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Sample records for chiral stationary phase

  1. [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.

  2. 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.

  3. 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.

  4. 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.

  5. Synthesis of novel chiral stationary phases for high-performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Xu Lin Tan; Shi Cong Hou; Qing Hua Bian; Min Wang

    2007-01-01

    Three novel chiral selectors 4a-c were synthesized from (S)-amino acids and (R)- 1-phenyl-2-(4-methylphenyl)ethylamine. 4a-c were connected to 3-aminopropylsilanized silica gel to be used as the chiral stationary phase for HPLC. Five amino acid derivatives and two pyrethroid insecticides were fairly resolved on these three new chiral stationary phases under normal phase condition.

  6. 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.

  7. Glucose, cellobiose, lactose and raffinose used as chiral stationary phases in HPLC

    Institute of Scientific and Technical Information of China (English)

    Jian Yu Wang; Feng Zhao; Mei Zhang; Ya Peng; Li Ming Yuan

    2008-01-01

    This paper presents the enantioseparation using glucose,cellobiose,lactose and raffinose as chiral selector bonded to silica gel via an arm in HPLC.Surprisingly,they also possess high enantioseparation selectivity,may be used in normal-phase and reversedphase mode.and there is a big chiral discriminating complementary.This work indicates that oligosacchafides could soon become very attractive as a new class of chiral stationary phase for HPLC.

  8. Enantioseparation of Timolol on a Novel β-Cyclodextrin Derivative Chiral Stationary Phase in HPLC.

    Science.gov (United States)

    Zhou, Jie; Sun, Fang; Du, Qiuzheng; Zhao, Suzhen; Pei, Wenjuan

    2016-01-01

    A novel chiral stationary phase was prepared by bonding a novel β-cyclodextrin derivative on silica gel, and it was used for the separation of timolol in high efficiency liquid phase. In the reverse mode, the factors such as the proportion of chiral additives, flow rate, column temperature, repeatability and stability were investigated. The optimum chromatographic conditions are as follows: column temperature was 25°C, flow rate was 0.6 mL min(-1) and mobile phase was methanol-25 mM KH2PO4 (80/20, v/v). The chiral column has good reproducibility (Rs = 4.49, 4.51 and 4.40, respectively) and a certain degree of stability (Rs = 4.49, 3.01 and 0.72, respectively). This chiral stationary phase presented good chiral recognition performance toward timolol with good resolution (Rs = 4.49).

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Effect of Single-walled Carbon Nanotubes on Cellulose Phenylcarbamate Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    CHANG Yin-xia; REN Chao-xing; RUAN Qiong; YUAN Li-ming

    2007-01-01

    Single-walled carbon nanotubes(SWNTs) have a high adsorption ability and nanoscale interactions. Cellulose trisphenylcarbamates possess high enantioseparation ability in high-performance liquid chromatography(HPLC). Single-walled carbon nanotubes mixed with cellulose trisphenylcarbamate are coated on the silica gel as chiral stationary phases and higher enantioseparation factors are obtained. After a single-walled carbon nanotube is linked to the 6-position of cellulose 2,3-bisphenylcarbamate, its enantioseparation resolution increases compared to that of the cellulose trisphenylcarbamate. It is the first time that SWNTs have been applied to enantioseparation. The results indicate that the single-walled carbon nanotubes are good promoters of chiral recognition. This method can be used to improve the enantioseparation efficiency of the polysaccharide chiral stationary phases.

  14. 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.

  15. Enantioseparation of Six Antihistamines with Immobilized Cellulose Chiral Stationary Phase by HPLC

    Science.gov (United States)

    Zhou, Jie; Luo, Pei; Chen, Shanshan; Meng, Lingchang; Sun, Chong; Du, Qiuzheng; Sun, Fang

    2016-01-01

    A stereoselective high performance liquid chromatography method has been developed for the chiral separation of the enantiomers of six antihistamines, doxylamine, carbinoxamine, dioxopromethazine, oxomemazine, cetirizine and hydroxyzine. The effects of mobile phase additive, column temperature and flow rate on the retention time and resolution were studied. Enantiomeric separation of cetirizine, doxylamine and hydroxyzine were achieved on cellulose tris-(3,5-dichlorophenylcarbamate) immobilized on silica gel chiral stationary phase known as Chiralpak IC (RS = 3.74, RS = 1.85 and RS = 1.74, respectively). PMID:26657408

  16. Enantioseparation of Six Antihistamines with Immobilized Cellulose Chiral Stationary Phase by HPLC.

    Science.gov (United States)

    Zhou, Jie; Luo, Pei; Chen, Shanshan; Meng, Lingchang; Sun, Chong; Du, Qiuzheng; Sun, Fang

    2016-04-01

    A stereoselective high performance liquid chromatography method has been developed for the chiral separation of the enantiomers of six antihistamines, doxylamine, carbinoxamine, dioxopromethazine, oxomemazine, cetirizine and hydroxyzine. The effects of mobile phase additive, column temperature and flow rate on the retention time and resolution were studied. Enantiomeric separation of cetirizine, doxylamine and hydroxyzine were achieved on cellulose tris-(3,5-dichlorophenylcarbamate) immobilized on silica gel chiral stationary phase known as Chiralpak IC (RS = 3.74, RS = 1.85 and RS = 1.74, respectively).

  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. 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.

  19. 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.

  20. Copolymerization preparation of cationic cyclodextrin chiral stationary phases for drug enantioseparation in chromatography

    OpenAIRE

    sprotocols

    2015-01-01

    Authors: Ren-Qi Wang, Teng-Teng Ong, Ke Huang, Weihua Tang & Siu-Choon Ng ### Abstract We described a facile and effective protocol wherein radical copolymerization is employed to covalently bond cationic β-cyclodextrin (β-CD) onto silica particles with extended linkage, resulting in a chiral stationary phase (IMPCSP) that can be used for the enantioseparation of racemic drugs in both high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). Start...

  1. Nanocellulose Derivative/Silica Hybrid Core-Shell Chiral Stationary Phase: Preparation and Enantioseparation Performance

    Directory of Open Access Journals (Sweden)

    Xiaoli Zhang

    2016-05-01

    Full Text Available Core-shell silica microspheres with a nanocellulose derivative in the hybrid shell were successfully prepared as a chiral stationary phase by a layer-by-layer self-assembly method. The hybrid shell assembled on the silica core was formed using a surfactant as template by the copolymerization reaction of tetraethyl orthosilicate and the nanocellulose derivative bearing triethoxysilyl and 3,5-dimethylphenyl groups. The resulting nanocellulose hybrid core-shell chiral packing materials (CPMs were characterized and packed into columns, and their enantioseparation performance was evaluated by high performance liquid chromatography. The results showed that CPMs exhibited uniform surface morphology and core-shell structures. Various types of chiral compounds were efficiently separated under normal and reversed phase mode. Moreover, chloroform and tetrahydrofuran as mobile phase additives could obviously improve the resolution during the chiral separation processes. CPMs still have good chiral separation property when eluted with solvent systems with a high content of tetrahydrofuran and chloroform, which proved the high solvent resistance of this new material.

  2. 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.

  3. HPLC Enantioseparation of Phenylcarbamic Acid Derivatives by Using Macrocyclic Chiral Stationary Phases

    Directory of Open Access Journals (Sweden)

    Hroboňová Katarína

    2016-06-01

    Full Text Available The HPLC by using chiral stationary phases based on macrocyclic antibiotics, dimethylphenyl carbamate cyklofructan 7 and β-cyclodextrin in terms of polar-organic separation mode (mobile phase methanol/acetonitrile/acetic acid/triethylamine were used for enantioseparation of alkoxy derivatives of phenylcarbamic acid. The effect of the analyte structures on the efficiency of enantioseparation was investigated. The most suitable stationary phase was teicoplanin aglycone, where the separations of the enantiomers were obtained (the resolution value from 0.65 to 2.90, depending on the structure of the analyte. Significant effect on the resolution of the enantiomers has position of alkoxy substituent in the hydrophobic part of the molecule. The enantiorecognition was achieved for 3-alkoxysubstituted derivatives.

  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. 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.

  6. Chiral anion exchangers applied to capillary electrochromatography enantioseparation of oppositely charged chiral analytes: investigation of stationary and mobile phase parameters.

    Science.gov (United States)

    Lämmerhofer, M; Tobler, E; Lindner, W

    2000-07-28

    Weak anion-exchange (WAX) type chiral stationary phases (CSPs) based on tert.-butyl carbamoyl quinine as chiral selector (SO) and different types of silica particles (porous and non-porous) as chromatographic support are evaluated in packed capillary electrochromatography (CEC). Their ability to resolve the enantiomers of negatively charged chiral analytes, e.g., N-derivatized amino acids, in the anion-exchange mode and their electrochromatographic characteristics are described in dependence of several mobile phase parameters (pH, buffer type and concentration, organic modifier type and concentration) and other experimental variables (electric field strength, capillary temperature). The inherent "zwitterionic" surface character of such silica-based WAX type CSPs (positively charged SO and negatively charged residual silanols) allows the reversal of the electroosmotic flow (EOF) towards the anode at pH values below the isoelectric point (pI) of the modified surface, whereas a cathodic EOF results at pH values above the pI. Since for negatively charged analytes also an electrophoretic transport increment has to be considered, which can be either in or against the EOF direction, several distinct modes of elution have been observed under different stationary phase and mobile phase conditions: (i) co-electrophoretic elution of the negatively charged solutes with the anodic EOF in the negative polarity mode, (ii) counter-electrophoretic elution with the cathodic EOF in the positive polarity mode, and (iii) electrophoretically dominated elution in the negative polarity mode with a cathodic EOF directed to the injection end of the capillary. Useful enantioseparations of chiral acids have been obtained with all three modes. Enantioselectivity values as high as under pressure-driven conditions and theoretical plate numbers up to 120000 per meter could be achieved under electrically driven conditions. A repeatability study yielded RSD values below 2% for retention times and

  7. Enantioseparation of Novel Chiral Tetrahedral Clusters on an Amylose Tris-(3,5-dimethylphenylcarbamate) Chiral Stationary Phase by Normal Phase HPLC

    Institute of Scientific and Technical Information of China (English)

    LI,Wen-Zhi(李文智); WANG,Xia(王霞); ZHANG,Wei-Qiang(张伟强); CHEN Li-Ren(陈立仁); LI,Yong-Min(李永民); MA,Chun-Lin(马春林); YIN,Yuan-Qi(殷元骐)

    2004-01-01

    Amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) coated on a kind of small particle silica gel was prepared. On this ADMPC chiral stationary phase (CSP), the direct enantiomeric separation of six novel chiral transition metal tetrahedral clusters has firstly been achieved using n-hexane as the mobile phase containing various alcohols as modifiers. The effect of mobile phase modifiers and the structural variation of the solutes on their retention factors (k′) and resolutions (Rs) were investigated. The result suggests that not only the structure and concentration of alcohol in mobile phase, but also the structural differences in racemates can have a pronounced effect on enantiomeric separation. ADMPC-CSP is a suitable CSP for the optical resolution of chiral tetrahedral cluster by HPLC.

  8. 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

  9. Preparation of new hybrid organic/inorganic polymeric chiral stationary phases for ligand-exchange chromatography

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three new hybrid organic/inorganic polymeric ligand-exchange chiral stationary phases were developed by radical chain transfer reaction and surface grafting on silica gel, and successfully used for the enantioseparations of DL-amino acids and DL-hydroxyl acids. The resolutions were achieved by using water containing 2.0 × 10-4 mol/L of CuAc2 as a mobile phase, column temperature of 40 ℃, flow rate of 1.0 mL/min and detection at UV 254 mn. The elution order of D-isomer before L-isomer was observed for all DL-amino acids resolved except DL-Pro.

  10. COVALENTLY BONDING CHIRAL POLYURETHANE ON AMINATED SILICA GEL: A NEW STRATEGY TO PREPARE CHIRAL STATIONARY PHASE FOR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

    Institute of Scientific and Technical Information of China (English)

    Shao-hua Huang; Zheng-wu Bai; Chuan-qi Yin; Shi-rong Li

    2006-01-01

    Two polyurethanes of different molecular weights were prepared by the copolymerization of phenyl diisocyanate and diisopropyl tartrate. The polyurethanes having terminal isocyanate groups were reacted with 3-aminopropyl silica gel to afford two chiral stationary phases. The (M-)n of the two polyurethanes were 4057 g/mol and 6442 g/mol. The polyurethanes and the corresponding chiral stationary phases were characterized by FT-IR, 1H NMR and elemental analysis. The loading capacities of the polyurethanes on silica gel were 0.68 mmol units/g and 0.61 mmol units/g, respectively. The separation performance and the influence of additives, triethylamine and trichloroacetic acid, on the separation of chiral compounds were investigated by HPLC. The chiral stationary phase prepared from polyurethane with (M-)n of 4057 g/mol demonstrated better enantioseparation capability than that with (M-)n of 6442 g/mol. Additionally, it was found that the addition of triethylamine and trichloroacetic acid in the mobile phases significantly improved the enantioseparation for these two chiral stationary phases.

  11. The Optical Resolution of Chiral Tetrahedrone-type Clusters Contai- ning SCoFeM (M=Mo or W) Using High Performance Liquid Chromatography Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ATPC-CSP.

  12. Improved Procedure for Preparation of Covalently Bonded Cellulose Tris-phenylcarbamate Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    秦峰; 陈小明; 刘月启; 邹汉法; 王俊德

    2005-01-01

    The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adooted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

  13. [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.

  14. Preparation and Evaluation of a Novel Cellulose Tris(N-3,5-dimethylphenylcarbamate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    GE,Jin; ZHAO,Liang; SHI,Yan-Ping

    2008-01-01

    A novel cellulose tris(N-3,5-dimethylphenylcarbamate) (CDMPC) chiral stationary phase (CSP) was prepared by coating CDMPC on TiO2/SiO2, which was prepared by coating titania nanoparticles on silica through a self-assemble technique. At first, 2-hydroxyl-phenyl acetonitrile and α-phenylethanol were separated on this new CSP to evaluate the chiral separation ability. Then, two pesticides, matalaxyl and diclofop-methyl were separated.The influence of the mobile phase composition on the enantioselectivity was discussed, and the repeatability and stability of the CSP were studied too.

  15. 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.

  16. Dynamic Behavior of Clobazam on High-Performance Liquid Chromatography Chiral Stationary Phases.

    Science.gov (United States)

    Sabia, Rocchina; De Martino, Michela; Cavazzini, Alberto; Villani, Claudio

    2016-01-01

    Clobazam, a 1,5-benzodiazepin-2,4-dione, is a chiral molecule because its ground state conformation features a nonplanar seven-membered ring lacking reflection symmetry elements. The two conformational enantiomers of clobazam interconvert at room temperature by a simple ring-flipping process. Variable temperature HPLC on the Pirkle type (R)-N-(3,5-dinitronenzoyl)phenylglycine and (R,R)-Whelk-O1 chiral stationary phases (CSPs) allowed us to separate for the first time the conformational enantiomers of clobazam and to observe peak coalescence-decoalescence phenomena due to concomitant separation and interconversion processes occurring on the same time scale. Clobazam showed temperature dependent dynamic high-performance liquid chromatography (HPLC) profiles with interconversion plateaus on the two CSPs indicative of on-column enantiomer interconversion. (enantiomerization) in the column temperature range between Tcol = 10°C and Tcol = 30°C, whereas on-column interconversion was absent at temperature close to or lower than Tcol = 5°C. Computer simulation of exchange-deformed HPLC profiles using a program based on the stochastic model yielded the apparent rate constants for the on-column enantiomerization and the corresponding free energy activation barriers. At Tcol = 20°C the averaged enantiomerization barriers, ΔG(‡), for clobazam were found in the range 21.08-21.53 kcal mol(-1) on the two CSPs. The experimental dynamic chromatograms and the corresponding interconversion barriers reported in this article are consistent with the literature data measured by DNMR at higher temperatures and in different solvents.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Recent development of oligosaccharides chiral stationary phases and their applications in chromatography%寡糖手性固定相研究进展

    Institute of Scientific and Technical Information of China (English)

    赵峰; 袁黎明; 熊汝琴

    2015-01-01

    In this paper ,The development of the Oligosaccharide chiral stationary phase for the HPLC chiral stationa‐ry phase is reviewed ,the study found that these sugars as the hplc chiral stationary phase is effect better ,more promis‐ing ,and the prospect of the chiral stationary phase is reviewed .%介绍了葡萄糖、纤维二塘、棉子糖、乳糖等用来作为高效液相色谱手性固定相的研究进展,研究发现这几种糖类作为高效液相色谱的手性固定相拆分效果比较好,比较有前途。同时展望了高效液相色谱手性固定相的发展前景。

  2. 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.

  3. 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.

  4. Enantioseparation Using Cellulose Tris(3,5-dimethylphenylcarbamate as Chiral Stationary Phase for HPLC: Influence of Molecular Weight of Cellulose

    Directory of Open Access Journals (Sweden)

    Yuji Okada

    2016-11-01

    Full Text Available The cellulose oligomers with different degrees of polymerization (DP, 7, 11, 18, 24, 26, 40 and 52, were prepared by hydrolysis of microcrystalline cellulose with phosphoric acid. These oligomers including the starting microcrystalline cellulose (DP 124 were converted to tris(3,5-dimethylphenylcarbamate (CDMPC derivatives by the reaction with an excess of 3,5-dimethylphenyl isocyanate to be used as the chiral stationary phase (CSP in high-performance liquid chromatography (HPLC. The structures of the CDMPC derivatives were investigated by infrared spectroscopy (IR, 1H-NMR, circular dichroism (CD and size exclusion chromatography (SEC, and the DPs of the derivatives estimated by SEC agreed with those estimated by 1H-NMR. After coating the derivatives on silica gel, their chiral recognition abilities were evaluated using eight racemates under a normal phase condition with a hexane-2-propanol (99/1 mixture as an eluent. The chiral recognition abilities of 7- and 11-mers, particularly the former, were lower than those of the higher oligomers from DP 18 to 52, which had rather similar abilities to that of 124-mer, although the abilities depended on the racemates. DP 18 seems to be sufficient for CDMPC to exhibit chiral recognition similar to that of the CDMPC with larger DPs.

  5. 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.

  6. Preparation and application of methylcalix[4]resorcinarene-bonded silica particles as chiral stationary phase in high-performance liquid chromatography.

    Science.gov (United States)

    Tan, Huey Min; Soh, Shu Fang; Zhao, Jia; Yong, E L; Gong, Yinhan

    2011-01-01

    Two new types of methylcalix[4]resorcinarene-bonded stationary phases, (3-(C-methylcalix[4]resorcinarene)-2-hydroxypropoxy)-propylsilyl-appended silica particles (MCR-HPS) and bromoacetate-substituted MCR-HPS particles (BAMCR-HPS), have been synthesized and used as chiral stationary phases for high-performance liquid chromatography (HPLC) for the first time. The synthetic stationary phases are characterized by means of elemental analysis and Fourier-transform infrared spectroscopy. The chromatographic behavior of MCR-HPS and BAMCR-HPS was studied with several disubstituted benzenes and some chiral drug compounds under both normal phase and reversed-phase conditions. The results show that MCR-HPS has excellent selectivity for the separation of aromatic positional isomers and BAMCR-HPS exhibits excellent performance for separation of enantiomers of chiral compounds.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Enantioselective determination of protein amino acids in fertilizers by liquid chromatography-tandem mass spectrometry on chiral teicoplanin stationary phase.

    Science.gov (United States)

    Taujenis, Lukas; Olšauskaitė, Vilma; Padarauskas, Audrius

    2014-11-19

    High-performance liquid chromatography on a glycopeptide antibiotic teicoplanin-based chiral stationary phase coupled with tandem mass spectrometry was developed for fast and reliable enantioseparation and determination of protein amino acids in hydrolyzed fertilizer samples. The effect of the mobile phase parameters (type and content of organic modifier and pH) and the column temperature on the enantioselectivity was investigated. Under optimized conditions, the majority (15 of 19) of d/l-amino acid pairs were resolved with a resolution factor (Rs) higher than 1.5 with a run time of 15 min. A triple quadrupole tandem mass spectrometer operating in multiple reaction monitoring mode with an electrospray ionization (ESI) ion source was employed for detection. The method was validated in terms of linearity, limits of detection, limits of quantitation, precision, and accuracy. Linear responses were obtained with determination coefficients higher than 0.998 for all analytes, and limits of detection were from 0.04 to 0.24 μg/mL. Sample spike/recovery experiments gave recovery values ranging from 73% for d-threonine to 116% for L-tryptophan. Relative standard deviations for inter- and intraday precision experiments were lower than 21.7%. The developed method was successfully applied for determination of the free amino acid enantiomers in five commercially available hydrolyzed protein fertilizer samples.

  15. 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.

  16. 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.

  17. 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.

  18. High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

    Science.gov (United States)

    Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

    2015-03-01

    Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

  19. 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.

  20. L—PROLINE—FUNCTIONALIZED POLYSTYRENE WITH 1—METHYLDECYLENE SPACER AS A CHIRAL STATIONARY PHASE FOR LIGAND—EXCHANGE CHROMATOGRAPHIC RESOLUTION OF AMINO ACID RECEMATES

    Institute of Scientific and Technical Information of China (English)

    MaJianbiao; ChenLi; 等

    1995-01-01

    The L-proline-functionalized polystyrene with 1-methyldecylene spacer was synthesized from 2% divinylbenzene-crosslinked polystyrene gel via 10-bromo-1-methyldecyl polystyrene intermediate.After complexed with copper(Ⅱ) ion,the polymer with L-proline ligand was used as the chiral stationary phase (CSP) for ligand exchange chromatography of amino acid racemates.The results showed that the CSP possessed powerful enantioselectivity and all racemates of the fifteen tried amino acids were completely separated.

  1. Chiral recognition of N-phthaloyl, N-tetrachlorophthaloyl, and N-naphthaloyl α-amino acids and their esters on polysaccharide-derived chiral stationary phases.

    Science.gov (United States)

    Kim, Byoung-Hyoun; Lee, Sang Uck; Moon, Dong Cheul

    2012-12-01

    Enantiomeric separations of N-phthaloyl (N-PHT), N-tetrachlorophthaloyl (N-TCPHT), and N-naphthaloyl (N-NPHT) α-amino acids and their esters were examined on several kinds of polysaccharide-derived chiral stationary phases (CSPs). Resolution capability of CSPs was greater Chiralcel OF than the others for N-PHT and N-NPHT α-amino acids and their esters. In N-TCPHT α-amino acids and their esters, good enantioselectivities showed Chiralcel OG for N-TCPHT α-amino acids, Chiralpak AD for N-TCPHT α-amino acid methyl esters, and Chiralcel OD for N-TCPHT α-amino acid ethyl esters, respectively. From the results of liquid chromatography and computational chemistry, it is concluded that l-form is preferred and more retained with electrostatic interaction in case of interaction between N-PHT α-amino acid derivatives and Chiralcel OF, N-TCPHT α-amino acid derivatives and Chiralcel OD, and N-NPHT α-amino acid derivatives and Chiracel OF. On the other hand, d-form is preferred and more retained with van der Waals interaction in case of interaction between N-TCPHT α-amino acid ester derivatives and Chiralcel OG and Chiralpak AD.

  2. 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.

  3. Preparation and characterization of silica monolith modified with bovine serum albumin-gold nanoparticles conjugates and its use as chiral stationary phases for capillary electrochromatography.

    Science.gov (United States)

    Lu, Junyu; Ye, Fanggui; Zhang, Aizhu; Wei, Zong; Peng, Yan; Zhao, Shulin

    2011-08-01

    This paper describes the development of silica monolith modified with bovine serum albumin-gold nanoparticles (BSA-GNPs) conjugates as chiral stationary phases for capillary electrochromatography (CEC). The bare monolithic silica column was prepared by a sol-gel process and has been modified chemically with 3-mercaptopropyltrimethoxysilane to provide thiol groups, followed by immobilization of gold nanoparticles via the formation of an Au-S bond and modification with BSA as the chiral selector via the nitrogen lone pair of electrons. It has been demonstrated that the monolithic chiral stationary phases can be used for the enantioseparation of a number of phenylthiocarbamyl amino acids (PTC-D/L-AAs) by CEC. Ten pairs of tested amino acids enantiomers were successfully resolved within 18 min under optimized conditions, and the resolution values were in the range of 1.486-2.083. With PTC-D/L-tryptophan used as the probe solute, the influences of applied voltage, organic modifier and buffer pH in mobile phase on apparent retention factor, enantioselectivity and resolution factor were also investigated.

  4. 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.

  5. 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.

  6. 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%.

  7. 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.

  8. Pirkle-type chiral stationary phase on core-shell and fully porous particles: Are superficially porous particles always the better choice toward ultrafast high-performance enantioseparations?

    Science.gov (United States)

    Ismail, Omar H; Pasti, Luisa; Ciogli, Alessia; Villani, Claudio; Kocergin, Jelena; Anderson, Scott; Gasparrini, Francesco; Cavazzini, Alberto; Catani, Martina

    2016-09-30

    Pirkle-type Whelk-O1 chiral stationary phase (CSP) was prepared on 2.6μm superficially porous particles (SPPs). The chromatographic behavior of columns packed with this new CSP was compared with that of columns packed respectively with 1.8 and 2.5μm Whelk-O1 fully porous particles (FPPs). In the comparison, both thermodynamic and kinetic aspects were considered. Contrary to initial expectations, chiral columns packed with 2.6μm SPPs were quasi-comparable to those packed with 2.5μm FPPs, apparently due to larger contributions to band broadening from both eddy dispersion and, especially for the second eluted enantiomer, adsorption-desorption kinetics. These findings raise the question if SPPs, in spite of the undeniable advantages of their morphology to speed up mass transfer, are always the best choice for high-efficient ultrafast chiral separations. The last part of the work focuses on the use of short columns (10mm long) and very high flow rates to realize the separation of the enantiomers of trans-stilbene oxide (TSO) in normal phase mode in less than 1s.

  9. 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.

  10. Liquid chromatography with mass spectrometry enantioseparation of pomalidomide on cyclodextrin-bonded chiral stationary phases and the elucidation of the chiral recognition mechanisms by NMR spectroscopy and molecular modeling.

    Science.gov (United States)

    Szabó, Zoltán-István; Szőcs, Levente; Horváth, Péter; Komjáti, Balázs; Nagy, József; Jánoska, Ádám; Muntean, Daniela-Lucia; Noszál, Béla; Tóth, Gergő

    2016-08-01

    A sensitive and validated liquid chromatography with mass spectrometry method was developed for the enantioseparation of the racemic mixture of pomalidomide, a novel, second-generation immunomodulatory drug, using β-cyclodextrin-bonded stationary phases. Four cyclodextrin columns (β-, hydroxypropyl-β-, carboxymethyl-β-, and sulfobutyl-β-cyclodextrin) were screened and the effects of eluent composition, flow rate, temperature, and organic modifier on enantioseparation were studied. Optimized parameters, offering baseline separation (resolution = 2.70 ± 0.02) were the following: β-cyclodextrin stationary phase, thermostatted at 15°C, and mobile phase consisting of methanol/0.1% acetic acid 10:90 v/v, delivered with 0.8 mL/min flow rate. For the optimized parameter at multiple reaction monitoring mode 274.1-201.0 transition with 20 eV collision energy and 100 V fragmentor voltage the limit of detection and limit of quantitation were 0.75 and 2.00 ng/mL, respectively. Since enantiopure standards were not available, elution order was determined upon comparison of the circular dichroism signals of the separated pomalidomide enantiomers with that of enantiopure thalidomide. The mechanisms underlying the chiral discrimination between the enantiomers were also investigated. Pomalidomide-β-cyclodextrin inclusion complex was characterized using nuclear magnetic resonance spectroscopy and molecular modeling. The thermodynamic aspects of chiral separation were also studied.

  11. 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.

  12. Numerical determination of competitive adsorption isotherm of mandelic acid enantiomers on cellulose-based chiral stationary phase.

    Science.gov (United States)

    Zhang, Yan; Rohani, Sohrab; Ray, Ajay K

    2008-08-15

    The use of inverse method for the determination of competitive adsorption isotherm of mandelic acid enantiomers on cellulose tris(3,5-diethylphenyl carbamate) stationary phase is proposed in this work. Non-dominated sorting genetic algorithm with jumping genes (NSGA-II-JG) was applied to acquire the isotherm parameters by minimizing the sum of square deviations of the model predictions from the measured elution profiles. Three different competitive isotherm models, i.e., Langmuir, biLangmuir and Tóth, combined with transport-dispersive chromatographic model were used in predicting the elution profiles. Orthogonal collocation on finite element (OCFE) method was applied to obtain the calculated elution profiles. Results indicate that biLangmuir isotherm and Tóth isotherm give remarkably similar equilibrium isotherms within the investigated liquid concentration range. Band profiles calculated from both isotherm models are in good agreement with the experimental data. The validity of the determined parameters was verified by comparing the model predictions with experimental elution profiles at various experimental conditions.

  13. 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...

  14. 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.

  15. 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.

  16. 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.

  17. Enantioseparation of pyroglutamide derivatives on polysaccharide based chiral stationary phases by high-performance liquid chromatography and supercritical fluid chromatography: a comparative study.

    Science.gov (United States)

    Baudelet, Davy; Schifano-Faux, Nadège; Ghinet, Alina; Dezitter, Xavier; Barbotin, Florent; Gautret, Philippe; Rigo, Benoit; Chavatte, Philippe; Millet, Régis; Furman, Christophe; Vaccher, Claude; Lipka, Emmanuelle

    2014-10-10

    Analytical enantioseparation of three pyroglutamide derivatives with pharmacological activity against the purinergic receptor P2X7, was run in both high-performance liquid chromatography and supercritical fluid chromatography. Four polysaccharide based chiral stationary phases, namely amylose and cellulose tris (3,5-dimethylphenylcarbamate), amylose tris ((S)-α-methylbenzylcarbamate) and cellulose tris (4-methylbenzoate) with various mobile phases consisted of either heptane/alcohol (ethanol and 2-propanol) or carbon dioxide/alcohol (methanol or ethanol) mixtures, were investigated. After analytical screenings, the best conditions were transposed, for compound 1, to semi-preparative scale. Each approach was fully validated to meet the International Conference on Harmonisation requirements and compared. Whereas the limits of detection and quantification were near six-fold better in HPLC than in SFC (respectively 0.20 and 0.66 μM versus 1.11 and 3.53 μM for one of the enantiomers), in terms of low solvent consumption (7.2 mL of EtOH versus 3.2 mL of EtOH plus 28.8 mL of toxic and inflammable heptane per injection in SFC and HPLC, respectively), time effective cost (9 min versus 40 min per injection in SFC and HPLC, respectively) and yields (98% versus 71% in SFC and HPLC, respectively), the latter method proved its ecological superiority.

  18. Comparison of polarimetry and crown ether-based HPLC chiral stationary phase method to determine (L)-amino acid optical purity.

    Science.gov (United States)

    Lee, Mee Sung; Khan, F Nawaz; Shin, Sung Chul; Jeong, Euh Duck; Kim, Hae Gyeong; Kim, Mi Jin; Cho, Yoon Jae; Cha, Jae-Young; Hyun, Myung Ho; Jin, Jong Sung

    2012-11-15

    Although various pharmacopoeias provide titration methods to assay (L)-amino acid content, none of these methods distinguish between (L)- and (D)-amino acids and do not consider the presence of enantiomeric impurities. Consequently, these methods are limited in scope to describe the relationship between content and specific rotation, [α]. In this study, the US Pharmacopoeia method was compared with the crown ether-based high performance liquid chromatographic (HPLC) chiral stationary phase (CSP) method to determine (L)-amino acid content and specific rotation. The (L)-amino acid content specified by the US Pharmacopoeia method was not consistent with the specific rotation in the presence of enantiomeric impurities, whereas the HPLC-CSP method was very effective for determining the (L)-amino acid content and the optical purity. The other advantage is that the HPLC-CSP method requires amino acid samples of quite low concentration (as low as 1 μg/mL), whereas the pharmacopoeia method requires higher concentrations (20-110 mg/mL).

  19. 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.

  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. 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 .

  2. 手性固定相AD、AS和OD的拆分性能%Enantioseparation behavior of chiral stationary phases AD,AS and OD

    Institute of Scientific and Technical Information of China (English)

    李丽群; 范军; 张晶; 陈晓东; 王泰; 贺建峰; 章伟光

    2016-01-01

    手性固定相-高效液相色谱法在手性药物、手性农药等的分离分析中应用广泛。本文采用3种多糖衍生物的手性固定相(即 EnantioPak AD、AS和 OD)对20种手性化合物开展手性分离研究,进而探讨样品分子结构、多糖骨架和衍生基团对手性分离的影响。结果表明,除化合物13外,其余化合物在 EnantioPak AD 上均实现基线分离,分离度多在2.0以上,在正己烷-醇流动相中加入酸碱添加剂可改善和优化酸性或碱性化合物的分离效果;芳香醇(化合物13~16)随着侧链碳数增加在色谱柱上的保留减弱,其分离度呈现增加的趋势;对比8种化合物在3种手性固定相上的分离结果可知,EnantioPak AD 表现出更优的分离性能。这为深入研究和了解多糖手性固定相、拓展其手性分离应用提供了参考。%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 aromat-ic alcohols( compounds 13-16),their retention in the EnantioPak AD column showed a weake-ning 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

  3. [[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.

  4. 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.

  5. 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

  6. 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

  7. Effect of the residual silanol group protection on the liquid chromatographic resolution of racemic primary amino compounds on a chiral stationary phase based on optically active (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6.

    Science.gov (United States)

    Hyun, Myung Ho; Han, Sang Cheol; Choi, Hee Jung; Kang, Bu Sung; Ha, Hyun Ju

    2007-01-05

    A liquid chromatographic chiral stationary phase (CSP) based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6, which has been utilized in the resolution of alpha-amino acids, amines and amino alcohols, was treated with excess of n-octyltriethoxysilane to prepare a new improved CSP. The residual silanol groups of the original CSP were protected by n-octyl groups in the new CSP. The chiral recognition ability of the new CSP was superior to that of the original CSP in the resolution of alpha-amino acids, amines and amino alcohols. Retention factors (k1) for the resolution of alpha-amino acids were lower on the new CSP than on the original CSP while those for the resolution of amines and amino alcohols were higher on the new CSP than on the original CSP. The improved chiral recognition ability of the new CSP and the retention behaviors of the two enantiomers on the new CSP have been rationalized to stem from the removal of the non-enantioselective interactions between the analytes and the residual silanol groups of the original CSP and the improved lipophilicity of the CSP.

  8. 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.

  9. 一种新型手性配体交换色谱键合固定相%A Novel Bonded Stationary Phase for Chiral Ligand Exchange-Chromatography

    Institute of Scientific and Technical Information of China (English)

    龙远德; 王群标; 等

    2001-01-01

    A novel chiral bonded stationary phase(CBSP) for ligand exchange chromatography was prepared by bonding (S)-1,2,3,4-tetrahydro-3-isoquinoline carboxylic acid prepared from L-Phe to YWG-80 silica gel via 3-glycidyloxypropyltrimethoxysilane as a coupling agent. Chromatographic resolutions of some DL-amino acids were achieved on the CBSP by using an aqueous solution of 2 mmol/L N(C2H5)3, 2 mmol/L HAc and 0.2 mmol/L Cu(Ac)2 as the mobile phase with a flow rate 1.0 mL/min, column temperature 50 ℃ and detection at 254 nm. The enantioselectivity α of the DL-amino acids on the CBSP was found to be between 1.11 and 1.51. The elution order of D-isomer before L-isomer on the CBSP was observed for all the DL-amino acids resolved except DL-Val. For DL-Pro, DL-Val and DL-Leu the elution order through the CBSP was different from that through the chiral ligand exchange phases prepared from L-Pro or L-hydroxyl proline with a five-membered ring structure.

  10. Rat dried blood spot analysis of (R,S)-(-)- and (S,R)-(+)- enantiomers of emtricitabin on immobilized tris-(3,5-dimethylphenyl carbamate) amylose silica as a chiral stationary phase.

    Science.gov (United States)

    Rao, Ramisetti Nageswara; Santhakumar, Kondapalli; Naidu, Challa Gangu

    2015-10-01

    An enantioselective high performance liquid chromatography method has been developed and validated by evaluating the suitability of newly introduced immobilized polysaccharide chiral stationary phases, the effect of different organic modifiers and temperature including the entropy and enthalpy on resolution of the (R,S)-(-) & (S,R)-(+) emtricitabine enantiomers on rat dried blood spots. Both the enantiomers were extracted from dried blood spots using ethanol: methanol (80:20 v/v) mixture and separated on an immobilized amylose tris-(3,5-dimethyl phenyl carbamate) chiral stationary phase using n-hexane:ethanol (65:35 v/v) as a mobile phase at a flow rate of 0.8mL/min. The detection was carried out at 280nm using photo diode array detector connected to a polarimeter in series to determine their order of eluton. The method was validated with respect to limits of detection and quantification, linearity, accuracy and precision. The calibration curves were linear over the concentration range of 0.5-500μg/mL for both enantiomers and the correlation coefficient (r(2)) was >0.998. The overall recovery of (R,S)- & (S,R)-enantiomers of emtricitabin from DBS were 90.4 and 90.6%, respectively. The limits of detection and quantification of enantiomers were 0.26, 0.30 and 0.85, 0.92μg/mL for (R,S)- and (S,R)-emtricitabin enantiomers, respectively. The assay was specific and precise (RSD <10%). The stability of emtricitabin was also performed and the results were found to be well within the limits. The effect of hematocrit on extraction of emtricitabin enantiomers from dried blood spots was evaluated and no interference from endogenous substances was observed.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Stationary phase deposition based on onium salts

    Science.gov (United States)

    Wheeler, David R.; Lewis, Patrick R.; Dirk, Shawn M.; Trudell, Daniel E.

    2008-01-01

    Onium salt chemistry can be used to deposit very uniform thickness stationary phases on the wall of a gas chromatography column. In particular, the stationary phase can be bonded to non-silicon based columns, especially microfabricated metal columns. Non-silicon microfabricated columns may be manufactured and processed at a fraction of the cost of silicon-based columns. In addition, the method can be used to phase-coat conventional capillary columns or silicon-based microfabricated columns.

  16. Preparation of a new chiral stationary phase for HPLC based on the (R)- 1-phenyl-2-(4-methylphenyl)ethylamine amide derivative of (S)-valine and 2-chloro-3,5-dinitrobenzoic acid: enantioseparation of amino acid derivatives and pyrethroid insecticides.

    Science.gov (United States)

    Tan, Xulin; Hou, Shicong; Jiang, Jingli; Wang, Min

    2007-08-01

    A novel chiral stationary phase (CSP) for HPLC was prepared by bonding (R)-1-phenyl-2-(4-methylphenyl)ethylamine amide derivative of (S)-valine to aminopropyl silica gel through a 2-amino-3,5-dinitro-1-carboxamido-benzene unit. The CSP was used for the separation of some amino acid derivatives and pyrethroid insecticides by chiral HPLC. Satisfactory baseline separation required optimization of the variables of mobile phase composition. Use of dichloromethane as modifier in the mobile phase gave baseline separations of amino acid derivatives. The two enantiomers of fenpropathrin and four stereoisomers of fenvalerate were baseline separated using hexane-dichloromethane-ethanol as mobile phase. The results show that the enantioselectivity of the new CSP is better than Pirkle type 1-A column for these compounds. Only partial separations were observed for the stereoisomers of cypermethrin and cyfluthrin, which gave even and eight peaks, respectively.

  17. Neutrino Oscillation Induced by Chiral Phase Transition

    Institute of Scientific and Technical Information of China (English)

    MU Cheng-Fu; SUN Gao-Feng; ZHUANG Peng-Fei

    2009-01-01

    Electric charge neutrality provides a relationship between chiral dynamics and neutrino propagation in compact stars.Due to the sudden drop of the electron density at the first-order chiral phase transition,the oscillation for low energy neutrinos is significant and can be regarded as a signature of chiral symmetry restoration in the core of compact stars.

  18. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  19. 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。

  20. Insights on some chiral smectic phases

    Indian Academy of Sciences (India)

    B Pansu

    2003-08-01

    Combining layered positional order as smectic order and chirality can generate complex architectures since twist parallel to the layers is not allowed. This paper will review some new experimental results on different phases resulting from the competition between smectic positional order and twist orientational order. It concerns the TGBA and the NL*, that is the liquid line phase as well as the SmQ phase. Chiral effects in the isotropic phase will also be discussed.

  1. Mass transfer mechanism in chiral reversed phase liquid chromatography.

    Science.gov (United States)

    Gritti, Fabrice; Guiochon, Georges

    2014-03-01

    The mechanism of mass transfer in chiral chromatography was investigated using an experimental protocol already applied in RPLC and HILIC chromatography. The different contributions to the reduced height equivalent to a theoretical plate (HETP) include the longitudinal diffusion HETP term, the solid-liquid mass transfer resistance HETP term, the short-range eddy dispersion HETP term, and the long-range eddy dispersion HETP term. Their accurate measurement permits the determination of the adsorption rate constant kads of trans-stilbene enantiomers on a column packed with Lux 5 μm Cellulose-1 particles. The experimental results demonstrate that the number of adsorption-desorption steps per unit time of chiral compounds on polysaccharide-based chiral stationary phases is four orders of magnitude smaller than that of achiral compounds.

  2. Tuning of mobile and stationary phase polarity for the separation of polar compounds by SFC.

    Science.gov (United States)

    Ibañez, E; Señoráns, F J

    2000-07-05

    The separation of polar compounds by supercritical-fluid chromatography (SFC) is reviewed. New developments in mobile and stationary phase tuning are reviewed for packed and packed capillary SFC. In terms of mobile phase polarity adjustment, new pure and multiple component fluids are presented. The approach of tuning the polarity of the stationary phase as a way of increasing the range of polar compounds analyzed by SFC using pure CO(2) is discussed using either silica-based or new materials as stationary phase. Chiral, liquid crystal and polymer-based stationary phases coated on particles are widely covered in this review as an interesting approach to separate polar compounds avoiding the major drawbacks associated to the use of modifiers in SFC.

  3. Chiral Liquid Crystals: Structures, Phases, Effects

    Directory of Open Access Journals (Sweden)

    Ingo Dierking

    2014-06-01

    Full Text Available The introduction of chirality, i.e., the lack of mirror symmetry, has a profound effect on liquid crystals, not only on the molecular scale but also on the supermolecular scale and phase. I review these effects, which are related to the formation of supermolecular helicity, the occurrence of novel thermodynamic phases, as well as electro-optic effects which can only be observed in chiral liquid crystalline materials. In particular, I will discuss the formation of helical superstructures in cholesteric, Twist Grain Boundary and ferroelectric phases. As examples for the occurrence of novel phases the Blue Phases and Twist Grain Boundary phases are introduced. Chirality related effects are demonstrated through the occurrence of ferroelectricity in both thermotropic as well as lyotropic liquid crystals. Lack of mirror symmetry is also discussed briefly for some biopolymers such as cellulose and DNA, together with its influence on liquid crystalline behavior.

  4. Chirality effects on 2D phase transitions

    DEFF Research Database (Denmark)

    Scalas, E.; Brezesinski, G.; Möhwald, H.

    1996-01-01

    -nearest neighbours (NNN) and an NNN-distorted lattice is observed. At 5 degrees C, the transition pressure is 15 mN m(-1), whereas at 20 degrees C it is 18 mN m(-1). Chirality destroys this transition: the pure enantiomer always exhibits an oblique lattice with tilted molecules, and the azimuths of tilt...... and distortion continuously vary from a direction close to NN to a direction close to NNN. The nature of the phase transition and the influence of chirality on it are discussed within the framework of Landau's theory of phase transitions....

  5. Enantioseparation of Salbutamol on the 3,4-Dichlorophenyl Isocyanate Vancomycin Chiral Stationary Phase%沙丁胺醇在3,4-二氯苯基异氰酸酯万古霉素手性柱上的对映体分离

    Institute of Scientific and Technical Information of China (English)

    于萍; 苏蕾; 刘光; 李丽

    2013-01-01

    Objective To establish a self-made chiral column for enantiomeric separation of salbutamol. Methods We used different concentrations of acid,alkali additives in the polar phase flow for enantiomers separation of salbutamol by using 3, 4-dichlorophenyl isocyanate vancomycin chiral column, and discussed the chiral recognition mechanism. Results The ratio of acid to alkali additive in the mobile phase was 0.01%:0.01% (V/V), the flow rate was 1ml/min, the column temperature was 25℃, and the best separation of enantiomers of salbutamol was obtained,the selective factor was 1.16, the separation degree reached 1.41. Conclusion Self-made 3, 4-two chlorophenyl isocyanate vancomycin chiral column is effective for salbutamol separation, and it can be as a reference for developing other similar chiral stationary phase.%目的:建立一种在自制手性柱上对沙丁胺醇进行了对映体分离的方法.方法利用极性流动相中不同浓度的酸、碱添加剂在自制的3,4-二氯苯基异氰酸酯万古霉素手性柱对沙丁胺醇对映体分离的研究,初步探讨了手性识别机理.结果流动相中酸、碱添加剂的比例为0.01%:0.01%(V/V),流速为1 mL/min,柱温为25℃时,沙丁胺醇获得了最好的对映体分离,选择因子为1.16,分离度达到1.41.结论自制的3,4-二氯苯基异氰酸酯万古霉素手性柱对沙丁胺醇有一定的分离效果,可以此为参考,开发其他类似的手性固定相.

  6. Stationary phases for superheated water chromatography

    CERN Document Server

    Saha, S

    2002-01-01

    This project focused on the comparison of conventional liquid chromatography and superheated water chromatography. It examined the differences in efficiency and retention of a range of different stationary phases. Alkyl aryl ketones and eight aromatic compounds were separated on PBD-zirconia, Xterra RP 18, Luna C sub 1 sub 8 (2) and Oasis HLB columns using conventional LC and superheated water chromatography system. The retention indices were determined in the different eluents. On changing the organic component of the eluent from methanol to acetonitrile to superheated water considerable improvements were found in the peak shapes and column efficiencies on the PBD-zirconia and Oasis HLB columns. PS-DVB, PBD-zirconia and Xterra RP 18 columns have been used in efficiency studies. It was found that simply elevating the column temperature did not increase the efficiency of a separation in superheated water chromatography. The efficiency depended on flow rate, injection volume and also mobile phase preheating sys...

  7. Stationary phase optimized selectivity supercritical fluid chromatography (SOS-SFC)

    OpenAIRE

    Delahaye, Sander; Lynen, Frederic

    2013-01-01

    In stationary phase optimized selectivity liquid chromatography (SOS-LC) the stationary phase becomes a tunable parameter by connecting column segments with variable lengths of different stationary phases. An optimization procedure and algorithm based on the PRISMA model for optimization of the mobile phase in LC was developed to apply this strategy for isocratic and gradient separations. An optimized column segment combination, giving the highest separation selectivity for all compounds in a...

  8. Preparation and characterization of highly stable hybrid organosilica cellulose derivative-based chiral stationary phase%高稳定性硅基杂化纤维素衍生物手性固定相的制备及其色谱拆分性能

    Institute of Scientific and Technical Information of China (English)

    罗飞; 翁西伦; 鲍宗必; 杨亦文; 任其龙

    2015-01-01

    Chiral chromatography plays an important role in obtaining optically pure enantiomers. The key to preparative chiral chromatography is the availability of chiral stationary phases (CSPs) with broad chiral recognition, high sample loading as well as solvent tolerance. In order to overcome the shortcoming of traditional coating-type or bonding-type cellulose-based CSPs, a novel hybrid CSP based on cellulose derivative bearing a small amount of 3-(triethoxysilyl)propyl groups was proposed, which was used to crosslink with bis(triethoxysilyl)ethane (BTSE)via a sol-gel reaction. The prepared stationary phase was then evaluated by HPLC. The experimental results indicated that the CSP showed excellent chiral recognition ability and could run steadily at back column pressure more than 2000 psi (1 psi=6894.76 Pa) with flow-rate up to 3 ml·min−1 in the mobile phase containing 10% chloroform. It was worth mentioning that the selectivity of 2,2,2-trifluoro-1-(9-anthryl)ethanol and trans-stilbene oxide up to 2.99 and 2.48 was achieved, respectively, confirming its excellent chiral recognition performance. In addition, the reported CSP showed a promising packing for application in preparative chromatography such as simulated moving bed chromatography.%合成了含少量3-(三乙氧基硅)丙基氨基甲酸酯的纤维素3,5-二甲基苯基氨基甲酸酯衍生物(CDMPC),并采用1,2-二(三乙氧基硅基)乙烷(BTSE)为偶联剂,通过溶胶-凝胶法成功制备得到新型硅基杂化手性固定相。该固定相的CDMPC含量达60%,在含有10%氯仿的流动相中保持良好的手性识别性能和机械强度。使用其拆分了多种手性化合物,拆分效果优于商品柱Chiralpak IB,其中对2,2,2-三氟-1-(9-蒽基)乙醇和反式二苯乙烯氧化物对映体的分离选择性分别达到2.99和2.48,表明该类硅基杂化类手性固定相在制备色谱领域中有潜在应用前景。

  9. Magnetic properties in the inhomogeneous chiral phase

    CERN Document Server

    Yoshiike, Ryo; Tatsumi, Toshitaka

    2016-01-01

    We investigate the magnetic properties of quark matter in the inhomogeneous chiral phase, where both scalar and pseudoscalar condensates spatially modulate. The energy spectrum of the lowest Landau level becomes asymmetric about zero in the external magnetic field, and gives rise to the remarkably magnetic properties: quark matter has a spontaneous magnetization, while the magnetic susceptibility does not diverge on the critical point.

  10. 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.

  11. Dynamics of the chiral phase transition

    CERN Document Server

    van Hees, H; Meistrenko, A; Greiner, C

    2013-01-01

    The intention of this study is the search for signatures of the chiral phase transition in heavy-ion collisions. To investigate the impact of fluctuations, e.g., of the baryon number, at the transition or at a critical point, the linear sigma model is treated in a dynamical (3+1)-dimensional numerical simulation. Chiral fields are approximated as classical mean fields, and quarks are described as quasi particles in a Vlasov equation. Additional dynamics is implemented by quark-quark and quark-sigma-field interactions. For a consistent description of field-particle interactions, a new Monte-Carlo-Langevin-like formalism has been developed and is discussed.

  12. 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.

  13. Synthesis of Novel Chiral Stationary Phase Based on Atom Transfer Radical Polymerization and Click Chemistry%基于原子转移自由基聚合和“Click”化学方法制备手性色谱固定相

    Institute of Scientific and Technical Information of China (English)

    王怀松; 彭江涛; 魏纪平; 姜安

    2012-01-01

    应用原子转移自由基聚合(ATRP)法和“Click”化学方法,以含叠氮基的烯类化合物为单体,在硅胶表面引发聚合,制备了“梳状”手性固定相.该固定相的合成采用“接出”方法接枝聚合物链,使接枝层更为均匀,并且避免了传统合成方法(如物理吸附等)稳定性差的缺点.所得到的“梳状”手性固定相实现了对一些手性药物的分离;并考察了该固定相中聚合物链的密度和长度对其手性分离能力的影响.%A novel chiral stationary phase was synthesized via the combination of atom transfer radical po- lymerization (ATRP) and click chemistry. In the synthesis, the silane coupling agent 3-(2-bromoisobutyryl)- propyl triethoxysilane (BPE) was chosen as the ATRP initiator and immobized on the porous silica gel. The polymer chains of poly(2-methyl-3-butyn-2-ol methacrylate) (pMBMA) were grafted on the silica substrates by surface-initiated ATRP. This "grafting-from" technique was used to synthesize polymers with controlla- ble molecular weight and narrow molecular weight distributions. For immobilizing the chiral selector, azide-modified β-cyclodextrin (β-CD) was synthesized and bounded on the pMBMA by click chemistry, which can avoid the side-reactions in the preparation. The materials with different pMBMA chain density and length on the silica gel surface were prepared. Several pharmaceuticals were used to evaluate the enantioseparation ability of the materials under reversed-phase high performance liquid chromatography. The results demonstrate that ATRP can well design the polymer structure, and click chemistry can provide an ef- fective route in the β-CD immobilization for chiral discrimination. It was found that the retention and separation factors of chiral compounds could be improved by adjusting the pMBMA chain density and length on the surface of silica gel.

  14. 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.

  15. Method development for impurity profiling in SFC: The selection of a dissimilar set of stationary phases.

    Science.gov (United States)

    Galea, Charlene; Mangelings, Debby; Heyden, Yvan Vander

    2015-01-01

    Supercritical fluid chromatography (SFC) is drawing considerable interest as separation technique in the pharmaceutical industry. The technique is already well established in chiral separations both analytically and on a preparative scale. The use of SFC as a technique for drug impurity profiling is examined here. To define starting conditions in method development for drug impurity profiling, a set of dissimilar stationary phases is screened in parallel. The possibility to select a set of dissimilar columns using the retention factors (k-values) for a set of 64 drugs measured on 27 columns in SFC was examined. Experiments were carried out at a back-pressure of 150 bar and 25 °C with a mobile phase consisting of CO2 and methanol with 0.1% isopropylamine (5-40% over 10 min) at a flow rate of 3 mL/min. These k-values were then used to calculate correlation coefficients on the one hand and to perform a principal component analysis on the other. The Kennard and Stone algorithm, besides dendrograms and correlation-coefficient colour maps were used to select a set of 6 dissimilar stationary phases. The stationary phase characterization results from this study were compared to those from previous studies found in the literature. Retention mechanisms for compounds possessing different properties were also evaluated. The dissimilarity of the selected subset of 6 stationary phases was validated using mixtures of compounds with similar properties and structures, as one can expect in a drug impurity profile.

  16. Chiral phase transition from string theory.

    Science.gov (United States)

    Parnachev, Andrei; Sahakyan, David A

    2006-09-15

    The low energy dynamics of a certain D-brane configuration in string theory is described at weak t'Hooft coupling by a nonlocal version of the Nambu-Jona-Lasinio model. We study this system at finite temperature and strong t'Hooft coupling, using the string theory dual. We show that for sufficiently low temperatures chiral symmetry is broken, while for temperatures larger then the critical value, it gets restored. We compute the latent heat and observe that the phase transition is of the first order.

  17. 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).

  18. Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

    Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

  19. Charge fluctuations in chiral models and the QCD phase transition

    CERN Document Server

    Skokov, V; Karsch, F; Redlich, K

    2011-01-01

    We consider the Polyakov loop-extended two flavor chiral quark--meson model and discuss critical phenomena related with the spontaneous breaking of the chiral symmetry. The model is explored beyond the mean-field approximation in the framework of the functional renormalisation group. We discuss properties of the net-quark number density fluctuations as well as their higher cumulants. We show that with the increasing net-quark number density, the higher order cumulants exhibit a strong sensitivity to the chiral crossover transition. We discuss their role as probes of the chiral phase transition in heavy-ion collisions at RHIC and LHC.

  20. Chiral phases of fundamental and adjoint quarks

    Energy Technology Data Exchange (ETDEWEB)

    Natale, A. A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC 09210-170, Santo André, SP (Brazil); Instituto de Física Teórica - UNESP Rua Dr. Bento T. Ferraz, 271, Bl.II - 01140-070, São Paulo, SP (Brazil)

    2016-01-22

    We consider a QCD chiral symmetry breaking model where the gap equation contains an effective confining propagator and a dressed gluon propagator with a dynamically generated mass. This model is able to explain the ratios between the chiral transition and deconfinement temperatures in the case of fundamental and adjoint quarks. It also predicts the recovery of the chiral symmetry for a large number of quarks (n{sub f} ≈ 11 – 13) in agreement with lattice data.

  1. Luciferase detection during stationary phase in Lactococcus lactis

    NARCIS (Netherlands)

    Bachmann, H.; Santos, dos F.; Kleerebezem, M.; Hylckama Vlieg, van J.E.T.

    2007-01-01

    The luminescence signal of luxAB-encoded bacterial luciferase strongly depends on the metabolic state of the host cell, which restricts the use of this reporter system to metabolically active bacteria. Here we show that in stationary-phase cells of Lactococcus lactis, detection of luciferase is sign

  2. The Enantiomer Separations of Allethrone and Propargyllone Using Two Long Chain Acylated β-Cyclodextrin Derivatives as CGC Capillary Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Using two β-cyclodextrin derivatives (CDs) with long chain of acyl groups as chiral stationary phases (CSPs) of capillary gas chromatography (CGC), the enantiomers of racemic allethrone and propargyllone were well resolved after derived with acetyl chloride. The enantiomer excess values (e.e.%) of 1S-allethrone and 1S-propargyllone were also determined successfully using these CDs.

  3. Suitability of teicoplanin-aglycone bonded stationary phase for simulated moving bed enantio separation of racemic amino acids employing composition-constrained eluents

    NARCIS (Netherlands)

    Bechtold, M; Heinemann, M; Panke, S

    2006-01-01

    The suitability of a teicoplanin-aglycone based chiral stationary phase for the simulated moving bed (SMB) enantioseparation of amino acids under enzyme-compatible conditions was shown following a procedure that is based solely on model-based simulations and HPLC experiments. A set of eight amino ac

  4. Peak of Chiral Susceptibility and Chiral Phase Transition in QED3

    Institute of Scientific and Technical Information of China (English)

    ZHOU Yu-Qing; YANG Yong-Hong

    2011-01-01

    A general expression for the scalar susceptibility in QEDs is given. We adopt the Dyson-Schwinger equation for the fermion propagator to solve xc within a range of the number of fermion flavors, N, in chiral symmetry breaking phase. We show that the scalar susceptibility has a peak and the corresponding N is less than the critical number of fermion flavors for chiral symmetry.%@@ A general expression for the scalar susceptibility in QED3 is given.We adopt the Dyson-Schwinger equation for the fermion propagator to solve Xc within a range of the number of fermion flavors, N, in chiral symmetry breaking phase.We show that the scalar susceptibility has a peak and the corresponding N is less than thecritical number of fermion flavors for chiral symmetry.

