosts form 1:2 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. NMR studies demonstrated that the receptors function as highly effective chiral shift reagents for determining the enantiomeric purity of a series of carboxylic acids.

  10. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis.

    Science.gov (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel

    2015-03-01

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  11. Consistent chiral kinetic theory in Weyl materials: chiral magnetic plasmons

    CERN Document Server

    Gorbar, E V; Shovkovy, I A; Sukhachov, P O

    2016-01-01

    We argue that the correct definition of the electric current in the chiral kinetic theory for Weyl materials should include the Chern--Simons contribution that makes the theory consistent with the local conservation of the electric charge in electromagnetic and strain-induced pseudoelectromagnetic fields. By making use of such a kinetic theory, we study the plasma frequencies of collective modes in Weyl materials in constant magnetic and pseudomagnetic fields taking into account the effects of dynamical electromagnetism. We show that the collective modes are chiral plasmons. While the plasma frequency of the longitudinal collective mode coincides with the Langmuir one, this mode is unusual because it is characterized not only by oscillations of the electric current density, but also oscillations of the chiral current density. The latter are triggered by a dynamical version of the chiral electric separation effect. We also find that the plasma frequencies of the transverse modes split up in a magnetic field. T...

  12. 安非他明类毒品的手性对映体气相色谱-质谱分析%Enantiomer Separation and Determination of Amphetamines with Chiral Derivatization by Gas Chromatography-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    孟品佳

    2001-01-01

    采用手性衍生化试剂:(S)(-)N-三氟乙酰-1-脯胺酰氯(TPC)和(R)(+)-α-甲氯基-α-三氟甲基苯乙酸(MTPA)与安非他明类对映体反应生成非对映体衍生化产物,通过常规的GC/MS方法将其分离。本文较系统地考察了这两种手性试剂衍生化反应中溶剂、手性试剂用量、加热温度、反应时间等因素对安非他明类对映体衍生化结果的影响。实现了Am、MAm、MDA、MDMA、MDEA、MBDB等几种毒品对映体间的良好分离。%Most drugs of amphetamines contain chiral centers, which form different optical isomers, or enantiomers. Because different enantiomers have different pharmcological effect and have different machnism of metabolism. Besides, the ratio of the two eanatiomers could reflect the route and method used in the synthesis of the drugs. So the separation and determination of these eanantiomers for seizured samples or for biological samples became very important in the sence of forensic science.The paper used two chiral reagents: N-trifluroacetylprolyl chloride (TPC) and ( R )-( + )-α-methoxy-α-(trifluormethyl)phenylacetic acid (MTPA) to reach the purpose. They reacted with amphetamine enantiomers to form diasteromeric pairs, which possess some diffeences in physical and chemical natures and could be separated by GC/MS. The paper examined in detail some fectors such as the solvents, chiral reagent amounts, reaction time,temperature,etc. on the effect of chiral derivatization. Some enantiomers of amphetamine (Am),N-methylamphetamine(MAm),3,4-methylenedioxyamphetamin (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA), 3, 4-methylenedioxy-N-ethylamphetamine ( MDEA ) and N-methyl-1-( 3, 4-methylenedioxy )-2-butanamine (MBDB) were well separated each other.

  13. Software Based Traffic Separation at the Access Layer

    Directory of Open Access Journals (Sweden)

    Yona Andegelile

    2014-07-01

    Full Text Available Access Network is the subscriber part of the telecommunications network or the network connecting the subscribers to the Internet Service Providers (ISP [1]. In many countries including Tanzania access network is still predominantly made up of the copper cable based or other point to point wireless connections. This has kept the network in large proportions passive, inflexible and relatively unreliable [2]. This traditional network has long been tailored to the services generally provided i.e. voice, leased lines, Internet, corporate data and video conference, sometimes each provided by separate equipment and networks. This paper presents the study on approaches used by ISP in Tanzania to separate traffic in the access network. The paper also presents the effective way of traffic separation, whereby multiple hardware used to separate traffic currently has been replaced with single hardware. The traffic separation technique is based on creating logical links (software based for each traffic type inside single physical link, providing a differentiated QoS support for each type of traffic according to its individual QoS requirements.

  14. Chiral Quantum Optics

    CERN Document Server

    Lodahl, Peter; Stobbe, Søren; Schneeweiss, Philipp; Volz, Jürgen; Rauschenbeutel, Arno; Pichler, Hannes; Zoller, Peter

    2016-01-01

    At the most fundamental level, the interaction between light and matter is manifested by the emission and absorption of single photons by single quantum emitters. Controlling light--matter interaction is the basis for diverse applications ranging from light technology to quantum--information processing. Many of these applications are nowadays based on photonic nanostructures strongly benefitting from their scalability and integrability. The confinement of light in such nanostructures imposes an inherent link between the local polarization and propagation direction of light. This leads to {\\em chiral light--matter interaction}, i.e., the emission and absorption of photons depend on the propagation direction and local polarization of light as well as the polarization of the emitter transition. The burgeoning research field of {\\em chiral quantum optics} offers fundamentally new functionalities and applications both for single emitters and ensembles thereof. For instance, a chiral light--matter interface enables...

  15. Applications Of Chiral Perturbation Theory

    CERN Document Server

    Mohta, V

    2005-01-01

    Effective field theory techniques are used to describe the spectrum and interactions of hadrons. The mathematics of classical field theory and perturbative quantum field theory are reviewed. The physics of effective field theory and, in particular, of chiral perturbation theory and heavy baryon chiral perturbation theory are also reviewed. The geometry underlying heavy baryon chiral perturbation theory is described in detail. Results by Coleman et. al. in the physics literature are stated precisely and proven. A chiral perturbation theory is developed for a multiplet containing the recently- observed exotic baryons. A small coupling expansion is identified that allows the calculation of self-energy corrections to the exotic baryon masses. Opportunities in lattice calculations are discussed. Chiral perturbation theory is used to study the possibility of two multiplets of exotic baryons mixed by quark masses. A new symmetry constraint on reduced partial widths is identified. Predictions in the literature based ...

  16. Preparation and separation of DNA-wrapped carbon nanotubes.

    Science.gov (United States)

    Ao, Geyou; Zheng, Ming

    2015-01-01

    Purification of single-chirality single-wall carbon nanotubes (SWCNTs) from their synthetic mixture is a prerequisite for many applications. DNA-controlled carbon nanotube (CNT) purification has evolved over a decade along with other separation techniques utilizing different types of dispersing agents such as surfactants and polymers. The size of single-stranded DNA (ssDNA) libraries affords practically unlimited ways of coating SWCNTs. Recent developments in separating surfactant-dispersed SWCNTs by polymer aqueous two-phase (ATP) extraction has enabled rapid and efficient SWCNT separation on a larger volume scale. Applying the ATP separation method to DNA-SWCNT hybrids opens a new route for effective sorting of nanotubes into each and every single-chirality species. Here, we report protocols for purifying as many as 15 single-chirality nanotube species from a synthetic mixture based on the separation of DNA-SWCNTs by the aqueous two-phase (ATP) method.

  17. Electromagnetic Response of the Chiral Magnetic Effect in Weyl Semimetals

    CERN Document Server

    Barnes, Edwin; Minic, Djordje

    2016-01-01

    Weyl semimetals are predicted to realize the three-dimensional axial anomaly first discussed in particle physics. The anomaly leads to unusual transport phenomena such as the chiral magnetic effect in which an applied magnetic field induces a current parallel to the field. Here we investigate diagnostics of the axial anomaly based on the fundamental equations of axion electrodynamics. We find that materials with Weyl nodes of opposite chirality and finite energy separation immersed in a uniform magnetic field exhibit an anomaly-induced oscillatory magnetic field with a period set by the chemical potential difference of the nodes. In the case where a chemical potential imbalance is created by applying parallel electric and magnetic fields, we find a suppression of the magnetic field component parallel to the electric field inside the material for rectangular samples, suggesting that the chiral magnetic current opposes this imbalance. For cylindrical geometries, we instead find an enhancement of this magnetic f...

  18. Chiral Nanoscience and Nanotechnology

    OpenAIRE

    Dibyendu S. Bag; T.C. Shami; K.U. Bhasker Rao

    2008-01-01

    The paper reviews nanoscale science and technology of chiral molecules/macromolecules-under twosubtopics-chiral nanotechnology and nano-chiral technology. Chiral nanotechnology discusses thenanotechnology, where molecular chirality plays a role in the properties of materials, including molecularswitches, molecular motors, and other molecular devices; chiral supramolecules and self-assembled nanotubesand their functions are also highlighted. Nano-chiral technology  describes the nanoscale appr...

  19. HYDROGEN BONDING IN POLYMERIC ADSORBENTS BASED ADSORPTION AND SEPARATION

    Institute of Scientific and Technical Information of China (English)

    XUMancai; SHIZuoqing; 等

    2000-01-01

    After a concise introduction of hydrogen bonding effects in solute-solute and solute-solvent bonding,the design of polymeric adsorbents based on hydrogen bonding ,selectivity in adsorption through hydrogen bonding,and characterization of hydrogen bonding in adsorption and separation were reviewed with 28 references.

  20. NH-type of chiral Ni(II) complexes of glycine Schiff base: design, structural evaluation, reactivity and synthetic applications.

    Science.gov (United States)

    Bergagnini, Mackenzie; Fukushi, Kazunobu; Han, Jianlin; Shibata, Norio; Roussel, Christian; Ellis, Trevor K; Aceña, José Luis; Soloshonok, Vadim A

    2014-02-28

    The work being reported here deals with the design of a new type of "N-H" Ni(II) complexes of glycine Schiff bases and study general aspects of their reactivity. It was confirmed that the presence of NH function in these Ni(II) complexes does not interfere with the homologation of the glycine residue, rendering these derivatives of high synthetic value for the general synthesis of α-amino acids. In particular, the practical application of these NH-type complexes was demonstrated by asymmetric synthesis of various β-substituted pyroglutamic acids via Michael addition reactions with chiral Michael acceptors.

  1. Effect of the water content on the retention and enantioselectivity of albendazole and fenbendazole sulfoxides using amylose-based chiral stationary phases in organic-aqueous conditions.

    Science.gov (United States)

    Materazzo, Sabrina; Carradori, Simone; Ferretti, Rosella; Gallinella, Bruno; Secci, Daniela; Cirilli, Roberto

    2014-01-31

    Four commercially available immobilized amylose-derived CSPs (Chiralpak IA-3, Chiralpak ID-3, Chiralpak IE-3 and Chiralpak IF-3) were used in the HPLC analysis of the chiral sulfoxides albendazole (ABZ-SO) and fenbendazole (FBZ-SO) and their in vivo sulfide precursor (ABZ and FBZ) and sulfone metabolite (ABZ-SO2 and FBZ-SO2) under organic-aqueous mode. U-shape retention maps, established by varying the water content in the acetonitrile- and ethanol-water mobile phases, were indicative of two retention mechanisms operating on the same CSP. The dual retention behavior of polysaccharide-based CSPs was exploited to design greener enantioselective and chemoselective separations in a short time frame. The enantiomers of ABZ-SO and FBZ-SO were baseline resolved with water-rich mobile phases (with the main component usually being 50-65% water in acetonitrile) on the IF-3 CSP and ethanol-water 100:5 mixture on the IA-3 and IE-3 CSPs. A simultaneous separation of ABZ (or FBZ), enantiomers of the corresponding sulfoxide and sulfone was achieved on the IA-3 using ethanol-water 100:60 (acetonitrile-water 100:100 for FBZ) as a mobile phase.

  2. 新型键合纤维素手性固定相的制备及其拆分性能评价%Preparation of a new immobilized cellulose-based chiral stationary phase and its enantioseparation behaviors

    Institute of Scientific and Technical Information of China (English)

    涂鸿盛; 范军; 谭艺; 林纯; 华江颖; 章伟光

    2014-01-01

    The immobilized polysaccharide-based chiral stationary phase has attracted consid-erable attention over the past decades due to its high chemical stability,good solvent resist-ance,great enantioseparation ability,etc. In this study,a new immobilized cellulose chiral sta-tionary phase(denoted as ImCel)was prepared through the Staudinger reaction of 6-azido-6-deoxy-cellulose-3,5-dichlorophenylcarbamate and aminopropyl silica gel. The enantioseparation performance of the Imcellfor 20 pairs of chiral analytes and the effect of non-standard solvents have been investigated by high performance liquid chromatography. Baseline separations of 17 pairs of enantiomers were achieved on the ImCel. The separation ability of the Imcellin the nor-mal mode was much better than in reversed mode. In addition,the Imcellshowed good chemi-cal stability in the non-standard mobile phase due to the covalent bonds between the cellulose chiral selectors and silica support. Moreover,it exhibited complementarity with another immo-bilized-cellulose chiral stationary phase containing 3,5-dimethylphenylcarbamate groups for the separation of a series of 9-fluorenylmethyloxycarbonyl ( fmoc )-derived amino acids. The reversal of enantiomer elution order induced by the difference of the substituents in chiral sta-tionary phase was observed under the same chromatographic conditions. In brief,a new immo-bilized cellulose chiral stationary phase with high stability and good separation performance was developed in this work.%键合型多糖手性固定相因具有化学稳定性高和溶剂耐受性好的特点而受到研究者的极大关注。采用施陶丁格( Staudinger)反应将6-叠氮-6-脱氧纤维素-3,5-二氯苯基氨基甲酸酯键合到氨丙基硅胶上得到一种新的键合型手性固定相( ImCel),研究了其手性分离性能,并探讨了非常规流动相(如氯仿、四氢呋喃等)的影响。结果表明,在20对手性化合物中,17对在合适的流动

  3. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    Science.gov (United States)

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids.

  4. Musical Sound Separation Based on Binary Time-Frequency Masking

    Directory of Open Access Journals (Sweden)

    Wang DeLiang

    2009-01-01

    Full Text Available The problem of overlapping harmonics is particularly acute in musical sound separation and has not been addressed adequately. We propose a monaural system based on binary time-frequency masking with an emphasis on robust decisions in time-frequency regions, where harmonics from different sources overlap. Our computational auditory scene analysis system exploits the observation that sounds from the same source tend to have similar spectral envelopes. Quantitative results show that utilizing spectral similarity helps binary decision making in overlapped time-frequency regions and significantly improves separation performance.

  5. Single channel blind source separation based on ICA feature extraction

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new technique is proposed to solve the blind source separation (BSS) given only a single channel observation. The basis functions and the density of the coefficients of source signals learned by ICA are used as the prior knowledge. Based on the learned prior information the learning rules of single channel BSS are presented by maximizing the joint log likelihood of the mixed sources to obtain source signals from single observation,in which the posterior density of the given measurements is maximized. The experimental results exhibit a successful separation performance for mixtures of speech and music signals.

  6. The determination of botanical origin of honeys based on enantiomer distribution of chiral volatile organic compounds.

    Science.gov (United States)

    Špánik, Ivan; Pažitná, Alexandra; Šiška, Peter; Szolcsányi, Peter

    2014-09-01

    The enantiomer ratios of chiral volatile organic compounds in rapeseed, chestnut, orange, acacia, sunflower and linden honeys were determined by multi-dimensional gas chromatography using solid phase microextraction (SPME) as a sample pre-treatment procedure. Linalool oxides, linalool and hotrienol were present at the highest concentration levels, while significantly lower amounts of α-terpineol, 4-terpineol and all isomers of lilac aldehydes were found in all studied samples. On the other hand, enantiomer distribution of some chiral organic compounds in honey depends on their botanical origin. The significant differences in enantiomer ratio of linalool were observed for rapeseed honey that allows us to distinguish this type of honey from the other ones. The enantiomer ratios of lilac aldehydes were useful for distinguishing of orange and acacia honey from other studied monofloral honeys. Similarly, different enantiomer ratio of 4-terpineol was found for sunflower honeys.

  7. Chiral Pd aqua complex-catalyzed asymmetric C-C bond-forming reactions: a Brønsted acid-base cooperative system.

    Science.gov (United States)

    Sodeoka, Mikiko; Hamashima, Yoshitaka

    2009-10-21

    Chiral cationic Pd aqua complexes can function as acid-base catalysts, effectively activating active methylene and methine compounds to give chiral Pd enolates. It is noteworthy that such enolate formation occurs with concomitant formation of a strong protic acid. Although the reactivity of the Pd enolate itself is not sufficient for reactions with carbon-based electrophiles, its cooperative action with the protic acid to activate the electrophiles allows the desired C-C bond-forming reactions to proceed smoothly in a highly enantioselective manner. Based on this mechanistic feature, reactions with acetals have been developed; these are difficult to achieve using conventional basic enolate chemistry.

  8. Enantioselective recognition at mesoporous chiral metal surfaces

    Science.gov (United States)

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-02-01

    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.

  9. Comparison of the Separation Performances of Cinchona Alkaloid-Based Zwitterionic Stationary Phases in the Enantioseparation of β2- and β3-Amino Acids

    Directory of Open Access Journals (Sweden)

    István Ilisz

    2014-12-01

    Full Text Available The enantiomers of twelve unusual β2- and β3-homoamino acids containing the same side-chains were separated on chiral stationary phases containing a quinine- or quinidine-based zwitterionic ion-exchanger as chiral selector. The effects of the mobile phase composition, the nature and concentration of the acid and base additives and temperature on the separations were investigated. The changes in standard enthalpy, ∆(∆H°, entropy, ∆(∆S°, and free energy, ∆(∆G°, were calculated from the linear van’t Hoff plots derived from the ln α vs. 1/T curves in the studied temperature range (10–50 °C. The values of the thermodynamic parameters depended on the nature of the selectors, the structures of the analytes, and the positions of the substituents on the analytes. A comparison of the zwitterionic stationary phases revealed that the quinidine-based ZWIX(−™ column exhibited much better selectivity for both β2- and β3-amino acids than the quinine-based ZWIX(+™ column, and the separation performances of both the ZWIX(+™ and ZWIX(−™ columns were better for β2-amino acids. The elution sequence was determined in some cases and was observed to be R < S and S < R on the ZWIX(+™ and ZWIX(−™ columns, respectively.

  10. Chiral Induction with Chiral Conformational Switches in the Limit of Low "Sergeants to Soldiers" Ratio

    DEFF Research Database (Denmark)

    Nuermaimaiti, Ajiguli; Bombis, Christian; Knudsen, Martin Markvard

    2014-01-01

    " mechanism for an oligo(phenylene ethynylene) based chiral conformational switch by coadsorbing it with an intrinsically chiral seed on Au(111). Through statistical analysis of scanning tunneling microscopy (STM) data we demonstrate successful chiral induction with a very low concentration of seeding...

  11. A PC based control system for the CERN ISOLDE separators

    Energy Technology Data Exchange (ETDEWEB)

    Billinge, R.; Bret, A.; Deloose, I.; Pace, A.; Shering, G. [European Organization for Nuclear Research, Geneva (Switzerland)

    1992-12-01

    The control system of the two isotope separators of CERN, named ISOLDE, is being completely redesigned with the goal of having a flexible, high performance and inexpensive system. A new architecture that makes heavy use of the commercial software and hardware available for the huge Personal Computer (PC) market is being implemented on the 1700 geographically distributed control channels of the separators. 8 MS-DOS{sup TM} i386-based PCs with about 80 acquisition/control boards are used to access the equipments while 3 other PCs running Microsoft Windows{sup TM} and Microsoft Excel{sup TM} are used as consoles, the whole through a Novell{sup TM} Local Area Network with a PC Disk Server used as a database. This paper describes the interesting solutions found and discusses the reduced programming work load and costs that are expected to build the system before the start of the separators in March 1992. (author).

  12. Shape-based separation of microparticles with magnetic fields

    Science.gov (United States)

    Wang, Cheng; Zhou, Ran

    2016-11-01

    Precise manipulations, e.g., sorting and focusing, of nonspherical micro-particles in fluidic environment has important applications in the fields of biology sciences and biomedical engineering. However, non-spherical microparticles are hard to manipulate because they tumble in shear flows. Most of existing techniques, including traditional filtration and centrifugation, and recent microfluidic technology, have difficulty in separating microparticles by shape. We demonstrate a novel shape-based separation technique by combining external magnetic fields with pressure-driven flows in a microchannel. Due to the magnetic field, prolate ellipsoidal particles migrate laterally at different speeds than the spherical ones, leading to effective separation. Our experimental investigations reveal the underlying physical mechanism of the observed shape-dependent migration. We find that the magnetic field breaks the rotational symmetry of the nonspherical particles, and induces shape-dependent lift force and migration velocity.

  13. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations). For a chiral molecule, which must crystallize in a chiral space group, the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant.

  14. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    NgSeikWng; HUSheng-Zhi

    2003-01-01

    This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations).For a chiral molecule,which must crystallize in a chiral space group,the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant.

  15. Towards the chiral metabolomics: Liquid chromatography–mass spectrometry based DL-amino acid analysis after labeling with a new chiral reagent, (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate, and the application to saliva of healthy volunteers

    Energy Technology Data Exchange (ETDEWEB)

    Mochizuki, Toshiki; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo’oka, Toshimasa, E-mail: toyooka@u-shizuoka-ken.ac.jp

    2015-05-22

    Highlights: • A novel chiral labeling reagent was synthesized. • Analysis of DL-amino acids was performed by UPLC–ESI-MS/MS. • Efficient enantioseparation and detection of DL-amino acids were performed. • DL-Amino acid in saliva was successfully determined under mild conditions. - Abstract: A novel triazine-type chiral derivatization reagent, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu), was developed for the highly sensitive and selective detection of chiral amines and amino acids by UPLC–MS/MS analysis. The enantiomers of amino acids were easily labeled with the reagents at room temperature within 40 min in an alkaline medium containing triethylamine. The diastereomers derived from proteolytic amino acids, except serine, were well separated under isocratic elution conditions by reversed-phase chromatography using an ODS column (R{sub s} = 1.2–9.0). DL-Serine was separated by use of an ADME column which has relatively higher polar surface than the conventional ODS column. The characteristic product ions, i.e., m/z 195.3 and m/z 209.3, were detected from all the diastereomers by the collision-induced dissociation of the protonated molecule. A highly sensitive detection on the amol–fmol level was obtained from the selected reaction monitoring (SRM) chromatogram. The chiral amines (e.g., adrenaline and noradrenaline) labeled with DMT-(S)-Pro-OSu were also well separated and sensitively detected by the present procedure. The method using DMT-(S)-Pro-OSu was used for the determination of DL-amino acids in the human saliva from healthy volunteers. Various L-amino acids were identified in the saliva. Furthermore, D-alanine (D-Ala) and D-proline (D-Pro) were also detected in relatively high concentrations (>5%). The ratio was higher in male saliva than in female saliva. However, the difference in the ratio of D-Ala for one day was not very high and the effect of foods and beverage

  16. Separating Stars and Galaxies Probabilistically Based on Color

    Science.gov (United States)

    Strait, Victoria

    2015-01-01

    Using photometric data from the Deep Lens Survey (DLS) we develop a star-galaxy separation algorithm based on objects' colors in six bands (B,V,R,z,J,K). Using a training set selected from a catalog of stars classified via their DLS shapes, we fit a third order polynomial to the filtered color-color data to approximate the stellar locus. Our algorithm produces a weighted probability of an object being a star. Based on each object's distance from the stellar locus in color-color space, we fit the resulting histogram as the sum of two Gaussians. We find that near-infrared information (J and K) provide the best separation, but explore using optical information alone to determine the classification as well. Our results demonstrate that the use of color information in a probabilistic algorithm has the potential to dramatically improve star-galaxy classification when used in conjunction with existing shape-based algorithms.​

  17. Resolution of the Chiral Drugs

    Institute of Scientific and Technical Information of China (English)

    DENG; JinGen

    2001-01-01

    Chiral drugs are generally not permitted to be used in racemic form so that unintended side effects and unnecessary environmental hazards are avoided. Moreover, homochiral molecules are required immediately to progress key toxicological and clinical studies in the drug discovery. One series of technologies which can rapidly supply homochiral compounds is the separation of racemates, and of those the technique of crystallization of diastereomers is extremely effective-principally because it is simple to operate and it affords both enantiomers. In classical resolution via diastereoisomeric salt formation, the resolved compounds are limited to a given racemic acid or base and the choice of a suitable resolving agent for a racemic target compound is achieved by time-consuming trial-and-error procedure.  ……

  18. Resolution of the Chiral Drugs

    Institute of Scientific and Technical Information of China (English)

    DENG JinGen; ZHU Jin

    2001-01-01

    @@ Chiral drugs are generally not permitted to be used in racemic form so that unintended side effects and unnecessary environmental hazards are avoided. Moreover, homochiral molecules are required immediately to progress key toxicological and clinical studies in the drug discovery. One series of technologies which can rapidly supply homochiral compounds is the separation of racemates, and of those the technique of crystallization of diastereomers is extremely effective-principally because it is simple to operate and it affords both enantiomers. In classical resolution via diastereoisomeric salt formation, the resolved compounds are limited to a given racemic acid or base and the choice of a suitable resolving agent for a racemic target compound is achieved by time-consuming trial-and-error procedure.

