Science.gov

Sample records for chiral derivatizing reagents

  1. Synthesis and evaluation of two coumarin-type derivatization reagents for fluorescence detection of chiral amines and chiral carboxylic acids.

    PubMed

    Mertens, Matthias D; Gütschow, Michael

    2013-12-01

    The synthesis of two fluorescent coumarin-type chiral derivatization agents (4 and 11) is reported. A chiral side chain was introduced at position 7 of the coumarin via Mitsunobu reaction. The two coumarins bear in this side chain either a free amino group or a carboxyl group, making them useful for further transformations. Conjugates of chiral prototype drugs with 4 or 11 were prepared by amide coupling of the analyte's carboxyl group to the reagent's amine group, or vice versa. The separation of seven diastereomeric conjugates through achiral high-performance liquid chromatography (HPLC) on a common C18 column is demonstrated. © 2013 Wiley Periodicals, Inc.

  2. A novel approach for LC-MS/MS-based chiral metabolomics fingerprinting and chiral metabolomics extraction using a pair of enantiomers of chiral derivatization reagents.

    PubMed

    Takayama, Takahiro; Mochizuki, Toshiki; Todoroki, Kenichiro; Min, Jun Zhe; Mizuno, Hajime; Inoue, Koichi; Akatsu, Hiroyasu; Noge, Ichiro; Toyo'oka, Toshimasa

    2015-10-22

    Chiral metabolites are found in a wide variety of living organisms and some of them are understood to be physiologically active compounds and biomarkers. However, the overall analysis of chiral metabolomics is quite difficult due to the high number of metabolites, the significant diversity in their physicochemical properties, and concentration range from metabolite-to-metabolite. To solve this difficulty, we developed a novel approach for chiral metabolomics fingerprinting and chiral metabolomics extraction, which is based on the labeling of a pair of enantiomers of chiral derivatization reagents (i.e., DMT-(S,R)-Pro-OSu and DMT-3(S,R)-Apy) and precursor ion scan chromatography of the derivatives. The multivariate statistics is also required for this strategy. The proposed procedures were evaluated by the detection of a diagnostic marker (i.e., d-lactic acid) using the saliva of diabetic patients. This method was used for the determination of biomarker candidates of chiral amines and carboxyls in Alzheimer's disease (AD) brain homogenates. As the results, l-phenylalanine (L-Phe) and l-lactic acid (L-LA) were identified as the decreased and increased biomarker candidates in the AD brain, respectively. Therefore, the proposed approach seems to be helpful for the determination of non-target chiral metabolomics possessing amines and carboxyls.

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

    PubMed

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

    2015-03-01

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

  4. Evaluation of a series of prolylamidepyridines as the chiral derivatization reagents for enantioseparation of carboxylic acids by LC-ESI-MS/MS and the application to human saliva.

    PubMed

    Kuwabara, Tomohiro; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

    2014-04-01

    Mass spectrometry has become a popular analytical tool because of its high sensitivity and specificity. The use of a chiral derivatization reagent for the mass spectrometry (MS) detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)-MS/MS analysis is very limited. According to these observations, we are currently in the process of developing novel labeling reagents for chiral molecules in MS/MS analysis. The derivatization reagent that is effective for enhancing not only the electrospray ionization-MS/MS sensitivity but also the reversed-phase LC resolution of carboxylic acid enantiomers should have a highly proton-affinitive moiety and an asymmetric structure near the reactive functional group. Furthermore, the resulting derivative has to provide a characteristic product ion suitable for the selected reaction monitoring. Based upon these considerations, a series of prolylamidepyridines ((S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-2-yl)amide (PCP2), (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-3-yl)amide, and (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-4-yl)amide) was synthesized as ideal labeling reagents for the enantioseparation of chiral carboxylic acids and evaluated in terms of separation efficiency and detection sensitivity by ultra-performance LC (UPLC)-MS/MS. Among the synthesized reagents, PCP2 was the most efficient chiral derivatization reagent for the enantioseparation of carboxylic acid. The Rs values and the detection limits of the derivatives of non-steroidal anti-inflammatory drugs, which were selected as the representative carboxylic acids, were in the range of 2.52-6.07 and 49-260 amol, respectively. The sensitive detection of biological carboxylic acids (detection limits, 32-520 amol) was also carried out by the proposed method using PCP2 and UPLC-MS/MS. The PCP2 was applied to the determination of carboxylic acids in human saliva. Several

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

    PubMed

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

    2013-12-01

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

  6. Rapid Quantitative Chiral Amphetamines Liquid Chromatography-Tandem Mass Spectrometry Method in Plasma and Oral Fluid with a Cost-effective Chiral Derivatizing Reagent

    PubMed Central

    Newmeyer, Matthew N.; Concheiro, Marta; Huestis, Marilyn A.

    2014-01-01

    Methamphetamine is a widely abused psychostimulant containing a chiral center. Consumption of over-the-counter and prescription medications may yield positive amphetamines results, but chiral separation of l- and d- methamphetamine and its metabolite amphetamine can help determine whether the source was licit or illicit. We present the first LC-MS/MS method with precolumn derivatization for methamphetamine and amphetamine chiral resolution in plasma and oral fluid collected with the Oral-Eze® and Quantisal™ devices. To 0.5 mL plasma, 0.75 mL Oral-Eze, or 1 mL Quantisal specimen racemic d11-methamphetamine and amphetamine internal standards were added, followed by protein precipitation. Samples were centrifuged and supernatants loaded onto pre-conditioned Phenomenex® Strata™-XC Polymeric Strong Cation solid phase extraction columns. After washing, analytes were eluted with 5% ammonium hydroxide in methanol. The eluate was evaporated to dryness and reconstituted in water. Derivatization was performed with 1-fluoro-2,4-dinitrophenyl-5-l-alanineamide (Marfey's reagent) and heating at 45°C for 1 h. Derivatized enantiomer separations were performed under isocratic conditions (methanol:water, 60:40) with a Phenomenex® Kinetex® 2.6 μm C18 column. Analytes were identified and quantified by two MRM transitions and their ratio on a 3200 QTrap (AB Sciex) mass spectrometer in ESI negative mode. In all three matrices, the method was linear for all enantiomers from 1-500 μg/L, with imprecision and accuracy of ≤11.3% and 85.3-108%, respectively. Extraction efficiencies ranged from 67.4-117% and matrix effects from -17.0-468%, with variation always ≤19.1%. Authentic plasma and OF specimens were collected from an IRB-approved study that included controlled Vicks® VapoInhaler™ administration. The present method is sensitive, selective, economic and rapid (separations accomplished in <10 min), and improves methamphetamine result interpretation. PMID:25065924

  7. Rapid quantitative chiral amphetamines liquid chromatography-tandem mass spectrometry: method in plasma and oral fluid with a cost-effective chiral derivatizing reagent.

    PubMed

    Newmeyer, Matthew N; Concheiro, Marta; Huestis, Marilyn A

    2014-09-05

    Methamphetamine is a widely abused psychostimulant containing a chiral center. Consumption of over-the-counter and prescription medications may yield positive amphetamines results, but chiral separation of l- and d-methamphetamine and its metabolite amphetamine can help determine whether the source was licit or illicit. We present the first LC-MS/MS method with precolumn derivatization for methamphetamine and amphetamine chiral resolution in plasma and oral fluid collected with the Oral-Eze(®) and Quantisal™ devices. To 0.5mL plasma, 0.75mL Oral-Eze, or 1mL Quantisal specimen racemic d11-methamphetamine and amphetamine internal standards were added, followed by protein precipitation. Samples were centrifuged and supernatants loaded onto pre-conditioned Phenomenex(®) Strata™-XC Polymeric Strong Cation solid phase extraction columns. After washing, analytes were eluted with 5% ammonium hydroxide in methanol. The eluate was evaporated to dryness and reconstituted in water. Derivatization was performed with 1-fluoro-2,4-dinitrophenyl-5-l-alanineamide (Marfey's reagent) and heating at 45°C for 1h. Derivatized enantiomer separations were performed under isocratic conditions (methanol:water, 60:40) with a Phenomenex(®) Kinetex(®) 2.6μm C18 column. Analytes were identified and quantified by two MRM transitions and their ratio on a 3200 QTrap (AB Sciex) mass spectrometer in ESI negative mode. In all three matrices, the method was linear for all enantiomers from 1 to 500μg/L, with imprecision and accuracy of ≤11.3% and 85.3-108%, respectively. Extraction efficiencies ranged from 67.4 to 117% and matrix effects from -17.0 to 468%, with variation always ≤19.1%. Authentic plasma and OF specimens were collected from an IRB-approved study that included controlled Vicks(®) VapoInhaler™ administration. The present method is sensitive, selective, economic and rapid (separations accomplished in <10min), and improves methamphetamine result interpretation. Published

  8. Profiling of chiral and achiral carboxylic acid metabolomics: synthesis and evaluation of triazine-type chiral derivatization reagents for carboxylic acids by LC-ESI-MS/MS and the application to saliva of healthy volunteers and diabetic patients.

    PubMed

    Takayama, Takahiro; Kuwabara, Tomohiro; Maeda, Toshio; Noge, Ichiro; Kitagawa, Yutaka; Inoue, Koichi; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

    2015-01-01

    Novel triazine-type chiral derivatization reagents, i.e., (S)-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidin-3-amine (DMT-3(S)-Apy) and (S)-4,6-dimethoxy-N-(pyrrolidin-3-yl)-1,3,5-triazin-2-amine (DMT-1(S)-Apy), were developed for the highly sensitive and selective detection of chiral carboxylic acids by UPLC-MS/MS analysis. Among the synthesized reagents, DMT-3(S)-Apy was a more efficient chiral reagent for the enantiomeric separation of chiral carboxylic acids in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The DMT-3(S)-Apy was used for the determination of 13 carboxylic acids in human saliva of healthy volunteers and diabetic patients. Various biological carboxylic acids including chiral carboxylic acids, and mono- and di-carboxylic acids were clearly identified in the saliva of healthy persons and diabetic patients. The concentrations of carboxylic acids detected in the saliva of diabetic patients were relatively higher than those in the healthy persons. Furthermore, the concentration of D-lactic acid (LA) and the ratio of D/L-LA in the diabetic patients were significantly higher than those in the healthy persons. The low ratio of D/L-LA in healthy persons was also identified to be independent of age and sex. These results suggest that the determination of the D/L-LA ratio in saliva might be applicable for the diagnosis of diabetes. Based on these observations, DMT-3(S)-Apy seems to be a useful chiral derivatization reagent for the determination not only of chiral carboxylic acids but also achiral ones. In conclusion, the proposed method using DMT-3(S)-Apy is useful for the carboxylic acid metabolomics study of various specimens.

  9. Novel chiral derivatization reagents possessing a pyridylthiourea structure for enantiospecific determination of amines and carboxylic acids in high-throughput liquid chromatography and electrospray-ionization mass spectrometry for chiral metabolomics identification.

    PubMed

    Nagao, Ryuji; Tsutsui, Haruhito; Mochizuki, Toshiki; Takayama, Takahiro; Kuwabara, Tomohiro; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo'oka, Toshimasa

    2013-06-28

    This paper reports the synthesis and the application of novel derivatization reagents possessing a pyridylthiourea structure for the enantiospecific determination of chiral amines and carboxylic acids in high-throughput LC-ESI-MS/MS. The novel reagents, i.e., (R)-N-(3-pyridylthiocarbamoyl)pyrrolidine-2-carboxylic acid (PyT-C) and (S)-3-amino-1-(3-pyridylthiocarbamoyl)pyrrolidine (PyT-N), were evaluated as chiral derivatization reagents for the enantiomeric determination of chiral amines and carboxylic acids, respectively, in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The chiral amines and carboxylic acids were easily labeled with PyT-C and PyT-N, respectively, at 60°C in 60min in the presence of 2,2'-dipyridyl disulfide (DPDS) and triphenylphosphine (TPP) as the activation reagents. The resulting diastereomers were completely separated by reversed-phase chromatography using a small particle (1.7μm) ODS column (Rs=3.54-6.00 for carboxylic acids and Rs=3.07-4.75 for amines). A highly sensitive detection at the sub-fmol level was also obtained from the SRM chromatograms at a single monitoring ion, m/z 137.0 (0.72-1.46fmol for carboxylic acids and 0.55-1.89fmol for amines). The proposed procedure using PyT-C and PyT-N was applied to the determination of chiral amines and carboxylic acids spiked into human saliva, as a model study of chiral metabonomics identification. dl-Amino acid methyl esters and N-acetyl dl-amino acids, which are the representatives as the chiral amines and carboxylic acids, in the saliva were clearly identified by the present method. Because the same product ion at m/z 137.0 was obtained from collision-induced dissociation (CID) of protonated molecular ions of all the derivatives, the proposed procedure using both reagents (i.e., PyT-C and PyT-N) seems to be useful for chiral metabolomics identification having selected functional groups (i.e., amines and carboxylic acids).

  10. Application of optically pure amines as chiral auxiliaries to develop trichloro-s-triazine-based new chiral derivatizing reagents for reversed-phase high-performance liquid chromatographic enantioseparation of DL-selenomethionine.

    PubMed

    Bhushan, Ravi; Lal, Manohar

    2013-08-01

    (R)-(+)-naphthylethyl amine and (S)-(+)-1-benzyl-3-aminopyrrolidine were incorporated as chiral auxiliaries, by nucleophilic substitution of chlorine atoms, in cyanuric chloride (CC) or its 6-butoxy derivative. There were obtained four new chiral derivatizing reagents (CDRs) as two dichloro and two monochloro triazine reagents. The CDRs so obtained were characterized and their optical purity was ascertained. Diastereomers of dl-selenomethionine were synthesized under microwave irradiation for 60 or 90 s (at 80% power of 800 W). Reversed-phase high-performance liquid chromatographic separation of diastereomers was carried out on a C18 column using mixtures of acetonitrile with aqueous trifluoroacetic acid as mobile phase. The detection was made at 230 nm using a photodiode array detector. The separation behaviors in terms of retention times and resolutions were compared. The separation method was validated for limit of detection, linearity, accuracy, precision, and recovery.

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

    PubMed

    Bhushan, Ravi; Nagar, Hariom

    2015-03-01

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

  12. Reversed-phase liquid chromatographic resolution of diastereomers of protein and non-protein amino acids prepared with newly synthesized chiral derivatizing reagents based on cyanuric chloride.

    PubMed

    Bhushan, Ravi; Agarwal, Charu

    2011-02-01

    Two new chiral monochloro-s-triazines (MCT) were synthesized [viz N-(4-chloro-6-piperidinyl-[1,3,5]-triazine-2-yl)-L-leucine amide and N-(4-chloro-6-piperidinyl-[1,3,5]-triazine-2-yl)-L-leucine) (CDR 1 and 2, respectively)] by the nucleophilic displacement of chlorine atoms in s-triazine moiety. One of the Cl atoms was replaced with piperidine, and the second Cl atom in the 6-piperidinyl derivative was replaced with amino acid amide (viz L-Leu-NH(2)) and amino acid (L-Leu). These reagents were characterized and used as CDRs for chiral separation of protein and non-protein amino acids, and were separated on a reversed-phase C(18) column. The reaction conditions were optimized for the synthesis of diastereomers using one MCT reagent. The separation method was validated for limit of detection, linearity, accuracy, precision, and recovery.

  13. Comparison of amino acid derivatization reagents for LC-ESI-MS analysis. Introducing a novel phosphazene-based derivatization reagent.

    PubMed

    Rebane, Riin; Oldekop, Maarja-Liisa; Herodes, Koit

    2012-09-01

    Amino acid analysis with high performance liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS) is an emerging method. For more sensitive analysis, derivatization is used and next to commercially available derivatization reagents such as dansyl chloride (DNS), 9-fluorenylmethyl chloroformate (FMOC-Cl) and diethyl ethoxymethylenemalonate (DEEMM), new derivatization reagents are designed specially for LC-ESI-MS, like p-N,N,N-trimethylammonioanilyl N'-hydroxysuccinimidyl carbamate iodide (TAHS) which provides very low limits of detection. In this work, a novel phosphazene based derivatization reagent (FOSF) that provides comparable limits of quantitation (LoQ) to TAHS is introduced. Moreover, a thorough comparison between FOSF, TAHS, DNS, FMOC-Cl and DEEMM is carried out for 7 different amino acids - Arg, Asp, Gly, β-Ala, Pro, Trp and Phe. This is a first time that thorough comparison is carried out on the same instrument for amino acid derivatization reagents. Results on the same instrument for five amino acid derivatization reagents show that novel reagents are sensitive with LoQ values around 80 fmol but have disadvantages such as problematic chromatographic separation. Next to novel reagents, DEEMM offers very good LoQ-s (average of 150 fmol) and wide dynamic linear range.

  14. Reversed-phase high-performance liquid chromatographic separation of diastereomers of (R,S)-mexiletine prepared by microwave irradiation with four new chiral derivatizing reagents based on trichloro-s-triazine having amino acids as chiral auxiliaries and 10 others having amino acid amides.

    PubMed

    Bhushan, Ravi; Dixit, Shuchi

    2010-12-03

    A new series of chiral derivatizing reagents (CDRs) consisting of four dichloro-s-triazine reagents was synthesized by nucleophilic substitution of one chlorine atom in trichloro-s-triazine with amino acids, namely L-Leu, D-Phg, L-Val and L-Ala as chiral auxiliaries. Two other sets of CDRs consisting of four dichloro-s-triazine (DCT) and six monochloro-s-triazine (MCT) reagents were also prepared by nucleophilic substitution of chlorine atom(s) with different amino acid amides as chiral auxiliaries in trichloro-s-triazine and its 6-methoxy derivative, respectively. These 14 CDRs were used for the synthesis of diastereomers of (R,S)-mexiletine under microwave irradiation (i.e. 60s and 90 s at 85% power (of 800 W) using DCT and MCT reagents, respectively), which were resolved by reversed-phase high-performance liquid chromatography using C18 column and gradient eluting mixtures of methanol with aqueous trifluoroacetic acid (TFA) with UV detection at 230 nm. The resolution (R(s)), difference between retention times of resolved diastereomers (Δt) and retention factors (k) obtained for the three sets of diastereomers were compared among themselves and among the three groups. Explanations have been offered for longer retention times and better resolution of diastereomers prepared with DCT reagents in comparison of their MCT counterparts and, for the influence of hydrophobicity of the side chain R of the amino acid in the CDRs on retention times and resolution. The newly synthesized CDRs were observed to be superior as compared to their amide counterparts in terms of providing better resolution and cost effectiveness. The method was validated for limit of detection, linearity, accuracy and precision.

  15. Configuration and racemization determination of cysteine residues in peptides by chiral derivatization and HPLC: application to oxytocin peptides.

    PubMed

    Szabó, S; Szókán, G; Khlafulla, A M; Almás, M; Kiss, C; Rill, A; Schön, I

    2001-06-01

    An improved RP-HPLC method was developed for the determination of the configuration and stereochemical purity of cysteine residues in peptides. The method consists of oxidation of cysteine and cystine residues to cysteic acid, followed by hydrolysis and pre-column chiral derivatization with Val-Marfey's reagent.

  16. Recent advances in development and application of derivatization reagents having a benzofurazan structure: a brief overview.

    PubMed

    Santa, Tomofumi

    2014-06-01

    Chemical derivatization is often used to improve the separation efficiency and to enhance the detectability of the target compounds in high-performance liquid chromatography and capillary electrophoresis. The derivatization reagents having a benzofurazan (2,1,3-benzoxadiazole) structure are one of the most often used reagent for this purpose. In this paper, the recent advances in the development and the application of benzofurazan derivatization reagents are reviewed.

  17. Derivatized vancomycin stationary phases for LC chiral separations.

    PubMed

    Berthod, A; Nair, U B; Bagwill, C; Armstrong, D W

    1996-10-01

    In this work, synthetic and natural chiral selectors were combined to form two different chiral stationary phases (CSPs). These were made by bonding R- or S-(1-naphthylethyl) carbamate (R-NEC or S-NEC)-derivatized vancomycin molecules to a silica gel support. The two CSPs were evaluated using a set of 60 enantiomeric pairs. The results were compared to the ones obtained with the commercial underivatized vancomycin CSP. Three Chromatographic modes were used: (i) the normal-phase mode using a nonpolar mobile phase with different ratios of hexane and ethanol; (ii) the reversed-phase mode with hydro-organic mobile phases; and (iii) the polar aprotic organic mode with nonaqueous acetonitrile plus small amounts of methanol and an acid and/or base to control retention and selectivity. It is shown that the polarity of the underivatized vancomycin phase is higher than that of the two R- and S-NEC-derivatized CSPs. In the pH range 4-7, there is no ionization change of the chiral selector for the three CSPs. 43% of the studied compounds were resolved by the NEC-derivatized phases when they could not be resolved by the vancomycin CSP. However, the enantiorecognition for 12% of the compounds on the native vancomycin CSP was lost upon NEC derivatization. 45% of the studied compounds were resolved by the NEC-derivatized and native CSPs. The NEC derivatization procedure may block some useful active sites on the vancomycin molecule. Also, the R- and S-NEC moieties are chiral themselves and can contribute additional interaction sites not available on the native vancomycin molecule.

  18. Enantiomeric determination of amphetamine and methamphetamine in urine by precolumn derivatization with Marfey's reagent and HPLC.

    PubMed

    Foster, B S; Gilbert, D D; Hutchaleelaha, A; Mayersohn, M

    1998-01-01

    An analytical method was developed for enantiomeric determination of amphetamine and methamphetamine in human urine. The enantiomers were isolated from urine by solid-phase extraction, and diastereomers were formed by derivatization with the chiral Marfey's reagent (1-fluoro-2,4-dinitrophenyl-5-l-aniline amide). The diastereomers were separated by reversed-phase high-performance liquid chromatography in a water/methanol mobile phase and detected by absorbance spectrophotometry at 340 nm. Linear standard curves were obtained for all four enantiomers over a concentration range of 0.16-1.00 mg/L in urine. The detection limit was 0.16 mg/L urine for each enantiomer, and the limit of quantitation was 0.40 mg/L. The urine of 10 decedents was analyzed by this method and by a previously published precolumn derivatization procedure using (-)-1-(9-fluorenyl)ethyl chloroformate (FLEC) as the derivatizing agent and fluorescence detection. Comparison of the results of the two methods by linear regression showed comparable results for both d-amphetamine and d-methamphetamine. Neither method detected the presence of the l-enantiomers in the urine samples.

  19. Derivatization and photolysis of a photoaffinity reagent for probing protein and cell surface interactions

    SciTech Connect

    Murphy, H.; Harris, H.W. Jr.

    1986-05-01

    The synthesis of the novel, heterobifunctional, cleavable, photoactivable crosslinking reagent, N-(4-(p-azido-m-(/sup 125/I) iodophenylazo)benzoyl)-3-aminopropyl-N'-oxysulfosuccinimide has been described by Denny and Blobel. This reagent is desirable because after photolysis and azo bond cleavage the /sup 125/I is transferred from the reagent to the crosslinked molecule. The authors demonstrate that using the reported synthesis 99% of the desired reagent is destroyed during the chloramine-T iodination step. They report a synthesis revision which produces high yields of the uniodinated (U) reagent. The derivatized reagent may be used in its iodinated (I) or U forms. To study the U reagent, a horseradish peroxidase (HRP) molecule is derivatized with nine reagent molecules. The derivatized HRP has 70% of its original enzymatic activity. After photolysis, 14% of this activity is retained and SDS-PAGE electrophoresis shows a crosslinked complex of HRP molecules. After endocytosis by cells, photolysis attaches the soluble derivatized HRP to membranes allowing them to be traced in the electron microscope. To study the I reagent, an amino-dextran (MW 73-400) molecule is derivatized with three U reagent molecules. The U reagent molecules are then iodinated by the chloramine-T method. With photolysis and cleavage, the /sup 125/I labeled reagent on dextran transfers its label to bovine serum albumin or ovalbumin. The authors conclude this reagent is a versatile probe for study of protein or cell surface topography.