  5. 直链淀粉手性固定相拆分西那卡塞对映体%Enantiomeric separation of cinacalcet on amylase chiral stationary phase by high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    卢定强; 孙生柏; 凌岫泉; 王琦; 夏芙洁

    2015-01-01

    A quantitative analysis method for the determination of cinacalcet enantiomers by HPLC had been developed. The enanti-omers of cinacalcet were separated on a Chiralpak AD-H column and the UV detection wavelength was 224 nm. The influences of concentration of organic solvent,proportion of triethylamine,column temperature and flow rate on the enantiomeric separation were investigated. The optimal chromatographic conditions were as follows:the mobile phase was hexane-isopropanol-triethylamine(90∶10∶0. 1,V/V/V);the flow rate was 1. 0 mL·min-1;the column temperature was 30℃. Under the optimal conditions,the elution order of two enantiomers was S-cinacalcet before R-cinacalcet. It was simple,accurate,and reproducible HPLC method,and could be used for the analysis and quality control of cinacalcet.%建立了一种快速、准确的高效液相色谱分析方法。使用Chiralpak AD-H手性色谱柱,检测波长224nm,考察了流动相中极性调节剂的体积分数、流动相中三乙胺的体积分数、柱温及流速对西那卡塞对映体拆分的影响。确立了最佳拆分条件:流动相为正己烷-异丙醇-三乙胺(90∶10∶0.1,V/V/V);流速为1.0 mL·min-1;柱温为30℃。在此优化实验条件下,得到西那卡塞对映体的出峰顺序为:先S体,后R体。所建立的方法简单准确,重复性好,可用于西那卡塞的质量研究和控制。

  6. KN Phase Shifts in Chiral SU(3) Quark Model

    Institute of Scientific and Technical Information of China (English)

    HUANGFei; ZHANGZong-Ye; YUYou-Wen

    2004-01-01

    The isospin I = 0 and I = 1 kaon-nucleon S and P partial waves phase shifts have been studied in the chiral SU(3) quark model by solving a resonating group method equation. When the parameters of the chiral fields are taken in a reasonable region, the numerical results of S-wave are in good agreement with the experimental data, and the P-wave phase shifts can also be explained qualitatively by the calculation of only central force considered.

  7. Chiral Floquet Phases of Many-Body Localized Bosons

    Science.gov (United States)

    Po, Hoi Chun; Fidkowski, Lukasz; Morimoto, Takahiro; Potter, Andrew C.; Vishwanath, Ashvin

    2016-10-01

    We construct and classify chiral topological phases in driven (Floquet) systems of strongly interacting bosons, with finite-dimensional site Hilbert spaces, in two spatial dimensions. The construction proceeds by introducing exactly soluble models with chiral edges, which in the presence of many-body localization (MBL) in the bulk are argued to lead to stable chiral phases. These chiral phases do not require any symmetry and in fact owe their existence to the absence of energy conservation in driven systems. Surprisingly, we show that they are classified by a quantized many-body index, which is well defined for any MBL Floquet system. The value of this index, which is always the logarithm of a positive rational number, can be interpreted as the entropy per Floquet cycle pumped along the edge, formalizing the notion of quantum-information flow. We explicitly compute this index for specific models and show that the nontrivial topology leads to edge thermalization, which provides an interesting link between bulk topology and chaos at the edge. We also discuss chiral Floquet phases in interacting fermionic systems and their relation to chiral bosonic phases.

  8. On SU(3) effective models and chiral phase-transition

    CERN Document Server

    Tawfik, Abdel Nasser

    2015-01-01

    The sensitivity of Polyakov Nambu-Jona-Lasinio (PNJL) model as an effective theory of quark dynamics to chiral symmetry has been utilized in studying the QCD phase-diagram. Also, Poyakov linear sigma-model (PLSM), in which information about the confining glue sector of the theory was included through Polyakov-loop potential. Furthermore, from quasi-particle model (QPM), the gluonic sector of QPM is integrated to LSM in order to reproduce recent lattice calculations. We review PLSM, QLSM, PNJL and HRG with respect to their descriptions for the chiral phase-transition. We analyse chiral order-parameter M(T), normalized net-strange condensate Delta_{q,s}(T) and chiral phase-diagram and compare the results with lattice QCD. We conclude that PLSM works perfectly in reproducing M(T) and Delta_{q,s}(T). HRG model reproduces Delta_{q,s}(T), while PNJL and QLSM seem to fail. These differences are present in QCD chiral phase-diagram. PLSM chiral boundary is located in upper band of lattice QCD calculations and agree we...

  9. Characteristics of the chiral phase transition in nonlocal quark models

    CERN Document Server

    Dumm, D G

    2004-01-01

    The characteristics of the chiral phase transition are analyzed within the framework of chiral quark models with nonlocal interactions in the mean field approximation (MFA). In the chiral limit, we show that there is a region of low values of the chemical potential in which the transition is a second order one. In that region, it is possible to perform a Landau expansion and determine the critical exponents which, as expected, turn out to be the MFA ones. Our analysis also allows to obtain semi-analytical expressions for the transition curve and the location of the tricritical point. For the case of finite current quark masses, we study the behavior of various thermodynamical and chiral response functions across the phase transition.

  10. How tetraquarks can generate a second chiral phase transition

    CERN Document Server

    Pisarski, Robert D

    2016-01-01

    We consider how tetraquarks can affect the chiral phase transition in theories like QCD, with light quarks coupled to three colors. For two flavors the tetraquark field is an isosinglet, and its effect is minimal. For three flavors, however, the tetraquark field transforms in the same representation of the chiral symmetry group as the usual chiral order parameter, and so for very light quarks there may be two chiral phase transitions, which are both of first order. In QCD, results from the lattice indicate that any transition from the tetraquark condensate is a smooth crossover. In the plane of temperature and quark chemical potential, though, a crossover line for the tetraquark condensate is naturally related to the transition line for color superconductivity. For four flavors we suggest that a triquark field, antisymmetric in both flavor and color, combine to form hexaquarks.

  11. On SU(3 Effective Models and Chiral Phase Transition

    Directory of Open Access Journals (Sweden)

    Abdel Nasser Tawfik

    2015-01-01

    Full Text Available Sensitivity of Polyakov Nambu-Jona-Lasinio (PNJL model and Polyakov linear sigma-model (PLSM has been utilized in studying QCD phase-diagram. From quasi-particle model (QPM a gluonic sector is integrated into LSM. The hadron resonance gas (HRG model is used in calculating the thermal and dense dependence of quark-antiquark condensate. We review these four models with respect to their descriptions for the chiral phase transition. We analyze the chiral order parameter, normalized net-strange condensate, and chiral phase-diagram and compare the results with recent lattice calculations. We find that PLSM chiral boundary is located in upper band of the lattice QCD calculations and agree well with the freeze-out results deduced from various high-energy experiments and thermal models. Also, we find that the chiral temperature calculated from HRG is larger than that from PLSM. This is also larger than the freeze-out temperatures calculated in lattice QCD and deduced from experiments and thermal models. The corresponding temperature and chemical potential are very similar to that of PLSM. Although the results from PNJL and QLSM keep the same behavior, their chiral temperature is higher than that of PLSM and HRG. This might be interpreted due the very heavy quark masses implemented in both models.

  12. Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

    Science.gov (United States)

    Poole, Colin F; Lenca, Nicole

    2014-08-29

    Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present.

  13. Chiral Paramagnetic Skyrmion-like Phase in MnSi

    NARCIS (Netherlands)

    Pappas, C.; Lelièvre-Berna, E.; Falus, P.; Bentley, P.M.; Moskvin, E.; Grigoriev, S.; Fouquet, P.; Farago, B.

    2009-01-01

    We present a comprehensive study of chiral fluctuations in the reference helimagnet MnSi by polarized neutron scattering and neutron spin echo spectroscopy, which reveals the existence of a completely left-handed and dynamically disordered phase. This phase may be identified as a spontaneous Skyrmio

  14. Nonequilibrium stationary states and phase transitions in directed Ising models

    Science.gov (United States)

    Godrèche, Claude; Bray, Alan J.

    2009-12-01

    We study the nonequilibrium properties of directed Ising models with non-conserved dynamics, in which each spin is influenced by only a subset of its nearest neighbours. We treat the following models: (i) the one-dimensional chain; (ii) the two-dimensional square lattice; (iii) the two-dimensional triangular lattice and (iv) the three-dimensional cubic lattice. We raise and answer the question: (a) under what conditions is the stationary state described by the equilibrium Boltzmann-Gibbs distribution? We show that, for models (i), (ii) and (iii), in which each spin 'sees' only half of its neighbours, there is a unique set of transition rates, namely with exponential dependence in the local field, for which this is the case. For model (iv), we find that any rates satisfying the constraints required for the stationary measure to be Gibbsian should satisfy detailed balance, ruling out the possibility of directed dynamics. We finally show that directed models on lattices of coordination number z>=8 with exponential rates cannot accommodate a Gibbsian stationary state. We conjecture that this property extends to any form of the rates. We are thus led to the conclusion that directed models with Gibbsian stationary states only exist in dimensions one and two. We then raise the question: (b) do directed Ising models, augmented by Glauber dynamics, exhibit a phase transition to a ferromagnetic state? For the models considered above, the answers are open problems, with the exception of the simple cases (i) and (ii). For Cayley trees, where each spin sees only the spins further from the root, we show that there is a phase transition provided the branching ratio, q, satisfies q>=3.

  15. Chiral phase transition in QED$_3$ at finite temperature

    CERN Document Server

    Wei, Wei; Zong, Hong-Shi

    2016-01-01

    Chiral phase transition in (2+1)-dimensional quantum electrodynamics (QED$_3$) at finite temperature is investigated in the framework of truncated Dyson-Schwinger equations (DSEs). We go beyond the widely used instantaneous approximation and adopt a method that retains the full frequency dependence of the fermion self-energy. We also take further step to include the effects of wave-function renormalizations and introduce a minimal dressing of the bare vertex. Finally, with the more complete solutions of the truncated DSEs, we revisit the study of chiral phase transition in finite-temperature QED$_3$.

  16. Stationary phase optimized selectivity liquid chromatography: Basic possibilities of serially connected columns using the "PRISMA" principle.

    Science.gov (United States)

    Nyiredy, Sz; Szucs, Zoltán; Szepesy, L

    2007-07-20

    A new procedure (stationary phase optimized selectivity liquid chromatography: SOS-LC) is described for the optimization of the HPLC stationary phase, using serially connected columns and the principle of the "PRISMA" model. The retention factors (k) of the analytes were determined on three different stationary phases. By use of these data the k values were predicted applying theoretically combined stationary phases. These predictions resulted in numerous intermediate theoretical separations from among which only the optimal one was assembled and tested. The overall selectivity of this separation was better than that of any individual base stationary phase. SOS-LC is independent of the mechanism and the scale of separation.

  17. 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.

  18. Retention mechanism for polycyclic aromatic hydrocarbons in reversed-phase liquid chromatography with monomeric stationary phases.

    Science.gov (United States)

    Rafferty, Jake L; Siepmann, J Ilja; Schure, Mark R

    2011-12-23

    Reversed-phase liquid chromatography (RPLC) is the foremost technique for the separation of analytes that have very similar chemical functionalities, but differ only in their molecular shape. This ability is crucial in the analysis of various mixtures with environmental and biological importance including polycyclic aromatic hydrocarbons (PAHs) and steroids. A large amount of effort has been devoted to studying this phenomenon experimentally, but a detailed molecular-level description remains lacking. To provide some insight on the mechanism of shape selectivity in RPLC, particle-based simulations were carried out for stationary phases and chromatographic parameters that closely mimic those in an experimental study by Sentell and Dorsey [J. Chromatogr. 461 (1989) 193]. The retention of aromatic hydrocarbons ranging in size from benzene to the isomeric PAHs of the formula C(18)H(12) was examined for model RPLC systems consisting of monomeric dimethyl octadecylsilane (ODS) stationary phases with surface coverages ranging from 1.6 to 4.2 μmol/m(2) (i.e., stationary phases yielding low to intermediate shape selectivity) in contact with a 67/33 mol% acetonitrile/water mobile phase. The simulations show that the stationary phase acts as a very heterogeneous environment where analytes with different shapes prefer different spatial regions with specific local bonding environments of the ODS chains. However, these favorable retentive regions cannot be described as pre-existing cavities because the chain conformation in these local stationary phase regions adapts to accommodate the analytes.

  19. Enantioseparation and impurity determination of the enantiomers of novel phenylethanolamine derivatives by high performance liquid chromatography on amylose stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Yang Jing [Department of Analytical Chemistry, Shenyang Pharmaceutical University, Shenyang 110016 (China); Guan Jin [Department of Analytical Chemistry, Shenyang Pharmaceutical University, Shenyang 110016 (China); School of Applied Chemistry, Shenyang Institute of Chemical Technology, Shenyang 110142 (China); Pan Li [School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang 110016 (China); Jiang Kun [Department of Analytical Chemistry, Shenyang Pharmaceutical University, Shenyang 110016 (China); Cheng Maosheng [School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang 110016 (China); Li Famei [Department of Analytical Chemistry, Shenyang Pharmaceutical University, Shenyang 110016 (China)], E-mail: lifamei@syphu.edu.cn

    2008-03-10

    Simple and efficient analytical HPLC methods using Chiralpak AS-H as chiral stationary phase were developed for direct enantioseparation of 11 novel phenylethanolamine derivatives. The chromatographic experiments were performed in normal phase mode with n-hexane-ethanol-triethylamine (TEA) as mobile phase. Excellent baseline enantioseparation was obtained for most of compounds. The effects of the concentration of organic modifiers and column temperature were studied for the enantiomeric separation. The mechanism of chiral recognition was discussed based on the relationship between the thermodynamic parameters and structures of compounds. It was found that the enantioseparations were all enthalpy driven, and the tert-butyl groups of compounds had significant influence on the chiral recognition. Trantinterol enantiomers were resolved (R{sub s} = 2.73) within 14 min using n-hexane-ethanol-TEA (98:2:0.1, v/v/v) as mobile phase with a flow rate of 0.8 mL min{sup -1} at 30 deg. C. The optimized method was validated for linearity, precision, accuracy and stability in solution and proved to be robust. The limits of detection (LOD) and quantification (LOQ) for (+)-trantinterol were 0.15 and 0.46 {mu}g mL{sup -1}. The method was applied for enantiomeric impurity determination of (-)-trantinterol bulk samples.

  20. Phases of (Asymptotically) Safe Chiral Theories with(out) Scalars

    CERN Document Server

    Molgaard, Esben

    2016-01-01

    We unveil the dynamics of four dimensional chiral gauge-Yukawa theories featuring several scalar degrees of freedom transforming according to distinct representations of the underlying gauge group. We consider generalized Georgi-Glashow and Bars-Yankielowicz theories. We determine, to the maximum known order in perturbation theory, the phase diagram of these theories and further disentangle their ultraviolet asymptotic nature according to whether they are asymptotically free or safe. We therefore extend the number of theories that are known to be fundamental in the Wilsonian sense to the case of chiral gauge theories with scalars.

  1. Detecting, visualizing, and measuring gold nanoparticle chirality using helical pitch measurements in nematic liquid crystal phases.

    Science.gov (United States)

    Sharma, Anshul; Mori, Taizo; Lee, Huey-Charn; Worden, Matthew; Bidwell, Eric; Hegmann, Torsten

    2014-12-23

    Chirality at the nanoscale, or more precisely, the chirality or chiroptical effects of chiral ligand-capped metal nanoparticles (NPs) is an intriguing and rapidly evolving field in nanomaterial research with promising applications in catalysis, metamaterials, and chiral sensing. The aim of this work was to seek out a system that not only allows the detection and understanding of NP chirality but also permits visualization of the extent of chirality transfer to a surrounding medium. The nematic liquid crystal phase is an ideal candidate, displaying characteristic defect texture changes upon doping with chiral additives. To test this, we synthesized chiral cholesterol-capped gold NPs and prepared well-dispersed mixtures in two nematic liquid crystal hosts. Induced circular dichroism spectropolarimetry and polarized light optical microscopy revealed that all three gold NPs induce chiral nematic phases, and that those synthesized in the presence of a chiral bias (disulfide) are more powerful chiral inducers than those where the NP was formed in the absence of a chiral bias (prepared by conjugation of a chiral silane to preformed NPs). Helical pitch data here visually show a clear dependence on the NP size and the number of chiral ligands bound to the NP surface, thereby supporting earlier experimental and theoretical data that smaller metal NPs made in the presence of a chiral bias are stronger chiral inducers.

  2. The effect of the chiral chemical potential on the chiral phase transition in the NJL model with different regularization schemes

    CERN Document Server

    Yu, Lang; Huang, Mei

    2015-01-01

    We study the chiral phase transition in the presence of the chiral chemical potential $\\mu_5$ using the two-flavor Nambu--Jona-Lasinio model. In particular, we analyze the reason why one can obtain two opposite behaviors of the chiral critical temperature as a function of $\\mu_5$ in the framework of different regularization schemes. We compare the modifications of the chiral condensate and the critical temperature due to $\\mu_5$ in different regularization schemes, analytically and numerically. Finally, we find that, for the conventional hard-cutoff regularization scheme, the increasing dependence of the critical temperature on the chiral chemical potential is an artifact, which is caused by the fact that it does not include complete contribution from the thermal fluctuations. When the thermal contribution is fully taken into account, the chiral critical temperature should decrease with $\\mu_5$.

  3. Dynamic aspect of the chiral phase transition in the mode coupling theory

    CERN Document Server

    Ohnishi, K; Ohta, K

    2005-01-01

    We analyze the dynamic aspect of the chiral phase transition. We apply the mode coupling theory to the linear sigma model and derive the kinetic equation for the chiral phase transition. We challenge Hohenberg and Halperin's classification scheme of dynamic critical phenomena in which the dynamic universality class of the chiral phase transition has been identified with that of the antiferromagnet. We point out a crucial difference between the chiral dynamics and the antiferromagnet system. We also calculate the dynamic critical exponent for the chiral phase transition. Our result is $z=1-\\eta/2\\cong 0.98$ which is contrasted with $z=d/2=1.5$ of the antiferromagnet.

  4. Study of stationary phase metabolism via isotopomer analysis of amino acids from an isolated protein.

    Science.gov (United States)

    Shaikh, Afshan S; Tang, Yinjie J; Mukhopadhyay, Aindrila; Martín, Héctor García; Gin, Jennifer; Benke, Peter I; Keasling, Jay D

    2010-01-01

    Microbial production of many commercially important secondary metabolites occurs during stationary phase, and methods to measure metabolic flux during this growth phase would be valuable. Metabolic flux analysis is often based on isotopomer information from proteinogenic amino acids. As such, flux analysis primarily reflects the metabolism pertinent to the growth phase during which most proteins are synthesized. To investigate central metabolism and amino acids synthesis activity during stationary phase, addition of fully (13)C-labeled glucose followed by induction of green fluorescent protein (GFP) expression during stationary phase was used. Our results indicate that Escherichia coli was able to produce new proteins (i.e., GFP) in the stationary phase, and the amino acids in GFP were mostly from degraded proteins synthesized during the exponential growth phase. Among amino acid biosynthetic pathways, only those for serine, alanine, glutamate/glutamine, and aspartate/asparagine had significant activity during the stationary phase.

  5. Study of Stationary Phase Metabolism Via Isotopomer Analysis of Amino Acids from an Isolated Protein

    Energy Technology Data Exchange (ETDEWEB)

    Shaikh, AfshanS.; Tang, YinjieJ.; Mukhopadhyay, Aindrila; Martin, Hector Garcia; Gin, Jennifer; Benke, Peter; Keasling, Jay D.

    2009-09-14

    Microbial production of many commercially important secondary metabolites occurs during stationary phase, and methods to measure metabolic flux during this growth phase would be valuable. Metabolic flux analysis is often based on isotopomer information from proteinogenic amino acids. As such, flux analysis primarily reflects the metabolism pertinent to the growth phase during which most proteins are synthesized. To investigate central metabolism and amino acids synthesis activity during stationary phase, addition of fully 13C-labeled glucose followed by induction of green fluorescent protein (GFP) expression during stationary phase was used. Our results indicate that Escherichia coli was able to produce new proteins (i.e., GFP) in the stationary phase, and the amino acids in GFP were mostly from degraded proteins synthesized during the exponential growth phase. Among amino acid biosynthetic pathways, only those for serine, alanine, glutamate/glutamine, and aspartate/asparagine had significant activity during the stationary phase.

  6. Chiral Phase Transition at Finite Isospin Density in Linear Sigma Model

    Institute of Scientific and Technical Information of China (English)

    SHU Song; LI Jia-Rong

    2005-01-01

    Using the linear sigma model, we have introduced the pion isospin chemical potential. The chiral phase transition is studied at finite temperatures and finite isospin densities. We have studied the μ - T phase diagram for the chiral phase transition and found the transition cannot happen below a certain low temperature because of the BoseEinstein condensation in this system. Above that temperature, the chiral phase transition is studied by the isotherms of pressure versus density. We indicate that the transition, in the chiral limit, is a first-order transition from a low-density phase to a high-density phase like a gas-liquid phase transition.

  7. Disorienting the Chiral Condensate at the QCD Phase Transition

    CERN Document Server

    Rajagopal, K

    1997-01-01

    I sketch how long wavelength modes of the pion field can be amplified during the QCD phase transition. If nature had been kinder, and had made the pion mass significantly less than the critical temperature for the transition, then this phenomenon would have characterized the transition in thermal equilibrium. Instead, these long wavelength oscillations of the orientation of the chiral condensate can only arise out of equilibrium. There is a simple non-equilibrium mechanism, plausibly operational during heavy ion collisions, which naturally amplifies these oscillations. The characteristic signature of this phenomenon is large fluctuations in the ratio of the number of neutral pions to the total number of pions in regions of momentum space, that is in phase space in a detector. Detection in a heavy ion collision would imply an out of equilbrium chiral transition.

  8. On the Chiral Phase Transition in the Linear Sigma Model

    CERN Document Server

    Phat, T H; Hoa, L V; Phat, Tran Huu; Anh, Nguyen Tuan; Hoa, Le Viet

    2004-01-01

    The Cornwall-Jackiw-Tomboulis (CJT) effective action for composite operators at finite temperature is used to investigate the chiral phase transition within the framework of the linear sigma model as the low-energy effective model of quantum chromodynamics (QCD). A new renormalization prescription for the CJT effective action in the Hartree-Fock (HF) approximation is proposed. A numerical study, which incorporates both thermal and quantum effect, shows that in this approximation the phase transition is of first order. However, taking into account the higher-loop diagrams contribution the order of phase transition is unchanged.

  9. Extraction of Phenylalanine Phase Systems Containing Enantiomers by Aqueous Two Combinatorial Chiral Selector

    Institute of Scientific and Technical Information of China (English)

    陈晓青; 刘莉; 焦飞鹏; 王珍

    2012-01-01

    In order to obtain a better enantioselectivity of phenylalanine enantiomers and establish the optimal chiral ex- traction conditions, the distribution behavior was investigated in aqueous two-phase systems which were composed of polyethylene glycol and ammonium sulfate containing combinatorial chiral selector: β-cyclodextrin and HP-β-cyclodextrin. The influence of the molar concentration ratio of combinatorial chiral selectors, the total molar concentration of combinatorial chiral selectors, pH value, buffer type and its concentration were thoroughly studied, respectively. The results show that the enantioselectivity reaches 1.53 under the optimal chiral extraction conditions This extraction is a potential economical and effective way for chiral resolution.

  10. The QCD phase transition with physical-mass, chiral quarks

    CERN Document Server

    Bhattacharya, Tanmoy; Christ, Norman H; Ding, H -T; Gupta, Rajan; Jung, Chulwoo; Karsch, F; Lin, Zhongjie; Mawhinney, R D; McGlynn, Greg; Mukherjee, Swagato; Murphy, David; Petreczky, P; Schroeder, Chris; Soltz, R A; Vranas, P M; Yin, Hantao

    2014-01-01

    We report on the first lattice calculation of the QCD phase transition using chiral fermions at physical values of the quark masses. This calculation uses 2+1 quark flavors, spatial volumes between (4 fm$)^3$ and (11 fm$)^3$ and temperatures between 139 and 196 MeV . Each temperature was calculated using a single lattice spacing corresponding to a temporal Euclidean extent of $N_t=8$. The disconnected chiral susceptibility, $\\chi_{\\rm disc}$ shows a pronounced peak whose position and height depend sensitively on the quark mass. We find no metastability in the region of the peak and a peak height which does not change when a 5 fm spatial extent is increased to 10 fm. Each result is strong evidence that the QCD ``phase transition'' is not first order but a continuous cross-over for $m_\\pi=135$ MeV. The peak location determines a pseudo-critical temperature $T_c = 155(1)(8)$ MeV. Chiral $SU(2)_L\\times SU(2)_R$ symmetry is fully restored above 164 MeV, but anomalous $U(1)_A$ symmetry breaking is non-zero above $T...

  11. QCD phase transition with chiral quarks and physical quark masses.

    Science.gov (United States)

    Bhattacharya, Tanmoy; Buchoff, Michael I; Christ, Norman H; Ding, H-T; Gupta, Rajan; Jung, Chulwoo; Karsch, F; Lin, Zhongjie; Mawhinney, R D; McGlynn, Greg; Mukherjee, Swagato; Murphy, David; Petreczky, P; Renfrew, Dwight; Schroeder, Chris; Soltz, R A; Vranas, P M; Yin, Hantao

    2014-08-22

    We report on the first lattice calculation of the QCD phase transition using chiral fermions with physical quark masses. This calculation uses 2+1 quark flavors, spatial volumes between (4 fm)(3) and (11 fm)(3) and temperatures between 139 and 196 MeV. Each temperature is calculated at a single lattice spacing corresponding to a temporal Euclidean extent of N(t) = 8. The disconnected chiral susceptibility, χ(disc) shows a pronounced peak whose position and height depend sensitively on the quark mass. We find no metastability near the peak and a peak height which does not change when a 5 fm spatial extent is increased to 10 fm. Each result is strong evidence that the QCD "phase transition" is not first order but a continuous crossover for m(π) = 135 MeV. The peak location determines a pseudocritical temperature T(c) = 155(1)(8) MeV, in agreement with earlier staggered fermion results. However, the peak height is 50% greater than that suggested by previous staggered results. Chiral SU(2)(L) × SU(2)(R) symmetry is fully restored above 164 MeV, but anomalous U(1)(A) symmetry breaking is nonzero above T(c) and vanishes as T is increased to 196 MeV.

  12. Chiral-phase high-performance liquid chromatography of rotenoid racemates

    Science.gov (United States)

    Abidi, S.L.

    1987-01-01

    The high-performance liquid chromatograhic (HPLC) behavior of parent rotenoids (type I) and the hydroxyl-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on β-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attenmpts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (α values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (α = 1.00–1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring ot type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-pahse (PGS and TPS) HPLC modes, the less polar enantiomers were the 6aβ,12aβ-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.

  13. Separation performance of guanidinium-based ionic liquids as stationary phases for gas chromatography.

    Science.gov (United States)

    Qiao, Lizhen; Lu, Kai; Qi, Meiling; Fu, Ruonong

    2013-02-08

    Room temperature ionic liquids (RTILs) as stationary phases for gas chromatography (GC) have made great achievements in both research and applications over the last decades. Until now, all of the RTIL stationary phases reported have involved imidazolium, ammonium, pyrrolidinium, and phosphonium-based RTILs, and however, no publications are available using guanidinium-based ionic liquids (GBILs) as GC stationary phases except two preliminary reports from our group. In the present work, three hexaalkyl GBILs stationary phases, namely N, N,N',N'-tetramethyl-N″, N″-dioctylguanidinum hexafluophosphate (DOTMG-PF(6)), N,N,N',N'-tetramethyl-N″, N″-dioctylguanidinium bis (trifluoromethylsulfonyl) imide (DOTMG-NTf(2)), and N,N,N',N'-tetraoctyl-N″, N″-dimethylguanidinium bis (trifluoromethylsulfonyl) imide (TODMG-NTf(2)), were synthesized and used as stationary phases for GC separation after they were statically coated onto the inner walls of fused-silica capillary columns. The evaluation of DOTMG-PF(6) and TODMG-NTf(2) as GC stationary phases is reported here for the first time, whereas additional results on the DOTMG-NTf(2) stationary phase are added here on the basis of our previous report. In this work, McReynolds constants and Abraham solvation system constants are used to evaluate the average polarity and the solvation properties of the GBILs stationary phases for GC separation, respectively. The results show that the GBILs stationary phases exhibit medium polarity with an average polarity of 293-390, and that the major molecular interactions of the GBILs with analytes are dipole/polarizable interactions, H-bond basicity and dispersion forces, etc. After this, the separation performance and thermal stability of the GBILs stationary phases were evaluated, showing that these stationary phases achieve excellent separation for analytes of great variety covering hydrocarbons, alcohols, esters, aldehydes, ketones, amines, amides and aromatics, and exhibit

  14. New chiral reverse phase HPLC method for enantioselective analysis of ketorolac using chiral AGP column

    Institute of Scientific and Technical Information of China (English)

    Sunil K. Dubey; Jangala Hemanth; Chiranjeevi Venkatesh K.; R.N. Saha; S. Pasha

    2012-01-01

    A simple, specific, precise, sensitive and rapid reverse phase-HPLC method was developed for determination of ketorolac enantiomers, a potent nonnarcotic analgesic in pharmaceutical formulations. The method was developed on a chiral AGP column. Mobile phase was 0.1 M sodium phosphate buffer (pH 4.5): lsopropanol (98:2, v/v), at a flow rate of 1 mL/min with run time of 15 min. Ultraviolet detection was made at 322 nm. The linearity range was 0.02 10 μg/mL for each of the enantiomers. The mobile phase composition was systematically studied to find the optimum chromatographic conditions. Validation of the method under the conditions selected showed that it was selective and precise and that the detector response was linear function of ketorolac.

  15. Use of ionic liquids as stationary phases in hyphenated gas chromatography techniques.

    Science.gov (United States)

    Ragonese, Carla; Sciarrone, Danilo; Tranchida, Peter Quinto; Dugo, Paola; Mondello, Luigi

    2012-09-14

    In the past decades a consistent number of ionic liquids have been specifically synthesized and evaluated as stationary phase in gas chromatography. Ionic liquid, also defined as "molten salts", are a class of organic non-molecular solvents liquid at room temperature (RTILs) that satisfy most of the requirements of a GC stationary phase, among which a high viscosity, the possibility to tune the selectivity (by changing the cation-anion combination) and a high thermal stability. The choice of the proper stationary phase plays a key role in the improvement/optimization of a GC method, and although the use of IL as stationary phases is still not well-established, the general interest in their applications has greatly increased, thanks to their particular properties. The present contribution provides an overview on recent evaluations and applications of IL stationary phases, focusing in particular on the use of these novel tools in hyphenated GC-based techniques.

  16. Electromagnetic chirality-induced negative refraction with the same amplitude and anti-phase of the two chirality coefficients

    Institute of Scientific and Technical Information of China (English)

    Zhao Shun-Cai; Liu Zheng-Dong; Zheng Jun; Li Gen

    2011-01-01

    This paper suggests a scheme of electromagnetic chirality-induced negative refraction utilizing magneto-electric cross coupling in a four-level atomic system. The negative refraction can be achieved with the two chirality coefficients having the same amplitude but the opposite phase, without requiring the simultaneous presence of an electric-dipole and a magnetic-dipole transition near the same transition frequency.

  17. The search for more pH stable stationary phases for high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Carol H.; Silva, Cesar R.; Faria, Anizio M.; Collins, Kenneth E.; Jardim, Isabel Cristina S.F. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2009-07-01

    High performance liquid chromatographic (HPLC) separations are largely carried out using reversed phase conditions with stationary phases based on silica. A serious problem with these stationary phases is the tendency of silica to dissolve in high pH solutions often needed to separate basic compounds. The literature reports many different ways that have been tried to resolve this problem. This paper reports the results obtained in our laboratory with stationary phases prepared using silica supports having a layer of a metal oxide (zirconia or titania) attached on their surfaces, followed by immobilization of a polysiloxane or by organofunctionalization with a trimethoxyalkylsilane. Stability tests, also developed in our laboratory, indicate that the metal oxide layer increases the HPLC column lifetimes by making the stationary phase less susceptible to dissolution. (author)

  18. Transcriptional characterization of Salmonella TA100 in log and stationary phase: influence of growth phase on mutagenicity of MX.

    Science.gov (United States)

    Ward, William O; Swartz, Carol D; Hanley, Nancy M; DeMarini, David M

    2010-10-13

    The Salmonella mutagenicity assay can be performed using cells that are in different growth phases. Thus, the plate-incorporation assay involves plating stationary-phase cells with the mutagen, after which the cells undergo a brief lag phase and, consequently, are exposed to the mutagen and undergo mutagenesis while in the logarithmic (log) phase. In contrast, a liquid-suspension assay involves exposure of either log- or stationary-phase cells to the mutagen for a specified period of time, sometimes followed by a wash, resulting in the cells growing in medium in the absence of the mutagen. To explore global gene expression in Salmonella, and to test for possible effects of growth phase and transcriptional status on mutagenesis, we performed microarray analysis on cells of Salmonella strain TA100 exposed to the drinking-water mutagen MX in either the log or stationary phase. The genes in functional pathways involving amino acid transport and metabolism and energy metabolism were expressed differentially in log-phase cells, whereas genes in functional pathways involving protein trafficking, cell envelope, and two-component systems using common signal transduction were expressed differentially in stationary-phase cells. More than 90% of the ribosomal-protein biosynthesis genes were up-regulated in stationary- versus log-phase cells. MX was equally mutagenic to cells in log- and stationary-phase growth when the results were expressed as mutant frequencies (revertants/survivors/μM), but it was twice as mutagenic in stationary-phase cells when the results were expressed as mutant yields (revertants/nmole or revertants/μM). There was a complex transcriptional response underlying these results, with mucA/B being greatly up-regulated in log-phase cells but umuC/D up-regulated in stationary-phase cells. The transcriptional state of TA100 cells at the time of mutagen treatment may influence the outcome of mutagen treatment.

  19. Ceramic stationary gas turbine development. Final report, Phase 1

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-09-01

    This report summarizes work performed by Solar Turbines Inc. and its subcontractors during the period September 25, 1992 through April 30, 1993. The objective of the work is to improve the performance of stationary gas turbines in cogeneration through implementation of selected ceramic components.

  20. Chirality-dependent vapor-phase epitaxial growth and termination of single-wall carbon nanotubes.

    Science.gov (United States)

    Liu, Bilu; Liu, Jia; Tu, Xiaomin; Zhang, Jialu; Zheng, Ming; Zhou, Chongwu

    2013-09-11

    Structurally uniform and chirality-pure single-wall carbon nanotubes are highly desired for both fundamental study and many of their technological applications, such as electronics, optoelectronics, and biomedical imaging. Considerable efforts have been invested in the synthesis of nanotubes with defined chiralities by tuning the growth recipes but the approach has only limited success. Recently, we have shown that chirality-pure short nanotubes can be used as seeds for vapor-phase epitaxial cloning growth, opening up a new route toward chirality-controlled carbon nanotube synthesis. Nevertheless, the yield of vapor-phase epitaxial growth is rather limited at the present stage, due in large part to the lack of mechanistic understanding of the process. Here we report chirality-dependent growth kinetics and termination mechanism for the vapor-phase epitaxial growth of seven single-chirality nanotubes of (9, 1), (6, 5), (8, 3), (7, 6), (10, 2), (6, 6), and (7, 7), covering near zigzag, medium chiral angle, and near armchair semiconductors, as well as armchair metallic nanotubes. Our results reveal that the growth rates of nanotubes increase with their chiral angles while the active lifetimes of the growth hold opposite trend. Consequently, the chirality distribution of a nanotube ensemble is jointly determined by both growth rates and lifetimes. These results correlate nanotube structures and properties with their growth behaviors and deepen our understanding of chirality-controlled growth of nanotubes.

  1. Finite-Temperature Phase Structure in the Chiral σ-ω Model with Dilatons

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiao-Bing ZHANG Xiao-Bing; LI Xue-Qian; NING Ping-Zhi

    2000-01-01

    We investigate the finite-temperature phase structure in a scaled chiral model which includes the dilaton (glueball) field. It is shown that hot nuclear matter undergoes a discontinuous transition in the mean field of scalar mesons as well as the Lee-Wick abnormal transition. The corresponding behavior of the gluon condensate during the chiral phase transition is also studied.

  2. Topological String in Quantum-Chromodynamical Chiral Phase Transitions

    Institute of Scientific and Technical Information of China (English)

    LI Yun-De

    2005-01-01

    @@ It is pointed out that if in heavy ion collision processes, the quark-gluon plasma SU(2) chiral phase transition really takes place and the phase transition is a second order. Then the topological string, i.e., the π string, will be formed. The main effect of this phenomenon is that there will be a number of pions produced by decay of the π string in the final state. The pions from the decay of the π string lead to the same effect of decreasing the Hanbury-Brown-Twiss peak in two-pion spectra which is just as that of the long-lived hadronic resonances.At relativistic heavy-ion collision and large hadron collision energies, it is expected that the factors are about α~ 0.7 - 0.9 and α~ 0.6 - 0.85, respectively.

  3. Novel guanidinium-based ionic liquids as stationary phases for capillary gas chromatography

    Institute of Scientific and Technical Information of China (English)

    Li Zhen Qiao; Kai Lu; Mei Ling Qi; Ruo Nong Fu

    2010-01-01

    The present study describes guanidinium-based ionic liquids(GBILs)as stationary phases for capillary gas chromatography(CGC)and to the best of our knowledge,no related reports are available up to now.In this study,a hexaalkylguanidinium ionic liquid(DOTMG-NTf2)was synthesized and coated statically onto capillary columns.Selectivity of the stationary phase was evaluated by separating Grob test mixture,test mixture,alcohols mixture,and fatty acid methyl esters mixture,and thermal stability was investigated as well.The present study demonstrates that GBILs as CGC stationary phases exhibit satisfactory selectivity and thermal stability and have a great potential as new candidates for CGC stationary phases.

  4. Gold nanoparticle decorated graphene oxide/silica composite stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Liang, Xiaojing; Wang, Xusheng; Ren, Haixia; Jiang, Shengxiang; Wang, Licheng; Liu, Shujuan

    2014-06-01

    In the initial phase of this study, graphene oxide (GO)/silica was fabricated by assembling GO onto the silica particles, and then gold nanoparticles (GNPs) were used to modify the GO/silica to prepare a novel stationary phase for high-performance liquid chromatography. The new stationary phase could be used in both reversed-phase chromatography and hydrophilic interaction liquid chromatography modes. Good separations of alkylbenzenes, isomerides, amino acids, nucleosides, and nucleobases were achieved in both modes. Compared with the GO/silica phase and GNPs/silica phase, it is found that except for hydrophilicity, large π-electron systems, hydrophobicity, and coordination functions, this new stationary phase also exhibited special separation performance due to the combination of 2D GO with zero-dimensional GNPs.

  5. PEG-linked geminal dicationic ionic liquids as selective, high-stability gas chromatographic stationary phases.

    Science.gov (United States)

    Huang, Ke; Han, Xinxin; Zhang, Xiaotong; Armstrong, Daniel W

    2007-12-01

    It is known that room-temperature ionic liquids (RTILs) have wide applicability in many scientific and technological fields. In this work, a series of three new dicationic room-temperature ionic liquids functionalized with poly(ethylene glycol) (PEG) linkages were synthesized and characterized via a linear solvation model. The application of these ILs as new GC stationary phases was studied. The efficient separation of several mixtures containing compounds of different polarities and 24 components of a flavor and fragrance mixture indicated comparable or higher resolving power for the new IL stationary phases compared to the commercial polysiloxane and poly(ethylene glycol)-based stationary phases. In addition, the selectivities of the IL stationary phases could be quite unique. The separation of a homologous alkane and alcohol mixture displayed the "dual nature" of these ionic liquids as GC stationary phases. The thermal stability study showed the column robustness up to 350 degrees C. The high separation power, unique selectivity, high efficiency and high thermal stability of the new dicationic ionic liquids indicate that they may be applicable as a new type of robust GC stationary phase.

  6. Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

    Science.gov (United States)

    Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2014-02-21

    In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange.

  7. 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.

  8. Role of ppGpp in rpoS stationary-phase regulation in Escherichia coli.

    Science.gov (United States)

    Hirsch, Matthew; Elliott, Thomas

    2002-09-01

    The bacterial sigma factor RpoS is strongly induced under a variety of stress conditions and during growth into stationary phase. Here, we used rpoS-lac fusions in Escherichia coli to investigate control acting at the level of RpoS synthesis, which is especially evident when cells approach stationary phase in rich medium. Previous work has shown that the small molecule ppGpp is required for normal levels of RpoS in stationary phase. Despite the attraction of a model in which the ppGpp level controls stationary-phase induction of RpoS, careful measurement of rpoS-lac expression in a mutant lacking ppGpp showed similar effects during both exponential growth and stationary phase; the main effect of ppGpp was on basal expression. In addition, a modest regulatory defect was associated with the mutant lacking ppGpp, delaying the time at which full expression was achieved by 2 to 3 h. Deletion analysis showed that the defect in basal expression was distributed over several sequence elements, while the regulatory defect mapped to the region upstream of the rpoS ribosome-binding site (RBS) that contains a cis-acting antisense element. A number of other genes that have been suggested as regulators of rpoS were tested, including dksA, dsrA, barA, ppkx, and hfq. With the exception of the dksA mutant, which had a modest defect in Luria-Bertani medium, none of these mutants was defective for rpoS stationary-phase induction. Even a short rpoS segment starting at 24 nucleotides upstream of the AUG initiation codon was sufficient to confer substantial stationary-phase regulation, which was mainly posttranscriptional. The effect of RBS-proximal sequence was independent of all known trans-acting factors, including ppGpp.

  9. ({alpha},{eta}) phase diagrams in tilted chiral smectics

    Energy Technology Data Exchange (ETDEWEB)

    Rjili, M., E-mail: medrjili@yahoo.fr [Laboratoire de Physique de la Matiere Molle et de la Modelisation Electromagnetique, Faculte des Sciences de Tunis, Universite Tunis El Manar, 2092 El Manar Tunis (Tunisia); Marcerou, J.P., E-mail: marcerou@crpp-bordeaux.cnrs.fr [Centre de Recherches Paul Pascal, 115, Av. Albert-Schweitzer, 33600 Pessac (France); Gharbi, A.; Othman, T. [Laboratoire de Physique de la Matiere Molle et de la Modelisation Electromagnetique, Faculte des Sciences de Tunis, Universite Tunis El Manar, 2092 El Manar Tunis (Tunisia)

    2013-02-01

    The polymorphism of tilted chiral smectics liquid crystals is incredibly rich and encompasses many subphases such as SmC{sub A}{sup Low-Asterisk }; SmC{sub Fi1}{sup Low-Asterisk }; SmC{sub Fi2}{sup Low-Asterisk }; SmC{sup Low-Asterisk }; SmC{sub {alpha}}{sup Low-Asterisk }. The continuum theory established by Marcerou (2010) is used to derive an expression for the free energy density of those subphases. The minimization of this free energy is obtained through a combination of analytical and numerical methods. It leads to a phase diagram built in the ({alpha},{eta}) plane where {alpha} is local angular parameter and {eta} describes the variation of the temperature. From this graphical representation, many experimentally observed phase sequences of ferroelectric liquid crystals can be explained, even them including subphases which were recently observed like the SmC{sub 5}{sup Low-Asterisk} and the SmC{sub 6}{sup Low-Asterisk} ones. However, it should be emphasized that the details of predicted phase diagram are strongly dependent on the compound studied.

  10. 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.

  11. Synthesis of fluorescent label, DBD-beta-proline, and the resolution efficiency for chiral amines by reversed-phase chromatography.

    Science.gov (United States)

    Min, Jun Zhe; Toyo'oka, Toshimasa; Kato, Masaru; Fukushima, Takeshi

    2005-01-01

    DBD-d(and l)-beta-proline, new fluorescent chiral derivatization reagents, were synthesized from the reaction of 4-(N,N-dimethylaminosulfonyl)-7- fl uoro-2,1,3-benzoxadiazole (DBD-F) with beta-proline. The racemic mixture synthesized was separated by a chiral stationary phase (CSP) column, Chiralpak AD-H, with n-hexane-EtOH-TFA-diethylamine (70:30:0.1:0.1) as the mobile phase. The dl-forms were decided according to the results obtained from a circular dichroism (CD) detector after separation by the CSP column. The fractionated enantiomers reacted with chiral amine to produce a couple of diastereomers. The labeling proceeded in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and pyridine as the activation reagents. The reaction conditions were mild and no racemization occurred during the diastereomer formation. The resulting diastereomers fluoresced at around 570 nm (excitation at around 460 nm). Good linearity of the calibration curves was obtained in the range 1-75 pmol and the detection limits on chromatogram were less than 1 pmol. The separability of the diastereomers was compared with the diastereomers derived from DBD-d(or l)-proline. The resolution values (Rs) obtained from the diastereomers of three chiral amines with DBD-d(or l)-beta-proline were higher than those derived from DBD-d(or l)-proline, e.g. dl-phenylalanine methylester (dl-PAME), 2.23 vs 1.37; (R)(S)-1-phenylethylamine [(R)(S)-PEA], 2.09 vs 1.13; and (R)(S)-1-(1-naphthyl)ethylamines [(R)(S)-NEA], 5.19 vs 1.23. The results suggest that the position of COOH group on pyrrolidine moiety in the structures is one of the important factors for the efficient separation of a couple of the diastereomers.

  12. Efficiency enhancements in micellar liquid chromatography through selection of stationary phase and alcohol modifier.

    Science.gov (United States)

    Thomas, David P; Foley, Joe P

    2007-05-18

    Micellar liquid chromatography (MLC) remains hindered by reduced chromatographic efficiency compared to reversed phase liquid chromatography (RPLC) using hydro-organic mobile phases. The reduced efficiency has been partially explained by the adsorption of surfactant monomers onto the stationary phase, resulting in a slow mass transfer of the analyte within the interfacial region of the mobile phase and stationary phase. Using an array of 12 columns, the effects of various bonded stationary phases and silica pore sizes, including large-pore short alkyl chain, non-porous, superficially porous and perfluorinated, were evaluated to determine their impact on efficiency in MLC. Additionally, each stationary phase was evaluated using 1-propanol and 1-butanol as separate micellar mobile phase alcohol additives, with several columns also evaluated using 1-pentanol. A simplified equation for calculation of A' and C' terms from reduced plate height (h) versus reduced velocity (nu) plots was used to compare the efficiency data obtained with the different columns and mobile phases. Analyte diffusion coefficients needed for the h versus nu plots were determined by the Taylor-Aris dispersion technique. The use of a short alkyl chain, wide-pore silica column, specifically, Nucleosil C4, 1000A, was shown to have the most improved efficiency when using a micellar mobile phase compared to a hydro-organic mobile phase for all columns evaluated. The use of 1-propanol was also shown to provide improved efficiency over 1-butanol or 1-pentanol in most cases. In a second series of experiments, column temperatures were varied from 40 to 70 degrees C to determine the effect of temperature on efficiency for a subset of the stationary phases. Efficiency improvements ranging from 9% for a Chromegabond C8 column to 58% for a Zorbax ODS column were observed over the temperature range. Based on these observed improvements, higher column temperatures may often yield significant gains in column

  13. Ionic liquids as novel stationary phases in gas liquid chromatography: inverse or normal isotope effect?

    Science.gov (United States)

    Schmarr, Hans-Georg; Slabizki, Petra; Müntnich, Sabrina; Metzger, Carmen; Gracia-Moreno, Elisa

    2012-12-28

    The separation of deuterated and non-deuterated compounds in gas liquid partitioning chromatography (GLC) on silicone type stationary phase usually results in the inverse isotope effect. With ionic liquids (ILs) as stationary phase, however, this may show a totally different nature. The inverse isotope effect, in which heavier (deuterated) isotopic compounds (isotopologues) elute earlier, is to be expected when van der Waals (London) dispersion forces play a dominant role in the solute-stationary phase interaction. Such (apolar) interactions seem to play only a minor role when ILs are the stationary phases, leading to only a marginal inverse isotope effect, e.g. for the separation of 2,4,6-trichloroanisole and its [(2)H(5)]-isotopologue on 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethansulfonyl) amide (commercialized as SLB-IL59, Supelco). Indeed, with the most polar stationary phase available (commercialized as SLB-IL111; Supelco), this separation showed a normal isotope effect. Further examples are presented and the nature of the isotope effect observed is discussed.

  14. Regulation of Indole Signalling during the Transition of E. coli from Exponential to Stationary Phase.

    Science.gov (United States)

    Gaimster, Hannah; Summers, David

    2015-01-01

    During the transition from exponential to stationary phase E. coli produces a substantial quantity of the small, aromatic signalling molecule indole. In LB medium the supernatant indole concentration reaches a maximum of 0.5-1 mM. At this concentration indole has been implicated in many processes inducing acid resistance and the modulation of virulence. It has recently been shown that cell-associated indole transiently reaches a very high concentration (approx. 60 mM) during stationary phase entry, presumably because indole is being produced more rapidly than it can leave the cell. It is proposed that this indole pulse inhibits growth and cell division, causing the culture to enter stationary phase before nutrients are completely exhausted, with benefits for survival in long-term stationary phase. This study asks how E. coli cells rapidly upregulate indole production during stationary phase entry and why the indole pulse has a duration of only 10-15 min. We find that at the start of the pulse tryptophanase synthesis is triggered by glucose depletion and that this is correlates with the up-regulation of indole synthesis. The magnitude and duration of the resulting indole pulse are dependent upon the availability of exogenous tryptophan. Indole production stops when all the available tryptophan is depleted and the cell-associated indole equilibrates with the supernatant.

  15. The Proteome and Lipidome of Thermococcus kodakarensis across the Stationary Phase.

    Science.gov (United States)

    Gagen, Emma J; Yoshinaga, Marcos Y; Garcia Prado, Franka; Hinrichs, Kai-Uwe; Thomm, Michael

    2016-01-01

    The majority of cells in nature probably exist in a stationary-phase-like state, due to nutrient limitation in most environments. Studies on bacteria and yeast reveal morphological and physiological changes throughout the stationary phase, which lead to an increased ability to survive prolonged nutrient limitation. However, there is little information on archaeal stationary phase responses. We investigated protein- and lipid-level changes in Thermococcus kodakarensis with extended time in the stationary phase. Adaptations to time in stationary phase included increased proportion of membrane lipids with a tetraether backbone, synthesis of proteins that ensure translational fidelity, specific regulation of ABC transporters (upregulation of some, downregulation of others), and upregulation of proteins involved in coenzyme production. Given that the biological mechanism of tetraether synthesis is unknown, we also considered whether any of the protein-level changes in T. kodakarensis might shed light on the production of tetraether lipids across the same period. A putative carbon-nitrogen hydrolase, a TldE (a protease in Escherichia coli) homologue, and a membrane bound hydrogenase complex subunit were candidates for possible involvement in tetraether-related reactions, while upregulation of adenosylcobalamin synthesis proteins might lend support to a possible radical mechanism as a trigger for tetraether synthesis.

  16. The Proteome and Lipidome of Thermococcus kodakarensis across the Stationary Phase

    Directory of Open Access Journals (Sweden)

    Emma J. Gagen

    2016-01-01

    Full Text Available The majority of cells in nature probably exist in a stationary-phase-like state, due to nutrient limitation in most environments. Studies on bacteria and yeast reveal morphological and physiological changes throughout the stationary phase, which lead to an increased ability to survive prolonged nutrient limitation. However, there is little information on archaeal stationary phase responses. We investigated protein- and lipid-level changes in Thermococcus kodakarensis with extended time in the stationary phase. Adaptations to time in stationary phase included increased proportion of membrane lipids with a tetraether backbone, synthesis of proteins that ensure translational fidelity, specific regulation of ABC transporters (upregulation of some, downregulation of others, and upregulation of proteins involved in coenzyme production. Given that the biological mechanism of tetraether synthesis is unknown, we also considered whether any of the protein-level changes in T. kodakarensis might shed light on the production of tetraether lipids across the same period. A putative carbon-nitrogen hydrolase, a TldE (a protease in Escherichia coli homologue, and a membrane bound hydrogenase complex subunit were candidates for possible involvement in tetraether-related reactions, while upregulation of adenosylcobalamin synthesis proteins might lend support to a possible radical mechanism as a trigger for tetraether synthesis.

  17. Proteomic Analysis of Stationary Phase in the Marine Bacterium 'Candidatus Pelagibacter ubique'

    Energy Technology Data Exchange (ETDEWEB)

    Sowell, Sarah M.; Norbeck, Angela D.; Lipton, Mary S.; Nicora, Carrie D.; Callister, Stephen J.; Smith, Richard D.; Barofsky, Douglas F.; Giovannoni, Stephen J.

    2008-05-01

    Candidatus Pelagibacter ubique, an abundant marine alphaproteobacterium, subsists in nature at low ambient nutrient concentrations and may often be exposed to nutrient limitation, but its genome revealed no evidence of global regulatory adaptations to stationary phase. We used high-resolution capillary liquid chromatography (LC) coupled online to an LTQ mass spectrometer to build an Accurate Mass and Time (AMT) tag library, and employed the AMT tag approach to quantitatively examine proteome differences between exponentially growing and stationary phase Cand. P. ubique cells cultivated in a seawater medium. The AMT tag library represented 72% of the predicted protein coding genes. Stationary phase protein abundance increased for OsmC, which mitigates oxidative damage, and for molecular chaperones, enzymes involved in methionine and cysteine biosynthesis, proteins involved in rho-dependent transcription termination, and the signal transduction enzymes CheY-FisH and ChvG. Our findings indicate that Cand. P. ubique responds adaptively to stationary phase by increasing the abundance of a suite of proteins that contribute to homeostasis, but does not undergo major proteome remodeling. We speculate that this limited response may enable Cand. P. ubique to cope with ambient conditions in which nutrients are often insufficient for short periods, and the ability to resume growth overrides the capacity for long term survival afforded by more comprehensive global stationary phase responses.

  18. Modified Diatomaceous earth as a principal stationary phase component in TLC.

    Science.gov (United States)

    Ergül, Soner; Kadan, Imdat; Savaşci, Sahin; Ergül, Suzan

    2005-09-01

    Modified natural diatomaceous earth (DE) is a principal component of the stationary phase in normal thin-layer chromatography (TLC) applications and is mixed with commercial silica gel 60GF254 (Si-60GF254). Modification is carried out by flux calcination and refluxing with acid. Natural DE, modified DEs [flux calcinated (FC)DE and FCDE-I), and Si-60GF254 are characterized by scanning electron microscopy and Fourier-transform-IR spectroscopy. Particle size, specific surface area, pore distribution, pore volume, and surface hydroxyl group density parameters of materials are determined by various techniques. FCDE-I and Si-60GF254 are investigated for their usefulness in the stationary phase of TLC both individually and in composition. Commercially available red and blue ink samples are run on layers of Si-60GF254 and FCDE-I individually, and on various FCDE-I and Si-60GF254 mixtures. Butanol-ethanol-2M ammonia (3:1:1, v/v) and butanol-acetic acid-water (12:3:5, v/v) mixtures are used as mobile phases. The polarities of stationary phases decrease, and the retention factor (Rf) values of ink components increase when the FCDE-I content of the stationary phase increases. The properties of the stationary phase can be optimized by adding FCDE-I to Si-60GF254. This study may be useful in understanding both the systematic effects of stationary phase properties [e.g., specific surface area and surface hydroxyl group density, aOH(s)] and those of the mobile phase (e.g., polarity and acidity) on Rf values and the separability of components.

  19. Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

    Science.gov (United States)

    Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

    2016-10-07

    Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity.

  20. Liquid Crystal Phases of Molecular Bananas: Polarity and Chirality as Broken Symmetries

    Science.gov (United States)

    Clark, Noel

    2006-03-01

    The study of the interplay of chirality and polarity has been a particularly rich theme of soft matter science since Meyer's seminal discovery that tilted smectics of chiral molecules are macroscopically polar. This event, and the subsequent realization of polar domains and high-speed electro-optic switching in chiral smectics, engaged the liquid crystal community in a worldwide pursuit of novel smectics for applications, featured by the synthesis of more than 50,000 new liquid crystal compounds, and by a consequent broad diversification of the palette of liquid crystal phases and possibilities for supermolecular ordering. A current important activity in this scenario is the study of polar order in synthetically achiral molecules, for example, in molecular bananas, which, as their shape suggests, might be expected to organize in a polar way. Indeed they do, but beyond this, almost everything learned about them has been surprising, including their persistent tendency to exhibit chirality as a spontaneously broken symmetry. I will discuss some of these new phases and phenomena, including the discovery of fluid conglomerates (Pasteur's experiment in a fluid), triclinic fluid order, chiral twist grain boundary phases of achiral molecules, chirality flipping and field-induced deracemization, ferroelectric and antiferroelectric phases with supermolecular- scale polarization modulation, and chiral thermotropic sponge phases.