  19. Synthetic Applications of Chiral Furanboronate

    Institute of Scientific and Technical Information of China (English)

    CHAN KinFai; WONG Henry N,C.

    2001-01-01

    @@ We recently uncovered that consecutive reactions of chiral furfural-boronate 1 with a lithium alkoxide and a nucleophile led to the formation of alcohols 2 with good diastereoselection in favor of S-configuration at the newly generated chiral carbon. In addition, it was also found that 2a and 2b were chromatographically separable on a silica gel column. This reaction is believed to involve a tetrahedral borate intermediate, as can be substantiated by 11BNMR spectroscopic studies. Chiral furanmethanolboronates 2a(or 2b) underwent a palladium-catalyzed Suzuki coupling to form enantiomerically pure furans 3, which can be further converted to the synthetically useful hydroxypyranones 4.1,2,3 In addition, Mukaiyama reaction of 1 also led to chromatographically separable diastereomeric aldol-products. The scope and limitation of these conversions will be discussed.

  20. Synthetic Applications of Chiral Furanboronate

    Institute of Scientific and Technical Information of China (English)

    CHAN; KinFai

    2001-01-01

    We recently uncovered that consecutive reactions of chiral furfural-boronate 1 with a lithium alkoxide and a nucleophile led to the formation of alcohols 2 with good diastereoselection in favor of S-configuration at the newly generated chiral carbon. In addition, it was also found that 2a and 2b were chromatographically separable on a silica gel column. This reaction is believed to involve a tetrahedral borate intermediate, as can be substantiated by 11BNMR spectroscopic studies. Chiral furanmethanolboronates 2a(or 2b) underwent a palladium-catalyzed Suzuki coupling to form enantiomerically pure furans 3, which can be further converted to the synthetically useful hydroxypyranones 4.1,2,3 In addition, Mukaiyama reaction of 1 also led to chromatographically separable diastereomeric aldol-products. The scope and limitation of these conversions will be discussed.  ……

  1. Enantiomeric Separation and Determination of the Enantiomeric Impurity of Armodafinil by Capillary Electrophoresis with Sulfobutyl Ether-β-cyclodextrin as Chiral Selector

    Directory of Open Access Journals (Sweden)

    Bingren Xiang

    2011-12-01

    Full Text Available A selective capillary electrophoresis method using sulfobutyl ether-β-cyclodextrin as a chiral selector was developed and validated for the determination of the enantiomeric impurity of (R-modafinil, i.e., armodafinil. Several parameters were optimized for a satisfactory enantioresolution, including the type and concentration of chiral selector and organic modifier, pH of background electrolyte (BGE, capillary temperature. The finally adopted condition was: 20 mmol/L phosphate buffer at pH 7.5, containing 20 mmol/L sulfobutyl ether-β-cyclodextrin and 20% methanol, at temperature of 25 °C. A good resolution of 3.3 for the two enantiomers of modafinil was achieved by applying the optimal conditions. The limit of detection (LOD and limit of quantification (LOQ of (S-modafinil were 1.25 μg/mL and 2.50 μg/mL, respectively. The established method was also proven to display good selectivity, repeatability, linearity and accuracy. Finally, the method was used to investigate the enantiomeric purity of armodafinil in bulk samples.

  2. Enantiomeric separation and determination of the enantiomeric impurity of armodafinil by capillary electrophoresis with sulfobutyl ether-β-cyclodextrin as chiral selector.

    Science.gov (United States)

    Wang, Wei; Xiang, Suyun; Zhou, Xiaojuan; Ji, Yibing; Xiang, Bingren

    2011-12-30

    A selective capillary electrophoresis method using sulfobutyl ether-β-cyclodextrin as a chiral selector was developed and validated for the determination of the enantiomeric impurity of (R)-modafinil, i.e., armodafinil. Several parameters were optimized for a satisfactory enantioresolution, including the type and concentration of chiral selector and organic modifier, pH of background electrolyte (BGE), capillary temperature. The finally adopted condition was: 20 mmol/L phosphate buffer at pH 7.5, containing 20 mmol/L sulfobutyl ether-β-cyclodextrin and 20% methanol, at temperature of 25 °C. A good resolution of 3.3 for the two enantiomers of modafinil was achieved by applying the optimal conditions. The limit of detection (LOD) and limit of quantification (LOQ) of (S)-modafinil were 1.25 μg/mL and 2.50 μg/mL, respectively. The established method was also proven to display good selectivity, repeatability, linearity and accuracy. Finally, the method was used to investigate the enantiomeric purity of armodafinil in bulk samples.

  3. Evaluation of the chiral recognition properties as well as the column performance of four chiral stationary phases based on cellulose (3,5-dimethylphenylcarbamate) by parallel HPLC and SFC.

    Science.gov (United States)

    Nelander, Hanna; Andersson, Shalini; Ohlén, Kristina

    2011-12-30

    The performance of four commercially available cellulose tris(3,5-dimethylphenylcarbamate) based chiral stationary phases (CSPs) was evaluated with parallel high performance liquid chromatography (HPLC) and super critical fluid chromatography (SFC). Retention, enantioselectivity, resolution and efficiency were compared for a set of neutral, basic and acidic compounds having different physico-chemical properties by using different mobile phase conditions. Although the chiral selector is the same in all the four CSPs, a large difference in the ability to retain and resolve enantiomers was observed under the same chromatographic conditions. We believe that this is mainly due to differences in the silica matrix and immobilization techniques used by the different vendors. An extended study of metoprolol and structure analogues gave a deeper understanding of the accessibility of the chiral discriminating interactions and its impact on the resolution of the racemic compounds on the four CSPs studied. Also, a clear difference in enantioselectivity is observed between SFC and LC mode, hydrogen bonding was found to play an important role in the differential binding of the enantiomers to the CSPs.

  4. High-performance liquid chromatographic enantioseparation of cyclic β-aminohydroxamic acids on zwitterionic chiral stationary phases based on Cinchona alkaloids

    Energy Technology Data Exchange (ETDEWEB)

    Lajkó, Gyula [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Orosz, Tímea [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Grecsó, Nóra [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Fekete, Beáta; Palkó, Márta; Fülöp, Ferenc [Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Lindner, Wolfgang [Department of Analytical Chemistry, University of Vienna, Währingerstrasse 38, A-1090 Vienna (Austria); Péter, Antal [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Ilisz, István, E-mail: ilisz@chem.u-szeged.hu [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary)

    2016-05-19

    Cyclic β-aminohydroxamic acid enantiomer pairs were stereoselectively separated by high-performance liquid chromatography on the recently developed Cinchona alkaloid-based zwitterionic chiral stationary phases Chiralpak ZWIX(+)™, ZWIX(−)™, ZWIX(+A) and ZWIX(−A). The results of variation of the applied chromatographic conditions, such as the bulk solvent composition, the concentrations and ratio of the acid and base additives, the presence of water as mobile phase additive and the counter-ion concentration furnished a better understanding of the retention mechanism. A thermodynamic study in the temperature range 5–50 °C revealed enthalpy-controlled enantiodiscrimination in all cases. The structure–selectivity relationships clearly indicated the importance of the strereochemistry of the functional groups. From an enantiorecognition aspect, the diexo position of the functional groups always proved more favorable than the diendo position. The elution sequence was determined in all cases and was found to reversed when ZWIX(+)™ was changed to ZWIX(−)™ or ZWIX(+A) to ZWIX(−A). - Highlights: • Zwitterionic columns were applied for the enantioseparation of cyclic β-aminohydroxamic acids. • Enthalpy controlled enantiodiscriminations were observed. • Enantiorecognition depended on the stereochemistry of the functional group.

  5. Ultra-compact chiral metamaterial with negative refractive index based on miniaturized structure

    Science.gov (United States)

    Li, Minhua; Song, Jian; Wu, Fei

    2017-03-01

    An ultra-compact chiral metamaterial with thin thickness and small unit cells is proposed. Echelon meandered conjugated gammadions are introduced into the planar miniaturized design. In particular, the ratio between period (p) and resonant wavelength (λ) is as small as 1/10.8 in experiment. Negative refractive indexes for circularly polarized waves are demonstrated and the effective parameters are retrieved. The effects of the length of the swing arms, number of folded lines and dielectric layer thickness on the optical activity have also been investigated. This miniaturized structure has great potential application in electronic and photonic devices with small size and integration.

  6. Chiral manganese (IV) complexes derived from Schiff base ligands: Synthesis, characterization, in vitro cytotoxicity and DNA/BSA interaction.

    Science.gov (United States)

    Li, Zhen; Niu, Meiju; Chang, Guoliang; Zhao, Changqiu

    2015-12-01

    Two new couples of chiral manganese (IV) complexes with Schiff-base ligands, Λ-[Mn(R-L(1))2]·2(CH3OH) (Λ-1) and Δ-[Mn(S-L(1))2]·2(CH3OH) (Δ-1), Λ-[Mn(R-L(2))2]·(H2O)2 (Λ-2) and Δ-[Mn(S-L(2))2]·(H2O)2 (Δ-2), {H2L(1)=(R/S)-(±)-1-[(1-hydroxymethyl-propylimino)-methyl]-naphthalen-2-ol, H2L(2)=(R/S)-(±)-1-[(1-Hydroxymethyl-2-phenyl-ethylimino)-methyl]-naphthalen-2-ol} have been synthesized, and fully characterized by elemental analyses, UV-Vis spectrum, circular dichroism spectrum, FT-IR spectrum, mass spectrum, and single crystal X-ray diffraction (SXRD). The interaction of the four chiral Mn (IV) complexes with CT-DNA and BSA were also investigated by various spectroscopic techniques (UV-visible, fluorescence spectroscopic). The results show that the Δ-complexes exhibit more efficient CT-DNA interaction with respect to the Λ-complexes. All the complexes could quench the intrinsic fluorescence of BSA by a static quenching process. In addition, the vitro cytotoxicity of these complexes toward four kinds of cancerous cell lines (A549, HeLa, HL-60, and Caco-2) was assayed by the MTT method, which exhibited to be selectively active against certain cell lines.

  7. Ultra-broad band and dual-band highly efficient polarization conversion based on the three-layered chiral structure

    Science.gov (United States)

    Xu, Kai-kai; Xiao, Zhong-yin; Tang, Jing-yao; Liu, De-jun; Wang, Zi-hua

    2016-07-01

    In the paper, a novel three-layered chiral structure is proposed and investigated, which consists of a split-ring resonator sandwiched between two layers of sub-wavelength gratings. This designed structure can achieve simultaneously asymmetric transmission with an extremely broad bandwidth and high amplitude as well as multi-band 90° polarization rotator with very low dispersion. Numerical simulations adopted two kinds of softwares with different algorithms demonstrate that asymmetric parameter can reach a maximum of 0.99 and over than 0.8 from 4.6 to 16.8 GHz, which exhibit magnitude and bandwidth improvement over previous chiral metamaterials in microwave bands (S, C, X and Ku bands). Specifically, the reason of high amplitude is analyzed in detail based on the Fabry-perot like resonance. Subsequently, the highly efficient polarization conversion with very low dispersion between two orthogonal linearly polarized waves is also analyzed by the optical activity and ellipticity. Finally, the electric fields are also investigated and further demonstrate the correctness of the simulated and calculated results.

  8. Stegosaurus chirality

    OpenAIRE

    Cameron, R.P.; Cameron, J. A.; Barnett, S. M.

    2016-01-01

    We explain that Stegosaurus exhibited exterior chirality and observe that the largest plate in particular of USNM 4394, USNM 4714, DMNS 2818 and NHMUK R36730 appears to have tilted to the right rather than to the left in each case. Several instances in which Stegosaurus specimens have been confused with their distinct, hypothetical mirror-image forms are highlighted. We believe our findings to be consistent with the hypothesis that Stegosaurus's plates acted primarily as display structures. A...

  9. Fixed-point blind source separation algorithm based on ICA

    Institute of Scientific and Technical Information of China (English)

    Hongyan LI; Jianfen MA; Deng'ao LI; Huakui WANG

    2008-01-01

    This paper introduces the fixed-point learning algorithm based on independent component analysis (ICA);the model and process of this algorithm and simulation results are presented.Kurtosis was adopted as the estimation rule of independence.The results of the experiment show that compared with the traditional ICA algorithm based on random grads,this algorithm has advantages such as fast convergence and no necessity for any dynamic parameter,etc.The algorithm is a highly efficient and reliable method in blind signal separation.

  10. Correlation-based temperature and emissivity separation algorithm

    Institute of Scientific and Technical Information of China (English)

    CHENG Jie; LIU QinHuo; LI XiaoWen; XIAO Qing; LIU Qiang; DU YongMing

    2008-01-01

    Based on analyzing the relationship between the atmospheric downward radiance and surface emissivity, this paper proposes a correlation criterion to optimize surface temperature during the process of temperature and emissivity separation from thermal infrared hyperspectral data, and puts forward the correlation-based temperature and emissivity separation algorithm (CBTES). The algorithm uses the correlation between the atmospheric downward radiance and surface emissivity to optimize surface temperature, and obtains surface emissivity with this temperature. The accuracy of CBTES was evaluated by the simulated thermal infrared hyperspectral data. The simulated results show that the CBTES can achieve high accuracy of temperature and emissivity inversion. CBTES has been compared with the iterative spectrally smooth temperature/emissivity separation (ISSTES), and the comparison results show that they have relative accuracy. Besides, CBTES is insensitive to the instrumental random noise and the change of atmospheric downward radiance during the measurements. As regards the nonisothermal pixel, its radiometric temperature changes slowly with the wavenumber when its emissivity is defined as r-emissivity. The CBTES can be used to derive the equivalent temperature of nonisothermal pixel in a narrow spectral region when we assumed that the radiometric temperature is invariable in the narrow spectral region. The derived equivalent temperatures in multi-spectral regions in 714-250cm-1 can characterize the change trend of nonisothermal pixel's radiometric temperature.

  11. Correlation-based temperature and emissivity separation algorithm

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Based on analyzing the relationship between the atmospheric downward radiance and surface emis- sivity, this paper proposes a correlation criterion to optimize surface temperature during the process of temperature and emissivity separation from thermal infrared hyperspectral data, and puts forward the correlation-based temperature and emissivity separation algorithm (CBTES). The algorithm uses the correlation between the atmospheric downward radiance and surface emissivity to optimize surface temperature, and obtains surface emissivity with this temperature. The accuracy of CBTES was evalu- ated by the simulated thermal infrared hyperspectral data. The simulated results show that the CBTES can achieve high accuracy of temperature and emissivity inversion. CBTES has been compared with the iterative spectrally smooth temperature/emissivity separation (ISSTES), and the comparison results show that they have relative accuracy. Besides, CBTES is insensitive to the instrumental random noise and the change of atmospheric downward radiance during the measurements. As regards the noniso- thermal pixel, its radiometric temperature changes slowly with the wavenumber when its emissivity is defined as r-emissivity. The CBTES can be used to derive the equivalent temperature of nonisothermal pixel in a narrow spectral region when we assumed that the radiometric temperature is invariable in the narrow spectral region. The derived equivalent temperatures in multi-spectral regions in 714―1250 cm?1 can characterize the change trend of nonisothermal pixel’s radiometric temperature.

  12. Graphene based integrated tandem supercapacitors fabricated directly on separators

    KAUST Repository

    Chen, Wei

    2015-04-09

    It is of great importance to fabricate integrated supercapacitors with extended operation voltages as high energy density storage devices. In this work, we develop a novel direct electrode deposition on separator (DEDS) process to fabricate graphene based integrated tandem supercapacitors for the first time. The DEDS process generates compact graphene-polyaniline electrodes directly on the separators to form integrated supercapacitors. The integrated graphene-polyaniline tandem supercapacitors demonstrate ultrahigh volumetric energy density of 52.5 Wh L^(−1) at power density of 6037 W L^(−1) and excellent gravimetric energy density of 26.1 Wh kg^(−1) at power density of 3002 W kg^(−1) with outstanding electrochemical stability for over 10000 cycles. This study show great promises for the future development of integrated energy storage devices.

  13. Preparative separation and identification of derivatized beta-methylphenylalanine enantiomers by chiral SFC, HPLC and NMR for development of new peptide ligand mimetics in drug discovery.

    Science.gov (United States)

    Nogle, Lisa M; Mann, Charles W; Watts, William L; Zhang, Yingru

    2006-03-03

    A direct preparative purification of all four isomers of the unnatural amino acid beta-methylphenylalanine was achieved using supercritical fluid chromatography (SFC) with stacked-injection. Final purification of the Cbz-methyl ester derived isomers was performed on a Daicel Chiralpak AD-H column (20 mm x 250 mm), using 50:50 methanol/ethanol as the organic modifier and resulted in purification of over 3.4 g of material in 6.25 h with >90% total recovery. The absolute stereochemical assignment of the purified amino acids was determined through a combination of chiral HPLC, NMR and optical rotation studies. To our knowledge, this is the first reported preparative approach that has yielded all four compounds in a single chromatographic run.

  14. Chiral-catalyst-based convergent synthesis of HIV protease inhibitor GRL-06579A.

    Science.gov (United States)

    Mihara, Hisashi; Sohtome, Yoshihiro; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2008-02-01

    Catalytic asymmetric synthesis of GRL-06579A (1), an HIV-1 protease inhibitor effective against multi-protease-inhibitor-resistant viruses, is described. A convergent strategy that utilizes heterobimetallic multifunctional catalysts developed in our group is a key feature of the synthesis. The chirality of the bicyclic tetrahydrofuran unit of 1 was introduced through Al-Li-bis(binaphthoxide) (ALB) catalyst-controlled Michael addition of dimethyl malonate to racemic 4-O-protected cyclopentenone. ALB afforded not only the trans adduct with up to 96% ee from a matched substrate through kinetic resolution, but also the cis adduct with 99% ee through a catalyst-controlled Michael addition to a mismatched substrate. The Michael addition to produce the unusual cis adduct is described in detail. The framework of the bicyclic tetrahydrofuran was constructed by an intramolecular oxy-Michael reaction. The amino alcohol unit was constructed by an La-Li3-tris(binaphthoxide) (LLB)-catalyzed diastereoselective nitroaldol reaction of N-Boc aldehyde (Boc = tert-butoxycarbonyl) derived from L-phenylalanine. LLB promoted the nitroaldol reaction without racemization of the chiral aldehyde to give the nitroaldol adduct in 85% yield and with 93:7 diastereoselectivity and over 99% ee.

  15. Synthesis of novel glucose-based polymers and their applications as chiral stationary phases for high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Tomoyuki IKAI; Takayuki YAMADA

    2016-01-01

    Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases( CSPs) for high performance liquid chromatography( HPLC). The regioregular polymer( poly-5)shows clear resolution ability for the racemate of cobalt(Ⅲ)acetylacetonate( Co( acac)3 ),whereas the corresponding regioirregular polymer(poly-3)does not show any chiral recognition for Co(acac)3. The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.

  16. Chiral memory via chiral amplification and selective depolymerization of porphyrin aggregates.

    Science.gov (United States)

    Helmich, Floris; Lee, Cameron C; Schenning, Albertus P H J; Meijer, E W

    2010-12-01

    Chiral memory at the supramolecular level is obtained via a new approach using chiral Zn porphrins and achiral Cu porphyrins. In a "sergeant-and-soldiers" experiment, the Zn "sergeant" transfers its own chirality to Cu "soldiers" and, after chiral amplification, the "sergeant" is removed from the coaggregates by axial ligation with a Lewis base. After this extraction, the preferred helicity observed for the aggregates containing achiral Cu porphyrins reveals a chiral memory effect that is stable and can be erased and partially restored upon subsequent heating and cooling.

  17. Influence of Axial and Point Chirality in the Chiral Self-Assembly of Twin N-Annulated Perylenecarboxamides.

    Science.gov (United States)

    Buendía, Julia; Greciano, Elisa E; Sánchez, Luis

    2015-12-18

    The synthesis of three bis(N-annulated perylenecarboxamides) endowed with achiral or chiral side chains is reported. The restricted rotation of the perylene moieties yields atropisomers that can be separated by chiral HPLC. The CD spectra of the six stereoisomers show a dichroic pattern in a good solvent that changes drastically upon adding a poor solvent that favors the aggregation. The cooperative character of the supramolecular polymerization mechanism of 1-3 has been determined by denaturation experiments, which reveal that the formation of homochiral aggregates is favored over the formation of heterochiral aggregates. A complete set of amplification of chirality experiments have been carried out, revealing the preponderance of axial chirality over point chirality. The results presented herein shed relevant light on the structural conditions exhibited by molecular units endowed with different elements of asymmetry to generate chiral supramolecular structures and the supremacy of axial chirality over point chirality in the origin of homochirality.

  18. Base-catalyzed depolymerization of lignin : separation of monomers

    Energy Technology Data Exchange (ETDEWEB)

    Vigneault, A. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States); Chornet, E. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; National Renewable Energy Laboratory, Golden, CO (United States)

    2007-12-15

    Biofuels produced from residual lignocellulosic biomass range from ethanol to biodiesel. The use of lignin for the production of alternate biofuels and green chemicals has been studied with particular emphasis on the structure of lignin and its oxyaromatic nature. In an effort to fractionate lignocellulosic biomass and valorize specific constitutive fractions, the authors developed a strategy for the separation of 12 added value monomers produced during the hydrolytic base catalyzed depolymerization (BCD) of a Steam Exploded Aspen Lignin. The separation strategy was similar to vanillin purification to obtain pure monomers, but combining more steps after the lignin depolymerization such as acidification, batch liquid-liquid-extraction (LLE), followed by vacuum distillation, liquid chromatography (LC) and crystallization. The purpose was to develop basic data for an industrial size process flow diagram, and to evaluate both the monomer losses during the separation and the energy requirements. Experimentally testing of LLE, vacuum distillation and flash LC in the laboratory showed that batch vacuum distillation produced up to 4 fractions. Process simulation revealed that a series of 4 vacuum distillation columns could produce 5 distinct monomer streams, of which 3 require further chromatography and crystallization operations for purification. 22 refs., 4 tabs., 8 figs.

  19. Application of cyclodextrins in chiral capillary electrophoresis.

    Science.gov (United States)

    Rezanka, Pavel; Navrátilová, Klára; Rezanka, Michal; Král, Vladimír; Sýkora, David

    2014-10-01

    CE represents a very powerful separation tool in the area of chiral separations. CD-mediated chiral CE is a continuously flourishing technique within the frame of the electromigration methods. In this review, a brief overview of the synthetic procedures leading to modified CDs is provided first. Next, selected aspects related to the utilization of CDs in chiral CE are discussed specifically in the view of recently published data. Advantages of CDs and basic principles of chiral CE are remained. The topic of the determination of binding constants is touched. Particular attention is paid to the effort aiming at better understanding of the molecular level of the enantiorecognition between CDs and the analyte in the solution. Powerful approaches extensively utilized in this field are NMR, molecular modeling, and computer simulations. Then, a summary of applications of CDs in the CE enantioseparations is given, covering years 2008-2013. Finally, the general trend of modified CDs use in separation science is statistically evaluated.

  20. Hydrate-based heavy metal separation from aqueous solution

    Science.gov (United States)

    Song, Yongchen; Dong, Hongsheng; Yang, Lei; Yang, Mingjun; Li, Yanghui; Ling, Zheng; Zhao, Jiafei

    2016-02-01

    A novel hydrate-based method is proposed for separating heavy metal ions from aqueous solution. We report the first batch of experiments and removal characteristics in this paper, the effectiveness and feasibility of which are verified by Raman spectroscopy analysis and cross-experiment. 88.01-90.82% of removal efficiencies for Cr3+, Cu2+, Ni2+, and Zn2+ were obtained. Further study showed that higher R141b-effluent volume ratio contributed to higher enrichment factor and yield of dissociated water, while lower R141b-effluent volume ratio resulted in higher removal efficiency. This study provides insights into low-energy, intensive treatment of wastewater.

  1. Nitrogen Trifluoride-Based Fluoride- Volatility Separations Process: Initial Studies

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, Bruce K.; Scheele, Randall D.; Casella, Andrew M.; Kozelisky, Anne E.

    2011-09-28

    This document describes the results of our investigations on the potential use of nitrogen trifluoride as the fluorinating and oxidizing agent in fluoride volatility-based used nuclear fuel reprocessing. The conceptual process uses differences in reaction temperatures between nitrogen trifluoride and fuel constituents that produce volatile fluorides to achieve separations and recover valuable constituents. We provide results from our thermodynamic evaluations, thermo-analytical experiments, kinetic models, and provide a preliminary process flowsheet. The evaluations found that nitrogen trifluoride can effectively produce volatile fluorides at different temperatures dependent on the fuel constituent.