  20. Isotopic variants of light and heavy L-pyroglutamic acid succinimidyl esters as the derivatization reagents for DL-amino acid chiral metabolomics identification by liquid chromatography and electrospray ionization mass spectrometry.

    PubMed

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

    2014-02-06

    L-Pyroglutamic acid succinimidyl ester (L-PGA-OSu) and its isotopic variant (L-PGA[d5]-OSu) were newly synthesized and evaluated as the chiral labeling reagents for the enantioseparation of amino acids, in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The enantiomers of amino acids were easily labeled with the reagents at 60°C within 10 min in an alkaline medium containing triethylamine. Although all the diastereomers derived from 18 proteolytic amino acids could not be satisfactorily separated, the pairs of 9 amino acids were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs=1.95-8.05). The characteristic daughter ions, i.e., m/z 84.04 and m/z 89.04, were detected from all the derivatives by the collision induced dissociation of the protonated molecular ions. A highly sensitive detection at a low-fmol level (0.5-3.2 fmol) was also obtained from the selected reaction monitoring (SRM) chromatograms. An isotope labeling strategy using light and heavy L-PGA-OSu for the differential analysis of the DL-amino acids in different sample groups is also presented in this paper. The differential analysis of biological sample (i.e., human serum) and food product (i.e., yogurt) were tried to demonstrate the efficiency of the proposed method. The ratios of the DL-amino acids in human serum samples, spiked with the different concentrations of D-amino acids, were determined by the procedures using L-PGA-OSu and L-PGA[d5]-OSu. The D/L ratios in the two sample groups at different concentrations of amino acids were similar to the theoretical values. Furthermore, the ratios of D/L-alanine values in different yogurt products were comparable to the ratios obtained from the d/l values using only light reagent (i.e., L-PGA-OSu). Consequently, the proposed strategy is useful for the differential analysis not only in biological samples but also in food products.

  1. Chiral analysis of ammuxetine enantiomers in dog plasma using online SPE/liquid chromatography with tandem mass spectrometric detection after precolumn chiral derivatization.

    PubMed

    Yu, Jimei; Li, Xin; Zhou, Jiezhao; Xie, Xiangyang; Chen, Meiling; He, Xinhua; Yang, Yang; Zhang, Youzhi; Zheng, Aiping; Mei, Xingguo; Li, Ying

    2017-05-01

    Ammuxetine (AMT), a novel chiral antidepressant candidate compound, exhibits better antidepression effects than duloxetine in different animal models. In this article, a chiral derivatization method, combined with online solid phase extraction (online SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS), was developed for the chiral separation of AMT enantiomers after administration of racemic AMT to dogs. The derivatization reaction employed 2,3,4,6-tetra-O-acetyl-b-glucopyr-anosyl isothiocyanate (GITC) as a precolumn chiral derivatization reagent. A SPE column Retain PEP Javelin (10 × 2.1 mm) was used to remove proteins and other impurities in plasma samples. The enantiomeric derivatives were separated on a ZORBAX SB-C18 column (50 × 2.1 mm × 3.5 μm) with an isocratic elution procedure. The selected multiple reaction monitoring mode of the positive ion was performed and the parent to the product transitions m/z 681.0/543.1 and m/z 687.4/543.1 were used to measure the derivatives of AMT and duloxetine (internal standard) with electrospray ionization. The method was validated in terms of specificity, linearity, sensitivity, precision, accuracy, matrix effect, and stability. The method was applied to a pharmacokinetics study of AMT racemate in dogs. The results suggested that the pharmacokinetic of AMT enantiomers might be stereoselective in dogs. © 2017 Wiley Periodicals, Inc.

  2. Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Santa, Tomofumi

    2011-01-01

    Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds.

  3. Isothiocyanates as derivatization reagents for amines in liquid chromatography/electrospray ionization-tandem mass spectrometry.

    PubMed

    Santa, Tomofumi

    2010-09-01

    The applicability of 3-pyridyl isothiocyanate, p-(dimethylamino)phenyl isothiocyanate and m-nitrophenyl isothiocyanate as the derivatization reagents for amines in high-performance liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) was examined. The generated derivatives of amines with these reagents were favorably separated on the reversed-phase column and detected by ESI-MS/MS. The C-N bond of the generated thiourea structure was efficiently cleaved by collision-induced dissociation and gave the single and intense product ion. Among the three reagents, 3-pyridyl isothiocyanate was the most suitable as the derivatization reagent with regard to the reactivity to amines and the detection sensitivity.

  4. Qualitative and quantitative evaluation of derivatization reagents for different types of protein-bound carbonyl groups.

    PubMed

    Bollineni, Ravi Chand; Fedorova, Maria; Hoffmann, Ralf

    2013-09-07

    Mass spectrometry (MS) of 'carbonylated proteins' often involves derivatization of reactive carbonyl groups to facilitate their enrichment, identification and quantification. Among the many reported reagents, 2,4-dinitrophenylhydrazine (DNPH), biotin hydrazide (BHZ) and O-(biotinylcarbazoylmethyl) hydroxylamine (ARP) are the most frequently used. Despite their common use in carbonylation research, their reactivity towards protein-bound carbonyls has not been quantitatively evaluated in detail, to the best of our knowledge. Thus we studied the reactivity and specificity of these reagents towards different classes of reactive carbonyl groups (e.g. aldehydes, ketones and lactams), each being represented by a synthetic peptide carrying an accordingly modified residue. All three tagging reagents were selective for aliphatic aldehydes and ketones. Lactams and carbonyl-containing tryptophan oxidation products, however, were labelled only at low levels or not at all. Whereas DNPH derivatization was efficient under the published standard conditions, the derivatization conditions for BHZ and ARP had to be altered. Acidic conditions provided quantitative labelling yields for ARP. Peptides derivatized with DNPH, BHZ and ARP fragmented efficiently in tandem mass spectrometry, when the experimental conditions were chosen carefully for each reagent. Importantly, the tested carbonylated peptides did not cross-react with amino groups in other proteins present during sample preparations or enzymatic digestion. Thus, it appears favourable to digest proteins first and then derivatise the reactive carbonyl groups more efficiently at the peptide level under acidic conditions. The carbonylated model peptides used in this study might be valid internal standards for carbonylation proteomics.

  5. A rapid and sensitive detection of D-Aspartic acid in Crystallin by chiral derivatized liquid chromatography mass spectrometry.

    PubMed

    Mizuno, Hajime; Miyazaki, Yasuto; Ito, Keisuke; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

    2016-10-07

    A method for the determination of D-Aspartic acid (D-Asp) and its D/L ratio in peptides and proteins has been developed. This method was carried out with good separation of the D/L chiral peptide pairs by combination of a chiral derivatization and an ADME column separation. Furthermore, a cationic derivatization reagent, DBD-Py-NCS, increased the sensitivity of the ESI-MS/MS detection. To confirm the comprehensive peptide analysis, synthesized α-Crystallin tryptic peptides, which included D-Asp residues, were analyzed. The 5 pairs of D/L-Asp that included peptide diastereomers were well separated. Their peak resolutions were more than 1.5 and the results were reproducible (RSD<0.05, n=5). As an application of this method, we analyzed the α-Crystallin standard and UV irradiated α-Crystallin. After trypsin digestion and DBD-Py-NCS derivatization, the tryptic peptide derivatives were applied to LC-MS/MS. Based on the results of peptide sequence identification, almost all the tryptic peptides of the αA- and αB-Crystallin homologous subunits of α-Crystallin were detected as DBD-Py NCS derivatives. However, there was no D-Asp residue in the standard proteins. In the case of the UV irradiated α-Crystallin, Asp(76) and Asp(84) in the αA-Crystallin and Asp(96) in αB-Crystallin were racemized to D-Asp. These results show that this proposed chiral peptide LC-MS/MS method using chiral derivatization provides a rapid and sensitive analysis for post translational Asp racemization sites in aging proteins.

  6. [Separation and quantification of theanine enantiomers using high performance liquid chromatography coupled with chiral derivatization].

    PubMed

    Li, Yinhua; Liu, Zhonghua; Huang, Jian'an

    2007-09-01

    L-Theanine is a unique non-protein amino acid in tea, and shows many physiological functions. To directly extract L-theanine from tea is a lengthy and very costly process. Although the chemical synthesis of theanines is simple, the product is unfortunately a mixture of DL-enantiomers. A chiral derivatization method was developed for the separation and quantification of theanine enantiomers by reversed-phase high performance liquid chromatography (RP-HPLC). 1-Fluoro-2,4-dinitrophenyl-5-L-alanine amide (FDAA)was used as the chiral reagent. This method showed good linearity for both L-theanine (ranging from 1.732 x 10(-3) to 2.077 microg) and D-theanine (ranging from 1.696 x 10(-3) to 2.044 microg). The recoveries were in the range of 97.3% - 102.0% for L-theanine and 97.2% - 103.2% for D-theanine. This method also showed excellent limit of detection (approximately 5 x 10(-4) microg) and limit of quantification (approximately 1 x 10(-3) microg) for both L-theanine and D-theanine. The results demonstrated that this method is precise, accurate and can be used for the determination of theanine enantiomers.

  7. Stable isotope coded derivatizing reagents as internal standards in metabolite profiling.

    PubMed

    Bruheim, Per; Kvitvang, Hans Fredrik Nyvold; Villas-Boas, Silas G

    2013-06-28

    Gas chromatography (GC) and liquid chromatography (LC) coupled to mass spectrometric (MS) detection have become the two main techniques for the analysis of metabolite pools (i.e. Metabolomics). These technologies are especially suited for Metabolite Profiling analysis of various metabolite groups due to high separation capabilities of the chromatographs and high sensitivity of the mass analysers. The trend in quantitative Metabolite Profiling is to add more metabolites and metabolite groups in a single method. This should not be done by compromising the analytical precision. Mass spectrometric detection comes with certain limitations, especially in the quantitative aspects as standards are needed for conversion of ion abundance to concentration and ionization efficiencies are directly dependent on eluent conditions. This calls for novel strategies to counteract all variables that can influence the quantitative precision. Usually, internal standards are used to correct any technical variation. For quantitation of single or just a few analytes this can be executed with spiking isotopically labeled standards. However, for more comprehensive analytical tasks, e.g. profiling tens or hundreds of analytes simultaneously, this strategy becomes expensive and in many cases isotopically labeled standards are not available. An alternative is to introduce a derivatizing step where the sample is derivatized with naturally labeled reagent, while a standard solution is separately derivatized with isotopically labeled reagent and spiked into the sample solution prior to analysis. This strategy, named isotope coded derivatization - ICD, is attractive in the emerging field of quantitative Metabolite Profiling where current protocols can easily comprise over hundred metabolites. This review provides an overview of isotopically labeled derivatizing reagents that have been developed for important metabolite groups with the aim to improve analytical performance and precision.

  8. Study of Highly Selective and Efficient Thiol Derivatization using Selenium Reagents by Mass Spectrometry

    SciTech Connect

    Xu, Kehua; Zhang, Yun W.; Tang, Bo; Laskin, Julia; Roach, Patrick J.; Chen, Hao

    2010-08-15

    Biological thiols are critical physiological components and their detection often involves derivatization. This paper reports a systemic mass spectrometry (MS) investigation of the cleavage of Se-N bond by thiol to form a new Se-S bond, the new selenium chemistry for thiol labeling. Our data shows that the reaction is highly selective, rapid, reversible and efficient. For instance, among twenty amino acids, only cysteine was found to be reactive with Se-N containing reagents and the reaction takes place in seconds. By adding dithiothreitol (DTT), the newly formed Se-S bond of peptides/proteins can be reduced back to free thiol. The high selectivity and excellent reversibility of the reaction provide potential of using this chemistry for selective identification of thiol compounds or enriching and purifying thiol peptides/proteins. In addition, the derivatized thiol peptides have interesting dissociation behavior, which is tunable using different selenium reagents. For example, by introducing an adjacent nucleophilic group into the selenium reagent in the case of using ebselen, the reaction product of ebselen with glutathione (GSH) is easy to lose the selenium tag upon collision-induced dissociation (CID), which is useful to "fish out" those peptides containing free cysteine residues by precursor ion scan. By contrast, the selenium tag of N-(phenylseleno) phthalimide reagent can be stable and survive in CID process, which would be of value in pinpointing thiol location using a top-down proteomic approach. Also, the high conversion yield of the reaction allows the counting of total number of thiol in proteins. We believe that ebselen or N-(phenylseleno) phthalimide as tagging thiol-protein reagents will have important applications in both qualitative and quantitative analysis of different thiol-proteins derived from living cells by MS method.

  9. Design of chiral monochloro-s-triazine reagents for the liquid chromatographic separation of amino acid enantiomers.

    PubMed

    Brückner, H; Wachsmann, M

    2003-05-23

    A series of chiral derivatizing reagents (CDRs) was synthesized by nucleophilic replacement of one chlorine atom in cyanuric chloride (2,4,6-trichloro-1,3,5-triazine; s-triazine) by alkoxy (methoxy, butoxy, 1,1,1-trifluoroethoxy) or aryloxy groups (phenoxy, nitrophenoxy, phenylphenoxy, 4-methylcoumaryloxy), and displacement of a second chlorine by L-alanine amide, L-phenylalanine amide, L-proline tert.-butyl ester, or Boc-L-lysine tert.-butyl ester. Further, CDRs were investigated in which two chlorine atoms in cyanuric chloride were substituted consecutively by L-valine amide and L-phenylalanine amide. The resulting CDRs having a remaining reactive chlorine were tested for their capability of derivatizing DL-amino acids followed by liquid chromatographic separation of the resulting diastereomers.

  10. Enantiomeric purity determination of acetyl-L-carnitine by NMR with chiral lanthanide shift reagents.

    PubMed

    Kagawa, Miyuki; Machida, Yoshio; Nishi, Hiroyuki; Haginaka, Jun

    2005-08-10

    Enantiomer signal separation of acetyl-carnitine chloride was obtained on a 500 MHz Nuclear Magnetic Resonance (1H NMR) analysis by fast diastereomeric interaction with chiral shift reagents such as chiral lanthanide-camphorato or chiral samarium-pdta shift reagents. Effects of the kinds of chiral shift reagents and the molar ratio of chiral shift reagent to acetyl-carnitine chloride on enantiomer signal separation were investigated and evaluated. Optimization of the experimental conditions provided two significant split signals for the enantiomers, leading to the successful quantitative analysis. Distinguishment of 0.5% of the minor enantiomer (D-form) in acetyl-L-carnitine chloride was found to be possible by 1H NMR with tris[3-(heptafluoropropylhydroxymethylene)-D-camphorato] and praseodymium derivative, (Pr[hfc]3), as chiral shift reagents.

  11. Development of amino acid derivatization reagents for liquid chromatography electrospray ionization mass spectrometric analysis and ionization efficiency measurements.

    PubMed

    Rebane, Riin; Rodima, Toomas; Kütt, Agnes; Herodes, Koit

    2015-04-17

    Derivatization is one of the most common ways for improving chromatographic separation and sensitivity for LC-ESI-MS analysis. The aim of this work was to design new derivatization reagents for LC-ESI-MS analysis of amino acids which would (1) provide good reversed phase chromatographic separation, (2) most importantly, provide low detection limits, (3) be easily synthesized, (4) produce derivatives which are less susceptible to matrix influences and (5) have convenient derivatization procedure with stable derivatives suitable for automatization. In the current work two new LC-ESI-MS compatible derivatization reagents have been designed and synthesized, dibenzyl ethoxymethylene malonate (DBEMM) and benzyl ethyl ethoxymethylene malonate (EBEMM). The DBEMM meets all the goals set with instrumental detection limits as low as 1 femtomole for amino acids and 40 attomole for selenoamino acids.

  12. High-performance liquid chromatographic resolution of 1-(1,4-benzodioxane-2-formyl)-piperazine enantiomers after chiral derivatization.

    PubMed

    Chen, Zhiqiong; Yu, Yu; Li, Longjiang

    2005-02-01

    Chiral separation of racemic mixtures is of the greatest importance to the pharmaceutical industry, as the isomers of a given racemate may exhibit substantially different pharmacological effects, not to mention possibly differing toxicity behaviour. A novel chiral separation method is developed for the determination of 1-(1,4-benzodioxane-2-formyl)piperazine (BFP) enantiomers. The indirect resolution is performed by applying precolumn derivatization with the chiral reagent 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl isothiocyanate (GITC). The resulting diastereoisomers are separated on a reversed-phase ODS column with methanol-potassium dihydrogen phosphate (0.02mol/L, 50:50) as mobile phase. UV detection is at 250 nm. The effect of mobile phase composition upon resolution and analysis time is investigated. Two diastereoisomers show nearly base-line separation under optimal chromatographic conditions. The presented study provides a simple and accurate method for the enantiomeric quality control and the optical purity assay of BFP.

  13. A novel approach for HPLC determination of 2-cynaoacetamide using derivatization procedure with 2-hydroxyacetophenone as a new useful derivatization reagent.

    PubMed

    Douša, Michal; Břicháč, Jiří; Tkadlecová, Marcela; Man, Stanislav; Zezula, Josef; Hájíček, Josef; Pekárek, Tomáš

    2016-09-05

    A novel and sensitive derivatization procedure for the determination of 2-cynaoacetamide in pharmaceutical samples using liquid chromatography with the fluorescence detection was discovered. The method is based on derivatization of 2-cynaoacetamide using 2-hydroxyacetophenone as a new derivatization reagent. The product of derivatization reaction was isolated and characterized using spectroscopic techniques namely LC-MS, NMR and IR. The structure of 2-cyanoacetamide derivative was unambiguously assigned as a 2-amino-4-phenylfuran-3-carboxamide. Two derivatization systems were optimized in terms of reaction temperature, reaction time, pH and concentration of 2-hydroxyacetophenone, and a new pre- and post-derivatization HPLC methods were developed. The separations on HPLC with pre-column derivatization were accomplished using stationary phase based on a XBridge C18 column (100×4.6, 3.5μm) and isocratic elution using the mobile phase acetonitrile - 0.1% formic acid (30:70, v/v). The separations on the HPLC with post-column derivatization were performed on stationary phase on a TSKgel Amide-80 column (150×4.6mm, 3μm). The mobile phase was a mixture of acetonitrile, methanol and 10mM sodium formate buffer at pH=4.5 in ratio 3:2:95 (v/v). Both HPLC methods were fully validated in terms of linearity, sensitivity (limit of detection and limit of quantification), accuracy and precision according to ICH guidelines. The pre-column derivatization method was linear in the range 1.1-2000μg/l with method accuracy≥98.2% and method precision RSD≤4.8%. The post-column derivatization method was linear in the range 12-2000μg/l. Method accuracy≥96.3% and method precision RSD≤3.5%. Proposed new methods were proved to be highly sensitive, simple and rapid, and were successfully applied to the determinations of 2-cynaoacetamide in pregabalin.

  14. Chiral Separations

    NASA Astrophysics Data System (ADS)

    Stalcup, A. M.

    2010-07-01

    The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

  15. Enantiomeric derivatization on the Mars Organic Molecule Analyzer (MOMA) experiment aboard ExoMars 2018: how to unravel martian chirality

    NASA Astrophysics Data System (ADS)

    Freissinet, C.; Buch, A.; Szopa, C.; Morisson, M.; Grand, N.; Raulin, F.; Brinckerhoff, W.

    2015-10-01

    The origin of homochirality in life on Earth remains unknown. The answer to this question lies in the study of chirality elsewhere in the Solar System. The Sample Analysis at Mars (SAM) experiment aboard Curiosity established the presence of organic molecules indigenous to a clay-rich sample on Mars [1]. However, SAM does not have the ability to separate between the enantiomers of potential medium- or high- molecular weight organic molecules. One of the wet chemistry experiments to be used in the MOMA instrument of the Exomars mission is designed for the extraction and identification of refractory organic chemical components in solid samples using gas chromatography-mass spectrometry (GCMS), while keeping the chiral center of the molecules intact [2]. This derivatization technique, using dimethylformamide dimethylacetal (DMF-DMA) as a reagent, will allow MOMA to separate the enantiomers of molecules of interest for astrobiology, such as amino acids, sugars or carboxylic acids. We present here the results of laboratory experiments which display the feasability and limitations of the detection of an enantiomeric excess of complex organic molecules in various analog samples, depending on the mineralogy of the Mars analog solid sample.

  16. Resin-bound chiral derivatizing agents for assignment of configuration by NMR spectroscopy.

    PubMed

    Porto, Silvia; Seco, José Manuel; Espinosa, Juan Félix; Quiñoá, Emilio; Riguera, Ricardo

    2008-08-01

    A general methodology for assigning the configuration of chiral mono- and polyfunctional compounds by NMR is presented. The approach is based on the use of polystyrene-bound chiral derivatizing agents (CDA-resins) specifically designed to achieve the high-yield formation of the covalent linkages (amide or ester bonds) between the substrate and the chiral auxiliary within the NMR tube, without the need for other manipulations, on a microscale level and in a short time. The deuterated NMR solvents (CDCl3, CD3CN, CS2/CD2Cl2) are also the reaction solvents and separations, purifications or workups of any kind are not necessary prior to recording the spectra. The CDA-resins prepared included MPA, 9-AMA, BPG, MTPA, and 2-NTBA as auxiliary agents incorporated either as single enantiomers or as mixed combinations of the (R)- and the (S)-enantiomers at unequal and known ratios. The high versatility of these systems was successfully demonstrated in a variety of ways based on double and single derivatization, low temperature experiments, or the formation of metal complexes. The approach allowed the absolute configurations of chiral primary amines, primary and secondary alcohols, cyanohydrins, thiols, diols, triols, and amino alcohols to be determined. Extensive high-resolution magic angle spinning (HR-MAS) NMR experiments allowed the characterization of the new CDA-resins and enabled the study of their stability and regioselectivity.

  17. Determination of naftopidil enantiomers in rat plasma using chiral solid phases and pre-column derivatization high-performance liquid chromatography.