  1. Improved chiral SFC screening for analytical method development.

    Science.gov (United States)

    Schafer, Wes; Chandrasekaran, Tilak; Pirzada, Zainab; Zhang, Chaowei; Gong, Xiaoyi; Biba, Mirlinda; Regalado, Erik L; Welch, Christopher J

    2013-11-01

    In this study we describe the evaluation of a recently developed supercritical fluid chromatography (SFC) instrument for automated chiral SFC method development. The greatly improved gradient dwell volume and liquid flow control of the new instrument in combination with the use of shorter columns containing smaller stationary phase particles affords chiral SFC method development that is faster and more universal than previous systems.

  2. 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.

  3. Imidazolium embedded C8 based stationary phase for simultaneous reversed-phase/hydrophilic interaction mixed-mode chromatography.

    Science.gov (United States)

    Qiao, Xiaoqiang; Zhang, Lu; Zhang, Niu; Wang, Xin; Qin, Xinying; Yan, Hongyuan; Liu, Haiyan

    2015-06-26

    A new imidazolium embedded C8 based stationary phase (SIL-MPS-VOL) was facilely prepared by two steps and characterized by Fourier transform infrared spectrometry and thermogravimetric analysis. Due to the introduction of quaternary imidazolium group to the traditional C8 stationary phase, the developed SIL-MPS-VOL column demonstrated both reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) retention mechanisms. A series of hydrophobic and hydrophilic test samples, including benzene homologues, anilines, positional isomers, nucleosides and nucleotides, were used to evaluate the developed SIL-MPS-VOL stationary phase. A rapid separation time, high separation efficiency and planar selectivity were achieved, compared with the commercially available C8 column. Moreover, the developed stationary phase was further used to detect and separate of melamine in powdered infant formula and high polar component of secondary metabolites of Trichoderma, and improved separation efficiency was achieved, indicating the potential merits of the developed SIL-MPS-VOL stationary phase for simultaneous separation of complex hydrophobic and hydrophilic samples with high selectivity.

  4. Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

    Science.gov (United States)

    Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

    2016-10-01

    Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer

  5. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    Energy Technology Data Exchange (ETDEWEB)

    Read, Douglas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sillerud, Colin Halliday [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  6. Fast separation of hen egg white protein with a phosphorylcholine type zwitterionic ion chromatography stationary phase

    Institute of Scientific and Technical Information of China (English)

    Qian Qu; Xiu Juan Yu; Xi Wu; Fei Shi; Li Li Wang

    2012-01-01

    In this work,a kind of preparation method of zwitterionic ion chromatography (ZIC) stationary phase modified with phosphorylcholine (PC) was obtained by hydrolyzing after bonding phosphorylcholine dichloride to diol-silica to better explore the characteristics of the PC groups as ZIC stationary phase ligand in simultaneous separation of acidic proteins and basic proteins.The results showed that two kinds of acidic proteins and three kinds of basic proteins can be separated completely,meanwhile,hen egg white was separated and purified and three kinds of egg white components ovalbumin,G2 ovoglobulin and ovotransfemin proteins were separated completely by one single step on PC-ZIC column,the purity of all proteins reached above 95%.PC-ZIC stationary phase was successfully improved with better separation capacity and selectivity than previously reported in this paper.

  7. [Characteristics of electroosmotic flow in open-tubular capillary electrochromatography with magnetic nanoparticle coating as mixed-mode stationary phase].

    Science.gov (United States)

    Qin, Sasa; Zhou, Chaoran; Zhu, Yaxian; Ren, Zhiyu; Zhang, Lingyi; Fu, Honggang; Zhang, Weibing

    2011-09-01

    A novel open-tubular capillary electrochromatography (OT-CEC) column with magnetic nanoparticle coating as mixed-mode stationary phase was prepared. The mixed-mode stationary phases were obtained by mixing C18 and amino modified magnetic nanoparticles with different ratios. The mixed modified magnetic nanoparticles as stationary phase were introduced into the capillary by using external magnetic force. The magnetic nanoparticle coating can be easily regenerated by removing the external magnetic field, and applied to other separation modes. The characteristics of electroosmotic flow (EOF) were theoretically investigated through the effect of physicochemical properties of different stationary phases on EOF. The experiment was conducted under different ratios of mixed-mode stationary phases and coating lengths, and it was verified that the theoretical conclusions accorded with the experimental results. It was shown that the EOF can be easily adjusted by changing the ratio of stationary phases or the number of permanent magnets.

  8. Influence of boson mass on chiral phase transition in QED3

    Science.gov (United States)

    Feng, Hong-tao; Wang, Xiu-Zhen; Yu, Xin-hua; Zong, Hong-shi

    2016-08-01

    Based on the truncated Dyson-Schwinger equations for the fermion propagator with N fermion flavors at zero temperature, the chiral phase transition of quantum electrodynamics in 2 +1 dimensions (QED3 ) with boson mass—which is obtained via the Anderson-Higgs mechanism—is investigated. In the chiral limit, we find that the critical behavior of QED3 with a massless boson is different from that with a massive boson: the chiral phase transition in the presence of a nonzero boson mass reveals the typical second-order phase transition, at either the critical boson mass or a critical number of fermion flavors, while for a vanishing boson mass it exhibits a higher than second-order phase transition at the critical number of fermion flavors. Furthermore, it is shown that the system undergoes a crossover behavior from a small number of fermion flavors or boson mass to its larger one beyond the chiral limit.

  9. Detection of Zak phases and topological invariants in a chiral photonic quantum walk

    CERN Document Server

    Cardano, F; Dauphin, A; Maffei, M; Piccirillo, B; de Lisio, C; De Filippis, G; Cataudella, V; Santamato, E; Marrucci, L; Lewenstein, M; Massignan, P

    2016-01-01

    Topological insulators are fascinating states of matter exhibiting protected edge states and robust quantized features in their bulk. Here, we propose and validate experimentally a method to detect topological properties in the bulk of one-dimensional chiral systems. We first introduce the mean chiral displacement, and we show that it rapidly approaches a multiple of the Zak phase in the long time limit. Then we measure the Zak phase in a photonic quantum walk, by direct observation of the mean chiral displacement in its bulk. Next, we measure the Zak phase in an alternative, inequivalent timeframe, and combine the two windings to characterize the full phase diagram of this Floquet system. Finally, we prove the robustness of the measure by introducing dynamical disorder in the system. This detection method is extremely general, as it can be applied to all one-dimensional platforms simulating static or Floquet chiral systems.

  10. One-step synthesis of mussel-inspired molecularly imprinted magnetic polymer as stationary phase for chip-based open tubular capillary electrochromatography enantioseparation.

    Science.gov (United States)

    Wang, Xiao-Ni; Liang, Ru-Ping; Meng, Xiang-Ying; Qiu, Jian-Ding

    2014-10-03

    A facile approach for preparation of molecularly imprinted polymers was developed and successfully used as chiral stationary phase for rapid enantioseparation by open tubular capillary electrochromatography (OT-CEC). In this work, molecularly imprinted polymers were one-step prepared employing Fe3O4 nanoparticles (NPs) as the supporting substrate and dopamine as the functional monomer. By simply mixing Fe3O4 NPs with template molecules in a weak alkaline solution of dopamine, a thin adherent polydopamine (PDA) film imprinted with template molecules was formed by the self-polymerization of dopamine on the surface of Fe3O4 NPs. After extracting the embedded template molecules, the produced imprinted Fe3O4@PDA NPs are of three dimensional shape of template molecules favoring high binding capacity and magnetism property for easy manipulation. The imprinted Fe3O4@PDA NPs prepared with l-tryptophan, l-tyrosine, Gly-l-Phe or s-ofloxacin as template molecules were packed in the PDMS microchannel via magnetic field as novel stationary phase for the successful enantioseparation of corresponding target analysts. In addition, the imprinted Fe3O4@PDA NPs-based OT-CEC system exhibited excellent reproducibility, stability and repeatability, which provides a powerful protocol for separation enantiomers within a short analytical time and opens up a promising avenue for high-throughput screening of chiral compounds.

  11. O(N) universality and the chiral phase transition in QCD

    CERN Document Server

    Karsch, Frithjof

    2010-01-01

    We discuss universal scaling properties of (2+1)-flavor QCD in the vicinity of the chiral phase transition at vanishing as well as non-vanishing light quark chemical potential (mu_l). We provide evidence for O(N) scaling of the chiral order parameter in (2+1)-flavor QCD and show that the scaling analysis of its derivative with respect to the light quark chemical potential provides a unique approach to the determination of the curvature of the chiral phase transition line in the vicinity of mu_l/T=0.

  12. Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

    Science.gov (United States)

    Koury, Albert M.; Parcher, Jon F.

    1979-01-01

    Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

  13. 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.

  14. Profiling of Burkholderia cepacia secretome at mid-logarithmic and early-stationary phases of growth.

    Directory of Open Access Journals (Sweden)

    Vanitha Mariappan

    Full Text Available BACKGROUND: Burkholderia cepacia is a Gram-negative pathogen that causes serious respiratory infections in immunocompromised patients and individuals with cystic fibrosis. This bacterium is known to release extracellular proteins that may be involved in virulence. METHODOLOGY/PRINCIPAL FINDINGS: In the present study, B. cepacia grown to mid-logarithmic and early-stationary phases were investigated on their ability to invade and survive intracellularly in A549 lung epithelial cells in order to discern the fate of these bacteria in the pathogenesis of B. cepacia lung infections in in vitro condition. The early-stationary phase B. cepacia was demonstrated to be more invasive than mid-logarithmic phase. In addition, culture supernatants of B. cepacia obtained from these phases of growth were also demonstrated to cause different cytotoxic potency on the A549 human lung epithelial cells. Profiling of the supernatants using the gel-based proteomics approach identified 43 proteins that were commonly released in both the growth phases and 40 proteins newly-released at the early-stationary phase. The latter proteins may account for the higher cytotoxic activity of the early-stationary culture supernatant compared to that obtained at the mid-logarithmic phase. Among the newly-released proteins in the early-stationary phase supernatant were flagellar hook-associated domain protein (FliD, flagellar hook-associated protein (FlgK, TonB-dependent siderophore (Fiu, Elongation factor G (FusA, phosphoglycerate kinase (Pgk and sulfatase (AslA which are known for their virulence. CONCLUSION/SIGNIFICANCE: Differences in the ability of B. cepacia to invade and survive intracellularly inside the epithelial cells at different phases of growth may improve our understanding of the varied disease progressions associated with B. cepacia infections. In addition, the identified culture supernatant proteins may be used as targets for the development of new strategies to

  15. Quasi-stationary phase change heat transfer on a fin

    Science.gov (United States)

    Orzechowski, Tadeusz; Stokowiec, Katarzyna

    2016-03-01

    The paper presents heat transfer research basing on a long fin with a circular cross-section. Its basis is welded to the pipe where the hot liquid paraffin, having a temperature of 70°C at the inflow, is pumped. The analyzed element is a recurrent part of a refrigeration's condenser, which is immersed in a paraffin. The temperature of the inflowing liquid is higher than the temperature of the melting process for paraffin, which allows the paraffin to liquify. The temperature at the basis of the rib changes and it is assumed that the heat transfer is quasi-stationary. On this basis the estimation of the mean value of heat transfer coefficient was conducted. The unsteady thermal field of the investigated system was registered with an infrared camera V50 produced by a Polish company Vigo System. This device is equipped with a microbolometric detector with 384 × 288 elements and the single pixel size 25 × 25 μm. Their thermal resolution is lower than 70 mK at a temperature of 30 °C. The camera operates at 7,5 ÷ 14 μm long-wave infrared radiation range. For a typical lens 35 mm the special resolution is 0.7 mrad. The result of the calculations is mean heat transfer coefficient for the considered time series. It is equal to 50 W m -2 K-1 and 47 W m -2 K-1 on the left and right side of the fin, respectively. The distance between the experimental data and the curve approximating the temperature distribution was assessed with the standard deviation, Sd = 0.04 K.

  16. Quasi-stationary phase change heat transfer on a fin

    Directory of Open Access Journals (Sweden)

    Orzechowski Tadeusz

    2016-01-01

    Full Text Available The paper presents heat transfer research basing on a long fin with a circular cross-section. Its basis is welded to the pipe where the hot liquid paraffin, having a temperature of 70°C at the inflow, is pumped. The analyzed element is a recurrent part of a refrigeration’s condenser, which is immersed in a paraffin. The temperature of the inflowing liquid is higher than the temperature of the melting process for paraffin, which allows the paraffin to liquify. The temperature at the basis of the rib changes and it is assumed that the heat transfer is quasi-stationary. On this basis the estimation of the mean value of heat transfer coefficient was conducted. The unsteady thermal field of the investigated system was registered with an infrared camera V50 produced by a Polish company Vigo System. This device is equipped with a microbolometric detector with 384 × 288 elements and the single pixel size 25 × 25 μm. Their thermal resolution is lower than 70 mK at a temperature of 30 °C. The camera operates at 7,5 ÷ 14 μm long-wave infrared radiation range. For a typical lens 35 mm the special resolution is 0.7 mrad. The result of the calculations is mean heat transfer coefficient for the considered time series. It is equal to 50 W m −2 K−1 and 47 W m −2 K−1 on the left and right side of the fin, respectively. The distance between the experimental data and the curve approximating the temperature distribution was assessed with the standard deviation, Sd = 0.04 K.

  17. Plasmid DNA Supercoiling and Gyrase Activity in Escherichia coli Wild-Type and rpoS Stationary-Phase Cells

    Science.gov (United States)

    Reyes-Domínguez, Yazmid; Contreras-Ferrat, Gabriel; Ramírez-Santos, Jesús; Membrillo-Hernández, Jorge; Gómez-Eichelmann, M. Carmen

    2003-01-01

    Stationary-phase cells displayed a distribution of relaxed plasmids and had the ability to recover plasmid supercoiling as soon as nutrients became available. Preexisting gyrase molecules in these cells were responsible for this recovery. Stationary-phase rpoS cells showed a bimodal distribution of plasmids and failed to supercoil plasmids after the addition of nutrients, suggesting that rpoS plays a role in the regulation of plasmid topology during the stationary phase. PMID:12533486

  18. Separation of basic compounds by capillary electrochromatography on an X-Terra RP18 stationary phase.

    Science.gov (United States)

    Valette, J C; Bizet, A C; Demesmay, C; Rocca, J L; Verdon, E

    2004-09-17

    In this work we demonstrate that the X-Terra RP18 stationary phase, specially designed for the analysis of basic compounds in liquid chromatography, may be successfully used in capillary electrochromatography. Although this packing material does not afford a sufficient electroosmotic flow with classical hydro-organic mobile phases, the addition of a surfactant that adsorbs onto the stationary phase allows to generate a sustainable electroosmosis flow (EOF), the direction of which depends on the charge of the surfactant. The way of manipulating the electroosmotic flow is described (nature and concentration of the added surfactant, proportion of the organic modifier in the mobile phase, pH). It is then demonstrated that high efficiencies can be reached with this packing material (up to 220,000 plates/m with a mean diameter particles of 3.5 microm) when it is operated at high linear velocities. Then the separations of different classes of compounds such as amphenicol antibiotics, macrolide antibiotics or basic test solutes with mobile phases with pH up to 10.8 are described. The influence of the addition of sodium dodcylsulfate (SDS) to the mobile phase on the retention is described and the selectivity of the X-Terra RP18 stationary phase is compared to that of a more traditional phase, i.e. Hypersil C18 stationary phase with SDS added to the mobile phase. However, it is shown that a good repeatability of the retention factors can only be obtained when the ionization of the compounds is totally suppressed since electrolysis of the buffered hydro-organic mobile phase occurs in the buffer reservoirs leading to a variation of the mobile phase pH and consequently to a modification of the ionization degree of the solutes having their pKa close to the mobile phase pH.

  19. Combination of two different stationary phases for on-line pre-concentration and separation of basic drugs by using nano-liquid chromatography.

    Science.gov (United States)

    D'Orazio, Giovanni; Fanali, Salvatore

    2013-04-12

    Capillary columns were packed firstly with silica modified-teicoplanin (teico-CSP) particles for a short zone (1-5 cm) and then with a Cogent Bidentate C18 silica phase (25 cm). The first part of the column (inlet) was intended for focusing the sample model, consisted of selected basic compounds, while the second zone, containing RP18 particles, was used for their separation. For method optimization, some important experimental parameters were studied including the sample solvent, injected volume and teico-CSP particles length. 3 cm teico-CSP resulted to be effective for the on-line pre-concentration, before the separation, of acebutolol, alprenolol, nadolol, oxprenolol and terbutaline with limit of detection at levels of few ng/mL. The comparison of the data obtained in absence of the chiral stationary phase revealed that the use of this chiral short sector into the capillary allowed the increase of the sensitivity of 5-12 times. Injection of larger sample volumes were easily done using higher length of the teico-CSP into the capillary, however the use of 5 cm length was not appropriate because caused the partial chiral separation of some studied compounds.

  20. Ionic liquids as stationary phases in gas chromatography--an LSER investigation of six commercial phases and some applications.

    Science.gov (United States)

    Weber, Waldemar; Andersson, Jan T

    2014-09-01

    The separation properties of six novel stationary phases for gas chromatography, commercially available from Sigma-Aldrich (Supelco) and based on ionic liquids (ILs), were investigated. The linear solvation energy relationship model (LSER) was used to describe the molecular interactions between these stationary phases and 30 solutes. The solutes belong to different groups of compounds, like haloalkanes, alcohols, ketones, aromatics, aliphatics, and others. A good description of different interactions, as described by the LSER model, could be achieved. The calculated values of system constants for the ionic liquid phases were compared with constants of commonly used standard phases like a 5 % phenyl/95 % dimethyl siloxane and a polyethylene glycol phase. The solute descriptors are in good agreement with those found by previous authors who have used the LSER model for 44 different ionic liquids as stationary phase. The experiments were carried out at two temperatures to evaluate the influence on the phase parameters and separation characteristics. The interactions of different functional groups with the IL phases are discussed. These novel IL phases are a promising replacement of or an addition to common polar phases. Based on the evaluated phase properties, several possibilities for applications of these novel phases are shown.

  1. 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.

  2. Structure of chiral phase transitions at finite temperature in abelian gauge theories

    Energy Technology Data Exchange (ETDEWEB)

    Fukazawa, Kenji [Kure National College of Technology, Kure (Japan); Inagaki, Tomohiro [Information Media Center, Hiroshima Univ., Hiroshima (Japan); Mukaigawa, Seiji [Department of Electrical and Electronic Engineering, Faculty of Engineering, Iwate Univ., Iwate (Japan); Muta, Taizo [Department of Physics, Hiroshima Univ., Hiroshima (Japan)

    2001-06-01

    The mechanism of chiral symmetry breaking is investigated in strong-coupling Abelian gauge theories at finite temperature. The Schwinger-Dyson equation in the Landau gauge is employed in the real time formalism and is solved numerically within the framework of the instantaneous exchange approximation, including the effect of the thermal mass for the photon propagator. It is found that the chiral symmetry is broken below the critical temperature T for sufficiently large coupling {alpha}. The chiral phase transition is found to be of second order, and the phase diagram in the T-{alpha} plane is obtained. It is investigated how the structure of the chiral phase transition is affected by the thermal mass in the photon propagator. (author)

  3. Structure of chiral phase transitions at finite temperature in Abelian gauge theories

    CERN Document Server

    Fukazawa, K; Mukaigawa, S; Muta, T; Fukazawa, Kenji; Inagaki, Tomohiro; Mukaigawa, Seiji; Muta, Taizo

    1999-01-01

    The mechanism of the chiral symmetry breaking is investigated in the strong-coupling Abelian gauge theories at finite temperature. The Schwinger-Dyson equation in Landau gauge is employed in the real time formalism and is solved numerically within the framework of the instantaneous exchange approximation including the effect of the hard thermal loop for the photon propagator. It is found that the chiral symmetry is broken below the critical temperature T for sufficiently large coupling. The chiral phase transition is found to be of the 2nd order and the phase diagram on the $T-\\alpha$ plane is obtained. It is investigated how the structure of the chiral phase transition is affected by the hard thermal loops in the photon propagator.

  4. Evaluation of new ionic liquids as high stability selective stationary phases in gas chromatography.

    Science.gov (United States)

    González Álvarez, Jaime; Blanco Gomis, Domingo; Arias Abrodo, Pilar; Díaz Llorente, Daniel; Busto, Eduardo; Ríos Lombardía, Nicolás; Gotor Fernández, Vicente; Gutiérrez Álvarez, María Dolores

    2011-05-01

    Two ionic liquids (ILs), namely (S,S)-1-butyl-3-(2'-hydroxy-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate and (S,S)-1-butyl-3-(2'-acetyl-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate have been employed as stationary phases in capillary gas chromatography. These new phases exhibit a column efficiency of 1,600 and 2,100 plates m(-1) for IL 1 and IL 2, respectively, a wide operating temperature range and good thermal stability (bleeding temperature of 250 °C for IL 1 and 160 °C for IL 2). Inverse gas chromatography (GC) analyses were used to study the solvation properties of these ILs through a linear solvation energy model. The application of these ILs as new GC stationary phases was studied. These stationary phases exhibited unique selectivity for many organic substances, such as alkanes, ketones, esters, and aromatic compounds. The efficient separation of several mixtures containing compounds of different polarities and the good separation of fatty acid methyl esters (FAMEs) and cis/trans isomers indicate that these ILs may be applicable as a new type of GC stationary phases.

  5. Coating properties of a novel water stationary phase in capillary supercritical fluid chromatography.

    Science.gov (United States)

    Murakami, Jillian N; Thurbide, Kevin B

    2015-05-01

    The coating properties of a novel water stationary phase used in capillary supercritical fluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless-steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless-steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm(2) regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless-steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless-steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless-steel columns were more resistant to etching than 304 stainless-steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless-steel columns used with this supercritical fluid chromatography technique.

  6. CspC and CspD are essential for Caulobacter crescentus stationary phase survival.

    Science.gov (United States)

    Balhesteros, Heloise; Mazzon, Ricardo R; da Silva, Carolina A P T; Lang, Elza A S; Marques, Marilis V

    2010-09-01

    The cold shock response in bacteria involves the expression of low-molecular weight cold shock proteins (CSPs) containing a nucleic acid-binding cold shock domain (CSD), which are known to destabilize secondary structures on mRNAs, facilitating translation at low temperatures. Caulobacter crescentus cspA and cspB are induced upon cold shock, while cspC and cspD are induced during stationary phase. In this work, we determined a new coding sequence for the cspC gene, revealing that it encodes a protein containing two CSDs. The phenotypes of C. crescentus csp mutants were analyzed, and we found that cspC is important for cells to maintain viability during extended periods in stationary phase. Also, cspC and cspCD strains presented altered morphology, with frequent non-viable filamentous cells, and cspCD also showed a pronounced cell death at late stationary phase. In contrast, the cspAB mutant presented increased viability in this phase, which is accompanied by an altered expression of both cspC and cspD, but the triple cspABD mutant loses this characteristic. Taken together, our results suggest that there is a hierarchy of importance among the csp genes regarding stationary phase viability, which is probably achieved by a fine tune balance of the levels of these proteins.

  7. [Using barium fluoride fine particles as stationary phase for TLC/FTIR analysis].

    Science.gov (United States)

    Liu, Xi; Pan, Qing-hua; Ding, Jie; Zhu, Qing; He, An-qi; Yue, Shi-juan; Li, Xiao-pei; Hu, Li-ping; Xia, Jin-ming; Liu, Cui-ge; Wei, Yong-ju; Yu, Jiang; Yang, Zhan-lan; Zhu, Xi; Xu, Yi-zhuang; Wu, Jin-guang

    2011-07-01

    In situ TLC/FTIR technique has tremendous potential in the analysis of complex mixtures. However, the progress in this technique was quite slow. The reason is that conventional stationary phase such as silica gel etc. has strong absorption in FTIR spectrum and thus brings about severe interference in the detection of samples. To solve the problem, the authors propose to use barium fluoride fine particles as stationary phase of TLC plate. The reasons are as follows: Barium fluoride wafer has been extensively used as infrared window in FTIR experiments and it has no absorbance in an IR region between 4 000 and 800 cm'. As a matter of fact, the atomic mass of barium and fluoride is quite large, thus the normal vibration of BaF2 lattice is limited in far-IR region and low frequency part of mid-IR region. Therefore, the interference caused by IR absorption of stationary phase can be resolved if BaF2 is used as stationary phase of TLC plate. Moreover, BaF2 is quite stable and insolvable in water and most organic solvents and it will not be dissolved by mobile phase or react with samples in TLC separation. Additionally, decreasing the particle size of BaF2 is very important in TLC/FTIR analysis technique. The reason is two-fold: First, decreasing the particle size of stationary phase is helpful to improving the efficiency of separation by TLC plate; second, decreasing the size of BaFz particle can improve the quality of FTIR spectra by alleviating the problem of light scattering. By optimizing the synthetic conditions, fine particles of barium fluoride were obtained. SEM results indicate that the size of the BaF2 particles is around 500 nm. FTIR spectrum of the BaF2 particles shows that no absorption of impurity was observed. Moreover, the elevation of baseline caused by light scattering is insignificant. The authors have developed a new technique named "settlement volatilization method" to prepare TLC plate without polymeric adhesive that may bring about significant

  8. Shotgun proteomic monitoring of Clostridium acetobutylicum during stationary phase of butanol fermentation using xylose and comparison with the exponential phase

    Energy Technology Data Exchange (ETDEWEB)

    Sivagnanam, Kumaran [McGill University, Montreal, Quebec; Raghavan, Vijaya G. S. [McGill University, Montreal, Quebec; Shah, Manesh B [ORNL; Hettich, Robert {Bob} L [ORNL; Verberkmoes, Nathan C [ORNL; Lefsrud, Mark G [McGill University, Montreal, Quebec

    2012-01-01

    Economically viable production of solvents through acetone butanol ethanol (ABE) fermentation requires a detailed understanding of Clostridium acetobutylicum. This study focuses on the proteomic profiling of C. acetobutylicum ATCC 824 from the stationary phase of ABE fermentation using xylose and compares with the exponential growth by shotgun proteomics approach. Comparative proteomic analysis revealed 22.9% of the C. acetobutylicum genome and 18.6% was found to be common in both exponential and stationary phases. The proteomic profile of C. acetobutylicum changed during the ABE fermentation such that 17 proteins were significantly differentially expressed between the two phases. Specifically, the expression of five proteins namely, CAC2873, CAP0164, CAP0165, CAC3298, and CAC1742 involved in the solvent production pathway were found to be significantly lower in the stationary phase compared to the exponential growth. Similarly, the expression of fucose isomerase (CAC2610), xylulose kinase (CAC2612), and a putative uncharacterized protein (CAC2611) involved in the xylose utilization pathway were also significantly lower in the stationary phase. These findings provide an insight into the metabolic behavior of C. acetobutylicum between different phases of ABE fermentation using xylose.

  9. Analysis of Data on Xanthan Fermentation in Stationary Phase Using Black Box and Metabolic Network Models

    Institute of Scientific and Technical Information of China (English)

    马红武; 赵学明; 唐寅杰

    1999-01-01

    The xanthan fermentation data in the stationary phase was analyzed using the black box and the metabolic network models. The data consistency ls checked through the elemental balance in the black box model. In the metabolic network model, the metabolic flux distribution in the cell is calculated using the metabolic flux analysis method, then the maintenance coefficients is calculated.

  10. Planar gas chromatography column on aluminum plate with multi-walled carbon nanotubes as stationary phase

    Science.gov (United States)

    Platonov, I. A.; Platonov, V. I.; Pavelyev, V. S.

    2016-04-01

    The high selectivity of the adsorption layer for low-boiling alkanes is shown, the separation factor (α) couple iso-butane / butane is 1.9 at a column temperature of 50 °C.The paper presents sorption and selective properties of planar gas chromatography column on aluminum plate with multi-walled carbon nanotubes as the stationary phase.

  11. Surface modification of polytetrafluoroethylene column for two-stationary phase separations by counter-current chromatography.

    Science.gov (United States)

    Quan, Kai-jun; Huang, Xin-yi; Li, Xiao-ting; Wang, Gao-hong; Liu, Yan-juan; Duan, Wen-da; Di, Duo-long

    2015-11-27

    To improve the separation capability of CCC, a novel solid-liquid two-stationary phases CCC (ASP-CCC) column was prepared employing graphene oxide (GO) conjugated poly-dopamine (PD) coating (GO/PD) as auxiliary stationary phase (ASP). The results of Scanning electron microscopy (SEM), contact angle and X-ray photoelectron spectroscopy (XPS) indicated that nanostructured GO and PD were successfully grafted on the inner wall of the PTFE column. Three alkaloid compounds were selected as the target analytes to evaluate the performance of the novel column. Because of the intermolecular force (hydrogen bond, electrostatic interaction and π-π interaction) between the ASP and model compounds, three analytes were well separated with this novel ASP-CCC column. Additionally, the novel column exhibited higher stationary phase retention ratio, about 8%, than original column without changing the chromatographic condition. Furthermore, the eluotropic sequence of analytes on novel column was in accordance with that in the original column. This suggested that the novel column is a CCC column with auxiliary stationary phase (ASP) in its own right, and the present separation mode is the combination of partition chromatography and adsorption chromatography.

  12. Thiol-yne Click Adamantane Monolithic Stationary Phase for Capillary Electrochromatography

    Institute of Scientific and Technical Information of China (English)

    Dao, Thi Thu Hien; Guerrouache, Mohamed; Carbonnier, Benjamin

    2012-01-01

    A porous crosslinked organic polymer based on N-acryloxysuccinimide (NAS) and ethylene dimethacrylate (EDMA) was prepared inside 75 μm i.d. fused silica capillary as functionalizable monolithic stationary phase for electrochromatographic applications. Succinimide groups on the monolith surface provide reactive sites able to re- act readily through standard electrophile-nucleophile chemistry. Propargylamine was used to prepare alkyne func- tionalized poly(NAS-co-EDMA). Onto this thiol-reactive polymer surface was grafted adamantane units via a photochemically-driven addition reaction. Chemical characterization was performed in situ after each synthetic step by means of Raman spectroscopy and grafting kinetics was investigated to ensure quantitative grafting of 1-adamantanethiol. The as-designed monolithic stationary phase exhibited typical reversed-phase separation mechanism as evidenced by the linear increase of the logarithm of retention factor of neutral aromatic solutes with the increase of the aqueous buffer content in the mobile phase.

  13. Chiral phase transition in charge ordered 1T-TiSe2.

    Science.gov (United States)

    Castellan, John-Paul; Rosenkranz, Stephan; Osborn, Ray; Li, Qing'an; Gray, K E; Luo, X; Welp, U; Karapetrov, Goran; Ruff, J P C; van Wezel, Jasper

    2013-05-10

    It was recently discovered that the low-temperature, charge-ordered phase of 1T-TiSe(2) has a chiral character. This unexpected chirality in a system described by a scalar order parameter could be explained in a model where the emergence of relative phase shifts between three charge density wave components breaks the inversion symmetry of the lattice. Here, we present experimental evidence for the sequence of phase transitions predicted by that theory, going from disorder to nonchiral and finally to chiral charge order. Employing x-ray diffraction, specific heat, and electrical transport measurements, we find that a novel phase transition occurs ~7 K below the main charge ordering transition in TiSe(2), in agreement with the predicted hierarchy of charge-ordered phases.

  14. Phase structure of the massive chiral Gross-Neveu model from Hartree-Fock

    CERN Document Server

    Boehmer, Christian; Kraus, Sebastian; Thies, Michael

    2008-01-01

    The phase diagram of the massive chiral Gross-Neveu model (the massive Nambu-Jona-Lasinio model in 1+1 dimensions) is constructed. In the large N limit, the Hartree-Fock approach can be used. We find numerically a chiral crystal phase separated from a massive Fermi gas phase by a 1st order transition. Using perturbation theory, we also construct the critical sheet where the homogeneous phase becomes unstable in a 2nd order transition. A tricritical curve is located. The phase diagram is mapped out as a function of fermion mass, chemical potential and temperature and compared with the one of the discrete chiral Gross-Neveu model. As a by-product, we illustrate the crystal structure of matter at zero temperature for various densities and fermion masses.

  15. Amplification of Quantum Meson Modes in the Late Time of the Chiral Phase Transition

    CERN Document Server

    Watanabe, K

    2007-01-01

    We investigate the time evolution of the quantum meson modes in the late time of chiral phase transition. In particular, it is shown that there exists a possible solution to the equation of motion for the quantum meson modes, which reveals a parametric resonance and/or resonance through forced oscillation induced by the small oscillation of the chiral condensate. After that, we demonstrate the unstable regions for the quantum meson modes in both the cases of a uniform and spatially expanding system.

  16. The use of the stationary phase method as a mathematical tool to determine the path of optical beams

    OpenAIRE

    Carvalho, Silvânia A.; Leo, Stefano de

    2015-01-01

    We use the stationary phase method to determine the path of optical beams which propagate through a dielectric block. In the presence of partial internal reflection, we recover the geometrical result obtained by using the Snell law. For total internal reflection, the stationary phase method overreaches the Snell law predicting the Goos-Haenchen shift.

  17. Effects of tea tree (Melaleuca alternifolia) oil on Staphylococcus aureus in biofilms and stationary growth phase.

    Science.gov (United States)

    Kwieciński, Jakub; Eick, Sigrun; Wójcik, Kinga

    2009-04-01

    Tea tree oil (TTO) is known for its antimicrobial activity. In this study, we determined whether TTO is effective against Staphylococcus aureus in biofilms and how TTO activity is affected by the S. aureus growth phase. All clinical strains tested were killed by TTO both as planktonic cells and as biofilms. The minimum biofilm eradication concentration was usually two times higher than the minimum bactericidal concentration, yet it was never higher than 1% v/v. The fastest killing of biofilm occurred during the first 15min of contact with TTO and was not influenced by increasing TTO concentration above 1% v/v. Planktonic stationary phase cells exhibited decreased susceptibility to TTO compared with exponential phase cells. The killing rate for stationary phase cells was also less affected by increasing TTO concentration than that for exponential phase cells. These data show that TTO efficiently kills S. aureus in the stationary growth phase and within biofilms and is therefore a promising tool for S. aureus eradication.

  18. Preparation and Evaluation of Immobilized SE-30 Coated Stationary Phases for CEC

    Institute of Scientific and Technical Information of China (English)

    NingBaoming; ZhengJie; ZhangGuodong; XuBingjiu

    2001-01-01

    A new type of stationary phase for capillary electrochromatography (CEC), immobilized SE-30 coated silica gel, was developed and the columns packed with this new phase were prepared and evaluated. It was found that this phase could be used to make frits for the micro-columns as well as to pack the bulk of the column. By sticking together the particles in the whole of the column bed, this new packing resulted in columns with stable performance, even under rigorous conditions: more than 380 consecutive separations were effected with these columns with the mobile phase pH of 11.7.

  19. Characterization of five chemistries and three particle sizes of stationary phases used in supercritical fluid chromatography.

    Science.gov (United States)

    Khater, S; West, C; Lesellier, E

    2013-12-06

    Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercritical fluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEHEthyl-pyridine, X Select CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercritical fluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs).The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids,this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength.These changes could modify the retention and the selectivity of compounds in the case of method trans-fer, by using different particle sizes, from 5 down to 1.7 m. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid.

  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. The chicken or the egg; or Who ordered the chiral phase transition?

    CERN Document Server

    Kogan, I I; Tekin, B; Kogan, Ian I.; Kovner, Alex; Tekin, Bayram

    2001-01-01

    We draw an analogy between the deconfining transition in the 2+1 dimensional Georgi-Glashow model and the chiral phase transition in 3+1 dimensional QCD. Based on the detailed analysis of the former (hep-th/0010201) we suggest that the chiral symmetry restoration in QCD at high temperature is driven by the thermal ensemble of baryons and antibaryons. The chiral symmetry is restored when roughly half of the volume is occupied by the baryons. Surprisingly enough, even though baryons are rather heavy, a crude estimate for the critical temperature gives $T_c=180$ Mev. In this scenario the binding of the instantons is not the cause but rather a consequence of the chiral symmetry restoration.

  2. Multi critical point structure for chiral phase transition induce by charge neutrality and vector interaction

    CERN Document Server

    Zhang, Zhao

    2010-01-01

    The combined effect of the repulsive vector interaction and the positive electric chemical potential on the chiral phase transition is investigated by considering neutral color superconductivity. Under the charge-neutrality constraint, the chiral condensate, diquark condensate and quark number densities are obtained in two-plus-one-flavor Nambu-Jona-Lasinio model with the so called Kobayashi-Maskawa-'t Hooft term. We demonstrate that multiple chiral critical-point structures always exist in the Nambu-Jona-Lasinio model within the self-consistent mean-field approximation, and that the number of chiral critical points can vary from zero to four, which is dependent on the magnitudes of vector interaction and the diquark coupling.

  3. Chiral phase transition of $N_f$=2+1 QCD with the HISQ action

    CERN Document Server

    Ding, H -T; Karsch, F; Maezawa, Y; Mukherjee, Swagato; Petreczky, P

    2013-01-01

    We present studies of universal properties of the chiral phase transition in $N_f$=2+1 QCD based on the simulations using Highly Improved Staggered fermions on lattices with temporal extent $N_\\tau$=6. We analyze the quark mass and volume dependence of the chiral condensates and chiral susceptibilities in QCD with two degenerate light quarks and a strange quark. The strange quark mass is chosen to be fixed to its physical value ($m^{phy}_s$) and five values of light quark masses ($m_l$) that are varied in the interval 1/20$\\gtrsim m_l/m^{phy}_s \\gtrsim$1/80. Here various quark masses correspond to pseudo Goldstone pion masses ranging from about 160 MeV to about 80 MeV. The O(N) scaling of chiral observables and the influence of universal scaling on physical observables in the region of physical quark mass values are also discussed.

  4. 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.

  5. The extracellular proteome of Rhizobium etli CE3 in exponential and stationary growth phase

    Directory of Open Access Journals (Sweden)

    Mendoza-Hernández Guillermo

    2010-10-01

    Full Text Available Abstract Background The extracellular proteome or secretome of symbiotic bacteria like Rhizobium etli is presumed to be a key element of their infection strategy and survival. Rhizobia infect the roots of leguminous plants and establish a mutually beneficial symbiosis. To find out the possible role of secreted proteins we analyzed the extracellular proteome of R. etli CE3 in the exponential and stationary growth phases in minimal medium, supplemented with succinate-ammonium. Results The extracellular proteins were obtained by phenol extraction and identified by LC-ESI MS/MS. We identified 192 and 191 proteins for the exponential and stationary phases respectively. Using the software Signal P, we predicted signal peptides for 12.95% and 35.60% of the proteins identified in the exponential and stationary phases, respectively, which could therefore be secreted by the Sec pathway. For the exponential growth phase, we found in abundance proteins like the ribosomal proteins, toxins and proteins belonging to the group "defence mechanisms". For the stationary growth phase, we found that the most abundant proteins were those with unknown function, and in many of these we identified characteristic domains of proteases and peptidases. Conclusions Our study provided the first dataset of the secretome of R. etli and its modifications, which may lead to novel insights into the adaptive response of different stages of growth. In addition, we found a high number of proteins with unknown function; these proteins could be analyzed in future research to elucidate their role in the extracellular proteome of R. etli.

  6. Staphylococcus aureus aconitase inactivation unexpectedly inhibits post-exponential-phase growth and enhances stationary-phase survival.

    Science.gov (United States)

    Somerville, Greg A; Chaussee, Michael S; Morgan, Carrie I; Fitzgerald, J Ross; Dorward, David W; Reitzer, Lawrence J; Musser, James M

    2002-11-01

    Staphylococcus aureus preferentially catabolizes glucose, generating pyruvate, which is subsequently oxidized to acetate under aerobic growth conditions. Catabolite repression of the tricarboxylic acid (TCA) cycle results in the accumulation of acetate. TCA cycle derepression coincides with exit from the exponential growth phase, the onset of acetate catabolism, and the maximal expression of secreted virulence factors. These data suggest that carbon and energy for post-exponential-phase growth and virulence factor production are derived from the catabolism of acetate mediated by the TCA cycle. To test this hypothesis, the aconitase gene was genetically inactivated in a human isolate of S. aureus, and the effects on physiology, morphology, virulence factor production, virulence for mice, and stationary-phase survival were examined. TCA cycle inactivation prevented the post-exponential growth phase catabolism of acetate, resulting in premature entry into the stationary phase. This phenotype was accompanied by a significant reduction in the production of several virulence factors and alteration in host-pathogen interaction. Unexpectedly, aconitase inactivation enhanced stationary-phase survival relative to the wild-type strain. Aconitase is an iron-sulfur cluster-containing enzyme that is highly susceptible to oxidative inactivation. We speculate that reversible loss of the iron-sulfur cluster in wild-type organisms is a survival strategy used to circumvent oxidative stress induced during host-pathogen interactions. Taken together, these data demonstrate the importance of the TCA cycle in the life cycle of this medically important pathogen.

  7. Evaluation of thermally pretreated silica stationary phases under hydrophilic interaction chromatography conditions.

    Science.gov (United States)

    Mignot, Mélanie; Périat, Aurélie; Peulon-Agasse, Valérie; Cardinael, Pascal; Veuthey, Jean-Luc; Guillarme, Davy

    2016-05-01

    Three novel hydrophilic interaction chromatography columns packed with bare silica 2.6 μm superficially porous particles were evaluated. These stationary phases undergo a different pretreatment temperature (400, 525, and 900°C) that might influence their kinetic performance and thermodynamic properties. In the first instance, we demonstrated that the performance of these columns was inferior to the commercial ones in the low plate count range (10 000 plates), but was more favorable for N values beyond 40 000 plates. Thanks to its high permeability and reasonable flow resistance (φ = 695), together with a minimum reduced heights equivalent to a theoretical plate value of only 2.4, the stationary phase pretreated at 400°C was particularly attractive for N > 70 000 plates with a remarkably low impedance value (E = 2488). In a second step, the impact of pretreatment temperature was evaluated using two mixtures of polar substances, namely nucleobases and derivatives, as well as nicotine and derivatives. Retentions and selectivities achieved on the tested stationary phases were appropriate, but selectivity differences were minor when modifying pretreatment temperature from 400 to 525°C. When we increased the pretreatment temperature up to 900°C, the surface chemistry was more seriously modified. Finally, the columns presented a good stability even at high temperature (70°C), especially for the phases pretreated at 400 and 525°C.

  8. Low symmetry tetrahedral nematic liquid crystal phases: Ambidextrous chirality and ambidextrous helicity.

    Science.gov (United States)

    Pleiner, Harald; Brand, Helmut R

    2014-02-01

    We discuss the symmetry properties as well as the dynamic behavior of various non-polar nematic liquid crystal phases with tetrahedral order. We concentrate on systems that show biaxial nematic order coexisting with octupolar (tetrahedral) order. Non-polar examples are phases with D2 and S4 symmetries, which can be characterized as biaxial nematics lacking inversion symmetry. It is this combination that allows for new features in the statics and dynamics of these phases. The D2-symmetric phase is chiral, even for achiral molecules, and shows ambidextrous chirality in all three preferred directions. The achiral S4-symmetric phase allows for ambidextrous helicity, similar to the higher-symmetric D2d-symmetric phase. Such phases are candidates for nematic phases made from banana-shaped molecules.

  9. Correlations between the zeta potentials of silica hydride-based stationary phases, analyte retention behaviour and their ionic interaction descriptors.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Munera, Caesar; Tse, Colby; Matyska, Maria T; Pesek, Joseph J; Boysen, Reinhard I; Hearn, Milton T W

    2014-03-19

    In this study, the zeta potentials of type-B silica, bare silica hydride, the so-called Diamond Hydride™ and phenyl substituted silica hydride stationary phases have been measured in aqueous-organic media and correction procedures developed to account for the more negative zeta potential values in media containing different acetonitrile contents. Retention studies of 16 basic, acidic and neutral compounds were also performed with these four stationary phases with mobile phases containing 0.1% (v/v) formic acid and various acetonitrile-water compositions ranging from 0-90% (v/v) acetonitrile. The retention properties of these analytes were correlated to the corrected stationary phase zeta potentials measured under these different mobile phase conditions with R(2) values ranging from 0.01 to 1.00, depending on the stationary phase and analyte type. Using linear solvation energy relationships, stationary phase descriptors for each stationary phase have been developed for the different mobile phase conditions. Very high correlations of the zeta potentials with the ionic interaction descriptors were obtained for the type-B silica and the Diamond Hydride™ phases and good correlation with bare silica hydride material whilst there was no correlation observed for the phenyl substituted silica hydride phase. The nature of the retention mechanisms which gives rise to these different observations is discussed. The described methods represent a useful new approach to characterize and assess the retention properties of silica-hydride based chromatographic stationary phases of varying bonded-phase coverage and chemistries, as would be broadly applicable to other types of stationary phase used in the separation sciences.

  10. New hydrophilic interaction/reversed-phase mixed-mode stationary phase and its application for analysis of nonionic ethoxylated surfactants.

    Science.gov (United States)

    Liu, Xiaodong; Pohl, Christopher

    2008-05-16

    We have developed a new stationary phase that combines both hydrophilic interaction and reversed-phase characteristics. The new phase is based on high-purity, porous and spherical silica gel functionalized with a silyl ligand consisting of both hydrophilic and hydrophobic functionalities. This phase can be operated in both HILIC mode (high organic solvent) and RPLC mode (low organic solvent). An optimal balance of hydrophilic and hydrophobic moieties on the silica surface provides unique chromatographic properties that make it useful for determination of alkyl chain distribution and degree of ethoxylation (EO number) of nonionic ethoxylated surfactants.

  11. PHOTOINDUCED HOLOGRAPHIC PHASE GRATINGS BURIED IN AZOBENZENE SIDE-CHAIN POLYMER FILMS WITH A CHIRAL GROUP

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    An optically active polymer (PM1) containing azobenzene moieties with a chiral group (s-2-methyl-butyl) was synthesized by homopolymerization of monomer, 4-[2-(methacryloyloxy)ethyloxy]-4'-(s-2-methyl-1-butyloxycarbonyl)azobenzene, using the free radical polymerization method. The polymer dissolved in tetrahydrofuran (THF) could be easily processed into high optical quality films. The optical anisotropy of the polymer films was investigated by polarizing optical microscopy (POM). The experimental results showed that irradiation with a circularly polarized beam could align the orientation of the molecules in the polymer films. Moreover, the holographic phase gratings of photo-induced polymer films were detected by atomic force microscopy (AFM) and POM. In comparison with polymer containing no chiral group, it was found from the preliminary measurement of the photo-induced holographic phase gratings that PM1 containing a chiral group could form holographic phase gratings buried in the films.

  12. Polymeric imidazolium ionic liquids as valuable stationary phases in gas chromatography: chemical synthesis and full characterization.

    Science.gov (United States)

    González-Álvarez, Jaime; Blanco-Gomis, Domingo; Arias-Abrodo, Pilar; Díaz-Llorente, Daniel; Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gutiérrez-Álvarez, María Dolores

    2012-04-06

    Seven new functionalized polymerizable ionic liquids were chemically prepared, and later applied for the preparation of polymeric stationary phases in gas chromatography. These coated GC columns, which exhibited good thermal stabilities (240-300°C) and very high efficiencies (3120-4200 plates/m), have been characterized using the Abraham solvation parameter model. The chromatographic behavior of these polymeric IL columns has been deeply studied observing excellent selectivities in the separation of many organic substances such as alkanes, ketones, alcohols, amines or esters in mixtures of polar and non polar solvents or fragrances. Remarkably, the challenging separation of xylene isomers has been possible using a bis(trifluoromethylsulfonyl)amide based imidazolium IL coated column as a gas chromatography stationary phase.

  13. Nutrient control for stationary phase cellulase production in Trichoderma reesei Rut C-30.

    Science.gov (United States)

    Callow, Nicholas V; Ray, Christopher S; Kelbly, Matthew A; Ju, Lu-Kwang

    2016-01-01

    This work describes the use of nutrient limitations with Trichoderma reesei Rut C-30 to obtain a prolonged stationary phase cellulase production. This period of non-growth may allow for dependable cellulase production, extended fermentation periods, and the possibility to use pellet morphology for easy product separation. Phosphorus limitation was successful in halting growth and had a corresponding specific cellulase production of 5±2 FPU/g-h. Combined with the addition of Triton X-100 for fungal pellet formation and low shear conditions, a stationary phase cellulase production period in excess of 300 h was achieved, with a constant enzyme production rate of 7±1 FPU/g-h. While nitrogen limitation was also effective as a growth limiter, it, however, also prevented cellulase production.

  14. Temporal transcriptomic analysis of Desulfovibrio vulgaris Hildenborough transition into stationary phase growth during electrondonor depletion

    Energy Technology Data Exchange (ETDEWEB)

    Clark, M.E.; He, Q.; He, Z.; Huang, K.H.; Alm, E.J.; Wan, X.-F.; Hazen, T.C.; Arkin, A.P.; Wall, J.D.; Zhou, J.-Z.; Fields, M.W.

    2006-08-01

    Desulfovibrio vulgaris was cultivated in a defined medium, and biomass was sampled for approximately 70 h to characterize the shifts in gene expression as cells transitioned from the exponential to the stationary phase during electron donor depletion. In addition to temporal transcriptomics, total protein, carbohydrate, lactate, acetate, and sulfate levels were measured. The microarray data were examined for statistically significant expression changes, hierarchical cluster analysis, and promoter element prediction and were validated by quantitative PCR. As the cells transitioned from the exponential phase to the stationary phase, a majority of the down-expressed genes were involved in translation and transcription, and this trend continued at the remaining times. There were general increases in relative expression for intracellular trafficking and secretion, ion transport, and coenzyme metabolism as the cells entered the stationary phase. As expected, the DNA replication machinery was down-expressed, and the expression of genes involved in DNA repair increased during the stationary phase. Genes involved in amino acid acquisition, carbohydrate metabolism, energy production, and cell envelope biogenesis did not exhibit uniform transcriptional responses. Interestingly, most phage-related genes were up-expressed at the onset of the stationary phase. This result suggested that nutrient depletion may affect community dynamics and DNA transfer mechanisms of sulfate-reducing bacteria via the phage cycle. The putative feoAB system (in addition to other presumptive iron metabolism genes) was significantly up-expressed, and this suggested the possible importance of Fe{sup 2+} acquisition under metal-reducing conditions. The expression of a large subset of carbohydrate-related genes was altered, and the total cellular carbohydrate levels declined during the growth phase transition. Interestingly, the D. vulgaris genome does not contain a putative rpoS gene, a common attribute

  15. Enantiomeric separation of trimebutine, lafutidine and ondansetron by HPLC using chiral stationary phase%手性固定相色谱法直接拆分曲美布汀、拉呋替丁和昂丹司琼对映异构体

    Institute of Scientific and Technical Information of China (English)

    段明郁; 陈笑艳; 钟大放

    2006-01-01

    目的:建立直接拆分3种消化系统用药曲美布汀、拉呋替丁和昂丹司琼对映体的液相色谱方法.方法:采用以万古霉素为手性固定相的Chirobiotic V2(250 mmn×4.6 mm,5 μm)色谱柱,在流速均为1.0 mL·min-1,柱温均为20℃时,分离曲美布汀对映体、拉呋替丁对映体和昂丹司琼对映体的流动相分别为:甲醇-冰醋酸-三乙胺(100:0.075:0.025)、甲醇-冰醋酸-三乙胺(100:0.025:0.075)和20 mmol·L-1醋酸铵缓冲液(pH 4.5)-甲醇(50:50).采用以α1-酸糖蛋白手性固定相的Chiral-AGP(150 mmn ×4.6 mmn,5 μm)色谱柱,分离昂丹司琼对映体的色谱条件为:20 mmol·L-1醋酸铵缓冲液(pH4.5)-乙腈(99.8:0.2)为流动相,流速为0.9 mL·min-1,柱温为15℃.采用以卵类粘蛋白手性固定相的Ultron ES-OVM(150 mm×4.6 mm,5μm)色谱柱,分离昂丹司琼对映体的色谱条件为:乙腈-水-冰醋酸(2.5:97.5:0.0025)为流动相,流速为0.5mL·min-1,柱温为20℃.结果:曲美布汀和拉呋替丁对映体在万古霉素手性固定相上能够完全分离,分离度分别为2.75和3.58;昂丹司琼对映体在万古霉素手性固定相上分离较差,分离度为0.61,但在α1-酸糖蛋白手性固定相上分离较好,分离度为1.26,在卵类粘蛋白手性固定相上完全分离,分离度为1.50.结论:万古霉素手性固定相可以用于曲美布汀和拉呋替丁对映体的手性分离,卵类粘蛋白手性固定相可以用于昂丹司琼对映体的手性分离.

  16. Polystyrene-divinylbenzene-glycidyl methacrylate stationary phase grafted with poly (amidoamine) dendrimers for ion chromatography.

    Science.gov (United States)

    Guo, Dandan; Lou, Chaoyan; Zhang, Peimin; Zhang, Jiajie; Wang, Nani; Wu, Shuchao; Zhu, Yan

    2016-07-22

    In this work, a novel ion exchange stationary phase based on different generations of poly (amidoamine) dendrimers (PAMAM) was developed for the determination of inorganic anions and carbohydrates. Synthesis of the PAMAM was carried out with the polymerization reaction of ethylenediamine and methyl acrylate. The synthesized PAMAM was then grafted to the polystyrene-divinylbenzene-glycidyl methacrylate (PS-GMA) to form PAMAM-based beads. These beads were finally modified with 1,4-butanediol diglycidyl ether (BDDE) to generate the anion exchanger, which were characterized by scanning electron microscopy (SEM), brunauer-emmett-teller (BET), fourier transform infrared spectroscopy (FTIR), and elemental analysis. Elemental analysis, breakthrough curves and capacity factors showed that more epoxy groups and higher PAMAM generations in stationary phase could result in higher anion exchange capacity. The efficiency, durability and stability of the proposed anion exchanger were investigated by using six inorganic anions (fluoride, chloride, nitrite, bromide, nitrate and sulfate) and four carbohydrates (trehalose, glucose, maltotriose and galacturonic acid) as analytes, respectively. The reliability of the proposed ion chromatographic stationary phase was demonstrated by determining the content of galacturonic acid in polysaccharides from Poria cocos and Atractylodes macrocephala. The relative standard deviations of retention time, peak height, and peak area for galacturonic acid were 0.39%, 1.22%, and 2.02%, respectively. The spiked recoveries were in the range of 88.29%-100.51% for plant polysaccharides. Due to the good structural homogeneity, intense internal porosity, biological compatibility and high density of active groups in PAMAM, this grafted stationary phase showed good ion-exchange characteristics, especially in biological charged molecules.

  17. The stationary phase point method for transitional scattering: diffractive radio scintillation for pulsar

    CERN Document Server

    Zhang, C M

    2007-01-01

    The stationary phase point (SPP) method in one-dimensional case is introduced to treat the diffractive scintillation. From weak scattering, where the SPP number N=1, to strong scattering (N$\\gg$1), via transitional scattering regime (N$\\sim$2,3), we find that the modulation index of intensity experiences the monotonically increasing from 0 to 1 with the scattering strength, characterized by the ratio of Fresnel scale $\\rf$ to diffractive scale $\\rdiff$.

  18. The Chirality Of Life: From Phase Transitions To Astrobiology

    CERN Document Server

    Gleiser, Marcelo

    2008-01-01

    The search for life elsewhere in the universe is a pivotal question in modern science. However, to address whether life is common in the universe we must first understand the likelihood of abiogenesis by studying the origin of life on Earth. A key missing piece is the origin of biomolecular homochirality: permeating almost every life-form on Earth is the presence of exclusively levorotary amino acids and dextrorotary sugars. In this work we discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events in a mechanism referred to as punctuated chirality. Applying these arguments to other potentially life-bearing platforms has significant implications for the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic on average.

  19. Recent progress in understanding deconfinement and chiral restoration phase transitions

    CERN Document Server

    Shuryak, Edward

    2016-01-01

    Paradigme shift in gauge topology, from instantons to their constituents -- instanton-dyons -- has recently lead to very significant advances. Like instantons, they have fermionic zero modes, and their collectivization at sufficiently high density explains the chiral symmetry breaking. Unlike instantons, these objects have electric and magnetic charges. Their back reaction on the mean value of the Polyakov line (holonomy) allows to explain the deconfinement transition. The talk summarizes recent works on the dyon ensemble, done in the mean field approximation (MFA), and also by direct numerical statistical simulation. Introduction of non-trivial quark periodicity conditions leads to drastic changes in both deconfinement and chiral transitions. In particulaly, in the so called Z(N_c)-QCD model the former gets much stronger, while the latter does not seem to occur at all.

  20. Ionic liquids as stationary phases in gas chromatography: determination of chlorobenzenes in soils.

    Science.gov (United States)

    González Paredes, Rosa María; García Pinto, Carmelo; Pérez Pavón, José Luis; Moreno Cordero, Bernardo

    2014-06-01

    The present research focuses on the evaluation of different ionic liquid (IL) stationary phases in gas chromatography. The different IL columns were evaluated in terms of peak resolution (Rs) and peak symmetry for the separation of the chlorobenzenes. The determination of chlorobenzenes in soil samples by means of the optimal IL stationary phase (SLB-IL82) is proposed as an application. Soil pretreatment was based on a simplified quick, easy, cheap, effective, rugged, and safe extraction procedure and a large injection volume via a programed temperature vaporizer working in solvent vent mode. The retention time of the chlorobenzenes increased as the polarity of the IL column decreased. SLB-IL82 is the stationary phase that provides the best values as regards Rs and asymmetry factor. Soil sample blanks were spiked with the analytes before subjecting the sample to the extraction process. The existence of a matrix effect was checked and the analytical characteristics of the method were determined in a fortified garden soil sample. The method provided good linearity, good repeatability and reproducibility values, and the LODs were in the 0.1-4.7 μg/kg range. Two fortified soil samples were applied to validate the proposed methodology.