  2. Comparison of coal separation characteristics based on different separating approaches in dry coal beneficiation flowsheet

    Institute of Scientific and Technical Information of China (English)

    HE Jing-feng; ZHAO Yue-min; HE Ya-qun; LUO Zhen-fu; DUAN Chen-long

    2015-01-01

    The separation characteristic of raw coal from Luoyang mining area, China, was investigated by applying a dry coal beneficiation flowsheet with the dense medium gas-solid fluidized bed as main separating equipment. The experimental and simulation results indicate that the dense medium gas-solid fluidized bed can provide uniform distribution and stable fluctuation of bed densities at various heights. Two types of different separating approaches were compared using the dry coal beneficiation flowsheet. Compared with obtaining cleaning coal in the first stage of the flowsheet, a higher yield of the cleaning coal and better separation efficiency can be achieved when discharging gangue in the first stage. Finally, the results indicate that 64.86% pure cleaning coal with an ash content of 11.77% and 13.53% middlings were obtained, and 21.61% gangue was removed in two successive separation stages with the probable errors of 0.05 and 0.07 g/cm3, respectively.

  3. Authenticity of raspberry flavor in food products using SPME-chiral-GC-MS

    DEFF Research Database (Denmark)

    Hansen, Anne-Mette Sølvbjerg; Frandsen, Henrik Lauritz; Fromberg, Arvid

    2015-01-01

    A fast and simple method for authenticating raspberry flavors from food products was developed. The two enantiomers of the compound (E)-α-ionone from raspberry flavor were separated on a chiral gas chromatographic column. Based on the ratio of these two enantiomers the naturalness of a raspberry...

  4. Consistent Chiral Kinetic Theory in Weyl Materials: Chiral Magnetic Plasmons

    Science.gov (United States)

    Gorbar, E. V.; Miransky, V. A.; Shovkovy, I. A.; Sukhachov, P. O.

    2017-03-01

    We argue that the correct definition of the electric current in the chiral kinetic theory for Weyl materials should include the Chern-Simons contribution that makes the theory consistent with the local conservation of the electric charge in electromagnetic and strain-induced pseudoelectromagnetic fields. By making use of such a kinetic theory, we study the plasma frequencies of collective modes in Weyl materials in constant magnetic and pseudomagnetic fields, taking into account the effects of dynamical electromagnetism. We show that the collective modes are chiral plasmons. While the plasma frequency of the longitudinal collective mode coincides with the Langmuir one, this mode is unusual because it is characterized not only by oscillations of the electric current density, but also by oscillations of the chiral current density. The latter are triggered by a dynamical version of the chiral electric separation effect. We also find that the plasma frequencies of the transverse modes split up in a magnetic field. This finding suggests an efficient means of extracting the chiral shift parameter from the measurement of the plasma frequencies in Weyl materials.

  5. A simple reason based on supersymmetry for replication of chiral families

    Science.gov (United States)

    Babu, K. S.; Pati, Jogesh C.; Stremnitzer, Hanns

    1991-03-01

    In the context of the minimal flavon-chromon preon model, we show that supersymmetry, because of fermion-boson pairing in its field content, provides a rather simple reason for replication of composite quark-lepton families. At the level of minimum number of core constituents, which turns out to be three, it also provides a good reason why one may expect to have just three light chiral families. One crucial prediction is that there must exist complete vector-like families with mass of order 1 TeV for quark-like and few hundred GeV for lepton-like members. This can be tested at SSC, LHC and future high energy e-e+ machines.

  6. Description and Evaluation of Chiral Interactive Sites on Bonded Cyclodextrin Stationary Phases for Liquid Chromatography

    Science.gov (United States)

    Beesley, Thomas E.

    Development of chiral separations has been essential to the drug discovery and development process. The solubility requirements for a number of methods and/or the mobile phase requirements for application of certain detection systems have opened up many opportunities for cyclodextrin-based CSPs for liquid chromatography. Even though a few chiral stationary phases cover a wide area of enantioselectivity, they do not meet the entire needs of the industry. Cyclodextrin phases offer some unique mechanisms and opportunities to resolve chiral separation problems especially in the aqueous reversed-phase and non-aqueous polar organic modes. This chapter addresses the need to understand the chiral stationary phase structure, the mechanisms at work, and the role mobile phase composition plays in driving those mechanisms to produce enantioselectivity. In addition, the development of certain derivatives has played an essential part in expanding that basic role for certain chiral separations. What these derivatives contribute in concert with the basic structure is a critical part of the understanding to the effective use of these phases. During this study it was determined that the role of steric hindrance has been vastly underestimated, both to the extent that it has occurred and to its effectiveness for obtaining enantioselectivity. References to the entire 20-year history of the cyclodextrin phase development and application literature up to this current date have been reviewed and incorporated.

  7. Laser Writing of Multiscale Chiral Polymer Metamaterials

    Directory of Open Access Journals (Sweden)

    E. P. Furlani

    2012-01-01

    Full Text Available A new approach to metamaterials is presented that involves laser-based patterning of novel chiral polymer media, wherein chirality is realized at two distinct length scales, intrinsically at the molecular level and geometrically at a length scale on the order of the wavelength of the incident field. In this approach, femtosecond-pulsed laser-induced two-photon lithography (TPL is used to pattern a photoresist-chiral polymer mixture into planar chiral shapes. Enhanced bulk chirality can be realized by tuning the wavelength-dependent chiral response at both the molecular and geometric level to ensure an overlap of their respective spectra. The approach is demonstrated via the fabrication of a metamaterial consisting of a two-dimensional array of chiral polymer-based L-structures. The fabrication process is described and modeling is performed to demonstrate the distinction between molecular and planar geometric-based chirality and the effects of the enhanced multiscale chirality on the optical response of such media. This new approach to metamaterials holds promise for the development of tunable, polymer-based optical metamaterials with low loss.

  8. Synthesis of SB-β-CD and its application in nonaqueous capillary electrophoresis separation of basic chiral drugs%6-O-磺丁基-β-环糊精的合成及在非水毛细管电泳拆分碱性手性药物中的应用

    Institute of Scientific and Technical Information of China (English)

    邢文国; 孟宪兴; 冯维春; 李继宾; 何海林

    2013-01-01

    A new β-cyclodextrin (β-CD) derivative, SB-β-CD, was successfully synthesized and used as a chiral selector in nonaqueous capillary electrophoresis ( NACE ). The effects of organic solvents, the electrolytes, the concentrations of SB-p-CD and the pH of the buffer were investigated. Four basic chiral drugs, including chlorpheniramine, doxylamine, meclozine, and mianserin, were resolved, while the four basic chiral drugs can not be separated by β-CD under the same conditions. It demonstrated that SB-p-CD as a chiral selector had the special ability in the separation of basic chiral drugs. It was a rapid and accurate method for the separation of basic chiral drugs.%合成了新型环糊精衍生物6-O-磺丁基-β-环糊精(SB-β-CD),并以其作为手性选择剂,对扑尔敏、多西拉敏、美克洛嗪和米安舍林4种碱性手性药物进行非水毛细管电泳拆分.考察了有机溶剂、电解质、手性选择剂浓度以及pH对分离度的影响.研究结果表明:扑尔敏、多西拉敏、美克洛嗪和米安舍林4种碱性手性药物全部达到基线分离.可见SB-β-CD在碱性药物拆分方面具有特殊能力,为碱性手性药物的拆分提供了一种准确、简便的分析方法.

  9. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  10. Crystal structure of 2-{(R-[1-(4-bromophenylethyl]iminomethyl}-4-(phenyldiazenylphenol, a chiral photochromic Schiff base

    Directory of Open Access Journals (Sweden)

    Ryoji Moriwaki

    2015-11-01

    Full Text Available The title chiral photochromic Schiff base compound, C21H18BrN3O, was synthesized from (R-(+-1-(4-bromophenylethylamine and the salicylaldehyde of an azobenzene derivative. The molecule corresponds to the phenol–imine tautomer, the C=N and N—C bond distances being 1.285 (3 and 1.470 (3 Å, respectively. The diazenyl group adopts a trans form, with an N=N distance of 1.256 (3 Å. The hydroxy group is involved in intramolecular O—H...N hydrogen bonding. In the crystal, C—H...π interactions consolidate the crystal packing of one-dimensional chains, which exhibits short intermolecular Br...C contacts of 3.400 (3 Å.

  11. Chiral cardiovascular drugs: an overview.

    Science.gov (United States)

    Ranade, Vasant V; Somberg, John C

    2005-01-01

    Stereochemistry in drug molecules is rapidly becoming an important aspect in drug research, design, and development. Recently, individual stereoisomers of drug molecules with asymmetric centers such as fexofenadine, cetirizine, verapamil, fluoxetine, levalbutarol, and amphetamine, for example, have been separated and developed as individual drugs. These stereoisomers have different therapeutic activity, and each isomer has contributed differently with respect to its formulation's pharmacologic activity, side effects, and toxicity. The present overview discusses chirality among a select group of cardiovascular drugs, their stereochemical synthesis/preparation, isolation techniques using chiral chromatography, methods for confirmation of their enantiomeric purity, pharmacodynamics, and pharmacokinetics. Chirality has been visualized as an important factor in cardiovascular research. It is also becoming evident in other areas of therapeutics.

  12. Uplink User Signal Separation for OFDMA-Based Cognitive Radios

    Directory of Open Access Journals (Sweden)

    Guvenc Ismail

    2010-01-01

    Full Text Available Spectrum awareness of orthogonal frequency division multiple access- (OFDMA- based cognitive radios (CRs can be improved by enabling them to separate the primary user signals in the uplink (UL. Assuming availability of information about the basic parameters of the primary system as well as time synchronization to the first arriving user signal, two algorithms are proposed in this paper. The first one targets estimating the size of the frequency allocation block of the primary system. The performance of this algorithm is compared with the results of a Gaussian approximation-based approach that aims to determine the probability of correct block size estimation theoretically. The second one is a semiblind user separation algorithm, which estimates the carrier frequency offsets and time delays of each block by exploiting the cross-correlations over pilot subcarriers. A two-dimensional clustering method is then employed to group the estimates, where each group belongs to a different user. It is shown that the proposed algorithms can improve the spectrum opportunity detection of cognitive radios. Feasibility of the algorithms is proved through practical simulations.

  13. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris (4-methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol (98:2, vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  14. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris(4—methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    BaoHaiSHAO; XiuZhuXU; 等

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol(98:2,vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  15. Attempt to Resolute Chiral Clusters by Optically Active Hydrazide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new kind of hydrazone (I) diastereoisomers was prepared with enantiomeric hydazide (II) and chiral cluster (III), which was characterized by HMBC. Unfortunately, the mixture could not be separated into pure diastereoisomer. This could be a direction to separate the racemic chiral clusters.

  16. Synthesis, photochemical properties and DNA binding studies of dna cleaving agents based on chiral dipyridine dihydrodioxins salts

    Science.gov (United States)

    Shamaev, Alexei

    activated by UV-light. The mechanism of o-quinone release and intramolecular ET was studied in detail by methods of Ultrafast Transient Absortion Spectroscopy and supported by high-level quantum mechanical calculations. The binding properties of chiral intercalators based on PDHD to various DNA oligonucleotides were studied by various methods and DNA cleavage properties indicating strong binding and cleaving ability of the synthesized PDHDs. Also, a new method for synthesis of cyclohexa[e]pyrenes which possibly capable of intramolecular ET and electron transfer-oxidative stress (ET-OS) DNA cleavage was developed and partially accomplished.

  17. Chitosan-based membrane chromatography for protein adsorption and separation.

    Science.gov (United States)

    Liu, Yezhuo; Feng, Zhicheng; Shao, Zhengzhong; Chen, Xin

    2012-08-01

    A chitosan-based membrane chromatography was set up by using natural chitosan/carboxymethylchitosan (CS/CMCS) blend membrane as the matrix. The dynamic adsorption property for protein (lysozyme as model protein) was detailed discussed with the change in pore size of the membrane, the flow rate and the initial concentration of the feed solution, and the layer of membrane in membrane stack. The best dynamic adsorption capacity of lysozyme on the CS/CMCS membrane chromatography was found to be 15.3mg/mL under the optimal flow conditions. Moreover, the CS/CMCS membrane chromatography exhibited good repeatability and reusability with the desorption efficiency of ~90%. As an application, lysozyme and ovalbumin were successfully separated from their binary mixture through the CS/CMCS membrane chromatography. This implies that such a natural chitosan-based membrane chromatography may have great potential on the bioseparation field in the future.

  18. Hand posture recognizer based on separator wavelet networks

    Science.gov (United States)

    Bouchrika, Tahani; Jemai, Olfa; Zaied, Mourad; Ben Amar, Chokri

    2015-12-01

    This paper presents a novel hand posture recognizer based on separator wavelet networks (SWNs). Aiming at creating a robust and rapid hand posture recognizer, we have contributed by proposing a new training algorithm for the wavelet network classifier based on fast wavelet transform (FWN). So, the contribution resides in reducing the number of WNs modeling training data. To make that, inspiring from the adaboost feature selection method, we thought to create SWNs (n-1 WNs for n classes) instead of modeling each training sample by its wavelet network (WN). By proposing the new training algorithm, the recognition phase will be positively influenced. It will be more rapid thanks to the reduction of the number of comparisons between test images WNs and training WNs. Comparisons with other works, employing universal hand posture datasets are presented and discussed. Obtained results have shown that the new hand posture recognizer is comparable to previously established ones.

  19. Symmetries of Ginsparg-Wilson Chiral Fermions

    CERN Document Server

    Mandula, Jeffrey E

    2009-01-01

    The group structure of the variant chiral symmetry discovered by Luscher in the Ginsparg-Wilson description of lattice chiral fermions is analyzed. It is shown that the group contains an infinite number of linearly independent symmetry generators, and the Lie algebra is given explicitly. CP is an automorphism of this extended chiral group, and the CP transformation properties of the symmetry generators are found. The group has an infinite-parameter subgroup, and the factor group whose elements are its cosets is isomorphic to the continuum chiral symmetry group. Features of the currents associated with these symmetries are discussed, including the fact that some different, non-commuting symmetry generators lead to the same Noether current. These are universal features of lattice chiral fermions based on the Ginsparg-Wilson relation; they occur in the overlap, domain-wall, and perfect-action formulations. In a solvable example - free overlap fermions - these non-canonical elements of lattice chiral symmetry are...

  20. Direct Interconversion of BINOL and H8-BINOL-Based Chiral Brønsted Acids Using Single-Step Red/Ox Manipulations.

    Science.gov (United States)

    Tay, Jia-Hui; Arguelles, Alonso J; Nagorny, Pavel

    2015-08-07

    A direct single-step hydrogenation of BINOL-based chiral phosphoric acids, N-triflyl phosphoramides, and disulfonimides to the corresponding H8-BINOL Brønsted acids in excellent yields and chemoselectivities is described. In addition, the conditions for the single-step oxidation of H8-BINOL-based Brønsted acids into the corresponding BINOL-based acids have been identified and employed to accomplish these interconversions in 41-81% yield.

  1. Synthesis and Characterization of Water-Soluble Carboxymethyl-Cyclodextrin Polymer as Capillary Electrophoresis Chiral Selector

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The water-soluble carboxymethyl-cyclodextrin polymer (CM-CD polymer) was synthesized and used as capillary electrophoresis chiral selector.Verrapamil and thiopentorusodium were well separated using CM-CD polymer as chiral selector.

  2. Complex-wave retrieval based on blind signal separation

    Institute of Scientific and Technical Information of China (English)

    Xiaodong Chai; Chengpeng Zhou; Zhaoyan Feng; Yinhua Wang; Yansheng Zuo

    2006-01-01

    In the process of the reconstruction of digital holography, the traditional methods of diffraction and filtration are commonly adopted to recover the original complex-wave signal. Influenced by twin-image and zero-order terms, the above-mentioned methods, however, either limit the field of vision or result in the loss of the amplitude and phase. A new method for complex-wave retrieval is presented, which is based on blind signal separation. Three frames of holograms are captured by a charge coupled device (CCD)camera to form an observation signal. The term containing only amplitude and phase of complex-wave is separated, by means of independent component analysis, from the observation signal, which effectively eliminates the zero-order term. Finally, the complex-wave retrieval of pure phase wavefront is achieved.Experimental results show that this method can better recover the amplitude and phase of the original complex-wave even when there is a frequency spectrum mixture in the hologram.

  3. Localized Ambient Solidity Separation Algorithm Based Computer User Segmentation

    Directory of Open Access Journals (Sweden)

    Xiao Sun

    2015-01-01

    Full Text Available Most of popular clustering methods typically have some strong assumptions of the dataset. For example, the k-means implicitly assumes that all clusters come from spherical Gaussian distributions which have different means but the same covariance. However, when dealing with datasets that have diverse distribution shapes or high dimensionality, these assumptions might not be valid anymore. In order to overcome this weakness, we proposed a new clustering algorithm named localized ambient solidity separation (LASS algorithm, using a new isolation criterion called centroid distance. Compared with other density based isolation criteria, our proposed centroid distance isolation criterion addresses the problem caused by high dimensionality and varying density. The experiment on a designed two-dimensional benchmark dataset shows that our proposed LASS algorithm not only inherits the advantage of the original dissimilarity increments clustering method to separate naturally isolated clusters but also can identify the clusters which are adjacent, overlapping, and under background noise. Finally, we compared our LASS algorithm with the dissimilarity increments clustering method on a massive computer user dataset with over two million records that contains demographic and behaviors information. The results show that LASS algorithm works extremely well on this computer user dataset and can gain more knowledge from it.

  4. Localized Ambient Solidity Separation Algorithm Based Computer User Segmentation.

    Science.gov (United States)

    Sun, Xiao; Zhang, Tongda; Chai, Yueting; Liu, Yi

    2015-01-01

    Most of popular clustering methods typically have some strong assumptions of the dataset. For example, the k-means implicitly assumes that all clusters come from spherical Gaussian distributions which have different means but the same covariance. However, when dealing with datasets that have diverse distribution shapes or high dimensionality, these assumptions might not be valid anymore. In order to overcome this weakness, we proposed a new clustering algorithm named localized ambient solidity separation (LASS) algorithm, using a new isolation criterion called centroid distance. Compared with other density based isolation criteria, our proposed centroid distance isolation criterion addresses the problem caused by high dimensionality and varying density. The experiment on a designed two-dimensional benchmark dataset shows that our proposed LASS algorithm not only inherits the advantage of the original dissimilarity increments clustering method to separate naturally isolated clusters but also can identify the clusters which are adjacent, overlapping, and under background noise. Finally, we compared our LASS algorithm with the dissimilarity increments clustering method on a massive computer user dataset with over two million records that contains demographic and behaviors information. The results show that LASS algorithm works extremely well on this computer user dataset and can gain more knowledge from it.

  5. Association of two single-isomer anionic CD in NACE for the chiral and achiral separation of fenbendazole, its sulphoxide and sulphone metabolites: application to their determination after in vitro metabolism.

    Science.gov (United States)

    Rousseau, Anne; Gillotin, Florian; Chiap, Patrice; Crommen, Jacques; Fillet, Marianne; Servais, Anne-Catherine

    2010-05-01

    A NACE method was developed for the separation of fenbendazole (FBZ), a prochiral drug giving rise to chiral (oxfendazole or OFZ) and nonchiral (FBZ sulphone or FBZSO(2)) metabolites. First, the effect of the nature and the concentration of CD as well as that of the acidic BGE on the enantiomeric separation of OFZ were studied. OFZ enantiomers were completely resolved using a BGE made up of 10 mM ammonium formate and 0.5 M TFA in methanol containing 10 mM heptakis(2,3-di-O-acetyl-6-O-sulfo)-beta-CD and 10 mM heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-CD. Moreover, the NACE method was found to be particularly well suited to the simultaneous determination of FBZ, OFZ enantiomers, and FBZSO(2). Thiabendazole was selected as an internal standard. The CD-NACE potential was then evaluated for in vitro metabolism studies using FBZ as a model case. The OFZ enantiomers and FBZSO(2) could be detected after incubation of FBZ in the phenobarbital-induced male rat liver microsomes systems.

  6. Antibodies as Tailor-Made Chiral Selectors: an Interdisciplinary Approach to Enantiomer Separation and Detection%抗体作为特制的手性选择剂:一个跨学科的对映体分离和检测手段

    Institute of Scientific and Technical Information of China (English)

    HOFSTETTER Heike; HOFSTETTER Oliver

    2005-01-01

    It has long been known that the configurational isomers of biologically active compounds, e.g., nutrients, pesticides, and drugs, may exhibit different activities in a chiral environment such as the human body. Although the majority of drugs presently in development are chiral, analytical and preparative methods for the quantitative determination and purification of stereoisomers still lag behind. One reason is that commonly used chiral selectors for the direct resolution of enantiomers are not tailor-made for a specific analyte. The identification of suitable selectors for a particular pair of enantiomers still requires considerable experimentation and is generally demanding with regard to material, time and labor. The rational design of chiral host molecules, therefore, represents a challenge in facilitating enantiomer analysis. In this article, we describe how a combination of techniques ranging from organic synthesis to molecular biology yields antibodies of predetermined specificity and stereoselectivity that can be used as tailor-made chiral selectors for the chromatographic separation of enantiomers and their sensitive detection in immunosensors.

  7. Chiral mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Plum, Eric, E-mail: erp@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); Zheludev, Nikolay I., E-mail: niz@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); The Photonics Institute and Centre for Disruptive Photonic Technologies, Nanyang Technological University, Singapore 637378 (Singapore)

    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.

  8. Process for separating carbon dioxide from flue gas using sweep-based membrane separation and absorption steps

    Science.gov (United States)

    Wijmans, Johannes G.; Baker, Richard W.; Merkel, Timothy C.

    2012-08-21

    A gas separation process for treating flue gases from combustion processes, and combustion processes including such gas separation. The invention involves routing a first portion of the flue gas stream to be treated to an absorption-based carbon dioxide capture step, while simultaneously flowing a second portion of the flue gas across the feed side of a membrane, flowing a sweep gas stream, usually air, across the permeate side, then passing the permeate/sweep gas to the combustor.

  9. Chiral phase transition in QED3 at finite temperature

    Science.gov (United States)

    Yin, Pei-Lin; Xiao, Hai-Xiao; Wei, Wei; Feng, Hong-Tao; Zong, Hong-Shi

    2016-12-01

    In the framework of Dyson-Schwinger equations, we employ two kinds of criteria (one kind is the chiral condensate, the other kind is thermodynamic quantities, such as the pressure, the entropy, and the specific heat) to investigate the nature of chiral phase transitions in QED3 for different fermion flavors. It is found that the chiral phase transitions in QED3 for different fermion flavors are all typical second-order phase transitions; the critical temperature and order of the chiral phase transition obtained from the chiral condensate and susceptibility are the same with that obtained by the thermodynamic quantities, which means that they are equivalent in describing the chiral phase transition; the critical temperature decreases as the number of fermion flavors increases and there is a boundary that separates the Tc-Nf plane into chiral symmetry breaking and restoration regions.

  10. Molecular chirality at surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, Karl-Heinz [Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600 Duebendorf (Switzerland); Organic Chemistry Institute, University Zurich, 8057 Zuerich (Switzerland)

    2012-11-15

    With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self-assembly of chiral and prochiral molecules and the principles of mirror-symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long-range symmetry breaking in two-dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface-related sources of chiral topics completes this paper. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Use of peak sharpening effects to improve the separation of chiral compounds with molecularly imprinted porous polymer layer open-tubular capillaries.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Chowdhury, Jamil M; Boysen, Reinhard I; Hearn, Milton T W

    2017-02-17

    This investigation demonstrates the application of a new peak sharpening technique to improve the separation of difficult-to-resolve racemic mixtures in capillary electro-chromatography. Molecularly imprinted porous layer open tubular (MIP-PLOT) capillaries, prepared by a layer-on-layer polymerization approach with Z-l-Asp-OH as the template, were selected to validate the approach. SEM revealed that the polymer film thickness can be varied by changes in both the polymer composition and the layer-on-layer regime. Capillaries made with methacrylic acid as the functional monomer could not separate the Z-Asp-OH racemate, due to weak interactions between the MIP-PLOT material and the target analytes. In contrast, MIP-PLOT capillaries prepared with 4-vinylpyridine as the functional monomer resulted in increased ionic interactions with the target analytes. Separation of the enantiomers could be enhanced when a peak zone sharpening effect was exploited through the use of specific BGE compositions and by taking advantage of eigenpeak phenomena. In this manner, the position of a sharpening zone and the peak shape of the sample analytes could be fine-tuned, so that when the sharpening zone and the target analyte co-migrated the separation of the Z-l-Asp-OH enantiomer from its d-enantiomer in a racemic mixture could be achieved under overloading conditions.