    PubMed

    Liu, Xiawen; Zhang, Yunying; Yuan, Mu; Sun, Yinxiang

    2012-10-15

    Two bioanalytical HPLC methods (chiral solid phases (CSPs) HPLC and pre-column derivatization HPLC) were developed and validated for the determination of naftopidil enantiomers in rat plasma. Analytes were extracted from biomaterials by liquid-liquid extraction. The pre-column derivatization HPLC method employed (+)-diacetyl-L-tartaric anhydride (DATAN) as the pre-column derivatization reagent, and subsequent separation of diastereomers was conducted on an Agilent Hypersil ODS column with a mixture of methanol-acetonitrile-phosphate buffer (pH 4.1; 20 mM) (40:30:30, v/v/v) flowing at 1 mL/min as the mobile phase. The CSPs HPLC method utilized a Chiralpak IA column with a mobile phase of methanol-acetonitrile-acetate buffer (pH 5.3; 5 mM) (50:25:25, v/v/v) flowing at 0.5 mL/min. In both methods, the analytes were monitored using a fluorescence detector with an excitation wavelength of 290 nm and an emission wavelength of 340 nm. Both methods were consistent (RSD<15% by the derivatization method and<10% by the CSPs method) and linear (r>9950). Compared to the pre-column derivatization method, the CSPs method had lower quantification limits (10.6/9.6 ng/mL of (+)-/(-)-naftopidil by derivatization method and 1.1/1.8 ng/mL of (+)-/(-)-naftopidil by CSPs method), and was simpler to carry out. The validated CSPs method was successfully applied in a pharmacokinetic study of naftopidil enantiomers in rats, which showed that pharmacokinetic parameters of (+)- and (-)-NAF after intravenous administration of (±)-NAF were similar. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Compounds having thiourea moiety as derivatization reagents in liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS): synthesis of derivatization reagents for carboxylic acids.

    PubMed

    Inoda, Hirotaka; Nishiyama, Taihei; Yoshikado, Takashi; Suwanai, Yusuke; Santa, Tomofumi

    2011-06-01

    The derivatization reagents for carboxylic acids, N-(Pyridin-3-yl)hydrazinecarbothioamide, N-[4-(dimethylamino)phenyl]hydrazinecarbothioamide, 1-(2-aminoethyl)-3-(pyridin-3-yl)thiourea, 1-(2-aminoethyl)-3-[4-(dimethylamino)phenyl]thiourea and 4-(2-aminoethyl)-N-phenylpiperazine-1-carbothioamide were synthesized. These reagents reacted with carboxylic acids at 60°C for 45 min in the presence of the condensation reagents. The generated derivatives were favorably separated on the reversed-phase column and sensitively detected by electrospray ionization tandem mass spectrometry. These reagents enhanced the electrospray ionization response of the analyte and generated a particular product ion efficiently by collision-induced dissociation, and thus they were suitable for MS/MS detection.

  19. Evaluation of diazotized 4-amino-3,5-dinitrobenzoic acid (ADBA) as a new derivatizing reagent.

    PubMed

    Idowu, S O; Olaniyi, A A

    2001-09-01

    A preliminary evaluation of the reactivity of diazotized 4-amino-3,5-dinitrobenzoic acid (ADBA) towards selected aromatic compounds has been described. Successful diazo coupling of pharmaceuticals possessing aromatic rings of varying reactivities was achieved with the arenediazonium ion of ADBA at room (30 degrees C) or elevated temperature (80 degrees C). The adducts formed in spot-test reactions were coloured for some compounds (e.g, cloxacillin and chloroxylenol), others showed colour at elevated temperature of reaction (e.g., salicylic acid and aspirin), while others showed no detectable change in colour of reaction mixture, even at elevated temperature (e.g., imidazole and tinidazole). The coloured product formed at room temperature decomposed and the colour discharged at elevated temperature in some cases (e.g., beta-naphthol). However, thin layer chromatographic analysis suggested that a more lipophilic derivative, relative to the original compound was formed for some of the compounds studied which did not show any detectable colour change in the spot test reactions. The diazotized ADBA is thus shown to be a reactive coupling reagent with which a suitable derivatization methodology could be developed for a wide range of pharmaceuticals in ultraviolet/visible spectrophotometry and high performance liquid chromatographic (HPLC) analysis.

  20. HPLC enantioresolution of (R,S)-baclofen using three newly synthesized dichloro-s-triazine reagents having amines and five others having amino acids as chiral auxiliaries.

    PubMed

    Bhushan, Ravi; Dixit, Shuchi

    2012-06-01

    Enantioresolution of (R,S)-baclofen was accomplished using a newly synthesized set of three chiral derivatizing reagents (CDRs) having amines [(S)-(-)-α,4-dimethylbenzylamine, (-)-cis-myrtanylamine and (R)-(-)-1-cyclohexylethylamine] as chiral auxiliaries in cyanuric chloride and another set of five CDRs having amino acids (L-Leu, D-Phg, L-Val, L-Met and L-Ala) as chiral auxiliaries. These eight CDRs were used for synthesis of diastereomers of (R,S)-baclofen under microwave irradiation. The diastereomers were separated on a reversed-phase C(18) column using mixtures of methanol with aqueous trifluoroacetic acid with UV detection at 230 nm. Chromatographic data obtained for the two sets of diastereomers were compared among themselves and among the two groups. The method was validated for limit of detection, linearity, accuracy and precision.

  1. Stereoselective method development and validation for determination of concentrations of amphetamine-type stimulants and metabolites in human urine using a simultaneous extraction-chiral derivatization approach.

    PubMed

    Wan Raihana, W A; Gan, S H; Tan, S C

    2011-01-01

    Amphetamine-type stimulants (ATS) are a group of chiral amine drugs which are commonly abused for their sympathomimetic and stimulant properties. ATS are extensively metabolised by hepatic cytochrome P450 enzymes. As metabolism of ATS has been shown to be highly stereospecific, stereoselective analytical methods are essential for the quantitative determination of ATS concentrations for both in vivo and in vitro studies of ATS metabolism. This paper describes a new stereoselective method for the simultaneous determination of amphetamine (AM), methamphetamine (MA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), 4-hydroxy-3-methoxymethamphetamine (HMMA), 4-hydroxy-3-methoxyamphetamine (HMA), 3,4-hydroxymethamphetamine (HHMA) and 3,4-hydroxyamphetamine (HHA) in human urine samples validated according to the United States Food and Drug Administration guidelines. In this method, analytes are simultaneously extracted and derivatized with R-(-)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride (R-MTPCl) as the chiral derivatization reagent. Following this, the analytes were subjected to a second derivatization with N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) which targets the hydroxyl groups present in HMMA, HMA, HHMA and HHA. The derivatized analytes were separated and quantified using gas chromatography-mass spectrometry (GC-MS). The method was evaluated according to the established guidelines for specificity, linearity, precision, accuracy, recovery and stability using a five-day protocol. Intra-day precision ranged from 0.89 to 11.23% RSD whereas inter-day precision was between 1.03 and 12.95% RSD. Accuracy values for the analytes ranged from -5.29% to 13.75%. Limits of quantitation were 10 μg/L for AM, MA, MDMA, HMA and HMMA and 2μg/L for MDA, HMA and HHA. Recoveries and stability values were also within accepted values. The method was applied to authentic ATS-positive samples.

  2. LC-ESI-MS/MS analysis of testosterone at sub-picogram levels using a novel derivatization reagent.

    PubMed

    Star-Weinstock, Michal; Williamson, Brian L; Dey, Subhakar; Pillai, Sasi; Purkayastha, Subhasish

    2012-11-06

    Testosterone analysis by LC-MS/MS is becoming the analytical method of choice over immunoassays due to its specificity and accuracy. However, neutral steroid hormones possess poor ionization efficiency in MS/MS, resulting in insufficient sensitivity for analyzing samples with trace concentrations of the hormones. The method presented here utilizes a derivatization step involving a novel, permanently charged, quaternary aminooxy (QAO) reagent or MS-tag that reacts to the ketone functionality of testosterone and significantly enhances its ESI-MS/MS sensitivity. This derivatization method enabled quantitation of total testosterone in human serum (200 μL) with a lower limit of quantitation (LLOQ) of 1 pg/mL (3.47 pmol/L), total testosterone in dried blood spots (8-10 μL) with a LLOQ of 40 pg/mL, and free testosterone in serum ultrafiltrate (400 μL) with a LLOQ of 0.5 pg/mL. The linearity of each of the high sensitivity applications was maintained over a broad dynamic range of 1-5000 pg/mL for the serum samples and 40-10,000 pg/mL for the dried blood spots (DBS) with R(2) >0.998. The %CV at the LLOQ was <15 for all applications. The QAO derivatization and sample preparation workflows are quick, simple, and robust. Comparison of the derivatization method with an LC-ESI-MS/MS nonderivatization method yielded high correlation and agreement. The derivatization reagent is universal and reacts with other compounds containing ketone or aldehyde functionality.

  3. A micellar electrokinetic chromatography-mass spectrometry approach using in-capillary diastereomeric derivatization for fully automatized chiral analysis of amino acids.

    PubMed

    Moldovan, Radu-Cristian; Bodoki, Ede; Kacsó, Timea; Servais, Anne-Catherine; Crommen, Jacques; Oprean, Radu; Fillet, Marianne

    2016-10-07

    In the context of bioanalytical method development, process automatization is nowadays a necessity in order to save time, improve method reliability and reduce costs. For the first time, a fully automatized micellar electrokinetic chromatography-mass spectrometry (MEKC-MS) method with in-capillary derivatization was developed for the chiral analysis of d- and l-amino acids using (-)-1-(9-fluorenyl) ethyl chloroformate (FLEC) as labeling reagent. The derivatization procedure was optimized using an experimental design approach leading to the following conditions: sample and FLEC plugs in a 2:1 ratio (15s, 30mbar: 7.5s, 30mbar) followed by 15min of mixing using a voltage of 0.1kV. The formed diastereomers were then separated using a background electrolyte (BGE) consisting of 150mM ammonium perfluorooctanoate (APFO) (pH=9.5) and detected by mass spectrometry (MS). Complete chiral resolution was obtained for 8 amino acids, while partial separation was achieved for 6 other amino acid pairs. The method showed good reproducibility and linearity in the low micromolar concentration range. The applicability of the method to biological samples was tested by analyzing artificial cerebrospinal fluid (aCSF) samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Application of chiral derivatizing agents in the high-performance liquid chromatographic separation of amino acid enantiomers: a review.

    PubMed

    Ilisz, István; Berkecz, Robert; Péter, Antal

    2008-05-12

    The past 20 years has seen an explosive growth in the field of chirality, as illustrated by the rapid progress in the various facets of this intriguing field. The impetus for advances in chiral separation has been highest in the past decade and this still continues to be an area of high focus. This paper reviews indirect separation approaches, i.e. derivatization reactions aimed at creating the basis for the chromatographic resolution of biologically and pharmaceutically important enantiomers, with emphasis on the literature published in the last 12 years. The main aspects of the chiral derivatization of amino acids are discussed, i.e. derivatization on the amino group, transforming the molecules into covalently bonded diastereomeric derivatives through the use of homochiral derivatizing agents. The diastereomers formed (amides, urethanes, urea, thiourea derivatives, etc.) can be separated on achiral stationary phases. The applications are considered, and in some cases different derivatizing agents for the resolution of complex mixtures of proteinogenic d,l-amino acids, non-proteinogenic amino acids and peptides/amino acids from peptide syntheses or microorganisms are compared.

  5. Determination of malondialdehyde in biological fluids by high-performance liquid chromatography using rhodamine B hydrazide as the derivatization reagent.

    PubMed

    Li, Pingliang; Ding, Guanglong; Deng, Yufang; Punyapitak, Darunee; Li, Deguang; Cao, Yongsong

    2013-12-01

    Malondialdehyde (MDA) is a biomarker for lipid peroxidation, and studies of sensitive and selective analytical methods for it are very important for pathological research. The aim of this work was to develop and validate a novel HPLC method for the quantification of MDA in biological fluids using rhodamine B hydrazide (RBH) as the derivatization reagent. After pretreatment and derivatization in acid medium at 50 °C for 40 min, the RBH-derivatized MDA was separated on a Kromasil C18 column at 25 °C and detected by a fluorescence detector at excitation wavelength of 560 nm and emission wavelength of 580 nm. The results showed linearity in the range of 0.8-1500.0 nM with a detection limit of 0.25 nM (S/N = 3). The recovery of MDA from plasma and urine was 91.50 to 99.20%, with a relative standard deviation range of 1.45 to 3.26%. In comparison to other methods reported for the determination of MDA, the proposed method showed superiority in simplicity, more sensitivity, shorter derivatization time, and less interference. The developed method was applied to quantification of MDA in human biological fluids collected from five volunteers with a concentration range of 24.62-245.00 nM. Copyright © 2013. Published by Elsevier Inc.

  6. Method for the synthesis of chiral allylic alcohols utilizing selone based chiral derivatizing agents

    DOEpatents

    Silks, III, Louis A.

    2002-01-01

    Molecules containing a chiral 1,2-diol unit are synthesized from reactions between aldehydes and N-acyl selones. A chilled N-acyl selone is reacted with a Lewis acid such as TiCl.sub.4 and mixed with a tertiary amine such as diisopropylethylamine to generate an enolate solution. Upon further chilling of the enolate solution a desired aldehyde is added and after an acceptable reaction period a quencher is introduced and the product isolated.

  7. Trace analysis of ethosuximide in human plasma with a chemically removable derivatizing reagent and high-performance liquid chromatography.

    PubMed

    Chen, S H; Wu, H L; Shen, M C; Kou, H S

    1999-06-11

    A simple and sensitive liquid chromatographic method is described for the determination of ethosuximide in human plasma, as a highly sensitive derivative. Ethosuximide spiked in plasma was extracted with toluene and derivatized with a chemically removable derivatizing reagent, 2-(2-naphthoxy)ethyl 2-[1-(4-benzyl)piperazyl]ethanesulfonate, in a homogeneous system, using magnesium oxide as base catalyst. The resulting derivative was separated on a LiChrospher diol column with 1.2% isopropanol in n-hexane as the mobile phase and using coumarin as the internal standard. Several parameters affecting the extraction/derivatization of ethosuximide from spiked plasma were investigated. The linear range for the determination of ethosuximide in spiked plasma was over 30-700 nmol/ml. For ethosuximide in plasma, the detection limit (signal-to-noise ratio=3; sample size, 10 microl) was about 9 pmol; the relative standard deviation was 6.4% for intra-day assay (n=6) and 9.2% for inter-day assay (n=6) and the relative recovery was found greater than 94%.

  8. Stereoelectronic basis for the kinetic resolution of N-heterocycles with chiral acylating reagents.

    PubMed

    Hsieh, Sheng-Ying; Wanner, Benedikt; Wheeler, Philip; Beauchemin, André M; Rovis, Tomislav; Bode, Jeffrey W

    2014-06-10

    The kinetic resolution of N-heterocycles with chiral acylating agents reveals a previously unrecognized stereoelectronic effect in amine acylation. Combined with a new achiral hydroxamate, this effect makes possible the resolution of various N-heterocycles by using easily prepared reagents. A transition-state model to rationalize the stereochemical outcome of this kinetic resolution is also proposed.

  9. Enantioselective halocyclization using reagents tailored for chiral anion phase-transfer catalysis.

    PubMed

    Wang, Yi-Ming; Wu, Jeffrey; Hoong, Christina; Rauniyar, Vivek; Toste, F Dean

    2012-08-08

    A chiral anion phase-transfer system for enantioselective halogenation is described. Highly insoluble, ionic reagents were developed as electrophilic bromine and iodine sources, and application of this system to o-anilidostyrenes afforded halogenated 4H-3,1-benzoxazines with excellent yield and enantioselectivity.

  10. A new sensitive LC/MS/MS analysis of vitamin D metabolites using a click derivatization reagent, 2-nitrosopyridine.

    PubMed

    Wan, Debin; Yang, Jun; Barnych, Bogdan; Hwang, Sung Hee; Lee, Kin Sing Stephen; Cui, Yongliang; Niu, Jun; Watsky, Mitchell A; Hammock, Bruce D

    2017-04-01

    There is an increased demand for comprehensive analysis of vitamin D metabolites. This is a major challenge, especially for 1α,25-dihydroxyvitamin D [1α,25(OH)2VitD], because it is biologically active at picomolar concentrations. 4-Phenyl-1,2,4-triazoline-3,5-dione (PTAD) was a revolutionary reagent in dramatically increasing sensitivity of all diene metabolites and allowing the routine analysis of the bioactive, but minor, vitamin D metabolites. A second generation of reagents used large fixed charge groups that increased sensitivity at the cost of a deterioration in chromatographic separation of the vitamin D derivatives. This precludes a survey of numerous vitamin D metabolites without redesigning the chromatographic system used. 2-Nitrosopyridine (PyrNO) demonstrates that one can improve ionization and gain higher sensitivity over PTAD. The resulting vitamin D derivatives facilitate high-resolution chromatographic separation of the major metabolites. Additionally, a liquid-liquid extraction followed by solid-phase extraction (LLE-SPE) was developed to selectively extract 1α,25(OH)2VitD, while reducing 2- to 4-fold ion suppression compared with SPE alone. LLE-SPE followed by PyrNO derivatization and LC/MS/MS analysis is a promising new method for quantifying vitamin D metabolites in a smaller sample volume (100 µL of serum) than previously reported methods. The PyrNO derivatization method is based on the Diels-Alder reaction and thus is generally applicable to a variety diene analytes.

  11. Liquid chromatographic enantioseparation of three beta-adrenolytics using new derivatizing reagents synthesized from (S)-ketoprofen and confirmation of configuration of diastereomers.

    PubMed

    Alwera, Shiv; Bhushan, Ravi

    2016-11-01

    Diastereomers of racemic β-adrenolytic drugs [namely (RS)-propranolol, (RS)-metoprolol and (RS)-atenolol] were synthesized under microwave irradiation with (S)-ketoprofen based chiral derivatization reagents (CDRs) newly synthesized for this purpose. (S)-Ketoprofen was chosen for its high molar absorptivity (εo  ~ 40,000) and its availability as a pure (S)-enantiomer. Its -COOH group was activated with N-hydroxysuccinimide and N-hydroxybenzotriazole; these were easily introduced and also acted as good leaving groups during nucleophilic substitution by the amino group of the racemic β-adrenolytics. The CDRs were characterized by UV, IR, (1) H-NMR, HRMS and CHNS. Separation of diastereomers was achieved by RP HPLC and open column chromatography. Absolute configuration of the diastereomers was established with the help of (1) HNMR supported by developing their optimized lowest energy structures using Gaussian 09 Rev. A.02 program and hybrid density functional B3LYP with 6-31G* basis set (based on density functional theory), and elution order was established. RP HPLC conditions for separation were optimized and the separation method was validated. The limit of detection values were 0.308 and 0.302 ng mL(-1) . Copyright © 2016 John Wiley & Sons, Ltd.

  12. Use of chiral derivatization for the determination of dichlorprop in tea samples by ultra performance LC with fluorescence detection.

    PubMed

    Inoue, Koichi; Prayoonhan, Nuntawat; Tsutsui, Haruhito; Sakamoto, Tasuku; Nishimura, Maiko; Toyo'oka, Toshimasa

    2013-04-01

    Dichlorprop is available for agricultural use as a chiral pesticide. In this study, the stereoselective determination of dichlorprop enantiomers in tea samples such as green, black, jasmine, and oolong was developed by ultra performance LC with fluorescence spectrometry after covalent chiral derivatization. The separation was achieved on an Acquity BEH C18 column with the mobile phase consisting of 0.1% formic acid in acetonitrile/water at a flow rate of 0.4 mL/min. In the covalent chiral derivatization using (S)-(+)-4-(N,N-dimethylaminosulfonyl)-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole, the peak resolution between the S and R-dichlorprop enantiomers was 2.6. LODs and LOQs values were 10 and 50 ng/mL standard solution. The linearity of the calibration curves yielded the coefficients (r(2) > 0.99, ranging from 0.05 to 5 μg/mL) of determination of each of the dichlorprop enantiomers. SPE extraction was used for the sample preparation of dichlorprop in various tea samples. Recoveries were in the range of 82.4-97.6% with associated precision values (within-day: 82.4-95.8%, n = 6, and between-day: 83.7-97.6% for 3 days) for repeatability and reproducibility. Based on this result, our method has been proven to be highly efficient and suitable for the routine assay of dichlorprop enantiomers in various tea samples. We propose that the ultra performance LC assay after covalent chiral derivatization would be the renewed tools in the era of chiral stationary platform for chiral pesticide residues in foods.

  13. A novel derivatization procedure and chiral gas chromatographic method for enantiomeric purity screening of L-carnitine.

    PubMed

    Albreht, Alen; Zupančič, Borut; Vovk, Irena

    2014-01-01

    L-Carnitine is used extensively in functional foods and food supplements; consequently, the control of its enantiomeric purity is of paramount importance. A new derivatization procedure and chiral gas chromatographic method with flame ionization detection, using a cyclodextrin based stationary phase, enables prompt, simple, and inexpensive screening of the enantiomeric ratio of L- and D-carnitine in samples with different matrices. Conversion of carnitine to beta-acetoxy-gama-butyrolactone was optimized for maximum conversion (98% of the desired product lactone was formed and 2% of the side product gama-crotonolactone) and minimum racemization (no changes at the chiral center were detected) and time consumption. As it is shown in this study, a fast gas chromatographic method, with total run time of 7 min, together with the new derivatization procedure enables an effective enantiomeric purity screening of L-carnitine in real samples such as food supplements and L-carnitine raw ingredient.

  14. Enantiomeric resolution of biomarkers in space analysis: Chemical derivatization and signal processing for gas chromatography-mass spectrometry analysis of chiral amino acids.

    PubMed

    Pietrogrande, M C; Basaglia, G

    2010-02-12

    The work compares two GC-MS methods for enantioselective separation of amino acids as suitable candidate for stereochemical analysis of chiral amino acids on board spacecrafts in space exploration missions of solar system body environments. Different derivatization reagents are used: a mixture of alkyl chloroformate-alcohol-pyridine to obtain the alkyl alkoxy carbonyl esters and a mixture of perfluorinated alcohols and anhydrides to form perfluoroacyl perfluoroalkyl esters. 20 proteinogenic amino acids were derivatized with the two procedures and submitted to GC-MS analysis on a Chirasil-l-Val stationary phase. The results were then compared in terms of the enantiomeric separation achieved and intensity of MS response. The combination of methyl chloroformate (MCF) and heptafluoro-1-butanol (HFB) allows separation of 14 enantiomeric pairs, five of which display a resolution (R(s)>or=1.2) supposed to be sufficient to quantify the enantiomeric excess. Three mixtures of trifluoroacetic (TFAA) and heptafluorobutyric (HFBA) anhydrides were combined with the corresponding perfluorinated alcohols - TFE (2,2,2-trifluoro-1-ethanol) and HFB (2,2,3,3,4,4,4-heptafluoro-1-butanol) - to give three different reagents (TFAA-TFE, TFAA-HFB, HFBA-HFB): the derivatives obtained show separation of the same number of proteinogenic amino acids (14 of 20) at a temperature lower than column bleeding limit (200 degrees C) and 8 of them give a separation with R(s)>or=1.2. Linearity study and limit of detection (X(LOD)) computation show that both methods are suitable for quantitative determination of several amino acid diastereomers at trace level (X(LOD) approximately 0.5nmol as derivatized quantity). Both the procedures were coupled with automatic data handling to increase their suitability for space analysis: the simplified data treatment is especially helpful to handle the low quality data recovered from space experiments and labor and time are saved, as imposed by the space experiments

  15. Evaluation of two derivatization reagents for the determination by LC-MS/MS of ammonia in cigarette mainstream smoke.