  1. Enhanced dipicolinic acid production during the stationary phase in Bacillus subtilis by blocking acetoin synthesis.

    Science.gov (United States)

    Toya, Yoshihiro; Hirasawa, Takashi; Ishikawa, Shu; Chumsakul, Onuma; Morimoto, Takuya; Liu, Shenghao; Masuda, Kenta; Kageyama, Yasushi; Ozaki, Katsuya; Ogasawara, Naotake; Shimizu, Hiroshi

    2015-01-01

    Bacterial bio-production during the stationary phase is expected to lead to a high target yield because the cells do not consume the substrate for growth. Bacillus subtilis is widely used for bio-production, but little is known about the metabolism during the stationary phase. In this study, we focused on the dipicolinic acid (DPA) production by B. subtilis and investigated the metabolism. We found that DPA production competes with acetoin synthesis and that acetoin synthesis genes (alsSD) deletion increases DPA productivity by 1.4-fold. The mutant showed interesting features where the glucose uptake was inhibited, whereas the cell density increased by approximately 50%, resulting in similar volumetric glucose consumption to that of the parental strain. The metabolic profiles revealed accumulation of pyruvate, acetyl-CoA, and the TCA cycle intermediates in the alsSD mutant. Our results indicate that alsSD-deleted B. subtilis has potential as an effective host for stationary-phase production of compounds synthesized from these intermediates.

  2. Spontaneous magnetization of quark matter in the inhomogeneous chiral phase

    CERN Document Server

    Yoshiike, Ryo; Tatsumi, Tositaka

    2015-01-01

    Considering the density wave of scalar and pseudoscalar condensates, we study the response of quark matter to a weak external magnetic field. In an external magnetic field, the energy spectrum of the lowest Landau level becomes asymmetric about zero, which is closely related to chiral anomaly, and gives rise to the spontaneous magnetization. This mechanism may be one of candidates for the origin of the strong magnetic field in pulsars and/or magnetars.

  3. Spontaneous magnetization of quark matter in the inhomogeneous chiral phase

    Directory of Open Access Journals (Sweden)

    R. Yoshiike

    2015-12-01

    Full Text Available Considering the density wave of scalar and pseudoscalar condensates, we study the response of quark matter to a weak external magnetic field. In an external magnetic field, the energy spectrum of the lowest Landau level becomes asymmetric about zero, which is closely related to chiral anomaly, and gives rise to the spontaneous magnetization. This mechanism may be one of candidates for the origin of the strong magnetic field in pulsars and/or magnetars.

  4. Berry Phase of Light under Bragg Reflection by Chiral Liquid-Crystal Media

    Science.gov (United States)

    Barboza, Raouf; Bortolozzo, Umberto; Clerc, Marcel G.; Residori, Stefania

    2016-07-01

    A Berry phase is revealed for circularly polarized light when it is Bragg reflected by a chiral liquid-crystal medium of the same handedness. By using a chiral nematic layer we demonstrate that if the input plane of the layer is rotated with respect to a fixed reference frame, a geometric phase effect occurs for the circularly polarized light reflected by the periodic helical structure of the medium. Theory and numerical simulations are supported by an experimental observation, disclosing novel applications in the field of optical manipulation and fundamental optical phenomena.

  5. Berry phase of light Bragg-reflected by chiral liquid crystal media

    CERN Document Server

    Barboza, Raouf; Residori, Stefania; Clerc, Marcel G

    2016-01-01

    Berry phase is revealed for circularly polarized light when it is Bragg-reflected by a chiral liquid crystal medium of the same handedness. By using a chiral nematic layer we demonstrate that if the input plane of the layer is rotated with respect to a fixed reference frame, then, a geometric phase effect occurs for the circularly polarized light reflected by the periodic helical structure of the medium. Theory and numerical simulations are supported by an experimental observation, disclosing novel applications in the field of optical manipulation and fundamental optical phenomena.

  6. T-\\mu phase diagram of the chiral quark model from a large flavor number expansion

    CERN Document Server

    Jakovác, A; Szép, Z; Szépfalusy, P; Szep, Zs.

    2004-01-01

    The chiral phase boundary of strong matter is determined in the T-\\mu plane from the chiral quark model, applying a non-perturbatively renormalised treatment, involving chains of pion-bubbles and 1-loop fermion contributions. In the absence of explicit symmetry breaking the second order portion of the phase boundary and the location of the tricritical point (TCP) are determined analytically. Sensitivity of the results to the renormalisation scale is carefully investigated. The softening of the sigma-pole near the second order transitions is confirmed.

  7. The Development and Characterization of Protein-Based Stationary Phases for Studying Drug-Protein and Protein-Protein Interactions

    OpenAIRE

    Sanghvi, Mitesh; Moaddel, Ruin; Wainer, Irving W.

    2011-01-01

    Protein-based liquid chromatography stationary phases are used in bioaffinity chromatography for studying drug-protein interactions, the determination of binding affinities, competitive and allosteric interactions, as well as for studying protein-protein interactions. This review addresses the development and characterization of protein-based stationary phase, and the application of these phases using frontal and zonal chromatography techniques. The approach will be illustrated using immobili...

  8. Surface Confined Ionic Liquid-A New Stationary Phase for the Separation of Ephedrines in High-performance Liquid Chromatography

    Institute of Scientific and Technical Information of China (English)

    Shu Juan LIU; Feng ZHOU; Xiao Hua XIAO; Liang ZHAO; Xia LIU; Sheng Xiang JIANG

    2004-01-01

    In this article, a new and effective stationary phase based on ionic liquid modified silica is first reported and used for the separation of ephedrines in high-performance liquid chromatography (HPLC). The separation results indicate the high efficiency and reproducibility of the stationary phase. The electrostatic interaction, ion-exchange interaction between the solutes and the stationary phase are considered to attribute the effective separation. Moreover, the free silanols on the surface of the silica are effectively masked by the immobilized ionic liquid, a result of which is to decrease the non-specific absorption.

  9. Synthesis and characterization of a multimode stationary phase: Congo red derivatized silica in nano-flow HPLC.

    Science.gov (United States)

    Zhang, Yi; Zhang, Yan; Wang, Guan; Chen, Wujuan; He, Pingang; Wang, Qingjiang

    2016-02-01

    A novel Congo red (CR) derivatized silica stationary phase was prepared and packed into a fused silica capillary tube for nano-flow HPLC. A variety of analytes including poly-aromatic hydrocarbons, parabens, acids, sulfonamides, bases, and nucleosides were successfully separated using the CR. In comparison with commercial ODS columns, this new stationary phase has a different separation mechanism (hydrophobically-assisted ion-exchange), which was evident in the separation of benzoic acid derivatives and sulfonamides. The successful application of CR-bonded silica stationary phase in the HILIC and PALC modes demonstrates the effectiveness of this potential chromatographic material in nano flow HPLC.

  10. Theory for transitions between log and stationary phases: universal laws for lag time

    CERN Document Server

    Himeoka, Yusuke

    2016-01-01

    Quantitative characterization of bacterial growth has gathered substantial attention since Monod's pioneering study. Theoretical and experimental work has uncovered several laws for describing the log growth phase, in which the number of cells grows exponentially. However, microorganism growth also exhibits lag, stationary, and death phases under starvation conditions, in which cell growth is highly suppressed, while quantitative laws or theories for such phases are underdeveloped. In fact, models commonly adopted for the log phase that consist of autocatalytic chemical components, including ribosomes, can only show exponential growth or decay in a population, and phases that halt growth are not realized. Here, we propose a simple, coarse-grained cell model that includes inhibitor molecule species in addition to the autocatalytic active protein. The inhibitor forms a complex with active proteins to suppress the catalytic process. Depending on the nutrient condition, the model exhibits the typical transition a...

  11. Development of N-ferrocenyl(benzoyl)amino-acid esters stationary phase for high performance liquid chromatography.

    Science.gov (United States)

    Zhou, Xiaohua; Li, Xiaole; Cao, Aijuan; Lijun, Qiao; Yu, Ajuan; Zhang, Shusheng; Wu, Yangjie

    2015-11-01

    A new stationary phase for high-performance liquid chromatography was prepared by covalently bonding N-ferrocenyl(benzoyl)amino-acid esters (L(1)) onto silica gel using 3-aminopropyltriethoxysilane as coupling reagent. The structure of new material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. The chromatographic behavior of the phase was illustrated in reversed-phase (RP) and normal-phase (NP) modes using polycyclic aromatic hydrocarbons (PAHs), aromatics positional isomers, amines, 5-nitroimidazoles, organophosphorus pesticides and phenols as probes. Multiple mechanisms including hydrophobic, hydrogen bonding, π-π, dipole-dipole, charge-transfer and acid-base equilibrium interactions are involved. Thus, multi-interaction mechanisms and mixed-mode separation of the new phase can very likely guarantee its excellent chromatographic performance for the analysis of complex samples. The L(1) AminoSil column was successfully employed for the analysis of organophosphorus pesticides in vegetable.

  12. Diastereo- and enantioseparation of a N(α)-Boc amino acid with a zwitterionic quinine-based stationary phase: focus on the stereorecognition mechanism.

    Science.gov (United States)

    Ianni, Federica; Carotti, Andrea; Marinozzi, Maura; Marcelli, Gloria; Di Michele, Alessandro; Sardella, Roccaldo; Lindner, Wolfgang; Natalini, Benedetto

    2015-07-23

    A chiral chromatography method enabling the simultaneous diastereo- and enantioseparation of N(α)-Boc-N(4)-(hydroorotyl)-4-aminophenylalanine [Boc-Aph(Hor)-OH, 1] was optimized with a quinine-based zwitterionic stationary phase. The polar-ionic eluent system consisting of ACN:MeOH:water-49.7:49.7:0.6 (v/v/v) with formic acid (4.0mM) and diethylamine (2.5mM), allowed the successful separation of the four acid stereoisomers: αd,d-/d,l-1=1.08; αd,l-/l,d-1=1.08; αl,d-/l,l-1=1.40. According to the in-house developed synthetic procedure and the recorded electronic circular dichroism spectra, the following stereoisomeric elution order was readily established in the optimal chromatographic conditions: d,d-1chiral stationary phase and eluent components in the overall stereorecognition mechanism.

  13. Chiral phase transition of QCD with N f = 2 + 1 flavors from holography

    Science.gov (United States)

    Li, Danning; Huang, Mei

    2017-02-01

    Chiral phase transition for three-flavor N f = 2 + 1 QCD with m u = m d ≠ m s is investigated in a modified soft-wall holographic QCD model. Solving temperature dependent chiral condensates from equations of motion of the modified soft-wall model, we extract the quark mass dependence of the order of chiral phase transition in the case of N f = 2 + 1, and the result is in agreement with the "Columbia Plot", which is summarized from lattice simulations and other non-perturbative methods. First order phase transition is observed around the three flavor chiral limit m u/ d = 0, m s = 0, while at sufficient large quark masses it turns to be a crossover phase transition. The first order and crossover regions are separated by a second order phase transition line. The second order line is divided into two parts by the m u/ d = m s line, and the m s dependence of the transition temperature in these two parts are totally contrast, which might indicate that the two parts are governed by different universality classes.

  14. Polyakov SU(3) extended linear $\\sigma$-model: Sixteen mesonic states in chiral phase-structure

    CERN Document Server

    Tawfik, Abdel Nasser

    2014-01-01

    The derivative of the grand potential in mean field approximation, non-strange and strange condensates and deconfinement phase-transition in thermal and dense hadronic medium are verified in extended SU(3) linear sigma-model (eLSM). In determining the chiral phase-transition, the chiral condensates sigma_x and sigma_y are analysed. The chiral mesonic phase-structures in temperature- and density-dependence are taken as free parameters to be fitted. These parameters are classified corresponding to scalar meson nonets; (pseudo)-scalar and (axial)-vector. For deconfinement phase-transition, effective Polyakov loop-potentials phi and phi^* are utilized. We investigated the in-medium effects on the masses of sixteen mesonic states states. The results are presented for two different forms for the effective Polyakov loop-potential and compared with other models with and without anomalous terms. The Polyakov loop potential in LSM has considerable effects on the chiral phase-transition in meson masses so that the resto...

  15. Band-phase-randomized Surrogates to assess nonlinearity in non-stationary time series

    CERN Document Server

    Guarin, Diego; Orozco, Alvaro

    2011-01-01

    Testing for nonlinearity is one of the most important preprocessing steps in nonlinear time series analysis. Typically, this is done by means of the linear surrogate data methods. But it is a known fact that the validity of the results heavily depends on the stationarity of the time series. Since most physiological signals are non-stationary, it is easy to falsely detect nonlinearity using the linear surrogate data methods. In this document, we propose a methodology to extend the procedure for generating constrained surrogate time series in order to assess nonlinearity in non-stationary data. The method is based on the band-phase-randomized surrogates, which consists (contrary to the linear surrogate data methods) in randomizing only a portion of the Fourier phases in the high frequency band. Analysis of simulated time series showed that in comparison to the linear surrogate data method, our method is able to discriminate between linear stationarity, linear non-stationary and nonlinear time series. When apply...

  16. Thermodynamic studies of induced antiferroelectric phases in chiral and racemic systems

    Science.gov (United States)

    Filipowicz, M.; Kula, P.; Czuprynski, Krzysztof

    2004-09-01

    Bi- and multicomponent mixtures consisted of two groups of synclinic chiral esters: first one with a partially fluorinated terminal chain and the second one with hydrogenated terminal chain have been used for investigations. For some systems the induction of the anticlinic smectic CA* phase was observed. Enthalpies of the phase transitions for the systems with induced smectic CA phase upon compositions and specific heat were measured by DSC method.

  17. Chiral gas chromatography for the determination of 1,2-O-isopropylidene-sn-glycerol stereoisomers

    NARCIS (Netherlands)

    Dröge, M.J; Bos, R.; Woerdenbag, H.J.; Quax, Wim; Droge, MJ

    2003-01-01

    A stereospecific gas chromatography (GC) method using a (6-O-tButyldimethylsilyl-2,3-di-O-methyl)-beta-cyclodextrin as the chiral stationary phase has been developed and validated for the determination of the enantiomers of 1,2-O-isopropylidene-sn-glycerol (IPG), an important chiral synthon, in kine

  18. Preparation and Characterization of a New Quercetin-bonded Stationary Phase for High Performance Liquid Chromatography

    Institute of Scientific and Technical Information of China (English)

    李来生; 方奕珊; 陈红; 张杨

    2012-01-01

    A quercetin-bonded silica gel stationary phase (QUSP) containing natural flavonoid ligand was first prepared via γ-glycidoxypropyltrimethoxysilane (KH-560) as a coupling reagent for high-performance liquid chromatography. Its chemical structure was characterized by Fourier infrared spectroscopy, elemental analysis, thermal thermogravimetry and 13C cross polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR). The chromatographic property of QUSP was systematically evaluated by using neutral, basic and acidic aromatic com- pounds as probes. In order to clarify its retention mechanism, a comparative study of QUSP with conventional oc- tadecylsilyl-bonded stationary phase (ODS) was also carried out under the same conditions. The results showed that the new quercetin-bonded phase exhibited an excellent reversed-phase chromatographic property with relatively weak hydrophobicity. However, it has an advantage over ODS in the fast separation of polar aromatic compounds because the quercetin ligand could provide various sites besides hydrophobicity, such as hydrogen bonding, dipole-dipole, n-n staking and charge transfer interactions. QUSP was performed in the baseline separations of ion- ized polar basic or acidic compounds, including pyridines, anilines, pyrimidines, purines and phenols with symmet- ric peak shape in common mobile phases without buffer salt within relatively short time. The natural ligands from herbs are readily available and contain a variety of active sites, which facilitate the exploration of industrial chromatographic separation materials for green products.

  19. Spontaneous Magnetization of Quark Matter in Inhomogeneous Chiral Phase

    CERN Document Server

    Yoshiike, Ryo; Tatsumi, Toshitaka

    2015-01-01

    Considering the density wave of scalar and pseudoscalar condensates, we study the response of quark matter to a weak external magnetic field. In an external magnetic field, the energy spectrum of the lowest Landau level becomes asymmetric about zero, which is closely related to chiral anomaly. This spectral asymmetry gives rise to spontaneous magnetization. This mechanism may be one of candidates for the origin of the strong magnetic field in magnetars. Furthermore, using the generalized Ginzburg-Landau(gGL) expansion, we show that magnetic susceptibility exhibits a peculiar feature

  20. Resolution of DL-Pantolactone with Ethyldiamine Bridged Dimer Permethyβ-Cyclodextrin as GC Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Ethyldiamine bridged dimer permethy-β-CD and other cyclodextrins were used as GC stationary phase to resolute DL-pantolactone.It is found that this CD dimer has a good selectivity for DL-pantolactone.

  1. Time evolution of chiral phase transition at finite temperature and density in the linear sigma model

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Koide, Tomoi; Maruyama, Masahiro [Tohoku Univ., Faculty of Science, Sendai, Miyagi (Japan)

    1999-08-01

    There are various approaches to nonequilibrium system. We use the projection operator method investigated by F. Shibata and N. Hashitsume on the linear sigma model at finite temperature and density. We derive a differential equation of the time evolution for the order parameter and pion number density in chiral phase transition. (author)

  2. OPTICAL PHASE CONJUGATION RESPONSE OF PHOTOINDUCED POLYMER FILMS CONTAINING AZOBENZENE MOIETIES WITH CHIRAL GROUP

    Institute of Scientific and Technical Information of China (English)

    Ze-da Xu; Yong Zhang; Xing-he Fan; Xin-hua Wan; Qi-feng Zhou

    2002-01-01

    An optically active monomer containing azobenzene moieties with chiral group (s-2-methyl-butyl), 4-[2-(methacryloyloxy)ethyloxy]-4'-(s-2-methyl-1-butyloxycarbonyl) azobenzene (M1) was synthesized. Polymer (PM1) possessing optical phase conjugated response was obtained by homopolymerization of the optically active monomer (M1) using free radical polymerization. The polymer was very soluble in common solvents and good optical quality films could be easily fabricated by spin coating. The optical phase conjugated responses of the polymer PM1 were measured by degenerate four-wave mixing (DFWM). In comparison with polymer containing no chiral group, it was found from the preliminary measurement of photoisomeric change that optical phase conjugated response of the PM1 in the long-range order hexagonal symmetry microstructure could be easily controlled by choosing the appropriate polarization direction of the irradiating beams (514.5 nm) and the irradiating number, presumably due to the chiral group in the PM1 molecular structure. For the case of the polymer investigated here, a chiral group side chain was introduced to increase optical phase conjugated response intensity with different polarization directions of the irradiating beams, which aims originally at searching for a new photoactive material.

  3. Magnetic fluctuations and correlations in MnSi: Evidence for a chiral skyrmion spin liquid phase

    NARCIS (Netherlands)

    Pappas, C.; Lelièvre-Berna, E.; Bentley, P.; Falus, P.; Fouquet, P.; Farago, B.

    2011-01-01

    We present a comprehensive analysis of high-resolution neutron scattering data involving neutron spin echo spectroscopy and spherical polarimetry, which confirm the first-order nature of the helical transition in MnSi. The experiments reveal the existence of a totally chiral dynamic phase in a very

  4. Comparison of the mass transfer in totally porous and superficially porous stationary phases in liquid chromatography.

    Science.gov (United States)

    Kiss, Ibolya; Bacskay, Ivett; Kilár, Ferenc; Felinger, Attila

    2010-06-01

    The characterization of mass-transfer processes in a chromatographic column during a separation process is essential, since the influence of the mass-transfer kinetics on the shape of the chromatographic band profiles and on the efficiency of the separation is crucial. Several sources of mass transfer in a chromatographic bed have been identified and studied: the axial dispersion in the stream of mobile phase, the external mass-transfer resistance, intraparticle diffusion, and the kinetics of adsorption-desorption. We measured and compared the characteristics and performance of a new brand of shell particles and those of a conventional brand of totally porous silica particles. The shell stationary phase was made of 2.7-microm superficially porous particles (a 1.7-microm solid core is covered with a 0.5-microm-thick shell of porous silica). The other material consisted of totally porous particles of conventional 3.5-microm commercial silica. We measured the first and second central moments of the peaks of human insulin over a wide range of mobile phase velocities (from 0.02 to 1.3 mL/min) at 20 degrees C. The plate height equations were constructed and the axial dispersion, external mass transfer, as well as the intraparticle diffusion coefficients were calculated for the two stationary phases.

  5. Dynamic Proteome Changes of Shigella flexneri 2a During Transition from Exponential Growth to Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Shigella flexneri is an infectious pathogen that causes dysentery to human, which remains a serious threat to public health, particularly in developing countries. In this study, the global protein expression patterns of S. flexneri during transition from exponential growth to stationary phase in vitro were analyzed by using 2-D PAGE combined with MALDI-TOF MS. In a time-course experiment with five time points, the relative abundance of 49 protein spots varied significantly. In terestingly, a putative outer membrane protein YciD (OmpW) was almost not detected in the exponential growth phase but became one of the most abundant proteins in the whole stationary-phase proteome. Some proteins regulated by the global regulator FNR were also significantly induced (such as AnsB, AspA, FrdAB,and KatG) or repressed (such as AceEF, OmpX, SodA, and SucAB) during the growth phase transition. These proteins may be the key effectors of the bacterial cell cycle or play important roles in the cellular maintenance and stress responses.Our expression profile data provide valuable information for the study of bacterial physiology and form the basis for future proteomic analyses of this pathogen.

  6. Packed column supercritical fluid chromatography using stainless steel particles and water as a stationary phase.

    Science.gov (United States)

    Murakami, Jillian N; Thurbide, Kevin B

    2015-09-15

    Stainless steel (SS) particles were demonstrated as a novel useful support for a water stationary phase in packed column supercritical fluid chromatography using a CO2 mobile phase. Separations employed flame ionization detection, and the system was operated over a range of temperatures and pressures. Retention times reproduced well with RSD values of 2.6% or less. Compared to analogous separations employing a water stationary phase coated onto a SS capillary column, the packed column method provided separations that were about 10× faster, with nearly 8-fold larger analyte retention factors, while maintaining good peak shape and comparable column efficiency. Under normal operating conditions, the packed column contains about 131 ± 4 μL/m of water phase (around a 5% m/m coating), which is over 25× greater than the capillary column and also affords it a 20-fold larger sample capacity. Several applications of the packed column system are examined, and the results indicate that it is a useful alternative to the capillary column mode, particularly where analyte loads or sample matrix interference is a concern. Given its high sample capacity, this packed column method may also be useful to explore on a more preparative scale in the future.

  7. Sum of ranking differences to rank stationary phases used in packed column supercritical fluid chromatography.

    Science.gov (United States)

    West, Caroline; Khalikova, Maria A; Lesellier, Eric; Héberger, Károly

    2015-08-28

    The identification of a suitable stationary phase in supercritical fluid chromatography (SFC) is a major source of difficulty for those with little experience in this technique. Several protocols have been suggested for column classification in high-performance liquid chromatography (HPLC), gas chromatography (GC), and SFC. However, none of the proposed classification schemes received general acceptance. A fair way to compare columns was proposed with the sum of ranking differences (SRD). In this project, we used the retention data obtained for 86 test compounds with varied polarity and structure, analyzed on 71 different stationary phases encompassing the full range in polarity of commercial packed columns currently available to the SFC chromatographer, with a single set of mobile phase and operating conditions (carbon dioxide-methanol mobile phase, 25°C, 150bar outlet pressure, 3ml/min). First, a reference column was selected and the 70 remaining columns were ranked based on this reference column and the retention data obtained on the 86 analytes. As these analytes previously served for the calculation of linear solvation energy relationships (LSER) on the 71 columns, SRD ranks were compared to LSER methodology. Finally, an external comparison based on the analysis of 10 other analytes (UV filters) related the observed selectivity to SRD ranking. Comparison of elution orders of the UV filters to the SRD rankings is highly supportive of the adequacy of SRD methodology to select similar and dissimilar columns.

  8. The chiral phase transition in a random matrix model with molecular correlations

    CERN Document Server

    Wettig, T; Weidenmüller, H A; Wettig, Tilo

    1995-01-01

    The chiral phase transition of QCD is analyzed in a model combining random matrix elements of the Dirac operator with specially chosen non-random ones. The special form of the latter is motivated by the assumption that the fermionic quasi-zero modes associated with instanton and anti-instanton configurations determine the chiral properties of QCD. Our results show that the degree of correlation between these modes plays the decisive role. To reduce the value of the chiral condensate by more than a factor of 2 about 95 percent of the instantons and anti-instantons must form so-called molecules. This conclusion agrees with numerical results of the Stony Brook group.

  9. Chiral phase transition and Schwinger mechanism in a pure electric field

    CERN Document Server

    Cao, Gaoqing

    2016-01-01

    We systematically study the chiral symmetry breaking and restoration in the presence of a pure electric field in the Nambu--Jona-Lasinio (NJL) model at finite temperature and baryon chemical potential. In addition, we also study the effect of the chiral phase transition on the charged pair production due to the Schwinger mechanism. For these purposes, a general formalism for parallel electric and magnetic fields is developed at finite temperature and chemical potential for the first time. In the pure electric field limit $B\\rightarrow0$, we compute the order parameter, the transverse-to-longitudinal ratio of the Goldstone mode velocities, and the Schwinger pair production rate as functions of the electric field. The inverse catalysis effect of the electric field to chiral symmetry breaking is recovered. And the Goldstone mode is find to disperse anisotropically such that the transverse velocity is always smaller than the longitudinal one, especially at nonzero temperature and baryon chemical potential. As exp...

  10. Chiral Phase Transition in the Soft-Wall Model of AdS/QCD

    CERN Document Server

    Chelabi, Kaddour; Huang, Mei; Li, Danning; Wu, Yue-Liang

    2015-01-01

    We investigate the chiral phase transition in the soft-wall model of AdS/QCD at zero chemical potential for two-flavor and three-flavor cases, respectively. We show that there is no spontaneous chiral symmetry breaking in the original soft-wall model. After detailed analysis, we find that in order to realize chiral symmetry breaking and restoration, both profiles for the scalar potential and the dilaton field are essential. The scalar potential determines the possible solution structure of the chiral condensate, except the mass term, it takes another quartic term for the two-flavor case, and for the three-flavor case, one has to take into account an extra cubic term due to the t'Hooft determinant interaction. The profile of the dilaton field reflects the gluodynamics, which is negative at a certain ultraviolet scale and approaches positive quadratic behavior at far infrared region. With this set-up, the spontaneous chiral symmetry breaking in the vacuum and its restoration at finite temperature can be realize...

  11. Chiral-induced self-assembly sphere phase liquid crystal with fast switching time

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Ji-Liang; Ni, Shui-Bin; Ping Chen, Chao; Lu, Jian-Gang, E-mail: lujg@sjtu.edu.cn; Su, Yikai [National Engineering Lab for TFT-LCD Materials and Technologies, Department of Electronic Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Wu, Dong-Qing [College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Song, Xiao-Long; Chen, Chao-Yuan [The Jiangsu Hecheng Display Technology Co., Ltd., Nanjing 211300 (China); Shieh, Han-Ping D. [National Engineering Lab for TFT-LCD Materials and Technologies, Department of Electronic Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Department of Photonics and Display Institute, National Chiao Tung University, Hsinchu 300, Taiwan (China)

    2014-03-03

    A fluid self-assembly sphere phase (SP) of liquid crystal induced by chiral dopant is observed in a narrow temperature range between isotropic and blue phase or between isotropic and chiral nematic phase. The SP consists of three-dimensional twist spheres (3-DTSs) and disclinations among 3-DTSs. The temperature range of the SP has been broadened to more than 85 °C by stabilizing the disclinations with amorphous polymer chains. The electro-optical switching time of the polymer-stabilized SP is demonstrated in sub-millisecond with a low switching electric field of 4.4 V μm{sup −1}, which is of promising applications in displays, 3-D tunable photonic crystals, and phase modulators.

  12. Thermodynamic phases and mesonic fluctuations in a chiral nucleon-meson model

    CERN Document Server

    Drews, Matthias; Klein, Bertram; Weise, Wolfram

    2013-01-01

    Studies of the QCD phase diagram must properly include nucleonic degrees of freedom and their thermodynamics in the range of baryon chemical potentials characteristic of nuclear matter. A useful framework for incorporating relevant nuclear physics constraints in this context is a chiral nucleon-meson effective Lagrangian. In the present paper, such a chiral nucleon-meson model is extended with systematic inclusion of mesonic fluctuations using the functional renormalization group approach. The resulting description of the nuclear liquid-gas phase transition shows a remarkable agreement with three-loop calculations based on in-medium chiral effective field theory. No signs of a chiral first-order phase transition and its critical endpoint are found in the region of applicability of the model, at least up to twice the density of normal nuclear matter and at temperatures T<100 MeV. Fluctuations close to the critical point of the first-order liquid-gas transition are also examined with a detailed study of the ...

  13. Stationary phase expression of the arginine biosynthetic operon argCBH in Escherichia coli

    Directory of Open Access Journals (Sweden)

    Sun Yuan

    2006-02-01

    Full Text Available Abstract Background Arginine biosynthesis in Escherichia coli is elevated in response to nutrient limitation, stress or arginine restriction. Though control of the pathway in response to arginine limitation is largely modulated by the ArgR repressor, other factors may be involved in increased stationary phase and stress expression. Results In this study, we report that expression of the argCBH operon is induced in stationary phase cultures and is reduced in strains possessing a mutation in rpoS, which encodes an alternative sigma factor. Using strains carrying defined argR, and rpoS mutations, we evaluated the relative contributions of these two regulators to the expression of argH using operon-lacZ fusions. While ArgR was the main factor responsible for modulating expression of argCBH, RpoS was also required for full expression of this biosynthetic operon at low arginine concentrations (below 60 μM L-arginine, a level at which growth of an arginine auxotroph was limited by arginine. When the argCBH operon was fully de-repressed (arginine limited, levels of expression were only one third of those observed in ΔargR mutants, indicating that the argCBH operon is partially repressed by ArgR even in the absence of arginine. In addition, argCBH expression was 30-fold higher in ΔargR mutants relative to levels found in wild type, fully-repressed strains, and this expression was independent of RpoS. Conclusion The results of this study indicate that both derepression and positive control by RpoS are required for full control of arginine biosynthesis in stationary phase cultures of E. coli.

  14. Proteomic Analysis of Stationary Phase in the Marine Bacterium "Candidatus Pelagibacter ubique"

    Energy Technology Data Exchange (ETDEWEB)

    Sowell, S. M.; Norbeck, A. D.; Lipton, M. S.; Nicora, C. D.; Callister, S. J.; Smith, R. D.; Barofsky, D. F.; Giovannoni, S. J.

    2008-05-09

    The α-proteobacterium ‘Candidatus Pelagibacter ubique’ str. HTCC1062, and most other members of the SAR11 clade, lack genes for assimilatory sulfate reduction, making them dependent on organosulfur compounds that occur naturally in seawater. To investigate how these cells adapt to sulfur limitation, batch cultures were grown in defined media containing either limiting or non-limiting amounts of dimethylsulfoniopropionate (DMSP) as the sole sulfur source. Protein and mRNA expression were measured during exponential growth, immediately prior to stationary phase, and in late stationary phase. Two distinct responses were observed: one as DMSP became exhausted, and another as cells acclimated to a sulfur-limited environment. The first response was characterized by increased transcription and translation of all Ca. P. ubique genes downstream of previously confirmed S-adenosyl methionine (SAM) riboswitches: bhmT, mmuM, and metY. Proteins encoded by these genes were up to 33 times more abundant as DMSP became limiting. Their predicted function is to shunt all available sulfur to methionine. The secondary response, observed during sulfur-depleted stationary phase, was a 6-10 fold increase in transcription of the heme c shuttle ccmC and two small genes of unknown function (SAR11_1163 and SAR11_1164). This bacterium's strategy for coping with sulfur stress appears to be intracellular redistribution to support methionine biosynthesis, rather than increasing organosulfur import. Many of the genes and SAM riboswitches involved in this response are located in a hypervariable genome region (HVR). One of these HVR genes, ordL, is located downstream of a conserved motif that evidence suggests is a novel riboswitch.

  15. Trigonal tricationic ionic liquids: a generation of gas chromatographic stationary phases.

    Science.gov (United States)

    Payagala, Tharanga; Zhang, Ying; Wanigasekara, Eranda; Huang, Ke; Breitbach, Zachary S; Sharma, Pritesh S; Sidisky, Leonard M; Armstrong, Daniel W

    2009-01-01

    Trigonal tricationic ionic liquids (ILs) are a new class of ILs that appear to be unique when used as gas chromatographic stationary phases. They consist of four core structures; (1) A = mesitylene core, (2) B = benzene core, (3) C = triethylamine core, and (4) D = tri(2-hexanamido)ethylamine core; to which three identical imidazolium or phosphonium cationic moieties were attached. These were coated on fused silica capillaries, and their gas chromatographic properties were evaluated. They were characterized using a linear solvation parameter model and a number of test mixtures. On the basis of the literature, it is known that both monocationic and dicationic ILs possess almost identical polarities, solvation characteristics, and chromatographic selectivities. However, some of the trigonal tricationic ILs were quite different. The different solvation parameters and higher apparent polarities appear to generate from the more rigid trigonal geometry of these ILs, as well as their ability to retain the positive charges in relatively close proximity to one another in some cases. Their unique selectivities, retention behaviors, and separation efficiencies were demonstrated using the Grob mixture, a flavor and fragrance test mixture, alcohols/alkanes test, and FAME isomer separations. Two ILs C1 (methylimidazolium substitution) and C4 (2-hydroxyethylimidazolium substitution) had higher apparent polarities than any know IL (mono, di, and tricationic ILs) or commercial stationary phases. The tri(2-hexanamido)ethylamine core IL series proved to be very interesting in that it not only showed the highest separation efficiency for all test mixtures, but it also is the first IL stationary phase (containing NTf(2)(-) anions) that eliminates peak tailing for alcohols and other H-bonding analytes. The thermal stabilities were investigated using three methods: thermogravimetric analysis (TGA) method, temperature programmed gas chromatographic method (TPGC), and isothermal gas

  16. Continuous wavelet transform for non-stationary vibration detection with phase-OTDR.

    Science.gov (United States)

    Qin, Zengguang; Chen, Liang; Bao, Xiaoyi

    2012-08-27

    We propose the continuous wavelet transform for non-stationary vibration measurement by distributed vibration sensor based on phase optical time-domain reflectometry (OTDR). The continuous wavelet transform approach can give simultaneously the frequency and time information of the vibration event. Frequency evolution is obtained by the wavelet ridge detection method from the scalogram of the continuous wavelet transform. In addition, a novel signal processing algorithm based on the global wavelet spectrum is used to determine the location of vibration. Distributed vibration measurements of 500 Hz and 500 Hz to 1 kHz sweep events over 20 cm fiber length are demonstrated using a single mode fiber.

  17. Characterization of hexacationic imidazolium ionic liquids as effective and highly stable gas chromatography stationary phases.

    Science.gov (United States)

    González-Álvarez, Jaime; Blanco-Gomis, Domingo; Arias-Abrodo, Pilar; Díaz-Llorente, Daniel; Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gutiérrez-Álvarez, María D

    2012-01-01

    Polycationic ionic liquids (ILs) are an attractive class of ILs with great potential applicability as gas chromatography stationary phases. A family of hexacationic imidazolium ILs derived from the cycloalkanol family was chemically first prepared in a straightforward manner and then applied for analytical separation purposes. Four tuneable engineering vectors, namely cation ring size structure, anion nature, spatial disposition of cycloalkanol substituents and O-substitution, were considered as experimental parameters for the design of the desired ionic liquids. A total number of five new phases based on a common benzene core respectively exhibited column efficiencies around to 2500 plates/m, broad operating temperature ranges and also, even more importantly, good thermal stabilities (bleeding temperature between 260 and 365°C), finding variations in the selectivity and analytes elution orders depending on the IL structures. Their solvation characteristics were evaluated using the Abraham solvation parameter model, establishing clear correlations between their cation structure and retention capability with respect to certain analytes. The study of relationships between the ILs structure and solvation parameters gives us an idea of the IL stationary phase to be used for specific separations.

  18. Methylation of yeast ribosomal protein S2 is elevated during stationary phase growth conditions.

    Science.gov (United States)

    Ladror, Daniel T; Frey, Brian L; Scalf, Mark; Levenstein, Mark E; Artymiuk, Jacklyn M; Smith, Lloyd M

    2014-03-14

    Ribosomes, as the center of protein translation in the cell, require careful regulation via multiple pathways. While regulation of ribosomal synthesis and function has been widely studied on the transcriptional and translational "levels," the biological roles of ribosomal post-translational modifications (PTMs) are largely not understood. Here, we explore this matter by using quantitative mass spectrometry to compare the prevalence of ribosomal methylation and acetylation for yeast in the log phase and the stationary phase of growth. We find that of the 27 modified peptides identified, two peptides experience statistically significant changes in abundance: a 1.9-fold decrease in methylation for k(Me)VSGFKDEVLETV of ribosomal protein S1B (RPS1B), and a 10-fold increase in dimethylation for r(DiMe)GGFGGR of ribosomal protein S2 (RPS2). While the biological role of RPS1B methylation has largely been unexplored, RPS2 methylation is a modification known to have a role in processing and export of ribosomal RNA. This suggests that yeast in the stationary phase increase methylation of RPS2 in order to regulate ribosomal synthesis. These results demonstrate the utility of mass spectrometry for quantifying dynamic changes in ribosomal PTMs.

  19. Growth potential of exponential- and stationary-phase Salmonella Typhimurium during sausage fermentation

    DEFF Research Database (Denmark)

    Birk, Tina; Henriksen, Sidsel; Müller, K.;

    2016-01-01

    Raw meat for sausage production can be contaminated with Salmonella. For technical reasons, meat is often frozen prior to mincing but it is unknown how growth of Salmonella in meat prior to freezing affects its growth potential during sausage fermentation. We investigated survival of exponential......- and stationary-phase Salmonella Typhimurium (DT12 and DTU292) during freezing at − 18 °C and their subsequent growth potential during 72 h sausage fermentation at 25 °C. After 0, 7 and > 35 d of frozen storage, sausage batters were prepared with NaCl (3%) and NaNO2 (0, 100 ppm) and fermented with and without...... starter culture. With no starter culture, both strains grew in both growth phases. In general, a functional starter culture abolished S. Typhimurium growth independent of growth phase and we concluded that ensuring correct fermentation is important for sausage safety. However, despite efficient...

  20. Transcriptional Characterization of Salmonella TAl00 in Growth and Stationary Phase: Mutagenesis of MX in Both Types of Cells

    Science.gov (United States)

    The Salmonella (Ames) mutagenicity assay can be performed using cells that are in different growth phases. Thus, the plate-incorporation assay involves plating stationary-phase cells with the mutagen, after which the cells undergo a brief lag phase and, consequently, are exposed ...

  1. Phase diagram of 4D field theories with chiral anomaly from holography

    CERN Document Server

    Ammon, Martin; Macedo, Rodrigo P

    2016-01-01

    Within gauge/gravity duality, we study the class of four dimensional CFTs with chiral anomaly described by Einstein-Maxwell-Chern-Simons theory in five dimensions. In particular we determine the phase diagram at finite temperature, chemical potential and magnetic field. At high temperatures the solution is given by an electrically and magnetically charged AdS Reissner-Nordstroem black brane. For sufficiently large Chern-Simons coupling and at sufficiently low temperatures and small magnetic fields, we find a new phase with helical order, breaking translational invariance spontaneously. For the Chern-Simons couplings studied, the phase transition is second order with mean field exponents. Since the entropy density vanishes in the limit of zero temperature we are confident that this is the true ground state which is the holographic version of a chiral magnetic spiral.

  2. Generalized Ginzburg–Landau approach to inhomogeneous phases in nonlocal chiral quark models

    Energy Technology Data Exchange (ETDEWEB)

    Carlomagno, J.P. [IFLP, CONICET – Dpto. de Física, FCE, Universidad Nacional de La Plata, C.C. 67, 1900 La Plata (Argentina); CONICET, Rivadavia 1917, 1033 Buenos Aires (Argentina); Gómez Dumm, D., E-mail: dumm@fisica.unlp.edu.ar [IFLP, CONICET – Dpto. de Física, FCE, Universidad Nacional de La Plata, C.C. 67, 1900 La Plata (Argentina); CONICET, Rivadavia 1917, 1033 Buenos Aires (Argentina); Scoccola, N.N. [CONICET, Rivadavia 1917, 1033 Buenos Aires (Argentina); Physics Department, Comisión Nacional de Energía Atómica, Av. Libertador 8250, 1429 Buenos Aires (Argentina); Universidad Favaloro, Solís 453, 1078 Buenos Aires (Argentina)

    2015-05-18

    We analyze the presence of inhomogeneous phases in the QCD phase diagram within the framework of nonlocal chiral quark models. We concentrate in particular in the positions of the tricritical (TCP) and Lifshitz (LP) points, which are studied in a general context using a generalized Ginzburg–Landau approach. We find that for all the phenomenologically acceptable model parametrizations considered the TCP is located at a higher temperature and a lower chemical potential in comparison with the LP. Consequently, these models seem to favor a scenario in which the onset of the first order transition between homogeneous phases is not covered by an inhomogeneous, energetically favored phase.

  3. Battle of the Bacteria: Characterizing the Evolutionary Advantage of Stationary Phase Growth

    Directory of Open Access Journals (Sweden)

    Karin E. Kram

    2016-05-01

    Full Text Available Providing students with authentic research opportunities has been shown to enhance learning and increase retention in STEM majors. Accordingly, we have developed a novel microbiology lab module, which focuses on the molecular mechanisms of evolution in E. coli, by examining the growth advantage in stationary phase (GASP phenotype. The GASP phenotype is demonstrated by growing cells into long-term stationary phase (LTSP and then competing them against un-aged cells in a fresh culture. This module includes learning goals related to strengthening practical laboratory skills and improving student understanding of evolution. In addition, the students generate novel data regarding the effects of different environmental stresses on GASP and the relationship between evolution, genotypic change, mutation frequency, and cell stress. Pairs of students are provided with the experimental background, select a specific aspect of the growth medium to modify, and generate a hypothesis regarding how this alteration will impact the GASP phenotype. From this module, we have demonstrated that students are able to achieve the established learning goals and have produced data that has furthered our understanding of the GASP phenotype.

  4. Isolation and molecular characterization of a stationary phase promoter useful for gene expression in Gordonia.

    Science.gov (United States)

    Singh, Pooja; Chachan, Sahil; Singhi, Divya; Srivastava, Preeti

    2016-10-10

    Gordonia are gram-positive bacteria belonging to Actinomycetes family with a wide variety of industrial and environmental applications. The genetic toolbox, however, is limited for manipulation of these organisms. In the present study, a new promoter has been isolated from Gordonia sp. IITR 100 and characterized in detail. The promoter was found to be functional in Escherichia coli. The minimal promoter was identified in a 166bp fragment by deletion mapping. The putative -35 and -10 hexamer showed four and five nucleotide matches respectively with the E. coli consensus sequence. Three direct repeats and an imperfect inverted repeat upstream to -35 were found. The isolated promoter was found to be six times stronger than the Pkan promoter observed by cloning lacZ downstream to each of them in a plasmid in E. coli. The β-galactosidase activity was maximum at stationary phase and found to be ~800MU for Gordonia sp. IITR 100 and E. coli. This is the first report of a stationary phase promoter isolated and characterized from Gordonia.

  5. Utilization of a diol-stationary phase column in ion chromatographic separation of inorganic anions.

    Science.gov (United States)

    Arai, Kaori; Mori, Masanobu; Kozaki, Daisuke; Nakatani, Nobutake; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2012-12-28

    We describe the ion chromatographic separation of inorganic anions using a diol-stationary phase column (-CH(OH)CH(2)OH; diol-column) without charged functional groups. Anions were separated using acidic eluent as in typical anion-exchange chromatography. The retention volumes of anions on the diol-column increased with increasing H(+) concentration in the eluent. The anion-exchange capacities of diol-columns in the acidic eluent (pH 2.8) were larger than that of zwitterionic stationary phase column but smaller than that of an anion-exchange column. The separation of anions using the diol-column was strongly affected by the interaction of H(+) ions with the diol-functional groups and by the types of the eluents. In particular, the selection of the eluent was very important for controlling the retention time and resolution. Good separation was obtained using a diol-column (HILIC-10) with 5 mM phthalic acid as eluent. The limits of detection at a signal-to-noise ratio of 3 ranged from 1.2 to 2.7 μM with relative standard deviations (RSD, n=5) of 0.04-0.07% for the retention time and 0.4-2.0% for the peak areas. This method was successfully applied to the determination of H(2)PO(4)(-), Cl(-), and NO(3)(-) in a liquid fertilizer sample.

  6. Preparation of Medium Cation Exchange Stationary Phase of Polymeric Matrix and Their Chromatographic Properties

    Institute of Scientific and Technical Information of China (English)

    CHEN,Gang; GONG,Bo-Lin; BAI,Quan; GENG,Xin-Du

    2007-01-01

    Based on the monodisperse poly(glycidyl methacrylate-co-ethylenedimethacrylate) beads (PGMA/EDMA) with macropore as a medium, a new hydrophilic medium cation exchange (MCX) stationary phase for HPLC was synthesized by a new chemically modified method. The stationary phase was evaluated with the property of ion exchange, separability, reproducibility, hydrophilicity, effect of salt concentration, salt types, column loading and pH on the separation and retention of proteins in detail. It was found that it follows ion exchange chromatographic (IEC)retention mechanism. The measured bioactivity recovery for lysozyme was (96±5)%. The dynamic protein loading capacity of the synthesized MCX packings was 21.8 mg/g. Five proteins were almost completely separated within 6.0 min at a flow rate of 4 mL/min using the synthesized MCX resin. The MCX resin was also used for the rapid separation and purification of lysozyme from egg white with only one step. The purity and specific bioactivity of the purified lysozyme was found more than 95% and 70345 U/mg, respectively.

  7. Principle of stationary phase for propagating wave packets in the unidimensional scattering problem

    Energy Technology Data Exchange (ETDEWEB)

    Bernardini, A.E. [Universidade Federal de Sao Carlos, Departamento de Fisica, PO Box 676, Sao Carlos, SP (Brazil)

    2008-08-15

    We point out some incompatibilities which appear when one applies the stationary phase method for deriving phase times to obtain the spatial localization of wave packets scattered by a unidimensional potential barrier. We concentrate on the above barrier diffusion problem where the wave packet collision implies the possibility of multiple reflected and transmitted wave packets, which, depending on the boundary conditions, can overlap or stand in relative separation in space. We demonstrate that the indiscriminate use of the method for such a particular configuration leads to paradoxical results for which the correct interpretation, confirmed by analytical/numerical calculations, imposes the necessity of the appearance of multiple peaks as a consequence of multiple reflections by the barrier steps. (orig.)

  8. Adsorption of the Enantiomers of Tryptophan on Stationary Phase Bonded with Bovine Serum Albumin

    Institute of Scientific and Technical Information of China (English)

    ZHANG Fengbao; CHENG Ming; LI Shuang; LIU Liang; ZHANG Guoliang

    2006-01-01

    Frontal analysis is frequently applied to measuring single or multi-component adsorption isotherms. In this work, the competitive adsorption isotherm data of two enantiomers of tryptophan were obtained by competitive frontal analysis. The stationary phase in the column was silica-immobilized bovine serum albumin(BSA)by the derivative method, and the mobile phase was a phosphate buffer. These isotherm data were fitted by the competitive Bilangmuir model. This model can account for the behavior of both tryptophan enantiomers and these profiles were found to fit the experimental band profiles(square error is 0.999 6). The parameters obtained were used in numericai calculations to predict the band profiles of the racemic mixtures of tryptophan. The equilibriumdispersive model provides satisfactory prediction, with minor differences between the calculated and the experimental profiles.

  9. The phase delay and its complex time: From stationary states up to wave packets

    Energy Technology Data Exchange (ETDEWEB)

    Grossel, Ph., E-mail: philippe.grossel@univ-reims.fr

    2013-03-15

    Complex time is often invoked about tunneling effect where the classical phase delay is completed with a crucial filter effect. Usually the complex times are obtained by considering the flux-flux correlation function, but this can be obtained by a very simple approach using the search of the maximum of the generalized complex phase function, including the amplitude of the wave function. Various aspects of the phase delay are presented in the case of wave packets impinging on simple or resonant quantum barriers. Formal links with the classical mechanics give birth to quasi-trajectories of the quantum particle, totally compatible with the quantum mechanics. - Highlights: Black-Right-Pointing-Pointer The stationary phase method is extended in including the variations of the spectra. Black-Right-Pointing-Pointer The complex phase delay leads to a complex trajectory inside and out-side the barrier. Black-Right-Pointing-Pointer Examples of quasi-trajectories are given in case of different quantum barriers. Black-Right-Pointing-Pointer Phase delays are specified for resonant tunneling or above-barrier wave-packets. Black-Right-Pointing-Pointer The coherence between the quasi-trajectories and quantum mechanics is shown.

  10. Chiral phase transition in a planar four-Fermi model in a tilted magnetic field

    CERN Document Server

    Ramos, Rudnei O

    2013-01-01

    We study a planar four-Fermi Gross-Neveu model in the presence of a tilted magnetic field, with components parallel and perpendicular to the system's plane. We determine how this combination of magnetic field components, when applied simultaneously, affects the phase diagram of the model. It is shown that each component of the magnetic field causes a competing effect on the chiral symmetry in these fermionic systems. While the perpendicular component of the magnetic field tends to make the chiral symmetry breaking to become stronger, the effect of the parallel component of the field in these planar systems is to weaken the chiral symmetry. We show that this competing effect, when combined also with temperature and chemical potential, can lead to a rich phase diagram, with the emergence of multiple critical points and reentrant phase transitions. We also study how the presence of these multiple critical points and reentrant phases can manifest in the quantum Hall effect. Our results provide a possible way to p...

  11. 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.

  12. Poly(ethylene oxide)-bonded stationary phase for separation of inorganic anions in capillary ion chromatography.

    Science.gov (United States)

    Linda, Roza; Lim, Lee Wah; Takeuchi, Toyohide

    2013-06-14

    A tosylated-poly(ethylene oxide) (PEO) reagent was reacted with primary amino groups of an aminopropylsilica packing material (TSKgel NH2-60) in acetonitrile to form PEO-bonded stationary phase. The reaction was a single and simple step reaction. The prepared stationary phase was able to separate inorganic anions. The retention behavior of six common inorganic anions on the prepared stationary phase was examined under various eluent conditions in order to clarify its separation/retention mechanism. The elution order of the tested anions was iodate, bromate, bromide, nitrate, iodide, and thiocyanate, which was similar as observed in common ion chromatography. The retention of inorganic anions could be manipulated by ion exchange interaction which is expected that the eluent cation is coordinated among the PEO chains and it works as the anion-exchange site. Cations and anions of the eluent therefore affected the retention of sample anions. We demonstrated that the retention of the analyte anions decreased with increasing eluent concentration. The repeatability of retention time for the six anions was satisfactory on this column with relative standard deviation values from 1.1 to 4.3% when 10mM sodium chloride was used as the eluent. Compared with the unmodified TSKgel NH2-60, the prepared stationary phase retained inorganic anions more strongly and the selectivity was also improved. The present stationary phase was applied for the determination of inorganic anions contained in various water samples.

  13. Damage detection using transient trajectories in phase-space with extended random decrement technique under non-stationary excitations

    Science.gov (United States)

    Liu, Gang; Mao, Zhu; Todd, Michael

    2016-11-01

    This paper proposes a damage detection method based on the geometrical variation of transient trajectories in phase-space, and the proposed methodology is compatible with non-stationary excitations (e.g., earthquake-induced ground motion). The work presented assumes zero-mean non-stationary excitation, and extends the random decrement technique to convert non-stationary response signals of the structure into free-vibration data. Transient trajectories of the structure are reconstructed via the embedding theorem from the converted free-vibration data, and trajectories are mapped successively into phase-space to enhance statistical analysis. Based upon the characterized system dynamics in terms of phase-space, the time prediction error is adopted as the damage index. To identify the presence and severity of damage in a statistically rigorous way, receiver operating characteristic curves and the Bhattacharyya distance are employed. The results from both numerical simulations and experiments validate the proposed framework, when the test structures are subject to non-stationary excitations. The extension achieved in this paper enables the phase-space damage detection approach to be compatible with non-stationary scenarios, such as traffic, wind, and earthquake loadings. Moreover, the results indicate that this phase-state-based method is able to identify damage-induced nonlinearity in response, which is an intrinsic characteristic associated with most structural damage types.

  14. Simultaneous Chiral Symmetry Restoration and Deconfinement Consequences for the QCD Phase Diagram

    Science.gov (United States)

    Klähn, Thomas; Fischer, Tobias; Hempel, Matthias

    2017-02-01

    For studies of quark matter in astrophysical scenarios, the thermodynamic bag model is commonly employed. Although successful, it does not account for dynamical chiral symmetry breaking and repulsions due to the vector interaction which is crucial to explain recent observations of massive, two solar mass neutron stars. In Klähn & Fischer we developed the novel vBag quark matter model which takes these effects into account. This article extends vBag to finite temperatures and isospin asymmetry. Another particular feature of vBag is the determination of the deconfinement bag constant {B}{dc} from a given hadronic equation of state in order to ensure that chiral and deconfinement transitions coincide. We discuss consequences of this novel approach for the phase transition construction, the phase diagram, and implications for protoneutron stars.

  15. The $N_f= 2$ chiral phase transition from imaginary chemical potential with Wilson Fermions

    CERN Document Server

    Philipsen, Owe

    2015-01-01

    The order of the thermal transition in the chiral limit of QCD with two dynamical flavours of quarks is a long-standing issue. Still, it is not definitely known whether the transition is of first or second order in the continuum limit. Which of the two scenarios is realized has important implications for the QCD phase diagram and the existence of a critical endpoint at finite densities. Settling this issue by simulating at successively decreased pion mass was not conclusive yet. Recently, an alternative approach was proposed, extrapolating the first order phase transition found at imaginary chemical potential to zero chemical potential with known exponents, which are induced by the Roberge-Weiss symmetry. For staggered fermions on $N_t=4$ lattices, this results in a first order transition in the chiral limit. Here we report of $N_t=4$ simulations with Wilson fermions, where the first order region is found to be large.

  16. Simultaneous chiral symmetry restoration and deconfinement - Consequences for the QCD phase diagram

    CERN Document Server

    Klahn, Thomas; Hempel, Matthias

    2016-01-01

    For studies of quark matter in astrophysical scenarios the thermodynamic bag model (tdBag) is commonly employed. Although successful, it does not account for dynamical chiral symmetry breaking (D$\\chi$SB) and repulsions due to the vector interaction which is crucial to explain recent observations of massive, two solar mass neutron stars. In Kl\\"ahn & Fischer (2015) we developed the novel vBag quark matter model which takes these effects into account. This article extends vBag to finite temperatures and isospin asymmetry. Another particular feature of vBag is the determination of the deconfinement bag constant $B_{\\rm dc}$ from a given hadronic equation of state (EoS) in order to ensure that chiral and deconfinement transitions coincide. We discuss consequences of this novel approach for the phase transition construction and the phase diagram.

  17. Floquet topological phase transitions and chiral edge states in a kagome lattice

    Energy Technology Data Exchange (ETDEWEB)

    He, Chaocheng; Zhang, Zhiyong, E-mail: zyzhang@nju.edu.cn

    2014-09-05

    The Floquet topological phases and chiral edge states in a kagome lattice under a circularly-polarized driving field are studied. In the off-resonant case, the system exhibits the similar character as the kagome lattice model with staggered magnetic fluxes, but the total band width is damped in oscillation. In the on-resonant case, the degeneracy splitting at the Γ point does not always result in a gap. The positions of the other two gaps are influenced by the flat band. With the field intensity increased, these two gaps undergo closing-then-reopening processes, accompanied with the changing of the winding numbers. - Highlights: • A kagome lattice under a circularly-polarized driving field is studied. • The band structures and chiral edge states are studied via exact Floquet method. • Various modifications of the Floquet band structure are found. • Floquet topological phase transitions appear in both off- and on-resonant cases.

  18. The chiral phase transition in two-flavor QCD from imaginary chemical potential

    CERN Document Server

    Bonati, Claudio; D'Elia, Massimo; Philipsen, Owe; Sanfilippo, Francesco

    2014-01-01

    We investigate the order of the finite temperature chiral symmetry restoration transition for QCD with two massless fermions, by using a novel method, based on simulating imaginary values of the quark chemical potential $\\mu=i\\mu_i,\\mu_i\\in\\mathbb{R}$. Our method exploits the fact that, for low enough quark mass $m$ and large enough chemical potential $\\mu_i$, the chiral transition is decidedly first order, then turning into crossover at a critical mass $m_c(\\mu)$. It is thus possible to determine the critical line in the $m - \\mu^2$ plane, which can be safely extrapolated to the chiral limit by taking advantage of the known tricritical indices governing its shape. We test this method with standard staggered fermions and the result of our simulations is that $m_c(\\mu=0)$ is positive, so that the phase transition at zero density is definitely first order in the chiral limit, on our coarse $N_t=4$ lattices with $a\\simeq 0.3\\,\\mathrm{fm}$.