  12. Chiral extraction of ketoprofen enantiomers with chiral selector tartaric esters

    Institute of Scientific and Technical Information of China (English)

    ZHOU Dan; LIU Jia-jia; TANG Ke-wen; HUANG Ke-long

    2007-01-01

    Distribution behavior of ketoprofen enantiomers was examined in methanol aqueous and organic solvent mixture containing tartaric esters. The influence of length of alkyl chain of tartaric esters, concentration of L-tartaric esters and methanol aqueous, kind of organic solvent on partition ratio and separation factors was investigated. The results show that L-tartaric and D-tartaric esters have different chiral recognition abilities. S-ketoprofen is easily extracted by L-tartaric esters, and R-ketoprofen is easily extracted by D-tartaric esters. L-tartaric esters form more stable diastereomeric complexes with S-enantiomer than that with R-enantiomer. This distribution behavior is consistent with chiral recognition mechanism. With the increase of the concentration of tartaric ester from 0 to 0.3 mol/L, partition coefficient K and separation factor α increase. Also, the kind of organic solvent and the concentration of the methanol aqueous have significant influence on K and α.

  13. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  14. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  15. Chiral doublet bands and energy-level crossing

    Institute of Scientific and Technical Information of China (English)

    QI Bin; MENG Jie; ZHANG Shuang-Quan; WANG Shou-Yu; PENG Jing

    2009-01-01

    Different definitions for chiral doublet bands based on excitation energies, B(E2) and B(M1) respectively are discussed in the triaxial particle rotor model. For the ideal chiral geometry, the selection rules of the electromagnetic transitions in different band definitions are illustrated. It is also shown that the energy-level crossings between chiral doublet bands may occur.

  16. Novel Lifshitz point for chiral transition in the magnetic field

    Directory of Open Access Journals (Sweden)

    Toshitaka Tatsumi

    2015-04-01

    Full Text Available Based on the generalized Ginzburg–Landau theory, chiral phase transition is discussed in the presence of magnetic field. Considering the chiral density wave we show that chiral anomaly gives rise to an inhomogeneous chiral phase for nonzero quark-number chemical potential. Novel Lifshitz point appears on the vanishing chemical potential line, which may be directly explored by the lattice QCD simulation.

  17. Advanced material separation technique based on dual energy CT scanning

    Science.gov (United States)

    Zamyatin, Alexander A.; Natarajan, Anusha; Zou, Yu

    2009-02-01

    We propose a method for material separation using dual energy data. Our method is suitable to separation of three or more materials. In this work we describe our method and show results of numerical simulation and with real dual-energy data of a head phantom. The proposed method of constructing the material separation map consists of the following steps: Data-domain dual energy decomposition - Vector plot - Density plot - Clustering - Color assignment. Density plots are introduced to allow automatic cluster separation. We use special image processing methods, including Gaussian decomposition, to improve the accuracy of material separation. We also propose using the HSL color model for better visualization and to bring a new dimension in material separation display. We study applications of bone removal and virtual contrast removal. Evaluation shows improved accuracy compared to standard methods.

  18. Empirical Equation Based Chirality (n, m) Assignment of Semiconducting Single Wall Carbon Nanotubes from Resonant Raman Scattering Data

    Science.gov (United States)

    Arefin, Md Shamsul

    2012-01-01

    This work presents a technique for the chirality (n, m) assignment of semiconducting single wall carbon nanotubes by solving a set of empirical equations of the tight binding model parameters. The empirical equations of the nearest neighbor hopping parameters, relating the term (2n− m) with the first and second optical transition energies of the semiconducting single wall carbon nanotubes, are also proposed. They provide almost the same level of accuracy for lower and higher diameter nanotubes. An algorithm is presented to determine the chiral index (n, m) of any unknown semiconducting tube by solving these empirical equations using values of radial breathing mode frequency and the first or second optical transition energy from resonant Raman spectroscopy. In this paper, the chirality of 55 semiconducting nanotubes is assigned using the first and second optical transition energies. Unlike the existing methods of chirality assignment, this technique does not require graphical comparison or pattern recognition between existing experimental and theoretical Kataura plot.

  19. Empirical Equation Based Chirality (n, m Assignment of Semiconducting Single Wall Carbon Nanotubes from Resonant Raman Scattering Data

    Directory of Open Access Journals (Sweden)

    Md Shamsul Arefin

    2012-12-01

    Full Text Available This work presents a technique for the chirality (n, m assignment of semiconducting single wall carbon nanotubes by solving a set of empirical equations of the tight binding model parameters. The empirical equations of the nearest neighbor hopping parameters, relating the term (2n, m with the first and second optical transition energies of the semiconducting single wall carbon nanotubes, are also proposed. They provide almost the same level of accuracy for lower and higher diameter nanotubes. An algorithm is presented to determine the chiral index (n, m of any unknown semiconducting tube by solving these empirical equations using values of radial breathing mode frequency and the first or second optical transition energy from resonant Raman spectroscopy. In this paper, the chirality of 55 semiconducting nanotubes is assigned using the first and second optical transition energies. Unlike the existing methods of chirality assignment, this technique does not require graphical comparison or pattern recognition between existing experimental and theoretical Kataura plot.

  20. The effect of acidic and basic additives on the enantioseparation of basic drugs using polysaccharide-based chiral stationary phases.

    Science.gov (United States)

    Ye, Yun K; Stringham, Rodger W

    2006-08-01

    The enantioseparation of nine commercially available basic drugs was achieved on polysaccharide-based chiral stationary phases with the acidic additive ethanesulfonic acid and the basic additive butylamine. Seven different commercially available CSPs were used for the study (AD, AS, OD, OJ, OG, OB, and OC). Mobile phase additives have been proven to be essential in obtaining satisfactory enantio-resolution in terms of both efficiency and selectivity. Significantly improved selectivities were obtained for the basic probe drugs with the acidic additive, ethanesulfonic acid, rather than the basic additive, butylamine. This is best seen with Chiralpak AS CSP. No enantioseparation for the nine drugs was observed when butylamine was used as an additive; however, satisfactory enantioseparation for the nine drugs was achieved using ethanesulfonic acid. Higher column efficiencies were observed with the acidic additive, especially when isopropanol was used as a modifier. Higher sensitivity was also achieved with ethanesulfonic acid because of the significantly lower background at the UV detection wavelength. The acidic additive was demonstrated to be superior to the basic additive for the enantioseparation of basic drugs using seven different polysaccharide-based CSPs. These results are counterintuitive to the common "rule of thumb" in enantioseparation that states acidic additives work best for acidic analytes and basic additives work best for basic analytes. The beneficial effects of acidic additive in enantioseparations observed in this study could significantly improve the applicability of polysaccharide-based CSPs for the enantioseparation of basic analytes.

  1. Microstructure Effects for Casimir Forces in Chiral Metamaterials

    CERN Document Server

    McCauley, Alexander P; Reid, M T Homer; Rodriguez, Alejandro W; Zhou, Jiangfeng; Rosa, F S S; Joannopoulos, John D; Dalvit, D A R; Soukoulis, Costas M; Johnson, Steven G

    2010-01-01

    We examine a recent prediction for the chirality-dependence of the Casimir force in chiral metamaterials by numerical computation of the forces between the exact microstructures, rather than homogeneous approximations. We compute the exact force for a chiral bent-cross pattern, as well as forces for an idealized "omega"-particle medium in the dilute approximation and identify the effects of structural inhomogeneity (i.e. proximity forces and anisotropy). We find that these microstructure effects dominate the force for separations where chirality was predicted to have a strong influence. To get observations of chirality free from microstructure effects, one must go to large separations where the effect of chirality is at most $\\sim10^{-4}$ of the total force.

  2. Liquid chromatographic direct resolution of aryl alpha-amino ketones on a residual silanol group-protecting chiral stationary phase based on optically active (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6.

    Science.gov (United States)

    Choi, Hee Jung; Jin, Jong Sung; Hyun, Myung Ho

    2008-11-01

    A residual silanol group-protecting chiral stationary phase (CSP) based on optically active (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 was successfully applied to the resolution of racemic cathinone and it analogue aryl alpha-amino ketones. The separation factors (alpha) and the resolutions (Rs) for 12 analytes were in the ranges of 2.85-16.12 and 6.49-19.64, respectively. The chromatographic resolution behaviors were investigated as a function of the content and type of organic and acidic modifiers and the ammonium acetate concentration in aqueous mobile phase. The practical usefulness of the CSP in the determination of the enantiomeric purity of optically active cathinone and in the preparative resolution of racemic cathinone was demonstrated.

  3. Authenticity of raspberry flavor in food products using SPME-chiral-GC-MS

    DEFF Research Database (Denmark)

    Hansen, Anne-Mette Sølvbjerg; Frandsen, Henrik Lauritz; Fromberg, Arvid

    2015-01-01

    A fast and simple method for authenticating raspberry flavors from food products was developed. The two enantiomers of the compound (E)-α-ionone from raspberry flavor were separated on a chiral gas chromatographic column. Based on the ratio of these two enantiomers the naturalness of a raspberry...... flavor can be evaluated due to the fact that a natural flavor will consist almost exclusively of the R enantiomer, while a chemical synthesis of the same compound will result in a racemic mixture. 27 food products containing raspberry flavors where investigated using SPME-chiral-GC-MS. We found raspberry...

  4. A web site for calculating the degree of chirality.

    Science.gov (United States)

    Zayit, Amir; Pinsky, Mark; Elgavi, Hadassah; Dryzun, Chaim; Avnir, David

    2011-01-01

    The web site, http://www.csm.huji.ac.il/, uses the Continuous Chirality Measure to evaluate quantitatively the degree of chirality of a molecule, a structure, a fragment. The value of this measure ranges from zero, the molecule is achiral, to higher values (the upper limit is 100); the higher the chirality value, the more chiral the molecule is. The measure is based on the distance between the chiral molecule and the nearest structure that is achiral. Questions such as the following can be addressed: by how much is one molecule more chiral than the other? how does chirality change along conformational motions? is there a correlation between chirality and enantioselectivity in a series of molecules? Both elementary and advanced features are offered. Related calculation options are the symmetry measures and shape measures.

  5. Microscopic calculations based on chiral two- and three-nucleon forces for proton- and $^{4}$He-nucleus scattering

    CERN Document Server

    Toyokawa, Masakazu; Matsumoto, Takuma; Minomo, Kosho; Ogata, Kazuyuki; Kohno, Michio

    2015-01-01

    We investigate the effects of chiral three-nucleon force (3NF) on proton scattering at 65 MeV and $^{4}$He scattering at 72 MeV/nucleon from heavier targets, using the standard microscopic framework composed of the Brueckner-Hartree-Fock (BHF) method and the $g$-matrix folding model. For nuclear matter, the $g$ matrix is evaluated from chiral two-nucleon force (2NF) of N$^{3}$LO and chiral 3NF of NNLO by using the BHF method. Since the $g$ matrix thus obtained is numerical and nonlocal, an optimum local form is determined from the on-shell and near-on-shell components of $g$ matrix that are important for elastic scattering. For elastic scattering, the optical potentials are calculated by folding the local chiral $g$ matrix with projectile and target densities. This microscopic framework reproduces the experimental data without introducing any adjustable parameter. Chiral-3NF effects are small for proton scattering, but sizable for $^{4}$He scattering at middle angles where the data are available. Chiral 3NF, ...

  6. Novel carbamoyl type quinine and quinidine based chiral anion exchangers implementing alkyne-azide cycloaddition immobilization chemistry.

    Science.gov (United States)

    Hettegger, Hubert; Kohout, Michal; Mimini, Vebi; Lindner, Wolfgang

    2014-04-11

    The synthesis and chromatographic evaluation of a series of new Cinchona derived chiral weak anion exchangers is presented. Huisgen Cu(I) mediated alkyne-azide cycloaddition, so-called click chemistry, was used as an immobilization strategy. In this way it was possible to immobilize about 90% of offered selector via 1,2,3-triazole linker, which displays a more efficient way of binding the selector to modified silica compared to common radical mediated thiol-ene addition. Problems associated with potential radical scavenging properties of chiral selectors thereby could be circumvented. The evaluation of the synthesized chiral stationary phases regarding chromatographic behavior was carried out using polar organic mode mobile phase composition and a set of representative chiral organic acids. Different loading densities revealed an optimum selector density of about 310μmol/g chiral stationary phase with respect to resolution and selectivity. A decrease of performance was observed for higher loading, indicating mutual spatial influence of selector units leading to sterical hindrance. In addition, we observed that the effect of free azide groups on retention is negligible and the overall chromatographic behavior is comparable to other Cinchona derived chiral stationary phases.

  7. Chiral discrimination asserted by enantiomers of Ni (II), Cu (II) and Zn (II) Schiff base complexes in DNA binding, antioxidant and antibacterial activities.

    Science.gov (United States)

    Khan, Noor-ul Hasan; Pandya, Nirali; Prathap, K Jeya; Kureshy, Rukhsana Ilays; Abdi, Sayed Hasan Razi; Mishra, Sandhya; Bajaj, Hari Chandra

    2011-10-15

    Chiral Schiff base ligands (S)-H(2)L and (R)-H(2)L and their complexes (S-Ni-L, R-Ni-L, S-Cu-L, R-Cu-L, S-Zn-L and R-Zn-L) were synthesized, characterized and examined for their DNA binding, antioxidant and antibacterial activities. The complexes showed higher binding affinity to calf thymus DNA with binding constant ranging from 2.0×10(5) to 4.5×10(6) M(-1). All the complexes also exhibited remarkable superoxide (56-99%) and hydroxyl scavenging (45-89%) activities as well as antibacterial activities against gram (+) and gram (-) bacteria. However, none of the complexes showed antifungal activity. Conclusively, S enantiomers of the complexes were found to be relatively more efficient for DNA interaction, antioxidant and antibacterial activities than their R enantiomers. This study reveals the possible utilization of chiral Schiff base complexes for pharmaceutical applications.

  8. Metallic and semiconducting carbon nanotubes separation using an aqueous two-phase separation technique: a review

    Science.gov (United States)

    Tang, Malcolm S. Y.; Ng, Eng-Poh; Juan, Joon Ching; Ooi, Chien Wei; Ling, Tau Chuan; Woon, Kai Lin; Loke Show, Pau

    2016-08-01

    It is known that carbon nanotubes show desirable physical and chemical properties with a wide array of potential applications. Nonetheless, their potential has been hampered by the difficulties in acquiring high purity, chiral-specific tubes. Considerable advancement has been made in terms of the purification of carbon nanotubes, for instance chemical oxidation, physical separation, and myriad combinations of physical and chemical methods. The aqueous two-phase separation technique has recently been demonstrated to be able to sort carbon nanotubes based on their chirality. The technique requires low cost polymers and salt, and is able to sort the tubes based on their diameter as well as metallicity. In this review, we aim to provide a review that could stimulate innovative thought on the progress of a carbon nanotubes sorting method using the aqueous two-phase separation method, and present possible future work and an outlook that could enhance the methodology.

  9. 镇痛药地佐辛的毛细管电泳手性分离研究%The study of the chiral separation of dezocine in CE

    Institute of Scientific and Technical Information of China (English)

    吕勇智; 危冲

    2016-01-01

    地佐辛作为阿片类镇痛药常用于术后止痛、癌症痛等。目前临床上地佐辛以外消旋体的形式给药。本文以麦芽糊精为手性选择剂,手性离子液体四甲基胺-L-酒石酸盐为添加剂,构建了毛细管电泳手性协同分离体系,并将该体系成功的应用于地佐辛对映体的手性分离。%Dezocine,as one of opioid analgesics,was commonly used for postoperative pain,cancer pain etc.And it was cur⁃rently applied as racemic drug in clinical practice.In this paper,the synergistic system of tetramethylammonium-L-tartaric acid and maltodextrin were established ,which can be successfully applied for the chiral separation of the dezocine with a satisfactory recovery .

  10. Towards a natural gesture interface: LDA-based gesture separability

    CERN Document Server

    Romaszewski, Michał; Głomb, Przemysław

    2011-01-01

    The goal of this paper is to analyse a method of validating a subset of gestures to be used as elements of a HCI interface. We investigate the applicability of LDA for gesture data dimensionality reduction. An Gesture mutual separability analysis of a diverse dataset of 22 natural gestures captured with two motion-capture devices is provided. Fisher criterion is used to produce measures of class separability and class overlap.

  11. Nanomolar detection of hypochlorite by a rhodamine-based chiral hydrazide in absolute aqueous media: application in tap water analysis with live-cell imaging.

    Science.gov (United States)

    Goswami, Shyamaprosad; Das, Avijit Kumar; Manna, Abhishek; Maity, Anup Kumar; Saha, Partha; Quah, Ching Kheng; Fun, Hoong-Kun; Abdel-Aziz, Hatem A

    2014-07-01

    By employing the oxidation property of hypochlorite (OCl(-)), a novel rhodamine-based hydrazide of the chiral acid ((S)-(-)-2-pyrrolidone-5-carboxylic acid) (RHHP) was designed and synthesized for detection of OCl(-) absolutely in aqueous medium at nanomolar level. The structure of the chiral sensor was also proved by the X-ray crystallography. The bioactivity and the application of the probe for detection of OCl(-) in natural water system have been demonstrated. A plausible mechanism for oxidation of the sensor followed by hydrolysis is also proposed. The sensibility of the receptor toward OCl(-) was studied in absolute aqueous media, and the detection limit of hypochlorite-mediated oxidation to the receptor in nanomolar level makes this platform (RHHP) an ultrasensitive and unique system for OCl(-) oxidation.

  12. Highly photoresponsive and wavelength-selective circularly-polarized-light detector based on metal-oxides hetero-chiral thin film.

    Science.gov (United States)

    Lee, Seung Hee; Singh, Dhruv Pratap; Sung, Ji Ho; Jo, Moon-Ho; Kwon, Ki Chang; Kim, Soo Young; Jang, Ho Won; Kim, Jong Kyu

    2016-01-22

    A highly efficient circularly-polarized-light detector with excellent wavelength selectivity is demonstrated with an elegant and simple microelectronics-compatible way. The circularly-polarized-light detector based on a proper combination of the geometry-controlled TiO2-SnO2 hetero-chiral thin film as an effective chiroptical filter and the Si active layer shows excellent chiroptical response with external quantum efficiency as high as 30% and high helicity selectivity of ~15.8% in an intended wavelength range. Furthermore, we demonstrated the ability of manipulating both bandwidth and responsivity of the detector simultaneously in whole visible wavelength range by a precise control over the geometry and materials constituting hetero-chiral thin film. The high efficiency, wavelength selectivity and compatibility with conventional microelectronics processes enabled by the proposed device can result in remarkable developments in highly integrated photonic platforms utilizing chiroptical responses.

  13. Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers%手性金属有机骨架材料的合成及其在对映异构体选择性分离中的应用

    Institute of Scientific and Technical Information of China (English)

    祁晓月; 李先江; 白玉; 刘虎威

    2016-01-01

    手性现象在自然界中广泛存在,手性分离在药物研发、农用化学、药理学、环境科学和生物学等诸多领域具有重要意义。手性金属有机骨架化合物材料( MOFs)是一类具有特殊拓扑结构和可设计的孔道结构的新型多孔材料,加之其比表面积高、孔隙率大、热稳定性良好和溶剂耐受性好等特性,使得 MOFs 在分析化学领域的应用与研究日益深入。本文简要综述了手性 MOFs的合成方法,着重讨论了手性 MOFs在对映异构体选择性分离方面的应用及相关机理,最后对该类材料的发展前景做了展望。%Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development,agricultural chemistry,pharmacology,environmental science,biology and many other fields. Chiral metal-organic frameworks( MOFs ) are a new group of porous materials with special topology and designable pore structures,as well as their high specific surface area,porosity,excellent thermal stability,solvent resistance,etc. Thus,chiral MOFs are promising with various applications in the field of analytical chemistry. This review summa-rizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers,as well as related mechanism.

  14. Reducible chiral metamaterials

    CERN Document Server

    Ciattoni, Alessandro; Rizza, Carlo

    2016-01-01

    We introduce the concept of 3D reducible metamaterials whose constituent permittivity can be modelled by a factorized profile. The separated cartesian coordinates dependence, easily achieved in all-optical reconfigurable materials, allows to physically regard a reducible metamaterial as a superposition of three fictitious 1D generating media. We prove that, in the long-wavelength limit, the electromagnetic response of reducible metamaterials can be reconstructed from the properties of the 1D generating media whose interplay provides large freedom to control the electromagnetic chirality. Our approach introduces an unprecedented decomposition strategy in metamaterial science which allows the full ab-initio and flexible design of a complex 3D bianisotropic response by using 1D metamaterials as basic building blocks.

  15. Construction and NIR luminescent property of hetero-bimetallic Zn Nd complexes from two chiral salen-type Schiff-base ligands

    Science.gov (United States)

    Bi, Wei-Yu; Lü, Xing-Qiang; Chai, Wen-Li; Song, Ji-Rong; Wong, Wai-Yeung; Wong, Wai-Kwok; Jones, Richard A.

    2008-11-01

    Two new near-infrared (NIR) luminescent Zn-Nd complexes [ZnL 1Nd(OAc)(NO 3) 2] ( 3) and [ZnL 2Nd(DMF) 2(NO 3) 3] ( 4) have been obtained with two salen-type Schiff-base ligands H 2L 1 and H 2L 2, ( H 2L 1 = N, N'-bis(3-methoxysalicylidene)-(1s, 2s)-(-)1,2-dipheneylethylenediamine and H 2L 2 = N, N'-bis(3-methoxysalicylidene)-(s)-2,2-diamine-1,1'-binaphthyl) from the reaction of different chiral diamines with o-vanillin. The X-ray crystal structure analysis reveals that both of them crystallize in the chiral space groups with P2(1), a = 10.1669(6), b = 19.3775(11), c = 17.4639(10) Å, β = 94.8710(10)°, V = 3428.1(3) Å 3, Z = 4 for 3, and C2, a = 22.1914(13), b = 9.7886(6), c = 22.0138(13) Å, β = 118.9590(10)°, V = 4372.5(4) Å 3, Z = 4 for 4. Complexes 3- 4 are both dinuclear Zn-Nd structures, while suitable choice of chiral Schiff-base ligands could induce the different complexions of ligands and metal ions, and the functional control of ligand character shows a potentially effective way to the fine-tuning properties of NIR luminescence from Nd ions.

  16. A liquid crystalline chirality balance for vapours

    Science.gov (United States)

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-Ichi

    2014-04-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-basedchirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs).

  17. Dynamic chirality, chirality transfer and aggregation behaviour of dithienylethene switches

    NARCIS (Netherlands)

    de Jong, Jaap J. D.; van Rijn, Patrick; Tiemersma-Wegeman, Theodora D.; Lucas, Linda N.; Browne, Wesley R.; Kellogg, Richard M.; Uchida, Kingo; Van Esch, Jan H.; Feringa, Ben L.

    2008-01-01

    The synthesis and characterisation of a series of chiral and achiral low molecular weight organogelators (LMWGs) based on bis-amide substituted dithienylethene photochromic switches is reported. The LMWGs gelate a range of solvents depending on the specific functionalisation of the hydrogen bonding

  18. A method based on a separation of variables in magnetohydrodynamics (MHD); Une methode de separation des variables en magnetohydrodynamique

    Energy Technology Data Exchange (ETDEWEB)

    Cessenat, M.; Genta, P.

    1996-12-31

    We use a method based on a separation of variables for solving a system of first order partial differential equations, in a very simple modelling of MHD. The method consists in introducing three unknown variables {phi}1, {phi}2, {phi}3 in addition of the time variable {tau} and then searching a solution which is separated with respect to {phi}1 and {tau} only. This is allowed by a very simple relation, called a `metric separation equation`, which governs the type of solutions with respect to time. The families of solutions for the system of equations thus obtained, correspond to a radial evolution of the fluid. Solving the MHD equations is then reduced to find the transverse component H{sub {Sigma}} of the magnetic field on the unit sphere {Sigma} by solving a non linear partial differential equation on {Sigma}. Thus we generalize ideas due to Courant-Friedrichs and to Sedov on dimensional analysis and self-similar solutions. (authors).

  19. The Direct Resolution of the Enantiomers of Four Chiral Pesticides

    Institute of Scientific and Technical Information of China (English)

    Peng WANG; Shu Ren JIANG; Zhi Qiang ZHOU

    2004-01-01

    Cellulose-tris(3,5-dimethylphenylcarbamate)(CDMPC) were synthesized as highperformance liquid chromatography (HPLC) chiral stationary phase(CSP). The successful resolution of four chiral pesticides on the CSP was realized and the influence of the temperature on the separation was studied.

  20. Cyclodextrin-Functionalized Monolithic Capillary Columns: Preparation and Chiral Applications.

    Science.gov (United States)

    Adly, Frady G; Antwi, Nana Yaa; Ghanem, Ashraf

    2016-02-01

    In this review, the recently reported approaches for the preparation of cyclodextrin-functionalized capillary monolithic columns are highlighted, with few applications in chiral separations using capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Chirality 28:97-109, 2016. © 2015 Wiley Periodicals, Inc.