    PubMed

    Mottier, Nicolas; Jeanneret, Florent

    2011-01-12

    Ammonia in cigarette mainstream smoke was quantified by LC-MS/MS after derivatization. Two different reagents, fluorescamine and dansyl chloride, were investigated, but only the latter gave stable derivatives; therefore, it was considered the most appropriate choice. Smoke samples were collected on a Cambridge filter pad followed by an impinger containing a solution of hydrochloric acid. Ammonia was then derivatized with a 18.5 mM solution of dansyl chloride in acetonitrile at 70 °C for 30 min in a vial with the internal standard, (15)ND(4)Cl. The resulting derivative was analyzed by LC-MS/MS detection with an atmospheric pressure chemical ionization (APCI) interface in the positive ionization mode using multiple-reaction monitoring (MRM). Good linearity was obtained in the concentration range of 0.02-1.65 μg/mL (r(2) ≥ 0.999), and the limit of detection (LOD) was established at 0.006 μg/mL. This method has the advantage of being sensitive, efficient, and reliable and is not hindered by interferences from the sample matrix. It should thus be considered a reference method of choice for the determination of ammonia in smoke.

  16. Chiral derivatizations applied for the separation of unusual amino acid enantiomers by liquid chromatography and related techniques.

    PubMed

    Ilisz, István; Aranyi, Anita; Péter, Antal

    2013-06-28

    Amino acids are essential for life, and have many functions in metabolism. One particularly important function is to serve as the building blocks of peptides and proteins, giving rise complex three dimensional structures through disulfide bonds or crosslinked amino acids. Peptides are frequently cyclic and contain proteinogenic as well as nonproteinogenic amino acids in many instances. Since most of the proteinogenic α-amino acids contain at least one stereogenic center (with the exception of glycine), the stereoisomers of all these amino acids and the peptides in which they are to be found may possess differences in biological activity in living systems. The impetus for advances in chiral separation has been highest in the past 25 years and this still continues to be an area of high focus. The important analytical task of the separation of isomers is achieved mainly by chromatographic and electrophoretic methods. This paper reviews indirect separation approaches, i.e. derivatization reactions aimed at creating the basis for the chromatographic resolution of biologically and pharmaceutically important enantiomers of unusual amino acids and related compounds, with emphasis on the literature published from 1980s. The main aspects of the chiral derivatization of amino acids are discussed, i.e. derivatization on the amino group, transforming the molecules into covalently bonded diastereomeric derivatives through the use of homochiral derivatizing agents. The diastereomers formed (amides, urethanes, urea and thiourea derivatives, etc.) can be separated on achiral stationary phases. The applications are considered, and in some cases different derivatizing agents for the resolution of complex mixtures of proteinogenic d,l-amino acids, non-proteinogenic amino acids and peptides/amino acids from peptide syntheses or microorganisms are compared.

  17. Frozen Chirality of Tertiary Aromatic Amides: Access to Enantioenriched Tertiary α-Amino Acid or Amino Alcohol without Chiral Reagent.

    PubMed

    Mai, Thi Thoa; Viswambharan, Baby; Gori, Didier; Guillot, Régis; Naubron, Jean-Valère; Kouklovsky, Cyrille; Alezra, Valérie

    2017-04-27

    One of the fundamental and intriguing aspects of life is the homochirality of the essential molecules. In this field, the absolute asymmetric synthesis of α-amino acids is a major challenge. Herein, we report access, by chemical means, to tertiary α-amino acid derivatives in up to 96 % ee without using any chiral reagent. In our strategy, the dynamic axial chirality of tertiary aromatic amides is frozen in a crystal and is responsible for the stereoselectivity of the subsequent steps. Furthermore, we could control the configuration of the final product by manually sorting and selecting the initial crystals. Based on vibrational circular dichroism studies, we could rationalize the observed stereoselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A novel derivatization reagent possessing a bromoquinolinium structure for biological carboxylic acids in HPLC-ESI-MS/MS.

    PubMed

    Mochizuki, Yuko; Inagaki, Shinsuke; Suzuki, Mayu; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo'oka, Toshimasa

    2013-06-01

    A novel bromoquinolinium reagent, i.e. 1-(3-aminopropyl)-3-bromoquinolinium bromide (APBQ), was synthesized for the analysis of carboxylic acids. A simple and practical precolumn derivatization procedure using the APBQ in RP chromatography and MS (HPLC-MS) has been developed using bile acids and free fatty acids, as the representative carboxylic acids in biological samples. The APBQ efficiently reacted with carboxylic acids at 60°C for 60 min in the presence of N,N-dicyclohexylcarbodiimide and pyridine as the activation reagents. Because the APBQ possesses a bromine atom in the structure, the identification of a series of carboxylic acids was easily achieved due to the characteristic bromine isotope pattern in the mass spectra. The APBQ also has a quaternary amine structure, thus the positively charged derivatives are predominate for the highly sensitive detection of carboxylic acids. The APBQ was successfully applied to the selective determination of biological carboxylic acids in human plasma. The bile acids (chenodeoxycholic acid and deoxycholic acid) and several saturated (stearic acid and palmitic acid) and unsaturated free fatty acids (oleic acid and linoleic acid) were reasonably determined by HPLC-MS under the proposed procedure. Based on the results of analyses of human plasma and saliva, the proposed procedure using APBQ seems to be applicable for the qualitative and quantitative analyses of a series of carboxylic acids in biological samples.

  19. Enantioselective direct Mannich reactions of cyclic β-ketoesters catalyzed by chiral phosphine via a novel dual-reagent catalysis.

    PubMed

    Lou, Yan-Peng; Zheng, Chang-Wu; Pan, Ren-Ming; Jin, Qiao-Wen; Zhao, Gang; Li, Zhong

    2015-02-06

    A combination of an amino acid derived chiral phosphine catalyst and methyl acrylate efficiently catalyzed the direct Mannich reaction of cyclic β-ketoesters and N-Boc-aldimines. The dual-reagent catalysis was presumed to function through the formation of a zwitterion, which catalyzed the reaction with excellent stereocontrol via a hydrogen-bonding assisted chiral ion-pair pathway.

  20. The use of cyclohexanone as a "derivatizing" reagent for the GC-MS detection of amphetamines and ephedrines in seizures and the urine.

    PubMed

    El-Haj, B M; Al-Amri, A M; Hassan, M H; Ali, H S; Bin Khadem, R K

    2003-07-29

    A GC-MS method has been developed for the detection of amphetamine, methamphetamine, and the ephedrines, in seizures and the urine, based on on-GC condensation (derivatization) with cyclohexanone. The method is simple: the dried seizure material or the urine extract was mixed with cyclohexanone and injected into the GC-MS. The method was found to be superior to the methods based on acyl and trimethylsilyl (TMS) derivatization. Unlike for the acyl and TMS derivatives, the molecular and fragment ions of the cyclohexanone condensation products (cyclohexanone derivatives) were of substantial abundance, a useful property in unambiguous compound characterization. Furthermore, the high stability of the "derivatizing" reagent, cyclohexanone, compared with acyl and TMS derivatizing reagents, is a useful property in method development. The present method has proved selective and, tentatively, sensitive enough in the following areas (where methods based on acyl and TMS derivatization, as tested in this laboratory, have failed): (a) detection of amphetamine as a metabolite of methamphetamine; (b) detection of norpseudoephedrine as a metabolite of pseudoephedrine; (c) detection of amphetamine as an impurity of methamphetamine; (d) detection of cathine (norephedrine) as a constituent of Khat leaves; and (e) differentiation of Khat use from phenylpropanolamine use.

  1. Enantioselective capillary electrophoresis-mass spectrometry of amino acids in cerebrospinal fluid using a chiral derivatizing agent and volatile surfactant.

    PubMed

    Prior, A; Moldovan, R C; Crommen, J; Servais, A C; Fillet, M; de Jong, G J; Somsen, G W

    2016-10-12

    The sensitivity of coupled enantioselective capillary electrophoresis-mass spectrometry (CE-MS) of amino acids (AAs) is often hampered by the chiral selectors in the background electrolyte (BGE). A new method is presented in which the use of a chiral selector is circumvented by employing (+)-1-(9-fluorenyl)ethyl chloroformate (FLEC) as chiral AA derivatizing agent and ammonium perfluorooctanoate (APFO) as a volatile pseudostationary phase for separation of the formed diastereomers. Efficient AA derivatization with FLEC was completed within 10 min. Infusion experiments showed that the APFO concentration hardly affects the MS response of FLEC-AAs and presents significantly less ion suppression than equal concentrations of ammonium acetate. The effect of the pH and APFO concentration of the BGE and the capillary temperature were studied in order to achieve optimized enantioseparation. Optimization of CE-MS parameters, such as sheath-liquid composition and flow rate, ESI and MS settings was performed in order to prevent analyte fragmentation and achieve sensitive detection. Selective detection and quantification of 14 chiral proteinogenic AAs was achieved with chiral resolution between 1.2 and 8.6, and limits of detection ranging from 130 to 630 nM injected concentration. Aspartic acid and glutamic acid were detected, but not enantioseparated. The optimized method was applied to the analysis of chiral AAs in cerebrospinal fluid (CSF). Good linearity (R(2) > 0.99) and acceptable peak area and electrophoretic mobility repeatability (RSDs below 21% and 2.4%, respectively) were achieved for the chiral proteinogenic AAs, with sensitivity and chiral resolution mostly similar to obtained for standard solutions. Next to l-AAs, endogenous levels of d-serine and d-glutamine could be measured in CSF revealing enantiomeric ratios of 4.8%-8.0% and 0.34%-0.74%, respectively, and indicating the method's potential for the analysis of low concentrations of d-AAs in presence of

  2. Synthesis of benzofurazan derivatization reagents for carboxylic acids in liquid chromatography/electrospray ionization-tandem mass spectrometry.

    PubMed

    Santa, Tomofumi; Al-Dirbashi, Osama Y; Ichibangase, Tomoko; Fukushima, Takeshi; Rashed, Mohamed S; Funatsu, Takashi; Imai, Kazuhiro

    2007-11-01

    The applicability of benzofurazan derivatization regents to carboxylic acids analysis in LC/ESI-MS/MS (high-performance liquid chromatography/electrospray ionization tandem mass spectrometry) was examined. The product ion spectra of DAABD-AE {4-[2-(N,N-dimethylamino)ethylaminosulfonyl]-7-(2-aminoethylamino)-2,1,3-benzoxadiazole}, DAABD-PZ {4-[2-(N,N-dimethylamino)ethylaminosulfonyl]-7-N-piperazino-2,1,3-benzoxadiazole}, DAABD-PiCZ {4-[4-carbazoylpiperidin-1-yl]-7-[2-(N,N-dimethylamino)ethylaminosulfonyl]-2,1,3-benzoxadiazole}, DAABD-ProCZ {4-[2-carbazoylpyrrolidin-1-yl]-7-[2-(N,N-dimethylamino) ethylaminosulfonyl]-2,1,3-benzoxadiazole} and DAABD-Apy {4-[2-(N,N-dimethylamino)ethylaminosulfonyl]-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole}, and their acetylated compounds were obtained. An intense fragment ion at m/z 151 corresponding to (dimethylamino)ethylaminosulfonyl moiety was observed in each spectra, suggesting that these reagents were suitable for ESI-MS/MS analysis. DAABD-AE, DAABD-APy and DAABD-PZ were applied to the analysis of octanoic acid and it was found that DAABD-AE and DAABD-APy gave high signal intensity suitable for LC/ESI-MS/MS.

  3. Ethyl chloroformate as a derivatizing reagent for the gas chromatographic determination of isoniazid and hydrazine in pharmaceutical preparations.

    PubMed

    Khuhawar, Mohammad Yar; Zardari, Liaquat Ali

    2008-01-01

    Ethyl chloroformate was examined as a precolumn derivatizing reagent for the gas chromatographic (GC) determination of isoniazid (INH) and hydrazine (HZ). Phenylhydrazine (PHZ) was used as an internal standard. GC separation was carried out on an HP-5 column (30 m x 0.32 mm i.d.) with flame ionization detection. The elution was carried out at an initial column temperature of 150 degrees C for 1 min at a heating rate of 10 degrees C/min up to 250 degrees C, nitrogen flow rate of 4 ml/min and a split ratio of 10:1, v/v. The linear calibration ranges for INH and HZ were observed between 3.5-37.5 and 3.5-35 microg/ml with corresponding detection limits of 0.18 and 0.17 ng reaching the detector. The method was subsequently applied to the determination of INH and HZ in pharmaceutical preparations, achieving a relative standard deviation (RSD) of 3.8-5.8%. The recovery percentage of INH from isoniazid syrup was 98% with an RSD of 5.2%.

  4. Derivatization following hollow-fiber microextraction with tetramethylammonium acetate as a dual-function reagent for the determination of benzoic acid and sorbic acid by GC.

    PubMed

    Sun, Yang; Wang, Xiaoqing; Huang, Yilei; Pan, Zaifa; Wang, Lili

    2013-07-01

    Derivatization at the injection port following hollow-fiber-based liquid-liquid-liquid microextraction with tetramethylammonium acetate as a dual-function reagent, i.e. an acceptor and derivatization reagent, for the determination of benzoic acid (BA) and sorbic acid (SA) in real samples by GC was developed. BA and SA were extracted from aqueous samples to an organic phase impregnated into the pores of the hollow fiber wall, and then back-extracted to the acceptor solution located inside the lumen of the hollow fiber. Upon injection, the extracted analytes were quantitatively derivatized to their methyl esters with tetramethylammonium acetate in the GC injection port. Several parameters related to the derivatization and extraction efficiency were optimized. The linearity was satisfactory over a concentration range of 0.1-50 mg/L with r > 0.993 for both analytes. The LODs were 2.0 μg/L for SA and 20 μg/L for BA. The recoveries (83-116%) and precisions (RSDs of 1.2-11.4% (n = 3)) were examined by analyzing real spiked samples. The enrichment factors of BA and SA were 300 and 425. The results demonstrated that this is a simple, rapid, accurate, and sensitive method for the determination of BA and SA in various samples. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Micellar electrokinetic chromatography-chemiluminescent detection of biogenic amines using N-(4-aminobutyl)-N-ethylisoluminol as derivatization reagent and trivalent copper chelate as chemiluminescence enhancer.

    PubMed

    Li, Tao; Xie, Haoyue; Fu, Zhifeng

    2012-03-16

    A facile, sensitive and universal method was established for analysis of biogenic amines using micellar electrokinetic chromatography coupled with chemiluminescent (CL) detection. It was found that diperiodatocuprate (III) (K(5)[Cu(HIO(6))(2)], DPC), a transition metal chelate at unstable high oxidation state, could effectively enhance the reaction between luminol-type compound and hydrogen peroxide, to produce very strong CL signal. In addition, triethylamine was found to be able to effectively improve the yield of the derivatization reaction between biogenic amines and a luminol-type derivatization reagent, N-(4-aminobutyl)-N-ethylisoluminol (ABEI). Based on these facts, three biogenic amines were pre-column derivatized with ABEI, and post-column detected using high sensitive luminol-hydrogen peroxide-DPC CL system. Since the background was quite low, and the signal was quite strong, a considerable improved sensitivity was obtained. The presented method had been successfully applied to simultaneously analyze glycine, proline and phenylalanine with the detection limits (S/N=3) of 0.030 μmol L(-1), 0.23 μmol L(-1) and 0.21 μmol L(-1), respectively. To evaluate its potential application value, glycine in saliva and urine samples was detected using this method, and satisfied results were obtained. This approach can be further extended to detection of many other compounds such as peptides and drugs by using luminol-type derivatization reagent.

  6. Fluorine-Induced Chemiluminescence Detection of Biologically Methylated Tellurium, Selenium, and Sulfur Compounds and Methyldithiocarbhydrazide as a Formaldehyde Derivatization Reagent

    NASA Astrophysics Data System (ADS)

    Chasteen, Thomas Girard

    1990-01-01

    The first part of this dissertation describes capillary chromatography coupled to a fluorine-induced chemiluminescence detector as a sensitive method by which biologically methylated metalloids can be determined in the presence of high concentrations of potentially interfering molecules. With a wide linear range and excellent sensitivity, this method was applied to the detection of dimethyl selenide (DMSe), dimethyl diselenide (DMDSe), and dimethyl telluride (DMTe), often found in biological environments in the presence of interfering methylated sulfur gases, such as methanethiol, dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide. Detection limits for DMSe, DMDSe, and DMTe were 30, 9, and 7 picograms, respectively. This DMTe detection limit is the lowest reported to date for a volatile tellurium gas. A variety of selenium-resistant bacteria emitted mixtures of methylated sulfur/selenium gases when dosed with inorganic selenium salts in the presence of sulfur containing growth media. One of the gases detected was dimethyl selenenyl sulfide, CH_3SeSCH _3, reported here for the first time in headspace above microorganisms. In addition, this detector responded to reduced phosphorus compounds such as phosphine. The detection limit for this compound was 2.8 picograms. Detection limits for alkylated phosphines trimethyl and triethyl phosphine were 0.5 and 17 picograms respectively, based on the relative response of these compounds compared to dimethyl sulfide. This method can be used for the simultaneous determination of methylated sulfur, selenium, tellurium compounds found in biological systems. Part II of this dissertation describes work with methyldithiocarbhydrazide, a compound that has been synthesized for use as a derivatization reagent to capture formaldehyde in the gas phase. Chosen for its ability to react in a manner similar to 2,4-dinitrophenylhydrazine, this molecule was selected based on two structural characteristics: a hydrazine tag to react

  7. Determination of Diacetyl in Beer by a Precolumn Derivatization-HPLC-UV Method Using 4-(2,3-Dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a Derivatizing Reagent.

    PubMed

    Wang, Ji-Yu; Wang, Xin-Jie; Hui, Xian; Hua, Shui-Hong; Li, Heng; Gao, Wen-Yun

    2017-03-29

    Diacetyl is an important flavoring compound in many foods, especially in beer. In the present study, we developed and validated a new precolumn derivatization HPLC-UV method for the determination of diacetyl using 4-(2,3-dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a novel derivatizing reagent. After derivatization with the reagent at a pH value 4.0 at ambient temperature for 10 min, diacetyl was analyzed on an ODS column and detected at 254 nm. The results show that the correlation coefficient of the method is 0.9991 in the range of 0.10 to 100.0 μM diacetyl, and the limit of detection is 0.02 μM. The method was further evaluated in the analysis of beer samples with the recoveries ranging from 94.4 to 102.6% and RSDs from 1.36 to 3.33%. The concentrations of diacetyl in 8 beer samples were determined in the range of 0.19 to 0.42 μM. The method established in this study may be well suitable for the determination of diacetyl in beer.

  8. Simultaneous determination of amino acid and monoamine neurotransmitters in PC12 cells and rats models of Parkinson's disease using a sensitizing derivatization reagent by UHPLC-MS/MS.

    PubMed

    Zhao, Xian-En; Zhu, Shuyun; Yang, Hongmei; You, Jinmao; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

    2015-07-15

    Multi-analytes simultaneous monitoring of amino acid and monoamine neurotransmitters (NTs) has important scientific significance for their related pathology, physiology and drug screening. In this work, in virtue of a mass spectrometry sensitizing reagent 10-ethyl-acridone-3-sulfonyl chloride (EASC) as derivatization reagent, an Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry (UHPLC-MS/MS) method was developed and validated for simultaneous determination of six amino acid NTs, two monoamine ones and its one metabolite. The simple and rapid derivatization reaction was innovatively combined with plasma preparation by using EASC acetonitrile solution as protein precipitant. This interesting combination brought the advantages of speediness, simpleness and high-throughput in a cost-effective way. Under the optimized conditions, LODs (0.004-3.80nM) and LOQs (0.014-13.3nM) of EASC derivatized-NTs were calculated and found to be significantly lower than those of direct UHPLC-MS/MS detection about 11.5-275.0 and 14.4-371.4 times, respectively. Moreover, EASC derivatization significantly improved chromatographic resolution and matrix effect when compared with direct UPLC-MS/MS detection method without derivatization. Meanwhile, it also brought acceptable precision (3.0-13.0%, peak area CVs%), accuracy (86.4-112.9%), recovery (88.3-107.8%) and stability (3.8-8.5%, peak area CVs%) results. This method was successfully applied for the antiparkinsonian effect evaluation of levodopa and Ginsenoside Rg1 using PC12 cells and rats models by measuring multiple NTs. This provided a new method for the NTs related studies in the future.

  9. Direct aqueous measurement of 25-hydroxyvitamin D levels in a cellular environment by LC-MS/MS using the novel chemical derivatization reagent MDBP.

    PubMed

    Müller, Miriam J; Bruns, Heiko; Volmer, Dietrich A

    2017-01-30

    Vitamin D measurements in biological fluids by mass spectrometry are challenging at very low concentration levels. As a result, chemical derivatization is often employed to enhance the ionization properties of low abundant vitamin D compounds. Cookson-type reagents such as 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) or similar derivatives work well but require careful, water-free experimental conditions, as traces of water inactivate the reagent and inhibit or stop the derivatization reactions, thus making quantitative measurements in aqueous samples impossible. We describe a novel electrospray liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay for determining 25-hydroxyvitamin D3 (25(OH)D3) directly in aqueous cellular systems using a new derivatization reagent, the ionic liquid 12-(maleimidyl)dodecyl-tri-n-butylphosphonium bromide (MDBP). The proof-of-concept for the MDBP assay was demonstrated by measuring the levels of 25(OH)D3 in four different human cell types, namely T cells, helper T cells, B cells, and macrophages. In addition to the ability to determine the levels of 25(OH)D3 directly in aqueous samples, the cellular integrity was maintained in our application. We show the time-dependent uptake of 25(OH)D3 into the investigated cells to demonstrate the applicability of the new label. Furthermore, the MDBP derivatization technique may be equally useful in imaging mass spectrometry, where it could be used for response enhancements of spatially localized vitamin D metabolites on wet tissue surfaces, without destroying the integrity of the tissue surface. Graphical Abstract MDBP labelling of 25-hydroxyvitamin D in the extracellular space.

  10. Highly sensitive derivatization reagents possessing positively charged structures for the determination of oligosaccharides in glycoproteins by high-performance liquid chromatography electrospray ionization tandem mass spectrometry.

    PubMed

    Min, Jun Zhe; Nagai, Keisuke; Shi, Qing; Zhou, Wenjun; Todoroki, Kenichiro; Inoue, Koichi; Lee, Yong-Ill; Toyo'oka, Toshimasa

    2016-09-23

    We have developed three kinds of novel derivatization reagents (4-CEBTPP, 4-CBBTPP, 5-COTPP) with triphenylphosphine (TPP) as a basic structure carrying a permanent positive charge for resolution of the oligosaccharides in glycoprotein using high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The synthesized reagents reacted with the sialylglycosylamine of the sialylglycopeptide after treatment by PNGase F. The final derivatives were analyzed by ESI-MS and sensitively detected in the selected reaction monitoring (SRM) mode. Furthermore, the limits of detection (S/N=3) on the SRM chromatograms were at the fmol level (30fmol). Therefore, we used the limit of detection of the reagent products detected by the SRM and evaluated the utility of each reagent. Among the reagents, the positively charged 4-CEBTPP derivative's peak area was the highest; 4-CEBTPP with a positively charged structure showed about a 20 times greater sensitivity for the glycosylamine of the SGP product compared to the conventional fluorescence reagent, Fmoc-Cl. In addition, various fragment ions based on the carbohydrate units also appeared in the MS/MS spectra. Among the fragment ions, m/z 627.37 (CE=40eV) corresponding to 4-CEBTPP-GlcNAc and m/z 120.09 (CE=100eV) corresponding to 4-CEBTPP are the most important ones for identifying the oligosaccharide. 4-CEBTPP-SGA was easily identified by the selected-ion chromatogram in the product ion scan (m/z 120.09) and in the precursor ion scan (m/z 627.37) by MS/MS detection. The derivatized analytes have a high ionization efficiency and they are detected with a high sensitivity in the electrospray ionization. The novel derivatization reagent with a multi-function provided a higher sensitivity for the oligosaccharide analysis, as well as a better specificity and feasibility. Furthermore, several oligosaccharides in fetuin and ribonuclease B were successfully identified by the proposed procedure

  11. The use of hydrazine-based derivatization reagents for improved sensitivity and detection of carbonyl containing compounds using MALDI-MSI.