  19. Integrated Time and Phase Synchronization Strategy for a Multichannel Spaceborne-Stationary Bistatic SAR System

    Directory of Open Access Journals (Sweden)

    Feng Hong

    2016-07-01

    Full Text Available The spatial separation of the transmitter and receiver in Bistatic Synthetic Aperture Radar (BiSAR makes it a promising and useful supplement to a classical Monostatic SAR system (MonoSAR. This paper proposes a novel integrated time and phase synchronization strategy for a multichannel spaceborne-stationary BiSAR system. Firstly, the time synchronization strategy is proposed, which includes Pulse Repetition Frequency (PRF generation under noisy conditions, multichannel calibration and the alignment of the recorded data with the orbital data. Furthermore, the phase synchronization strategy, which fully considers the deteriorative factors in the BiSAR configuration, is well studied. The contribution of the phase synchronization strategy includes two aspects: it not only compensates the phase error, but also improves the Signal to Noise Ratio (SNR of the obtained signals. Specifically, all direct signals on different PRF time can be reconstructed with the shift and phase compensation operation using a reference signal. Besides, since the parameters of the reference signal can be estimated only once using the selected practical direct signal and a priori information, the processing complexity is well reduced. Final imaging results with and without compensation for real data are presented to validate the proposed synchronization strategy.

  20. Analysis of stereochemistry and biosynthesis of epicatechin in tea plants by chiral phase high performance liquid chromatography.

    Science.gov (United States)

    Qian, Yumei; Zhao, Xianqian; Zhao, Lei; Cui, Lilan; Liu, Li; Jiang, Xiaolan; Liu, Yajun; Gao, Liping; Xia, Tao

    2015-12-01

    Tea (Camellia sinensis) is rich in flavan-3-ols (catechins), especially epicatechin (EC), which is the predominant extension unit of polymeric proanthocyanidins (PAs). However, studies assessing EC's stereochemistry are scarce. Here, a high performance liquid chromatography column using amylose tris-(3, 5-dimethylphenylcarbamate) immobilized on silica-gel as chiral stationary phases (CSPs) was applied to explore its stereochemistry and biosynthetic pathway in tea plants. The results revealed (-)-epicatechin [(-)-EC] was the predominant di-hyroxy-non-galloylated-catechins, while (+)-epicatechin [(+)-EC] was not detected. Interestingly, (-)-EC was the only product obtained from cyanidin using the partially purified native C. sinensis anthocyanidin reductase (CsANR) in the presence of reduction nicotinamide adenine dinucleotide phosphate (NADPH); meanwhile, (+)-EC was the main product using recombinant CsANR in the same conditions. In addition, (-)-EC could be obtained from (+)-catechin [(+)-C] using recombinant CsANR, which displayed C3-epimerase activity in the presence of oxidation nicotinamide adenine dinucleotide phosphate (NADP(+)). But the partially purified native CsANR did not possess this function. Finally, (-)-EC could result from the de-gallate acid reaction of epicatechin gallate (ECG) catalyzed by a novel partially purified native galloylated catechins hydrolase (GCH) from tea leaves. In summary, (-)-EC is likely the product of native protein from the tea plants, and (+)-EC is only produced in a reaction catalyzed by recombinant CsANR in vitro.

  1. Novel local symmetries and chiral-symmetry-broken phases in S = 1/2 triangular-lattice Heisenberg model

    Science.gov (United States)

    Baskaran, G.

    1989-01-01

    Using a nonmean-field approach the triangular-lattice S = 1/2 Heisenberg antiferromagnet with nearest- and next-nearest-neighbor couplings is shown undergo an Ising-type phase transition into a chiral-symmetry-broken phase (Kalmeyer-Laughlin-like state) at small T. Removal of next-nearest-neighbor coupling introduces a local Z2 symmetry, thereby suppressing any finite-T chiral order.

  2. Phenomena at the QCD phase transition in nonequilibrium chiral fluid dynamics (NχFD)

    Energy Technology Data Exchange (ETDEWEB)

    Nahrgang, Marlene [Duke University, Department of Physics, Durham, NC (United States); Herold, Christoph [Suranaree University of Technology, School of Physics, Nakhon Ratchasima (Thailand)

    2016-08-15

    Heavy-ion collisions performed in the beam energy range accessible by the NICA collider facility are expected to produce systems of extreme net-baryon densities and can thus reach yet unexplored regions of the QCD phase diagram. Here, one expects the phase transition between the plasma of deconfined quarks and gluons and the hadronic matter to be of first order. A discovery of the first-order phase transition would as well prove the existence of the QCD critical point, a landmark in the phase diagram. In order to understand possible signals of the first-order phase transition in heavy-ion collision experiments it is very important to develop dynamical models of the phase transition. Here, we discuss the opportunities of studying dynamical effects at the QCD first-order phase transition within our model of nonequilibrium chiral fluid dynamics. (orig.)

  3. Resolution of α-cyclohexyl-mandelic acid enantiomers by two-phase (O/W) recognition chiral extraction

    Institute of Scientific and Technical Information of China (English)

    TANG; KeWen; ZHANG; GuoLi; HUANG; KeLong; LI; Yuanjian; YI; JianMin

    2007-01-01

    This paper presents a new chiral separation technology: two-phase (O/W) recognition chiral extraction. Distribution behavior of α-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-isobutyl tartrate in 1,2-dichloroethane organic phase and β-CD derivatives in aqueous phase, and the influence of the kind and concentration of extractant and pH on extraction performance was investigated. The experimental results indicate that two-phase (O/W) recognition chiral extraction is of strong chiral separation ability. HP-β-CD, HE-β-CD and Me-β-CD have higher recognition ability for S-CHMA than that for R-CHMA, among which HP-β-CD has the strongest ability; whereas, D-isobutyl tartrate has reversed recognition ability for them. In the extraction system containing HP-β-CD and D-isobutyl tartrate, e.e.% of S-CHMA in aqueous phase reached 27.6% by one stage extraction, and the distribution ratio for R-CHMA(kR) and for S-CHMA(kS) and separation factor (α) are 2.44, 0.89 and 2.49, respectively. Meanwhile, pH and concentration of extractant have great effects on chiral separation ability. Two-phase (O/W) recognition chiral extraction has great significance for preparative separation of racemic compounds.

  4. 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

  5. Growth potential of exponential- and stationary-phase Salmonella Typhimurium during sausage fermentation.

    Science.gov (United States)

    Birk, T; Henriksen, S; Müller, K; Hansen, T B; Aabo, S

    2016-11-01

    Raw meat for sausage production can be contaminated with Salmonella. For technical reasons, meat is often frozen prior to mincing but it is unknown how growth of Salmonella in meat prior to freezing affects its growth potential during sausage fermentation. We investigated survival of exponential- and stationary-phase Salmonella Typhimurium (DT12 and DTU292) during freezing at -18°C and their subsequent growth potential during 72h sausage fermentation at 25°C. After 0, 7 and >35d of frozen storage, sausage batters were prepared with NaCl (3%) and NaNO2 (0, 100ppm) and fermented with and without starter culture. With no starter culture, both strains grew in both growth phases. In general, a functional starter culture abolished S. Typhimurium growth independent of growth phase and we concluded that ensuring correct fermentation is important for sausage safety. However, despite efficient fermentation, sporadic growth of exponential-phase cells of S. Typhimurium was observed drawing attention to the handling and storage of sausage meat.

  6. Preparation, characterization, and analytical applications of a novel polymer stationary phase with embedded or grafted carbon fibers.

    Science.gov (United States)

    Zhong, Yingying; Zhou, Wenfang; Zhang, Peimin; Zhu, Yan

    2010-09-15

    A polymer-based chromatographic stationary phase with embedded or grafted multi-walled carbon nanotubes (MWCNTs) has been developed. Three different synthetic methods were utilized to combine the nano-fibers with the substrate of polystyrene-divinylbenzene (PS-DVB). After optimizing the synthetic conditions, this novel polystyrene-divinylbenzene-carbon nanotube (PS-DVB-CNT) stationary phase was characterized by scanning electron microscopy, Raman spectroscopy, thermogravimetric analysis, chemical adsorption and desorption measurement, and mechanical stability test. Compared to PS-DVB particles, PS-DVB-CNT particles have certain improvement in physical and chromatographic performances because the addition of MWCNTs has altered the structures of the particles. The novel stationary phase owns satisfactory resolution, wide pH endurance, and long lifetime, which can be used as an extent to normal HPLC.

  7. Oriented circular dichroism analysis of chiral surface-anchored metal-organic frameworks grown by liquid-phase epitaxy and upon loading with chiral guest compounds

    KAUST Repository

    Gu, Zhigang

    2014-06-17

    Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam) 2x(Lcam)2-2x(dabco)]n (dabco=1,4-diazabicyclo- [2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)] n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu 2(Dcam)2(dabco)]n and [Cu2(Lcam) 2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A novel amide stationary phase for hydrophilic interaction liquid chromatography and ion chromatography.

    Science.gov (United States)

    Shen, Guobin; Zhang, Feifang; Yang, Bingcheng; Chu, Changhu; Liang, Xinmiao

    2013-10-15

    A novel amide stationary phase (ASP) for hydrophilic interaction liquid chromatography (HILIC) has been prepared via the Click chemistry method. It was based on the strategy that the amino group of Asparagine was easily transferred to the corresponding azido group and then clicked onto terminal alkyne-silica gel in the presence of Cu(I)-based catalyst. For the tested polar compounds including nucleosides and nucleic acid bases, ASP-based column has demonstrated good performance in terms of separation efficiency and column stability, and the retention mechanism was found to match well the typical HILIC retention. In addition, the ASP described here showed much better selectivity in separation of inorganic anions under ion chromatography mode relative to other kinds of commercial ASP.

  9. Convective Interaction Media (CIM)--short layer monolithic chromatographic stationary phases.

    Science.gov (United States)

    Podgornik, Ales; Strancar, Ales

    2005-01-01

    Modern downstream processing requires fast and highly effective methods to obtain large quantities of highly pure substances. Commonly applied method for this purpose is chromatography. However, its main drawback is its throughput since purification, especially of large molecules, requires long process time. To overcome this problem several new stationary phases were introduced, among which short layer monoliths show superior properties for many applications. The purpose of this review is to give an overview about short methacrylate monolithic columns commercialised under the trademark Convective Interaction Media (CIM). Their unique properties are described from different perspectives, explaining reasons for their application on various areas. Approaches to prepare large volume methacrylate monolithic column are discussed and optimal solutions are given. Different examples of CIM monolithic column implementation are summarised in the last part of the article to give the reader an idea about their advantages.

  10. Quark matter in a parallel electric and magnetic field background: Chiral phase transition and equilibration of chiral density

    Science.gov (United States)

    Ruggieri, M.; Peng, G. X.

    2016-05-01

    In this article, we study spontaneous chiral symmetry breaking for quark matter in the background of static and homogeneous parallel electric field E and magnetic field B . We use a Nambu-Jona-Lasinio model with a local kernel interaction to compute the relevant quantities to describe chiral symmetry breaking at a finite temperature for a wide range of E and B . We study the effect of this background on the inverse catalysis of chiral symmetry breaking for E and B of the same order of magnitude. We then focus on the effect of the equilibration of chiral density n5 , produced dynamically by an axial anomaly on the critical temperature. The equilibration of n5 , a consequence of chirality-flipping processes in the thermal bath, allows for the introduction of the chiral chemical potential μ5, which is computed self-consistently as a function of the temperature and field strength by coupling the number equation to the gap equation and solving the two within an expansion in E /T2 , B /T2 , and μ52/T2 . We find that even if chirality is produced and equilibrates within a relaxation time τM , it does not change drastically the thermodynamics, with particular reference to the inverse catalysis induced by the external fields, as long as the average μ5 at equilibrium is not too large.

  11. Scaling behavior of chiral phase transition in two-flavor QCD with improved Wilson quarks at finite density

    CERN Document Server

    Ejiri, S; Aoki, S; Kanaya, K; Ohno, H; Saito, H; Hatsuda, T; Maezawa, Y; Umeda, T

    2010-01-01

    We study scaling behavior of a chiral order parameter performing a simulation of two-flavor QCD with improved Wilson quarks. It has been shown that the scaling behavior of the chiral order parameter defined by a Ward-Takahashi identity agrees with the scaling function of the three-dimensional O(4) spin model at zero chemical potential. We extend the scaling study to finite density QCD. Calculating derivatives of the chiral order parameter with respect to the chemical potential in two-flavor QCD, the scaling property of chiral phase transition is discussed in the low density region. We moreover calculate the curvature of the phase boundary of the chirl phase transition in the temperature and chemical potential plane assuming the O(4) scaling relation.

  12. Fundamental and practical studies on high-performance liquid affinity chromatography of biopolymers with novel stationary phases

    Energy Technology Data Exchange (ETDEWEB)

    Bacolod, M.D.

    1992-01-01

    Rigid microparticulate stationary phases having surface-bound metal chelating functions were developed and evaluated in high performance metal chelate affinity chromatography of proteins. Silica- and polystyrene-divinylbenzene-based metal chelate sorbents were produced in wide pore and in non-porous type of column packings. A major effort has been placed on development of non-porous highly crosslinked polystyrene-divinylbenzene (PSDVB). These PSDVB microparticles were produced by a two-step swelling polymerization, and exhibited excellent mechanical strength over a wide range of flow-rates and composition used in high performance liquid chromatography (HPLC). Simple and reproducible hydrophilic coatings were developed for the surface modification of hydrophobic PSDVB supports. A tetradentate metal chelating ligand, ethylenediamine-N, N[prime]-diacetic acid (EDDA), was covalently bound to the surface of the various supports. Sorbents having iminodiacetic acid (IDA) metal chelating functions were also evaluated. The hydrophilic character and surface coverage of various stationary phases were assessed chromatographically. Studies concerning the effects of eluent pH as well as the nature and concentration of salts on retention and selectivity with different metal chelate stationary phases having various immobilized metal ions were carried out. Elution schemes were developed for rapid separation of proteins in metal chelate affinity chromatography. EDDA stationary phases in metal forms can be viewed as complementary to IDA stationary phases since they afforded different selectivity and retentivity toward proteins. Hydrophilic PSDVB could be functionalized with IDA or EDDA metal chelating ligands or lectins. The non-porous metal chelate stationary phases afforded rapid separation of proteins by the development of multiple gradient systems, which permitted higher column peak capacity, enabling the separation of a greater number of proteins in a single chromatographic run.

  13. Separations of corticosteroids using electrochemically modulated liquid chromatography: Selectivity enhancements at a porous graphitic carbon stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Ting, E.Y.; Porter, M.D. [Ames Lab., IA (United States)]|[Iowa State Univ., Ames, IA (United States)

    1997-02-15

    Electrochemically modulated liquid chromatography has been applied to the separation of a mixture of structurally similar corticosteroids (i.e., prednisone, prednisolone, cortisone, and hydrocortisone) using a porous graphitic carbon stationary phase. Changes in the voltage applied to the column markedly affected the efficiency as well as the elution order of the separation, with the mixture fully resolved at large negative values of applied potential. Mechanistic aspects in terms of the influence of changes in the applied voltage on the extent of the interactions between these analytes and the stationary phase are briefly discussed. 19 refs., 2 figs.

  14. Pulse and quench induced dynamical phase transition in a chiral multiferroic spin chain

    Science.gov (United States)

    Azimi, M.; Sekania, M.; Mishra, S. K.; Chotorlishvili, L.; Toklikishvili, Z.; Berakdar, J.

    2016-08-01

    Quantum dynamics of magnetic order in a chiral multiferroic chain is studied. We consider two different scenarios: ultrashort terahertz excitations or a sudden electric field quench. Performing analytical and numerical exact diagonalization calculations, we trace the pulse induced spin dynamics and extract quantities that are relevant to quantum information processing. In particular, we analyze the dynamics of the system chirality, the von Neumann entropy, and the pairwise and many-body entanglement. If the characteristic frequencies of the generated states are noncommensurate, then a partial loss of pair concurrence occurs. Increasing the system size, this effect becomes even more pronounced. Many-particle entanglement and chirality are robust and persist in the incommensurate phase. To analyze the dynamical quantum transitions for the quenched and pulsed dynamics we combined the Weierstrass factorization technique for entire functions and the Lanczos exact diagonalization method. For a small system we obtained analytical results including the rate function of the Loschmidt echo. Exact numerical calculations for a system up to 40 spins confirm phase transition. Quench-induced dynamical transitions have been extensively studied recently. Here we show that related dynamical transitions can be achieved and controlled by appropriate electric field pulses.

  15. Asymmetric cyclopropanation of chalcones using chiral phase-transfer catalysts

    OpenAIRE

    2013-01-01

    The first phase-transfer catalyzed cyclopropanation reaction of chalcones using bromomalonates as the nucleophiles in a Michael Initiated Ring Closing reaction (MIRC) was developed. Key to success was the use of a free OH-containing cinchona alkaloid ammonium salt catalyst and carefully optimized liquid/liquid reaction conditions. The reaction performed well for electron neutral and electron deficient chalcones giving the products in yields up to 98% and with enantiomeric ratios up to 91:9.

  16. New studies on molecular chirality in the gas phase: enantiomer differentiation and determination of enantiomeric excess.

    Science.gov (United States)

    Patterson, David; Schnell, Melanie

    2014-06-21

    Chirality plays a fundamental role in the activity of biological molecules and broad classes of chemical reactions. The chemistry of life is built almost exclusively on left-handed amino acids and right-handed sugars, a phenomenon known as "homochirality of life". Furthermore, most drugs developed in the last decade are of specified chirality. Thus, fast and reliable methods that can differentiate molecules of different handedness, determine the enantiomeric excess of even molecular mixtures, and allow for an unambiguous determination of molecular handedness are of great interest, in particular with respect to complex mixtures. In this perspective article, we discuss the recent developments, with an emphasis on modern spectroscopic methods using gas-phase samples, such as photoelectron circular dichroism, Coulomb explosion imaging, and microwave three-wave mixing.

  17. The effect of the Polyakov loop on the chiral phase transition

    Directory of Open Access Journals (Sweden)

    Szép Zs.

    2011-04-01

    Full Text Available The Polyakov loop is included in the S U(2L × S U(2R chiral quark-meson model by considering the propagation of the constituent quarks, coupled to the (σ, π meson multiplet, on the homogeneous background of a temporal gauge field, diagonal in color space. The model is solved at finite temperature and quark baryon chemical potential both in the chiral limit and for the physical value of the pion mass by using an expansion in the number of flavors Nf. Keeping the fermion propagator at its tree-level, a resummation on the pion propagator is constructed which resums infinitely many orders in 1/Nf, where O(1/Nf represents the order at which the fermions start to contribute in the pion propagator. The influence of the Polyakov loop on the tricritical or the critical point in the µq – T phase diagram is studied for various forms of the Polyakov loop potential.

  18. Peptidoglycan Recycling in Gram-Positive Bacteria Is Crucial for Survival in Stationary Phase

    Science.gov (United States)

    Borisova, Marina; Gaupp, Rosmarie; Duckworth, Amanda; Schneider, Alexander; Dalügge, Désirée; Mühleck, Maraike; Deubel, Denise; Unsleber, Sandra; Yu, Wenqi; Muth, Günther; Bischoff, Markus; Götz, Friedrich

    2016-01-01

    ABSTRACT Peptidoglycan recycling is a metabolic process by which Gram-negative bacteria reutilize up to half of their cell wall within one generation during vegetative growth. Whether peptidoglycan recycling also occurs in Gram-positive bacteria has so far remained unclear. We show here that three Gram-positive model organisms, Staphylococcus aureus, Bacillus subtilis, and Streptomyces coelicolor, all recycle the sugar N-acetylmuramic acid (MurNAc) of their peptidoglycan during growth in rich medium. They possess MurNAc-6-phosphate (MurNAc-6P) etherase (MurQ in E. coli) enzymes, which are responsible for the intracellular conversion of MurNAc-6P to N-acetylglucosamine-6-phosphate and d-lactate. By applying mass spectrometry, we observed accumulation of MurNAc-6P in MurNAc-6P etherase deletion mutants but not in either the isogenic parental strains or complemented strains, suggesting that MurQ orthologs are required for the recycling of cell wall-derived MurNAc in these bacteria. Quantification of MurNAc-6P in ΔmurQ cells of S. aureus and B. subtilis revealed small amounts during exponential growth phase (0.19 nmol and 0.03 nmol, respectively, per ml of cells at an optical density at 600 nm [OD600] of 1) but large amounts during transition (0.56 nmol and 0.52 nmol) and stationary (0.53 nmol and 1.36 nmol) phases. The addition of MurNAc to ΔmurQ cultures greatly increased the levels of intracellular MurNAc-6P in all growth phases. The ΔmurQ mutants of S. aureus and B. subtilis showed no growth deficiency in rich medium compared to the growth of the respective parental strains, but intriguingly, they had a severe survival disadvantage in late stationary phase. Thus, although peptidoglycan recycling is apparently not essential for the growth of Gram-positive bacteria, it provides a benefit for long-term survival. PMID:27729505

  19. Quark Matter in a Parallel Electric and Magnetic Field Background: Equilibrated Chiral Density Effect on Chiral Phase Transition

    CERN Document Server

    Ruggieri, M

    2016-01-01

    In this article we study spontaneous chiral symmetry breaking for quark matter in the background of an electric-magnetic flux tube with static, homogeneous and parallel electric field $\\bm E$ and magnetic field $\\bm B$. We use a Nambu-Jona-Lasinio model with a local kernel interaction to compute the relevant quantities to describe chiral symmetry breaking at finite temperature for a wide range of $E$ and $B$. We study the effect of the flux tube background on inverse catalysis of chiral symmetry breaking for $E$ and $B$ of the same order of magnitude. We then focus on the effect of equilibration of chiral density, $n_5$, produced dynamically by axial anomaly on the critical temperature. The equilibration of $n_5$, a consequence of chirality flipping processes in the thermal bath, allows for the introduction of the chiral chemical potential, $\\mu_5$, which is computed self-consistently as a function of temperature and field strength by coupling the number equation to the gap equation. We find that even if chir...

  20. Diastereo- and enantioseparation of a N{sup α}-Boc amino acid with a zwitterionic quinine-based stationary phase: Focus on the stereorecognition mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Ianni, Federica; Carotti, Andrea; Marinozzi, Maura; Marcelli, Gloria [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy); Di Michele, Alessandro [Department of Physics and Geology, University of Perugia, Via Pascoli 1, 06123 Perugia (Italy); Sardella, Roccaldo, E-mail: roccaldo.sardella@unipg.it [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy); Lindner, Wolfgang [Department of Analytical Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna (Austria); Natalini, Benedetto [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy)

    2015-07-23

    Highlights: • The ZWIX(+) column allowed getting the Boc-Aph(Hor)-OH (1) isomeric peaks resolved. • ECD studies and molecular dynamic simulations allowed to assign the elution order. • Molecular descriptors revealed the active role of achiral elements of the CSP. - Abstract: A chiral chromatography method enabling the simultaneous diastereo- and enantioseparation of N{sup α}-Boc-N{sup 4}-(hydroorotyl)-4-aminophenylalanine [Boc-Aph(Hor)-OH, 1] was optimized with a quinine-based zwitterionic stationary phase. The polar-ionic eluent system consisting of ACN:MeOH:water—49.7:49.7:0.6 (v/v/v) with formic acid (4.0 mM) and diethylamine (2.5 mM), allowed the successful separation of the four acid stereoisomers: α{sub D,D-/D,L-1} = 1.08; α{sub D,L-/L,D-1} = 1.08; α{sub L,D-/L,L-1} = 1.40. According to the in-house developed synthetic procedure and the recorded electronic circular dichroism spectra, the following stereoisomeric elution order was readily established in the optimal chromatographic conditions: D,D-1 < D,L-1 < L,D-1 < L,L-1. With the aim of better understanding the molecular basis of the retention behaviour of the four stereoisomers in the employed chromatographic system and conditions, a computational protocol consisting in molecular dynamics simulations was applied. The use of the three descriptors INTER (in kcal mol{sup −1}, encoding for the interaction energy between the selector SO unit and the whole system), INTER-SA (in kcal mol{sup −1}, encoding for the interaction energy between SO and the sole selectand SA), and SELF (in kcal mol{sup −1}, encoding for the conformational energy of SA relative to its minimum energy registered by the collected snapshots) revealed the active role of achiral sub-structural elements of the chiral stationary phase and eluent components in the overall stereorecognition mechanism.

  1. A new imidazolium-embedded C{sub 18} stationary phase with enhanced performance in reversed-phase liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Qiu Hongdeng [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000 (China); Mallik, Abul K. [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Takafuji, Makoto [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), Kumamoto 862-0901 (Japan); Liu Xia; Jiang Shengxiang [Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000 (China); Ihara, Hirotaka, E-mail: ihara@kumamoto-u.ac.jp [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), Kumamoto 862-0901 (Japan)

    2012-08-13

    Highlights: Black-Right-Pointing-Pointer Imidazolium-embedded C{sub 18} stationary phase was prepared and characterized. Black-Right-Pointing-Pointer Enhanced chromatographic selectivity was observed in SiImC{sub 18} column. Black-Right-Pointing-Pointer Seven nucleosides and bases were separated using only water as eluent within 8 min. Black-Right-Pointing-Pointer Multiple-interactions induced by embedded polar imidazolium was investigated. - Abstract: In this paper, a new imidazolium-embedded C{sub 18} stationary phase (SiImC{sub 18}) for reversed-phase high-performance liquid chromatography is described. 1-Allyl-3-octadecylimidazolium bromide ionic liquid compound having a long alkyl chain and reactive groups was newly prepared and grafted onto 3-mercaptopropyltrimethoxysilane-modified silica via a surface-initiated radical-chain transfer addition reaction. The SiImC{sub 18} obtained was characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, diffuse reflectance infrared Fourier transform, and solid-state {sup 13}C and {sup 29}Si cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy. The selectivity toward polycyclic aromatic hydrocarbons relative to that toward alkylbenzenes exhibited by SiImC{sub 18} was higher than the corresponding selectivity exhibited by a conventional octadecyl silica (ODS) column, which could be explained by electrostatic {pi}-{pi} interaction cationic imidazolium and electron-rich aromatic rings. On the other hand, SiImC{sub 18} also showed high selectivity for polar compounds, which was based on the multiple interaction and retention mechanisms of this phase with different analytes. 1,6-Dinitropyrene and 1,8-dinitropyrene, which form a positional isomer pair of dipolar compounds, were separated successfully with the SiImC{sub 18} phase. Seven nucleosides and bases (i.e. cytidine, uracil, uridine, thymine, guanosine, xanthosine, and adenosine) were separated using only water as

  2. Simultaneous separation of hydrophobic and hydrophilic peptides with a silica hydride stationary phase using aqueous normal phase conditions.

    Science.gov (United States)

    Boysen, Reinhard I; Yang, Yuanzhong; Chowdhury, Jamil; Matyska, Maria T; Pesek, Joseph J; Hearn, Milton T W

    2011-11-04

    The application of a silica hydride modified stationary phase with low organic loading has been investigated as a new type of chromatographic material suitable for the separation and analysis of peptides with electrospray ionization mass spectrometric detection. Retention maps were established to delineate the chromatographic characteristics of a series of peptides with physical properties ranging from strongly hydrophobic to very hydrophilic and encompassing a broad range of pI values (pI 5.5-9.4). The effects of low concentrations of two additives (formic acid and acetic acid) in the mobile phase were also investigated with respect to their contribution to separation selectivity and retention under comparable conditions. Significantly, strong retention of both the hydrophobic and the hydrophilic peptides was observed when high-organic low-aqueous mobile phases were employed, thus providing a new avenue to achieve high resolution peptide separations. For example, simultaneous separation of hydrophobic and hydrophilic peptides was achieved under aqueous normal phase (ANP) chromatographic conditions with linear gradient elution procedures in a single run, whilst further gradient optimization enabled improved peak efficiencies of the more strongly retained hydrophobic and hydrophilic peptides.

  3. Poly(L-lactic acid)-modified silica stationary phase for reversed-phase and hydrophilic interaction liquid chromatography.

    Science.gov (United States)

    Ohyama, Kaname; Takasago, Shizuka; Kishikawa, Naoya; Kuroda, Naotaka

    2015-03-01

    Poly(L-lactic acid) is a linear aliphatic thermoplastic polyester that can be produced from renewable resources. A poly(L-lactic acid)-modified silica stationary phase was newly prepared by amide bond reaction between amino groups on aminopropyl silica and carboxylic acid groups at the end of the poly(L-lactic acid) chain. The poly(L-lactic acid)-silica column was characterized in reversed-phase liquid chromatography and hydrophilic interaction liquid chromatography with the use of different mobile phase compositions. The poly(L-lactic acid)-silica column was found to work in both modes, and the retention of test compounds depending on acetonitrile content exhibited "U-shaped" curves, which was an indicator of reversed-phase liquid chromatography/hydrophilic interaction liquid chromatography mixed-mode retention behavior. In addition, carbonyl groups included into the poly(L-lactic acid) backbone work as an electron-accepting group toward a polycyclic aromatic hydrocarbon and provide π-π interactions.

  4. Lateral shift in one-dimensional quasiperiodic chiral photonic crystal

    Energy Technology Data Exchange (ETDEWEB)

    Da, Jian, E-mail: dajian521@sina.com [Department of Information Engineering, Huaian Senior Vocational and Technical School, Feiyao road, Huaian 223005, Jiangsu Province (China); Mo, Qi, E-mail: moqiyueyang@163.com [School of Software, Yunnan University, Cuihu Bai Road, Kunming City, Yunnan Province 650091 (China); Cheng, Yaokun [Department of Information Engineering, Huaian Senior Vocational and Technical School, Feiyao road, Huaian 223005, Jiangsu Province (China); Liu, Taixiang [Taishan Vocational College of Nursing, Shandong Province 271000 (China)

    2015-02-01

    We investigate the lateral shift of a one-dimensional quasiperiodic photonic crystal consisting of chiral and conventional dielectric materials. The effect of structural irregularity on lateral shift is evaluated by stationary-phase approach. Our results show that the lateral shift can be modulated by varying the structural irregularity in quasiperiodic structure. Besides, the position of peak in lateral shift spectrum stays sensitive to the chiral factor of chiral materials. In comparison with that of periodic structure, quasiperiodic structure provides an extra degree of freedom to manipulate the lateral shift.

  5. Preparation of a novel carboxyl stationary phase by "thiol-ene" click chemistry for hydrophilic interaction chromatography.

    Science.gov (United States)

    Peng, Xi-Tian; Liu, Tao; Ji, Shu-Xian; Feng, Yu-Qi

    2013-08-01

    A novel carboxyl-bonded silica stationary phase was prepared by "thiol-ene" click chemistry. The resultant Thiol-Click-COOH phase was evaluated under hydrophilic interaction liquid chromatography (HILIC) mobile phase conditions. A comparison of the chromatographic performance of Thiol-Click-COOH and pure silica columns was performed according to the retention behaviors of analytes and the charged state of the stationary phases. The results indicated that the newly developed Thiol-Click-COOH column has a higher surface charge and stronger hydrophilicity than the pure silica column. Furthermore, the chromatographic behaviors of five nucleosides on the Thiol-Click-COOH phase were investigated in detail. Finally, a good separation of 13 nucleosides and bases, and four water-soluble vitamins was achieved.

  6. Enantioseparation of Dencichine and D-Isomer on L-Cysteine Derivative Phase by Ligand-exchange Chromatography

    Institute of Scientific and Technical Information of China (English)

    Yan Shun MA; Qing Hua MENG; Hong Yu SHI; Yuan De LONG; Tian Bao HUANG

    2006-01-01

    The enantioseparation of dencichine and its D-isomer was achieved on a novel chiral stationary phase via coating N-(2-hydroxyl-3-octoxyl) propyl-S-benzyl-(L)-cysteine on YWG-C18phase by ligand exchange chromatography.

  7. Characterization and classification of stationary phases in HPLC and SFC – a review.

    Science.gov (United States)

    Galea, Charlene; Mangelings, Debby; Vander Heyden, Yvan

    2015-07-30

    Packed column supercritical fluid chromatography (pSFC) is an attractive technique in drug discovery related analysis because it offers several advantages over the more commonly used high-performance liquid chromatography (HPLC) technique. The environmental-friendly CO2 mobile phase, the high-throughput capacity, the increased efficiency and the lower operational costs give SFC additional benefits over HPLC in analysis related to drug development. The latter technique is well established and has been used for decades in the pharmaceutical industry. On the other hand, SFC is still in its infancy, even though the technique has been known for decades and researchers are still discovering the possibilities and limitations of this technique. Column characterization aims to obtain a quantitative understanding of the properties of a column that influence the selectivity of a separation. Columns have been extensively characterized in HPLC using several approaches. However, limited column characterization has been done in SFC. Determining column properties allows the rapid selection of appropriate columns for method development for a particular application. Hence, they also show which columns will provide similar or dissimilar separations. The aim of this review is to compare and contrast approaches used to characterize stationary phases in HPLC and SFC, and to highlight points that still may need to be researched further.

  8. Effect of benzalkonium chloride on viability and energy metabolism in exponential- and stationary-growth-phase cells of Listeria monocytogenes

    NARCIS (Netherlands)

    Luppens, S.B.I.; Abee, T.; Oosterom, J.

    2001-01-01

    The difference in killing exponential- and stationary-phase cells of Listeria monocytogenes by benzalkonium chloride (BAC) was investigated by plate counting and linked to relevant bioenergetic parameters. At a low concentration of BAC (8 mg liter-1), a similar reduction in viable cell numbers was o

  9. Lipidic ionic liquid stationary phases for the separation of aliphatic hydrocarbons by comprehensive two-dimensional gas chromatography.

    Science.gov (United States)

    Nan, He; Zhang, Cheng; O'Brien, Richard A; Benchea, Adela; Davis, James H; Anderson, Jared L

    2017-01-20

    Lipidic ionic liquids (ILs) possessing long alkyl chains as well as low melting points have the potential to provide unique selectivity as well as wide operating ranges when used as stationary phases in gas chromatography. In this study, a total of eleven lipidic ILs containing various structural features (i.e., double bonds, linear thioether chains, and cyclopropanyl groups) were examined as stationary phases in comprehensive two dimensional gas chromatography (GC×GC) for the separation of nonpolar analytes in kerosene. N-alkyl-N'-methyl-imidazolium-based ILs containing different alkyl side chains were used as model structures to investigate the effects of alkyl moieties with different structural features on the selectivities and operating temperature ranges of the IL-based stationary phases. Compared to a homologous series of ILs containing saturated side chains, lipidic ILs exhibit improved selectivity toward the aliphatic hydrocarbons in kerosene. The palmitoleyl IL provided the highest selectivity compared to all other lipidic ILs as well as the commercial SUPELCOWAX 10 column. The linoleyl IL containing two double bonds within the alkyl side chain showed the lowest chromatographic selectivity. The lipidic IL possessing a cyclopropanyl group within the alkyl moiety exhibited the highest thermal stability. The Abraham solvation parameter model was used to evaluate the solvation properties of the lipidic ILs. This study provides the first comprehensive examination into the relation between lipidic IL structure and the resulting solvation characteristics. Furthermore, these results establish a basis for applying lipidic ILs as stationary phases for solute specific separations in GC×GC.

  10. Recombinant Staphylococcal protein A with cysteine residue for preparation of affinity chromatography stationary phase and immunosensor applications

    Directory of Open Access Journals (Sweden)

    Gorbatiuk O. B.

    2015-04-01

    Full Text Available Aim. Engineering of recombinant Staphylococcal protein A with cysteine residue (SPA-Cys for preparation of affinity chromatography stationary phase and formation of bioselective element of immunosensor. Methods. DNA sequences encoding IgG-binding region of SPA, His-tag and cysteine were genetically fused and expressed in E. coli. SPA-Cys was immobilized on maleimide-functionalized silica beads for affinity chromatography stationary phase preparation and on a gold sensor surface as a bioselective element of immunosensor. Results. SPA-Cys was expressed at a high-level in a soluble form. The target protein was purified and showed a high IgG-binding activity. The capacity of the obtained SPA-Cys-based affinity chromatography stationary phase was 10–12 mg of IgG /ml. The purity of eluted IgG was more than 95 % in one-step purification procedure. The developed SPA-Cys-based bioselective element of immunosensor selectively interacted with human IgG and did not interact with the control proteins. Conclusions. The recombinant Staphylococcal protein A with cysteine residue was successfully used for the preparation of affinity chromatography stationary phase and formation of the bioselective element of immunosensor.

  11. Stationary-phase production of the antibiotic actinorhodin in Streptomyces coelicolor A3(2) is transcriptionally regulated

    NARCIS (Netherlands)

    Gramajo, Hugo C.; Takano, Eriko; Bibb, Mervyn J.

    1993-01-01

    Production of actinorhodin, a polyketide antibiotic made by Streptomyces coelicolor A3(2), normally occurs only in stationary-phase cultures. S1 nuclease protection experiments showed that transcription of actII-ORF4, the activator gene required for expression of the biosynthetic structural genes, i

  12. Pre-stack time migration based on stationary-phase stacking in the dip-angle domain

    Science.gov (United States)

    Xu, Jincheng; Zhang, Hao; Zhang, Jianfeng; Li, Zhengwei; Liu, Wei

    2017-03-01

    The Kirchhoff-type migration approach often suffers from migration noise, aliasing artifacts due to operator error, or weak noise from a truncated aperture or pre-stacked data. These noises can be attenuated by using stationary-phase migration, which only stacks the reflection energy within the Fresnel zone rather than along the whole migration aperture, and therefore obtains a higher signal-to-noise ratio (SNR) for the migration results. This paper proposes a new implementation for the pre-stack time migration (PSTM) approach, which is based on stationary-phase stacking in the dip-angle domain. This implementation generates a pair of migrated dip-angle gathers in the image domain using PSTM. We can obtain the dip-angle field corresponding to the contribution of the Fresnel zones from the migrated dip-angle gathers, which allows us to remove noise outside the Fresnel zones and significantly improves the SNR of the image gathers. The proposed stationary-phase PSTM could effectively handle the problem of low SNR in migrated images, especially in the presence of steeply dipping structures. We test the method by applying stationary-phase PSTM to an overthrust model example and a three-dimensional field data set, and both examples demonstrate that the resulting images are of good quality with the method.

  13. The $N_f=2 chiral phase transition from imaginary chemical potential with Wilson Fermions

    CERN Document Server

    Cuteri, Francesca; Philipsen, Owe; Pinke, Christopher

    2015-01-01

    The finite temperature chiral and deconfinement phase transitions at zero density for light and heavy quarks, respectively, have analytic continuations to imaginary chemical potential. At some critical imaginary chemical potential, they meet the Roberge-Weiss transition between adjacent $Z3$ sectors. For light and heavy quarks, where the chiral and deconfinement transitions are first order, the transition lines meet in a triple point. For intermediate masses chiral or deconfinement transitions are crossover and the Roberge-Weiss transition ends in a second order point. At the boundary between these regimes the junction is a tricritical point, as shown in studies with $N_f=2,3$ flavors of staggered and Wilson quarks on $N_\\tau=4$ lattices. Employing finite size scaling we investigate the nature of this point as a function of quark mass for $N_f=2$ flavors of Wilson fermions with a temporal lattice extent of $N_\\tau=6$. In particular we are interested in the change of the location of tricritical points compared...

  14. Characterisation of reversed-phase liquid chromatography stationary phases for the analysis of basic pharmaceuticals : eluent properties and comparison of empirical test methods

    NARCIS (Netherlands)

    Vervoort, RJM; Ruyter, E; Debets, AJJ; Claessens, HA; Cramers, CA; de Jong, GJ

    2001-01-01

    The reversed-phase liquid chromatographic analysis of basic pharmaceuticals can be problematic. Both the properties of the eluent and the stationary phase can influence the chromatographic performance. Therefore selection of suitable experimental conditions for the analysis of basic compounds can be

  15. Floquet engineering of Haldane Chern insulators and chiral bosonic phase transitions

    Science.gov (United States)

    Plekhanov, Kirill; Roux, Guillaume; Le Hur, Karyn

    2017-01-01

    The realization of synthetic gauge fields has attracted a lot of attention recently in relation to periodically driven systems and the Floquet theory. In ultracold atom systems in optical lattices and photonic networks, this allows one to simulate exotic phases of matter such as quantum Hall phases, anomalous quantum Hall phases, and analogs of topological insulators. In this paper, we apply the Floquet theory to engineer anisotropic Haldane models on the honeycomb lattice and two-leg ladder systems. We show that these anisotropic Haldane models still possess a topologically nontrivial band structure associated with chiral edge modes. Focusing on (interacting) boson systems in s -wave bands of the lattice, we show how to engineer through the Floquet theory, a quantum phase transition (QPT) between a uniform superfluid and a Bose-Einstein condensate analog of Fulde-Ferrell-Larkin-Ovchinnikov states, where bosons condense at nonzero wave vectors. We perform a Ginzburg-Landau analysis of the QPT on the graphene lattice, and compute observables such as chiral currents and the momentum distribution. The results are supported by exact diagonalization calculations and compared with those of the isotropic situation. The validity of high-frequency expansion in the Floquet theory is also tested using time-dependent simulations for various parameters of the model. Last, we show that the anisotropic choice for the effective vector potential allows a bosonization approach in equivalent ladder (strip) geometries.

  16. Phase transitions and ordering structures of a model of a chiral helimagnet in three dimensions

    Science.gov (United States)

    Nishikawa, Yoshihiko; Hukushima, Koji

    2016-08-01

    Phase transitions in a classical Heisenberg spin model of a chiral helimagnet with the Dzyaloshinskii-Moriya interaction in three dimensions are numerically studied. By using the event-chain Monte Carlo algorithm recently developed for particle and continuous spin systems, we perform equilibrium Monte Carlo simulations for large systems up to about 106 spins. Without magnetic fields, the system undergoes a continuous phase transition with critical exponents of the three-dimensional XY model, and a uniaxial periodic helical structure emerges in the low-temperature region. In the presence of a magnetic field perpendicular to the axis of the helical structure, it is found that there exists a critical point on the temperature and magnetic-field phase diagram and that above the critical point the system exhibits a phase transition with strong divergence of the specific heat and the uniform magnetic susceptibility.

  17. Characterization of the properties of stationary phases for liquid chromatography in aqueous mobile phases using aromatic sulphonic acids as the test compounds.

    Science.gov (United States)

    Jandera, P; Bocian, S; Molíková, M; Buszewski, B

    2009-01-09

    We investigated the effects of the concentration of naphthalene sulphonic acids (NSAs) as anionic test compounds in the injected sample and of the salt additives to the mobile phase on ion-exclusion. The retention behaviour of NSAs sensitively reflects even minor changes in the ionic and hydrophobic interactions and can be useful for predicting the effects of the stationary phases in reversed-phase chromatography of polar and ionic compounds, both small ones and biopolymers, e.g., oligonucleotides. We studied chromatographic properties of several stationary phases intended for separations in aqueous mobile phases: a C18 column end-capped with polar hydrophilic groups, a densely bonded C8 column doubly end-capped with short alkyl groups, a short alkyl stationary phase designed to keep full pore accessibility in highly-aqueous mobile phases and a Bidentate column with "bridged" C18 groups attached to the silica hydride support. The chemistry and pore structure of various types of column packing materials and of the salt additives to the mobile phase affect the proportion of the pore volume non-accessible to anions due to ion-exclusion and consequently the peak asymmetry and hydrophobic selectivity in reversed-phase chromatography of organic acids. We also addressed the problems connected with the determination of column hold-up volume in aqueous mobile phases. The accessibility of the stationary phase for anionic compounds in contact with the sample zone is affected by ion-exclusion due to repulsive interactions with the negatively charged surface in the pores of the stationary phase. The accessible part of the stationary phase increases and consequently the migration velocity along the column decreases with increasing concentration of the sample in the zone moving along the column. Because of a limited access to the stationary phase, its capacity can be easily overloaded. The combination of the column overload and ion-exclusion effects may result in fronting or

  18. 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

  19. Deconvoluting the effects of buffer salt concentration in hydrophilic interaction chromatography on a zwitterionic stationary phase.

    Science.gov (United States)

    West, Caroline; Auroux, Emeline

    2016-08-26

    Quantitative structure-retention relationships (QSRRs) furnish a detailed and reliable description of the role and extent of different molecular interactions that can be established between the analytes and the chromatographic system. Among QSRRs, the solvation parameter model using Abraham descriptors has gained acceptance as a general tool to explore the factors affecting retention in chromatographic systems. We have previously shown how a modified version of the solvation parameter model, with two extra terms to take account of interactions occurring with ionic and ionizable species (with positive and/or negative charges), could be applied to the characterization of hydrophilic interaction chromatographic (HILIC) systems. In the present study, we will show how this methodology can be used to evaluate the effects of increasing buffer salt concentration on retention and separation in a HILIC system. A commercial stationary phase possessing a sulfobetaine zwitterionic bonded ligand (Nucleodur HILIC) was used with a mobile phase composed of 80% acetonitrile and 20% pwwH4 ammonium acetate buffer, with aqueous buffer concentrations varying from 10 to 100mM, resulting in overall concentrations ranging from 2 to 20mM in the mobile phase. Retention factors were measured for a selection of 76 probe analytes. The chosen compounds are small molecules presenting a wide diversity of molecular structures and are relevant to biomedical and pharmaceutical applications. The QSRR models obtained allow for a rationalization of the interactions contributing to retention and separation in the HILIC system considered and shed some light on the effect of varying buffer salt concentration, namely the progressive transition from ion-exchange and electrostatic-repulsion mechanisms to hydrophilic partitioning.

  20. A new imidazolium-embedded C18 stationary phase with enhanced performance in reversed-phase liquid chromatography.

    Science.gov (United States)

    Qiu, Hongdeng; Mallik, Abul K; Takafuji, Makoto; Liu, Xia; Jiang, Shengxiang; Ihara, Hirotaka

    2012-08-13

    In this paper, a new imidazolium-embedded C(18) stationary phase (SiImC(18)) for reversed-phase high-performance liquid chromatography is described. 1-Allyl-3-octadecylimidazolium bromide ionic liquid compound having a long alkyl chain and reactive groups was newly prepared and grafted onto 3-mercaptopropyltrimethoxysilane-modified silica via a surface-initiated radical-chain transfer addition reaction. The SiImC(18) obtained was characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, diffuse reflectance infrared Fourier transform, and solid-state (13)C and (29)Si cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy. The selectivity toward polycyclic aromatic hydrocarbons relative to that toward alkylbenzenes exhibited by SiImC(18) was higher than the corresponding selectivity exhibited by a conventional octadecyl silica (ODS) column, which could be explained by electrostatic π-π interaction cationic imidazolium and electron-rich aromatic rings. On the other hand, SiImC(18) also showed high selectivity for polar compounds, which was based on the multiple interaction and retention mechanisms of this phase with different analytes. 1,6-Dinitropyrene and 1,8-dinitropyrene, which form a positional isomer pair of dipolar compounds, were separated successfully with the SiImC(18) phase. Seven nucleosides and bases (i.e. cytidine, uracil, uridine, thymine, guanosine, xanthosine, and adenosine) were separated using only water as the mobile phase within 8min, which is difficult to achieve when using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions is important for the effective separation of such basic compounds without the use of any organic additive as the eluent in the octadecylimidazolium column.

  1. Microchip free flow planar reversed phase electrochromatography with monolithic stationary phase.

    Science.gov (United States)

    Wang, Pingli; Tao, Dingyin; Zhang, Lihua; Liang, Zhen; Zhang, Yukui

    2009-08-01

    In this study, microchip free flow planar RP electrochromatography (microFF-PRPEC) was developed by in situ polymerization of monolithic materials in microchamber, and successfully applied for the separation of dyes and proteins. Poly(butyle methyacrylate-co-ethylene dimethacrylate) was prepared by UV-initiated polymerization in a glass microchamber (42 mm long, 23 mm wide, and 28 microm deep). A mixture of 1-propanol, 1,4-butanediol, and water was chosen as porogens, and 1.2% (wt%) 2-acrylamide-2-methyl-propanesulfonic acid (AMPS) was added into the polymerization solution to generate EOF. With 30% v/v ACN-15 mM Tris-HCl as the mobile phase, rhodamine B and methyl green were separated from each other with 400 V transverse voltage applied, and resolution as high as 4.6 was obtained, much higher than that obtained by microFFE under optimal conditions. Furthermore, microFF-PRPEC was also successfully applied into the separation of lysozyme and ribonuclease B, and resolution as high as 9.4 was obtained. All these results demonstrate that microFF-RPPEC might have great potential in the microscale continuous preparation of samples with improved resolution compared to microFFE.

  2. Stationary-point approach to the phase transition of the classical XY chain with power-law interactions.

    Science.gov (United States)

    Kastner, Michael

    2011-03-01

    The stationary points of the potential energy function V of the classical XY chain with power-law pair interactions (i.e., interactions decaying like r{-α} with the distance) are analyzed. For a class of "spinwave-type" stationary points, the asymptotic behavior of the Hessian determinant of V is computed analytically in the limit of large system size. The computation is based on the Toeplitz property of the Hessian and makes use of a Szegö-type theorem. The results serve to illustrate a recently discovered relation between phase transitions and the properties of stationary points of classical many-body potentials. In agreement with this relation, the exact phase transition potential energy of the model can be read off from the behavior of the Hessian determinant for exponents α between zero and one. For α between one and two, the phase transition is not manifest in the behavior of the determinant, and it might be necessary to consider larger classes of stationary points.

  3. Progress in vacuum susceptibilities and their applications to the chiral phase transition of QCD

    CERN Document Server

    Cui, Zhu-Fang; Shi, Yuan-Mei; Wang, Yong-Long; Zong, Hong-Shi

    2015-01-01

    The QCD vacuum condensates and various vacuum susceptibilities are all important parameters which characterize the nonperturbative properties of the QCD vacuum. In the QCD sum rules external field formula, various QCD vacuum susceptibilities play important roles in determining the properties of hadrons. In this paper, we review the recent progress in studies of vacuum susceptibilities together with their applications to the chiral phase transition of QCD. The results of the tensor, the vector, the axial-vector, the scalar, and the pseudo-scalar vacuum susceptibilities are shown in detail in the framework of Dyson-Schwinger equations.

  4. Progress in vacuum susceptibilities and their applications to the chiral phase transition of QCD

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Zhu-Fang, E-mail: phycui@nju.edu.cn [Department of Physics, Nanjing University, Nanjing 210093 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, CAS, Beijing, 100190 (China); Hou, Feng-Yao [Institute of Theoretical Physics, CAS, Beijing 100190 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, CAS, Beijing, 100190 (China); Shi, Yuan-Mei [Department of Physics, Nanjing University, Nanjing 210093 (China); Department of Physics and Electronic Engineering, Nanjing Xiaozhuang University, Nanjing 211171 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, CAS, Beijing, 100190 (China); Wang, Yong-Long [Department of Physics, Nanjing University, Nanjing 210093 (China); Department of Physics, School of Science, Linyi University, Linyi 276005 (China); Zong, Hong-Shi, E-mail: zonghs@nju.edu.cn [Department of Physics, Nanjing University, Nanjing 210093 (China); Joint Center for Particle, Nuclear Physics and Cosmology, Nanjing 210093 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, CAS, Beijing, 100190 (China)

    2015-07-15

    The QCD vacuum condensates and various vacuum susceptibilities are all important parameters which characterize the nonperturbative properties of the QCD vacuum. In the QCD sum rules external field formula, various QCD vacuum susceptibilities play important roles in determining the properties of hadrons. In this paper, we review the recent progress in studies of vacuum susceptibilities together with their applications to the chiral phase transition of QCD. The results of the tensor, the vector, the axial–vector, the scalar, and the pseudo-scalar vacuum susceptibilities are shown in detail in the framework of Dyson–Schwinger equations.

  5. Stationary phase modulation in liquid chromatography through the serial coupling of columns: A review.

    Science.gov (United States)

    Alvarez-Segura, T; Torres-Lapasió, J R; Ortiz-Bolsico, C; García-Alvarez-Coque, M C

    2016-06-01

    Liquid chromatography with single columns often does not succeed in the analysis of complex samples, in terms of resolution and analysis time. A relatively simple solution to enhance chromatographic resolution is the modulation of the stationary phase through the serial coupling of columns. This can be implemented with any type of column using compatible elution conditions and conventional instruments. This review describes the key features of column coupling and published procedures, where two or more columns were coupled in series to solve separation problems. In all reports, the authors could not resolve their samples with single columns, whereas significant enhancement in chromatographic performance was obtained when the columns were combined. Particularly interesting is the reduction in the analysis time in the isocratic mode, which alleviates the "general elution problem" of liquid chromatography, and may represent a stimulus for the proposal of new procedures, especially in combination with mass spectrometric, electrochemical and refractometric detection. Developments proposed to make the serial coupling of columns useful in routine and research laboratories are outlined, including optimisation strategies that facilitate the selection of the appropriate column combination and elution conditions (solvent content, flow rate or temperature) in both isocratic and gradient modes. The availability of zero dead volume couplers, able to connect standard columns, and the commercialisation of short columns with multiple lengths, have expanded the possibilities of success.

  6. Site-Specific Ser/Thr/Tyr Phosphoproteome of Sinorhizobium meliloti at Stationary Phase.

    Science.gov (United States)

    Liu, Tao; Tian, Chang Fu; Chen, Wen Xin

    2015-01-01

    Sinorhizobium meliloti, a facultative microsymbiont of alfalfa, should fine-tune its cellular processes to live saprophytically in soils characterized with limited nutrients and diverse stresses. In this study, TiO2 enrichment and LC-MS/MS were used to uncover the site-specific Ser/Thr/Tyr phosphoproteome of S. meliloti in minimum medium at stationary phase. There are a total of 96 unique phosphorylated sites, with a Ser/Thr/Tyr distribution of 63:28:5, in 77 proteins. Phosphoproteins identified in S. meliloti showed a wide distribution pattern regarding to functional categories, such as replication, transcription, translation, posttranslational modification, transport and metabolism of amino acids, carbohydrate, inorganic ion, succinoglycan etc. Ser/Thr/Tyr phosphosites identified within the conserved motif in proteins of key cellular function indicate a crucial role of phosphorylation in modulating cellular physiology. Moreover, phosphorylation in proteins involved in processes related to rhizobial adaptation was also discussed, such as those identified in SMa0114 and PhaP2 (polyhydroxybutyrate synthesis), ActR (pH stress and microaerobic adaption), SupA (potassium stress), chaperonin GroEL2 (viability and potentially symbiosis), and ExoP (succinoglycan synthesis and secretion). These Ser/Thr/Tyr phosphosites identified herein would be helpful for our further investigation and understanding of the role of phosphorylation in rhizobial physiology.

  7. Site-Specific Ser/Thr/Tyr Phosphoproteome of Sinorhizobium meliloti at Stationary Phase.

    Directory of Open Access Journals (Sweden)

    Tao Liu

    Full Text Available Sinorhizobium meliloti, a facultative microsymbiont of alfalfa, should fine-tune its cellular processes to live saprophytically in soils characterized with limited nutrients and diverse stresses. In this study, TiO2 enrichment and LC-MS/MS were used to uncover the site-specific Ser/Thr/Tyr phosphoproteome of S. meliloti in minimum medium at stationary phase. There are a total of 96 unique phosphorylated sites, with a Ser/Thr/Tyr distribution of 63:28:5, in 77 proteins. Phosphoproteins identified in S. meliloti showed a wide distribution pattern regarding to functional categories, such as replication, transcription, translation, posttranslational modification, transport and metabolism of amino acids, carbohydrate, inorganic ion, succinoglycan etc. Ser/Thr/Tyr phosphosites identified within the conserved motif in proteins of key cellular function indicate a crucial role of phosphorylation in modulating cellular physiology. Moreover, phosphorylation in proteins involved in processes related to rhizobial adaptation was also discussed, such as those identified in SMa0114 and PhaP2 (polyhydroxybutyrate synthesis, ActR (pH stress and microaerobic adaption, SupA (potassium stress, chaperonin GroEL2 (viability and potentially symbiosis, and ExoP (succinoglycan synthesis and secretion. These Ser/Thr/Tyr phosphosites identified herein would be helpful for our further investigation and understanding of the role of phosphorylation in rhizobial physiology.

  8. Numerical study of the phase separation in binary lipid membrane containing protein inclusions under stationary shear flow.

    Science.gov (United States)

    Chen, Xiao-Bo; Shi, Hui-Ji; Niu, Li-Sha

    2009-03-26

    The phase separation of lipids is believed to be responsible for the formation of lipid rafts in biological cell membrane. In the present work, a continuum model and a particle model are constructed to study the phase separation in binary lipid membrane containing inclusions under stationary shear flow. In each model, employing the cell dynamical system (CDS) approach, the kinetic equations of the confusion-advection process are numerically solved. Snapshot figures of the phase morphology are performed to intuitively display such phase evolving process. Considering the effects from both the inclusions and the shear flow, the time growth law of the characteristic domain size is discussed.

  9. Fractal butterflies of chiral fermions in bilayer graphene: Phase transitions and emergent properties

    Science.gov (United States)

    Ghazaryan, Areg; Chakraborty, Tapash

    2015-12-01

    We have studied the influence of electron-electron interaction on the fractal butterfly spectrum of Dirac fermions in biased bilayer graphene in the fractional quantum Hall effect (FQHE) regime. We demonstrate that the butterfly spectrum exhibits remarkable phase transitions between the FQHE gap and the butterfly gap for chiral electrons in bilayer graphene, when the periodic potential strength or the bias voltage is varied. We also find that, in addition to those phase transitions, by varying the bias voltage one can effectively control the periodic potential strength experienced by the electrons. The electron-electron interaction causes the butterfly spectrum to exhibit new gaps inside the Bloch sub-bands not found in the single-particle case. We expect that both the observed phase transition and other new features in the butterfly spectrum of interacting Dirac fermions will be of great interest to researchers from diverse fields.