  1. Baryons and Chiral Symmetry

    CERN Document Server

    Liu, Keh-Fei

    2016-01-01

    The relevance of chiral symmetry in baryons is highlighted in three examples in the nucleon spectroscopy and structure. The first one is the importance of chiral dynamics in understanding the Roper resonance. The second one is the role of chiral symmetry in the lattice calculation of $\\pi N \\sigma$ term and strangeness. The third one is the role of chiral $U(1)$ anomaly in the anomalous Ward identity in evaluating the quark spin and the quark orbital angular momentum. Finally, the chiral effective theory for baryons is discussed.

  2. Blind source separation based on generalized gaussian model

    Institute of Scientific and Technical Information of China (English)

    YANG Bin; KONG Wei; ZHOU Yue

    2007-01-01

    Since in most blind source separation (BSS) algorithms the estimations of probability density function (pdf) of sources are fixed or can only switch between one sup-Gaussian and other sub-Gaussian model,they may not be efficient to separate sources with different distributions. So to solve the problem of pdf mismatch and the separation of hybrid mixture in BSS, the generalized Gaussian model (GGM) is introduced to model the pdf of the sources since it can provide a general structure of univariate distributions. Its great advantage is that only one parameter needs to be determined in modeling the pdf of different sources, so it is less complex than Gaussian mixture model. By using maximum likelihood (ML) approach, the convergence of the proposed algorithm is improved. The computer simulations show that it is more efficient and valid than conventional methods with fixed pdf estimation.

  3. Evaporation-based Ge/.sup.68 Ga Separation

    Science.gov (United States)

    Mirzadeh, Saed; Whipple, Richard E.; Grant, Patrick M.; O'Brien, Jr., Harold A.

    1981-01-01

    Micro concentrations of .sup.68 Ga in secular equilibrium with .sup.68 Ge in strong aqueous HCl solution may readily be separated in ionic form from the .sup.68 Ge for biomedical use by evaporating the solution to dryness and then leaching the .sup.68 Ga from the container walls with dilute aqueous solutions of HCl or NaCl. The chloro-germanide produced during the evaporation may be quantitatively recovered to be used again as a source of .sup.68 Ga. If the solution is distilled to remove any oxidizing agents which may be present as impurities, the separation factor may easily exceed 10.sup.5. The separation is easily completed and the .sup.68 Ga made available in ionic form in 30 minutes or less.

  4. Particle Residence Time in Column Flotation Based on Cyclonic Separation

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xiao-hua; LIU Jiong-tian

    2007-01-01

    The cyclonic static micro-bubble column flotation (FCSMC) is an effective separation device for fine particle treatment. The high mineralization rate and short flotation time of this equipment can be attributed to its unique cyclonic force field. It also has been observed that the presence of a cyclonic force field leads to a lower bottom separation size limit and a reduction of unselective entrainment. The collection zone of the column is considered to consist of two parts, a column separation zone and a cyclonic zone. Total recovery of the collection zone was developed. For our study, we analyzed the particle movement in the cyclonic zone. Particle residence time equations for the cyclonic zone were derived by force analysis. Results obtained in this study provide a theoretical foundation for the design and scale-up of the FCSMC.

  5. Solvent-driven chiral-interaction reversion for organogel formation.

    Science.gov (United States)

    Qing, Guangyan; Shan, Xingxing; Chen, Wenrui; Lv, Ziyu; Xiong, Peng; Sun, Taolei

    2014-02-17

    For chiral gels and related applications, one of the critical issues is how to modulate the stereoselective interaction between the gel and the chiral guest precisely, as well as how to translate this information into the macroscopic properties of materials. Herein, we report that this process can also be modulated by nonchiral solvents, which can induce a chiral-interaction reversion for organogel formation. This process could be observed through the clear difference in gelation speed and the morphology of the resulting self-assembly. This chiral effect was successfully applied in the selective separation of quinine enantiomers and imparts "smart" merits to the gel materials.

  6. Nematic twist cell: Strong chirality induced at the surfaces

    Science.gov (United States)

    Lin, Tzu-Chieh; Nemitz, Ian R.; Pendery, Joel S.; Schubert, Christopher P. J.; Lemieux, Robert P.; Rosenblatt, Charles

    2013-04-01

    A nematic twist cell having a thickness gradient was filled with a mixture containing a configurationally achiral liquid crystal (LC) and chiral dopant. A chiral-based linear electrooptic effect was observed on application of an ac electric field. This "electroclinic effect" varied monotonically with d, changing sign at d =d0 where the chiral dopant exactly compensated the imposed twist. The results indicate that a significant chiral electrooptic effect always exists near the surfaces of a twist cell containing molecules that can be conformationally deracemized. Additionally, this approach can be used to measure the helical twisting power (HTP) of a chiral dopant in a liquid crystal.

  7. Chiral Rotational Spectroscopy

    CERN Document Server

    Cameron, Robert P; Barnett, Stephen M

    2015-01-01

    We introduce chiral rotational spectroscopy: a new technique that enables the determination of the individual optical activity polarisability components $G_{XX}'$, $G_{YY}'$, $G_{ZZ}'$, $A_{X,YZ}$, $A_{Y,ZX}$ and $A_{Z,XY}$ of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample whilst yielding an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral by virtue of their isotopic constitution and molecules with multiple chiral centres. The principles that underpin chiral rotational spectroscopy can also be exploited in the search for molecular chirality in space, which, if found, may add weight to hypotheses that biological homochirality and indeed life itself are of cosmic origin.

  8. Effective Chirality Transfer in [3+2] Reaction between Allenyl-Rhodium and Enal: Mechanistic Study Based on DFT Calculations.

    Science.gov (United States)

    Qi, Xiaotian; Liu, Song; Zhang, Tao; Long, Rong; Huang, Jun; Gong, Jianxian; Yang, Zhen; Lan, Yu

    2016-09-16

    Theoretical calculation was performed to study the chirality transfer in a newly reported intramolecular [3+2] cycloaddition of enal and alleno rhodium species, generated in situ from an enynol precursor. [3.3.0] bicyclic system which contains two bridgehead quaternary carbons that can be achieved, the chirality of which are controlled by those of the starting material, and the product stereoselectivity is only determined by the α-position of the acetylene moiety. Density functional theory calculations predicted that only the cis [3.3.0] bicyclic product could be generated, regardless of either erythro or threo substrate, which was also confirmed by experimental observations.

  9. Convenient Syntheses of Some C4 Chiral Building Blocks Starting From (S)-Malic Acid

    Institute of Scientific and Technical Information of China (English)

    WU TianJun; YU XianYong; ZHENG Xiao; HUANG PeiQiang

    2001-01-01

    @@ In the field of chiral technology, the synthesis of chiral intermediates and chiral building blocks occupies an important position. Chiral building blocks bearing double and / or multiple functionalities is particularly useful for the synthesis of chiral pharmaceuticals and chiral agrochemicals. In the recent years, we have been engaged in the development of synthetic methodology based on (S)-malic acid1-s. In these studies, malimide 2, easily accessible from (S)-malic acid, was shown to be a useful multifunctional building block in the asymmetric synthesis of natural products and chiral drugs (Scheme 1).

  10. Convenient Syntheses of Some C4 Chiral Building Blocks Starting From (S)-Malic Acid

    Institute of Scientific and Technical Information of China (English)

    WU; TianJun

    2001-01-01

    In the field of chiral technology, the synthesis of chiral intermediates and chiral building blocks occupies an important position. Chiral building blocks bearing double and / or multiple functionalities is particularly useful for the synthesis of chiral pharmaceuticals and chiral agrochemicals.  In the recent years, we have been engaged in the development of synthetic methodology based on (S)-malic acid1-s. In these studies, malimide 2, easily accessible from (S)-malic acid, was shown to be a useful multifunctional building block in the asymmetric synthesis of natural products and chiral drugs (Scheme 1).  ……

  11. On chiral and non chiral 1D supermultiplets

    Energy Technology Data Exchange (ETDEWEB)

    Toppan, Francesco, E-mail: toppan@cbpf.b [Centro Brasileiro de Pesquisas Fisicas (TEO/CBPF), Rio de Janeiro, RJ (Brazil). Coordenacao de Fisica Teorica

    2011-07-01

    In this talk I discuss and clarify some issues concerning chiral and non chiral properties of the one-dimensional supermultiplets of the N-extended supersymmetry. Quaternionic chirality can be defined for N = 4, 5, 6, 7, 8. Octonionic chirality for N = 8 and beyond. Inequivalent chiralities only arise when considering several copies of N = 4 or N = 8 supermultiplets. (author)

  12. Carbon Nanotube-Based Separation Columns for Microchip Electrochromatography

    DEFF Research Database (Denmark)

    Mogensen, Klaus Bo; Delacourt, B.; Kutter, Jörg Peter

    2015-01-01

    Fabrication of the stationary phase for microchip chromatography is most often done by packing of the individual separation channel after fabrication of the microfluidic chip, which is a very time-consuming and costly process (Kutter. J Chromatogr A 1221:72–82, 2012). Here, we describe in detail...

  13. Environmental Consequences of Future Biogas Technologies based on Separated Slurry

    DEFF Research Database (Denmark)

    Hamelin, Lorie; Wesnæs, Marianne; Wenzel, Henrik

    2011-01-01

    This consequential life cycle assessment study highlights the key environmental aspects of producing biogas from separated pig and cow slurry, a relatively new but probable scenario for future biogas production, as it avoids the reliance on constrained carbon cosubstrates. Three scenarios involvi...

  14. Risk-Based Causal Modeling of Airborne Loss of Separation

    Science.gov (United States)

    Geuther, Steven C.; Shih, Ann T.

    2015-01-01

    Maintaining safe separation between aircraft remains one of the key aviation challenges as the Next Generation Air Transportation System (NextGen) emerges. The goals of the NextGen are to increase capacity and reduce flight delays to meet the aviation demand growth through the 2025 time frame while maintaining safety and efficiency. The envisioned NextGen is expected to enable high air traffic density, diverse fleet operations in the airspace, and a decrease in separation distance. All of these factors contribute to the potential for Loss of Separation (LOS) between aircraft. LOS is a precursor to a potential mid-air collision (MAC). The NASA Airspace Operations and Safety Program (AOSP) is committed to developing aircraft separation assurance concepts and technologies to mitigate LOS instances, therefore, preventing MAC. This paper focuses on the analysis of causal and contributing factors of LOS accidents and incidents leading to MAC occurrences. Mid-air collisions among large commercial aircraft are rare in the past decade, therefore, the LOS instances in this study are for general aviation using visual flight rules in the years 2000-2010. The study includes the investigation of causal paths leading to LOS, and the development of the Airborne Loss of Separation Analysis Model (ALOSAM) using Bayesian Belief Networks (BBN) to capture the multi-dependent relations of causal factors. The ALOSAM is currently a qualitative model, although further development could lead to a quantitative model. ALOSAM could then be used to perform impact analysis of concepts and technologies in the AOSP portfolio on the reduction of LOS risk.

  15. Chiral symmetry and chiral-symmetry breaking

    Energy Technology Data Exchange (ETDEWEB)

    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)

  16. Prospects of Source-Separation-Based Sanitation Concepts: A Model-Based Study

    NARCIS (Netherlands)

    Tervahauta, T.H.; Trang Hoang,; Hernández, L.; Zeeman, G.; Buisman, C.J.N.

    2013-01-01

    Separation of different domestic wastewater streams and targeted on-site treatment for resource recovery has been recognized as one of the most promising sanitation concepts to re-establish the balance in carbon, nutrient and water cycles. In this study a model was developed based on literature data

  17. Enantiomer separation of polychlorinated biphenyls on chiral chromatographic columns of cellulose and amylose by high-performance liquid chromatography%多氯联苯在纤维素和直链淀粉衍生物类手性色谱柱上的拆分

    Institute of Scientific and Technical Information of China (English)

    尹文华; 吴丞往; 方力; 张安平

    2012-01-01

    由于多氯联苯(Polychlorinated biphenyls)的纯对映体样品非常难得,国内外大多数的研究工作仅局限于外消旋体,而较少对其对映体的环境行为、生物毒性进行研究.采用三种不同的手性色谱柱对21种手性多氯联苯在不同流动相体系进行了拆分.最终有17种手性多氯联苯达到基线或部分分离,在纯正己烷流动相体系的拆分效果最佳.直链淀粉-三(5-氯-2-甲基苯基氨基甲酸酯)固定相具有很强的手性识别能力,Lux 3u Amylose-2柱可以作为Lux 3u Cellulose-1柱手性拆分的很好补充.当手性多氯联苯分子只含一个4号位氯代或同时含有5,5,号位氯代时,三种手性色谱柱较难对其分离完全.该方法分离速度快,可以作为纯对映体样品的制备方法.%Due to the enantiomer of polychlorinated biphenyls is rare, most of researches were focused on racemes, rather than environmental behavior or biotoxicity of enantiomer at home and abroad. The work investigated enantiomeric separation of 21 kinds of polychlorinated biphenyls with different chiral chromatographic columns by high-performance liquid chromatography. 17 kinds of PCBs achieved baseline or were at least partially separated. This was proved to be the most efficient for the chiral separation of 100% n-hexane mobile phase. As a kind of chiral stationary phases (CSPs), amylose tris (5-chlorine 2-methylphenylcarbamate) has a strong capacity of chiral recognition. Lux 3u Amylose-2 CSP is a great complementary for the chiral separation of Lux 3u Cellulose-1 CSP. The separations are difficult to be achieved for these three CSPs when polychlorinated biphenyls with chlorine substitution only in 4 position or in 5, 5' positions simultaneously. However, this approach could be used to obtain pure enantiomer of PCBs.

  18. Chirality-Controlled Synthesis and Applications of Single-Wall Carbon Nanotubes.

    Science.gov (United States)

    Liu, Bilu; Wu, Fanqi; Gui, Hui; Zheng, Ming; Zhou, Chongwu

    2017-01-24

    Preparation of chirality-defined single-wall carbon nanotubes (SWCNTs) is the top challenge in the nanotube field. In recent years, great progress has been made toward preparing single-chirality SWCNTs through both direct controlled synthesis and postsynthesis separation approaches. Accordingly, the uses of single-chirality-dominated SWCNTs for various applications have emerged as a new front in nanotube research. In this Review, we review recent progress made in the chirality-controlled synthesis of SWCNTs, including metal-catalyst-free SWCNT cloning by vapor-phase epitaxy elongation of purified single-chirality nanotube seeds, chirality-specific growth of SWCNTs on bimetallic solid alloy catalysts, chirality-controlled synthesis of SWCNTs using bottom-up synthetic strategy from carbonaceous molecular end-cap precursors, etc. Recent major progresses in postsynthesis separation of single-chirality SWCNT species, as well as methods for chirality characterization of SWCNTs, are also highlighted. Moreover, we discuss some examples where single-chirality SWCNTs have shown clear advantages over SWCNTs with broad chirality distributions. We hope this review could inspire more research on the chirality-controlled preparation of SWCNTs and equally important inspire the use of single-chirality SWCNT samples for more fundamental studies and practical applications.

  19. Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Bhushan, Ravi; Dixit, Shuchi

    2012-04-01

    Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

  20. Effects of gauge boson mass on chiral and deconfinement phase transitions in QED$_{3}$

    CERN Document Server

    Yin, Pei-Lin; Feng, Hong-Tao; Zong, Hong-Shi

    2016-01-01

    Based on the experimental observation that there is a coexisting region between the antiferromagnetic (AF) and $\\textit{d}$-wave superconducting ($\\textit{d}$SC) phases, the influences of gauge boson mass $m_{a}$ on chiral symmetry restoration and deconfinement phase transitions in QED$_{3}$ are investigated simultaneously within a unified framework, i.e., Dyson-Schwinger equations. The results show that the chiral symmetry restoration phase transition in the presence of the gauge boson mass $m_{a}$ is a typical second-order phase transition; the chiral symmetry restoration and deconfinement phase transitions are coincident; the critical number of fermion flavors $N^{c}_{f}$ decreases as the gauge boson mass $m_{a}$ increases and there exists a boundary that separates the $N^{c}_{f}$-$m_{a}$ plane into chiral symmetry breaking/confinement region for ($N_{f}^{c}$, $m_{a}$) below the boundary and chiral symmetry restoration/deconfinement region for ($N_{f}^{c}$, $m_{a}$) above it.

  1. Extrinsic electromagnetic chirality in metamaterials

    OpenAIRE

    Plum, E.; Fedotov, V. A.; Zheludev, N. I.

    2009-01-01

    Three- and two-dimensional chirality arising from the mutual orientation of non-chiral planar metamaterial structures and the incident electromagnetic wave (extrinsic chirality) lead to pronounced optical activity, circular dichroism and asymmetric transmission indistinguishable from those seen in media consisting of three- and two-dimensionally chiral molecules (intrinsic chirality).

  2. Online blind source separation based on joint diagonalization

    Institute of Scientific and Technical Information of China (English)

    Li Ronghua; Zhou Guoxu; Fang Zuyuan; Xie Shengli

    2009-01-01

    A now algorithm is proposed for joint diagonalization. With a modified objective function, the now algorithm not only excludes trivial and unbalanced solutions successfully, but is also easily optimized. In addition, with the new objective function, the proposed algorithm can work well in online blind source separation (BSS) for the first time, although this family of algorithms is always thought to be valid only in batch-mode BSS by far. Simulations show that it is a very competitive joint diagonalization algorithm.

  3. Bacteriophage-based nanoprobes for rapid bacteria separation

    Science.gov (United States)

    Chen, Juhong; Duncan, Bradley; Wang, Ziyuan; Wang, Li-Sheng; Rotello, Vincent M.; Nugen, Sam R.

    2015-10-01

    The lack of practical methods for bacterial separation remains a hindrance for the low-cost and successful development of rapid detection methods from complex samples. Antibody-tagged magnetic particles are commonly used to pull analytes from a liquid sample. While this method is well-established, improvements in capture efficiencies would result in an increase of the overall detection assay performance. Bacteriophages represent a low-cost and more consistent biorecognition element as compared to antibodies. We have developed nanoscale bacteriophage-tagged magnetic probes, where T7 bacteriophages were bound to magnetic nanoparticles. The nanoprobe allowed the specific recognition and attachment to E. coli cells. The phage magnetic nanprobes were directly compared to antibody-conjugated magnetic nanoprobes. The capture efficiencies of bacteriophages and antibodies on nanoparticles for the separation of E. coli K12 at varying concentrations were determined. The results indicated a similar bacteria capture efficiency between the two nanoprobes.The lack of practical methods for bacterial separation remains a hindrance for the low-cost and successful development of rapid detection methods from complex samples. Antibody-tagged magnetic particles are commonly used to pull analytes from a liquid sample. While this method is well-established, improvements in capture efficiencies would result in an increase of the overall detection assay performance. Bacteriophages represent a low-cost and more consistent biorecognition element as compared to antibodies. We have developed nanoscale bacteriophage-tagged magnetic probes, where T7 bacteriophages were bound to magnetic nanoparticles. The nanoprobe allowed the specific recognition and attachment to E. coli cells. The phage magnetic nanprobes were directly compared to antibody-conjugated magnetic nanoprobes. The capture efficiencies of bacteriophages and antibodies on nanoparticles for the separation of E. coli K12 at varying

  4. Wind-Induced Ventilation Based on the Separated Flow Region

    Directory of Open Access Journals (Sweden)

    Mostafa Rahimi

    2016-01-01

    Full Text Available An experimental investigation was conducted to study the potential use of the pressure reduction within the separated flow region followed by the wake at the leeward direction of a solid surface in natural ventilation of buildings. Air flow with mean velocity up to 7 m/s was directed onto a solid surface (circular plate and a semi-spherical surface behind which the top end of a vertical vent pipe had been placed. Pressure reduction at the exit section of the pipe, which was well inside the separated flow region, induced an air flow within the pipe. This air flow rate from the stagnant surroundings into the wake region was measured under different geometrical configurations and for various wind velocities. The study revealed that the pressure reduction within the separated flow region would be applicable for natural ventilation of different spaces at least as an auxiliary system. The spaces include; sanitary places, crop protection stocks, industrial workshops and other spaces where no regular ventilation is required.

  5. Detection of zinc ions under aqueous conditions using chirality assisted solid-state fluorescence of a bipyridyl based fluorophore.

    Science.gov (United States)

    Sreejith, Sivaramapanicker; Divya, Kizhumuri P; Ajayaghosh, Ayyappanpillai

    2008-07-07

    A pyrrole end-capped bipyridyl ligand incorporating a chiral handle exhibited high solid-state emission when compared to the achiral analogue 1b and to the racemic molecule 1c which allowed the design of a reusable fluorescent probe for the selective detection of Zn2+ under aqueous conditions.

  6. Preparation of molecularly imprinted resin based on chitosan for chiral recognition of S-mandelic acid.

    Science.gov (United States)

    Monier, M; El-Mekabaty, A

    2013-04-01

    An enantioselective S-mandelic acid (S-MA) imprinted chitosan (SMIC) was prepared by cross-linking of chitosan using formaldehyde cross-linker, in the presence of S-MA as an imprint template molecule and 0.5% acetic acid solution as a solvent. Non-imprinted cross-linked chitosan (NIC) as control was also prepared by the same procedure in absence of template molecules. The surface morphology of both SMIC and NIC were examined by scanning electron microscope (SEM). SMIC particles were applied to determine the optimum operational condition for S-MA separation from dilute aqueous solution. In adsorption step, optimum pH and retention time were 3.5 and 60 min, while corresponding values in extraction step were 1 and 40 min, respectively. Also, the adsorption isotherms indicated that the maximum adsorption capacities of S- and R-MA on SMIC were 100 ± 0.5 and 64 ± 0.8 mg/g, respectively, while in the case of NIC, both R- and S-MA present the same maximum adsorption.

  7. Cooperative expression of atomic chirality in inorganic nanostructures

    Science.gov (United States)

    Wang, Peng-Peng; Yu, Shang-Jie; Govorov, Alexander O.; Ouyang, Min

    2017-02-01

    Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks.

  8. Gelation induced supramolecular chirality: chirality transfer, amplification and application.

    Science.gov (United States)

    Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

    2014-08-14

    Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

  9. Microstructure effects for Casimir forces in chiral metamaterials

    Science.gov (United States)

    McCauley, Alexander P.; Zhao, Rongkuo; Reid, M. T. Homer; Rodriguez, Alejandro W.; Zhou, Jiangfeng; Rosa, F. S. S.; Joannopoulos, John D.; Dalvit, D. A. R.; Soukoulis, Costas M.; Johnson, Steven G.

    2010-10-01

    We examine a recent prediction for the chirality dependence of the Casimir force in chiral metamaterials by numerical computation of the forces between the exact microstructures, rather than homogeneous approximations. Although repulsion in the metamaterial regime is rigorously impossible, it is unknown whether a reduction in the attractive force can be achieved through suitable material engineering. We compute the exact force for a chiral bent-cross pattern, as well as forces for an idealized “omega”-particle medium in the dilute approximation and identify the effects of structural inhomogeneity (i.e., proximity forces and anisotropy). We find that these microstructure effects dominate the force for separations where chirality was predicted to have a strong influence. At separations where the homogeneous approximation is valid, in even the most ideal circumstances the effects of chirality are less than 10-4 of the total force, making them virtually undetectable in experiments.

  10. Novel electrochemical method for the characterization of the degree of chirality in chiral polyaniline.

    Science.gov (United States)

    Feng, Zhang; Li, Ma; Yan, Yang; Jihai, Tang; Xiao, Li; Wanglin, Li

    2013-01-01

    A novel method to indicate the degree of chirality in polyaniline (PANI) was developed. The (D-camphorsulfonic acid)- and (HCl)-PANI-based electrodes exhibited significantly different electrochemical performances in D- and L-Alanine (Ala) aqueous solution, respectively, which can be used for the characterization the optical activity of chiral PANI. Cyclic voltammogram, tafel, and open circuit potential of PANI-based electrodes were measured within D- and L-Ala electrolyte solution, respectively. The open circuit potentials under different reacting conditions were analyzed by Doblhofer model formula, in which [C(+)](poly1)/[C(+)](poly2) was used as a parameter to characterize the degree of chirality in chiral PANI. The results showed that [C(+)](poly1)/[C(+)](poly2) can be increased with increasing concentrations of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid. In addition, we detected that appropriate response time and lower temperature are necessary to improve the degree of chirality.

  11. Separation of single-walled carbon nanotubes by gel-based chromatography using surfactant step-gradient techniques and development of new instrumentation for studying SWCNT reaction processes

    Science.gov (United States)

    Breindel, Leonard M.