    PubMed

    Flinders, Bryn; Morrell, Josie; Marshall, Peter S; Ranshaw, Lisa E; Clench, Malcolm R

    2015-03-01

    Hydrazine-based derivatization reagents have been used to detect the presence of the carbonyl containing glucocorticoid fluticasone proprionate in rat lung tissue by MALDI-MSI. Such reagents also act as a matrix for analysis by MALDI-MS and have been termed "reactive matrices". Cryosections of rat lung tissue (12 μm), spotted with a range of concentrations of fluticasone proprionate, were derivatized in situ with 2,4-dinitrophenylhydrazine (DNPH) and 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH) by the use of an acoustic reagent spotter. It has been demonstrated that DMNTH gave superior results compared to DNPH and that analysis of samples immediately after application of DMNTH resulted in the detection of the protonated hydrazone derivative ([MD + H](+)) of fluticasone propionate at a concentration of 500 ng/μL. It has been further shown that a prolonged reaction time (~48 h) improves the detection limit of the protonated hydrazone derivative to 50 ng/μL and that improvements in sensitivity and limits of detection are obtained when a conventional MALDI matrix CHCA is employed in conjunction with the DNPH/DMNTH reactive matrix.

  12. Development and validation of a simple and sensitive HPLC-UV method for the determination of captopril in human plasma using a new derivatizing reagent 2-naphthyl propiolate.

    PubMed

    Rastkari, Noushin; Khoobi, Mehdi; Shafiee, Abbas; Khoshayand, Mohammad Reza; Ahmadkhaniha, Reza

    2013-08-01

    In this study, a simple, sensitive and reliable HPLC-UV method applying rapid sample preparation technique for the determination of captopril in human plasma was developed and validated. The method is based on pre-column derivatization of captopril and 2-propene-1-thiol (internal standard) with a new reagent 2-naphthyl propiolate. Sample clean-up, derivatization and extraction were carried out in two steps, totally less than 30min. The extracts were chromatographed on a C18 column (5μm, 150mm×4.6mmi.d.). The mobile phase consisted of methanol (75%, v/v) and phosphate buffer (25%, pH=8, 0.01M). UV detection was performed at 290nm. To obtain the best reaction yield, the factors that could influence the derivatization process, including the concentration of derivatization reagent, pH of sample solution and temperature were investigated in detail and optimized using Box-Behnken response surface methodology. Under optimized conditions the average extraction recovery of captopril and internal standard were >86%. The achieved lower limit of quantification (LLOQ) was 3ng/mL; the assay exhibited a linear dynamic range of 3-2000ng/mL with correlation coefficient (r(2)) of ≥0.99. The precision was satisfactory in the whole calibration range with RSD of 5.9-12.4% (accuracy: from 97.5% to 93.6%) and of 6.4-12.8% (accuracy: from 97.3% to 95.2%) for intra- and inter-assay, respectively. The method stability was confirmed in a series of experiments including: freeze-thaw, short- and long-term stability testing. Lastly, the developed method was successfully applied to the bioequivalence study of captopril administrated as a single oral dose (50mg) to 12 healthy male volunteers. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Ethyl propiolate as a post-column derivatization reagent for thiols: development of a green liquid chromatographic method for the determination of glutathione in vegetables.

    PubMed

    Zacharis, Constantinos K; Tzanavaras, Paraskevas D; Zotou, Anastasia

    2011-03-25

    The present study reports the development, validation and application of a new green liquid chromatographic method for the determination of glutathione (GSH) in vegetable samples. In this work we introduce-for the first time-ethyl propiolate (EP) as an advantageous post-column derivatization reagent for thiolic compounds. GSH (t(R)=6.60 min) and N-acetylcysteine (NAC, internal standard) (t(R)=11.80 min) were separated efficiently from matrix endogenous compounds by using a 100% aqueous mobile phase (0.1%, v/v CH(3)COOH in 1 mmol L(-1) EDTA, Q(V)=0.5 mL min(-1)) and a Prevail(®) reversed phase column that offers the advantage of stable packing material in aqueous mobile phases. The parameters of the post-column reaction (pH, amount concentration of the reagent, flow rates, length of the reaction coil and temperature) were studied. The linear determination range for GSH was 1-200 μmol L(-1) and the LOD was 0.1 μmol L(-1) (S/N=3). Total endogenous GSH was determined in broccoli, potato, asparagus and Brussels sprouts using the standards addition approach. The accuracy was evaluated by both recovery experiments (R=91-110%) and comparison to an o-phthalaldehyde/glycine corroborative post-column derivatization fluorimetric method. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Determination of efficacy of fingermark enhancement reagents; the use of propyl chloroformate for the derivatization of fingerprint amino acids extracted from paper.

    PubMed

    Mink, Tineke; Voorhaar, Annelies; Stoel, Reinoud; de Puit, Marcel

    2013-09-01

    The analysis of the constituents of fingerprints has been described numerous times, mainly with the purpose of determining the aging effect on fingerprints or showing the differences between donors or groups of donors. In this paper we describe the use of derivatized amino acids to determine the efficacy of the visualization reagents 1,8-diazafluoren-9-one (DFO) and ninhydrin. At present certain conditions are used for the application of these reagents, as determined by trial-and-error investigations, to the effect on fingerprints. The recovery of amino acids from a porous surface can be used as a measure for the efficacy of a visualization agent. In this paper we describe a method for the determination of the amount of amino acid left after reaction with well known fingerprint visualization reagents. This will allow a more scientific approach to method development for fingermark enhancement techniques. Furthermore, investigations on the influence of the concentration of fingermark amino acids, the order of application of and exposure time to reagents and the influence of age of the amino acids were carried out. These studies have resulted in a broader understanding of the mechanism involved in visualization of fingermarks using DFO and ninhydrin.

  15. Study of a new derivatizing reagent that improves the analysis of amino acids by HPLC with fluorescence detection: application to hydrolyzed rape bee pollen.

    PubMed

    You, Jinmao; Liu, Lingjun; Zhao, Wenchen; Zhao, Xianen; Suo, Yourui; Wang, Honglun; Li, Yulin

    2007-04-01

    A simple and sensitive method for evaluating the chemical compositions of protein amino acids, including cystine (Cys)(2) and tryptophane (Try) has been developed, based on the use of a sensitive labeling reagent 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) along with fluorescence detection. The chromophore of the 1,2-benzo-3,4-dihydrocarbazole-ethyl chloroformate (BCEOC-Cl) molecule was replaced with the 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl functional group, yielding the sensitive fluorescence molecule BCEC-Cl. The new reagent BCEC-Cl could then be substituted for labeling reagents commonly used in amino acid derivatization. The BCEC-amino acid derivatives exhibited very high detection sensitivities, particularly in the cases of (Cys)(2) and Try, which cannot be determined using traditional labeling reagents such as 9-fluorenyl methylchloroformate (FMOC-Cl) and ortho-phthaldialdehyde (OPA). The fluorescence detection intensities for the BCEC derivatives were compared to those obtained when using FMOC-Cl and BCEOC-Cl as labeling reagents. The ratios I (BCEC)/I (BCEOC) = 1.17-3.57, I (BCEC)/I (FMOC) = 1.13-8.21, and UV(BCEC)/UV(BCEOC) = 1.67-4.90 (where I is the fluorescence intensity and UV is the ultraviolet absorbance). Derivative separation was optimized on a Hypersil BDS C(18) column. The detection limits calculated from 1.0 pmol injections, at a signal-to-noise ratio of 3, ranged from 7.2 fmol for Try to 8.4 fmol for (Cys)(2). Excellent linear responses were observed, with coefficients of >0.9994. When coupled with high-performance liquid chromatography, the method established here allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids including (Cys)(2) and Try from bee-collected pollen (bee pollen) samples.

  16. Chiral NHC Ligands Bearing a Pyridine Moiety in Copper-Catalyzed 1,2-Addition of Dialkylzinc Reagents to β-Aryl-α,β-unsaturated N-Tosylaldimines.

    PubMed

    Soeta, Takahiro; Ishizaka, Tomohiro; Ukaji, Yutaka

    2016-04-01

    Asymmetric 1,2-addition of dialkylzinc reagents to α,β-unsaturated N-tosylaldimines was catalyzed by copper salt in the presence of chiral imidazolium salts having a pyridine ring, which were derived from amino acid, to afford the corresponding chiral allylic amines with up to 91% ee in reasonably high yields. The chiral N-heterocyclic carbene (NHC) ligand played an important role in controlling chemoselectivity.

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

    PubMed

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

    2015-05-22

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

  18. Sensitive, accurate and rapid detection of trace aliphatic amines in environmental samples with ultrasonic-assisted derivatization microextraction using a new fluorescent reagent for high performance liquid chromatography.

    PubMed

    Chen, Guang; Liu, Jianjun; Liu, Mengge; Li, Guoliang; Sun, Zhiwei; Zhang, Shijuan; Song, Cuihua; Wang, Hua; Suo, Yourui; You, Jinmao

    2014-07-25

    A new fluorescent reagent, 1-(1H-imidazol-1-yl)-2-(2-phenyl-1H-phenanthro[9,10-d]imidazol-1-yl)ethanone (IPPIE), is synthesized, and a simple pretreatment based on ultrasonic-assisted derivatization microextraction (UDME) with IPPIE is proposed for the selective derivatization of 12 aliphatic amines (C1: methylamine-C12: dodecylamine) in complex matrix samples (irrigation water, river water, waste water, cultivated soil, riverbank soil and riverbed soil). Under the optimal experimental conditions (solvent: ACN-HCl, catalyst: none, molar ratio: 4.3, time: 8 min and temperature: 80°C), micro amount of sample (40 μL; 5mg) can be pretreated in only 10 min, with no preconcentration, evaporation or other additional manual operations required. The interfering substances (aromatic amines, aliphatic alcohols and phenols) get the derivatization yields of <5%, causing insignificant matrix effects (<4%). IPPIE-analyte derivatives are separated by high performance liquid chromatography (HPLC) and quantified by fluorescence detection (FD). The very low instrumental detection limits (IDL: 0.66-4.02 ng/L) and method detection limits (MDL: 0.04-0.33 ng/g; 5.96-45.61 ng/L) are achieved. Analytes are further identified from adjacent peaks by on-line ion trap mass spectrometry (MS), thereby avoiding additional operations for impurities. With this UDME-HPLC-FD-MS method, the accuracy (-0.73-2.12%), precision (intra-day: 0.87-3.39%; inter-day: 0.16-4.12%), recovery (97.01-104.10%) and sensitivity were significantly improved. Successful applications in environmental samples demonstrate the superiority of this method in the sensitive, accurate and rapid determination of trace aliphatic amines in micro amount of complex samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Determination of ultra-trace formaldehyde in air using ammonium sulfate as derivatization reagent and capillary electrophoresis coupled with on-line electrochemiluminescence detection.

    PubMed

    Deng, Biyang; Liu, Yang; Yin, Huihui; Ning, Xi; Lu, Hua; Ye, Li; Xu, Quanxiu

    2012-03-15

    The reaction between formaldehyde and ammonium ion to produce hexamethylenetetramine is well known. The reaction conditions are very easily controlled in situ and the experiment operation is very simple. However, such derivatization reaction for trace formaldehyde determination using capillary electrophoresis (CE) electrochemiluminescence (ECL) has not been reported before. In this study, the application of ammoniun sulfate as derivatization reagent to in-situ determination of formaldehyde in air was reported. Based on ECL enhancement of tris(2,2'-bipyridyl)ruthenium(II) with hexamethylenetetramine, a novel approach for the determination of ultra-trace formaldehyde in air using CE coupled with on-line ECL of tris(2,2'-bipyridyl)ruthenium(II) has been developed. The parameters affecting separation and detection such as detection potential, concentration and pH of phosphate buffer, and electrokinetic voltage, were investigated. Under the optimal conditions, the linear concentration range of formaldehyde in air was from 0.48 μg/m(3) to 96 mg/m(3) (linear range covering 5 orders of magnitude). The limit of detection (3σ) was 0.15 μg/m(3). The relative standard deviations of peak height and migration time for six consecutive injection of 1 ng/mL formaldehyde derivative were 0.9% and 0.8%, respectively. The recoveries of formaldehyde in air were between 99.3% and 101%. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Determination of the optical purity of (R)-terbutaline by 1H-NMR and RP-LC using chiral derivatizing agent, (S)-(-)-alpha-methylbenzyl isocyanate.

    PubMed

    Kim, K H; Kim, H J; Kim, J H; Lee, J H; Lee, S C

    2001-07-01

    A simple, convenient and precise 1H-NMR and indirect HPLC methods were used for the determination of (S)-terbutaline in (R)-terbutaline. The enantiomers were converted to diastereomeric derivatives using (S)-(-)-alpha-methylbenzyl isocyanate and were successfully separated on an ODS column within 40 min with RS=1.41 and alpha=1.09. Interaction between chiral solutes by the formation of the diastereomeric complexes also led to differentiations of the 1H-NMR spectra of enantiomers and optical purities were determined on the basis of the peak area of the enantiomeric amine proton resonance. The effect of various experimental parameter, such as reaction time, reaction temperature and concentration of chiral derivatizing agent on the derivatization reaction and composition of mobile phase on the ODS column is discussed. Validation data such as recovery, linearity and detection limit are also presented. The results from 1H-NMR and RP-HPLC methods were compared with those from chiral HPLC method and no racemization was found during the experiments. NMR results had agreed with those obtained by indirect HPLC method and two methods could be used as a quality control method for the enantiomeric purity determination of (R)-terbutaline.

  1. Study of the matrix effects and sample dilution influence on the LC-ESI-MS/MS analysis using four derivatization reagents.

    PubMed

    Oldekop, Maarja-Liisa; Herodes, Koit; Rebane, Riin

    2014-09-15

    For liquid chromatographic analysis of amino acids involving derivatization and mass-spectrometric detection, it becomes more important to evaluate the presence of matrix effects in complex samples. This is somewhat complicated for amino acid analysis where analyte free sample matrix is often unavailable. In this work, matrix effects were investigated using post-column infusion method for 9-fluorenylmethyl chloroformate (FMOC-Cl) derivatives of β-Ala, Gly and Phe and diethyl ethoxymethylenemalonate (DEEMM) derivative of β-Ala. While for DEEMM derivatives, the main signal suppression was due to the borate buffer, in case of FMOC-Cl, other FMOC-derivatives caused signal suppression. Analysis of amino acids in tea and honey with DEEMM, FMOC-Cl, p-N,N,N-trimethylammonioanilyl N'-hydroxysuccinimidyl carbamate iodide (TAHS) and dansyl chloride (DNS) showed that amino acid concentrations found with different reagents do not agree well. Sample dilution experiments indicated that the sample matrix affected the analysis results obtained with DEEMM the least, but with FMOC-Cl, TAHS and DNS, sample dilution had an influence on the results. When sample dilution and extrapolative dilution approach were applied on the latter results, an agreement of amino acid concentrations measured with different reagents was achieved within relative standard deviation (RSD) of 22% for most cases.

  2. Sensitive Determination of Onco-metabolites of D- and L-2-hydroxyglutarate Enantiomers by Chiral Derivatization Combined with Liquid Chromatography/Mass Spectrometry Analysis.

    PubMed

    Cheng, Qing-Yun; Xiong, Jun; Huang, Wei; Ma, Qin; Ci, Weimin; Feng, Yu-Qi; Yuan, Bi-Feng

    2015-10-13

    2-hydroxyglutarate (2HG) is a potent competitor of α-ketoglutarate (α-KG) and can inhibit multiple α-KG dependent dioxygenases that function on the epigenetic modifications. The accumulation of 2HG contributes to elevated risk of malignant tumors. 2HG carries an asymmetric carbon atom in its carbon backbone and differentiation between D-2-hydroxyglutarate (D-2HG) and L-2-hydroxyglutarate (L-2HG) is crucially important for accurate diagnosis of 2HG related diseases. Here we developed a strategy by chiral derivatization combined with liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) analysis for highly sensitive determination of D-2HG and L-2HG enantiomers. N-(p-toluenesulfonyl)-L-phenylalanyl chloride (TSPC) was used to derivatize 2HG. The formed diastereomers by TSPC labeling can efficiently improve the chromatographic separation of D-2HG and L-2HG. And derivatization by TSPC could also markedly increase the detection sensitivities by 291 and 346 folds for D-2HG and L-2HG, respectively. Using the developed method, we measured the contents of D-2HG and L-2HG in clear cell renal cell carcinoma (ccRCC) tissues. We observed 12.9 and 29.8 folds increase of D-2HG and L-2HG, respectively, in human ccRCC tissues compared to adjacent normal tissues. The developed chiral derivatization combined with LC-ESI-MS/MS analysis offers sensitive determination of D-2HG and L-2HG enantiomers, which benefits the precise diagnosis of 2HG related metabolic diseases.

  3. Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: construction of chiral quaternary centers.

    PubMed

    Vuagnoux-d'Augustin, Magali; Alexakis, Alexandre

    2007-01-01

    Me3Al, Et3Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.

  4. High-performance liquid chromatography evaluation of the enantiomeric purity of amino acids by means of automated precolumn derivatization with ortho-phthalaldehyde and chiral thiols.

    PubMed

    Kühnreich, Raphael; Holzgrabe, Ulrike

    2016-12-01

    The use of ortho-phthalaldehyde (OPA) for the derivatization of amino acids (AA) is well known. It enables the separation of the derivatives on common reversed phase columns and improves the sensitivity with fluorescence detection. With the use of a chiral thiol an indirect enantioseparation of chiral amines and AAs is feasible. The major drawback of the OPA-derivatization is the poor stability of the products. Here, a method with an in-needle derivatization procedure is optimized to facilitate a quantitative conversion of the AA with OPA and the chiral thiols N-acetyl-L-cysteine or N-isobutyryl-L-cysteine, followed by a subsequent analysis, eluding the stability issue. Both enantiomers of a single AA were separated as OPA-derivatives with a pentafluorophenyl column and a gradient program consisting of 50 mM sodium acetate buffer pH = 5.0 and acetonitrile. Fluorescence detection is commonly used to achieve sufficient sensitivity. In this study, the enantiomeric impurity of an AA can be detected indirectly with common UV spectrophotometric detection with a limit of quantitation of 0.04%. Seventeen different L-AAs were tested and the amount of D-AA for each individual AA was calculated by means of area normalization, which ranged from not detectable up to 4.29%. The recovery of the minor enantiomer of L- and D-AA was demonstrated for three AAs at a 0.04% level and ranged between 92.3 and 113.3%, with the relative standard deviation between 1.7 and 8.2%.

  5. Trimethylsulfonium hydroxide as derivatization reagent for the chemical investigation of drying oils in works of art by gas chromatography.

    PubMed

    Dron, Julien; Linke, Robert; Rosenberg, Erwin; Schreiner, Manfred

    2004-08-20

    A procedure for the determination of fatty acids (FA) and glycerol in oils has been developed. The method includes a derivatization step of the FAs into their methyl esters or a transesterification of the triacylglycerols with trimethylsulfonium hydroxide (TMSH), respectively. The analysis is carried out by gas chromatography with parallel flame ionization and mass spectrometric detection. The parameters involved in the transesterification reaction were optimized. Only the stoichiometric ratio of TMSH:total FA amount showed a significant influence on the reaction yield. Relative standard deviations for 10 replicates were below 3% for all FAs studied and their linearity range was 0.5-50 mmol/L, when using heptadecanoic acid as an internal standard. The final procedure was rapid and required little sample handling. It was then tested on fresh oil samples and presented satisfying results, in agreement with previous works.

  6. Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination.

    PubMed

    Niu, Dawen; Buchwald, Stephen L

    2015-08-05

    The CuH-catalyzed hydroamination of alkenes and alkynes using a silane and an amine transfer reagent represents a simple strategy to access chiral amine products. We have recently reported methods to prepare chiral amines with high efficiency and stereoselectivity using this approach. However, the current technology is limited to the synthesis of trialkylamines from dialkylamine transfer reagents (R2NOBz). When monoalkylamine transfer reagents [RN(H)OBz] were used for the synthesis of chiral secondary amines, competitive, nonproductive consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a modified type of amine transfer reagent that addresses this limitation. This effort has enabled us to develop a CuH-catalyzed synthesis of chiral secondary amines using a variety of amine coupling partners, including those derived from amino acid esters, carbohydrates, and steroids. Mechanistic investigations indicated that the modified amine transfer reagents are less susceptible to direct reaction with CuH.

  7. Pre-Column Derivatization HPLC Procedure for the Quantitation of Aluminium Chlorohydrate in Antiperspirant Creams Using Quercetin as Chromogenic Reagent.

    PubMed

    Kalogria, Eleni; Varvaresou, Athanasia; Papageorgiou, Spyridon; Protopapa, Evaggelia; Tsaknis, Ioannis; Matikas, Alexios; Panderi, Irene

    2014-01-01

    This article describes the development and validation of a selective high-performance liquid chromatography method that allows, after liquid-liquid extraction and pre-column derivatization reaction with quercetin, the quantification of aluminium chlorohydrate in antiperspirant creams. Chromatographic separation was achieved on an XTerra MS C18 analytical column (150 × 3.0 mm i.d., particle size 5 μm) using a mobile phase of acetonitrile:water (15:85, v/v) containing 0.08 % trifluoroacetic acid at a flow rate of 0.30 mL min(-1). Ultraviolet spectrophotometric detection at 415 nm was used. The assay was linear over a concentration range of 3.7-30.6 μg mL(-1) for aluminium with a limit of quantitation of 3.74 μg mL(-1). Quality control samples (4.4, 17.1 and 30.6 μg mL(-1)) in five replicates from five different runs of analysis demonstrated intra-assay precision (% coefficient of variation <3.8 %), inter-assay precision (% coefficient of variation <5.4 %) and an overall accuracy (% recovery) between 96 and 101 %. The method was used to quantify aluminium in antiperspirant creams containing 11.0, 13.0 and 16.0 % (w/w) aluminium chlorohydrate, respectively.

  8. Chiral N-heterocyclic carbene ligands bearing a pyridine moiety for the copper-catalyzed alkylation of N-sulfonylimines with dialkylzinc reagents.

    PubMed

    Soeta, Takahiro; Ishizaka, Tomohiro; Tabatake, Yuta; Ukaji, Yutaka

    2014-12-08

    Amino acid-derived chiral imidazolium salts, each bearing a pyridine ring, were developed as N-heterocyclic carbene ligands. The copper-catalyzed asymmetric alkylation of various N-sulfonylimines with dialkylzinc reagents in the presence of these chiral imidazolium salts afforded the corresponding alkylated products with high enantioselectivity (up to 99 % ee). The addition of HMPA to the reaction mixture as a co-solvent is critical in terms of chemical yield and enantioselectivity. A wide range of N-sulfonylimines and dialkylzinc reagents were found to be applicable to this reaction.

  9. Sample preconcentration with chemical derivatization in capillary electrophoresis. Capillary as preconcentrator, microreactor and chiral selector for high-throughput metabolite screening.