  10. Phase diagrams of charged colloidal rods: Can a uniaxial charge distribution break chiral symmetry?

    Science.gov (United States)

    Drwenski, Tara; Dussi, Simone; Hermes, Michiel; Dijkstra, Marjolein; van Roij, René

    2016-03-07

    We construct phase diagrams for charged rodlike colloids within the second-virial approximation as a function of rod concentration, salt concentration, and colloidal charge. Besides the expected isotropic-nematic transition, we also find parameter regimes with a coexistence between a nematic and a second, more highly aligned nematic phase including an isotropic-nematic-nematic triple point and a nematic-nematic critical point, which can all be explained in terms of the twisting effect. We compute the Frank elastic constants to see if the twist elastic constant can become negative, which would indicate the possibility of a cholesteric phase spontaneously forming. Although the twisting effect reduces the twist elastic constant, we find that it always remains positive. In addition, we find that for finite aspect-ratio rods the twist elastic constant is also always positive, such that there is no evidence of chiral symmetry breaking due to a uniaxial charge distribution.

  11. 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.

  12. A micro gas chromatography with separation capability enhanced by polydimethylsiloxane stationary phase functionalized by carbon nanotubes and graphene.

    Science.gov (United States)

    Li, Yubo; Zhang, Runzhou; Wang, Tao; Wang, Youhao; Wang, Yonghuan; Li, Lingfeng; Zhao, Weijun; Wang, Xiaozhi; Luo, Jikui

    2016-07-01

    Polydimethylsiloxane (PDMS) stationary phases functionalized with multi-walled carbon nanotubes (MWCNTs) and graphene, respectively, for the columns in micro gas chromatography are presented in this paper. To exploit the merits of MWCNTs and graphene in terms of their high specific surface area, low surface energy and chemical inertness, experimental conditions for separation (heating rate and final temperature of temperature programming, flow rate of carrier gas and the volume of samples injection) are investigated, and separations of both polar and nonpolar compound mixtures under these conditions are performed. Compared with PDMS-only coated stationary phases, the functionalization of the phases with carbon nano-materials improves the performance of columns in separation, repeatability, stability and revolution significantly.

  13. Study on the Chromatographic Behavior of Bases on Dodecylamine-N,N-dimethylenephosphonic Acid-Modified Zirconia Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    Yao Lifeng; Feng Yuqi; Da Shilu

    2006-01-01

    A new zirconia-based stationary phase(DPZ)was prepared by modifying zirconia with dodecylamine-N,N-dimethylenephosphonic acid(DDPA).DDPA was adsorbed on zirconia with only one phosphonic group,with the other being free.Besides the hydrophobic interaction provided by nonpolar dodecyl,DPZ also has dipolar interaction,ion-exchange or electrostatic repellent interaction provided by the free phosphonic group and amino group at different conditions.Separation of bases on this stationary phase was achieved with satisfaction owing to the various retention mechanisms.The influence of methanol content,pH value,ion types,and ionic strength of mobile phase are studied in detail.

  14. Influence of Mobile Phase Composition on the Enantioseparation of Methoxyl Flavanones with Self-prepared CDMPC Column and Chiral Recognition Mechanism

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The influence of different alcohol modifiers in mobile phase on the chiral separation of 4`-methoxyl flavanone, 5-methoxyl flavanone and 6-methoxyl flavanone on cellulose tris (3, 5-dimethylphenylcarbamate) (CDMPC) column was studied and the chiral recognition mechanism was discussed. Using hexane-tert-butanol (1.31 mol L-1) as the mobile phase, those three methoxyl flavanones were excellently separated on CDMPC chiral column.

  15. Crosslinked structurally-tuned polymeric ionic liquids as stationary phases for the analysis of hydrocarbons in kerosene and diesel fuels by comprehensive two-dimensional gas chromatography.

    Science.gov (United States)

    Zhang, Cheng; Park, Rodney A; Anderson, Jared L

    2016-04-01

    Structurally-tuned ionic liquids (ILs) have been previously applied as the second dimension column in comprehensive two-dimensional gas chromatography (GC×GC) and have demonstrated high selectivity in the separation of individual aliphatic hydrocarbons from other aliphatic hydrocarbons. However, the maximum operating temperatures of these stationary phases limit the separation of analytes with high boiling points. In order to address this issue, a series of polymeric ionic liquid (PIL)-based stationary phases were prepared in this study using imidazolium-based IL monomers via in-column free radical polymerization. The IL monomers were functionalized with long alkyl chain substituents to provide the needed selectivity for the separation of aliphatic hydrocarbons. Columns were prepared with different film thicknesses to identify the best performing stationary phase for the separation of kerosene. The bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-))-based PIL stationary phase with larger film thickness (0.28μm) exhibited higher selectivity for aliphatic hydrocarbons and showed a maximum allowable operating temperature of 300°C. PIL-based stationary phases containing varied amount of IL-based crosslinker were prepared to study the effect of the crosslinker on the selectivity and thermal stability of the resulting stationary phase. The optimal resolution of aliphatic hydrocarbons was achieved when 50% (w/w) of crosslinker was incorporated into the PIL-based stationary phase. The resulting stationary phase exhibited good selectivity for different groups of aliphatic hydrocarbons even after being conditioned at 325°C. Finally, the crosslinked PIL-based stationary phase was compared with SUPELCOWAX 10 and DB-17 columns for the separation of aliphatic hydrocarbons in diesel fuel. Better resolution of aliphatic hydrocarbons was obtained when employing the crosslinked PIL-based stationary phase as the second dimension column.

  16. 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.

  17. Microstructure-based analysis and simulation of flow and mass transfer in chromatographic stationary phases

    Science.gov (United States)

    Koku, Harun

    Limitations of mass transfer in chromatographic bioseparations employing traditional packed particles have fuelled the inception and development of alternative stationary phases with improved performance characteristics. This work investigates case studies in two categories of these alternative media, namely polymer-modified packed particles and continuous monolithic phases, for insight into their enhanced properties. Specifically, high-resolution microscopy techniques and image-based analysis algorithms were implemented to extract morphology information for these materials, in an attempt to elucidate the relation between microstructure and performance. For the monolith, mesoscopic simulation methods were also employed for a more rigorous analysis of the flow and dispersion behavior. Scanning and transmission electron microscopy images of the commercial polymer-modified, agarose-based particle Sepharose XL were compared to those for its unmodified counterpart, Sepharose FF. Local regions in the composite dextran-agarose Sepharose XL particles were noted to exhibit a denser network of fibers and smaller pore sizes overall, compared to those in the traditional Sepharose FF particles. Images of particles equilibrated with high concentrations of protein revealed a significant difference in protein localization patterns, with the stained protein in XL occupying a markedly higher area fraction of the images. This suggests a higher volume available for adsorption and provides visual clues into how the consistently higher static capacity of these polymer-modified particles is manifested. Treatment of the XL particles with dextranase, an enzyme that breaks down dextran, resulted in a reduction of protein coverage, providing evidence that it is indeed the dextran that is responsible for the improved static capacity in this polymer-modified stationary phase. Imaging and image analysis techniques were also used to analyze the commercial CIM(TM) disk monolith. Two- and three

  18. The helical phase of chiral nematic liquid crystals as the Bianchi VII(0) group manifold

    CERN Document Server

    Gibbons, G W

    2011-01-01

    We show that the optical structure of the helical phase of a chiral nematic is naturally associated with the Bianchi VII(0) group manifold. The Joets-Ribotta metric governing propagation of the extraordinary rays is invariant under the simply transitive action of the universal cover of the three dimensional Euclidean group of two dimensions. Thus extraordinary light rays are geodesics of a left-invariant metric on this Bianchi type VII(0) group. We are able to solve by separation of variables both the wave equation and the Hamilton-Jacobi equation for this metric. The former reduces to Mathieu's equation and the later to the quadrantal pendulum equation. We further discuss Maxwell's equations for uniaxial optical materials where the configuration is invariant under a group action. The material is not assumed to be impedance matched, thus going beyond the usual scope of transformation optics. We show that for a chiral nematic in its helical phase Maxwell's equations reduce to a generalised Mathieu equation. Ou...

  19. Development and Validation of a Reversed-Phase Chiral HPLC Method to Determine the Chiral Purity of Bulk Batches of (S)-Enantiomer in Afoxolaner.

    Science.gov (United States)

    Kumar, Satish; Rustum, Abu; Padivitage, Nilusha

    2016-10-13

    Afoxolaner is a new antiparasitic molecule from the isoxazoline family that acts on insect acarine γ-aminobutyric acid and glutamate receptors. Afoxolaner is a racemic mixture, which has a chiral center at the isoxazoline ring. A reversed-phase chiral HPLC method has been developed to determine the chiral purity of bulk batches of (S)-enantiomer in afoxolaner for the first time. This method can also be used to verify that afoxolaner is a racemic mixture, which was demonstrated by specific rotation. ChromSword, an artificial intelligence method development tool, was used for initial method development. The column selected for the final method was CHIRALPAK AD-RH (150 × 4.6 mm, 5 μm particle size), maintained at 45°C, and isocratic elution using water-isopropanol-acetonitrile (40 + 50 + 10, v/v/v) as the mobile phase with a detection wavelength of 312 nm. The run time for the method was 11 min. The resolution and selectivity factors of the two enantiomers were 2.3 and 1.24, respectively. LOQ and LOD of the method were 1.6 and 0.8 μg/mL, respectively. This method was appropriately validated according to International Conference on Harmonization guidelines for its intended use.

  20. Silica gel microspheres decorated with covalent triazine-based frameworks as an improved stationary phase for high performance liquid chromatography.

    Science.gov (United States)

    Zhao, Wenjie; Hu, Kai; Hu, Chenchen; Wang, Xiaoyu; Yu, Ajuan; Zhang, Shusheng

    2017-03-03

    A new stationary phase for high performance liquid chromatography (HPLC) applications based on silica gel microspheres decorated with covalent triazine-based frameworks (CTF-SiO2) composite has been reported here. In this new hybrid material, sheet-like covalent triazine-based frameworks (CTF) were grown onto the supporting silica spheres, in order to achieve improved chromatographic separation and selectivity. The new material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. The chromatographic performance and retention mechanism of the new stationary phase were investigated in reversed-phase mode and compared against standard C18 and cyano-modified silica (CN-SiO2) columns. A variety of different probe molecules were analyzed, including mono-substituted benzenes, polycyclic aromatic hydrocarbons, phenols, anilines and bases. The synergism of triazine and aromatic moieties provided several different retention mechanisms, thus improving the selectivity in the CTF-SiO2 composite. The good column packing properties of the uniform silica microspheres combined with the separation ability of the CTF frameworks make the new CTF-SiO2 material a potentially useful stationary phase for the analysis of complex samples.

  1. Immunoassay of paralytic shellfish toxins by moving magnetic particles in a stationary liquid-phase lab-on-a-chip.

    Science.gov (United States)

    Kim, Myoung-Ho; Choi, Suk-Jung

    2015-04-15

    In this study, we devised a stationary liquid-phase lab-on-a-chip (SLP LOC), which was operated by moving solid-phase magnetic particles in the stationary liquid phase. The SLP LOC consisted of a sample chamber to which a sample and reactants were added, a detection chamber containing enzyme substrate solution, and a narrow channel connecting the two chambers and filled with buffer. As a model system, competitive immunoassays of saxitoxin (STX), a paralytic shellfish toxin, were conducted in the SLP LOC using protein G-coupled magnetic particles (G-MPs) as the solid phase. Anti-STX antibodies, STX-horseradish peroxidase conjugate, G-MPs, and a STX sample were added to the sample chamber and reacted by shaking. While liquids were in the stationary state, G-MPs were transported from the sample chamber to the detection chamber by moving a magnet below the LOC. After incubation to allow the enzymatic reaction to occur, the absorbance of the detection chamber solution was found to be reciprocally related to the STX concentration of the sample. Thus, the SLP LOC may represent a novel, simple format for point-of-care testing applications of enzyme-linked immunosorbent assays by eliminating complicated liquid handling steps.

  2. Nuclear magnetic resonance and high-performance liquid chromatographic evaluation of polymer-based stationary phases immobilized on silica.

    Science.gov (United States)

    Meyer, Christoph; Skogsberg, Urban; Welsch, Norbert; Albert, Klaus

    2005-06-01

    Three poly(ethylene-co-acrylic) acid copolymers (-CH(2)CH(2)-)(x)[CH(2)CH(CO(2)H)-](y) with different chain lengths and mass fractions of acrylic acid were covalently immobilized as stationary phases on silica via two variants of spacer molecules (3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane). Different mobilities of the alkyl chains in the stationary phases were observed using (13)C solid-state NMR spectroscopy. The stationary phases with more rigid trans-ordered alkyl chains had better selectivity for geometric beta-carotene and xanthophyll isomers (provitamin A derivatives). Also, all the separations of the analytes were affected by polar interactions with the chromatographic sorbent. This was further proved by separating more polar cis/trans retinoic acid isomers (vitamin A derivatives). (13)C high-resolution/magic-angle spinning (HR/MAS) NMR measurements of the chromatographic sorbents suspended in the mobile phase confirmed a dependence of molecular shape recognition ability on alkyl chain conformation.

  3. Consequences of simultaneous chiral symmetry breaking and deconfinement for the isospin symmetric phase diagram

    Science.gov (United States)

    Fischer, Tobias; Klähn, Thomas; Hempel, Matthias

    2016-08-01

    The thermodynamic bag model (tdBag) has been applied widely to model quark matter properties in both heavy-ion and astrophysics communities. Several fundamental physics aspects are missing in tdBag, e.g., dynamical chiral symmetry breaking (D χ SB) and repulsions due to the vector interaction are both included explicitly in the novel vBag quark matter model of Klähn and Fischer (Astrophys. J. 810, 134 (2015)). An important feature of vBag is the simultaneous D χ SB and deconfinement, where the latter links vBag to a given hadronic model for the construction of the phase transition. In this article we discuss the extension to finite temperatures and the resulting phase diagram for the isospin symmetric medium.

  4. Kagome Chiral Spin Liquid as a Gauged U (1 ) Symmetry Protected Topological Phase

    Science.gov (United States)

    He, Yin-Chen; Bhattacharjee, Subhro; Pollmann, Frank; Moessner, R.

    2015-12-01

    While the existence of a chiral spin liquid (CSL) on a class of spin-1 /2 kagome antiferromagnets is by now well established numerically, a controlled theoretical path from the lattice model leading to a low-energy topological field theory is still lacking. This we provide via an explicit construction starting from reformulating a microscopic model for a CSL as a lattice gauge theory and deriving the low-energy form of its continuum limit. A crucial ingredient is the realization that the bosonic spinons of the gauge theory exhibit a U (1 ) symmetry protected topological (SPT) phase, which upon promoting its U (1 ) global symmetry to a local gauge structure ("gauging"), yields the CSL. We suggest that such an explicit lattice-based construction involving gauging of a SPT phase can be applied more generally to understand topological spin liquids.

  5. Consequences of simultaneous chiral symmetry breaking and deconfinement for the isospin symmetric phase diagram

    CERN Document Server

    Fischer, Tobias; Hempel, Matthias

    2016-01-01

    The thermodynamic bag model (tdBag) has been applied widely to model quark matter properties in both heavy-ion and astrophysics communities. Several fundamental physics aspects are missing in tdBag, e.g., dynamical chiral symmetry breaking (D$\\chi$SB) and repulsions due to the vector interaction are both included explicitly in the novel vBag quark matter model of Kl\\"ahn and Fischer (2015) (Astrophys. J. 810, 134 (2015)). An important feature of vBag is the simultaneous D$\\chi$SB and deconfinement, where the latter links vBag to a given hadronic model for the construction of the phase transition. In this article we discuss the extension to finite temperatures and the resulting phase diagram for the isospin symmetric medium.

  6. Low-Energy Kπ Phase Shifts in Chiral SU(3) Quark Model

    Institute of Scientific and Technical Information of China (English)

    HUANG Fei; ZHANG Zong-Ye; YU You-Wen

    2005-01-01

    The low-energy region kaon-pion S- and P-wave phase shifts with isospin I = 1/2 and I = 3/2 are dynamically studied in the chiral SU(3) quark model by solving a resonating group method equation. The model parameters are taken to be the values fitted by the energies of the baryon ground states and the kaon-nucleon elastic scattering phase shifts of different partial waves. As a preliminary study the s-channel q(-q) annihilation interactions are not included since they only act in the very short range and are subsequently assumed to be unimportant in the low-energy domain. The numerical results are in qualitative agreement with the experimental data.

  7. Consequences of simultaneous chiral symmetry breaking and deconfinement for the isospin symmetric phase diagram

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Tobias; Klaehn, Thomas [University of Wroclaw, Institute of Theoretical Physics, Wroclaw (Poland); Hempel, Matthias [University of Basel, Department of Physics, Basel (Switzerland)

    2016-08-15

    The thermodynamic bag model (tdBag) has been applied widely to model quark matter properties in both heavy-ion and astrophysics communities. Several fundamental physics aspects are missing in tdBag, e.g., dynamical chiral symmetry breaking (D χ SB) and repulsions due to the vector interaction are both included explicitly in the novel vBag quark matter model of Klaehn and Fischer (Astrophys. J. 810, 134 (2015)). An important feature of vBag is the simultaneous D χ SB and deconfinement, where the latter links vBag to a given hadronic model for the construction of the phase transition. In this article we discuss the extension to finite temperatures and the resulting phase diagram for the isospin symmetric medium. (orig.)

  8. Kagome Chiral Spin Liquid as a Gauged U(1) Symmetry Protected Topological Phase.

    Science.gov (United States)

    He, Yin-Chen; Bhattacharjee, Subhro; Pollmann, Frank; Moessner, R

    2015-12-31

    While the existence of a chiral spin liquid (CSL) on a class of spin-1/2 kagome antiferromagnets is by now well established numerically, a controlled theoretical path from the lattice model leading to a low-energy topological field theory is still lacking. This we provide via an explicit construction starting from reformulating a microscopic model for a CSL as a lattice gauge theory and deriving the low-energy form of its continuum limit. A crucial ingredient is the realization that the bosonic spinons of the gauge theory exhibit a U(1) symmetry protected topological (SPT) phase, which upon promoting its U(1) global symmetry to a local gauge structure ("gauging"), yields the CSL. We suggest that such an explicit lattice-based construction involving gauging of a SPT phase can be applied more generally to understand topological spin liquids.

  9. Regenerated silica gel as stationary phase on vacuum column chromatography to purify temulawak’s extracts

    Energy Technology Data Exchange (ETDEWEB)

    Cahyono, Bambang; Maduwu, Ratna Dewi; Widayat,; Suzery, Meiny [Organic Chemistry Laboratory, Departement of Chemistry, Diponegoro University Jln Prof. Soedharto SH, Tembalang, Semarang 50275, Indonesia Tel / Fax: (024) 7460058 (Indonesia)

    2015-12-29

    Commercial silica gel only used once by many researchers and affected high cost for purification process, also less support the green chemistry program. This research focused in regeneration silica gel that used purification of temulawak’s extracts (Curcuma xanthorrhiza Roxb) by vacuum column chromatography. Sample extracts (contains 10.1195±0.5971% of curcuminoids) was purified by vacuum column chromatography (pressure: 45 kPa, column: 100mm on length and 16mm on diameter). Ethanol 96% and acetone were compared as eluent. The amount of solvent and yield of curcuminoids used as indicator purification. The silica gel was regenerated with heating in 600°C for 8 hours The silica gels were analyzed by IR spectroscopy and X-ray diffraction. Furthermore, regenerated silica gel was used as the stationary phase in vacuum column chromatography under the same conditions with the previous purification. All the purification experiments were performed in three repetitions. Based on regression equation, y=0.132x+0.0011 (r{sup 2}=0.9997) the yield of curcuminoids on purified products using ethanol as the eluent was improved 4.26% (to 14.3724±0.5749%) and by acetone was improved 3,03% (to 13.1450 ±0.6318%). The IR spectrum of both silica gel showed the same vibration profile and also there were three crystallinity peaks missing on its X-ray diffraction. Regenerated silica gel has the same performance with new silica gel in purification of temulawak’s extract: by ethanol has increased 4.08% (14.1947±0.7415%) and 2.93% (13.0447±0.4822) by acetone. In addition, all purification products showed similar TLC profiles. Purification using regenerated silica gel as the adsorbent on vacuum column chromatography has exactly same potential with the new silica gel.

  10. A mechanistic model of ion-exchange chromatography on polymer fiber stationary phases.

    Science.gov (United States)

    Winderl, Johannes; Hahn, Tobias; Hubbuch, Jürgen

    2016-12-02

    Fibers are prominent among novel stationary phase supports for preparative chromatography. Several recent studies have highlighted the potential of fiber-based adsorbents for high productivity downstream processing in both batch and continuous mode, but so far the development of these materials and of processes employing these materials has solely been based on experimental data. In this study we assessed whether mechanistic modeling can be performed on fiber-based adsorbents. With a column randomly filled with short cut hydrogel grafted anion exchange fibers, we tested whether tracer, linear gradient elution, and breakthrough data could be reproduced by mechanistic models. Successful modeling was achieved for all of the considered experiments, for both non-retained and retained molecules. For the fibers used in this study the best results were obtained with a transport-dispersive model in combination with a steric mass action isotherm. This approach accurately accounted for the convection and dispersion of non-retained tracers, and the breakthrough and elution behaviors of three different proteins with sizes ranging from 6 to 160kDa were accurately modeled, with simulation results closely resembling the experimental data. The estimated model parameters were plausible both from their physical meaning, and from an analysis of the underlying model assumptions. Parameters were determined within good confidence levels; the average confidence estimate was below 7% for confidence levels of 95%. This shows that fiber-based adsorbents can be modeled mechanistically, which will be valuable for the future design and evaluation of these novel materials and for the development of processes employing such materials.

  11. Regenerated silica gel as stationary phase on vacuum column chromatography to purify temulawak's extracts

    Science.gov (United States)

    Cahyono, Bambang; Maduwu, Ratna Dewi; Widayat, Suzery, Meiny

    2015-12-01

    Commercial silica gel only used once by many researchers and affected high cost for purification process, also less support the green chemistry program. This research focused in regeneration silica gel that used purification of temulawak's extracts (Curcuma xanthorrhiza Roxb) by vacuum column chromatography. Sample extracts (contains 10.1195±0.5971% of curcuminoids) was purified by vacuum column chromatography (pressure: 45 kPa, column: 100mm on length and 16mm on diameter). Ethanol 96% and acetone were compared as eluent. The amount of solvent and yield of curcuminoids used as indicator purification. The silica gel was regenerated with heating in 600°C for 8 hours The silica gels were analyzed by IR spectroscopy and X-ray diffraction. Furthermore, regenerated silica gel was used as the stationary phase in vacuum column chromatography under the same conditions with the previous purification. All the purification experiments were performed in three repetitions. Based on regression equation, y=0.132x+0.0011 (r2=0.9997) the yield of curcuminoids on purified products using ethanol as the eluent was improved 4.26% (to 14.3724±0.5749%) and by acetone was improved 3,03% (to 13.1450 ±0.6318%). The IR spectrum of both silica gel showed the same vibration profile and also there were three crystallinity peaks missing on its X-ray diffraction. Regenerated silica gel has the same performance with new silica gel in purification of temulawak's extract: by ethanol has increased 4.08% (14.1947±0.7415%) and 2.93% (13.0447±0.4822) by acetone. In addition, all purification products showed similar TLC profiles. Purification using regenerated silica gel as the adsorbent on vacuum column chromatography has exactly same potential with the new silica gel.

  12. Numerical simulation of the phase separation in binary lipid membrane under the effect of stationary shear flow.

    Science.gov (United States)

    Chen, Xiao-Bo; Niu, Li-Sha; Shi, Hui-Ji

    2008-06-01

    A numerical simulation of the phase separation in binary lipid membrane under the effect of stationary shear flow is performed. We numerically solved the modified two-dimensional time-dependent Ginzburg-Landau (TDGL) equations with an external velocity term, employing the CDS (i.e., Cell Dynamical System) technique. In the present simulation, stationary shear flows with different shear rates are taken into account. The evolution process of the phase separation is illustrated macroscopically via the snapshot figures and simulated scattering patterns at several typical moments. For each case, the growth exponents of the characteristic domain sizes in both directions parallel and perpendicular to the flow are studied, and the domain area as well. Also, the behavior of the excess viscosity has been investigated, which is a peculiar rheological indicator of such a membrane system with domain structures.

  13. Topological electromagnetic responses of bosonic quantum Hall, topological insulator, and chiral semimetal phases in all dimensions

    Science.gov (United States)

    Lapa, Matthew F.; Jian, Chao-Ming; Ye, Peng; Hughes, Taylor L.

    2017-01-01

    We calculate the topological part of the electromagnetic response of bosonic integer quantum Hall (BIQH) phases in odd (space-time) dimensions, and bosonic topological insulator (BTI) and bosonic chiral semimetal (BCSM) phases in even dimensions. To do this, we use the nonlinear sigma model (NLSM) description of bosonic symmetry-protected topological (SPT) phases, and the method of gauged Wess-Zumino (WZ) actions. We find the surprising result that for BIQH states in dimension 2 m -1 (m =1 ,2 ,⋯ ), the bulk response to an electromagnetic field Aμ is characterized by a Chern-Simons term for Aμ with a level quantized in integer multiples of m ! (factorial). We also show that BTI states (which have an extra Z2 symmetry) can exhibit a Z2-breaking quantum Hall effect on their boundaries, with this boundary quantum Hall effect described by a Chern-Simons term at level m/! 2 . We show that the factor of m ! can be understood by requiring gauge invariance of the exponential of the Chern-Simons term on a general Euclidean manifold, and we also use this argument to characterize the electromagnetic and gravitational responses of fermionic SPT phases with U(1 ) symmetry in all odd dimensions. We then use our gauged boundary actions for the BIQH and BTI states to (i) construct a bosonic analog of a chiral semimetal (BCSM) in even dimensions, (ii) show that the boundary of the BTI state exhibits a bosonic analog of the parity anomaly of Dirac fermions in odd dimensions, and (iii) study anomaly inflow at domain walls on the boundary of BTI states. In a series of Appendixes we derive important formulas and additional results. In particular, in Appendix A we use the connection between equivariant cohomology and gauged WZ actions to give a mathematical interpretation of the actions for the BIQH and BTI boundaries constructed in this paper.

  14. Vacuum Polarization and Dynamical Chiral Symmetry Breaking: Phase Diagram of QED with Four-Fermion Contact Interaction

    CERN Document Server

    Akram, F; Gutierrez-Guerrero, L X; Masud, B; Rodriguez-Quintero, J; Calcaneo-Roldan, C; Tejeda-Yeomans, M E

    2012-01-01

    We study chiral symmetry breaking for fundamental charged fermions coupled electromagnetically to photons with the inclusion of four-fermion contact self-interaction term. We employ multiplicatively renormalizable models for the photon dressing function and the electron-photon vertex which minimally ensures mass anomalous dimension = 1. Vacuum polarization screens the interaction strength. Consequently, the pattern of dynamical mass generation for fermions is characterized by a critical number of massless fermion flavors above which chiral symmetry is restored. This effect is in diametrical opposition to the existence of criticality for the minimum interaction strength necessary to break chiral symmetry dynamically. The presence of virtual fermions dictates the nature of phase transition. Miransky scaling laws for the electromagnetic interaction strength and the four-fermion coupling, observed for quenched QED, are replaced by a mean-field power law behavior corresponding to a second order phase transition. T...

  15. Evaluation of a medium-polarity ionic liquid stationary phase in the analysis of flavor and fragrance compounds.

    Science.gov (United States)

    Ragonese, Carla; Sciarrone, Danilo; Tranchida, Peter Quinto; Dugo, Paola; Dugo, Giovanni; Mondello, Luigi

    2011-10-15

    The present research is focused on the evaluation, in terms of efficiency and polarity, of a recently introduced gas chromatography (GC) column, coated with a 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethansulfonyl) amide ionic-liquid stationary phase (SLB-IL59) and its application to the analysis of a complex essential oil. The ionic liquid column demonstrated very good efficiency, in terms of plate number, and a polarity close to that of the 100% poly(ethyleneglycol) stationary phase. In this preliminary evaluation, the SLB-IL59 30 m column was subjected to bleeding measurements, by means of conventional gas chromatography/mass spectrometry (GC/MS) and, in addition, of comprehensive 2D GC. The SLB-IL59 column (30 m × 0.20 μm d(f), 0.25 mm i.d.) was then evaluated in the analysis of typical essential oil constituents, in the form of pure standard compounds. Resolution toward several analytes was measured and the results were compared to those obtained with both apolar [silphenylene polymer, equivalent to poly(5% diphenyl/95% dimethylsiloxane)] and medium-polarity [100% poly(ethyleneglycol)] stationary phases, namely, the most common columns employed in the analysis of essential oils; peak symmetry, for different essential oil constituents, was also measured and expressed through tailing factors (at 10% of peak height). The final part of the investigation was devoted to the GC/MS analysis of lemon essential oil, with GC-flame ionization detection (FID) used for quantification. Linear retention indices of all the identified compounds were determined, and the data obtained were compared to those attained on the apolar and "wax" columns. The results obtained in the present investigation reveal the great potential of this novel stationary phase, as a medium-polarity alternative, in the analysis of essential oils.

  16. Synthesis and characterization of novel stationary phases for small scale liquid chromatographic separations of proteins and nanoparticles

    Science.gov (United States)

    Hutanu, Daniela

    The emerging field of nanotechnology strictly requires the micro-scaling of the available separation technology and the design of novel devices for separations of molecules of interest. The separation of proteins and nanoparticles is challenging due to their relatively large size, non-specific adherence to surfaces and instability in many solvents. This dissertation presents the synthesis and characterization of novel stationary phases for use in separations of proteins or nanoparticles in both capillary and microchip formats. In order to separate blood proteins with high specificity, a DNA aptamer selected for alpha-thrombin was employed as an affinity component of the stationary phases. Silica surfaces and organic monoliths were modified with the aptamer via an azlactone linkage and have demonstrated highly efficient separations of thrombin from a mixture in the microscale. The high efficiency of the protein separation (HETP = 276 mum, RS = 1.7) is comparable with macroscale results using antibodies as the affinity factor. Novel hybrid inorganic-organic polysilsesquioxane stationary phases were synthesized by way of surfactant templated polymerization of bridged alcoxy-silyl ethane monomers, in presence of sodium hydroxide. The novel materials were successful in size exclusion separation of polystyrene standards with molecular diameters of 0.3-2.4 nm. A hybrid inorganic-organic polysilsesquioxane sorbent also proved useful for small scale separations of triphenyl phosphine protected gold nanoparticles, based on a sorptive mechanism instead of a size exclusion mechanism. Polysilsesquioxanes were easily synthesized in-situ inside fused silica capillary columns and PMMA microchip channels in order to facilitate integration with a micro-reactor. The novel stationary phases proved efficient for separation of proteins and nanoparticles in the micro-scale format and can further be utilized for online purification and separation of these difficult compounds.

  17. Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones.

    Science.gov (United States)

    Aral, Hayriye; Aral, Tarık; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

    2013-11-15

    A novel amide-bonded silica stationary phase was prepared starting from N-Boc-phenylalanine, cyclohexylamine and spherical silica gel (4 µm, 60 Å). The amide ligand was synthesised with high yield. The resulting amide bonded stationary phase was characterised by SEM, IR and elemental analysis. The resulting selector bearing a polar amide group is used for the reversed-phase chromatography separation of different classes of thirteen phytohormones (plant hormones). The chromatographic behaviours of these analytes on the amide-silica stationary phase were compared with those of RP-C18 column under same conditions. The effects of different separation conditions, such as mobile phase, pH value, flow rate and temperature, on the separation and retention behaviours of the 13 phytohormones in this system were studied. The optimum separation was achieved using reversed-phase HPLC gradient elution with an aqueous mobile phase containing pH=6.85 potassium phosphate buffer (20 mM) and acetonitrile with a 22 °C column temperature. Under these experimental conditions, the 12 phytohormones could be separated and detected at 230 or 270 nm within 26 min.

  18. Schizosaccharomyces pombe Homologs of Human DJ-1 Are Stationary Phase-Associated Proteins That Are Involved in Autophagy and Oxidative Stress Resistance.

    Directory of Open Access Journals (Sweden)

    Yang Su

    Full Text Available The Parkinson's disease protein DJ-1 is involved in various cellular functions including detoxification of dicarbonyl compounds, autophagy and oxidative stress response. DJ-1 homologs are widely found in both prokaryotes and eukaryotes, constituting a superfamily of proteins that appear to be involved in stress response. Schizosaccharomyces pombe contains six DJ-1 homologs, designated Hsp3101-Hsp3105 and Sdj1 (previously named SpDJ-1. Here we show that deletion of any one of these six genes somehow affects autophagy during prolonged stationary phase. Furthermore, deletions of each of these DJ-1 homologs result in reduced stationary phase survival. Deletion of sdj1 also increases the sensitivity of stationary-phase cells to oxidative stress induced by hydrogen peroxide (H2O2 whereas overexpression of sdj1 has the opposite effect. Consistent with their role in stationary phase, expression of hsp3101, hsp3102, hsp3105 and sdj1, and to a lesser extent hsp3103 and hsp3104, is increased in stationary phase. The induction of hsp3101, hsp3102, hsp3105 and sdj1 involves the Sty1-regulated transcription factor Atf1 but not the transcription factor Pap1. Our results firmly establish that S. pombe homologs of DJ-1 are stationary-phase associated proteins and are likely involved in autophagy and antioxidant defense in stationary phase of S. pombe cells.

  19. Topology in the SU(Nf) chiral symmetry restored phase of unquenched QCD and axion cosmology

    CERN Document Server

    Azcoiti, Vicente

    2016-01-01

    We investigate the topological properties of unquenched QCD on the basis of numerical results of simulations at fixed topological charge, recently reported by Borsanyi et al., and analytical predictions of the dilute instanton gas approximation. We demonstrate that the mean value of the chiral condensate at fixed topological charge is, in both cases, inconsistent with the analytical prediction of the large volume expansion around the saddle point, and argue that the most plausible explanation for the failure of the saddle point expansion is a vacuum energy density theta-independent at high temperatures, but surprisingly not too high (T\\sim 2T_c), a result which would imply a vanishing topological susceptibility, and the absence of all physical effects of the U(1) axial anomaly at these temperatures. We also show that under a general assumption concerning the high temperature phase of QCD, where the SU(Nf)_A symmetry is restored, the analytical prediction for the chiral condensate at fixed topological charge i...

  20. Topology in the S U (Nf) chiral symmetry restored phase of unquenched QCD and axion cosmology

    Science.gov (United States)

    Azcoiti, Vicente

    2016-11-01

    We investigate the topological properties of unquenched QCD on the basis of numerical results of simulations at fixed topological charge, recently reported by Borsanyi et al. We demonstrate that their results for the mean value of the chiral condensate at fixed topological charge are inconsistent with the analytical prediction of the large-volume expansion around the saddle point, and argue that the most plausible explanation for the failure of the saddle-point expansion is a vacuum energy density that is θ -independent at high temperatures, but surprisingly not too high (T ˜2 Tc), a result which would imply a vanishing topological susceptibility and the absence of all physical effects of the U (1 ) axial anomaly at these temperatures. We also show that under a general assumption concerning the high-temperature phase of QCD, where the S U (Nf)A symmetry is restored, the analytical prediction for the chiral condensate at fixed topological charge is in very good agreement with the numerical results of Borsanyi et al., all effects of the axial anomaly should disappear, the topological susceptibility and all the θ derivatives of the vacuum energy density vanish, and the theory becomes θ independent at any T >Tc in the infinite-volume limit.

  1. Thermodynamics of the sorption of organic compounds on polyethylene glycol 400-permethylated β-cyclodextrin stationary phase and its enantioselectivity in gas chromatography

    Science.gov (United States)

    Kuraeva, Yu. G.; Onuchak, L. A.; Evdokimova, M. A.

    2016-08-01

    The thermodynamic characteristics of sorption of 24 organic compounds of various classes from the gas phase on the binary stationary phase based on polyethylene glycol 400 and permethylated β-cyclodextrin were determined. The influence of geometrical structure and optical activity of organic compounds on the possibility of forming sorbate-macrocycle complexes was examined. It was found that the studied stationary phase shows the enantioselectivity towards low-polar terpenes under the conditions of gas chromatography.

  2. Preparation, characterization and application of a reversed phase liquid chromatography/hydrophilic interaction chromatography mixed-mode C18-DTT stationary phase.

    Science.gov (United States)

    Wang, Qing; Long, Yao; Yao, Lin; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

    2016-01-01

    A mixed-mode chromatographic stationary phase, C18-DTT (dithiothreitol) silica (SiO2) was prepared through "thiol-ene" click chemistry. The obtained material was characterized by fourier transform infrared spectroscope, nitrogen adsorption analysis and contact angle analysis. Chromatographic performance of the C18-DTT was systemically evaluated by studying the effect of acetonitrile content, pH, buffer concentration of the mobile phase and column temperature. It was demonstrated that the novel stationary phase possessed reversed phase liquid chromatography (RPLC)/hydrophilic interaction liquid chromatography (HILIC) mixed-mode property. The stop-flow test revealed that C18-DTT exhibited excellent compatibility with 100% aqueous mobile phase. Additionally, the stability and column-to-column reproducibility of the C18-DTT material were satisfactory, with relative standard deviations of retention factor of the tested analytes (verapamil, fenbufen, guanine, tetrandrine and nicotinic acid) in the range of 1.82-3.72% and 0.85-1.93%, respectively. Finally, the application of C18-DTT column was demonstrated in the separation of non-steroidal anti-inflammatory drugs, aromatic carboxylic acids, alkaloids, nucleo-analytes and polycyclic aromatic hydrocarbons. It had great resolving power in the analysis of various compounds in HILIC and RPLC chromatographic conditions and was a promising RPLC/HILIC mixed-mode stationary phase.

  3. Multi-mode application of graphene quantum dots bonded silica stationary phase for high performance liquid chromatography.

    Science.gov (United States)

    Wu, Qi; Sun, Yaming; Zhang, Xiaoli; Zhang, Xia; Dong, Shuqing; Qiu, Hongdeng; Wang, Litao; Zhao, Liang

    2017-04-07

    Graphene quantum dots (GQDs), which possess hydrophobic, hydrophilic, π-π stacking and hydrogen bonding properties, have great prospect in HPLC. In this study, a novel GQDs bonded silica stationary phase was prepared and applied in multiple separation modes including normal phase, reversed phase and hydrophilic chromatography mode. Alkaloids, nucleosides and nucleobases were chosen as test compounds to evaluate the separation performance of this column in hydrophilic chromatographic mode. The tested polar compounds achieved baseline separation and the resolutions reached 2.32, 4.62, 7.79, 1.68 for thymidine, uridine, adenosine, cytidine and guanosine. This new column showed satisfactory chromatographic performance for anilines, phenols and polycyclic aromatic hydrocarbons in normal and reversed phase mode. Five anilines were completely separated within 10min under the condition of mobile phase containing only 10% methanol. The effect of water content, buffer concentration and pH on chromatographic separation was further investigated, founding that this new stationary phase showed a complex retention mechanism of partitioning, adsorption and electrostatic interaction in hydrophilic chromatography mode, and the multiple retention interactions such as π-π stacking and π-π electron-donor-acceptor interaction played an important role during the separation process. This GQDs bonded column, which allows us to adjust appropriate chromatography mode according to the properties of analytes, has possibility in actual application after further research.

  4. Effects of Tsallis distribution on parametric resonance in chiral phase transitions

    CERN Document Server

    Ishihara, Masamichi

    2016-01-01

    The parametric resonance was studied in chiral phase transitions when the momentum distribution is described by a Tsallis distribution. A Tsallis distribution has two parameters, the temperature $T$ and the entropic index $q$. The amplification was estimated in two cases: 1) expansionless case and 2) one dimensional expansion case. In an expansionless case, the temperature $T$ is constant, and the amplified modes as a function of $T$ were calculated for various $q$. In one dimensional expansion case, the temperature $T$ decreases as a function of the proper time, and the amplification as a function of the transverse momentum was calculated for various $q$. In the expansionless case, the following facts were found: 1) the larger the value $q$ is, the softer the amplified modes are for the first and second resonance bands, 2) the amplified mode of the first resonance band decreases and vanishes, as the temperature $T$ increases, and 3) the amplified mode of the second resonance band decreases and approaches to ...

  5. Porous silicon as a stationary phase for shear-driven chromatography

    NARCIS (Netherlands)

    Clicq, D.; Tjerkstra, R.W.; Gardeniers, J.G.E.; Berg, van den Albert; Baron, G.V.; Desmet, G.

    2004-01-01

    We report on the possibility to strongly increase the mass loadability and retention capacity of shear-driven chromatography (SDC) channels by growing a thin porous silicon layer on the stationary wall part. The thickness of the produced porous silicon layers was found to increase linearly with the

  6. Preparation and evaluation of monolithic molecularly imprinted stationary phase for S-naproxen

    Institute of Scientific and Technical Information of China (English)

    De-Miao Chen; Qiang Fu; Wei Du; Si-Juan Sun; Ping Huang; Chun Chang

    2011-01-01

    An S-naproxen(S-NAP)molecularly imprinted monolithic stationary phase(MIMSP)with specific recognition for S-NAP and naproxen(NAP)was prepared by in situ technique,utilizing 4-vinylpridine(4-VP)as a function monomer,ethylene glycol dimethacrylate(EDMA)as a

  7. Growth advantage in stationary-phase (GASP) phenotype in long-term survival strains of Geobacter sulfurreducens.

    Science.gov (United States)

    Helmus, Ruth A; Liermann, Laura J; Brantley, Susan L; Tien, Ming

    2012-01-01

    Geobacter sulfurreducens exists in the subsurface and has been identified in sites contaminated with radioactive metals, consistent with its ability to reduce metals under anaerobic conditions. The natural state of organisms in the environment is one that lacks access to high concentrations of nutrients, namely electron donors and terminal electron acceptors (TEAs). Most studies have investigated G. sulfurreducens under high-nutrient conditions or have enriched for it in environmental systems via acetate amendments. We replicated the starvation state through long-term batch culture of G. sulfurreducens, where both electron donor and TEA were scarce. The growth curve revealed lag, log, stationary, death, and survival phases using acetate as electron donor and either fumarate or iron(III) citrate as TEA. In survival phase, G. sulfurreducens persisted at a constant cell count for as long as 23 months without replenishment of growth medium. Geobacter sulfurreducens demonstrated an ability to acquire a growth advantage in stationary-phase phenotype (GASP), with strains derived from subpopulations from death- or survival phase being able to out-compete mid-log-phase populations when co-cultured. The molecular basis for GASP was not because of any detectable mutation in the rpoS gene (GSU1525) nor because of a mutation in a putative homolog to Escherichia coli lrp, GSU3370.

  8. Scaling properties of the chiral phase transition in the low density region of two-flavor QCD with improved Wilson fermions

    CERN Document Server

    Umeda, T; Kanaya, K; Maezawa, Y; Nakagawa, Y; Ohno, H; Saito, H; Yoshida, S

    2013-01-01

    We study scaling behavior of a chiral order parameter in the low density region, performing a simulation of two-flavor QCD with improved Wilson quarks. The scaling behavior of the chiral order parameter defined by a Ward-Takahashi identity agrees with the scaling function of the three-dimensional O(4) spin model at zero chemical potential. We extend the scaling study to finite density QCD. Applying the reweighting method and calculating derivatives of the chiral order parameter with respect to the chemical potential, the scaling properties of the chiral phase transition are discussed in the low density region. We moreover calculate the curvature of the phase boundary of the chiral phase transition in the temperature and chemical potential plane assuming the O(4) scaling relation.

  9. Prediction of the zeta potentials and ionic descriptors of a silica hydride stationary phase with mobile phases of different pH and ionic strength.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Matyska, Maria T; Pesek, Joseph J; Boysen, Reinhard I; Hearn, Milton T W

    2015-02-15

    In this study, the zeta potentials of a silica hydride stationary phase (Diamond Hydride™) in the presence of different water-acetonitrile mixtures (from 0-80% (v/v) acetonitrile) of different ionic strengths (from 0-40mM) and pH values (from pH 3.0-7.0) have been investigated. Debye-Hückel theory was applied to explain the effect of changes in the pH and ionic strength of these aqueous media on the negative zeta potential of this stationary phase. The experimental zeta potentials of the Diamond Hydride™ particles as a function of acetonitrile content up to 50% (v/v) correlated (R(2)=0.998) with the predicted zeta potential values based on this established theory, when the values of the dissociation constant of all related species, as well as viscosity, dielectric constant and refractive index of the aqueous medium were taken into consideration. Further, the retention behavior of basic, acidic and neutral analytes was investigated under mobile phase conditions of higher pH and lower ionic strength. Under these conditions, the Diamond Hydride™ stationary phase surface became more negative, as assessed from the increasingly more negative zeta potentials, resulting in the ion exchange characteristics becoming more dominant and the basic analytes showing increasing retention. Ionic descriptors were derived from these chromatographic experiments based on the assumption that linear solvation energy relationships prevail. The results were compared with predicted ionic descriptors based on the different calculated zeta potential values resulting in an overall correlation of R(2)=0.888. These studies provide fundamental insights into the impact on the separation performance of changes in the zeta potential of the Diamond Hydride™ surface with the results relevant to other silica hydride and, potentially, to other types of stationary phase materials.

  10. Preparation and chromatographic evaluation of a newly designed steviol glycoside modified-silica stationary phase in hydrophilic interaction liquid chromatography and reversed phase liquid chromatography.

    Science.gov (United States)

    Liang, Tu; Fu, Qing; Shen, Aijin; Wang, Hui; Jin, Yu; Xin, Huaxia; Ke, Yanxiong; Guo, Zhimou; Liang, Xinmiao

    2015-04-03

    A diterpene glycoside compound, rebaudioside A (commonly abbreviated as RA), was immobilized onto porous silica surface through "thiol-ene" click chemistry strategy. The successful immobilization of the RA on the silica support was confirmed by FT-IR and elemental analysis. Chromatographic characteristics of the new stationary phase, named Click TE-RA, were evaluated by a set of diverse analytes such as carbohydrates, nucleosides, and organic acids in hydrophilic interaction liquid chromatography (HILIC) mode. The effects of water content, buffer pH and concentration were investigated and a typical HILIC retention feature of Click TE-RA was observed at high organic modifier content. The Click TE-RA stationary phase was further studied by a series of glycoside compounds. Tunable retention mechanisms from hydrophilic to hydrophobic interactions were observed. Separation of very polar compounds including oligosaccharides, nucleic acid bases and nucleosides using Click TE-RA in HILIC mode was successfully accomplished. In addition, separation of saponins both in HILIC and reversed-phase liquid chromatography (RPLC) modes was performed, demonstrating the presence of orthogonality between two different modes on Click TE-RA column. The multiple interactions induced by polar sugar group and hydrophobic aglycone group allowed this Click TE-RA to serve as a multi-mode stationary phase in two-dimensional liquid chromatography.

  11. Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

    Science.gov (United States)

    Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2015-05-29

    Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples.

  12. A humic acid stationary phase for the high performance liquid chromatography separation of buckminsterfullerenes: Theoretical and practical aspects

    Energy Technology Data Exchange (ETDEWEB)

    Casadei, Nicolas [Equipe des Sciences Separatives et Biopharmaceutiques (2SB)-EA 3924, Laboratoire de Chimie Analytique, Faculte de Medecine Pharmacie, Place Saint Jacques, 25030 Besancon Cedex (France); Thomassin, Mireille [Equipe des Sciences Separatives et Biopharmaceutiques (2SB)-EA 3924, Laboratoire de Chimie Analytique, Faculte de Medecine Pharmacie, Place Saint Jacques, 25030 Besancon Cedex (France); Guillaume, Yves-Claude [Equipe des Sciences Separatives et Biopharmaceutiques (2SB)-EA 3924, Laboratoire de Chimie Analytique, Faculte de Medecine Pharmacie, Place Saint Jacques, 25030 Besancon Cedex (France)]. E-mail: yves.guillaume@univ-fcomte.fr; Andre, Claire [Equipe des Sciences Separatives et Biopharmaceutiques (2SB)-EA 3924, Laboratoire de Chimie Analytique, Faculte de Medecine Pharmacie, Place Saint Jacques, 25030 Besancon Cedex (France)

    2007-04-11

    The influence of the mobile phase composition and column temperature on the chromatographic separation of five buckminsterfullerenes (C60, C70, C76, C78, C84) on a stationary phase based on silica gel with chemically bonded humic acid (Bonded humic acid column (BHAC)) was studied. The retention behavior of the fullerenes was measured under isocratic conditions with different mobile phase compositions, ranging from 0.05-0.70 (v/v) of toluene in cyclohexane. The column temperature was analysed in the range 35-75 deg. C. The retention factors of the five fullerenes do not depend linearly on the toluene fraction but follow a quadratic relationship. The best chromatographic conditions for baseline separation of the five fullerenes were selected. The retention of the fullerenes on the HA stationary phase was strongly affected by temperature. Positive values of thermodynamic parameters (changes of enthalpy and entropy) were due to the abnormal solubility behaviour of fullerenes in toluene in the temperature range 35-75 deg. C. The information obtained in this work makes this BHAC very simple to prepare and low cost, useful for fullerene research applications.

  13. Evaluation of innovative stationary phase ligand chemistries and analytical conditions for the analysis of basic drugs by supercritical fluid chromatography.

    Science.gov (United States)

    Desfontaine, Vincent; Veuthey, Jean-Luc; Guillarme, Davy

    2016-03-18

    Similar to reversed phase liquid chromatography, basic compounds can be highly challenging to analyze by supercritical fluid chromatography (SFC), as they tend to exhibit poor peak shape, especially those with high pKa values. In this study, three new stationary phase ligand chemistries available in sub -2 μm particle sizes, namely 2-picolylamine (2-PIC), 1-aminoanthracene (1-AA) and diethylamine (DEA), were tested in SFC conditions for the analysis of basic drugs. Due to the basic properties of these ligands, it is expected that the repulsive forces may improve peak shape of basic substances, similarly to the widely used 2-ethypyridine (2-EP) phase. However, among the 38 tested basic drugs, less of 10% displayed Gaussian peaks (asymmetry between 0.8 and 1.4) using pure CO2/methanol on these phases. The addition of 10mM ammonium formate as mobile phase additive, drastically improved peak shapes and increased this proportion to 67% on 2-PIC. Introducing the additive in the injection solvent rather than in the organic modifier, gave acceptable results for 2-PIC only, with 31% of Gaussian peaks with an average asymmetry of 1.89 for the 38 selected basic drugs. These columns were also compared to hybrid silica (BEH), DIOL and 2-EP stationary phases, commonly employed in SFC. These phases commonly exhibit alternative retention and selectivity. In the end, the two most interesting ligands used as complementary columns were 2-PIC and BEH, as they provided suitable peak shapes for the basic drugs and almost orthogonal selectivities.

  14. The phase boundary for the chiral transition in (2+1)-flavor QCD at small values of the chemical potential

    CERN Document Server

    Karsch, F; Miao, C; Mukherjee, S; Petreczky, P; Schmidt, C; Soeldner, W; Unger, W

    2010-01-01

    We determine the chiral phase transition line in (2+1)-flavor QCD for small values of the light quark chemical potential. We show that for small values of the chemical potential the curvature of the phase transition line can be deduced from an analysis of scaling properties of the chiral condensate and its susceptibilities. To do so we extend earlier studies of the magnetic equation of state in (2+1)-flavor QCD to finer lattice spacings, aT=1/8. We use these universal scaling properties of the chiral order parameter to extract the curvature of the transition line at two values of the cut-off, aT=1/4 and 1/8. We find that cut-off effects are small for the curvature parameter and determine the transition line in the chiral limit to leading order in the light quark chemical potential. We obtain Tc(\\mu_q)/Tc(0) = 1 - 0.059(2)(4) (\\mu_q/T)^2 +O(\\mu_q^4).

  15. 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.

  16. Magnetic anisotropy and the phase diagram of chiral MnSb2O6

    Science.gov (United States)

    Werner, J.; Koo, C.; Klingeler, R.; Vasiliev, A. N.; Ovchenkov, Y. A.; Polovkova, A. S.; Raganyan, G. V.; Zvereva, E. A.

    2016-09-01

    The magnetic phase diagram and low-energy magnon excitations of structurally and magnetically chiral MnSb2O6 are reported. The specific heat and the static magnetization are investigated in magnetic fields up to 9 and 30 T, respectively, while the dynamic magnetic properties are probed by X-band as well as tunable high-frequency electron spin-resonance spectroscopy. Below TN=11.5 K, we observe antiferromagnetic resonance modes which imply small but finite planar anisotropy showing up in a zero-field splitting of 20 GHz. The data are well described by means of an easy-plane two-sublattice model with the anisotropy field BA=0.02 T. The exchange field BE=13 T is obtained from the saturation field derived from the pulsed-field magnetization. A crucial role of the small anisotropy for the spin structure is reflected by competing antiferromagnetic phases appearing, at T =2 K, in small magnetic fields at BC 1 ≈0.5 T and BC 2=0.9 T. We discuss the results in terms of spin reorientation and of small magnetic fields favoring helical spin structure over the cycloidal ground state which, at B =0 , is stabilized by the planar anisotropy. Above TN, short-range magnetic correlations up to ≳60 K and magnetic entropy changes well above TN reflect the frustrated triangular arrangement of Mn2 + ions in MnSb2O6 .

  17. Phase diagram and two-particle structure of the $Z_3$-chiral Potts model

    CERN Document Server

    Von Gehlen, G

    1992-01-01

    We calculate the low-lying part of the spectrum of the $Z_3$-symmetrical chiral Potts quantum chain in its self-dual and integrable versions, using numerical diagonalisation of the hamiltonian for $N \\leq 12$ sites and extrapolation $N \\ra \\infty$. From the sequences of levels crossing we show that the massive phases have oscillatory correlation functions. We calculate the wave vector scaling exponent. In the high-temperature massive phase the pattern of the low-lying levels can be explained assuming the existence of two particles, with $Z_3$-charge $Q\\!=\\!1$ and $Q\\!=\\!2$, and their scattering states. In the superintegrable case the $Q\\!=\\!2$-particle has twice the mass of the $Q\\!=\\!1$-particle. Exponential convergence in $N$ is observed for the single particle gaps, while power convergence is seen for the scattering levels. In the high temperature limit of the self-dual model the parity violation in the particle dispersion relation is equivalent to the presence of a macroscopic momentum $P_m = \\pm \\vph/3$,...

  18. 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.

  19. Chromatographic retention behaviour, modelling and separation optimisation of the quaternary ammonium salt isometamidium chloride and related compounds on a range of reversed-phase liquid chromatographic stationary phases.

    Science.gov (United States)

    Schad, Gesa J; Euerby, Melvin R; Skellern, Graham G; Tettey, Justice N A

    2012-07-01

    This paper describes the reversed-phase liquid chromatographic behaviour of the trypanocidal quaternary ammonium salt isometamidium chloride and its related compounds on a range of liquid chromatographic phases possessing alkyl and phenyl ligands on the same inert silica. In a parallel study with various extended polar selectivity phases which possessed different hydrophobic/silanophilic (hydrogen bonding) activity ratios, the chromatographic retention/selectivities of the quaternary ammonium salts was shown to be due to a co-operative mechanism between hydrophobic and silanophilic interactions. The highly aromatic and planar isometamidium compounds were found to be substantially retained on stationary phases containing aromatic functionality via strong π-π interactions. The chemometric approach of principal component analysis was used to characterise the chromatographic behaviour of the isometamidium compounds on the differing phases and to help identify the dominant retention mechanism(s). Two-dimensional (temperature/gradient) retention modelling was employed to develop and optimise a rapid liquid chromatography method for the separation of the six quaternary ammonium salts within 2.5 min which would be suitable for bioanalysis using liquid chromatography-mass spectrometry. This is the first reported systematic study of the relationship between stationary phase chemistries and retention/selectivity for a group of quaternary ammonium salts.

  20. Separation performance of cucurbit[7]uril in ionic liquid-based sol-gel coating as stationary phase for capillary gas chromatography.

    Science.gov (United States)

    Wang, Xiaogang; Qi, Meiling; Fu, Ruonong

    2014-12-05

    Here we report the separation performance of a new stationary phase of cucurbit[7]uril (CB7) incorporated into an ionic liquid-based sol-gel coating (CB7-SG) for capillary gas chromatography (GC). The CB7-SG stationary phase showed an average polarity of 455, suggesting its polar nature. Abraham system constants revealed that its major interactions with analytes include H-bond basicity (a), dipole-dipole (s) and dispersive (l) interactions. The CB7-SG stationary phase achieved baseline separation for a wide range of analytes with symmetrical peak shapes and showed advantages over the conventional polar stationary phase that failed to resolve some critical analytes. Also, it exhibited different retention behaviors from the conventional stationary phase in terms of retention times and elution order. Most interestingly, in contrast to the conventional polar phase, the CB7-SG stationary phase exhibited longer retentions for analytes of lower polarity but relatively comparable retentions for polar analytes such as alcohols and phenols. The high resolving ability and unique retention behaviors of the CB7-SG stationary phase may stem from the comprehensive interactions of the aforementioned interactions and shape selectivity. Moreover, the CB7-SG column showed good peak shapes for analytes prone to peak tailing, good thermal stability up to 280°C and separation repeatability with RSD values in the range of 0.01-0.11% for intra-day, 0.04-0.41% for inter-day and 2.5-6.0% for column-to-column, respectively. As demonstrated, the proposed coating method can simultaneously address the solubility problem with CBs for the intended purpose and achieve outstanding GC separation performance.