    Single-walled carbon nanotube (SWCNT) synthesis methods such as CoMoCATTM, HiPcoTM, pulsed laser vaporization (PLV), and catalytic chemical vapor deposition (CCVD) produce several different distributions of (n,m) SWCNT structures, where ( n,m) defines the nanotube diameter and chiral wrapping angle. Post-synthesis processing such as functionalization and/or separations must therefore be employed to yield high purity electronic or single (n,m) samples. Through the use of a surfactant gradient across a gel-based chromatographic column, separations of single (n,m) species can be achieved. Anionic surfactants such as SDS, SDBS, and AOT display different separation effectiveness for single (n,m) species. Results of near-infrared optical absorption for separated SWCNT surfactant suspensions will be discussed, leading to a broader understanding of the important factors necessary for the gel chromatography separation technique. In particular, the effects of SWCNT/surfactant micelle structure are found to be key to achieving fast, simple SWCNT electronic type separations. Additionally, development of new instrumentation for the near-infrared spectrofluorimetric analysis (NIR-SFA) of SWCNTs is useful to the advancement of fundamental SWCNT research and applications. NIR-SFA, for instance, allows for the (n,m) structures of a sample to be identified and monitored during the progress of a chemical reaction or separation experiment. Seeking to achieve the time resolutions necessary for such experiments, the design and optimizations of a system utilizing single-wavelength excitation by diode lasers coupled with a fast NIR detection system are presented.

  12. Enhanced Chiral Recognition by Cyclodextrin Dimers

    Directory of Open Access Journals (Sweden)

    Bart Jan Ravoo

    2011-07-01

    Full Text Available In this article we investigate the effect of multivalency in chiral recognition. To this end, we measured the host-guest interaction of a β-cyclodextrin dimer with divalent chiral guests. We report the synthesis of carbohydrate-based water soluble chiral guests functionalized with two borneol, menthol, or isopinocampheol units in either (+ or (– configuration. We determined the interaction of these divalent guests with a β-cyclodextrin dimer using isothermal titration calorimetry. It was found that—in spite of a highly unfavorable conformation—the cyclodextrin dimer binds to guest dimers with an increased enantioselectivity, which clearly reflects the effect of multivalency.

  13. Profiling of chiral and achiral carboxylic acid metabolomics: synthesis and evaluation of triazine-type chiral derivatization reagents for carboxylic acids by LC-ESI-MS/MS and the application to saliva of healthy volunteers and diabetic patients.

    Science.gov (United States)

    Takayama, Takahiro; Kuwabara, Tomohiro; Maeda, Toshio; Noge, Ichiro; Kitagawa, Yutaka; Inoue, Koichi; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

    2015-01-01

    Novel triazine-type chiral derivatization reagents, i.e., (S)-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidin-3-amine (DMT-3(S)-Apy) and (S)-4,6-dimethoxy-N-(pyrrolidin-3-yl)-1,3,5-triazin-2-amine (DMT-1(S)-Apy), were developed for the highly sensitive and selective detection of chiral carboxylic acids by UPLC-MS/MS analysis. Among the synthesized reagents, DMT-3(S)-Apy was a more efficient chiral reagent for the enantiomeric separation of chiral carboxylic acids in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The DMT-3(S)-Apy was used for the determination of 13 carboxylic acids in human saliva of healthy volunteers and diabetic patients. Various biological carboxylic acids including chiral carboxylic acids, and mono- and di-carboxylic acids were clearly identified in the saliva of healthy persons and diabetic patients. The concentrations of carboxylic acids detected in the saliva of diabetic patients were relatively higher than those in the healthy persons. Furthermore, the concentration of D-lactic acid (LA) and the ratio of D/L-LA in the diabetic patients were significantly higher than those in the healthy persons. The low ratio of D/L-LA in healthy persons was also identified to be independent of age and sex. These results suggest that the determination of the D/L-LA ratio in saliva might be applicable for the diagnosis of diabetes. Based on these observations, DMT-3(S)-Apy seems to be a useful chiral derivatization reagent for the determination not only of chiral carboxylic acids but also achiral ones. In conclusion, the proposed method using DMT-3(S)-Apy is useful for the carboxylic acid metabolomics study of various specimens.

  14. Chiral rotational spectroscopy

    Science.gov (United States)

    Cameron, Robert P.; Götte, Jörg B.; Barnett, Stephen M.

    2016-09-01

    We introduce chiral rotational spectroscopy, a technique that enables the determination of the orientated optical activity pseudotensor components BX X, BY Y, and BZ Z of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centers. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarizability components αX X, αY Y, and αZ Z as by-products, which could see it find use even for achiral molecules.

  15. Chiral Superfluidity for QCD

    CERN Document Server

    Kalaydzhyan, Tigran

    2014-01-01

    We argue that the strongly coupled quark-gluon plasma formed at LHC and RHIC can be considered as a chiral superfluid. The "normal" component of the fluid is the thermalized matter in common sense, while the "superfluid" part consists of long wavelength (chiral) fermionic states moving independently. We use the bosonization procedure with a finite cut-off and obtain a dynamical axion-like field out of the chiral fermionic modes. Then we use relativistic hydrodynamics for macroscopic description of the effective theory obtained after the bosonization. Finally, solving the hydrodynamic equations in gradient expansion, we find that in the presence of external electromagnetic fields or rotation the motion of the "superfluid" component gives rise to the chiral magnetic, chiral vortical, chiral electric and dipole wave effects. Latter two effects are specific for a two-component fluid, which provides us with crucial experimental tests of the model.

  16. Emerging chirality in nanoscience.

    Science.gov (United States)

    Wang, Yong; Xu, Jun; Wang, Yawen; Chen, Hongyu

    2013-04-07

    Chirality in nanoscience may offer new opportunities for applications beyond the traditional fields of chirality, such as the asymmetric catalysts in the molecular world and the chiral propellers in the macroscopic world. In the last two decades, there has been an amazing array of chiral nanostructures reported in the literature. This review aims to explore and categorize the common mechanisms underlying these systems. We start by analyzing the origin of chirality in simple systems such as the helical spring and hair vortex. Then, the chiral nanostructures in the literature were categorized according to their material composition and underlying mechanism. Special attention is paid to highlight systems with original discoveries, exceptional structural characteristics, or unique mechanisms.

  17. An investigation of paper based microfluidic devices for size based separation and extraction applications.

    Science.gov (United States)

    Zhong, Z W; Wu, R G; Wang, Z P; Tan, H L

    2015-09-01

    Conventional microfluidic devices are typically complex and expensive. The devices require the use of pneumatic control systems or highly precise pumps to control the flow in the devices. This work investigates an alternative method using paper based microfluidic devices to replace conventional microfluidic devices. Size based separation and extraction experiments conducted were able to separate free dye from a mixed protein and dye solution. Experimental results showed that pure fluorescein isothiocyanate could be separated from a solution of mixed fluorescein isothiocyanate and fluorescein isothiocyanate labeled bovine serum albumin. The analysis readings obtained from a spectrophotometer clearly show that the extracted tartrazine sample did not contain any amount of Blue-BSA, because its absorbance value was 0.000 measured at a wavelength of 590nm, which correlated to Blue-BSA. These demonstrate that paper based microfluidic devices, which are inexpensive and easy to implement, can potentially replace their conventional counterparts by the use of simple geometry designs and the capillary action. These findings will potentially help in future developments of paper based microfluidic devices.

  18. Nuclear chiral dynamics and thermodynamics

    Science.gov (United States)

    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.

  19. Chiral Shock Waves

    CERN Document Server

    Sen, Srimoyee

    2016-01-01

    We study shock waves in relativistic chiral matter. We argue that the conventional Rankine- Hugoinot relations are modified due to the presence of chiral transport phenomena. We show that the entropy discontinuity in a weak shock wave is linearly proportional to the pressure discontinuity when the effect of chiral transport becomes sufficiently large. We also show that rarefaction shock waves, which do not exist in usual nonchiral fluids, can appear in chiral matter. These features are exemplified by shock propagation in dense neutrino matter in the hydrodynamic regime.

  20. Anomalous chiral superfluidity

    Energy Technology Data Exchange (ETDEWEB)

    Lublinsky, Michael, E-mail: lublinsky@phys.uconn.ed [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States); Physics Department, Ben-Gurion University, Beer Sheva 84105 (Israel); Zahed, Ismail [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States)

    2010-02-08

    We discuss both the anomalous Cartan currents and the energy-momentum tensor in a left chiral theory with flavor anomalies as an effective theory for flavored chiral phonons in a chiral superfluid with the gauged Wess-Zumino-Witten term. In the mean-field (leading tadpole) approximation the anomalous Cartan currents and the energy-momentum tensor take the form of constitutive currents in the chiral superfluid state. The pertinence of higher order corrections and the Adler-Bardeen theorem is briefly noted.

  1. Doped Chiral Polymer Metamaterials Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Doped Chiral Polymer Metamaterials (DCPM) with tunable resonance frequencies have been developed by adding plasmonic inclusions into chiral polymers with variable...

  2. Electromagnetic Signatures of the Chiral Anomaly in Weyl Semimetals

    Science.gov (United States)

    Barnes, Edwin; Heremans, J. J.; Minic, Djordje

    2016-11-01

    Weyl semimetals are predicted to realize the three-dimensional axial anomaly first discussed in particle physics. The anomaly leads to unusual transport phenomena such as the chiral magnetic effect in which an applied magnetic field induces a current parallel to the field. Here we investigate diagnostics of the axial anomaly based on the fundamental equations of axion electrodynamics. We find that materials with Weyl nodes of opposite chirality and finite energy separation immersed in a uniform magnetic field exhibit an anomaly-induced oscillatory magnetic field with a period set by the chemical potential difference of the nodes. In the case where a chemical potential imbalance is created by applying parallel electric and magnetic fields, we find a suppression of the magnetic-field component parallel to the electric field inside the material for rectangular samples, suggesting that the chiral magnetic current opposes this imbalance. For cylindrical geometries, we instead find an enhancement of this magnetic-field component along with an anomaly-induced azimuthal component. We propose experiments to detect such magnetic signatures of the axial anomaly.

  3. Lab-chip HPLC with integrated droplet-based microfluidics for separation and high frequency compartmentalisation.

    Science.gov (United States)

    Kim, Jin-Young; Cho, Soong-Won; Kang, Dong-Ku; Edel, Joshua B; Chang, Soo-Ik; deMello, Andrew J; O'Hare, Danny

    2012-09-21

    We demonstrate the integration of a droplet-based microfluidic device with high performance liquid chromatography (HPLC) in a monolithic format. Sequential operations of separation, compartmentalisation and concentration counter were conducted on a monolithic chip. This describes the use of droplet-based microfluidics for the preservation of chromatographic separations, and its potential application as a high frequency fraction collector.

  4. Fe-Ti-O based catalyst for large-chiral-angle single-walled carbon nanotube growth

    DEFF Research Database (Denmark)

    He, Maoshuai; Zhang, Lili; Jiang, Hua

    2016-01-01

    Catalyst selection is very crucial for controlled growth of single-walled carbon nanotubes (SWNTs). Here we introduce a well-designed Fe-Ti-O solid solution for SWNT growth with a high preference to large chiral angles. The Fe-Ti-O catalyst was prepared by combining Ti layer deposition onto premade...... Fe nanoparticles with subsequent high-temperature air calcination, which favours the formation of a homogeneous Fe-Ti-O solid solution. Using CO as the carbon feedstock, chemical vapour deposition growth of SWNTs at 800 °C was demonstrated on the Fe-Ti-O catalyst. Nanobeam electron diffraction...... characterization on a number of individual SWNTs revealed that more than 94% of SWNTs have chiral angles larger than 15°. In situ environmental transmission electron microscopy study was carried out to reveal the catalyst dynamics upon reduction. Our results identify that the phase segregation through reducing Fe...

  5. Chirality in thiolate-protected gold clusters.

    Science.gov (United States)

    Knoppe, Stefan; Bürgi, Thomas

    2014-04-15

    Over recent years, research on thiolate-protected gold clusters Au(m)(SR)n has gained significant interest. Milestones were the successful determination of a series of crystal structures (Au102(SR)44, Au25(SR)18, Au38(SR)24, Au36(SR)24, and Au28(SR)20). For Au102(SR)44, Au38(SR)24, and Au28(SR)20, intrinsic chirality was found. Strong Cotton effects (circular dichroism, CD) of gold clusters protected by chiral ligands have been reported a long time ago, indicating the transfer of chiral information from the ligand into the cluster core. Our lab has done extensive studies on chiral thiolate-protected gold clusters, including those protected with chiral ligands. We demonstrated that vibrational circular dichroism can serve as a useful tool for the determination of conformation of the ligand on the surface of the cluster. The first reports on crystal structures of Au102(SR)44 and Au38(SR)24 revealed the intrinsic chirality of these clusters. Their chirality mainly arises from the arrangement of the ligands on the surface of the cluster cores. As achiral ligands are used to stabilize the clusters, racemic mixtures are obtained. However, the separation of the enantiomers by HPLC was demonstrated which enabled the measurement of their CD spectra. Thermally induced inversion allows determination of the activation parameters for their racemization. The inversion demonstrates that the gold-thiolate interface is anything but fixed; in contrast, it is rather flexible. This result is of fundamental interest and needs to be considered in future applications. A second line of our research is the selective introduction of chiral, bidentate ligands into the ligand layer of intrinsically chiral gold clusters. The ligand exchange reaction is highly diastereoselective. The bidentate ligand connects two of the protecting units on the cluster surface and thus effectively stabilizes the cluster against thermally induced inversion. A minor (but significant) influence of chiral ligands to

  6. Magnetic separation of iron-based nanosorbents from watery solutions

    Science.gov (United States)

    Medvedeva, Irina; Bakhteeva, Iuliia; Zhakov, Sergey; Baerner, Klaus

    2016-04-01

    Iron and iron oxide magnetic nanoparticles (MNP) both naked and with chemically modified surface are promising agents for different environmental applications, in particular for water purification and for analytical control of water and soil pollution. The MNP can be used as sorbents with selective abilities due to designed surface functionalization. While a lot of research has been devoted to the impurity sorption processes, the second part, that is the efficient removal of the MNP sorbents from the watery solution, has not been sufficiently studied so far. For that particles with magnetic cores are especially attractive due to the possibility of their subsequent magnetic separation from water without using coagulants, i.e. without a secondary water pollution, just by applying external magnetic fields B. In order to remove magnetic sorbent nanoparticles ( 10-100 nm) effectively from the water solution gradient magnetic fields are required. Depending on the MNP size, the magnetic moment, the chemical properties of the solution, the water purification conditions , either the low gradient magnetic separation (LGMS) with dB/dz 100 T/m is used. The gradient magnetic field is provided by permanent magnets or electromagnets of different configuration. In this work the sedimentation dynamics of naked Fe3O4 and Fe3O4@SiO2 nanoparticles (10-30 nm) in water was studied in a vertical gradient magnetic field (B1 ≤ 0.3T, dB/dz ≤ 0.13 T/cm). By this LGMS , the sedimentation time of the naked Fe3O4 NP is reduced down from several days to several minutes. The sedimentation time for Fe3O4@SiO2 decreases from several weeks to several hours and to several minutes when salts Na2SO4, CaCl2, NaH2PO4 are added to the solution. The results are interpreted in terms of MNP aggregate formation caused by electrostatic, steric and magnetic inter-particle interactions in the watery solution. ACKNOWLEDGMENTS The work was supported in part by the Ural Branch, Russian Academy of Sciences

  7. Sample injection and electrophoretic separation on a simple laminated paper based analytical device.

    Science.gov (United States)

    Xu, Chunxiu; Zhong, Minghua; Cai, Longfei; Zheng, Qingyu; Zhang, Xiaojun

    2016-02-01

    We described a strategy to perform multistep operations on a simple laminated paper-based separation device by using electrokinetic flow to manipulate the fluids. A laminated crossed-channel paper-based separation device was fabricated by cutting a filter paper sheet followed by lamination. Multiple function units including sample loading, sample injection, and electrophoretic separation were integrated on a single paper based analytical device for the first time, by applying potential at different reservoirs for sample, sample waste, buffer, and buffer waste. As a proof-of-concept demonstration, mixed sample solution containing carmine and sunset yellow were loaded in the sampling channel, and then injected into separation channel followed by electrophoretic separation, by adjusting the potentials applied at the four terminals of sampling and separation channel. The effects of buffer pH, buffer concentration, channel width, and separation time on resolution of electrophoretic separation were studied. This strategy may be used to perform multistep operations such as reagent dilution, sample injection, mixing, reaction, and separation on a single microfluidic paper based analytical device, which is very attractive for building micro total analysis systems on microfluidic paper based analytical devices.

  8. A flexible and versatile strategy for the covalent immobilization of chiral catalysts based on pyridinebis(oxazoline) ligands.

    Science.gov (United States)

    Cornejo, Alfonso; Fraile, José M; García, José I; Gil, María J; Luis, Santiago V; Martínez-Merino, Víctor; Mayoral, José A

    2005-07-08

    [reaction: see text] Flexible and versatile methods have been developed for the immobilization of chiral pyridinebis(oxazoline) ligands by covalent bonding to a solid support, either by grafting or by polymerization. Different spacers can easily be introduced to modulate the support-ligand distance and the electronic properties of the chiral ligand. As an example, 2,6-bis[(S)-4-isopropyloxazolin-2-yl]pyridine has been immobilized on polystyrene resins, both on a Merrifield-type resin by grafting and on supports prepared by polymerization of 4-vinyl-substituted ligands. The corresponding Ru complexes have been tested as catalysts in the cyclopropanation reaction between styrene and ethyl diazoacetate. The catalytic activity, the enantioselectivity, and the recyclability are strongly dependent on the catalyst preparation method and the total exclusion of oxygen and moisture in the filtration process. Under such optimized conditions, yields over 60% with up to 90% ee can be obtained in four successive reactions-the best cyclopropanation results described to date for a chiral solid ruthenium catalyst.

  9. Plasma For-Injector of Separable Material Based on the Beam-Plasma Discharge for Ion-Atomic Separation Technologies. Conception

    OpenAIRE

    Skibenko, E. I.; Yu. V. Kovtun; V.B. Yuferov

    2010-01-01

    In the paper, the functional definition of a plasma for-injector of separable material is presented, and the requirements to it are formulated. The version of a device for the material separation into elements based on the beam-plasma discharge is under consideration. The dimensions of a pilot separating device are determined. The following quantities are estimated: the particle concentration per unit length of the separating device, effective length of the beam-plasma interaction (BPI) withi...

  10. Evaluation of sulfated maltodextrin as a novel anionic chiral selector for the enantioseparation of basic chiral drugs by capillary electrophoresis.

    Science.gov (United States)

    Tabani, Hadi; Mahyari, Mojtaba; Sahragard, Ali; Fakhari, Ali Reza; Shaabani, Ahmad

    2015-01-01

    Introducing a new class of chiral selectors is an interesting work and this issue is still one of the hot topics in separation science and chirality. In this study, for the first time, sulfated maltodextrin (MD) was synthesized as a new anionic chiral selector and then it was successfully applied for the enantioseparation of five basic drugs (amlodipine, hydroxyzine, fluoxetine, tolterodine, and tramadol) as model chiral compounds using CE. This chiral selector has two recognition sites: a helical structure and a sulfated group which contribute to three corresponding driving forces; inclusion complexation, electrostatic interaction, and hydrogen binding. Under the optimized condition (buffer solution: 50 mM phosphate (pH 3.0) and 2% w/v sulfated MD; applied voltage: 18 kV; temperature: 20°C), baseline enantioseparation was observed for all mentioned chiral drugs. When instead of sulfated MD neutral MD was used under the same condition, no enantioseparation was observed which means the resolution power of sulfated MD is higher than neutral MD due to the electrostatic interaction between sulfated groups and protonated chiral drugs. Also, the countercurrent mobility of negatively charged MD (sulfated MD) allows more interactions between the chiral selector and chiral drugs and this in turn results in a successful resolution for the enantiomers. Furthermore, a higher concentration of neutral MD (approximately five times) is necessary to achieve the equivalent resolution compared with the negatively charged MD.

  11. Separation of thorium and uranium in nitric acid solution using silica based anion exchange resin.

    Science.gov (United States)

    Chen, Yanliang; Wei, Yuezhou; He, Linfeng; Tang, Fangdong

    2016-09-30

    To separate thorium and uranium in nitric acid solution using anion exchange process, a strong base silica-based anion exchange resin (SiPyR-N4) was synthesized. Batch experiments were conducted and the separation factor of thorium and uranium in 9M nitric acid was about 10. Ion exchange chromatography was applied to separate thorium and uranium in different ratios. Uranium could be eluted by 9M nitric acid and thorium was eluted by 0.1M nitric acid. It was proved that thorium and uranium can be separated and recovered successfully by this method.

  12. Research and Simulation of FECG Signal Blind Separation Algorithm Based on Gradient Method

    Directory of Open Access Journals (Sweden)

    Yu Chen

    2012-08-01

    Full Text Available Independent Component Analysis (ICA is a new developed signal separation and digital analysis technology in recent years. ICA has widely used because it does not need to know the signal prior information, which has became the hot spot in signal processing field research. In this study, we firstly introduce the principle, meaning and blind source separation algorithm based on the gradient. By using the traditional natural gradient algorithm and Equi-variant Adaptive Source Separation via Independent (EASI blind separation algorithm, mixing ECG signals with noises had been separated effectively into the Maternal Electrocardiograph (MECG signal, Fetal Electrocardiograph (FECG signal and noise signal. The algorithm separation test showed that EASI algorithm can better separate the fetal ECG signal and because the gradient algorithm is a kind of online algorithm, which can be used for clinical fetal ECG signal of the real-time detection with important practical value and research significance.

  13. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Solution Self-Aggregation and Recognition.

    Science.gov (United States)

    Sorrenti, Alessandro; Illa, Ona; Pons, Ramon; Ortuño, Rosa M

    2015-09-08

    Novel diastereomeric anionic amphiphiles based on the rigid cyclobutane β-amino acid scaffold have been synthesized and deeply investigated with the aim of generating new functional supramolecular architectures on the basis of the rational design of original amphiphilic molecules and the control of their self-assembly. The main interest has been focused on the effect that cis/trans stereochemistry exerts on their molecular organization and recognition. In diluted solutions, the relative stereochemistry mainly influences the headgroup solvation and anionic-charge stabilization, i.e., better stabilized in the cis diastereoisomer due to intramolecular hydrogen-bonding and/or charge-dipole interactions. This provokes differences in their physicochemical behavior (pKa, cmc, conductivity) as well as in the structural parameters of the spherical micelles formed. Although both diastereoisomers form fibers that evolve with time from the spherical micelles, they display markedly different morphology and kinetics of formation. In the lyotropic liquid crystal domain, the greatest differences are observed at the highest concentrations and can be ascribed to different hydrogen-bonding and molecular packing imposed by the stereochemical constraints. Remarkably, the spherical micelles of the two anionic surfactants show dramatically diverse enantioselection ability for bilirubin enantiomers. In addition, both the surfactants form heteroaggregates with bilirubin at submicellar concentrations but with a different expression of supramolecular chirality. This points out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates. All these differential features can be appropriate and useful for the design and development of new soft materials with

  14. Designing large scale chiral metamaterials by nanosphere shadowing lithography

    Science.gov (United States)

    He, Yizhuo; Zhao, Yiping

    2016-09-01

    A scalable nanofabrication technique for chiral metamaterials is presented, which combines the dynamic shadowing growth and self-assembled nanosphere monolayers, and is also known as nanosphere shadowing lithography. We have developed two strategies based on nanosphere shadowing lithography to prepare chiral nanostructures. The first strategy is to create a quasi-three-dimensional single-layer fan-shaped chiral nanostructure on nanospheres with one plasmonic material. The second strategy is to create three-dimensional multi-layers helical nanostructures with one plasmonic material and one dielectric material. Both strategies can produce large-area chiral nanostructures with strong chiral optical response, which makes nanosphere shadowing lithography suitable for producing chiral metamaterial based devices such as an ultrathin narrow-band circular polarizer.

  15. Chiral metamaterial design using optimized pixelated inclusions with genetic algorithm

    Science.gov (United States)

    Akturk, Cemal; Karaaslan, Muharrem; Ozdemir, Ersin; Ozkaner, Vedat; Dincer, Furkan; Bakir, Mehmet; Ozer, Zafer

    2015-03-01

    Chiral metamaterials have been a research area for many researchers due to their polarization rotation properties on electromagnetic waves. However, most of the proposed chiral metamaterials are designed depending on experience or time-consuming inefficient simulations. A method is investigated for designing a chiral metamaterial with a strong and natural chirality admittance by optimizing a grid of metallic pixels through both sides of a dielectric sheet placed perpendicular to the incident wave by using a genetic algorithm (GA) technique based on finite element method solver. The effective medium parameters are obtained by using constitutive equations and S parameters. The proposed methodology is very efficient for designing a chiral metamaterial with the desired effective medium parameters. By using GA-based topology, it is proven that a chiral metamaterial can be designed and manufactured more easily and with a low cost.

  16. Chiral dynamics with (non)strange quarks

    Science.gov (United States)

    Kubis, Bastian; Meißner, Ulf-G.