    PubMed

    Ptolemy, Adam S; Britz-McKibbin, Philip

    2006-02-17

    New strategies for integrating sample pretreatment with chemical analyses under a single format is required for rapid, sensitive and enantioselective analyses of low abundance metabolites in complex biological samples. Capillary electrophoresis (CE) offers a unique environment for controlling analyte/reagent band dispersion and electromigration properties using discontinuous electrolyte systems. Recent work in our laboratory towards developing a high-throughput CE platform for low abundance metabolites via on-line sample preconcentration with chemical derivatization (SPCD) is primarily examined in this review, as there have been surprisingly only a few strategies reported in the literature to date. In-capillary sample preconcentration serves to enhance concentration sensitivity via electrokinetic focusing of long sample injection volumes for lower detection limits, whereas chemical derivatization by zone passing is used to expand detectability and selectivity, notably for enantiomeric resolution of metabolites lacking intrinsic chromophores using nanolitre volumes of reagent. Together, on-line SPCD-CE can provide over a 100-fold improvement in concentration sensitivity, shorter total analysis times, reduced sample handling and improved reliability for a variety of amino acid and amino sugar metabolites, which is also amenable to automated high-throughput screening. This review will highlight basic method development and optimization parameters relevant to SPCD-CE, including applications to bacterial metabolite flux and biomarker analyses. Insight into the mechanism of analyte focusing and labeling by SPCD-CE is also discussed, as well as future directions for continued research.

  10. Application of solid-phase microextraction combined with derivatization to the enantiomeric determination of amphetamines.

    PubMed

    Cháfer-Pericás, C; Campíns-Falcó, P; Herráez-Hernández, R

    2006-03-18

    The utility of combining chiral derivatization and solid-phase microextraction (SPME) for the enantiomeric analysis of primary amphetamines by liquid chromatography has been investigated. Different derivatization/extraction strategies have been evaluated and compared using the chiral reagent o-phthaldialdehyde (OPA)-N-acetyl-l-cysteine (NAC) and fibres with a Carbowax-templated resin coating. Amphetamine, norephedrine and 3,4-methylenedioxyamphetamine (MDA) were used as model compounds. On the basis of the results obtained, a new method is presented based on the derivatization of the analytes in solution followed by SPME of the OPA-NAC derivatives formed. The proposed conditions have been applied to determine the compounds of interest at low ppm levels (

  11. Determination of histamine in microdialysis samples from rat brain by microbore column liquid chromatography following intramolecular excimer-forming derivatization with pyrene-labeling reagent.

    PubMed

    Yoshitake, Takashi; Yamaguchi, Masatoshi; Nohta, Hitoshi; Ichinose, Fumio; Yoshida, Hideyuki; Yoshitake, Shimako; Fuxe, Kjell; Kehr, Jan

    2003-07-15

    This paper describes a sensitive and selective liquid chromatographic method with fluorescence detection for determination of histamine in brain microdialysis samples from awake rats. Samples containing histamine (10 microl) were derivatized with 20 microl of the reagent consisting of 3 mM 4-(1-pyrene)butyric acid N-hydroxysuccinimide ester (PSE), 3 mM potassium carbonate and acetonitrile (1:1:18, v/v), thereafter 20 microl volume was injected onto the microbore column packed with C18 silica gel. The histamine derivative contained two pyrene moieties, which generated intramolecular excimer fluorescence (450-540 nm) and allowed clear discrimination from the monomer fluorescence (360-420 nm) emitted by PSE itself. The separation of histamine-pyrene derivative was achieved within 25 min, the detection limit (S/N=3) was 0.3 fmol histamine in 20 microl injected. The basal extracellular levels of histamine collected in 10-min fractions (fmol per 10 microl, mean+/-S.D., not corrected for recovery, n=10 rats) were 35.45+/-4.56 (hypothalamus), 9.05+/-1.56 (prefrontal cortex), 7.83+/-0.86 (hippocampus) and 6.54+/-0.66 (striatum). The voltage-sensitive release of histamine was evaluated by perfusing the probes with high (100 mM) concentration of potassium ions or with sodium channel blocker tetrodotoxin (1 microM), and the calcium-dependent release was tested by perfusion with calcium-free Ringer solution. These data, together with physiologically induced increase of extracellular histamine in four examined brain regions during forced swimming demonstrate that this method is suitable for high-sensitive determination of neuronally released histamine under various pharmacological and physiological conditions.

  12. Development and Validation of Chiral HPLC Method for Quantification of 3-(S)-Quinuclidinol in Pharmaceutically Important Precursor, 3-(R)-Quinuclidinol, by Precolumn Derivatization.

    PubMed

    Gaykar, Santosh K; Shinde, Ravindra B; Bhalgat, Chetan M; Harlikar, Jayvant; Gangrade, Manish; Pullela, Srinivas V

    2016-11-01

    A sensitive and specific high-performance liquid chromatography (HPLC) method for the separation and quantification of 3-(S)-quinuclidinol in 3-(R)-quinuclidinol, precursor for active pharmaceutical ingredients (solifenacin, revatropate and talsaclidine), has been developed and validated by precolumn derivatization. Several chiral columns were tested in a normal phase system. Excellent enantioseparation with the resolution more than 11.4 was achieved on Chiralpak IC column using isocratic mobile phase consisting of n-hexane, ethanol, 2-propanol and diethylamine (80:8:12:0.4, v/v). The detection was carried out using UV detector at 230 nm. The influence of mobile phase composition, namely organic modifiers, additives, aliphatic alkanes and water content in mobile phase, on retention and enantioseparation was studied. Validation of the developed method including specificity, system suitability, limit of detection, limit of quantification, linearity, repeatability, intermediate precision, accuracy and solution stability was performed according to the International Conference on Harmonization guidelines. The advantage of the method is a good HPLC enantioseparation by precolumn derivatization using reaction mixture as sample, simpler UV detection, short analysis time (<30 min), and therefore this method is suitable option for routine quantification of 3-(S)-quinuclidinol in 3-(R)-quinuclidinol.

  13. Chiral trimethylsilylated C2-symmetrical diamines as phosphorous derivatizing agents for the determination of the enantiomeric excess of chiral alcohols by 1H NMR

    PubMed Central

    Chauvin, Anne-Sophie; Alexakis, Alexandre

    2006-01-01

    The use of organophosphorus derivatising agents, prepared from C2 symmetric trimethylsilylated diamines, for the 1H NMR and 31P NMR determination of the enantiomeric composition of chiral alcohols is described. PMID:16566844

  14. Isotope-coded derivatization based LC/ESI-MS/MS methods using a pair of novel reagents for quantification of hydroxycinnamic acids and hydroxybenzoic acids in fermented brown rice product.

    PubMed

    Ogawa, Shoujiro; Takafuji, Kiriko; Tsubuku, Sumi; Horie, Yukiko; Ikegawa, Shigeo; Higashi, Tatsuya

    2017-08-05

    Hydroxycinnamic acids (HCAs) and hydroxybenzoic acids (HBAs) are antioxidant phytochemicals found in rice and effective for the prevention of human diseases including cancer. FBRA, which is a functional food manufactured by fermenting brown rice and rice bran with Aspergillus oryzae, has been demonstrated to have chemopreventive effects against carcinogenesis in various organs. In this study, we developed methods for the relative and absolute quantification of ferulic acid, sinapic acid, caffeic acid, protocatechuic acid and syringic acid in the FBRA and raw material (RM; unfermented brown rice and rice bran) samples by LC/ESI-MS/MS combined with derivatization using a newly developed reagent, N-(2-aminoethyl)-4-(diethylamino)benzamide (ADB) and its deuterium-coded analog, d-ADB. For the relative quantification, the FBRA and RM samples were derivatized with ADB and d-ADB, respectively, then the resulting derivatives were mixed and subjected to LC/ESI-MS/MS; by this method, we found that the fermentation process significantly increased the free HCA and HBA contents. The HCA and HBA contents in the FBRA were also determined, in which the d-ADB-derivatized standards of known amounts were used as the internal standards. The ADB-derivatization enabled the sensitive and specific detection, and the use of d-ADB significantly improved the assay precision. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. First principles design of derivatizing agent for direct determination of enantiomeric purity of chiral alcohols and amines by NMR spectroscopy.

    PubMed

    Orlov, Nikolay V; Ananikov, Valentine P

    2010-05-14

    (77)Se NMR offers superior sensing of chirality within the structure of the diastereomers (Deltadelta up to 6.1 ppm), compared to (13)C (Deltadelta < 1 ppm) and (1)H (Deltadelta < 0.2 ppm). The developed procedure is equally well suitable for determination of the enantiomeric purity of chiral alcohols and amines as pure samples as well as reaction mixtures and crude products.

  16. Aqueous-phase quantitative NMR determination of amino acid enantiomer ratio by 13C-NMR using chiral neodymium shift reagent.

    PubMed

    Florini, Nicola; Faglioni, Francesco; Zucchi, Claudia; Caglioti, Luciano; Pályi, Gyula

    2010-05-01

    A neodymium-(S)-PDTA (PDTA = N,N,N',N'-tetrakis[(hydroxycarbonyl)methyl]-1,2-diaminopropane) complex was found exceptionally useful in the quantitative determination of enantiomer ratios of water-soluble natural amino acids by (13)C-NMR. The method is demonstrated on mixtures of L- and D-enantiomers of various amino acids. The interactions of the chiral shift reagent with the amino acid molecules were rationalized by molecular orbital calculations.

  17. Dysprosium(III)-diethylenetriaminepentaacetate complexes of aminocyclodextrins as chiral NMR shift reagents.

    PubMed

    Wenzel, T J; Miles, R D; Zomlefer, K; Frederique, D E; Roan, M A; Troughton, J S; Pond, B V; Colby, A L

    2000-01-01

    A metal chelating ligand is bonded to alpha-, beta-, and gamma-cyclodextrin by the reaction of diethylenetraminepentaacetic dianhydride with the corresponding 6-mono- and 2-mono(amine)cyclodextrin. Adding Dy(III) to the cyclodextrin derivatives causes shifts in the (1)H-NMR spectra of substrates such as propranolol, tryptophan, aspartame, carbinoxamine, pheniramine, doxylamine, and 1-anilino-8-naphthalenesulfonate. The Dy(III)-induced shifts enhance the enantiomeric resolution in the NMR spectra of several substrates. Enhancements in enantiomeric resolution using cyclodextrin derivatives with the amine tether are compared to previously described compounds in which the chelating ligand is attached through an ethylenediamine tether. In general, the Dy(III) complex of the 6-beta-derivative with the amine tether is a more effective chiral resolving agent than the complex with the ethylenediamine tether. The opposite trend is observed with the 2-beta-derivatives. The presence of the chelating ligand in the 2-beta-derivative hinders certain substrates from entering the cavity. For cationic substrates, evidence suggests that a cooperative association involving inclusion in the cavity and association with the Dy(III) unit occurs. Enhancements in enantiomeric resolution in the spectrum of tryptophan are greater for the secondary alpha- and gamma-derivatives than the beta-derivative.

  18. Diagnostic Approach to Disease Using Non-invasive Samples Based on Derivatization and LC-ESI-MS/MS.

    PubMed

    Toyo'oka, Toshimasa

    2016-01-01

    The determination of biologically-active molecules is very important in order to understand biological functions. A novel approach for the highly sensitive and specific determination seems to be essential for this purpose. Based on this consideration, we synthesized various types of fluorogenic and fluorescent reagents for the derivatization of chiral and achiral molecules. The fluorescence analysis is excellent for the analysis of target molecules and generally provides good expected results. However, the trace analysis of the bioactive molecules in complex matrices, such as plasma and urine, is not always satisfactory even using high-performance fluorometry. In such a situation, mass spectrometry (MS) is another technique for the selective and sensitive determination of biological components. Therefore, various derivatization reagents for MS/MS detection were developed and used for the determination of amines and carboxyls including chiral molecules. These newly developed reagents were also adopted for the biomarker detection related to diseases using non-invasive samples (i.e., saliva, nail, hair). Although the determination of the targeted chiral molecules is relatively easy, it is very difficult to identify and/or determine the enantiomeric biomarker in real samples. To solve this difficulty, we proposed the strategy called "chiral metabolomics," which means the total analysis of the enantiomers of various chiral metabolites in complex matrices. This review paper focused on the development of various new derivatization reagents for amines and carboxyls by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis and the detection of the biomarker candidates related to several diseases in non-invasive samples (i.e., hair, nail, saliva) using these reagents.

  19. Gas phase enantiomeric distinction of (R)- and (S)-aromatic hydroxy esters by negative ion chemical ionization mass spectrometry using a chiral reagent gas

    NASA Astrophysics Data System (ADS)

    Mancel, Valérie; Sellier, Nicole; Lesage, Denis; Fournier, Françoise; Tabet, Jean-Claude

    2004-10-01

    Negative ion chemical ionization (NICI) using a chiral reagent gas such as (2S,3S) butanediol (GSS) allows the differentiation of chiral [alpha] hydroxy esters (MR or MS). The distinction is significantly enhanced by using CID on the deprotonated hetero dimer [M + (GSS-H)]-. The contribution of a non covalent [M + (GSS-H)]- competitive form is very minor. In fact, a covalent form appears favored. To produce a covalent adduct ion, an enantioselectivity of the alkoxide attack on the electrophilic ester site to form a tetravalent adduct is suggested by the product ion abundances. This observed steric control is consistent with the one observed in solution (Cram-Felkin addition/reduction orientation). The dissociations under collision conditions of the product deprotonated diastereomeric compounds show a stereospecific effect in the elimination of alcohol from the tetravalent adduct ions rather than a regeneration of the deprotonated diol reagent as expected from non-covalent heterodimer. This study shows an orientation with a chiral compound that allows, from an analytical point of view, the distinction of enantiomers and the attribution of chirality in the gas phase under NICI conditions.

  20. Chiral gas chromatography as a tool for investigations into illicitly manufactured methylamphetamine.

    PubMed

    Morrison, Calum; Smith, Frank J; Tomaszewski, Tomasz; Stawiarska, Karolina; Biziuk, Marek

    2011-08-01

    The aim of this study was to develop a chiral gas chromatographic method for the separation of compounds likely to be found in the EMDE synthesis of methylamphetamine, a heavily abused stimulant drug. Here we describe the separation of the enantiomers of ephedrine, pseudoephedrine, chlorinated intermediates and methylamphetamine using fluorinated acid anhydrides as chemical derivatization reagents prior to gas chromatographic analysis on a 2,3-di-O-methyl-6-t-butyl silyl-β-cyclodextrin stationary phase (CHIRALDEX™ B-DM). Separation of the enantiomers of pseudoephedrine, methylamphetamine and chloro-intermediates was achieved using PFPA derivatization, and enantiomers of ephedrine using TFAA derivatization, in run times of less than 40 minutes. The use of HFBA as a derivatization reagent for this set of analytes is also discussed. Copyright © 2011 Wiley-Liss, Inc.

  1. Reagent Precoated Targets for Rapid In-Tissue Derivatization of the Anti-Tuberculosis Drug Isoniazid Followed by MALDI Imaging Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Manier, M. Lisa; Reyzer, Michelle L.; Goh, Anne; Dartois, Veronique; Via, Laura E.; Barry, Clifton E.; Caprioli, Richard M.

    2011-08-01

    Isoniazid (INH) is an important component of front-line anti-tuberculosis therapy with good serum pharmacokinetics but unknown ability to penetrate tuberculous lesions. However, endogenous background interferences hinder our ability to directly analyze INH in tissues. Chemical derivatization has been successfully used to measure isoniazid directly from tissue samples using matrix-assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS). MALDI targets were pretreated with trans-cinnamaldehyde (CA) prior to mounting tissue slices. Isoniazid present in the tissues was efficiently derivatized and the INH-CA product measured by MS/MS. Precoating of MALDI targets allows the tissues to be directly thaw-mounted and derivatized, thus simplifying the preparation. A time-course series of tissues from tuberculosis infected/INH dosed animals were assayed and the MALDI MS/MS response correlates well with the amount of INH determined to be in the tissues by high-performance liquid chromatography (HPLC)-MS/MS.

  2. 9-fluorenylmethyl chloroformate as a fluorescence-labeling reagent for derivatization of carboxylic acid moiety of sodium valproate using liquid chromatography/tandem mass spectrometry for binding characterization: a human pharmacokinetic study.

    PubMed

    Mohammadi, Bahareh; Majnooni, Mohammad Bagher; Khatabi, Pyman Malek; Jalili, Ronak; Bahrami, Gholamreza

    2012-01-01

    In High Performance Liquid Chromatographic (HPLC) determination of chemicals with acidic functions, different labeling agents are used to improve sensitivity of the assay. 9-Fluorenylmethyl chloroformate (FMOC-Cl), on the other hand, is a suitable labeling agent, which reacts with both primary and secondary amines and less readily with hydroxyl groups in alkaline conditions. However, the reagent has not been applied in labeling of chemicals with acidic function yet. In this study which is the first report on application of FMOC-Cl in derivatization and analysis of a drug with acidic function, valproic acid (VPA), one of a series of fatty carboxylic acids with anticonvulsant activity, was derivatized using the reagent and quantified in serum samples by HPLC with fluorescence detection. In addition, to document the reaction between the labeling agent and carboxylic acid moiety of the drug, we developed a liquid chromatography-tandem MS/MS (LC-MS/MS) method. Following liquid-liquid extraction, derivatization of the drug and an internal standard was achieved in alkaline medium. The elute was monitored by a fluorescence detector with respective excitation and emission wavelengths of 265 and 315 nm. The present method is more sensitive comparing with other published HPLC procedures for analysis of VPA. The assay is sensitive enough to measure drug levels obtained in human single dose studies with a limit of quantification of 0.01 μg/mL. Also the method is linear over the concentrations range of 0.01-32 μg/mL of VPA in human serum using 100 μL serum sample and 5 μL injection. The coefficient variation values of both inter and intra day analysis were less than 12% and the percentage error was less than 4%. The method performance was studied and the validated procedure applied in a randomized cross-over bioequivalence study of two different VPA preparations in 24 healthy volunteers.

  3. A validated LC-MS/MS method for the sensitive quantitation of serum 7alpha hydroxy-, 7beta hydroxy- and 7keto-dehydroepiandrosterone using a novel derivatization reagent.

    PubMed

    Ke, Yuyong; Gonthier, Renaud; Simard, Jean-Nicolas; Labrie, Fernand

    2016-04-01

    7alpha hydroxy-, 7beta hydroxy- and 7keto-dehydroepiandrosterone (7α OH-DHEA, 7β OH-DHEA and 7 oxo-DHEA) are oxidized metabolites of dehydroepiandrosterone (DHEA). Their concentrations are low in the circulation, especially in postmenopausal women, thus resulting in a considerable challenge for their reliable measurement. A sensitive and accurate LC-MS/MS method has been developed using a simple sample preparation procedure and a novel derivatization with 1-amino-4-methyl piperazine (MP). The derivatized metabolites are stable in high water content reagents. A 10 pg/mL (0.2 pg on column) for the low limit of quantitation (LLOQ) has been achieved for all three compounds. A proper choice of multiple reaction monitoring (MRM) transitions provides good specificity. The excess amount of reagent can be removed from the sample during the derivatization process. Within the calibration range of 10-2000 pg/mL, a good linearity was obtained with R>0.99 where the weighing factor is 1/X while the bias and coefficient of variance (CV) are within 8% for all levels of QCs and calibration curves. This method has been fully validated according to the FDA guidelines, where the results of the matrix effect meet the acceptance criteria while freeze-thaw stability, short and long term stability in matrix and solution as well as post-processed sample stability meet the requirements. With this method, the concentrations of 7α OH-DHEA, 7β OH-DHEA and 7 oxo-DHEA were measured in premenopausal and postmenopausal serum. The average concentration of 7α OH-DHEA is equivalent to that of 7β OH-DHEA in both types of sera. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis

    PubMed Central

    Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

    2012-01-01

    The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC. PMID:22649749

  5. 1,2-Dimethylimidazole-4-sulfonyl Chloride, a Novel Derivatization Reagent for the Analysis of Phenolic Compounds by Liquid Chromatography Electrospray Tandem Mass Spectrometry

    PubMed Central

    Xu, Li; Spink, David C.

    2007-01-01

    A novel derivatization method employing 1,2-dimethylimidazole-4-sulfonyl chloride (DMISC) to improve the mass spectrometric response for phenolic compounds in liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) and tandem mass spectrometry (LC-ESI-MS/MS) is described. Several environmentally relevant compounds, including chloro-, aryl- and alkylphenols, steroidal estrogens, and hydroxy-polycyclic aromatic hydrocarbons (OHPAHs), were selected to evaluate this technique. A facile derivatization procedure employing DMISC results in dimethylimidazolesulfonyl (DMIS) derivatives that are stable in aqueous solution. These DMIS derivatives produced intense [M+H]+ ions in positive-ion LC-ESI-MS. The product ion spectra of the [M+H]+ ions of simple phenols were dominated by ions representing the DMIS and dimethylimidazole moieties, whereas product ion spectra of the DMIS derivatives of OHPAHs with three or more fused aromatic rings showed prominent ArO+ ions, the relative intensity of which increased with the number of rings. The DMIS derivatives of the selected phenolic compounds showed excellent chromatographic properties. To substantiate the utility of derivatization with DMISC, an analytical method employing enzyme hydrolysis, solid phase extraction, derivatization with DMISC, and analysis by LC-ESI-MS/MS with multiple reaction monitoring for determination in human urine of 1-hydroxypyrene, a widely used biomarker for the assessment of human exposure to PAHs, was developed and validated. PMID:17524972

  6. Derivatization in Capillary Electrophoresis.

    PubMed

    Marina, M Luisa; Castro-Puyana, María

    2016-01-01

    Capillary electrophoresis is a well-established separation technique in analytical research laboratories worldwide. Its interesting advantages make CE an efficient and potent alternative to other chromatographic techniques. However, it is also recognized that its main drawback is the relatively poor sensitivity when using optical detection. One way to overcome this limitation is to perform a derivatization reaction which is intended to provide the analyte more suitable analytical characteristics enabling a high sensitive detection. Based on the analytical step where the CE derivatization takes place, it can be classified as precapillary (before separation), in-capillary (during separation), or postcapillary (after separation). This chapter describes the application of four different derivatization protocols (in-capillary and precapillary modes) to carry out the achiral and chiral analysis of different compounds in food and biological samples with three different detection modes (UV, LIF, and MS).

  7. 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride as an enantioseparation enhancer for fluorescence chiral derivatization-liquid chromatographic analysis of dl-lactic acid.

    PubMed

    Todoroki, Kenichiro; Goto, Kanoko; Nakano, Tatsuki; Ishii, Yasuhiro; Min, Jun Zhe; Inoue, Koichi; Toyo'oka, Toshimasa

    2014-09-19

    This paper reports a novel fluorescence chiral derivatization-liquid chromatography (LC) method for the analysis of d- and l-lactic acids (LAs) using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) as an enantioseparation enhancer. In this method, the dl-LAs were fluorescently derivatized with (S)-(+)-4-(N,N-dimethylaminosulfonyl)-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole [(S)-(+)-DBD-APy] in the presence of DMT-MM as a condensing agent. These conditions resulted in the hydroxyl group of the LA derivative being etherified by the triazine unit of DMT-MM, producing sterically bulky diastereoisomers. The resulting fluorescent diastereoisomers of d- and l-LAs could be discriminated and successfully enantioseparated through reversed-phase LC. The enhancement effect of the derivatization agent DMT-MM when using seven other commercially available chiral amines was also demonstrated. Finally, this method was successfully applied to quantification of dl-LAs in foodstuffs (yogurts and fermented milk drinks).