  1. The VrrA sRNA controls a stationary phase survival factor Vrp of Vibrio cholerae.

    Science.gov (United States)

    Sabharwal, Dharmesh; Song, Tianyan; Papenfort, Kai; Wai, Sun Nyunt

    2015-01-01

    Small non-coding RNAs (sRNAs) are emerging regulatory elements in bacteria. The Vibrio cholerae sRNA VrrA has previously been shown to down-regulate outer membrane proteins (OmpA and OmpT) and biofilm matrix protein (RbmC) by base-pairing with the 5' region of the corresponding mRNAs. In this study, we present an additional target of VrrA in V. cholerae, the mRNA coding for the ribosome binding protein Vrp. Vrp is homologous to ribosome-associated inhibitor A (RaiA) of Escherichia coli which facilitates stationary phase survival through ribosome hibernation. We show that VrrA down-regulates Vrp protein synthesis by base-pairing to the 5' region of vrp mRNA and that the regulation requires the RNA chaperone protein, Hfq. We further demonstrate that Vrp is highly expressed during stationary phase growth and associates with the ribosome of V. cholerae. The effect of the Vrp protein in starvation survival is synergistic with that of the VC2530 protein, a homolog of the E. coli hibernation promoting factor HPF, suggesting a combined role for these proteins in ribosome hibernation in V. cholerae. Vrp and VC2530 are important for V. cholerae starvation survival under nutrient deficient conditions. While VC2530 is down-regulated in cells lacking vrrA, mutation of vrp results in VC2530 activation. This is the first report indicating a regulatory role for an sRNA, modulating stationary factors involved in bacterial ribosome hibernation.

  2. Enantiomeric Excess Determination for Monosaccharides Using Chiral Transmission to Cold Gas-Phase Tryptophan in Ultraviolet Photodissociation

    Science.gov (United States)

    Fujihara, Akimasa; Maeda, Naoto; Doan, Thuc N.; Hayakawa, Shigeo

    2017-02-01

    Chiral transmission between monosaccharides and amino acids via photodissociation in the gas phase was examined using a tandem mass spectrometer fitted with an electrospray ionization source and a cold ion trap in order to investigate the origin of the homochirality of biomolecules in molecular clouds. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of the monosaccharide enantiomers glucose (Glc) and galactose (Gal) with protonated l-tryptophan H+( l-Trp) were obtained by photoexcitation of the indole ring of l-Trp. l-Trp dissociated via Cα-Cβ bond cleavage when noncovalently complexed with d-Glc; however, no dissociation of l-Trp occurred in the homochiral H+( l-Trp)( l-Glc) noncovalent complex, where the energy absorbed by l-Trp was released through the evaporation of l-Glc. This enantioselective photodissociation of Trp was due to the transmission of chirality from Glc to Trp via photodissociation in the gas-phase noncovalent complexes, and was applied to the quantitative chiral analysis of monosaccharides. The enantiomeric excess of monosaccharides in solution could be determined by measuring the relative abundance of the two product ions in a single photodissociation mass spectrum of the cold gas-phase noncovalent complex with H+( l-Trp), and by referring to the linear relationships derived in this work.

  3. Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase.

    Science.gov (United States)

    Šatínský, Dalibor; Brabcová, Ivana; Maroušková, Alena; Chocholouš, Petr; Solich, Petr

    2013-07-01

    A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A "green" mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04% (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15 × 4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min(-1). The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid-base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, -0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914-0.99997, n = 6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100 ± 5% for all compounds

  4. An immobilized carboxyl containing metal-organic framework-5 stationary phase for open-tubular capillary electrochromatography.

    Science.gov (United States)

    Bao, Tao; Tang, Pingxiu; Mao, Zhenkun; Chen, Zilin

    2016-07-01

    A novel capillary column with metal-organic framework-5 (MOF-5) as the stationary phase was prepared for open-tubular capillary electrochromatography (OT-CEC). To grow MOF-5, the fused-silica capillary was functionalized firstly using 3-aminopropyltriethoxysilane and glutaraldehyde as covalent linkers; and then MOF-5 would be immobilized on the inner wall of COOH-terminated capillary by epitaxial growth, to produce a MOF-5-modified capillary. The successful growth of MOF-5 has been characterized and confirmed by scanning electron microscopy, X-Ray diffraction and Fourier transform infrared spectra. The influence of pH value and methanol on electroosmotic flow (EOF) of the MOF-5-modified capillary column was investigated. The EOF showed a pH-dependent from anode to cathode. The immobilization of MOF-5 improved the interactions between analytes and layer on inner wall of the capillary. Excellent separations of substituted benzenes and acidic and basic analytes were obtained on the fabricated capillary columns. The MOF-5-modified capillary columns exhibited good repeatability, with relative standard deviations for intra-day, inter-day runs and column-to-column less than 1.87%, 3.53%, and 8.49%, respectively. Our successful application of MOF-5 paved the way for introducing series of dicarboxylate-based isoreticular MOFs to OT-CEC as novel stationary phase.

  5. Purification of Monoclonal Antibodies Using a Fiber Based Cation-Exchange Stationary Phase: Parameter Determination and Modeling

    Directory of Open Access Journals (Sweden)

    Jan Schwellenbach

    2016-10-01

    Full Text Available Monoclonal antibodies (mAb currently dominate the market for protein therapeutics. Because chromatography unit operations are critical for the purification of therapeutic proteins, the process integration of novel chromatographic stationary phases, driven by the demand for more economic process schemes, is a field of ongoing research. Within this study it was demonstrated that the description and prediction of mAb purification on a novel fiber based cation-exchange stationary phase can be achieved using a physico-chemical model. All relevant mass-transport phenomena during a bind and elute chromatographic cycle, namely convection, axial dispersion, boundary layer mass-transfer, and the salt dependent binding behavior in the fiber bed were described. This work highlights the combination of model adaption, simulation, and experimental parameter determination through separate measurements, correlations, or geometric considerations, independent from the chromatographic cycle. The salt dependent binding behavior of a purified mAb was determined by the measurement of adsorption isotherms using batch adsorption experiments. Utilizing a combination of size exclusion and protein A chromatography as analytic techniques, this approach can be extended to a cell culture broth, describing the salt dependent binding behavior of multiple components. Model testing and validation was performed with experimental bind and elute cycles using purified mAb as well as a clarified cell culture broth. A comparison between model calculations and experimental data showed a good agreement. The influence of the model parameters is discussed in detail.

  6. Polystyrene-divinylbenzene stationary phases agglomerated with quaternized multi-walled carbon nanotubes for anion exchange chromatography.

    Science.gov (United States)

    Huang, Zhongping; Wu, Hongwei; Wang, Fengli; Yan, Wenwu; Guo, Weiqiang; Zhu, Yan

    2013-06-14

    This work explores the potential of multi-walled carbon nanotubes as an agglomerated material for ion chromatography stationary phases for the separation of inorganic anions. Polyelectrolytes with quaternary ammonium groups were introduced onto the carbon nanotube surface, based on condensation polymerization of 1,4-butanediol diglycidyl ether (BDDE) and methylamine (MA). Quaternized multi-walled carbon nanotubes (Q-MWCNTs) were electrostatically adsorbed onto the surface of sulfonated polystyrene-divinylbenzene (PS-DVB) beads to generate the anion exchanger, which were confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). A 100mm×4.0mm i.d. column was packed with Q-MWCNTs agglomerated PS-DVB particles, with a capacity of 56μequiv./column. Separation of inorganic anions, such as F(-), Cl(-), NO2(-), Br(-), NO3(-), SO4(2-) and PO4(3-) were performed. The stationary phase was rigid, chemically stable and showed good ion-exchange characteristics.

  7. Identification of new compounds with high activity against stationary phase Borrelia burgdorferi from the NCI compound collection.

    Science.gov (United States)

    Feng, Jie; Shi, Wanliang; Zhang, Shuo; Zhang, Ying

    2015-06-03

    Lyme disease is the leading tick-borne disease in the USA. Whereas the majority of Lyme disease patients with early disease can be cured with standard treatment, some patients suffer from chronic fatigue and joint and muscular pain despite treatment, a syndrome called posttreatment Lyme disease syndrome. Although the cause is unclear, ineffective killing of Borrelia burgdorferi persisters by current Lyme disease antibiotics is one possible explanation. We took advantage of our recently developed high-throughput viability assay and screened the National Cancer Institute compound library collection consisting of 2526 compounds against stationary phase B. burgdorferi. We identified the top 30 new active hits, including the top six anthracycline antibiotics daunomycin 3-oxime, dimethyldaunomycin, daunomycin, NSC299187, NSC363998 and nogalamycin, along with other compounds, including prodigiosin, mitomycin, nanaomycin and dactinomycin, as having excellent activity against B. burgdorferi stationary phase culture. The anthracycline or anthraquinone compounds, which are known to have both anti-cancer and antibacterial activities, also had high activity against growing B. burgdorferi with low minimum inhibitory concentration. Future studies on the structure-activity relationship and mechanisms of action of anthracyclines/anthraquinones are warranted. In addition, drug combination studies with the anthracycline class of compounds and the current Lyme antibiotics to eradicate B. burgdorferi persisters in vitro and in animal models are needed to determine if they improve the treatment of Lyme disease.

  8. High-resolution profiling of stationary-phase survival reveals yeast longevity factors and their genetic interactions.

    Directory of Open Access Journals (Sweden)

    Erika Garay

    2014-02-01

    Full Text Available Lifespan is influenced by a large number of conserved proteins and gene-regulatory pathways. Here, we introduce a strategy for systematically finding such longevity factors in Saccharomyces cerevisiae and scoring the genetic interactions (epistasis among these factors. Specifically, we developed an automated competition-based assay for chronological lifespan, defined as stationary-phase survival of yeast populations, and used it to phenotype over 5,600 single- or double-gene knockouts at unprecedented quantitative resolution. We found that 14% of the viable yeast mutant strains were affected in their stationary-phase survival; the extent of true-positive chronological lifespan factors was estimated by accounting for the effects of culture aeration and adaptive regrowth. We show that lifespan extension by dietary restriction depends on the Swr1 histone-exchange complex and that a functional link between autophagy and the lipid-homeostasis factor Arv1 has an impact on cellular lifespan. Importantly, we describe the first genetic interaction network based on aging phenotypes, which successfully recapitulated the core-autophagy machinery and confirmed a role of the human tumor suppressor PTEN homologue in yeast lifespan and phosphatidylinositol phosphate metabolism. Our quantitative analysis of longevity factors and their genetic interactions provides insights into the gene-network interactions of aging cells.

  9. High-resolution profiling of stationary-phase survival reveals yeast longevity factors and their genetic interactions.

    Science.gov (United States)

    Garay, Erika; Campos, Sergio E; González de la Cruz, Jorge; Gaspar, Ana P; Jinich, Adrian; Deluna, Alexander

    2014-02-01

    Lifespan is influenced by a large number of conserved proteins and gene-regulatory pathways. Here, we introduce a strategy for systematically finding such longevity factors in Saccharomyces cerevisiae and scoring the genetic interactions (epistasis) among these factors. Specifically, we developed an automated competition-based assay for chronological lifespan, defined as stationary-phase survival of yeast populations, and used it to phenotype over 5,600 single- or double-gene knockouts at unprecedented quantitative resolution. We found that 14% of the viable yeast mutant strains were affected in their stationary-phase survival; the extent of true-positive chronological lifespan factors was estimated by accounting for the effects of culture aeration and adaptive regrowth. We show that lifespan extension by dietary restriction depends on the Swr1 histone-exchange complex and that a functional link between autophagy and the lipid-homeostasis factor Arv1 has an impact on cellular lifespan. Importantly, we describe the first genetic interaction network based on aging phenotypes, which successfully recapitulated the core-autophagy machinery and confirmed a role of the human tumor suppressor PTEN homologue in yeast lifespan and phosphatidylinositol phosphate metabolism. Our quantitative analysis of longevity factors and their genetic interactions provides insights into the gene-network interactions of aging cells.

  10. Ultra high performance liquid chromatography versus high performance liquid chromatography: stationary phase selectivity for generic carotenoid screening.

    Science.gov (United States)

    Bijttebier, Sebastiaan; D'Hondt, Els; Noten, Bart; Hermans, Nina; Apers, Sandra; Voorspoels, Stefan

    2014-03-07

    Aim of study was to find the most suitable LC column for generic carotenoid screening. To represent the diversity of carotenoids in nature and to optimize chromatographic separation, a set of carotenoid standards was carefully chosen to account for the various classes of carotenoids. The HPLC C30 column has since long been the 'golden standard' in the chromatographic separation of carotenoids. Since approximately one decade, new UHPLC technology has led to much shorter analysis times, smaller peak widths and higher chromatographic resolution. However, there are currently no UHPLC columns on the market containing the specific stationary phase chemistry of the HPLC C30 column. Therefore during this study, we investigated the separation of carotenoids on a set of UHPLC columns and compared it to their separation on the HPLC C30 column. Comparison of carotenoids separations on the different stationary phases with objective column comparison parameters clearly indicated that the HPLC C30 column is an overall better performer in the separation of carotenoids. This is due to the lack of UHPLC column chemistries that are adapted for carotenoid analysis. However, analysis time on the HPLC C30 column takes about four times longer compared to UHPLC analysis. Therefore, with the range of columns that are commercially available nowadays, a choice has to be made between very high selectivity (HPLC C30 column) and analysis times that are adapted to modern laboratory requirements (UHPLC technology). Therefore, carotenoid separations would be even more performing if an appropriate UHPLC C30 column would be available.

  11. Helicity-selective phase-matching and quasi-phase matching of circularly polarized high-order harmonics: towards chiral attosecond pulses

    Science.gov (United States)

    Kfir, Ofer; Grychtol, Patrik; Turgut, Emrah; Knut, Ronny; Zusin, Dmitriy; Fleischer, Avner; Bordo, Eliyahu; Fan, Tingting; Popmintchev, Dimitar; Popmintchev, Tenio; Kapteyn, Henry; Murnane, Margaret; Cohen, Oren

    2016-06-01

    Phase matching of circularly polarized high-order harmonics driven by counter-rotating bi-chromatic lasers was recently predicted theoretically and demonstrated experimentally. In that work, phase matching was analyzed by assuming that the total energy, spin angular momentum and linear momentum of the photons participating in the process are conserved. Here we propose a new perspective on phase matching of circularly polarized high harmonics. We derive an extended phase matching condition by requiring a new propagation matching condition between the classical vectorial bi-chromatic laser pump and harmonics fields. This allows us to include the influence of the laser pulse envelopes on phase matching. We find that the helicity dependent phase matching facilitates generation of high harmonics beams with a high degree of chirality. Indeed, we present an experimentally measured chiral spectrum that can support a train of attosecond pulses with a high degree of circular polarization. Moreover, while the degree of circularity of the most intense pulse approaches unity, all other pulses exhibit reduced circularity. This feature suggests the possibility of using a train of attosecond pulses as an isolated attosecond probe for chiral-sensitive experiments.

  12. 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.

  13. Phase diagram of hot QCD in an external magnetic field: possible splitting of deconfinement and chiral transitions

    CERN Document Server

    Mizher, A J; Fraga, E S

    2010-01-01

    The structure of the phase diagram for strong interactions becomes richer in the presence of a magnetic background, which enters as a new control parameter for the thermodynamics. Motivated by the relevance of this physical setting for current and future high-energy heavy ion collision experiments and for the cosmological QCD transitions, we use the linear sigma model coupled to quarks and to Polyakov loops as an effective theory to investigate how the chiral and the deconfining transitions are affected, and present a general picture for the temperature--magnetic field phase diagram. We compute and discuss each contribution to the effective potential for the approximate order parameters, and uncover new phenomena such as the paramagnetically-induced breaking of global $\\mathbb{Z}_3$ symmetry, and possible splitting of deconfinement and chiral transitions in a strong magnetic field.

  14. 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.

  15. Stationary States in Saturated Two-Photon Processes and Generation of Phase-Averaged Mixtures of Even and Odd Quantum States

    CERN Document Server

    Dodonov, V V

    1998-01-01

    We consider a relaxation of a single mode of the quantized field in a presence of one- and two-photon absorption and emission processes. Exact stationary solutions of the master equation for the diagonal elements of the density matrix in the Fock basis are found in the case of completely saturated two-photon emission. If two-photon processes dominate over single-photon ones, the stationary state is a mixture of phase averaged even and odd coherent states.

  16. [Preparations and biological properties of chiral compounds].

    Science.gov (United States)

    Sinko, Goran

    2005-12-01

    Enantiomers of chiral compounds may express various biological activities and also different toxicities. Examples of different pharmacological effects of some chiral drugs such as fluoxetine, penicillamine, ibuprofen and albuterol are provided in this paper. Due to possible differences in activity, the chiral drugs are required to be pure enantiomeric compounds in order to be more effective and safer to use. In the laboratory, enantiomers are mainly synthesized as racemates (an equimolar mixture of enantiomers) while in biological pathways only one enantiomeric form is produced, such as amino acids, sugars and lipids. This paper presents the principles of chirality, general information about enantiomers and their biological aspects. It gives an outline of stereoselective methods for chromatographic resolution of enantiomers with stereoselective protein stationary phases, i.e. capillary electrochromatography (CEC) and high performance liquid chromatography (HPLC). The use of enzyme biotransformations (hydrolysis, oxidation and reduction) in chiral syntheses of carboxyl-, phosphoryl- or beta-hydroxy esters, alcohols, epoxides and cis-carboxyl sulphoxide is described. This article also includes an example of lipase stereoselectivity improvement by amino acid mutations within the enzyme active site.

  17. A Model for Solving the Maxwell Quasi Stationary Equations in a 3-Phase Electric Reduction Furnace

    Directory of Open Access Journals (Sweden)

    S. Ekrann

    1982-10-01

    Full Text Available A computer code has been developed for the approximate computation of electric and magnetic fields within an electric reduction furnace. The paper describes the numerical methods used to solve Maxwell's quasi-stationary equations, which are the governing equations for this problem. The equations are discretized by a staggered grid finite difference technique. The resulting algebraic equations are solved by iterating between computations of electric and magnetic quantities. This 'outer' iteration converges only when the skin depth is larger or of about the same magnitude as the linear dimensions of the computational domain. In solving for electric quantities with magnetic quantities being regarded as known, and vice versa, the central computational task is the solution of a Poisson equation for a scalar potential. These equations are solved by line successive overrelaxation combined with a rebalancing technique.

  18. Evaluation and comparison of n-alkyl chain and polar ligand bonded stationary phases for protein separation in reversed-phase liquid chromatography.

    Science.gov (United States)

    Ding, Ling; Guo, Zhimou; Xiao, Yuansheng; Xue, Xingya; Zhang, Xiuli; Liang, Xinmiao

    2014-09-01

    Protein retention is very sensitive to the change of solvent composition in reversed-phase liquid chromatography for so called "on-off" mechanism, leading to difficulty in mobile phase optimization. In this study, a novel 3-chloropropyl trichlorosilane ligand bonded column was prepared for protein separation. The differences in retention characteristics between the 3-chloropropyl trichlorosilane ligand bonded column and n-alkyl chain modified (C2, C4, C8) stationary phases were elucidated by the retention equation l nk=a+cC(B). Retention parameters (a and c) of nine standard proteins with different molecular weights were calculated by using homemade software. Results showed that retention times of nine proteins were similar on four columns, but the 3-chloropropyl trichlorosilane ligand bonded column obtained the lowest retention parameter values of larger proteins. It meant that their retention behavior affected by acetonitrile concentration would be different due to lower |c| values. More specifically, protein elution windows were broader, and retentions were less sensitive to the change of acetonitrile concentration on the 3-chloropropyl trichlorosilane ligand bonded column than that on other columns. Meanwhile, the 3-chloropropyl trichlorosilane ligand bonded column displayed distinctive selectivity for some proteins. Our results indicated that stationary phase with polar ligand provided potential solutions to the "on-off" problem and optimization in protein separation.

  19. A weak cation-exchange monolith as stationary phase for the separation of peptide diastereomers by CEC.

    Science.gov (United States)

    Ludewig, Ronny; Nietzsche, Sandor; Scriba, Gerhard K E

    2011-01-01

    A CEC weak cation-exchange monolith has been prepared by in situ polymerization of acrylamide, methylenebisacrylamide and 4-acrylamidobutyric acid in a decanol-dimethylsulfoxide mixture as porogen. The columns were evaluated by SEM and characterized with regard to the separation of diastereomers and α/β-isomers of aspartyl peptides. Column preparation was reproducible as evidenced by comparison of the analyte retention times of several columns prepared simultaneously. Analyte separation was achieved using mobile phases consisting of acidic phosphate buffer and ACN. Under these conditions the peptides migrated due to their electrophoretic mobility but the EOF also contributed as driving force as a function of the pH of the mobile phase due to increasing dissociation of the carboxyl groups of the polymer. Raising the pH of the mobile phase also resulted in deprotonation of the peptides reducing analyte mobility. Due to these mechanisms each pair of diastereomeric peptides displayed the highest resolution at a different pH of the buffer component of the mobile phase. Comparing the weak-cation exchange monolith to an RP monolith and a strong cation-exchange monolith different elution order of some peptide diastereomers was observed, clearly illustrating that interactions with the stationary phase contribute to the CEC separations.

  20. Development of a V-shape bis(tetraoxacalix[2]arene[2]triazine) stationary phase for high performance liquid chromatography.

    Science.gov (United States)

    Hu, Kai; Feng, Suxiang; Wu, Mingxia; Wang, Shuang; Zhao, Wenjie; Jiang, Qiong; Yu, Ajuan; Zhang, Shusheng

    2014-12-01

    A new stationary phase for high-performance liquid chromatography was prepared by covalently bonding a V-shape cage heteroatom-bridged calixarene onto silica gel using 3-aminopropyltriethoxysilane as coupling reagent. The structure of the new material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. Linear solvation energy relationship method was successfully employed to evaluate the new phase with a set of 34 solutes. The retention characteristic of the new phase shows significant similarities with ODS, as well as distinctive features. Multiple mechanisms including hydrophobic, hydrogen bonding, π-π and n-π interaction are involved. The chromatographic behavior of the phase was illustrated by using alkylbenzenes, aromatics positional isomers and flavonoids as probes. Moreover, inorganic anions were individually separated in anion-exchange mode by using the same column. Thus, multi-interaction mechanisms and mixed-mode separation of the new phase can very likely guarantee its excellent chromatographic performance for the analysis of complex samples. The column has been successfully employed for the analysis of clenbuterol in animal urine, and it is demonstrated to be suitable and a competitive alternative analytical method for the determination of clenbuterol.

  1. Comparison of analytical protein separation characteristics for three amine-based capillary-channeled polymer (C-CP) stationary phases.

    Science.gov (United States)

    Jiang, Liuwei; Marcus, R Kenneth

    2016-02-01

    Capillary-channeled polymer (C-CP) fiber stationary phases are finding utility in the realms of protein analytics as well as downstream processing. We have recently described the modification of poly(ethylene terephthalate) (PET) C-CP fibers to affect amine-rich phases for the weak anion-exchange (WAX) separation of proteins. Polyethylenimine (PEI) is covalently coupled to the PET surface, with subsequent cross-linking imparted by treatment with 1,4-butanediol diglycidyl ether (BUDGE). These modifications yield vastly improved dynamic binding capacities over the unmodified fibers. We have also previously employed native (unmodified) nylon 6 C-CP fibers as weak anion/cation-exchange (mixed-mode) and hydrophobic interaction chromatography (HIC) phases for protein separations. Polyamide, nylon 6, consists of amide groups along the polymer backbone, with primary amines and carboxylic acid end groups. The analytical separation characteristics of these three amine-based C-CP fiber phases are compared here. Each of the C-CP fiber columns in this study was shown to be able to separate a bovine serum albumin/hemoglobin/lysozyme mixture at high mobile phase linear velocity (∼70 mm s(-1)) but with different elution characteristics. These differences reflect the types of protein-surface interactions that are occurring, based on the active group composition of the fiber surfaces. This study provides important fundamental understanding for the development of surface-modified C-CP fiber columns for protein separation.

  2. Preparation, characterization and application of N-methylene phosphonic acid chitosan grafted magnesia–zirconia stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qing; Chen, Jie; Huang, Kun; Zhang, Xin; Xu, Li [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Shi, Zhi-guo, E-mail: shizg@whu.edu.cn [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2015-01-07

    Highlights: • N-methylene phosphonic acid chitosan grafted MgO–ZrO{sub 2} was prepared. • It exhibited superior HILIC chromatographic performance to the bare MgO–ZrO{sub 2}. • Monosaccharides, phospholipids and peptides were successfully separated. • It was a promising HILIC stationary phase. - Abstract: A hydrophilic stationary phase (SP) was prepared through grafting N-methylene phosphonic acid chitosan on magnesia–zirconia particles (P-CTS-MgO–ZrO{sub 2}) via Lewis acid–base interaction. The resulting material was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscope and nitrogen adsorption analysis. The chromatographic performance of P-CTS-MgO–ZrO{sub 2} was systemically evaluated by studying effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the novel SP provided hydrophilic, electrostatic-repulsion and ion-exchange interactions. Compared to the bare MgO–ZrO{sub 2}, P-CTS-MgO–ZrO{sub 2} exhibited superior peak shape, reasonable resolution and reduced analysis time in separation of basic analytes. Besides, remarkable resolving power of acids, i.e. six non-steroidal anti-inflammatory drugs which failed to be eluted from the bare MgO–ZrO{sub 2}, was obtained with the theoretical plate number (N/m) of 4653–31313, asymmetry factor <1.21 and the resolution of 1.6–3.4. Finally, P-CTS-MgO–ZrO{sub 2} SP was applied to separate monosaccharides, phospholipids and peptides. P-CTS-MgO–ZrO{sub 2} was a promising hydrophilic SP for wide applications.

  3. Determination of competitive adsorption isotherm parameters of pindolol enantiomers on alpha1-acid glycoprotein chiral stationary phase.

    Science.gov (United States)

    Zhang, Yan; Hidajat, Kus; Ray, Ajay K

    2006-10-27

    In this paper, inverse method (IM) was used to determine the binary competitive adsorption isotherm of pindolol enantiomers by a least-square fitting of the proposed model to the experimentally measured elution curves of racemic pindolol. The isotherm parameters were determined by minimizing the least-square error using an adaptation of genetic algorithm, non-dominated sorting genetic algorithm with jumping genes (NSGA-II-JG). An equilibrium dispersive (ED) model combined with bi-Langmuir isotherm was used in predicting the elution profiles. The determined parameters show good agreement with the experimental profiles at various experimental conditions such as sample volume, concentration and flow rates of the racemic mixture. Robustness and validity of the isotherm parameters were also verified by frontal analyses at various step inputs. Results from both the pulse tests and the frontal analysis indicate that adsorption isotherm derived from the inverse method is quite reliable. This method requires relatively less number of experiments to be performed and therefore, lower experimental costs confirming that inverse method is an attractive alternative approach of experimental technique in determining the competitive adsorption isotherm for binary systems.

  4. Preparation of mixed stationary phase of cellulose and polysiloxane ionic liquid for gas chromatography%纤维素/聚硅氧烷离子液体混合气相色谱固定相的制备

    Institute of Scientific and Technical Information of China (English)

    陈刚; 赵晓洁; 邢钧; 姚玉华; 郑京京

    2014-01-01

    纤维素是液相色谱中应用十分广泛的一类固定相,可是由于涂渍性能不佳,纤维素在气相色谱中的应用鲜有报道。本论文首先通过酯化反应合成了脂溶性较好的三醋酸纤维素( CTA ),然后与自制的聚硅氧烷离子液体( PIL-C12-NTf2)混配,制备了含纤维素的气相色谱固定相( CTA@ PIL-C12-NTf2),并涂渍了毛细管柱。其柱效为3165 plates/m(110℃,萘,k=4.95)。麦氏常数及溶剂化参数模型的测试结果证明,该固定相属中强极性固定相,主要作用力是氢键碱性作用和偶极作用。值得注意的是,引入纤维素可明显改善三取代芳香化合物位置异构体及壬烷( C9)同分异构体的分离选择性。此外,该固定相对正构烷烃、醇、脂肪酸酯及邻苯二甲酸酯等也具有良好的分离选择性。该研究不仅初步展现了纤维素在分离选择性上的特点,而且也为探索纤维素衍生物在气相色谱中的应用提供了一条新的途径。%Cellulose has been widely used to synthesize chiral stationary phases for liquid chro-matography,but it is still absent in the family of stationary phases of gas chromatography due to its poor film-forming property. Based on the unique dissolution characteristic,ionic liquids provide a great chance to solve this problem. In this paper,cellulose triacetate( CTA)was syn-thesized,and then mixed with the home-made polysiloxane ionic liquid(PIL-C12-NTf2)to pro-duce a novel mixed stationary phase(CTA@PIL-C12-NTf2). After that,it was used to prepare a capillary column for gas chromatography. The column efficiency was measured to be 3 165 plates/m(110 ℃,naphthalene,k=4. 95),demonstrating the excellent film-forming capability of this stationary phase,and then the solvation parameter model was employed to find out the interaction parameters of CTA@ PIL-C12-NTf2. In the aspect of selectivity,CTA was firstly demonstrated to be able to improve the

  5. Heat and pulsed electric field resistance of pigmented and non-pigmented enterotoxigenic strains of Staphylococcus aureus in exponential and stationary phase of growth.

    Science.gov (United States)

    Cebrián, G; Sagarzazu, N; Pagán, R; Condón, S; Mañas, P

    2007-09-30

    The survival of four enterotoxigenic strains of Staphylococcus aureus (with different pigment content) to heat and to pulsed electric fields (PEF) treatments, and the increase in resistance to both processing stresses associated with entrance into stationary phase was examined. Survival curves to heat (58 degrees C) and to PEF (26 kV/cm) of cells in the stationary and in the exponential phase of growth were obtained. Whereas a wide variation in resistance to heat treatments was detected amongst the four strains, with decimal reduction time values at 58 degrees C (D(58 degrees C)) ranging from 0.93 to 0.20 min, the resistance to PEF was very similar. The occurrence of a higher tolerance to heat in stationary phase was coincident with a higher content in carotenoid pigmentation in S. aureus colonies. However, cells of the most heat resistant (pigmented) and the most heat sensitive (non-pigmented) strains in the mid-exponential phase of growth showed similar resistance to heat and to PEF. Therefore the increase in thermotolerance upon entrance into stationary phase of growth was more marked for the pigmented strains. Recovery in anaerobic conditions particularly enhanced survival to heat treatments in a non-pigmented strain. Strain CECT 4630, which possess a deficient sigma B activity, showed low heat resistance, low pigmentation, and reduced increase in thermotolerance in stationary phase. These results indicate that the magnitude of the development of a higher heat resistance in S. aureus in stationary phase is positively related to the carotenoid content of the strain. The development of tolerance to pulsed electric field was less relevant and not linked to the carotenoid content.

  6. Anomalous dimension, chiral phase transition and inverse magnetic catalysis in soft-wall AdS/QCD

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhen, E-mail: fangzhen@itp.ac.cn [Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Science, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing (China)

    2016-07-10

    A modified soft-wall AdS/QCD model with a z-dependent bulk scalar mass is proposed. We argue for the necessity of a modified bulk scalar mass from the quark mass anomalous dimension and carefully constrain the form of bulk mass by the corresponding UV and IR asymptotics. After fixing the form of bulk scalar mass, we calculate the mass spectra of (axial-)vector and pseudoscalar mesons, which have a good agreement with the experimental data. The behavior of chiral phase transition is also investigated, and the results are consistent with the standard scenario and lattice simulations. Finally, the issue of chiral magnetic effects is addressed. We find that the inverse magnetic catalysis emerges naturally from the modified soft-wall model, which is consistent with the recent lattice simulations.

  7. Structural and dynamical properties of the chiral smectic C phase of ferroelectric liquid crystals showing high spontaneous polarizations

    Energy Technology Data Exchange (ETDEWEB)

    Hemine, J. [Laboratoire de Physique de la Matiere Condensee, Universite Hassan II, F.S.T. Mohammedia BP 146 (Morocco)]. E-mail: hemine1@yahoo.fr; Daoudi, A. [Laboratoire de Thermophysique de la Matiere, Universite du Littoral-Cote d' Opale, 145, Avenue Maurice Schumann, 59 140 Dunkerque, France. (France); Legrand, C. [Laboratoire d' Etude des Materiaux et des Composants pour l' Electronique, EA 2601, Universite du Littoral-Cote d' Opale BP 717, Calais (France); Isaert, N. [Laboratoire de Dynamique et Structures des Materiaux Moleculaires, URA No 801, Universite de Lille 1, 59655 Villeneuve d' Ascq (France); El kaaouachi, A. [Laboratoire de Physique de la Matiere Condensee, Faculte des Sciences Ibnou Zohr, BP 28/S 80000, Agadir (Morocco); Nguyen, H.T. [Centre de Recherche Paul Pascal, Universite de Bordeaux 1, 33600 Pessac (France)

    2007-10-01

    Electro-optical and dielectric investigations of a ferroelectric liquid crystal (FLC) exhibiting the chiral smectic C phase (SmC*) have been carried out as a function of temperature. These experimental studies have been applied to a new FLC having high spontaneous polarization and relaxation frequency. The Goldstone relaxation mode was studied from the dielectric response of FLC cells without DC bias voltage. The rotational viscosity corresponding to molecular motion in the SmC* phase was also determined from both electro-optical and dielectric measurements. An Arrhenius-type behaviour of the rotational viscosity was obtained and the corresponding activation energies were evaluated.

  8. Chiral symmetry breaking, color superconductivity and quark matter phase diagram: a variational approach 12.38.Gc

    CERN Document Server

    Mishra, H

    2001-01-01

    We discuss in this note simultaneous existence of chiral symmetry breaking and color superconductivity at finite temperature and density in a Nambu-Jona-Lasinio type model. The methodology involves an explicit construction of a variational ground state and minimisation of the thermodynamic potential. There exist nontrivial solutions to the gap equations at finite densities with both quark-antiquark as well as diquark condensates for the 'ground' state. However, such a phase is thermodynamically unstable with the pressure being negative in this region. We also compute the equation of state, and obtain the structure of the phase diagram in the model.

  9. 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.

  10. 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]  ……

  11. Silica-based 2-(N,N-dimethylamino)-1,3-propanediol hydrophilic interaction liquid chromatography stationary phase for separating cephalosporins and carbapenems.

    Science.gov (United States)

    Yin, Wei; Cheng, Lingping; Chai, Huihui; Guo, Ruiqiang; Liu, Renhua; Chu, Changhu; Palasota, John A; Cai, Xiaohui

    2015-08-01

    A silica-based stationary phase bearing both hydrophilic hydroxyl and amino groups was developed by covalently bonding a small molecular N,N-dimethylamino 1,3-propanediol moiety onto silica beads via copper(I)-catalyzed Huisgen azide-alkyne 1,3-dipolar cycloaddition (CuAAC). This new stationary phase showed good HILIC characteristics and high column efficiency (the theoretical plate number is up to 37000 plates m(-1) in the case of inosine) in the separation of polar compounds, such as nucleosides and bases, organic acids, cephalosporins, and carbapenems.

  12. Two-Dimensional Micro-TLC Phenolic Fingerprints of Selected Mentha sp. on Cyano-Bonded Polar Stationary Phase.

    Science.gov (United States)

    Hawrył, Mirosław A; Niemiec, Małgorzata A; Słomka, Kamil; Waksmundzka-Hajnos, Monika; Szymczak, Grażyna

    2016-01-01

    Micro-thin-layer chromatography in two-dimensional (2D-mTLC) mode in normal- (NP) and reversed-phase (RP) systems by use of cyanopropyl-bonded stationary phases was applied to make fingerprints of 11 species of Mentha genus and two finished pharmaceutical products. Non-aqueous eluents were used in the NP systems. Mixtures of acetonitrile with water and methanol with water were used in the RP chromatographic systems. Optimization of one-dimensional systems was performed by determining RM vs. composition of mobile phase dependencies for standards occurring in various Mentha sp. On the basis of these dependencies, the most selective chromatographic systems for each run were chosen. Then most selective eluents were applied to optimize two-dimensional systems by creating RF in NP systems vs. RF in RP systems correlations. The best two-dimensional systems were chosen on the basis of R(2) values for RF vs. RF correlations (the lowest values of R(2) coefficients). The 2D-mTLC optimized systems were applied to separate phenolic compounds and make fingerprints of the examined plant materials.

  13. Chromatographic analysis of some drugs employed in erectile dysfunction therapy: qualitative and quantitative studies using calixarene stationary phase.

    Science.gov (United States)

    Hashem, Hisham; Ibrahim, Adel Ehab; Elhenawee, Magda

    2014-10-01

    In this study, the effect of change in chromatographic process variables on the retention behavior of four drugs employed in erectile dysfunction therapy on a calixarene stationary phase is described. Three of these drugs are known to treat erectile dysfunction, namely, sildenafil citrate, tadalafil, and apomorphine hydrochloride, and one drug that is used as opioid analgesic, tramadol hydrochloride, which is quiet widely misused to treat premature ejaculation. The results indicate the importance of considering the structure and pKa values of drugs to be separated along with mobile phase composition. A new optimized, rapid, and accurate liquid chromatography method is also established for simultaneous determination of sildenafil citrate, tadalafil, and apomorphine hydrochloride in pharmaceutical preparations and bulk powders. The chromatographic separation of the three pharmaceuticals was achieved on a calixarene column in less than 10 min using a binary mobile phase of 35% acetonitrile and 65% 50 mM sodium perchlorate pH2.5 at 1 mL/min flow rate. The method was validated for system efficiency, linearity, accuracy, precision, limits of detection and quantitation, specificity, stability, and robustness. Statistical analysis proved that the method enabled reproducible and selective quantification of all three analytes in bulk drugs and in pharmaceutical preparations.

  14. Characterization and classification of pseudo-stationary phases in micellar electrokinetic chromatography using chemometric methods.

    Science.gov (United States)

    Fu, Cexiong; Khaledi, Morteza G

    2014-03-04

    Two types of chemometric methods, principal component analysis (PCA) and cluster analysis, are employed to characterize and classify a total of 70 pseudostationary phases (54 distinct systems and 16 decoy systems) in micellar electrokinetic chromatography (MEKC). PCA excels at removing redundant information for micellar phase characterization and retaining principal determinants for phase classification. While PCA is useful in the characterization of micelle selectivities, it is ineffective in defining the grouping of micellar phases. Hierarchical clustering yields a complete dendrogram of cluster structures but provides only limited cluster characterizations. The combination of these two chemometric methods leads to a comprehensive interpretation of the micellar phase classification. Moreover, the k-means analysis can further discern subtle differences among those closely located micellar phases. All three chemometric methods result in similar classifications with respect to the similarities and differences of the 70 micelle systems investigated. These systems are categorized into 3 major clusters: fluoro-surfactants represent cluster I, identified as strong hydrogen bond donors and dipolar but weak hydrogen bond acceptors. Cluster II includes sulfonated acrylamide/acrylate copolymers and surfactants with trimethylammonium head groups, characterized by strong hydrophobicity (v) and weak hydrogen bond acidity (b). The last cluster consists of two subclusters: clusters III and IV. Cluster III includes siloxane-based polymeric micelles, exhibiting weak hydrophobicity and medium hydrogen bond acidity and basicity (a), and the cluster IV micellar systems are characterized by their strong hydrophobicity and medium hydrogen bond acidity and basicity but rather weak dipolarity. Cluster III differs from cluster IV by its slightly weaker hydrophobicity and hydrogen bond donating capability. The classification by chemometric methods is in good agreement with the

  15. Chiral phase transition of $N_f$=2+1 and 3 QCD at vanishing baryon chemical potential

    CERN Document Server

    Ding, Heng-Tong

    2015-01-01

    We present updated results on chiral phase structure in (2+1)-flavor ($N_f$=2+1) and 3-flavor ($N_f=3$) QCD based on the simulations using Highly Improved Staggered Quarks on lattices with temporal extent $N_\\tau$ =6 at vanishing baryon chemical potential. In $N_f$=2+1 QCD we have performed simulations with a strange quark fixed to its physical value and two degenerate light quarks whose values are adjusted to have 5 values of Goldstone pion masses in the region of 160 - 80 MeV in the continuum limit. The universal scaling behavior of chiral condensates as well as chiral susceptibilities is discussed and the tri-critical point is suggested to be located below the physical point, i.e. at smaller than physical strange quark mass. In $N_f$=3 QCD simulations with 6 different masses of 3 degenerate quarks corresponding to the Goldstone pion masses in the region of 230 - 80 MeV have also been performed. Our results suggest that the QCD transition with these values of quark masses is of crossover type and an upper b...

  16. Simultaneous achiral-chiral analysis of pharmaceutical compounds using two-dimensional reversed phase liquid chromatography-supercritical fluid chromatography.

    Science.gov (United States)

    Venkatramani, C J; Al-Sayah, Mohammad; Li, Guannan; Goel, Meenakshi; Girotti, James; Zang, Lisa; Wigman, Larry; Yehl, Peter; Chetwyn, Nik

    2016-02-01

    A new interface was designed to enable the coupling of reversed phase liquid chromatography (RPLC) and supercritical fluid chromatography (SFC). This online two-dimensional chromatographic system utilizing RPLC in the first dimension and SFC in the second was developed to achieve simultaneous achiral and chiral analysis of pharmaceutical compounds. The interface consists of an eight-port, dual-position switching valve with small volume C-18 trapping columns. The peaks of interest eluting from the first RPLC dimension column were effectively focused as sharp concentration pulses on small volume C-18 trapping column/s and then injected onto the second dimension SFC column. The first dimension RPLC separation provides the achiral purity result, and the second dimension SFC separation provides the chiral purity result (enantiomeric excess). The results are quantitative enabling simultaneous achiral, chiral analysis of compounds. The interface design and proof of concept demonstration are presented. Additionally, comparative studies to conventional SFC and case studies of the applications of 2D LC-SFC in pharmaceutical analysis is presented.

  17. Electric-field-induced transport of microspheres in the isotropic and chiral nematic phase of liquid crystals

    Science.gov (United States)

    Oh, Jiyoung; Gleeson, Helen F.; Dierking, Ingo

    2017-02-01

    The application of an electric field to microspheres suspended in a liquid crystal causes particle translation in a plane perpendicular to the applied field direction. Depending on applied electric field amplitude and frequency, a wealth of different motion modes may be observed above a threshold, which can lead to linear, circular, or random particle trajectories. We present the stability diagram for these different translational modes of particles suspended in the isotropic and the chiral nematic phase of a liquid crystal and investigate the angular velocity, circular diameter, and linear velocity as a function of electric field amplitude and frequency. In the isotropic phase a narrow field amplitude-frequency regime is observed to exhibit circular particle motion whose angular velocity increases with applied electric field amplitude but is independent of applied frequency. The diameter of the circular trajectory decreases with field amplitude as well as frequency. In the cholesteric phase linear as well as circular particle motion is observed. The former exhibits an increasing velocity with field amplitude, while decreasing with frequency. For the latter, the angular velocity exhibits an increase with field amplitude and frequency. The rotational sense of the particles on a circular trajectory in the chiral nematic phase is independent of the helicity of the liquid crystalline structure, as is demonstrated by employing a cholesteric twist inversion compound.

  18. Enantioseparation of Citalopram by RP-HPLC, Using Sulfobutyl Ether-β-Cyclodextrin as a Chiral Mobile Phase Additive.

    Science.gov (United States)

    Peng, Yangfeng; He, Quan Sophia; Cai, Jiang

    2016-01-01

    Enantiomeric separation of citalopram (CIT) was developed using a reversed phase HPLC (RP-HPLC) with sulfobutylether-β-cyclodextrin (SBE-β-CD) as a chiral mobile phase additive. The effects of the pH value of aqueous buffer, concentration of chiral additive, composition of mobile phase, and column temperature on the enantioseparation of CIT were investigated on the Hedera ODS-2 C18 column (250 mm × 4.6 mm × 5.0 um). A satisfactory resolution was achieved at 25°C using a mobile phase consisting of a mixture of aqueous buffer (pH of 2.5, 5 mM sodium dihydrogen phosphate, and 12 mM SBE-β-CD), methanol, and acetonitrile with a volumetric ratio of 21 : 3 : 1 and flow rate of 1.0 mL/min. This analytical method was evaluated by examining the precision (lower than 3.0%), linearity (regression coefficients close to 1), limit of detection (0.070 µg/mL for (R)-CIT and 0.076 µg/mL for (S)-CIT), and limit of quantitation (0.235 µg/mL for (R)-CIT and 0.254 µg/mL for (S)-CIT).

  19. Enantioseparation of Citalopram by RP-HPLC, Using Sulfobutyl Ether-β-Cyclodextrin as a Chiral Mobile Phase Additive

    Directory of Open Access Journals (Sweden)

    Yangfeng Peng

    2016-01-01

    Full Text Available Enantiomeric separation of citalopram (CIT was developed using a reversed phase HPLC (RP-HPLC with sulfobutylether-β-cyclodextrin (SBE-β-CD as a chiral mobile phase additive. The effects of the pH value of aqueous buffer, concentration of chiral additive, composition of mobile phase, and column temperature on the enantioseparation of CIT were investigated on the Hedera ODS-2 C18 column (250 mm × 4.6 mm × 5.0 um. A satisfactory resolution was achieved at 25°C using a mobile phase consisting of a mixture of aqueous buffer (pH of 2.5, 5 mM sodium dihydrogen phosphate, and 12 mM SBE-β-CD, methanol, and acetonitrile with a volumetric ratio of 21 : 3 : 1 and flow rate of 1.0 mL/min. This analytical method was evaluated by examining the precision (lower than 3.0%, linearity (regression coefficients close to 1, limit of detection (0.070 µg/mL for (R-CIT and 0.076 µg/mL for (S-CIT, and limit of quantitation (0.235 µg/mL for (R-CIT and 0.254 µg/mL for (S-CIT.

  20. Gas phase synthesis of non-bundled, small diameter single-walled carbon nanotubes with near-armchair chiralities

    Energy Technology Data Exchange (ETDEWEB)

    Mustonen, K.; Laiho, P.; Kaskela, A.; Zhu, Z.; Reynaud, O.; Houbenov, N.; Tian, Y.; Jiang, H.; Kauppinen, E. I., E-mail: esko.kauppinen@aalto.fi [Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, FI-00076 Aalto (Finland); Susi, T. [Faculty of Physics, University of Vienna, Boltzmanngasse 5, A-1090 Vienna (Austria); Nasibulin, A. G. [Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, FI-00076 Aalto (Finland); Skolkovo Institute of Science and Technology, Nobel str. 3, 143026 (Russian Federation); Saint-Petersburg State Polytechnical University, 29 Polytechniheskaya st., St. Petersburg, 195251 (Russian Federation)

    2015-07-06

    We present a floating catalyst synthesis route for individual, i.e., non-bundled, small diameter single-walled carbon nanotubes (SWCNTs) with a narrow chiral angle distribution peaking at high chiralities near the armchair species. An ex situ spark discharge generator was used to form iron particles with geometric number mean diameters of 3–4 nm and fed into a laminar flow chemical vapour deposition reactor for the continuous synthesis of long and high-quality SWCNTs from ambient pressure carbon monoxide. The intensity ratio of G/D peaks in Raman spectra up to 48 and mean tube lengths up to 4 μm were observed. The chiral distributions, as directly determined by electron diffraction in the transmission electron microscope, clustered around the (n,m) indices (7,6), (8,6), (8,7), and (9,6), with up to 70% of tubes having chiral angles over 20°. The mean diameter of SWCNTs was reduced from 1.10 to 1.04 nm by decreasing the growth temperature from 880 to 750 °C, which simultaneously increased the fraction of semiconducting tubes from 67% to 80%. Limiting the nanotube gas phase number concentration to ∼10{sup 5 }cm{sup −3} prevented nanotube bundle formation that is due to collisions induced by Brownian diffusion. Up to 80% of 500 as-deposited tubes observed by atomic force and transmission electron microscopy were individual. Transparent conducting films deposited from these SWCNTs exhibited record low sheet resistances of 63 Ω/□ at 90% transparency for 550 nm light.

  1. Diastereomeric resolution directed towards chirality determination focussing on gas-phase energetics of coordinated sodium dissociation

    Science.gov (United States)

    Kanie, Osamu; Shioiri, Yuki; Ogata, Koji; Uchida, Waka; Daikoku, Shusaku; Suzuki, Katsuhiko; Nakamura, Shinichiro; Ito, Yukishige

    2016-01-01

    Defining chiral centres is addressed by introducing a pair of chiral auxiliary groups. Ions of diastereomeric pairs of molecules could be distinguished utilising energy-resolved mass spectrometry, and the applicability of the method to a series of compounds carrying amine, carboxylic acid, alcohol, and all the amino acids was verified. The method was further strengthened by distinguishing diastereomeric ions that did not undergo fragmentation. Mass spectrometric evaluation of the dissociation process of adducted sodium cations from the diastereomeric precursors agreed with the theoretical calculations, indicating the potential usefulness of the method for the determination of absolute configurations. PMID:27040078

  2. The primary transcriptome of Salmonella enterica Serovar Typhimurium and its dependence on ppGpp during late stationary phase.

    Directory of Open Access Journals (Sweden)

    Vinoy K Ramachandran

    Full Text Available We have used differential RNA-seq (dRNA-seq to characterise the transcriptomic architecture of S. Typhimurium SL1344, and its dependence on the bacterial alarmone, guanosine tetraphosphate (ppGpp during late stationary phase, (LSP. Under LSP conditions we were able to identify the transcriptional start sites (TSSs for 53% of the S. Typhimurium open reading frames (ORFs and discovered 282 candidate non-coding RNAs (ncRNAs. The mapping of LSP TSSs enabled a detailed comparison with a previous dRNA-seq study of the early stationary phase (ESP transcriptional architecture of S. Typhimurium SL1344 and its dependence on ppGpp. For the purposes of this study, LSP was defined as an aerobic LB culture grown to a later optical density reading (OD600 = 3.6 compared to ESP (OD600 = 2.3. The precise nucleotide positions of the majority of S. Typhimurium TSSs at LSP agreed closely with those identified at ESP. However, the identification of TSSs at different positions, or where additional or fewer TSSs were found at LSP compared to ESP enabled the genome-wide categorisation of growth phase dependent changes in promoter structure, the first time such an analysis has been done on this scale. Comparison of the ppGpp-dependency LSP and ESP TSSs for mRNAs and ncRNAs revealed a similar breadth of ppGpp-activation and repression. However, we note several ncRNAs previously shown to be involved in virulence were highly ppGpp-dependent at LSP. Finally, although SPI1 was expressed at ESP, we found SPI1 was not as highly expressed at LSP, instead we observed elevated expression of SPI2 encoded genes. We therefore also report an analysis of SPI2 transcriptional architecture at LSP resulting in localisation of SsrB binding sites and identification of a previously unreported SPI2 TSS. We also show that ppGpp is required for nearly all of SPI2 expression at LSP as well as for expression of SPI1 at ESP.

  3. The primary transcriptome of Salmonella enterica Serovar Typhimurium and its dependence on ppGpp during late stationary phase.

    Science.gov (United States)

    Ramachandran, Vinoy K; Shearer, Neil; Thompson, Arthur

    2014-01-01

    We have used differential RNA-seq (dRNA-seq) to characterise the transcriptomic architecture of S. Typhimurium SL1344, and its dependence on the bacterial alarmone, guanosine tetraphosphate (ppGpp) during late stationary phase, (LSP). Under LSP conditions we were able to identify the transcriptional start sites (TSSs) for 53% of the S. Typhimurium open reading frames (ORFs) and discovered 282 candidate non-coding RNAs (ncRNAs). The mapping of LSP TSSs enabled a detailed comparison with a previous dRNA-seq study of the early stationary phase (ESP) transcriptional architecture of S. Typhimurium SL1344 and its dependence on ppGpp. For the purposes of this study, LSP was defined as an aerobic LB culture grown to a later optical density reading (OD600 = 3.6) compared to ESP (OD600 = 2.3). The precise nucleotide positions of the majority of S. Typhimurium TSSs at LSP agreed closely with those identified at ESP. However, the identification of TSSs at different positions, or where additional or fewer TSSs were found at LSP compared to ESP enabled the genome-wide categorisation of growth phase dependent changes in promoter structure, the first time such an analysis has been done on this scale. Comparison of the ppGpp-dependency LSP and ESP TSSs for mRNAs and ncRNAs revealed a similar breadth of ppGpp-activation and repression. However, we note several ncRNAs previously shown to be involved in virulence were highly ppGpp-dependent at LSP. Finally, although SPI1 was expressed at ESP, we found SPI1 was not as highly expressed at LSP, instead we observed elevated expression of SPI2 encoded genes. We therefore also report an analysis of SPI2 transcriptional architecture at LSP resulting in localisation of SsrB binding sites and identification of a previously unreported SPI2 TSS. We also show that ppGpp is required for nearly all of SPI2 expression at LSP as well as for expression of SPI1 at ESP.

  4. Staphylococcus aureus aconitase inactivation unexpectedly inhibits post-exponential-phase growth and enhances stationary-phase survival

    OpenAIRE

    Somerville, Greg A.; Chaussee, Michael S.; Morgan, Carrie I; Fitzgerald, Ross; Dorward, D W; Reitzer, Lawrence J.; Musser, James M.

    2002-01-01

    Staphylococcus aureus preferentially catabolizes glucose, generating pyruvate, which is subsequently oxidized to acetate under aerobic growth conditions. Catabolite repression of the tricarboxylic acid (TCA) cycle results in the accumulation of acetate. TCA cycle derepression coincides with exit from the exponential growth phase, the onset of acetate catabolism, and the maximal expression of secreted virulence factors. These data suggest that carbon and energy for post-exponential-phase growt...

  5. Time-Frequency Integrals and the Stationary Phase Method in Problems of Waves Propagation from Moving Sources

    Directory of Open Access Journals (Sweden)

    Gennadiy Burlak

    2012-12-01

    Full Text Available The time-frequency integrals and the two-dimensional stationary phase method are applied to study the electromagnetic waves radiated by moving modulated sources in dispersive media. We show that such unified approach leads to explicit expressions for the field amplitudes and simple relations for the field eigenfrequencies and the retardation time that become the coupled variables. The main features of the technique are illustrated by examples of the moving source fields in the plasma and the Cherenkov radiation. It is emphasized that the deeper insight to the wave effects in dispersive case already requires the explicit formulation of the dispersive material model. As the advanced application we have considered the Doppler frequency shift in a complex single-resonant dispersive metamaterial (Lorenz model where in some frequency ranges the negativity of the real part of the refraction index can be reached. We have demonstrated that in dispersive case the Doppler frequency shift acquires a nonlinear dependence on the modulating frequency of the radiated particle. The detailed frequency dependence of such a shift and spectral behavior of phase and group velocities (that have the opposite directions are studied numerically.

  6. Modeling, analysis, and design of stationary reference frame droop controlled parallel three-phase voltage source inverters

    DEFF Research Database (Denmark)

    Vasquez, Juan Carlos; Guerrero, Josep M.; Savaghebi, Mehdi;

    2013-01-01

    Power electronics based MicroGrids consist of a number of voltage source inverters (VSIs) operating in parallel. In this paper, the modeling, control design, and stability analysis of parallel connected three-phase VSIs are derived. The proposed voltage and current inner control loops and the mat......Power electronics based MicroGrids consist of a number of voltage source inverters (VSIs) operating in parallel. In this paper, the modeling, control design, and stability analysis of parallel connected three-phase VSIs are derived. The proposed voltage and current inner control loops...... and the mathematical models of the VSIs are based on the stationary reference frame. A hierarchical control scheme for the paralleled VSI system is developed comprising two levels. The primary control includes the droop method and the virtual impedance loops, in order to share active and reactive power. The secondary...... control restores the frequency and amplitude deviations produced by the primary control. Also, a synchronization algorithm is presented in order to connect the MicroGrid to the grid. Experimental results are provided to validate the performance and robustness of the parallel VSI system control...

  7. Enhanced resolution of Mentha piperita volatile fraction using a novel medium-polarity ionic liquid gas chromatography stationary phase.

    Science.gov (United States)

    Ragonese, Carla; Sciarrone, Danilo; Grasso, Elisa; Dugo, Paola; Mondello, Luigi

    2016-02-01

    The evaluation of a novel medium-polarity ionic-liquid-based gas chromatography column, SLB-IL60, towards the analysis of a complex essential oil, namely, a peppermint essential oil sample, is reported. The SLB-IL60 30 m column was subjected to bleeding measurements, by means of conventional gas chromatography with mass spectrometry. The SLB-IL60 column was then evaluated in the analysis of pure standard compounds, chosen as typical constituents of peppermint essential oil. Resolution and peak symmetry (expressed as tailing factors at 10% of peak height) were measured and the results were compared to those obtained on the most widely used columns in such an application, namely a medium-polarity [100% poly(ethyleneglycol)] stationary phase, and an apolar 5% diphenyl/95% dimethyl siloxane. The final part of the evaluation was dedicated to the gas chromatography with mass spectrometry analysis of a peppermint essential oil sample and again the data were compared to those obtained on the 100% poly(ethyleneglycol) and the 5% diphenyl/95% dimethyl siloxane phase. Linear retention indices were determined for all the identified components on the ionic liquid capillary.