    2017-01-01

    We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405), the dynamical generation of the lowest S11 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy-Steiner analysis of pion-nucleon scattering, a high-precision extraction of the elusive pion-nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

  17. Microfabricated palladium-based membranes for hydrogen separation

    NARCIS (Netherlands)

    Tong, Duy Hien

    2004-01-01

    The goal of this project was to fabricate thin and defect-free Pd-based membranes. This is thought to be accomplished by using techniques of microfabrication technology [60-62]. In order to show their potential, the fabricated membranes are then used as hydrogen purifiers to get high quality hydroge

  18. On Charge Conjugation, Chirality and Helicity of the Dirac and Majorana Equation for Massive Leptons

    Directory of Open Access Journals (Sweden)

    Eckart Marsch

    2015-04-01

    Full Text Available We revisit the charge-conjugation operation for the Dirac equation in its chiral representation. A new decomposition of the Dirac spinor field is suggested and achieved by means of projection operators based on charge conjugation, which is discussed here in a non-standard way. Thus, two separate two-component Majorana-type field equations for the eigenfields of the charge-conjugation operator are obtained. The corresponding free fields are entirely separated without a gauge field, but remain mixed and coupled together through an electromagnetic field term. For fermions that are charged and, thus, subjected to the gauge field of electrodynamics, these two Majorana fields can be reassembled into a doublet, which is equivalent to a standard four-component Dirac spinor field. In this way, the Dirac equation is retained in a new guise, which is fully equivalent to that equation in its chiral form.

  19. Chirality-specific lift forces of helix under shear flows: Helix perpendicular to shear plane.

    Science.gov (United States)

    Zhang, Qi-Yi

    2017-02-01

    Chiral objects in shear flow experience a chirality-specific lift force. Shear flows past helices in a low Reynolds number regime were studied using slender-body theory. The chirality-specific lift forces in the vorticity direction experienced by helices are dominated by a set of helix geometry parameters: helix radius, pitch length, number of turns, and helix phase angle. Its analytical formula is given. The chirality-specific forces are the physical reasons for the chiral separation of helices in shear flow. Our results are well supported by the latest experimental observations.

  20. Engineering of radiation of optically active molecules with chiral nano-meta-particles

    CERN Document Server

    Klimov, Vasily V; Ducloy, Martial

    2011-01-01

    The radiation of optically active (chiral) molecule placed near chiral nanoparticle is investigated. The optimal conditions for engineering of radiation of optically active (chiral) molecules with the help of chiral nanoparticles are derived. It is shown that for this purpose, the substance of the chiral particle must have both \\epsilon_and \\mu_negative (double negative material (DNG)) or negative \\mu_and positive \\epsilon_(\\mu_negative material (MNG)). Our results pave the way to an effective engineering of radiation of "left" and "right" molecules and to creating pure optical devices for separation of drugs enantiomers.

  1. Engineering of radiation of optically active molecules with chiral nano-meta-particles

    Science.gov (United States)

    Klimov, V. V.; Guzatov, D. V.; Ducloy, M.

    2012-02-01

    The radiation of an optically active (chiral) molecule placed near a chiral nanosphere is investigated. The optimal conditions for engineering of radiation of optically active (chiral) molecules with the help of chiral nanoparticles are derived. It is shown that for this purpose, the substance of the chiral particle must have both ɛ and μ negative (double negative material (DNG)) or negative μ and positive ɛ (μ negative material (MNG)). Our results pave the way to an effective engineering of radiation of "left" and "right" molecules and to creating pure optical devices for separation of drugs enantiomers.

  2. Separation of enantiomers by capillary electrophoresis using pentosan polysulfate.

    Science.gov (United States)

    Wang, X; Lee, J T; Armstrong, D W

    1999-01-01

    Pentosan polysulfate, a semisynthetic polysaccharide, was employed as a chiral run buffer additive in capillary electrophoresis. Twenty-eight racemic analytes were resolved. The separations were successful only at low pH when the analytes were significantly protonated. This suggests that ionic interactions were the dominant associative interactions between the anionic pentosan polysulfate and the positively charged analytes. Compared to other linear, carbohydrate-based chiral selectors (i.e., chondroitin sulfates, heparin and dextran sulfate) pentosan polysulfate has some characteristics common of anionic polysaccharides; yet it has several differences in its structure and properties which account for its unusual enantioselectivity. The effects of pH, concentration of phosphate buffer, concentration of pentosan polysulfate and the type and concentration of organic modifier on the enantiomeric separations were investigated. The optimization of these separations were dependent on the nature of the analytes and could be achieved by the proper choice of experimental conditions.

  3. Interference Phenomenon for Different Chiral Bosonization Schemes

    CERN Document Server

    Abreu, Everton M C; Abreu, Everton M C; Wotzasek, Clovis

    1998-01-01

    We study the relationship between different chiral bosonization schemes (CBS) in the context of the soldering formalism\\cite{MS}, that considers the phenomenon of interference in the quantum field theory\\cite{ABW}. This analysis is done in the framework put forward by Siegel\\cite{WS} and by Floreanini and Jackiw\\cite{FJ} (FJ). We propose a field redefinition that discloses the presence of a noton, a non dynamical field, in Siegel's formulation for chiral bosons. The presence of a noton in the Siegel CBS is a new and surprising result, that separates dynamics from symmetry by diagonalising the Siegel action into the FJ and the noton action. While the first describes the chiral dynamics, the noton carries the symmetry contents, acquiring dynamics upon quantization and is fully responsible for the Siegel anomaly. The diagonal representation proposed here is used to study the effect of quantum interference between gauged rightons and leftons.

  4. Synthesis and structural characterization of a new chiral porous hybrid organic–inorganic material based on γ-zirconium phosphates and L-(+)-phosphoserine

    Energy Technology Data Exchange (ETDEWEB)

    Alhendawi, Hussein M.H., E-mail: hussein.alhendawi@yahoo.com [Department of Chemistry, Faculty of Science, Al-Azhar University of Gaza, 1277 Gaza, Palestine (Country Unknown)

    2013-05-01

    In the present work, a chiral layered derivative of γ-zirconium phosphate (γ-ZrP) containing L-(+)-phosphoserine (γ-ZrP-PS*) covalently attached to inorganic layers has been prepared by means of topotactic exchange reaction. This organic–inorganic derivative is characterized by X-ray diffractometry, Solid {sup 13}C–NMR and FT-IR spectrophotometries and thermal analyses. A maximum level of topotactic replacement of 20% is achieved. Under both the acidic environment of the interlayer region of γ-ZrP and the acidic synthesis conditions, the hydrolysis of the ester bond of PS* is expected to take place to some extent. For this reason, it was impossible to exceed the recent percentage, which in turn reflects the relative moderate stability of the above mentioned bond under these conditions. In order to be more certain with regard to an expected further hydrolysis for this bond after separation, a sample of γ-ZrP-PS* was stored in a desiccator over a saturated solution of BaCl{sub 2} (90% relative humidity) for three months, and then the sample re-analyzed once again. Surprisingly, the results show that the sample still keeps almost the same level of exchange (i.e., 20%). Second, it is revealed that the sample almost gives the same spectroscopic and thermal behavior. This could be attributed to the less acidic character of the partially exchanged inorganic layers of the sample in comparison with that of the precursor γ-ZrP. Therefore, the PS* molecules persist and stay there into the interlayer gallery without further hydrolysis. - Graphical abstract: • Red: oxygen • White: zirconium • Cyan: carbon • Yellow: phosphorus • Blue: nitrogen. Highlights: • L-(+)-Phosphoserine (PS*) is exchanged with γ-ZrP by means of topotactic exchange. • The maximum exchange level is 20%. • γ-ZrP is functionalized with chiral amino acid group. • γ-ZrP-PS* has large chiral space for huge guest molecules to be intercalated.

  5. THE SEPARATION OF BASE METALS FROM PLATINUM METALS BY ION EXCHANGE

    Institute of Scientific and Technical Information of China (English)

    JIANGLingen; HUANGYan

    1992-01-01

    In this paper the separation of base metals Fe,Co,Ni and Cu from the platinum metals on a cation exchanger column was studies.The convenient separation conditions are 0.5mol·dm-3 NaCl,pH=2. The recovery efficiency of Rh is 98%.

  6. Determination of Optimal Energy Efficient Separation Schemes based on Driving Forces

    DEFF Research Database (Denmark)

    Bek-Pedersen, Erik; Gani, Rafiqul; Levaux, O.

    2000-01-01

    A new integrated approach for synthesis, design and operation of separation schemes is presented. This integrated approach is based on driving forces that promote the desired separation for different separation techniques. A set of algorithms needed by the integrated approach for sequencing...... and design of distillation columns and for generating hybrid separation schemes are presented. The main feature of these algorithms is that they provide a 'visual' solution that also appears to be near optimal in terms of energy consumption. Several illustrative examples highlighting the application...

  7. Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries

    Science.gov (United States)

    Miao, Yue-E.; Zhu, Guan-Nan; Hou, Haoqing; Xia, Yong-Yao; Liu, Tianxi

    2013-03-01

    Polyimide (PI) nanofiber-based nonwovens have been fabricated via electrospinning for the separators of lithium-ion batteries (LIBs). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and hot oven tests show that the PI nanofiber-based nonwovens are thermally stable at a high temperature of 500 °C while the commercial Celgard membrane exhibits great shrinkage at 150 °C and even goes melting over 167 °C, indicating a superior thermal stability of PI nanofiber-based nonwovens than that of the Celgard membrane. Moreover, the PI nanofiber-based nonwovens exhibit better wettability for the polar electrolyte compared to the Celgard membrane. The PI nanofiber-based nonwoven separators are also evaluated to have higher capacity, lower resistance and higher rate capability compared to the Celgard membrane separator, which proves that they are ideal candidates for separators of high-performance rechargeable LIBs.

  8. Development of chiral sulfoxide ligands for asymmetric catalysis.

    Science.gov (United States)

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  9. Sound field separating on arbitrary surfaces enclosing a sound scatterer based on combined integral equations.

    Science.gov (United States)

    Fan, Zongwei; Mei, Deqing; Yang, Keji; Chen, Zichen

    2014-12-01

    To eliminate the limitations of the conventional sound field separation methods which are only applicable to regular surfaces, a sound field separation method based on combined integral equations is proposed to separate sound fields directly in the spatial domain. In virtue of the Helmholtz integral equations for the incident and scattering fields outside a sound scatterer, combined integral equations are derived for sound field separation, which build the quantitative relationship between the sound fields on two arbitrary separation surfaces enclosing the sound scatterer. Through boundary element discretization of the two surfaces, corresponding systems of linear equations are obtained for practical application. Numerical simulations are performed for sound field separation on different shaped surfaces. The influences induced by the aspect ratio of the separation surfaces and the signal noise in the measurement data are also investigated. The separated incident and scattering sound fields agree well with the original corresponding fields described by analytical expressions, which validates the effectiveness and accuracy of the combined integral equations based separation method.

  10. "On-the-fly" kinetics of enzymatic racemization using deuterium NMR in DNA-based chiral oriented media.

    Science.gov (United States)

    Chan-Huot, Monique; Lesot, Philippe; Pelupessy, Philippe; Duma, Luminita; Bodenhausen, Geoffrey; Duchambon, Patricia; Toney, Michael D; Reddy, U Venkateswara; Suryaprakash, N

    2013-05-07

    We report the in situ and real-time monitoring of the interconversion of L- and D-alanine-d3 by alanine racemase from Bacillus stearothermophilus directly observed by (2)H NMR spectroscopy in anisotropic phase. The enantiomers are distinguished by the difference of their (2)H quadrupolar splittings in a chiral liquid crystal containing short DNA fragments. The proof-of-principle, the reliability, and the robustness of this new method is demonstrated by the determination of the turnover rates of the enzyme using the Michaelis-Menten model.

  11. Direct high-performance liquid chromatography enantioseparation of terazosin on an immobilised polysaccharide-based chiral stationary phase under polar organic and reversed-phase conditions.

    Science.gov (United States)

    Ferretti, Rosella; Gallinella, Bruno; La Torre, Francesco; Zanitti, Leo; Turchetto, Luciana; Mosca, Antonina; Cirilli, Roberto

    2009-07-10

    High-performance liquid chromatography (HPLC) enantioseparation of terazosin (TER) was accomplished on the immobilised-type Chiralpak IC chiral stationary phase (CSP) under both polar organic and reversed-phase modes. A simple analytical method was validated using a mixture of methanol-water-DEA 95:5:0.1 (v/v/v) as a mobile phase. Under reversed-phase conditions good linearities were obtained over the concentration range 8.76-26.28 microg mL(-1) for both enantiomers. The limits of detection and quantification were 10 and 30 ng mL(-1), respectively. The intra- and inter-day assay precision was less than 1.66% (RSD%). The optimised conditions also allowed to resolve chiral and achiral impurities from the enantiomers of TER. The proposed HPLC method supports pharmacological studies on the biological effects of the both forms of TER and analytical investigations of potential drug formulations based on a single enantiomer. At the semipreparative scale, 5.3 mg of racemic sample were resolved with elution times less than 12 min using a mobile phase consisting of methanol-DEA 100:0.1 (v/v) and both enantiomers were isolated with a purity of > or = 99% enantiomeric excess (ee). The absolute configuration of TER enantiomers was assigned by comparison of the measured specific rotations with those reported in the literature.

  12. A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

    Science.gov (United States)

    Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

    2015-10-30

    Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance.

  13. Applications of chiral symmetry

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. An incentive-based source separation model for sustainable municipal solid waste management in China.

    Science.gov (United States)

    Xu, Wanying; Zhou, Chuanbin; Lan, Yajun; Jin, Jiasheng; Cao, Aixin

    2015-05-01

    Municipal solid waste (MSW) management (MSWM) is most important and challenging in large urban communities. Sound community-based waste management systems normally include waste reduction and material recycling elements, often entailing the separation of recyclable materials by the residents. To increase the efficiency of source separation and recycling, an incentive-based source separation model was designed and this model was tested in 76 households in Guiyang, a city of almost three million people in southwest China. This model embraced the concepts of rewarding households for sorting organic waste, government funds for waste reduction, and introducing small recycling enterprises for promoting source separation. Results show that after one year of operation, the waste reduction rate was 87.3%, and the comprehensive net benefit under the incentive-based source separation model increased by 18.3 CNY tonne(-1) (2.4 Euros tonne(-1)), compared to that under the normal model. The stakeholder analysis (SA) shows that the centralized MSW disposal enterprises had minimum interest and may oppose the start-up of a new recycling system, while small recycling enterprises had a primary interest in promoting the incentive-based source separation model, but they had the least ability to make any change to the current recycling system. The strategies for promoting this incentive-based source separation model are also discussed in this study.

  15. Synthesis and applications of novel bis(ammonium) chiral ionic liquids derived from isomannide

    DEFF Research Database (Denmark)

    Kumar, Vineet; Olsen, Carl Erik; Schäffer, Susan J.;

    2007-01-01

    Carbohydrate-based novel bis(ammonium) chiral ionic liquids have been synthesized by following a straightforward protocol using isomannide as the substrate. Their applications in chiral discrimination and optical resolution of racemates have been established.......Carbohydrate-based novel bis(ammonium) chiral ionic liquids have been synthesized by following a straightforward protocol using isomannide as the substrate. Their applications in chiral discrimination and optical resolution of racemates have been established....

  16. Chiral nucleon-nucleon forces in nuclear structure calculations

    Directory of Open Access Journals (Sweden)

    Coraggio L.

    2016-01-01

    Full Text Available Realistic nuclear potentials, derived within chiral perturbation theory, are a major breakthrough in modern nuclear structure theory, since they provide a direct link between nuclear physics and its underlying theory, namely the QCD. As a matter of fact, chiral potentials are tailored on the low-energy regime of nuclear structure physics, and chiral perturbation theory provides on the same footing two-nucleon forces as well as many-body ones. This feature fits well with modern advances in ab-initio methods and realistic shell-model. Here, we will review recent nuclear structure calculations, based on realistic chiral potentials, for both finite nuclei and infinite nuclear matter.

  17. Blind Source Separation Based on Covariance Ratio and Artificial Bee Colony Algorithm

    Directory of Open Access Journals (Sweden)

    Lei Chen

    2014-01-01

    Full Text Available The computation amount in blind source separation based on bioinspired intelligence optimization is high. In order to solve this problem, we propose an effective blind source separation algorithm based on the artificial bee colony algorithm. In the proposed algorithm, the covariance ratio of the signals is utilized as the objective function and the artificial bee colony algorithm is used to solve it. The source signal component which is separated out, is then wiped off from mixtures using the deflation method. All the source signals can be recovered successfully by repeating the separation process. Simulation experiments demonstrate that significant improvement of the computation amount and the quality of signal separation is achieved by the proposed algorithm when compared to previous algorithms.

  18. Normal and polar-organic-phase high-performance liquid chromatographic enantioresolution of omeprazole, rabeprazole, lansoprazole and pantoprazole using monochloro-methylated cellulose-based chiral stationary phase and determination of dexrabeprazole.

    Science.gov (United States)

    Dixit, Shuchi; Dubey, Rituraj; Bhushan, Ravi

    2014-01-01

    Enantioresolution of four anti-ulcer drugs (chiral sulfoxides), namely, omeprazole, rabeprazole, lansoprazole and pantoprazole, was carried out by high-performance liquid chromatography using a polysaccharide-based chiral stationary phase consisting of monochloromethylated cellulose (Lux cellulose-2) under normal and polar-organic-phase conditions with ultraviolet detection at 285 nm. The method was validated for linearity, accuracy, precision, robustness and limit of detection. The optimized enantioresolution method was compared for both the elution modes. The optimized method was further utilized to check the enantiomeric purity of dexrabeprazole.

  19. ICA Based Speckle Filtering for Target Extraction in SAR Images Using Adaptive Space Separation

    Institute of Scientific and Technical Information of China (English)

    LI Yu-tong; ZHOU Yue; YANG Lei

    2008-01-01

    A novel approach based on independent component analysis (ICA) for speckle filtering and target extraction of synthetic aperture radar (SAR) images is proposed using adaptive space separation with weighted information entropy (WIE) incorporated. First the basis and the independent components are respectively obtained by ICA technique, and WIE of the image is computed; then based on the threshold computed from function T-WIE (threshold versus weighted-information-entropy), independent components are adaptively separated and the bases are classified accordingly. Thus, the image space is separated into two subspaces: "clean" and "noise". Then, a proposed nonlinear operator ABO is applied on each component of the 'clean' subspace for further optimization. Finally, recovery image is obtained reconstructing this subspace and target is easily extracted with binarisation. Note that here T-WIE is an interpolated function based on several representative target SAR images using proposed space separation algorithm.

  20. Spectral signatures of chirality

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2009-01-01

    We present a new way of measuring chirality, via the spectral shift of photonic band gaps in one-dimensional structures. We derive an explicit mapping of the problem of oblique incidence of circularly polarized light on a chiral one-dimensional photonic crystal with negligible index contrast...... to the formally equivalent problem of linearly polarized light incident on-axis on a non-chiral structure with index contrast. We derive analytical expressions for the first-order shifts of the band gaps for negligible index contrast. These are modified to give good approximations to the band gap shifts also...

  1. Chiral supergravity and anomalies

    CERN Document Server

    Mielke, E W; Macias, Alfredo; Mielke, Eckehard W.

    1999-01-01

    Similarily as in the Ashtekar approach, the translational Chern-Simons term is, as a generating function, instrumental for a chiral reformulation of simple (N=1) supergravity. After applying the algebraic Cartan relation between spin and torsion, the resulting canonical transformation induces not only decomposition of the gravitational fields into selfdual and antiselfdual modes, but also a splitting of the Rarita-Schwinger fields into their chiral parts in a natural way. In some detail, we also analyze the consequences for axial and chiral anomalies.

  2. Computational screening of MOF-based mixed matrix membranes for CO2/N2 separations

    OpenAIRE

    Avcı, Seda Keskin; Sümer, Zeynep

    2016-01-01

    Atomically detailed simulations were used to examine CO2/N-2 separation potential of metal organic framework- (MOF-) based mixed matrix membranes (mmms) in this study. Gas permeability and selectivity of 700 new mmms composed of 70 different mofs and 10 different polymers were calculated for CO2/N-2 separation. This is the largest number of MOF-based mmms for which computational screening is done to date. Selecting the appropriate mofs as filler particles in polymers resulted in mmms that hav...

  3. Enantiomer separation by complexation SFC on immobilized Chirasil-nickel and Chirasil-zinc.

    Science.gov (United States)

    Schurig, V; Fluck, M

    2000-07-05

    The use of complexation SFC for enantiomer separation of Lewis base selectands on chiral nickel(II)- and zinc(II)-bis[(3-heptafluorobutanoyl)-10-methylene-(1R)-camphora te] chemically bonded to poly(dimethylsiloxane) (Chirasil-nickel and Chirasil-zinc) and employed as Lewis acid selectors is described. The method is especially suited for less volatile and configurationally labile racemates. The variation of the experimental parameters temperature T, pressure p and density rho of the mobile phase carbon dioxide on the retention factor k, relative retention r and chiral separation factor alpha is studied, providing insights into the mechanisms of chiral recognition under supercritical conditions. For mecoprop methyl ester (methyl 2-(4-chloro-2-methylphenoxy)propanoate) an unusual increase of alpha at increased temperature is observed on Chirasil-nickel. Supercritical carbon dioxide does not inadvertently affect the complexation equilibria between Lewis donor selectands and the Lewis acid metal selectors during complexation SFC.

  4. Catalysis of Dynamical Chiral Symmetry Breaking by Chiral Chemical Potential

    CERN Document Server

    Braguta, V V

    2016-01-01

    In this paper we study the properties of media with chiral imbalance parameterized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus the chiral chemical potential plays a role of the catalyst of dynamical chiral symmetry breaking. Physically this effect results from the appearance of the Fermi surface and additional fermion states on this surface which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  5. Enantioselective nano liquid chromatographic separation of racemic pharmaceuticals: a facile one-pot in situ preparation of lipase-based polymer monoliths in capillary format.

    Science.gov (United States)

    Ahmed, Marwa; Ghanem, Ashraf

    2014-11-01

    New affinity monolithic capillary columns of 150 µm internal diameter were prepared in situ fused glass capillary via either immobilization or encapsulation of Candida antarctica lipase B (CALB) on or within polymer monoliths, respectively. The immobilized lipase-based monoliths were prepared via copolymerization of 19.1% monomers (8.9% MMA and 10.2% GMA), 19.8% EDMA, and 61.1% porogens (54.2% formamide and 6.9% 1-propanol) w/w or 20% GMA, 20% EDMA, and 60% porogens (51.6% cyclohexanol and 8.4% 1-dodecanol) in the presence of AIBN (1%) as a radical initiator. This was followed by pumping a solution of lipase through the capillaries and rinsing with potassium phosphate buffer. On the other hand, the encapsulated lipase-based monoliths were prepared via copolymerization of 20% monomers (GMA), 20% EDMA, and 60% porogens (48% 1-propanol, 6% 1,4-butanediol) or 16.4% monomers (16% BuMA, 0.4% SPMA), 23.6% EDMA, and 60% porogens (36% 1-propanol, 18% 1,4-butanediol along with 6% lipase aqueous solution in potassium phosphate buffer. The prepared capillary columns were investigated for the enantioselective nano liquid chromatographic separation of a set of different classes of racemic pharmaceuticals, namely, α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs. Run-to-run repeatability was quite satisfactory. The encapsulated lipase-based capillary monolith showed better enantioselective separations of most of the investigated compounds. Baseline separation was achieved for alprenolol, atenolol, bromoglutithimide, carbuterol, chloropheneramine, cizolertine carbinol, 4-hydroxy-3-methoxymandelic acid, desmethylcizolertine, nomifensine, normetanephrine, and sulconazole under reversed phase chromatographic conditions. A speculation about the understanding of the chiral recognition mechanism of

  6. Conductivity of carbonate- and perfluoropolyether-based electrolytes in porous separators

    Science.gov (United States)

    Devaux, Didier; Chang, Yu H.; Villaluenga, Irune; Chen, X. Chelsea; Chintapalli, Mahati; DeSimone, Joseph M.; Balsara, Nitash P.

    2016-08-01

    In lithium batteries, a porous separator filled with an electrolyte is placed in between the electrodes. Properties of the separator such as porosity and wettability strongly influence the conductivity of the electrolyte-separator composite. This study focuses on three commercial separators: a single layer polypropylene (Celgard 2500), a trilayer polypropylene-polyethylene-polypropylene (PP-PE-PP), and a porous polytetrafluoroethylene (PTFE). Electron microscopy was used to characterize the pore structure, and these experiments reveal large differences in pore morphology. The separators were soaked in both carbonate- and perfluoropolyether-based electrolytes. The conductivity of the neat electrolytes (σ0) varied from 6.46 × 10-6 to 1.76 × 10-2 S cm-1. The porosity and wettability of the separator affect the electrolyte uptake that in turn affect the conductivity of electrolyte-separator composites. The conductivity of the electrolyte-separator composites (σ) was found to follow a master equation, σ = 0.51·σ0·ϕc3.2±0.2, where ϕc is the volume fraction of the electrolyte in each separator.