  8. [Preparation of 1-(2-naphthyl) -3-methyl-5-pyrazolone as pre-column derivatization reagent for the determination of saccharides using high performance liquid chromatography-mass spectrometry].

    PubMed

    Sun, Zhiwei; Liu, Lingjun; Hu, Baojun; Sheng, Xiao; Wang, Xiaoyan; Suo, Yourui; You, Jinmao

    2008-03-01

    Eight saccharides were derivatized using 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) as pre-column derivatizing reagent, and separated on a reversed-phase Hypersil ODS 2 column (4.6 mm x 200 mm, 5 microm), by high performance liquid chromatography (HPLC) in conjunction with a gradient elution, detected by a diode array detector (DAD), and identified by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. NMP reacted with reductive saccharides easily in the presence of 17% ammonia water at 70 degrees C. All linear correlation coefficients for saccharide derivatives were over 0.998 5. The detection limits (at signal-to-noise of 3:1) were 0.58 - 1.1 pmol for saccharide derivatives. The characteristic fragment ions, especially m/z 473, from the cleavage of NMP-labeled saccharides exhibited high regularity for the identification of the composition of saccharide mixture. The established method is sensitive and repeatable for the determination of saccharides.

  9. Qualitative and quantitative analysis of hyaluronan oligosaccharides with high performance thin layer chromatography using reagent-free derivatization on amino-modified silica and electrospray ionization-quadrupole time-of-flight mass spectrometry coupling on normal phase.

    PubMed

    Rothenhöfer, Martin; Scherübl, Rosmarie; Bernhardt, Günther; Heilmann, Jörg; Buschauer, Armin

    2012-07-27

    Purified oligomers of hyalobiuronic acid are indispensable tools to elucidate the physiological and pathophysiological role of hyaluronan degradation by various hyaluronidase isoenzymes. Therefore, we established and validated a novel sensitive, convenient, rapid, and cost-effective high performance thin layer chromatography (HPTLC) method for the qualitative and quantitative analysis of small saturated hyaluronan oligosaccharides consisting of 2-4 hyalobiuronic acid moieties. The use of amino-modified silica as stationary phase allows a simple reagent-free in situ derivatization by heating, resulting in a very low limit of detection (7-19 pmol per band, depending on the analyzed saturated oligosaccharide). By this derivatization procedure for the first time densitometric quantification of the analytes could be performed by HPTLC. The validated method showed a quantification limit of 37-71 pmol per band and was proven to be superior in comparison to conventional detection of hyaluronan oligosaccharides. The analytes were identified by hyphenation of normal phase planar chromatography to mass spectrometry (TLC-MS) using electrospray ionization. As an alternative to sequential techniques such as high performance liquid chromatography (HPLC) and capillary electrophoresis (CE), the validated HPTLC quantification method can easily be automated and is applicable to the analysis of multiple samples in parallel. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Determination of the enantiomeric excess of chiral carboxylic acids by 31P NMR with phosphorylated derivatizing agents from C2-symmetrical diamines containing the (S)-alpha-phenylethyl group.

    PubMed

    Mastranzo, Virginia M; Quintero, Leticia; de Parrodi, Cecilia Anaya

    2007-06-01

    The use of P(III) and P(V) organophosphorus derivatizing agents prepared from C(2) symmetrical (1R,2R)- and (1S,2S)-trans-N,N'-bis-[(S)-alpha-phenylethyl]-cyclohexane-1,2-diamines 1 and 2, as well as (1R,2R)- and (1S,2S)-trans-N,N'-bis-[(S)-alpha-phenylethyl]-4-cyclohexene-1,2-diamines 3 and 4 for the determination of enantiomeric composition of chiral carboxylic acids by (31)P NMR, is described.

  11. High-performance liquid chromatography of N-terminal tyrosine-containing oligopeptides by pre-column fluorescence derivatization with hydroxylamine, cobalt (II) and borate reagents.

    PubMed

    Nakano, M; Kai, M; Ohno, M; Ohkura, Y

    1987-12-18

    A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of N-terminal tyrosine-containing oligopeptides involving methionine-enkephalin and leucine-enkephalin. The peptides are converted into fluorescent derivatives by heating in a weakly alkaline medium (pH 8.5) containing hydroxylamine, cobalt(II) ion and borate. The derivatives are separated on a reversed-phase column (TSKgel ODS-120T) by gradient elution of acetonitrile in a mobile phase containing borate buffer (pH 8.5) and tetra-n-butylammonium chloride, and then determined by fluorimetry. The derivatization provides a single fluorescent product for each N-terminal tyrosine-containing oligopeptide, but does not allow the production of fluorescent derivatives for peptides having no tyrosyl residue at the N-terminal. The method is selective and sensitive; the lower limits of detection for the N-terminal tyrosine-containing oligopeptides tested were 140-310 fmol per 100 microliters injected.

  12. Synthesis of the isotope-labeled derivatization reagent for carboxylic acids, 7-(N,N-dimethylaminosulfonyl)-4-(aminoethyl)piperazino-2,1,3-benzoxadiazole (d6) [DBD-PZ-NH2 (D)], and its application to the quantification and the determination of relative amount of fatty acids in rat plasma samples by high-performance liquid chromatography/mass spectrometry.

    PubMed

    Tsukamoto, Yuhki; Santa, Tomofumi; Yoshida, Hiroo; Miyano, Hiroshi; Fukushima, Takeshi; Hirayama, Kazuo; Imai, Kazuhiro; Funatsu, Takashi

    2006-04-01

    The isotope-labeled benzofurazan derivatization reagent for carboxylic acids, 7-(N,N-dimethylaminosulfonyl)-4-(aminoethyl)piperazino-2,1,3-benzoxadiazole (d6) [DBD-PZ-NH2 (D)] was synthesized. DBD-PZ-NH2 (D) was used for the accurate quantification of fatty acids by liquid chromatography/mass spectrometry (LC/MS). The standard fatty acids were derivatized with DBD-PZ-NH2 (D) to the stable isotope-labeled compounds for the fatty acids derivatives of DBD-PZ-NH2 and used for the internal standards. The obtained calibration curves for fatty acids were linear over the range 0.1-200 microM (r2 > 0.999). Fatty acids in plasma samples were determined after derivatization with DBD-PZ-NH2 and analyzed by LC/MS using standard fatty acid DBD-PZ-NH2 (D) derivatives as internal standards. Furthermore, the relative amounts of fatty acids in two plasma samples were determined after derivatization with DBD-PZ-NH2 and DBD-PZ-NH2) (D). The isotope-labeled derivatization reagent was useful for accurate quantification and the determination of relative amounts of the metabolites in biological samples having the target functional group.

  13. GC separation of amino acid enantiomers via derivatization with heptafluorobutyl chloroformate and Chirasil-L-Val column.

    PubMed

    Zahradnícková, Helena; Husek, Petr; Simek, Petr

    2009-11-01

    Heptafluorobutyl chloroformate (HFBCF), a recently introduced derivatization reagent, was examined in enantioseparation of amino acids (AAs) by GC. Twenty proteinogenic AAs, plus ornithine, cystine and 4-fluorophenylalanine (internal standard) were treated with the reagent and separation properties of the derivatives were assessed on a Chirasil-Val capillary column. Nineteen AA enantiomers were efficiently separated in 43 min except proline, arginine and cystine. The HFBCF derivatives of the studied DL-AAs show improved separation over other chloroformate-based derivatives hitherto reported. A combination of the improved and faster separation with a simple derivatization protocol, involving an immediate one-step reaction-extraction in two-phase aqueous-organic medium, and low elution temperatures extend application of HFBCF to chiral AA analysis.

  14. Chiral separation of amino acids and peptides by capillary electrophoresis.

    PubMed

    Wan, H; Blomberg, L G

    2000-04-14

    Chiral separation of amino acids and peptides by capillary electrophoresis (CE) is reviewed regarding the separation principles of different approaches, advantages and limitations, chiral recognition mechanisms and applications. The direct approach details various chiral selectors with an emphasis on cyclodextrins and their derivatives, antibiotics and chiral surfactants as the chiral selectors. The indirect approach deals with various chiral reagents applied for diastereomer formation and types of separation media such as micelles and polymeric pseudo-stationary phases. Many derivatization reagents used for high sensitivity detection of amino acids and peptides are also discussed and their characteristics are summarized in tables. A large number of relevant examples is presented illustrating the current status of enantiomeric and diastereomeric separation of amino acids and peptides. Strategies to enhance the selectivity and optimize separation parameters by the application of experimental designs are described. The reversal of enantiomeric elution order and the effects of organic modifiers on the selectivity are illustrated in both direct and indirect methods. Some applications of chiral amino acid and peptide analysis, in particular, regarding the determination of trace enantiomeric impurities, are given. This review selects more than 200 articles published between 1988 and 1999.

  15. Sensitive determination of thiols in wine samples by a stable isotope-coded derivatization reagent d0/d4-acridone-10-ethyl-N-maleimide coupled with high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry analysis.

    PubMed

    Lv, Zhengxian; You, Jinmao; Lu, Shuaimin; Sun, Weidi; Ji, Zhongyin; Sun, Zhiwei; Song, Cuihua; Chen, Guang; Li, Guoliang; Hu, Na; Zhou, Wu; Suo, Yourui

    2017-03-31

    As the key aroma compounds, varietal thiols are the crucial odorants responsible for the flavor of wines. Quantitative analysis of thiols can provide crucial information for the aroma profiles of different wine styles. In this study, a rapid and sensitive method for the simultaneous determination of six thiols in wine using d0/d4-acridone-10-ethyl-N-maleimide (d0/d4-AENM) as stable isotope-coded derivatization reagent (SICD) by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) has been developed. Quantification of thiols was performed by using d4-AENM labeled thiols as the internal standards (IS), followed by stable isotope dilution HPLC-ESI-MS/MS analysis. The AENM derivatization combined with multiple reactions monitoring (MRM) not only allowed trace analysis of thiols due to the extremely high sensitivity, but also efficiently corrected the matrix effects during HPLC-MS/MS and the fluctuation in MS/MS signal intensity due to instrument. The obtained internal standard calibration curves for six thiols were linear over the range of 25-10,000pmol/L (R(2)≥0.9961). Detection limits (LODs) for most of analytes were below 6.3pmol/L. The proposed method was successfully applied for the simultaneous determination of six kinds of thiols in wine samples with precisions ≤3.5% and recoveries ≥78.1%. In conclusion, the developed method is expected to be a promising tool for detection of trace thiols in wine and also in other complex matrix. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Ultrasensitive quantification of endogenous brassinosteroids in milligram fresh plant with a quaternary ammonium derivatization reagent by pipette-tip solid-phase extraction coupled with ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Deng, Ting; Wu, Dapeng; Duan, Chunfeng; Guan, Yafeng

    2016-07-22

    Determination of endogenous brassinosteroids (BRs) in limited sample amount is vital to elucidating their tissue- and even local tissue-specific signaling pathway and physiological effects on plant growth and development. In this work, an ultra-sensitive quantification method was established for endogenous BRs in milligram fresh plant by using pipette-tip solid-phase extraction coupled with ultra-performance liquid chromatography tandem mass spectrometry (PT-SPE-UPLC-MS/MS), in which a quaternary ammonium phenyl boronic acid, 4-borono-N,N,N-trimethylbenzenaminium iodide (BTBA) was first developed for chemical derivatization of BRs. Due to the cationic quaternary ammonium group of BTBA, the ionization efficiencies of the BRs chelates with BTBA (BTBA-BRs) were enhanced by 1190-448785 times, which is the highest response enhancement factor among all derivatization reagents reported for BRs. In addition, PT-SPE packed with C18 sorbent was first used for purifying BRs from plant extracts, so the required sample amount was minimized, and recoveries higher than 91% were achieved. Under the optimized conditions, the minimal detectable amounts (MDA) of five target BRs were in the range of 27-94 amol, and the correlation coefficients (R(2)) were >0.9985 over four orders of magnitude. The relative recoveries of 75.8-104.9% were obtained with the intra- and inter-day relative standard deviations (RSDs) less than 18.7% and 19.6%, respectively. Finally, three BRs were successfully quantified in only 5mg fresh rice plant samples, and 24-epiBL can even be detected in only 0.5mg FW rice leaf segments. It is the first time that the BRs content in sub-milligram fresh plant sample has been quantified. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. An easy-to-use excimer fluorescence derivatization reagent, 2-chloro-4-methoxy-6-(4-(pyren-4-yl)butoxy)-1,3,5-triazine, for use in the highly sensitive and selective liquid chromatography analysis of histamine in Japanese soy sauces.

    PubMed

    Nakano, Tatsuki; Todoroki, Kenichiro; Ishii, Yasuhiro; Miyauchi, Chiemi; Palee, Arpaporn; Min, Jun Zhe; Inoue, Koichi; Suzuki, Kuniaki; Toyo'oka, Toshimasa

    2015-06-23

    In this study, a novel pre-column excimer fluorescence derivatization reagent, 2-chloro-4-methoxy-6-(4-(pyren-4-yl)butoxy)-1,3,5-triazine (CMPT), was developed for polyamines, specifically histamine. By CMPT derivatization, the polyamines, histamine and tyramine were converted to polypyrene derivatives, and emitted intra-molecular excimer fluorescence at 475nm. This could clearly be distinguished from the normal fluorescence emitted from reagent blanks at 375 nm. Unlike conventional excimer fluorescence derivatization reagents, CMPT is chemically stable and its reactivity sustained over at least 36 days even in solution state. We successfully applied this reagent to the sensitive and selective analysis of histamine in different kinds of Japanese commercial soy sauces. The detection and quantification limits of histamine were 15 and 50 μg L(-1), respectively, equating to 1.35 pmol and 4.5 pmol for a 6 μL injection. This sensitivity helped the direct analysis of soy sauce samples only treated by one-step liquid-liquid extraction without concentration. The histamine levels of commercial soy sauce samples (koikuchi, usukuchi and saishikomi) investigated were 1.24-768.5 mg L(-1).

  18. Suppression of thiol exchange reaction in the determination of reduced-form thiols by high-performance liquid chromatography with fluorescence detection after derivatization with fluorogenic benzofurazan reagent, 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate and 4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole.

    PubMed

    Santa, Tomofumi; Aoyama, Chiaki; Fukushima, Takeshi; Imai, Kazuhiro; Funatsu, Takashi

    2006-01-01

    The derivatization of the reduced-form thiols with SBD-F (7-fluoro-2,1,3-benzoxadiazole-4-sulfonate) and ABD-F (4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole) was studied. The yields of the derivatives of the reduced-form thiols (cysteine, homocysteine, reduced-form glutathione) with SBD-F at 60 degrees C for 45 min in the borate buffer (pH 9.3) were significantly decreased in the presence of the oxidized-form thiols (cystine, homocystine, oxidized-form glutathione) because of the thiol exchange reaction between the reduced-form and the oxidized-form thiols. The use of ABD-F at low temperature enabled the suppression of these thiol exchange reactions, and the recommended conditions were below 5 degrees C for 90 min in borate buffer (pH 9.3). These results suggest that ABD-F is a preferred derivatization reagent for the accurate determination of the reduced-form thiols in samples containing the oxidized-form thiols. In addition, it was also suggested that the derivatization of the reduced-form thiols should also be performed at low temperature when derivatization reagents such as o-phthalaldehyde (OPA) and monobromobimane (BrB) are used.

  19. Chemically Derivatized Semiconductor Photoelectrodes.

    DTIC Science & Technology

    1982-01-04

    as Si, Ge, and GaAs derivatized with reagents based on ferrocene such as those represented by I and II. Work with p-type semiconductor photoelectrode...Concerning n-type Si it was found that EtOH/0.1 M En-Bu4N)C104 solutions containing A = ferrocene and A+ = ferri-- cinium result in a constant output of...electrical energy from an illuminated photoelectrochemical device configured as in Scheme II.(20) The ferrocene captures the photogenerated h+ at a rate -4

  20. Sensitive and simple determination of bromate in foods disinfected with hypochlorite reagents using high performance liquid chromatography with post-column derivatization.

    PubMed

    Yokota, Azusa; Kubota, Hiroki; Komiya, Satomi; Sato, Kyoko; Akiyama, Hiroshi; Koshiishi, Ichiro

    2012-11-02

    A novel analytical method for the quantification of bromate in fresh foods using high performance liquid chromatography (HPLC) with a post-column reaction has been developed. The fresh food sample solutions were pretreated with homogenization, centrifugal ultrafiltration and subsequent solid phase extraction using a strong anion-exchange resin. After separation on a strong anion-exchange chromatography column using a highly concentrated NaCl solution (0.3M) as the eluent, the bromate was quantified by detection using a post-column reaction with a non-carcinogenic reagent (tetramethylbenzidine). The developed HPLC technique made it possible to quantify bromate in salt-rich fresh foods. The recoveries from fresh foods spiked with bromate at low levels (2 or 10 ng/g) satisfactorily ranged from 75.3 to 90.7%. The lowest quantification limit in fresh foods was estimated to be 0.6 ng/g as bromic acid. The method should be helpful for the quantification of bromate in fresh foods disinfected with hypochlorite solutions. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Tandem Mass Spectrometric Characterization of Thiol Peptides Modified by the Chemoselective Cationic Sulfhydryl Reagent (4-Iodobutyl)Triphenylphosphonium—. Effects of a Cationic Thiol Derivatization on Peptide Fragmentation

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Zhang, Jie; Arbogast, Brian; Maier, Claudia S.

    2011-10-01

    Fixed charge chemical modifications on peptides and proteins can impact fragmentation behaviors in tandem mass spectrometry (MS/MS). In this study, we employed a thiol-specific cationic alkylation reagent, (4-iodobutyl)triphenylphosphonium (IBTP), to selectively modify cysteine thiol groups in mitochondrial proteome samples. Tandem mass spectrometric characteristics of butyltriphenylphosphonium (BTP)-modified peptides were evaluated by comparison to their carbamidomethylated (CAM) analogues using a quadrupole time-of-flight (Q-TOF) instrument under low energy collision-induced dissociation (CID) conditions. Introduction of the fixed charge modification resulted in the observation of peptide and fragment (bn and yn) ions with higher charge states than those observed for CAM-modified analogues. The charged BTP moiety had a significant effect on the neighboring amide bond fragmentation products. A decrease in relative abundances of the product ions at the corresponding cleavage sites was observed compared with those from the CAM-modified derivatives. This effect was particularly noticeable when an Xxx-Pro bond was in the vicinity of a BTP group. We hypothesized that the presence of a phosphonium moiety will reduce the tendency for protonation of the proximal amide bonds in the peptide backbone. Indeed, calculations indicated that proton affinities of backbone amide bonds close to the modified cysteine residues were generally 20-50 kcal/mol lower for BTP-modified peptides than for the unmodified or CAM-modified analogues with the sequence motif -Ala-Cys-Alan-Ala2-, -Ala-Cys-Alan-Pro-Ala-, and -Ala-Pro-Alan-Cys-Ala-, n = 0-3.

  2. Synthesis of chiral triazine coupling reagents based on esters of N-alkylproline and their application in the enantioselective incorporation of D or L amino acid residue directly from racemic substrate.

    PubMed

    Kasperowicz-Frankowska, Katarzyna; Gzik, Anna; Dziemidkiewicz, Michał; Kolesińska, Beata; Kamiński, Zbigniew J

    2014-01-01

    Esters of N-methylproline and N-allylproline were prepared and used as component for synthesis of chiral triazine based coupling reagents. N-Triazinylammonium tetrafluoroborate obtained from methylester of L-N-methylproline, 2-chloro-4,6-dimethozxy-1,3,5-triazine and tetrafluoroboric acid in the coupling of rac-Z- A1a-OH with glycine methylester preferred formation of D-Z-AlaGly-OMe with L/D ratio 21/79. Coupling reagent prepared from D enantiomer of N-methylproline gave L-Z-AlaGly-OMe with L/D ratio 75/25.

  3. Study on determination of iron, cobalt, nickel, copper, zinc and manganese in drinking water by solid-phase extraction and RP-HPLC with 2-(2-quinolinylazo)-5-diethylaminophenol as precolumn derivatizing reagent.

    PubMed

    Hu, Qiufen; Yang, Guanyu; Yang, Jihong; Yin, Jiayuan

    2002-12-01

    A new method for the determination of iron, cobalt, nickel, copper, zinc and manganese in drinking water by the reversed-phase high-performance liquid chromatography (RP-HPLC) with 2-(2-quinolinylazo)-5-diethylaminophenol (QADEAP) as precolumn derivatizing reagent was studied in this paper. The iron, cobalt, nickel, copper, zinc, and manganese ions react with QADEAP to form color chelates in the presence of cetyl trimethylammonium bromide (CTMAB) and acetic acid-sodium acetic buffer solution medium of pH 4.0. These chelates were enriched by solid-phase extraction with a Waters Nova-Pak C18 cartridge and eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The enrichment factor of 100 was achieved. Then the chelates were separated on a Waters Nova-Pak C18 column (3.9 x 150 mm, 5 microm) by gradient elution with methanol (containing 0.2% of acetic acid and 0.1% of CTMAB) and 0.05 mol L(-1) acetic acid-sodium acetic buffer solution (containing 0.1% of CTMAB) (pH 4.0) as mobile phase at a flow rate of 0.5 ml min(-1), and monitored with a photodiode array detector from 450 approximately 700 nm. The detection limits (S/N = 3) of iron, cobalt, nickel, copper, zinc and manganese are 0.8, 1.1, 0.9, 1.1, 1.5 and 2.0 ng L(-1), respectively, in the original sample. This method can be applied to determination at the microg L(-1) level of iron, cobalt, nickel, copper, zinc and manganese in drinking water with good results.

  4. Quantitative and isomeric determination of amphetamine and methamphetamine from urine using a nonprotic elution solvent and R(-)-alpha-methoxy-alpha-trifluoromethylphenylacetic acid chloride derivatization.

    PubMed

    Holler, Justin M; Vorce, Shawn P; Bosy, Thomas Z; Jacobs, Aaron

    2005-10-01

    Forensic Urine Drug Testing Laboratories often requires two confirmatory methods for a methamphetamine positive screen. First, methamphetamine is identified and quantitated using gas chromatography-mass spectrometry. If the total methamphetamine concentration is above the administrative cutoff level, the isomeric composition must be determined. This eliminates a possible contribution by over-the-counter cold medications that contain l-methamphetamine (Vick's inhalers). Products that contain only the l-isomer of methamphetamine must be distinguishable from prescription or illicitly manufactured methamphetamine, which consists mainly of the d-isomer. Optically impure derivatizing reagents will produce an impure mixture from a pure isomeric compound. Therefore, methods utilizing impure reagents can prove problematic when interpreting results. Use of an optically pure chiral derivatizing reagent, such as R(-)-alpha-methoxy-alpha-trifluoromethylphenylacetic acid chloride, allows for the creation and measurement of chromatographically separable isomeric compounds. The novel method described here utilizes a polymer-based solid-phase column adapted to a positive pressure manifold extraction system and a one-step derivatization process that occurs directly in the elution solvent. This methodology eliminates an elution solvent dry-down step that may adversely affect recovery of volatile amphetamine compounds. Although the method was designed for the quantitative analysis of the isomers of amphetamine and methamphetamine, it can be adapted for use with a wide range of phenethylamines including methylenedioxyamphetamine, N-methylenedioxymethamphetamine, and possibly N-methylenedioxyethylamphetamine. The linear range for quantitation was 25-10,000 ng/mL for d,l-methamphetamine and d,l-amphetamine, and correlation coefficients were 0.997 or better. The coefficient of variation for all four analytes did not exceed 2.8%. Concentrations analyzed ranged from 500 to 4000 ng/mL (n=40

  5. Laboratory Reagents

    SciTech Connect

    CARLSON, D.D.