  8. Study of Some Alkanes Thermodynamic Parameters Using New Liquid Crystals Containing Sulfur as Stationary Phases

    Directory of Open Access Journals (Sweden)

    Mebrouk Djedid

    2015-06-01

    Full Text Available Most of the synthesized compounds which have liquid crystalline character in their composition comprise aromatic molecules. Furthermore there are few jobs that replace this type of molecules by inhomogeneous molecules that have LC character. We will replace the aromatic rings by units of 1,3,4-oxadiazole and study the effects of these new components of the transition temperatures and the Thermodynamic characteristics of n- alkanes in these two LC's phases. have been investigated by inverse gas chromatography. The transition temperatures obtained by GC are in good agreement with those found by DSC. The results are interpreted in terms of parameters “b” and related thermodynamic quantities

  9. Phenyl Functionalized Sol-gel Silica Sorbent for Capillary Microextraction and Chromia-Based Sol-gel Ucon Stationary Phase for Capillary Gas Chromatography

    Science.gov (United States)

    McLean, Michael M.

    The first chapter of this thesis presents an introduction to sol-gel methodology whose usefulness as a synthetic route will be demonstrated with two applications in chromatography. The first application involves the fabrication of a capillary micro-extraction (CME) device by coating a phenyl functionalized extracting phase on the inner surface of a fused silica capillary for analyte pre-concentration. The device was coupled on-line to a RP-HPLC system and practicality was demonstrated using allergens as target analytes. The allergens chosen as model analytes are typically found in fragrance products and food. Most of the 26 fragrance allergens that are monitored by various government authorities have a phenyl organic moiety (a strong chromophore), thus making them appropriate probes for exploring the extraction efficiency of the coating using a UV detector. The CME device showed ppt level limit of detection which makes it suitable for trace analyses of allergens and similar compounds in a variety of matrices. The second application explores the feasibility of using sol-gel derived chromia-based stationary phase in gas chromatographic columns. The organic moiety of the stationary phase was derived from Ucon 75-H-90,000 while the inorganic backbone was prepared using chromium(III) dichloride hydroxide - methacrylic acid - aqua complex, 40% in isopropanol/acetone . Usefulness of prepared chromia-based GC stationary phase was examined for petrochemical application. Promising results were obtained using aliphatic-aromatics, polyaromatic hydrocarbons, BTEX test mixture, cycloalkanes, branched alkanes and akylbenzenes. The column was able to perform without degradation despite being rinsed multiples times sequentially with the following solvents: dichloromethane, methanol, water and finally methanol again. Maximum theoretical plate number calculated is around 2,400 plates/m. The plate number clearly needs improvement but is a promising result for the newly explored

  10. Temperature effects on the chromatographic behaviour of racemic 2-amidotetralins on a Whelk-O 1 stationary phase in super- and subcritical fluid chromatography

    NARCIS (Netherlands)

    Selditz, U; Copinga, S; Grol, CJ; Franke, JP; de Zeeuw, RA; Wikstrom, H; Gyllenhaal, O

    1999-01-01

    The chromatographic behaviour of thirty structurally related racemic 2-amidotetralins on a cis-(3R, 4S)-Whelk-O 1 stationary phase was investigated at five different temperatures between 50 and -15 degrees C using super- or subscritical fluid chromatography (SFC/SubFC). Generally, low selectivity fa

  11. Identifying important structural features of ionic liquid stationary phases for the selective separation of nonpolar analytes by comprehensive two-dimensional gas chromatography.

    Science.gov (United States)

    Zhang, Cheng; Ingram, Isaiah C; Hantao, Leandro W; Anderson, Jared L

    2015-03-20

    A series of dicationic ionic liquid (IL)-based stationary phases were evaluated as secondary columns in comprehensive two-dimensional gas chromatography (GC×GC) for the separation of aliphatic hydrocarbons from kerosene. In order to understand the role that structural features of ILs play on the selectivity of nonpolar analytes, the solvation parameter model was used to probe the solvation properties of the IL-based stationary phases. It was observed that room temperature ILs containing long free alkyl side chain substituents and long linker chains between the two cations possess less cohesive forces and exhibited the highest resolution of aliphatic hydrocarbons. The anion component of the IL did not contribute significantly to the overall separation, as similar selectivities toward aliphatic hydrocarbons were observed when examining ILs with identical cations and different anions. In an attempt to further examine the separation capabilities of the IL-based GC stationary phases, columns of the best performing stationary phases were prepared with higher film thickness and resulted in enhanced selectivity of aliphatic hydrocarbons.

  12. Mass-transfer properties of insulin on core-shell and fully porous stationary phases.

    Science.gov (United States)

    Lambert, Nándor; Kiss, Ibolya; Felinger, Attila

    2014-10-31

    The mass-transfer properties of three superficially-porous packing materials, with 2.6 and 3.6μm particle and 1.9, 2.6, and 3.2μm inner core diameter, respectively, were investigated and compared with those of fully porous packings with similar particle properties. Several sources of band spreading in the chromatographic bed have been identified and studied according to the general rate model of chromatography. Besides the axial dispersion in the stream of the mobile phase, and the external mass transfer resistance, the intraparticle diffusion was studied in depth. The first absolute and the second central moments of the peaks of human insulin, over a wide range of mobile phase velocities were measured and used for the calculation of the mass-transfer coefficients. The experimental data were also analyzed using the stochastic or molecular dynamic model of Giddings and Eyring. The dissimilarities of the mass-transfer observed in the different columns were identified and evaluated.

  13. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids.

    Science.gov (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean

    2014-04-09

    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  14. (Global and local) fluctuations of phase space contraction in deterministic stationary nonequilibrium.

    Science.gov (United States)

    Bonetto, F.; Chernov, N. I.; Lebowitz, J. L.

    1998-12-01

    We studied numerically the validity of the fluctuation relation introduced in Evans et al. [Phys. Rev. Lett. 71, 2401-2404 (1993)] and proved under suitable conditions by Gallavotti and Cohen [J. Stat. Phys. 80, 931-970 (1995)] for a two-dimensional system of particles maintained in a steady shear flow by Maxwell demon boundary conditions [Chernov and Lebowitz, J. Stat. Phys. 86, 953-990 (1997)]. The theorem was found to hold if one considers the total phase space contraction sigma occurring at collisions with both walls: sigma=sigma( upward arrow )+sigma( downward arrow ). An attempt to extend it to more local quantities sigma( upward arrow ) and sigma( downward arrow ), corresponding to the collisions with the top or bottom wall only, gave negative results. The time decay of the correlations in sigma( upward arrow, downward arrow ) was very slow compared to that of sigma. (c) 1998 American Institute of Physics.

  15. Sinorhizobium meliloti sigma factors RpoE1 and RpoE4 are activated in stationary phase in response to sulfite.

    Science.gov (United States)

    Bastiat, Bénédicte; Sauviac, Laurent; Picheraux, Carole; Rossignol, Michel; Bruand, Claude

    2012-01-01

    Rhizobia are soil bacteria able to establish a nitrogen-fixing symbiosis with legume plants. Both in soil and in planta, rhizobia spend non-growing periods resembling the stationary phase of in vitro-cultured bacteria. The primary objective of this work was to better characterize gene regulation in this biologically relevant growth stage in Sinorhizobium meliloti. By a tap-tag/mass spectrometry approach, we identified five sigma factors co-purifying with the RNA polymerase in stationary phase: the general stress response regulator RpoE2, the heat shock sigma factor RpoH2, and three extra-cytoplasmic function sigma factors (RpoE1, RpoE3 and RpoE4) belonging to the poorly characterized ECF26 subgroup. We then showed that RpoE1 and RpoE4 i) are activated upon metabolism of sulfite-generating compounds (thiosulfate and taurine), ii) display overlapping regulatory activities, iii) govern a dedicated sulfite response by controlling expression of the sulfite dehydrogenase SorT, iv) are activated in stationary phase, likely as a result of endogenous sulfite generation during bacterial growth. We showed that SorT is required for optimal growth of S. meliloti in the presence of sulfite, suggesting that the response governed by RpoE1 and RpoE4 may be advantageous for bacteria in stationary phase either by providing a sulfite detoxification function or by contributing to energy production through sulfite respiration. This paper therefore reports the first characterization of ECF26 sigma factors, the first description of sigma factors involved in control of sulphur metabolism, and the first indication that endogenous sulfite may act as a signal for regulation of gene expression upon entry of bacteria in stationary phase.

  16. Sinorhizobium meliloti sigma factors RpoE1 and RpoE4 are activated in stationary phase in response to sulfite.

    Directory of Open Access Journals (Sweden)

    Bénédicte Bastiat

    Full Text Available Rhizobia are soil bacteria able to establish a nitrogen-fixing symbiosis with legume plants. Both in soil and in planta, rhizobia spend non-growing periods resembling the stationary phase of in vitro-cultured bacteria. The primary objective of this work was to better characterize gene regulation in this biologically relevant growth stage in Sinorhizobium meliloti. By a tap-tag/mass spectrometry approach, we identified five sigma factors co-purifying with the RNA polymerase in stationary phase: the general stress response regulator RpoE2, the heat shock sigma factor RpoH2, and three extra-cytoplasmic function sigma factors (RpoE1, RpoE3 and RpoE4 belonging to the poorly characterized ECF26 subgroup. We then showed that RpoE1 and RpoE4 i are activated upon metabolism of sulfite-generating compounds (thiosulfate and taurine, ii display overlapping regulatory activities, iii govern a dedicated sulfite response by controlling expression of the sulfite dehydrogenase SorT, iv are activated in stationary phase, likely as a result of endogenous sulfite generation during bacterial growth. We showed that SorT is required for optimal growth of S. meliloti in the presence of sulfite, suggesting that the response governed by RpoE1 and RpoE4 may be advantageous for bacteria in stationary phase either by providing a sulfite detoxification function or by contributing to energy production through sulfite respiration. This paper therefore reports the first characterization of ECF26 sigma factors, the first description of sigma factors involved in control of sulphur metabolism, and the first indication that endogenous sulfite may act as a signal for regulation of gene expression upon entry of bacteria in stationary phase.

  17. 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.)

  18. Development and validation of a liquid chromatographic method for the stability study of a pharmaceutical formulation containing voriconazole using cellulose tris(4-chloro-3-methylphenylcarbamate) as chiral selector and polar organic mobile phases.

    Science.gov (United States)

    Servais, Anne-Catherine; Moldovan, Radu; Farcas, Elena; Crommen, Jacques; Roland, Isabelle; Fillet, Marianne

    2014-10-10

    The ophthalmic solution of voriconazole, i.e. (2R,3S)-2-(2,4-difluorophenyl)-3-(5-fluoropyrimidin-4-yl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, made from an injection formulation which also contains sulfobutylether-β-cyclodextrin sodium salt as an excipient (Vfend), is used for the treatment of fungal keratitis. A liquid chromatographic (LC) method using polar organic mobile phase and cellulose tris(4-chloro-3-methylphenylcarbamate) coated on silica as chiral stationary phase was successfully developed to evaluate the chiral stability of the ophthalmic solution. The percentage of methanol (MeOH) in the mobile phase containing acetonitrile (ACN) as the main solvent significantly influenced the retention and resolution of voriconazole and its enantiomer ((2S,3R)-2-(2,4-difluorophenyl)-3-(5-fluoropyrimidin-4-yl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol). The optimized mobile phase consisted of ACN/MeOH/diethylamine/trifluoroacetic acid (80/20/0.1/0.1; v/v/v/v). The method was found to be selective not only regarding the enantiomer of voriconazole but also regarding the specified impurities described in the monograph from the European Pharmacopoeia. The LC method was then fully validated applying the strategy based on total measurement error and accuracy profiles. Under the selected conditions, the determination of 0.1% of voriconazole enantiomer could be performed. Finally, a stability study of the ophthalmic solution was conducted using the validated LC method.

  19. Nano-electrospray tandem mass spectrometric analysis of the acetylation state of histones H3 and H4 in stationary phase in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Patterton Hugh G

    2011-07-01

    Full Text Available Abstract Background The involvement of histone acetylation in facilitating gene expression is well-established, particularly in the case of histones H3 and H4. It was previously shown in Saccharomyces cerevisiae that gene expression was significantly down-regulated and chromatin more condensed in stationary phase compared to exponential phase. We were therefore interested in establishing the acetylation state of histone H3 and H4 in stationary and in exponential phase, since the regulation of this modification could contribute to transcriptional shut-down and chromatin compaction during semi-quiescence. Results We made use of nano-spray tandem mass spectrometry to perform a precursor ion scan to detect an m/z 126 immonium ion, diagnostic of an Nε-acetylated lysine residue that allowed unambiguous identification of acetylated as opposed to tri-methylated lysine. The fragmentation spectra of peptides thus identified were searched with Mascot against the Swiss-Prot database, and the y-ion and b-ion fragmentation series subsequently analyzed for mass shifts compatible with acetylated lysine residues. We found that K9, K14 and K36 of histone H3 and K12 and K16 of histone H4 were acetylated in exponential phase (bulk histones, but could not detect these modifications in histones isolated from stationary phase cells at the sensitivity level of the mass spectrometer. The corresponding un-acetylated peptides were, however, observed. A significantly higher level of acetylation of these residues in exponential phase was confirmed by immuno-blotting. Conclusion H4K16 acetylation was previously shown to disrupt formation of condensed chromatin in vitro. We propose that de-acetylation of H4K16 allowed formation of condensed chromatin in stationary phase, and that acetylation of H3K9, H3K14, H3K36, and H4K12 reflected the active transcriptional state of the yeast genome in exponential phase.

  20. 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.

  1. Stationary Frame Current Control Evaluations for Three-Phase Grid-Connected Inverters with PVR-based Active Damped LCL Filters

    DEFF Research Database (Denmark)

    Han, Yang; Shen, Pan; Guerrero, Josep M.

    2016-01-01

    under highly distorted grid conditions. In this paper, a synchronous reference frame equivalent proportional-integral (SRF-EPI) controller in αβ stationary frame using the parallel virtual resistance-based active damping (PVR -AD) strategy for grid-interfaced distributed generation (DG) systems...... to suppress the LCL resonance is proposed. Although both proportional-resonant (PR) controller in αβ stationary frame and PI controller in dq synchronous frame achieve zero steady-state error, the amplitude- and phase-frequency characteristics differ greatly from each other except for the reference tracking...... at fundamental frequency. Therefore, an accurate SRF-EPI controller in αβ stationary frame is established to achieve precise tracking accuracy. Moreover, the robustness, harmonic rejection capabilities, and influence of control delay are investigated by the Nyquist stability criterion when the PVR-based AD...

  2. Polymer-coated fibrous materials as the stationary phase in packed capillary gas chromatography.

    Science.gov (United States)

    Saito, Yoshihiro; Tahara, Ai; Imaizumi, Motohiro; Takeichi, Tsutomu; Wada, Hiroo; Jinno, Kiyokatsu

    2003-10-15

    Synthetic polymer filaments have been introduced as the support material in packed capillary gas chromatography (GC). The filaments of the heat-resistant polymers, Zylon, Kevlar, Nomex, and Technora, were longitudinally packed into a short fused-silica capillary, followed by the conventional coating process for open-tubular GC columns. The separation of several test mixtures such as n-alkylbenzenes and n-alkanes was carried out with these polymer-coated fiber-packed capillary columns. With the coating by various polymeric materials on the surface of these filaments, the retentivity was significantly improved over the parent fiber-packed column (without polymer coating) as well as a conventional open-tubular capillary of the same length. The results demonstrated a good combination of Zylon as the support and poly(dimethylsiloxane)-based materials as the coating liquid-phase for the successful GC separation of n-alkanes and polycyclic aromatic hydrocarbons (PAHs), while successful applications for other separations such as poly(ethylene glycol) coating for the separation of alcohols were also obtained. From the results it has been suggested that the selectivity of the fiber-packed column could be tuned by selecting different coating materials, indicating the promising possibility for a novel usage of fine fibrous polymers as the support material that can be combined with newly synthesized coating materials specially designed for particular separations. Taking advantage of good thermal stability of the fibers, the column temperature could be elevated to higher than 350 degrees C with the combination of a short metallic capillary.

  3. The $N_f=2$ QCD chiral phase transition with Wilson fermions at zero and imaginary chemical potential

    CERN Document Server

    Philipsen, Owe

    2016-01-01

    The order of the thermal phase transition in the chiral limit of Quantum Chromodynamics (QCD) with two dynamical flavors of quarks is a long-standing issue and still not known in the continuum limit. Whether the transition is first or second order has important implications for the QCD phase diagram and the existence of a critical endpoint at finite densities. We follow a recently proposed approach to explicitly determine the region of first order chiral transitions at imaginary chemical potential, where it is large enough to be simulated, and extrapolate it to zero chemical potential with known critical exponents. Using unimproved Wilson fermions on coarse $N_t=4$ lattices, the first order region turns out to be so large that no extrapolation is necessary. The critical pion mass $m_\\pi^c\\approx 560$ MeV is by nearly a factor 10 larger than the corresponding one using staggered fermions. Our results are in line with investigations of three-flavour QCD using improved Wilson fermions and indicate that the syste...

  4. A chromatographic estimate of the degree of surface heterogeneity of reversed-phase liquid chromatography packing materials II-Endcapped monomeric C18-bonded stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Gritti, Fabrice [University of Tennessee, Knoxville (UTK); Guiochon, Georges A [ORNL

    2006-01-01

    In a previous report, the heterogeneity of a non-endcapped C{sub 30}-bonded stationary phase was investigated, based on the results of the measurements of the adsorption isotherms of two neutral compounds (phenol and caffeine) and two ionizable compounds (sodium naphthalene sulfonate and propranololium chloride) by frontal analysis (FA). The same method is applied here for the characterization of the surface heterogeneity of two new brands of endcapped C{sub 18}-bonded stationary phases (Gemini and Sunfire). The adsorption isotherms of the same four chemicals were measured by FA and the results confirmed by the independent calculation of the adsorption energy distribution (AED), using the expectation-maximization (EM) method. The effect of the length of the bonded alkyl chain was investigated. Shorter alkyl-bonded-chains (C{sub 18} versus C{sub 30}) and the end-capping of the silica surface contribute to decrease the surface heterogeneity under the same experimental conditions (30% methanol, 25 mM NaCl). The AEDs of phenol and caffeine are bimodal with the C{sub 18}-bonded columns while they are trimodal and quadrimodal, respectively, with a non-endcapped C{sub 30}-bonded column. The 'supersites' (adsorption energy >20 kJ/mol) found on the C{sub 30}-Prontosil column and attributed to a cation exchange mechanism completely disappear on the C{sub 18}-Gemini and C{sub 18}-Sunfire, probably because the end-capping of the silica surface eliminates most if not all the ionic interactions.

  5. Separation of monoclonal antibody charge state variants by open tubular capillary electrochromatography with immobilised protein as stationary phase.

    Science.gov (United States)

    Zhang, Yamin; Wang, Wentao; Xiao, Xue; Jia, Li

    2016-09-30

    Monoclonal antibodies (mAbs) are highly heterogeneous and complex glycoproteins requiring powerful analytical tools for characterization and quality control. In this work, we utilize adsorbed bovine serum albumin (BSA) as a stationary phase in open tubular (OT) capillary electrochromatography for separation of charge state variants of mAbs. Poly(diallydimethylammonium chloride) (PDDA) was used to assist fabrication of BSA coated OT column by electrostatic self-assembly. Scanning electron microscopy and electroosmotic flow measurement were carried out to characterize the as-prepared BSA coated PDDA OT columns. The electrochromatographic performance of the OT columns was evaluated by separation of basic proteins and different charge state variants of mAbs. The effects of background solution pH and concentration on separation were investigated. A rapid separation of charge state variants of mAbs was successfully achieved in the BSA coated PDDA OT column. Separation of seven variants of the mAb cetuximab was achieved using the prepared column. Two basic variants and one acidic variant of rituximab, and two basic variants and four acidic variants of trastuximab were successfully distinguished from the main forms. In addition, the columns demonstrated good repeatability and stability with the run-to-run, day-to-day and batch-to-batch relative standard deviations of migration times less than 3.7%.

  6. Preparation of chitosan-graft-(β-cyclodextrin) based sol-gel stationary phase for open-tubular capillary electrochromatography.

    Science.gov (United States)

    Lü, Haixia; Li, Qingyin; Yu, Xiaowei; Yi, Jiaojiao; Xie, Zenghong

    2013-07-01

    A novel open-tubular CEC column coated with chitosan-graft-(β-CD) (CDCS) was prepared using sol-gel technique. In the sol-gel approach, owing to the 3D network of sol-gel and the strong chemical bond between the stationary phase and the surface of capillary columns, good chromatographic characteristics and unique selectivity in separating isomers were shown. The column efficiencies of 55,000∼163,000 plates/m for the isomeric xanthopterin and phenoxy acid herbicides using the sol-gel-derived CDCS columns were achieved. Good stabilities were demonstrated that the RSD values for the retention time of thiourea and isoxanthopterin were 1.3 and 1.4% (run to run, n = 5), 1.6 and 2.0% (day to day, n = 3), 2.9 and 3.1% (column to column, n = 3), respectively. The sol-gel-coated CDCS columns have shown improved separations of isomeric xanthopterin in comparison with CDCS-bonded capillary column.

  7. Interaction between Antibacterial Peptide Apep10 and Escherichia coli Membrane Lipids Evaluated Using Liposome as Pseudo-Stationary Phase

    Science.gov (United States)

    Li, Man

    2017-01-01

    Liposomes constructed from Escherichia coli membrane lipids were used as a pseudo-stationary phase in capillary electrophoresis and immobilised liposome chromatography to evaluate the interaction between antibacterial peptide (ABP) Apep10 and bacterial membrane lipids. The peptide mobility decreased as the concentration of liposomes increased, providing evidence for the existence of this interaction. The binding constant between Apep10 and the Escherichia coli membranes lipid liposome was higher than that of Apep10 with a mixed phospholipids liposome at the same temperature. The capillary electrophoresis results indicate that the binding ability of Apep10 with a liposome was dependent on the liposome’s lipid compositions. Thermodynamic analysis by immobilised liposome chromatography indicated that hydrophobic and electrostatic effects contributed to the partitioning of Apep10 in the membrane lipids. The liposomes constructed from bacterial membrane lipid were more suitable as the model membranes used to study dynamic ABP/membrane interactions than those constructed from specific ratios of particular phospholipids, with its more biomimetic phospholipid composition and contents. This study provides an appropriate model for the evaluation of ABP-membrane interactions. PMID:28052090

  8. X-Ray Solution Scattering Study of Four Escherichia coli Enzymes Involved in Stationary-Phase Metabolism.

    Directory of Open Access Journals (Sweden)

    Liubov A Dadinova

    Full Text Available The structural analyses of four metabolic enzymes that maintain and regulate the stationary growth phase of Escherichia coli have been performed primarily drawing on the results obtained from solution small angle X-ray scattering (SAXS and other structural techniques. The proteins are (i class I fructose-1,6-bisphosphate aldolase (FbaB; (ii inorganic pyrophosphatase (PPase; (iii 5-keto-4-deoxyuronate isomerase (KduI; and (iv glutamate decarboxylase (GadA. The enzyme FbaB, that until now had an unknown structure, is predicted to fold into a TIM-barrel motif that form globular protomers which SAXS experiments show associate into decameric assemblies. In agreement with previously reported crystal structures, PPase forms hexamers in solution that are similar to the previously reported X-ray crystal structure. Both KduI and GadA that are responsible for carbohydrate (pectin metabolism and acid stress responses, respectively, form polydisperse mixtures consisting of different oligomeric states. Overall the SAXS experiments yield additional insights into shape and organization of these metabolic enzymes and further demonstrate the utility of hybrid methods, i.e., solution SAXS combined with X-ray crystallography, bioinformatics and predictive 3D-structural modeling, as tools to enrich structural studies. The results highlight the structural complexity that the protein components of metabolic networks may adopt which cannot be fully captured using individual structural biology techniques.

  9. Selective high performance liquid chromatography imprinted-stationary phases for the screening of phenylurea herbicides in vegetable samples.

    Science.gov (United States)

    Tamayo, F G; Martin-Esteban, A

    2005-12-09

    Molecularly imprinted polymers (MIPs) for the determination of phenylurea herbicides have been synthesized by polymerisation of the appropriated reagents mixture within the pores of preformed spherical silica particles leading to a silica-MIP composite material. Subsequently, the silica matrix was etched away resulting in MIP beads which can be considered the "mirror image" of the original silica mold. The MIP particles were packed in stainless steal HPLC columns (125mmx4.6mm I.D.) and the materials were evaluated as imprinted-stationary phases for phenylurea herbicides. The imprinting effect of the originated specific binding sites for the selective recognition of phenylurea herbicides was clearly demonstrated. An efficient separation of a mixture of phenylurea herbicides in two groups, with or without a methoxy group in the chemical structure, was achieved and well shaped and defined peaks were obtained. Finally, the optimum imprinted column (prepared using linuron as template, 2-(trifluoromethyl)-acrylic acid as monomer, 72h of polymerisation time and the subsequent dissolution of silica matrix) was used for the LC-UV screening of phenylurea herbicides directly from vegetable sample extracts without any previous clean-up step at low concentration level in less than 10min.

  10. Single-walled carbon nanotubes as stationary phase in gas chromatographic separation and determination of argon, carbon dioxide and hydrogen.

    Science.gov (United States)

    Safavi, Afsaneh; Maleki, Norooz; Doroodmand, Mohammad Mahdi

    2010-08-24

    A chromatographic technique is introduced based on single-walled carbon nanotubes (SWCNTs) as stationary phase for separation of Ar, CO(2) and H(2) at parts per million (ppm) levels. The efficiency of SWCNTs was compared with solid materials such as molecular sieve, charcoal, multi-walled carbon nanotubes and carbon nanofibers. The morphology of SWCNTs was optimized for maximum adsorption of H(2), CO(2) and Ar and minimum adsorption of gases such as N(2), O(2), CO and H(2)O vapour. To control temperature of the gas chromatography column, peltier cooler was used. Mixtures of Ar, CO(2) and H(2) were separated according to column temperature program. Relative standard deviation for nine replicate analyses of 0.2 mL H(2) containing 10 microL of each Ar or CO(2) was 2.5% for Ar, 2.8% for CO(2) and 3.6% for H(2). The interfering effects of CO, and O(2) were investigated. Working ranges were evaluated as 40-600 ppm for Ar, 30-850 ppm for CO(2) and 10-1200 ppm for H(2). Significant sensitivity, small relative standard deviation (RSD) and acceptable limit of detection (LOD) were obtained for each analyte, showing capability of SWCNTs for gas separation and determination processes. Finally, the method was used to evaluate the contents of CO(2) in air sample.

  11. Thin film phase and local chirality of surface-bound MOP4 nanofibers

    DEFF Research Database (Denmark)

    Balzer, Frank; Röthel, Christian; Rubahn, Horst-Günter

    2016-01-01

    Vacuum deposition of the methoxy-functionalized p-quaterphenylene MOP4 on muscovite mica at elevated temperatures led to the formation of several ten micrometer long nanofibers. As shown by X-ray diffraction and polarized optical microscopy, the fibers are formed by lying molecules which grow epi...... by atomic force microscopy (AFM). The fibers represent chiral organization into single-handed aggregates of both handednesses, which is not affected by aging. On a global level, the sample remained achiral....

  12. 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.

  13. Chromatographic performance of synthetic polycrystalline diamond as a stationary phase in normal phase high performance liquid chromatography.

    Science.gov (United States)

    Peristyy, Anton; Paull, Brett; Nesterenko, Pavel N

    2015-04-24

    The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated in normal phase mode of high performance liquid chromatography. Purified nonporous irregular shape particles of average particles size 1.2 μm and specific surface area 5.1 m(2) g(-1) were used for packing 100×4.6 mm ID or 50×4.6 mm ID stainless steel columns. The retention behaviour of several classes of compounds including alkyl benzenes, polyaromatic hydrocarbons (PAH), alkylphenylketones, phenols, aromatic acids and bases were studied using n-hexane-2-propanol mixtures as mobile phase. The results are compared with those observed for microdispersed sintered detonation nanodiamond (MSDN) and porous graphitic carbon (PGC). HPHT diamond revealed distinctive separation selectivity, which is orthogonal to that observed for porous graphitic carbon; while selectivities of HPHT diamond and microdispersed sintered detonation nanodiamonds are similar. Owing to non-porous particle nature, columns packed with high pressure high temperature diamond exhibited excellent mass transfer and produce separations with maximum column efficiency of 128,200 theoretical plates per meter.

  14. Formate hydrogen lyase mediates stationary-phase deacidification and increases survival during sugar fermentation in acetoin-producing enterobacteria

    Directory of Open Access Journals (Sweden)

    Bram eVivijs

    2015-02-01

    Full Text Available Two fermentation types exist in the Enterobacteriaceae family. Mixed-acid fermenters produce substantial amounts of lactate, formate, acetate and succinate, resulting in lethal medium acidification. On the other hand, 2,3-butanediol fermenters switch to the production of the neutral compounds acetoin and 2,3-butanediol and even deacidify the environment after an initial acidification phase, thereby avoiding cell death. We equipped three mixed-acid fermenters (Salmonella Typhimurium, S. Enteritidis and Shigella flexneri with the acetoin pathway from Serratia plymuthica to investigate the mechanisms of deacidification. Acetoin production caused attenuated acidification during exponential growth in all three bacteria, but stationary-phase deacidification was only observed in Escherichia coli and Salmonella, suggesting that it was not due to the consumption of protons accompanying acetoin production. To identify the mechanism, 34 transposon mutants of acetoin-producing E. coli that no longer deacidified the culture medium were isolated. The mutations mapped to 16 genes, all involved in formate metabolism. Formate is an end product of mixed-acid fermentation that can be converted to H2 and CO2 by the formate hydrogen lyase (FHL complex, a reaction that consumes protons and thus can explain medium deacidification. When hycE, encoding the large subunit of hydrogenase 3 that is part of the FHL complex, was deleted in acetoin-producing E. coli, deacidification capacity was lost. Metabolite analysis in E. coli showed that introduction of the acetoin pathway reduced lactate and acetate production, but increased glucose consumption and formate and ethanol production. Analysis of a hycE mutant in S. plymuthica confirmed that medium deacidification in this organism is also mediated by FHL. These findings improve our understanding of the physiology and function of fermentation pathways in Enterobacteriaceae.

  15. Synthesis and characterization of a novel stationary phase, Si-Zr/Ti(PMTDS), based upon ternary oxide support for high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Amparo, Maura R.; Marques, Fabiana A.; Faria, Anizio M., E-mail: anizio@pontal.ufu.br [Universidade Federal de Uberlandia (FACIP/UFU), Ituiutaba, MG (Brazil). Faculdade de Ciencias Integradas do Pontal

    2013-09-15

    A new stationary phase based on the thermal immobilization of poly(methyltetradecylsiloxane) (PMTDS) on silica particles coated with a mixture of zirconia and titania was prepared and evaluated for the chromatographic separation of test mixtures. The spherical particles were characterized by elemental analysis, SEM, FTIR and {sup 29}Si NMR. The physicochemical properties of PMTDS phase supported on Si-Zr/Ti were intermediate between PMTDS phases supported on titanized silica and zirconized silica. The chromatographic performance of Si-Zr/Ti(PMTDS) phase was similar to PMTDS phases based on metal oxide coated silica having only one metal oxide and the preparation of a Si-Zr/Ti(PMTDS) phase allowed evaluation of the effect of each oxide, zirconia and titania, on the separation process and on the stability of the immobilized polymer phase. The hydrolytic stability of Si-Zr/Ti(PMTDS) stationary phase was similar to the Si-Ti(PMTDS) phase, improving the chemical stability of the silica-based PMTDS phase by about 100%. (author)

  16. Growth phase-dependent switch in osmolyte strategy in a moderate halophile: ectoine is a minor osmolyte but major stationary phase solute in Halobacillus halophilus.

    Science.gov (United States)

    Saum, Stephan H; Müller, Volker

    2008-03-01

    The moderately halophilic, chloride-dependent bacterium Halobacillus halophilus switches its osmolyte strategy with the salinity in its environment by the production of different compatible solutes. Ectoine is produced predominantly at very high salinities, along with proline. Interestingly, ectoine production is growth phase dependent which led to a more than 1000-fold change in the ectoine : proline ratio from 0.04 in exponential to 27.4 in late stationary phase cultures. The genes encoding the ectoine biosynthesis pathway were identified on the chromosome in the order ectABC. They form an operon that is expressed in a salinity-dependent manner with low-level expression below 1.5 M NaCl but 10-fold and 23-fold increased expression at 2.5 and 3.0 M NaCl respectively. The temporal expression of genes involved in osmoresponse is different with gdh/gln and pro genes being first, followed by ect genes. Chloride had no effect on expression of ect genes, but stimulated cellular EctC synthesis as well as ectoine production. These data demonstrate, for the first time, a growth-phase dependent switch in osmolyte strategy in a moderate halophile and, additionally, represent another piece of the chloride regulon of H. halophilus.

  17. Preparation of a weak anion exchange/hydrophobic interaction dual-function mixed-mode chromatography stationary phase for protein separation using click chemistry.

    Science.gov (United States)

    Zhao, Kailou; Yang, Fan; Xia, Hongjun; Wang, Fei; Song, Qingguo; Bai, Quan

    2015-03-01

    In this study, 3-diethylamino-1-propyne was covalently bonded to the azide-silica by a click reaction to obtain a novel dual-function mixed-mode chromatography stationary phase for protein separation with a ligand containing tertiary amine and two ethyl groups capable of electrostatic and hydrophobic interaction functionalities, which can display hydrophobic interaction chromatography character in a high-salt-concentration mobile phase and weak anion exchange character in a low-salt-concentration mobile phase employed for protein separation. As a result, it can be employed to separate proteins with weak anion exchange and hydrophobic interaction modes, respectively. The resolution and selectivity of the stationary phase were evaluated in both hydrophobic interaction and ion exchange modes with standard proteins, respectively, which can be comparable to that of conventional weak anion exchange and hydrophobic interaction chromatography columns. Therefore, the synthesized weak anion exchange/hydrophobic interaction dual-function mixed-mode chromatography column can be used to replace two corresponding conventional weak anion exchange and hydrophobic interaction chromatography columns to separate proteins. Based on this mixed-mode chromatography stationary phase, a new off-line two-dimensional liquid chromatography technology using only a single dual-function mixed-mode chromatography column was developed. Nine kinds of tested proteins can be separated completely using the developed method within 2.0 h.

  18. Retention and chiral recognition mechanism of organo-phosphorus compounds in high-performance liquid chroma-tography

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In normal phase condition, a series of chiral phosphorus organic compounds have been separated by high-performance liquid chromatography. In order to study the retention and chiral recognition mechanism, the method of quantitative structure-enantioselectivity retention relationships (QSERRs) has been investigated from the quantitative equations established between the chromatographic retention of enantiomers and their molecular descriptors of physicochemical properties. The results show that on the Pirkle-type chiral stationary phase (CSP) of Sumichiral OA4700, it is the parameter of LUMO that gives the most contribution to the chromatographic re-tention of O-ethyl O-(substituted) phenyl N-isopropyl phosphoroamidothioates resulting from the interaction of hydrogen bond and (or) p-p interaction. Meanwhile, the chiral recognition is formed from the contribution of logP and LUMO.

  19. 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.

  20. Long-term high-temperature and pH stability assessment of modern commercially available stationary phases by using retention factor analysis.

    Science.gov (United States)

    Haun, Jakob; Oeste, Katja; Teutenberg, Thorsten; Schmidt, Torsten C

    2012-11-09

    High-temperature liquid chromatography provides several advantages concerning HPLC method development and is needed to realize special hyphenation techniques. However, hardware limitations and stationary phase degradation can prevent the successful application of this technique. Therefore, column stability is of major importance. The presented study contains results of long-term high-temperature stability tests for eight modern commercially available HPLC stationary phases. Six of them were silica-based reversed-phase C18 columns tested according to an earlier reported procedure (Teutenberg, 2009 [12]). On the basis of the extended data set that covers a wide range of column technologies, a comparative approach using retention factor analysis was evaluated in order to categorize the columns according to their long-term high-temperature stability at 150 °C and changing pH value. This approach offers a more objective alternative to conventional listings in which temperature maxima are compared for columns tested under different conditions. Additionally, customized tests are presented for one promising polymer-based C18 stationary phase and an amide column for hydrophilic interaction liquid chromatography.

  1. Comparison of three development approaches for Stationary Phase Optimised Selectivity Liquid Chromatography based screening methods Part II: A group of structural analogues (PDE-5 inhibitors in food supplements).

    Science.gov (United States)

    Deconinck, E; Ghijs, L; Kamugisha, A; Courselle, P

    2016-02-01

    Three approaches for the development of a screening method to detect adulterated dietary supplements, based on Stationary Phase Optimised Selectivity Liquid Chromatography were compared for their easiness/speed of development and the performance of the optimal method obtained. This comparison was performed for a heterogeneous group of molecules, i.e. slimming agents (Part I) and a group of structural analogues, i.e. PDE-5 inhibitors (Part II). The first approach makes use of primary runs at one isocratic level, the second of primary runs in gradient mode and the third of primary runs at three isocratic levels to calculate the optimal combination of segments of stationary phases. In each approach the selection of the stationary phase was followed by a gradient optimisation. For the PDE-5 inhibitors, the group of structural analogues, only the method obtained with the third approach was able to differentiate between all the molecules in the development set. Although not all molecules are baseline separated, the method allows the identification of the selected adulterants in dietary supplements using only diode array detection. Though, due to the mobile phases used, the method could also be coupled to mass spectrometry. The method was validated for its selectivity following the guidelines as described for the screening of pesticide residues and residues of veterinary medicines in food.

  2. Preparation of a novel weak cation exchange/hydrophobic interaction chromatography dual-function polymer-based stationary phase for protein separation using "thiol-ene click chemistry".

    Science.gov (United States)

    Yang, Fan; Bai, Quan; Zhao, Kailou; Gao, Dong; Tian, Lei

    2015-02-01

    A novel dual-function mixed-mode stationary phase based on poly(glycidyl methacrylate-co-ethylene dimethacrylate) microspheres was synthesized by thiol-ene click chemistry and characterized by infrared spectroscopy and elemental analysis. The new system displays both hydrophobic interaction chromatography (HIC) character in a high salt concentration mobile phase, and weak cation exchange (WCX) chromatography character in a low salt concentration mobile phase. It can be used to separate proteins in both ion-exchange chromatography (IEC) mode and HIC mode. The resolution and selectivity of the stationary phase were evaluated in both HIC mode and IEC mode using protein standards. In comparison with the conventional WCX and HIC columns, the results were satisfactory and acceptable. Protein mass and bioactivity recoveries of more than 96% can be achieved in both HIC mode and IEC mode using this column. The results indicate that the novel dual-function mixed-mode column in many cases can replace the use of two individual WCX and HIC columns. In addition, the effects on protein separation of different ligand structures in the dual-function stationary phase and the pH of the mobile phase used were also investigated in detail. The results show that electrostatic interaction of the ligand with proteins must match the hydrophobicity of the ligand, which is an important factor to prepare the dual-function stationary phase. On the basis of this dual-function mixed-mode chromatography column, a new two-dimensional liquid chromatography technology with a single column system was also developed in this study, and was used to renature and purify recombinant human interferon-γ from inclusion bodies. The mass recovery, purity, and specific bioactivity obtained for the purified recombinant human interferon-γ were 87.2%, 92.4%, and 2.8 × 10(7) IU/mg, respectively, in IEC mode, and 83.4%, 95.2%, and 4.3 × 10(7) IU/mg, respectively, in HIC mode. The results indicate that the

  3. Separation of opiate alkaloids by electrokinetic chromatography with sulfated-cyclodextrin as a pseudo-stationary phase.

    Science.gov (United States)

    Zakaria, Philip; Macka, Miroslav; Haddad, Paul R

    2003-01-24

    The separation of six related opiate alkaloids (morphine, thebaine, 10-hydroxythebaine, codeine, oripavine and laudanine) was studied using sulfated-cyclodextrin (s-CD) as a cation-exchange pseudo-stationary phase. Cation-exchange interactions between the cationic analytes and the anionic s-CD (7-11 mol of sulfate groups per mole CD) were found to bethe predominant mechanism, allowing the separations to be performed at low pH where the opiates are protonated and exhibit very similar mobilities. The concentrations of the s-CD and the competing ion (Na+ or Mg2+) in the electrolyte were used to govern the extent of the ion-exchange interactions. Interactions with the sulfated-cyclodextrin differed for each analyte, with oripavine exhibiting the strongest interaction and 10-thebaine and laudanine showing the weakest interactions. Despite the very similar structures of the analytes, these differences resulted in significant changes in separation selectivity. The separation was modelled using a migration equation derived from first principles and based on ion-exchange interactions between the s-CD and the opiates. Constants within the model were obtained by non-linear regression using a small subset of experimentally determined migration times. These constants related to the ion-exchange affinities of the s-CD for the various opiates. When the model was used to predict migration times under other experimental conditions, a very good correlation was obtained between observed and predicted mobilities (r2=0.996). Optimisation of the system was performed using the normalised resolution product and minimum resolution criteria and this process provided two optimised separations, each exhibiting a different separation selectivity.

  4. Impact of substituents on the enantioseparation of racemic 2-amidotetralins on polysaccharide stationary phases .1. Chiralcel OD

    NARCIS (Netherlands)

    Selditz, U; Copinga, S; Franke, JP; Wikstrom, H; deZeeuw, RA

    1996-01-01

    The direct enantiomeric separation of 32 racemic 2-amidotetralins on the commercially available tris-(3,5-dimethylphenylcarbamate) derivative of cellulose, coated on silica gel (Chiralcel OD), is presented. To date, the selection of a column for the chiral separation of a racemic mixture is done emp

  5. Synthesis of a new cyclosporine-based stationary phase and separation behaviors toward aromatic positional isomers by high-performance liquid chromatography.

    Science.gov (United States)

    Liu, Wen-na; Fan, Jun; Lin, Chun; Zheng, Sheng-run; Zhang, Wei-guang

    2015-04-01

    A new cyclosporine-bonded stationary phase has been synthesized through the Staudinger reaction between azido cyclosporine A (CsA) and aminopropyl silica gel and applied in separations of six disubstituted aromatic analytes by high-performance liquid chromatography. For dimethyl phthalate, nitroaniline and chloronitrobenzene, their positional isomers were well-separated on this CsA stationary phase, in which the separation factor for m-/o-dimethyl phthalates was the biggest. For nitrotoluene, dichlorobenzene and benzenediol, the m-/o-isomers were co-eluted. Then, effects of chromatographic conditions (such as types and content of alcoholic modifiers) on separation of nitroaniline positional isomers have been investigated. Retention behaviors of nitroaniline isomers on the column exhibited the strengthening trend along with increasing carbon number of alcohols, from ethanol to 1-propanol, and to 1-butanol. A similar phenomenon was observed by lowering the content of alcohol.

  6. Perpentylated (2, 3, 6-Tri-O-pentyl)-β-cyclodextrin Used as Capillary Gas Chromatographic Stationary Phase Prepared by Sol-gel Technology

    Institute of Scientific and Technical Information of China (English)

    Min Min LIANG; Mei Ling QI; Yu LENG; Ruo Nong FU

    2005-01-01

    Capillary column preparation using perpentylated (2,3,6-tri-O-pentyl)-β-cyclodextrin as stationary phase by sol-gel technology with simplicity and rapidity is described. Multiple preparation steps in conventional column technology were avoided. The prepared columns exhibit satisfactory chromatographic performances and pronounced selectivity for a wide range of test solutes, and have been successfully used for the separation of nitrotoluene, dimethoxybenzene,alcohols, alkanes, dimethylphenol and cresol isomers.

  7. Involvement of GDH3-encoded NADP+-dependent glutamate dehydrogenase in yeast cell resistance to stress-induced apoptosis in stationary phase cells.

    Science.gov (United States)

    Lee, Yong Joo; Kim, Kyung Jin; Kang, Hong Yong; Kim, Hye-Rim; Maeng, Pil Jae

    2012-12-28

    Glutamate metabolism is linked to a number of fundamental metabolic pathways such as amino acid metabolism, the TCA cycle, and glutathione (GSH) synthesis. In the yeast Saccharomyces cerevisiae, glutamate is synthesized from α-ketoglutarate by two NADP(+)-dependent glutamate dehydrogenases (NADP-GDH) encoded by GDH1 and GDH3. Here, we report the relationship between the function of the NADP-GDH and stress-induced apoptosis. Gdh3-null cells showed accelerated chronological aging and hypersusceptibility to thermal and oxidative stress during stationary phase. Upon exposure to oxidative stress, Gdh3-null strains displayed a rapid loss in viability associated with typical apoptotic hallmarks, i.e. reactive oxygen species accumulation, nuclear fragmentation, DNA breakage, and phosphatidylserine translocation. In addition, Gdh3-null cells, but not Gdh1-null cells, had a higher tendency toward GSH depletion and subsequent reactive oxygen species accumulation than did WT cells. GSH depletion was rescued by exogenous GSH or glutamate. The hypersusceptibility of stationary phase Gdh3-null cells to stress-induced apoptosis was suppressed by deletion of GDH2. Promoter swapping and site-directed mutagenesis of GDH1 and GDH3 indicated that the necessity of GDH3 for the resistance to stress-induced apoptosis and chronological aging is due to the stationary phase-specific expression of GDH3 and concurrent degradation of Gdh1 in which the Lys-426 residue plays an essential role.

  8. Involvement of GDH3-encoded NADP+-dependent Glutamate Dehydrogenase in Yeast Cell Resistance to Stress-induced Apoptosis in Stationary Phase Cells*

    Science.gov (United States)

    Lee, Yong Joo; Kim, Kyung Jin; Kang, Hong Yong; Kim, Hye-Rim; Maeng, Pil Jae

    2012-01-01

    Glutamate metabolism is linked to a number of fundamental metabolic pathways such as amino acid metabolism, the TCA cycle, and glutathione (GSH) synthesis. In the yeast Saccharomyces cerevisiae, glutamate is synthesized from α-ketoglutarate by two NADP+-dependent glutamate dehydrogenases (NADP-GDH) encoded by GDH1 and GDH3. Here, we report the relationship between the function of the NADP-GDH and stress-induced apoptosis. Gdh3-null cells showed accelerated chronological aging and hypersusceptibility to thermal and oxidative stress during stationary phase. Upon exposure to oxidative stress, Gdh3-null strains displayed a rapid loss in viability associated with typical apoptotic hallmarks, i.e. reactive oxygen species accumulation, nuclear fragmentation, DNA breakage, and phosphatidylserine translocation. In addition, Gdh3-null cells, but not Gdh1-null cells, had a higher tendency toward GSH depletion and subsequent reactive oxygen species accumulation than did WT cells. GSH depletion was rescued by exogenous GSH or glutamate. The hypersusceptibility of stationary phase Gdh3-null cells to stress-induced apoptosis was suppressed by deletion of GDH2. Promoter swapping and site-directed mutagenesis of GDH1 and GDH3 indicated that the necessity of GDH3 for the resistance to stress-induced apoptosis and chronological aging is due to the stationary phase-specific expression of GDH3 and concurrent degradation of Gdh1 in which the Lys-426 residue plays an essential role. PMID:23105103

  9. A new anion-exchange/hydrophobic monolith as stationary phase for nano liquid chromatography of small organic molecules and inorganic anions.

    Science.gov (United States)

    Aydoğan, Cemil

    2015-05-01

    In this study, an anion-exchange/hydrophobic polymethacrylate-based stationary phase was prepared for nano-liquid chromatography of small organic molecules and inorganic anions. The stationary phase was synthesized by in situ polymerization of 3-chloro-2-hydroxypropylmethacrylate and ethylene dimethacrylate inside silanized 100 μm i.d. fused silica capillary. The porogen mixture consisted of toluene and dodecanol. The pore size distrubution profiles of the resulting monolith were determined by mercury intrusion porosimetry and the morphology of the prepared monolith was investigated by scanning electron microscope. Good permeability, stability and column efficiency were observed on the monolithic column with nano flow. The produced monolithic column, which contains reactive chloro groups, was then modified by reaction with N,N-dimethyl-N-dodecylamine to obtain an anion-exchange/hydrophobic monolithic stationary phase. The functionalized monolith contained ionizable amine groups and hydrophobic groups that are useful of anion-exchange/hydrophobic mixed-mode chromatography. The final monolithic column performance with respect to anion-exchange and hydrophobic interactions was assesed by the separation of alkylbenzene derivatives, phenolic compounds and inorganic anions, respectively. Theoretical plate numbers up to 23,000 plates/m were successfully achieved in the separation of inorganic anions.

  10. Stationary phase induction of dnaN and recF, two genes of Escherichia coli involved in DNA replication and repair.

    Science.gov (United States)

    Villarroya, M; Pérez-Roger, I; Macián, F; Armengod, M E

    1998-03-16

    The beta subunit of DNA polymerase III holoenzyme, the Escherichia coli chromosomal replicase, is a sliding DNA clamp responsible for tethering the polymerase to DNA and endowing it with high processivity. The gene encoding beta, dnaN, maps between dnaA and recF, which are involved in initiation of DNA replication at oriC and resumption of DNA replication at disrupted replication forks, respectively. In exponentially growing cells, dnaN and recF are expressed predominantly from the dnaA promoters. However, we have found that stationary phase induction of the dnaN promoters drastically changes the expression pattern of the dnaA operon genes. As a striking consequence, synthesis of the beta subunit and RecF protein increases when cell metabolism is slowing down. Such an induction is dependent on the stationary phase sigma factor, RpoS, although the accumulation of this factor alone is not sufficient to activate the dnaN promoters. These promoters are located in DNA regions without static bending, and the -35 hexamer element is essential for their RpoS-dependent induction. Our results suggest that stationary phase-dependent mechanisms have evolved in order to coordinate expression of dnaN and recF independently of the dnaA regulatory region. These mechanisms might be part of a developmental programme aimed at maintaining DNA integrity under stress conditions.

  11. Geometric phase and o-mode blue shift in a chiral anisotropic medium inside a Fabry-P\\'erot cavity

    CERN Document Server

    Timofeev, I V; Sutormin, V S; Myslivets, S A; Arkhipkin, V G; Vetrov, S Ya; Lee, W; Zyryanov, V Ya

    2015-01-01

    Anomalous spectral shift of transmission peaks is observed in a Fabry--P\\'erot cavity filled with a chiral anisotropic medium. The effective refractive index value resides out of the interval between the ordinary and the extraordinary refractive indices. The spectral shift is explained by contribution of a geometric phase. The problem is solved analytically using the approximate Jones matrix method, numerically using the accurate Berreman method and geometrically using the generalized Mauguin--Poincar\\'e rolling cone method. The $o$-mode blue shift is measured for a 4-methoxybenzylidene-4'-$n$-butylaniline twisted--nematic layer inside the Fabry--P\\'erot cavity. The twist is electrically induced due to the homeoplanar--twisted configuration transition in an ionic-surfactant-doped liquid crystal layer. Experimental evidence confirms the validity of the theoretical model.

  12. Monte-Carlo approach to particle-field interactions and the kinetics of the chiral phase transition

    CERN Document Server

    Greiner, Carsten; van Hees, Hendrik; Meistrenko, Alex

    2015-01-01

    The kinetics of the chiral phase transition is studied within a linear quark-meson-$\\sigma$ model, using a Monte-Carlo approach to semiclassical particle-field dynamics. The meson fields are described on the mean-field level and quarks and antiquarks as ensembles of test particles. Collisions between quarks and antiquarks as well as the $q\\overline{q}$ annihilation to $\\sigma$ mesons and the decay of $\\sigma$ mesons is treated, using the corresponding transition-matrix elements from the underlying quantum field theory, obeying strictly the rule of detailed balance and energy-momentum conservation. The approach allows to study fluctuations without making ad hoc assumptions concerning the statistical nature of the random process as necessary in Langevin-Fokker-Planck frameworks.

  13. Geometric phase and o-mode blueshift in a chiral anisotropic medium inside a Fabry-Pérot cavity.

    Science.gov (United States)

    Timofeev, Ivan V; Gunyakov, Vladimir A; Sutormin, Vitaly S; Myslivets, Sergey A; Arkhipkin, Vasily G; Vetrov, Stepan Ya; Lee, Wei; Zyryanov, Victor Ya

    2015-11-01

    Anomalous spectral shift of transmission peaks is observed in a Fabry-Pérot cavity filled with a chiral anisotropic medium. The effective refractive index value resides out of the interval between the ordinary and the extraordinary refractive indices. The spectral shift is explained by contribution of a geometric phase. The problem is solved analytically using the approximate Jones matrix method, numerically using the accurate Berreman method, and geometrically using the generalized Mauguin-Poincaré rolling cone method. The o-mode blueshift is measured for a 4-methoxybenzylidene-4'-n-butylaniline twisted-nematic layer inside the Fabry-Pérot cavity. The twist is electrically induced due to the homeoplanar-twisted configuration transition in an ionic-surfactant-doped liquid crystal layer. Experimental evidence confirms the validity of the theoretical model.

  14. 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.

  15. pi-Selective stationary phases: (I) Influence of the spacer chain length of phenyl type phases on the aromatic and methylene selectivity of aromatic compounds in reversed phase high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Mayfield, Kirsty [University of Western Sydney, Australia; Dennis, Gary [University of Western Sydney, Australia; Gritti, Fabrice [University of Tennessee, Knoxville (UTK); Guiochon, Georges A [ORNL; Shalliker, R. Andrew [University of Western Sydney, Australia

    2010-01-01

    Phenyl type stationary phases of increasing spacer chain length (phenyl, methyl phenyl, ethyl phenyl, propyl phenyl and butyl phenyl, with 0-4 carbon atoms in the spacer chain, respectively) were synthesized and packed in house to determine the impact that the spacer chain length has on the retention process. Two trends in the aromatic selectivity, q{sub aromatic}, were observed, depending on whether the number of carbon atoms in the spacer chain is even or odd. Linear log k' vs {phi} plots were obtained for each stationary phase and the S coefficient was determined from the gradient of these plots. For the phenyl type phases, the S vs n{sub c} plots of the retention factors of linear polycyclic aromatic hydrocarbons vs the number of rings exhibit a distinct discontinuity that between 3 and 4 rings, which increases with increasing spacer chain length for even phases but decreases for odd phases. Accordingly, we suggest that the retention factors depend differently on the number of carbon atoms in the spacer chain depending on whether this number is even or odd and that this effect is caused by different orientations of the aromatic ring relative to the silica surface.

  16. Adsorption mechanism in reversed-phase liquid chromatography. Effect of the surface coverage of a monomeric C18-silica stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Gritti, Fabrice [University of Tennessee, Knoxville (UTK); Guiochon, Georges A [ORNL

    2006-04-01

    The effect of the bonding density of the octadecyl chains onto the same silica on the adsorption and retention properties of low molecular weight compounds (phenol, caffeine, and sodium 2-naphthalene sulfonate) was investigated. The same mobile phase (methanol:water, 20:80, v/v) and temperature (T = 298 K) were applied and two duplicate columns (A and B) from each batch of packing material (neat silica, simply endcapped or C{sub 1} phase, 0.42, 1.01, 2.03, and 3.15 {micro}mol/m{sup 2} of C{sub 18} alkyl chains) were tested. Adsorption data of the three compounds were acquired by frontal analysis (FA) and the adsorption energy distributions (AEDs) were calculated using the expectation-maximization method. Results confirmed earlier findings in linear chromatography of a retention maximum at an intermediate bonding density. From a general point of view, the saturation capacity of the adsorbent tends to decrease with increasing bonding density, due to the vanishing space intercalated between the C{sub 18} bonded chains and to the decrease of the specific surface area of the stationary phase. The equilibrium constants are maximum for an intermediary bonding density ({approx}2 {micro}mol/m{sup 2}). An enthalpy-entropy compensation was found for the thermodynamic parameters of the isotherm data. Weak equilibrium constants (small {Delta}H) and high saturation capacities (large {Delta}S) were observed at low bonding densities, higher equilibrium constants and lower saturation capacities at high bonding densities, the combinations leading to similar apparent retention in RPLC. The use of a low surface coverage column is recommended for preparative purposes.

  17. Stabilization of the chiral phase of the SU (6 m ) Heisenberg model on the honeycomb lattice with m particles per site for m larger than 1

    Science.gov (United States)

    Dufour, Jérôme; Mila, Frédéric

    2016-09-01

    We show that, when N is a multiple of 6 (N =6 m , where m is an integer), the SU (N) Heisenberg model on the honeycomb lattice with m particles per site has a clear tendency toward chiral order as soon as m ≥2 . This conclusion has been reached by a systematic variational Monte Carlo investigation of Gutzwiller projected wave functions as a function of m between the case of one particle per site (m =1 ), for which the ground state has recently been shown to be in a plaquette singlet state, and the m →∞ limit, where a mean-field approach has established that the ground state has chiral order. This demonstrates that the chiral phase can indeed be stabilized for not too large values of m , opening the way to its experimental realizations in other lattices.

  18. Topological phase transitions and chiral inelastic transport induced by the squeezing of light

    Science.gov (United States)

    Peano, Vittorio; Houde, Martin; Brendel, Christian; Marquardt, Florian; Clerk, Aashish A.

    2016-01-01

    There is enormous interest in engineering topological photonic systems. Despite intense activity, most works on topological photonic states (and more generally bosonic states) amount in the end to replicating a well-known fermionic single-particle Hamiltonian. Here we show how the squeezing of light can lead to the formation of qualitatively new kinds of topological states. Such states are characterized by non-trivial Chern numbers, and exhibit protected edge modes, which give rise to chiral elastic and inelastic photon transport. These topological bosonic states are not equivalent to their fermionic (topological superconductor) counterparts and, in addition, cannot be mapped by a local transformation onto topological states found in particle-conserving models. They thus represent a new type of topological system. We study this physics in detail in the case of a kagome lattice model, and discuss possible realizations using nonlinear photonic crystals or superconducting circuits. PMID:26931620

  19. Large scale chiral chromatography for the separation of an enantiomer to accelerate drug development.</