  7. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

    2013-04-28

    ) modified by a variety of chiral templates. • Demonstrated enantioselective separation of racemic PO on chemically synthesized chiral gold nanoparticles. • Discovery of zwitterionic adsorption states of amino acids on Pd(111). • First structure determinations of adsorbed amino acids and identification of tetrameric chiral template structures. • Exploration of the enantiospecific interaction of PO and R-3-MCHO adsorption on chirally modified Cu(100), Cu(110) and Cu(111). One-to-One Interactions • Determination of cinchona orientation on Pt surfaces in situ at the solid-liquid interface using FT-IRAS. • Systematic study of the influence of solution properties on the adsorption of modified cinchonas alkaloids onto Pt surfaces. • Correlation of cinchona adsorption with catalytic activity, as affected by concentration, the nature of the solvent, and dissolved gases in the liquid phase. • Measurement of enantioselective chemisorption on 1-(1-naphthyl) ethylamine (NEA) modified Pt(111) and Pd(111) surfaces. • Imaging of chiral docking complexes between NEA and methyl pyruvate on Pd(111). Chiral Catalyst Synthesis • Anchoring of cinchona alkaloid to surfaces • Synthesis of chiral Au nanoparticles and demonstration of their enantiospecific interactions with R- and S-PO. • Elucidation of the driving forces for chiral imprinting of Cu(100) by L- and D-lysine to form Cu(3,1,17)R&S facets.

  8. Chiral Brownian heat pump

    OpenAIRE

    Van Den Broek, Martijn; Van Den Broeck, Christian

    2007-01-01

    We present the exact analysis of a chiral Brownian motor and heat pump. Optimization of the construction predicts, for a nanoscale device, frequencies of the order of kHz and cooling rates of the order of femtojoule per second.

  9. Chiral brownian heat pump.

    Science.gov (United States)

    van den Broek, M; Van den Broeck, C

    2008-04-04

    We present the exact analysis of a chiral Brownian motor and heat pump. Optimization of the construction predicts, for a nanoscale device, frequencies of the order of kHz and cooling rates of the order of femtojoule per second.

  10. Color chiral solitons

    CERN Document Server

    Novozhilov, V Yu; Novozhilov, Victor; Novozhilov, Yuri

    2002-01-01

    We discuss specific features of color chiral solitons (asymptotics, possibility of confainment, quantization) at example of isolated SU(2) color skyrmions, i.e. skyrmions in a background field which is the vacuum field forming the gluon condensate.

  11. Chiral resolution of salbutamol in plasma sample by a new chiral ligand-exchange chromatography method after its extraction with nano-sized imprinted polymer.

    Science.gov (United States)

    Alizadeh, Taher; Shamkhali, Amir Naser

    2016-01-15

    A new chromatographic procedure, based upon chiral ligand-exchange principal, was developed for the resolution of salbutamol enantiomers. The separation was carried out on a C18 column. (l)-Alanine and Cu(2+) were applied as chiral resolving agent and complexing ion, respectively. The kind of copper salt had definitive effect on the enantioseparation. Density functional theory (DFT) was used to substantiate the effect of various anions, accompanying Cu(2+), on the formation of ternary complexes, assumed to be created during separation process. The DFT results showed that the anion kind had huge effect on the stability difference between two corresponding diastereomeric complexes and their chemical structures. It was shown that the extent of participation of the chiral selector in the ternary diastereomeric complexes formation was managed by the anion kind, affecting thus the enantioseparation efficiency of the developed method. Water/methanol (70:30) mixture containing (l)-alanine-Cu(2+) (4:1) was found to be the best mobile phase for salbutamol enantioseparation. In order to analyze sulbutamol enantiomers in plasma samples, racemic salbutamol was first extracted from the samples via nano-sized salbutamol-imprinted polymer and then enantioseparated by the developed method.

  12. High Temperature Stable Separator for Lithium Batteries Based on SiO₂ and Hydroxypropyl Guar Gum.

    Science.gov (United States)

    Carvalho, Diogo Vieira; Loeffler, Nicholas; Kim, Guk-Tae; Passerini, Stefano

    2015-10-23

    A novel membrane based on silicon dioxide (SiO₂) and hydroxypropyl guar gum (HPG) as binder is presented and tested as a separator for lithium-ion batteries. The separator is made with renewable and low cost materials and an environmentally friendly manufacturing processing using only water as solvent. The separator offers superior wettability and high electrolyte uptake due to the optimized porosity and the good affinity of SiO₂ and guar gum microstructure towards organic liquid electrolytes. Additionally, the separator shows high thermal stability and no dimensional-shrinkage at high temperatures due to the use of the ceramic filler and the thermally stable natural polymer. The electrochemical tests show the good electrochemical stability of the separator in a wide range of potential, as well as its outstanding cycle performance.

  13. Chiral Odd GPDs

    Directory of Open Access Journals (Sweden)

    Goldstein Gary R.

    2015-01-01

    Full Text Available Nucleon spin structure, transversity and the tensor charge are of central importance to understanding the role of QCD in hadronic physics. A new approach to measuring orbital angular momenta of quarks in the proton via twist 3 GPDs is shown. The “flexible parametrization” of chiral even GPDs is reviewed and its transformation into the chiral odd sector is discussed. The resulting parametrization is applied to recent data on π0 and η electroproduction.

  14. Continuous size-based separation of microparticles in a microchannel with symmetric sharp corner structures.

    Science.gov (United States)

    Fan, Liang-Liang; He, Xu-Kun; Han, Yu; Du, Li; Zhao, Liang; Zhe, Jiang

    2014-03-01

    A new microchannel with a series of symmetric sharp corner structures is reported for passive size-dependent particle separation. Micro particles of different sizes can be completely separated based on the combination of the inertial lift force and the centrifugal force induced by the sharp corner structures in the microchannel. At appropriate flow rate and Reynolds number, the centrifugal force effect on large particles, induced by the sharp corner structures, is stronger than that on small particles; hence after passing a series of symmetric sharp corner structures, large particles are focused to the center of the microchannel, while small particles are focused at two particle streams near the two side walls of the microchannel. Particles of different sizes can then be completely separated. Particle separation with this device was demonstrated using 7.32 μm and 15.5 μm micro particles. Experiments show that in comparison with the prior multi-orifice flow fractionation microchannel and multistage-multiorifice flow fractionation microchannel, this device can completely separate two-size particles with narrower particle stream band and larger separation distance between particle streams. In addition, it requires no sheath flow and complex multi-stage separation structures, avoiding the dilution of analyte sample and complex operations. The device has potentials to be used for continuous, complete particle separation in a variety of lab-on-a-chip and biomedical applications.

  15. Coordination Chemistry and Asymmetric Catalysis with a Chiral Diphosphonite

    NARCIS (Netherlands)

    Vlugt, Jarl Ivar; Paulusse, Jos M.J.; Zijp, Eric J.; Tijmensen, Jason A.; Mills, Allison M.; Spek, Anthony L.; Claver, Carmen; Vogt, Dieter

    2004-01-01

    The improved synthesis of the chiral diphosphonite, XantBino (1), based on a xanthene backbone and bearing chiral binaphthyl groups on both P-atoms is described together with its PdII and RhI complexes. The 31P NMR spectra of both complexes point out that the two phosphorus atoms are chemically ineq

  16. Circular dichroism of graphene oxide: the chiral structure model

    Institute of Scientific and Technical Information of China (English)

    Jing CAO; Hua-Jie YIN; Rui SONG

    2013-01-01

    We have observed the circular dichroism signal of dilute graphene oxide (GO), then systematically investigated the chirality of GO and established a probable chiral unit model, This study may open up a new field for understanding the structure of GO and lay the foundation for fabrication of GO-based materials.

  17. Dynamic control of chirality in phosphine ligands for enantioselective catalysis

    NARCIS (Netherlands)

    Zhao, Depeng; Neubauer, Thomas M; Feringa, Ben L

    2015-01-01

    Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly

  18. New Enantiomerically Pure Alkylimido Mo-Based Complexes. Synthesis, Characterization, and Activity as Chiral Olefin Metathesis Catalysts

    Science.gov (United States)

    Pilyugina, Tatiana S.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    Molybdenum olefin metathesis catalysts that contain aliphatic 1-phenylcyclohexylimido (NPhCy) and 2-phenyl-2-adamantylimido (NPhAd) groups and (S)-Biphen or (R)-Trip)(THF) ligands (Biphen = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate; Trip = 3,3′-bis(2,4,6-triisopropylphenyl)-2,2′-binaphtholate) have been prepared. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross-metathesis of substituted norborneols with styrene were compared to the results obtained with the only known alkylimido catalyst Mo(NAd)(CHCMe2Ph)[(S)-Biphen]. The activities and enantioselectivities provided by these new chiral complexes vary significantly, but in virtually all instances explored were not superior to the adamantylimido analogs. PMID:19079732

  19. Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II-based metalloradical catalysis

    Directory of Open Access Journals (Sweden)

    Jingran Tao

    2014-06-01

    Full Text Available The Co(II complex of a new D2-symmetric chiral porphyrin 3,5-DiMes-QingPhyrin, [Co(P6], can catalyze asymmetric aziridination of alkenes with bis(2,2,2-trichloroethylphosphoryl azide (TcepN3 as a nitrene source. This new Co(II-based metalloradical aziridination is suitable for different aromatic olefins, producing the corresponding N-phosphorylaziridines in good to excellent yields (up to 99% with moderate to high enantioselectivities (up to 85% ee. In addition to mild reaction conditions and generation of N2 as the only byproduct, this new metalloradical catalytic system is highlighted with a practical protocol that operates under neutral and non-oxidative conditions.

  20. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation.

    Science.gov (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min

    2013-10-07

    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  1. Crystal structure of 2-{(R)-[1-(4-bromo-phen-yl)eth-yl]imino-meth-yl}-4-(phenyl-diazen-yl)phenol, a chiral photochromic Schiff base.

    Science.gov (United States)

    Moriwaki, Ryoji; Akitsu, Takashiro

    2015-11-01

    The title chiral photochromic Schiff base compound, C21H18BrN3O, was synthesized from (R)-(+)-1-(4-bromo-phen-yl)ethyl-amine and the salicyl-aldehyde of an azo-benzene derivative. The mol-ecule corresponds to the phenol-imine tautomer, the C=N and N-C bond distances being 1.285 (3) and 1.470 (3) Å, respectively. The diazenyl group adopts a trans form, with an N=N distance of 1.256 (3) Å. The hy-droxy group is involved in intra-molecular O-H⋯N hydrogen bonding. In the crystal, C-H⋯π inter-actions consolidate the crystal packing of one-dimensional chains, which exhibits short inter-molecular Br⋯C contacts of 3.400 (3) Å.

  2. Reflection and transmission matrices at a free-space-chiral interface based on the invariant constitutive relations for gyrotropic media and the Drude-Born-Federov constitutive relations.

    Science.gov (United States)

    Bahar, Ezekiel

    2009-08-01

    The expressions for the linear and cross-polarized reflection and transmission coefficients based on the invariant gyrotropic constitutive relations and the Drude-Born-Federov constitutive relations are compared. A physical interpretation for the first-order terms in the gyrotropic parameter and the chiral parameter is presented for normal and oblique angles of incidence. The analytical expressions for the linear cross-polarized or circular-like polarized reflection coefficients are proportional to the product of the gyrotropic measure, the tangent squared of the angle of refraction in the host medium, the round trip transmission coefficients for the horizontally and vertically polarized waves, and the polarization dependent reflection coefficients for a perfectly conducting mirror. These analytical results are consistent with the observed enhancement of the differential circular reflection for near-grazing incidence.

  3. Single channel source separation of radar fuze mixed signal based on phase difference analysis

    Institute of Scientific and Technical Information of China (English)

    Hang ZHU; Shu-ning ZHANG; Hui-chang ZHAO

    2014-01-01

    A new method based on phase difference analysis is proposed for the single-channel mixed signal separation of single-channel radar fuze. This method is used to estimate the mixing coefficients of de-noised signals through the cumulants of mixed signals, solve the candidate data set by the mixing coefficients and signal analytical form, and resolve the problem of vector ambiguity by analyzing the phase differences. The signal separation is realized by exchanging data of the solutions. The waveform similarity coefficients are calculated, and the timeefrequency dis-tributions of separated signals are analyzed. The results show that the proposed method is effective.

  4. Spintronics and chirality: spin selectivity in electron transport through chiral molecules.

    Science.gov (United States)

    Naaman, Ron; Waldeck, David H

    2015-04-01

    Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electron's transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices.

  5. Ultra-microporous triptycene-based polyimide membranes for high-performance gas separation

    KAUST Repository

    Ghanem, Bader

    2014-03-11

    A highly permeable and highly selective polyimide of intrinsic microporosity is prepared using a 9,10-diisopropyl-triptycene contortion center. The three-dimensionality and shape-persistence of triptycene afford exceptional sieving-based gas separation performance transcending the latest permeability/selectivity trade-offs for industrial gas separations involving oxygen and hydrogen. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Cellulose acetate-based molecularly imprinted polymeric membrane for separation of vanillin and o-vanillin

    OpenAIRE

    Chunjing Zhang; Shian Zhong; Zhengpeng Yang

    2008-01-01

    Cellulose acetate-based molecularly imprinted polymeric membranes were prepared using vanillin as template molecule. The microscopic structure of the resultant polymeric membranes was characterized by SEM and FTIR spectroscopy, and the selective binding properties and separation capacity of the membranes for vanillin and o-vanillin were tested with binding experiments and separate experiments, respectively. The results showed that the vanillin-imprinted polymeric membranes displayed higher bi...

  7. Tracking method based on separation and combination of the measurements for radar and IR fusion system

    Institute of Scientific and Technical Information of China (English)

    Wang Qingchao; Wang Wenfei

    2009-01-01

    A new distributed fusion method of radar/infrared (IR) tracking system based on separation and combination of the measurements is proposed by analyzing the influence of rate measurement. The rate information separated from the radar measurements together with measurements of IR form a pseudo vector of IR, and the corresponding filter is designed. The results indicate that the method not only makes a great improvement to the local tracker's performance, but also improves the global tracking precision efficiently.

  8. Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

    Science.gov (United States)

    Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

    2016-01-01

    The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

  9. Ionic liquid-based materials: a platform to design engineered CO2 separation membranes.

    Science.gov (United States)

    Tomé, Liliana C; Marrucho, Isabel M

    2016-05-21

    During the past decade, significant advances in ionic liquid-based materials for the development of CO2 separation membranes have been accomplished. This review presents a perspective on different strategies that use ionic liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation membranes. Based on compilation and analysis of the data hitherto reported, we provide a judicious assessment of the CO2 separation efficiency of different membranes, and highlight breakthroughs and key challenges in this field. In particular, configurations such as supported ionic liquid membranes, polymer/ionic liquid composite membranes, gelled ionic liquid membranes and poly(ionic liquid)-based membranes are detailed, discussed and evaluated in terms of their efficiency, which is attributed to their chemical and structural features. Finally, an integrated perspective on technology, economy and sustainability is provided.

  10. Aldol Reactions of Axially Chiral 5-Methyl-2-(o-arylimino-3-(o-aryl-thiazolidine-4-ones

    Directory of Open Access Journals (Sweden)

    Sule Erol Gunal

    2016-06-01

    Full Text Available Axially chiral 5-methyl-2-(o-arylimino-3-(o-aryl-thiazolidine-4-ones have been subjected to aldol reactions with benzaldehyde to produce secondary carbinols which have been found to be separable by HPLC on a chiral stationary phase. Based on the reaction done on a single enantiomer resolved via a chromatographic separation from a racemic mixture of 5-methyl-2-(α-naphthylimino-3-(α-naphthyl-thiazolidine-4-one by HPLC on a chiral stationary phase, the aldol reaction was shown to proceed via an enolate intermediate. The axially chiral enolate of the thiazolidine-4-one was found to shield one face of the heterocyclic ring rendering face selectivity with respect to the enolate. The selectivities observed at C-5 of the ring varied from none to 11.5:1 depending on the size of the ortho substituent. Although the aldol reaction proceeded with a lack of face selectivity with respect to benzaldehyde, recrystallization returned highly diastereomerically enriched products.

  11. Separation of base flow from streamflow using groundwater levels - illustrated for the Pang catchment (UK)

    NARCIS (Netherlands)

    Peters, E.; Lanen, van H.A.J.

    2005-01-01

    A new filter to separate base flow from streamflow has developed that uses observed groundwater levels. To relate the base flow to the observed groundwater levels, a non-linear relation was used. This relation is suitable for unconfined aquifers with deep groundwater levels that do not respond to in

  12. Chiral Random Matrix Theory and Chiral Perturbation Theory

    CERN Document Server

    Damgaard, P H

    2011-01-01

    Spontaneous breaking of chiral symmetry in QCD has traditionally been inferred indirectly through low-energy theorems and comparison with experiments. Thanks to the understanding of an unexpected connection between chiral Random Matrix Theory and chiral Perturbation Theory, the spontaneous breaking of chiral symmetry in QCD can now be shown unequivocally from first principles and lattice simulations. In these lectures I give an introduction to the subject, starting with an elementary discussion of spontaneous breaking of global symmetries.

  13. Chiral Random Matrix Theory and Chiral Perturbation Theory

    Energy Technology Data Exchange (ETDEWEB)

    Damgaard, Poul H, E-mail: phdamg@nbi.dk [Niels Bohr International Academy and Discovery Center, The Niels Bohr Institute, Blegdamsvej 17, DK-2100 Copenhagen (Denmark)

    2011-04-01

    Spontaneous breaking of chiral symmetry in QCD has traditionally been inferred indirectly through low-energy theorems and comparison with experiments. Thanks to the understanding of an unexpected connection between chiral Random Matrix Theory and chiral Perturbation Theory, the spontaneous breaking of chiral symmetry in QCD can now be shown unequivocally from first principles and lattice simulations. In these lectures I give an introduction to the subject, starting with an elementary discussion of spontaneous breaking of global symmetries.

  14. Fabrication and testing of novel blood separation devices based on microchannel bend structures

    Science.gov (United States)

    Blattert, C.; Jurischka, R.; Schoth, A.; Kerth, P.; Menz, W.

    2005-02-01

    Most clinical chemistry tests are performed on cell-free serum or plasma. Therefore micro assay devices for blood tests require integrated on-chip microfluidics for separation of plasma or serum from blood. Polymers are ideally suited for these applications due to their material properties and their applicability for high volume production. These requirements are achieved by a new on-chip blood separation technique based on microchannel bend structures and a rapid processing technology for micro assay devices using injection molding or hot embossing. Different prototype polymer chips with channel dimensions down to 20 μm and aspect ratios of 4 have been fabricated by injection molding and hot embossing. The inserts for the molding tools were fabricated by an UV-LIGA technology. The separation efficiency of these chips has been tested with human blood samples. The results show different separation efficiencies up to 100 % for blood cells and plasma depending on microchannel geometry as well as cell concentration. As compared to present microfluidic devices for the separation of blood cells like filters, membranes or filtration by diffusion the microchannel bend is an integrated on-chip blood separation method. It combines the advantages of rapid separation times and a simple geometry that leads to cost-effective high volume production using injection molding.

  15. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Condensed Phase and Monolayer Structure.

    Science.gov (United States)

    Sorrenti, Alessandro; Illa, Ona; Ortuño, Rosa M; Pons, Ramon

    2016-07-12

    New diastereomeric nonionic amphiphiles, cis- and trans-1, based on an optically pure cyclobutane β-amino ester moiety have been investigated to gain insight into the influence exerted by cis/trans stereochemistry and stereochemical constraints on the physicochemical behavior, molecular organization, and morphology of their Langmuir monolayers and dry solid states. All these features are relevant to the rational design of functional materials. trans-1 showed a higher thermal stability than cis-1. For the latter, a higher fluidity of its monolayers was observed when compared with the films formed by trans-1 whose BAM images revealed the formation of condensed phase domains with a dendritic shape, which are chiral, and all of them feature the same chiral sign. Although the formation of LC phase domains was not observed by BAM for cis-1, compact dendritic crystals floating on a fluid subphase were observed beyond the collapse, which are attributable to multilayered 3D structures. These differences can be explained by the formation of hydrogen bonds between the amide groups of consecutive molecules allowing the formation of extended chains for trans-1 giving ordered arrangements. However, for cis-1, this alignment coexists with another one that allows the simultaneous formation of two hydrogen bonds between the amide and the ester groups of adjacent molecules. In addition, the propensity to form intramolecular hydrogen bonds must be considered to justify the formation of different patterns of hydrogen bonding and, consequently, the formation of less ordered phases. Those characteristics are congruent also with the results obtained from SAXS-WAXS experiments which suggest a more bent configuration for cis-1 than for trans-1.

  16. Blind Separation of Acoustic Signals Combining SIMO-Model-Based Independent Component Analysis and Binary Masking

    Directory of Open Access Journals (Sweden)

    Hiekata Takashi

    2006-01-01

    Full Text Available A new two-stage blind source separation (BSS method for convolutive mixtures of speech is proposed, in which a single-input multiple-output (SIMO-model-based independent component analysis (ICA and a new SIMO-model-based binary masking are combined. SIMO-model-based ICA enables us to separate the mixed signals, not into monaural source signals but into SIMO-model-based signals from independent sources in their original form at the microphones. Thus, the separated signals of SIMO-model-based ICA can maintain the spatial qualities of each sound source. Owing to this attractive property, our novel SIMO-model-based binary masking can be applied to efficiently remove the residual interference components after SIMO-model-based ICA. The experimental results reveal that the separation performance can be considerably improved by the proposed method compared with that achieved by conventional BSS methods. In addition, the real-time implementation of the proposed BSS is illustrated.

  17. Superconductivity in a chiral nanotube

    Science.gov (United States)

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-02-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity--unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  18. Chiral anomalies and differential geometry

    Energy Technology Data Exchange (ETDEWEB)

    Zumino, B.

    1983-10-01

    Some properties of chiral anomalies are described from a geometric point of view. Topics include chiral anomalies and differential forms, transformation properties of the anomalies, identification and use of the anomalies, and normalization of the anomalies. 22 references. (WHK)

  19. High temperature stable Li-ion battery separators based on polyetherimides with improved electrolyte compatibility

    Science.gov (United States)

    l'Abee, Roy; DaRosa, Fabien; Armstrong, Mark J.; Hantel, Moritz M.; Mourzagh, Djamel

    2017-03-01

    We report (electro-)chemically stable, high temperature resistant and fast wetting Li-ion battery separators produced through a phase inversion process using novel polyetherimides (PEI) based on bisphenol-aceton diphthalic anhydride (BPADA) and para-phenylenediamine (pPD). In contrast to previous studies using PEI based on BPADA and meta-phenylenediamine (mPD), the separators reported herein show limited swelling in electrolytes and do not require fillers to render sufficient mechanical strength and ionic conductivity. In this work, the produced 15-25 μm thick PEI-pPD separators show excellent electrolyte compatibility, proven by low degrees of swelling in electrolyte solvents, low contact angles, fast electrolyte wicking and high electrolyte uptake. The separators cover a tunable range of morphologies and properties, leading to a wide range of ionic conductivities as studied by Electrochemical Impedance Spectroscopy (EIS). Dynamic Mechanical Analysis (DMA) demonstrated dimensional stability up to 220 °C. Finally, single layer graphite/lithium nickel manganese cobalt oxide (NMC) pouch cells were assembled using this novel PEI-pPD separator, showing an excellent capacity retention of 89.3% after 1000 1C/2C cycles, with a mean Coulombic efficiency of 99.77% and limited resistance build-up. We conclude that PEI-pPD is a promising new material candidate for high performance separators.

  20. Community-based surveillance to monitor trends in unaccompanied and separated children in eastern DRC.

    Science.gov (United States)

    Rubenstein, Beth L; Spencer, Craig; Mansourian, Hani; Noble, Eva; Munganga, Gustave B; Stark, Lindsay

    2015-12-01

    Children who are separated from their families and usual caregivers in emergencies face a multitude of risks. The humanitarian community lacks methods to systematically capture changes in the frequency and nature of such separations over time. A mobile phone-based community surveillance system was piloted in the Democratic Republic of the Congo. The goal was to identify new cases of unaccompanied and separated children on a weekly basis. Over an 11-week period, community focal points reported 62 cases of separation across 10 communities. The majority of children had been under the care of their parents prior to separation. More than half of the children were unaccompanied, meaning that they were living without an adult relative or customary caregiver. The pilot results suggest that implementing a mobile phone-based surveillance system in a humanitarian setting may be feasible and cost-effective and fills a critical gap in the measurement of separated and unaccompanied children in emergencies. A longer pilot to better understand how the system performs over time is recommended.