    1999-10-08

    Replaced by WMH-310, Section 4.17. This document outlined the basic methodology for preparing laboratory reagents used in the 222-S Standards Laboratory. Included were general guidelines for drying, weighing, transferring, dissolving, and diluting techniques common when preparing laboratory reagents and standards. Appendix A contained some of the reagents prepared by the laboratory.

  6. Simultaneous analysis of D-alanine, D-aspartic acid, and D-serine using chiral high-performance liquid chromatography-tandem mass spectrometry and its application to the rat plasma and tissues.

    PubMed

    Karakawa, Sachise; Shimbo, Kazutaka; Yamada, Naoyuki; Mizukoshi, Toshimi; Miyano, Hiroshi; Mita, Masashi; Lindner, Wolfgang; Hamase, Kenji

    2015-11-10

    A highly sensitive and selective chiral LC-MS/MS method for D-alanine, D-aspartic acid and D-serine has been developed using the precolumn derivatization reagents, 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AccQ-Tag) or p-N,N,N-trimethylammonioanilyl N'-hydroxysuccinimidyl carbamate iodide (TAHS). The thus N-tagged enantiomers of the derivatized amino acids were nicely separated within 20min using the cinchona alkaloid-based zwittterionic ion-exchange type enantioselective column, Chiralpak ZWIX(+). The selected reaction monitoring was applied for detecting the target d-amino acids in biological matrices. By using the present chiral LC-MS/MS method, the three d-amino acids and their l-forms could be simultaneously determined in the range of 0.1-500nmol/mL. Finally, the technique was successfully applied to rat plasma and tissue samples.

  7. A Method for Simultaneous Determination of 25-Hydroxyvitamin D3 and Its 3-Sulfate in Newborn Plasma by LC/ESI-MS/MS after Derivatization with a Proton-Affinitive Cookson-Type Reagent

    PubMed Central

    Higashi, Tatsuya; Yokota, Mai; Goto, Ayaka; Komatsu, Kenji; Sugiura, Takahiro; Ogawa, Shoujiro; Satoh, Mamoru; Nomura, Fumio

    2016-01-01

    A method for the simultaneous determination of 25-hydroxyvitamin D3 [25(OH)D3] and its 3-sulfate [25(OH)D3S] in newborn plasma, which is expected to be helpful in the assessment of the vitamin D status, using stable isotope-dilution liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) has been developed and validated. The plasma was pretreated based on the deproteinization and solid-phase extraction, then subjected to derivatization with 4-(4-dimethylaminophenyl)-1,2,4-triazoline-3,5-dione (DAPTAD). The derivatization enabled the accurate quantification of 25(OH)D3 without interference from 3-epi-25(OH)D3 and also facilitated the simultaneous determination of the two metabolites by LC/positive ESI-MS/MS. Quantification was based on the selected reaction monitoring with the characteristic fragmentation of the DAPTAD-derivatives during MS/MS. This method was reproducible (intra- and inter-assay relative standard deviations of 7.8% or lower for both metabolites) and accurate (analytical recovery, 95.4–105.6%). The limits of quantification were 1.0 ng/mL and 2.5 ng/mL for 25(OH)D3 and 25(OH)D3S, respectively, when using a 20-μL sample. The developed method was applied to the simultaneous determination of plasma 25(OH)D3 and 25(OH)D3S in newborns; it was recognized that the plasma concentration of 25(OH)D3S is significantly higher than that of 25(OH)D3, and preterm newborns have lower plasma 25(OH)D3S concentrations than full-term newborns. PMID:27656337

  8. Simultaneous determination of norethindrone and ethinyl estradiol in human plasma by high performance liquid chromatography with tandem mass spectrometry--experiences on developing a highly selective method using derivatization reagent for enhancing sensitivity.

    PubMed

    Li, Wenkui; Li, Ying-He; Li, Austin C; Zhou, Shaolian; Naidong, Weng

    2005-10-25

    In the present work, for the first time, a liquid chromatographic method with tandem mass spectrometric detection (LC-MS/MS) for the simultaneous analysis of norethindrone, and ethinyl estradiol, was developed and validated over the concentration range of 50-10000pg/ml and 2.5-500pg/ml, respectively, using 0.5 ml of plasma sample. Norethindrone, ethinyl estradiol, and their internal standards norethindrone-(13)C2, and ethinyl estradiol-d4, were extracted from human plasma matrix with n-butyl chloride. After evaporation of the organic solvent, the extract was derivatized with dansyl chloride and the mixture was injected onto the LC-MS/MS system. The gradient chromatographic elution was achieved on a Genesis RP-18 (50 mm x 4.6 mm, 3 microm) column with mobile phase consisted of acetonitrile, water and formic acid. The flow rate was 1.0 ml/min and the total run time was 5.0 min. Important parameters such as sensitivity, linearity, matrix effect, reproducibility, stability, carry-over and recovery were investigated during the validation. The inter-day precision and accuracy of the quality control samples at low, medium and high concentration levels were <6.8% relative standard deviation (RSD) and 4.4% relative error (RE) for norethindrone, and 4.2% RSD and 5.9% RE for ethinyl estradiol, respectively. Chromatographic conditions were optimized to separate analytes of interest from the potential interference peaks, arising from the derivatization. This method could be used for pharmacokinetic and drug-drug interaction studies in human subjects.

  9. [Development of novel fluorescence-derivatization-HPLC methods enabling highly sensitive and selective analysis of biological compounds].

    PubMed

    Todoroki, Kenichiro

    2011-01-01

    Fluorescence-derivatization-HPLC methods are powerful tools for performing the analysis of bioactive compounds with high sensitivity and selectivity. In this paper, the author reviews the development of the following four types of novel fluorescence-derivatization-HPLC analytical systems: (1) simultaneous HPLC analysis of melatonin and its related compounds through post-column electrochemical demethylation and fluorescence derivatization, (2) HPLC analysis of 5-hydroxyindoles based on fluorescence derivatization by online pre-column photocatalytic oxidation with benzylamine, (3) reagent peak-free HPLC analysis for aliphatic amines and amino acids using F-trap pyrene as a fluorous tag-bound fluorescence derivatization reagent, and (4) reagent peak-free HPLC analysis for carboxylic acids using a fluorous scavenging-derivatization method. The authors have also successfully applied these systems to biological and pharmaceutical analyses.

  10. Determination of plasma total homocysteine and cysteine using HPLC with fluorescence detection and an ammonium 7-fluoro-2, 1, 3-benzoxadiazole-4-sulphonate (SBD-F) derivatization protocol optimized for antioxidant concentration, derivatization reagent concentration, temperature and matrix pH.

    PubMed

    Daskalakis, I; Lucock, M D; Anderson, A; Wild, J; Schorah, C J; Levene, M I

    1996-01-01

    A sensitive HPLC-fluorescence method for determining total endogenous plasma homocysteine (Hcy), cysteine (Cys) and cysteinylglycine (Cys-Gly) following derivatization with ammonium 7-fluoro 2,1,3-benzoxadiazole-4-sulphonate (SBD-F) is described. Quantitation utilizes an internal standard, 2-mercaptoethylamine. The derivatization procedure has been optimized for concentration of SBD-F, reducing agent (tributylphosphine) and temperature. Findings indicate that values for plasma determinations vary according to the nature of the matrix in which calibration standards are made up. If quantitation is based on a peak height ratio, then standards should be made up in either pH 7.4 phosphate buffered saline or plasma taking into account the endogenous thiol concentration. These findings are based on calibration data, and 30 plasma samples quantified using thiol standards made up in plasma, pH 7.4 and pH 9.5 buffers. By defining how this matrix/pH effect influences thiol quantitation, it should be possible to make a more meaningful comparison of Hcy measurements between laboratories. The chromatographic separation was investigated at several mobile-phase pH values with the following conditions ascertained to be optimal: a mobile phase consisting of 5% (v/v) acetonitrile in 0.1 M KH2PO4, pH 2.15 was run at a flow rate of 0.5 mL/min. It was used in conjunction with a Supelco LC-18 base deactivated analytical column (150 x 4.6 cm i.d. 3 microM bonded silica). The internal standard and thiols were measured by fluorescence detection at 385 nm excitation and 515 nm emmission. Plasma levels are easily measured in a 100 microL volume. Storage for 2 months at -20 degrees C resulted in no deterioration of thiols. Furthermore, no difference in thiol levels was observed between bloods collected in lithium heparin and EDTA. Collected blood should, however, be separated as soon as possible to avoid red cell metabolism of Hcy which was observed in a case of hyperhomocysteinemia. Once

  11. Development of a pair of differential H/D isotope-coded derivatization reagents d(0)/d(3)-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine and its application for determination of aldehydes in selected aquatic products by liquid chromatography-tandem mass spectrometry.

    PubMed

    Sun, Zhiwei; Wang, Xiaoxiang; Cai, Yiping; Fu, Junqing; You, Jinmao

    2014-03-01

    A new pair of derivatization reagents, d0-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d0-MPIA) and d3-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d3-MPIA) have been designed and synthesized. It was successfully used to label aliphatic aldehydes and the aldehyde derivatives were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The new isotope-coded reagents could easily label aldehydes under acidic conditions in the presence of NaCNBH3. The target derivatives exhibited intense [M+H](+) and regular product ions with electrospray ionization source in positive mode. The d0/d3-MPIA-aldehydes were monitored by the transitions of [M+H](+)→m/z 322 and [M+H](+)→m/z 165, and the obtained detection limits were in the range of 0.18-15.9 pg/mL at signal to noise ratio of 3. The global isotope internal standard technology was employed for quantification analysis with d3-MPIA-aldehyde as internal standard for corresponding d0-MPIA-aldehyde. Excellent linear responses for relative quantification were observed in the range of 1/10-10/1 with coefficients >0.998. The developed method has been applied to the quantification of aliphatic aldehydes in selected aquatic products with RSD<3.6% and recoveries >85.2%. © 2013 Elsevier B.V. All rights reserved.

  12. Enantiomeric separation of D,L-tryptophan and D,L-kynurenine by HPLC using pre-column fluorescence derivatization with R(-)-DBD-PyNCS.

    PubMed

    Iizuka, Hideaki; Hirasa, Yasushi; Kubo, Kazumi; Ishii, Kana; Toyo'oka, Toshimasa; Fukushima, Takeshi

    2011-07-01

    The enantiomeric separation of D,L-tryptophan (Trp) and D,L-kynurenine (KYN) was investigated by high-performance liquid chromatography using pre-column fluorescence derivatization with a chiral fluorescent labeling reagent, R(-)-4-(3-isothiocyanatopyrrolidin-1-yl)-7- (N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole [R(-)-DBD-PyNCS]. Using an octadecylsilica column, namely, an Inertsil ODS-3 column (250 x 2.0 mm; i.d., 3 μm), four fluorescence peaks of D- and L-Trp as well as D- and L-KYN derivatized with R(-)-DBD-PyNCS were clearly observed, and their chemical structures were confirmed by HPLC-time-of-flight-mass spectrometry. Simultaneous separation was achieved under the mobile phase condition of 1.5% acetic acid in H₂O-CH₃CN (60:40), and the separation factors of D,L-Trp and D,L-KYN derivatized with R(-)-DBD-PyNCS were 1.22 and 1.19, respectively. Fluorescence detection was carried out by setting the emission wavelength at 565 nm, and the excitation wavelength at 440 nm, and the detection limits were approximately 0.3-0.5 pmol (signal-to-noise ratio of 3).

  13. Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling

    DOE PAGES

    O'Maille, Grace; Go, Eden P.; Hoang, Linh; ...

    2008-01-01

    Comprehensive detection and quantitation of metabolites from a biological source constitute the major challenges of current metabolomics research. Two chemical derivatization methodologies, butylation and amination, were applied to human serum for ionization enhancement of a broad spectrum of metabolite classes, including steroids and amino acids. LC-ESI-MS analysis of the derivatized serum samples provided a significant signal elevation across the total ion chromatogram to over a 100-fold increase in ionization efficiency. It was also demonstrated that derivatization combined with isotopically labeled reagents facilitated the relative quantitation of derivatized metabolites from individual as well as pooled samples.

  14. Enhanced analysis of steroids by gas chromatography/mass spectrometry using microwave-accelerated derivatization.

    PubMed

    Bowden, John A; Colosi, Dominic M; Stutts, Whitney L; Mora-Montero, Diana C; Garrett, Timothy J; Yost, Richard A

    2009-08-15

    Derivatization of steroids is typically required before analysis by gas chromatography/mass spectrometry (GC/MS); nevertheless, the derivatization process can often be time-consuming and irreproducible. Although several strategies have been employed to enhance this process, few have the potential of microwave-accelerated derivatization (MAD) to be more efficient than traditional thermal derivatization methods. MAD using a synthesis microwave system was evaluated and compared to traditional thermal derivatization methods in terms of yield, reproducibility, and overall analysis time. Parameters affecting MAD, including reaction temperature, time, and power, were systematically optimized for several silyl reagents (BSTFA with TMCS, MSTFA, and BSA) and other derivatization procedures (MOX reagent and MTBSTFA). MSTFA was found to derivatize best with the microwave, as demonstrated by the enhanced relative response factors (RRFs). BSTFA with TMCS, on the other hand, did not couple as well, but RRF values improved significantly upon addition of polar solvents. The rapid (1 min) derivatization reactions associated with MAD had comparable RRFs for all reagents with those obtained with thermal heating (>30 min). This study highlights the best methods for analyzing a comprehensive variety of steroids and also provides ideal strategies for MAD of steroids on an individual or class level.

  15. New osmium-based reagent for the dihydroxylation of alkenes.

    PubMed

    Donohoe, Timothy J; Harris, Robert M; Butterworth, Sam; Burrows, Jeremy N; Cowley, Andrew; Parker, Jeremy S

    2006-06-09

    The cis dihydroxylation of alkenes is most efficiently accomplished by reaction with osmium tetroxide. Recently, the expense and toxicity of osmium tetroxide have led to a number of attempts to harness alternative osmium-based reagents, including microencapsulation and solid support techniques. We describe here the development of a new nonvolatile, stable, and recoverable osmium-based reagent devised for the stoichiometric cis dihydroxylation of alkenes. Although attempts to make this new dihydroxylation work with catalytic amounts of this reagent were unsuccessful, we did develop a sensitive test for free osmium tetroxide leached from the reagent in situ: this test may well have uses in probing future applications of derivatized osmium reagents.

  16. Chiral separation and quantification of R/S-amphetamine, R/S-methamphetamine, R/S-MDA, R/S-MDMA, and R/S-MDEA in whole blood by GC-EI-MS.

    PubMed

    Rasmussen, Louise Bang; Olsen, Kristine Høje; Johansen, Sys Stybe

    2006-10-02

    The enantioselective composition of the amphetamines is of interest, as the enantiomers show differences in their pharmacological effects and several methods for chiral separation of amphetamines have been described. Only a few methods have used whole blood as matrix and none of these separates both classic amphetamines (amphetamine and methamphetamine) and designer amphetamines (MDA, MDMA and MDEA). The aim of this study was, therefore, to develop a method for enantioselective analysis of AM, MA, MDA, MDMA, and MDEA in whole blood. The amphetamines were extracted from 0.5 g of whole blood by liquid-liquid extraction. After derivatization with R-MTPCl, the resulting diastereomers were separated by GC on a HP-5MS column and detected by SIM-MS. R-MTPCl was used as derivatization reagent because of the stability of this reagent and good separation of these analytes. Through the method, development time and temperature of the derivatization were optimized, and by admixture of 0.02% triethylamine it became possible to detect the amphetamines in adequately low concentrations as more analytes were derivatized. The method was validated and it was linear from 0.004 to 3 microg/g per enantiomer. The accuracy was within 91-115%, while the repeatability and reproducibility were < or =15% R.S.D. A method suitable for enantioselective separation and analysis of the amphetamines has been achieved, and the method was applied to analysis of whole blood samples originating from traffic and criminal cases and post mortem cases.

  17. (2-Naphthoxy)acetyl chloride, a simple fluorescent reagent.

    PubMed

    Duh, Tsai-Hui; Wu, Hsin-Lung; Kou, Hwang-Shang; Lu, Chi-Yu

    2003-02-14

    In continuing the search for fluorescent reagents for analytical derivatization in chromatography, we found a simple chemical, (2-naphthoxy)acetyl chloride, with potential fluorophore/chromophore characteristics for the highly sensitive detection of analytes with an amino function. The reagent has an auxochrome (a substituted alkoxy moiety) attached to the fluorophoric/chromophoric naphthalene system, resulting in favorable spectrophotometric properties. The reagent can be easily prepared from (2-naphthoxy)acetic acid and has been used in organic synthesis; it is initially introduced as a fluorescent reagent to derivatise amantadine and memantine (amino pharmaceuticals) as model analytes. The resulting naphthoxy derivatives of the drugs can be analyzed at sub-microM levels by HPLC with fluorimetric detection (excitation wavelength 227 nm, emission wavelength 348 nm). Application of the reagent to the fluorimetric derivatization of important biological amines for sensitive detection can be expected.

  18. Asymmetric catalysis with chiral ferrocene ligands.

    PubMed

    Dai, Li-Xin; Tu, Tao; You, Shu-Li; Deng, Wei-Ping; Hou, Xue-Long

    2003-09-01

    Chiral ferrocene ligands have been widely used in asymmetric catalysis. The advantages of using ferrocene as a scaffold for chiral ligands are described, particularly those regarding planar chirality, rigid bulkiness, and ease of derivatization. The role of planar chirality in 1,2- and 1,1'-disubstituted ferrocene systems is discussed. By using a bulky ferrocene fragment, novel ferrocene ligands were designed, and high enantioselectivity and regioselectivity were achieved in the allylic substitution reaction of monosubstituted allyl substrates. Using the tunable electronic properties of a diphosphine-oxazoline ferrocenyl ligand, the regioselectivity of the intermolecular asymmetric Heck reaction was also examined.

  19. Catalytically-Promoted Analyte Derivatization Inside a Gas Chromatographic Inlet

    PubMed Central

    Fowler, William K.; Gamble, Kelly J.; Wright, Amber R.

    2010-01-01

    Reported here is a preliminary assessment of the feasibility of catalyzing on-line derivatization reactions inside the inlet (i.e., the injection port) of a gas chromatograph (GC) with solid heterogeneous catalysts. The experiments described here entail the installation of candidate catalysts inside the GC inlet liner and the subsequent injection of analyte/reagent mixtures onto the catalyst beds. Two catalysts are identified, each of which clearly catalyzes one of the chosen model derivatization reactions in the inlet of a GC. This result supports our hypothesis that on-line derivatizations can, in principle, be reproducibly catalyzed inside the GC inlet by solid heterogeneous catalysts and that the presence of such catalysts in the inlet do not necessarily cause a serious loss of instrument performance or chromatographic efficiency. PMID:20822662

  20. In situ search for organics by gas chromatography analysis: new derivatization / thermochemolysis approach

    NASA Astrophysics Data System (ADS)

    Geffroy, Claude; Buch, Arnaud; David, Marc; Aissat, Lyes; El Mufleh, Amel; Papot, S.; Sternberg, Robert

    Many organic molecules are present in interstellar clouds and might be carried to the early Earth by comets and meteorites during the heavy bombardment phase in the first few hundred million years of the solar system. It has been suggested that extraterrestrial organic material may well represent an important part of the organic material available for the origin of life. Until samples, brought by future space missions, are available on Earth, in situ measurements are one of the way to get unaltered and non-contaminated samples for analysis. The analytical technique has to be robust, sensitive and non-specific due to the large scope of targets molecules. The only currently flight qualified technique of analysis of organic molecules in space is gas chromatography (Viking, Cassini-Huygens, SAM-MSL, COSAC-Rosetta). The main objective of this work is to present a new approach with multi step analysis using derivatisation and thermochemolysis reagents for a one pot in situ analysis of volatile and refractory organics in surface or sub-surface samples (Mars, comets).Indeed, no single technology enables to identify all organic compounds because naturally occurring molecules have different polarities, molecular weights, being extractible or recalcitrant, bonded trapped or adsorbed on minerals. Thus, we propose to wider the scope of chemical reagent already validated for in situ wet chemistry such as MTBSTFA (Rodier et al. 2001, 2002), DMF-DMA (Rodier et al. 2002), or TMAH (Rodier et al, 2005, Geffroy-Rodier et al; 2009) to analyze enantiomers of amino acids, carbohydrates and lipids in a one pot several steps sub system using a multi reagent and multi step approach. Thus using a new derivatizing agent, we successfully identified twenty one amino acids including twelve of the twenty proteinic amino acids without inhibiting following multi step thermochemolysis. *Geffroy-Rodier C, Grasset L, Sternberg R. Buch A. Amblès A. (2009) Thermochemolysis in search for organics in

  1. Determination of methamphetamine enantiomer composition in human hair by non-chiral liquid chromatography-tandem mass spectrometry method.

    PubMed

    Shu, Irene; Alexander, Amy; Jones, Mary; Jones, Joseph; Negrusz, Adam

    2016-08-15

    Chiral separation is crucial for investigating methamphetamine positive cases. While (S)-(+)-enantiomer of methamphetamine (S-MAMP) is a schedule II controlled substance, (R)-(-)-enantiomer (R-MAMP) is an active ingredient of a few over-the-counter drugs in the United States. Among biological specimen types, hair provides greater detection window than blood, urine or oral fluid, and are therefore regarded with particular interest. Herein we describe a novel non-chiral liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to directly determine methamphetamine enantiomeric composition (percentage) in hair specimens. Hair samples were washed once with acetone, powdered, incubated overnight at 53°C in 0.1M hydrochloric acid (HCl), and subjected to a solid phase extraction (SPE). The extracts were derivatized using Marfey's reagent at 53°C for 60min. The final mixture was analyzed by LC-MS/MS. Chromatographic separation was achieved using a C18 Kinetex analytical column and 60% (v/v) aqueous methanol as mobile phase (isocratic). Triple quadrupole mass spectrometer was equipped with an electro-spray ionization (ESI) source operating in negative mode and the chromatograms were acquired using a multiple-reaction monitoring (MRM) approach. The results were expressed as ratio of R- to S-MAMP and then derived to composition percentages without requiring quantitating each enantiomer. The method was precise and accurate across 0-100% S-composition at a range of 80-18,000pg/mg. The performance of the new method was compared with an (S)-(-)-N-trifluoroacetylprolyl chloride (S-TPC) derivatization and gas chromatography-mass spectrometry (GC-MS) method on authentic methamphetamine-positive hair samples. Not only the new Marfey's reagent approach presented satisfactory correlation with the S-TPC approach, but it also exhibited significantly improved quality (e.g., S/N) of the chromatograms. In summary, our protocol employs cost effective and minimally hazardous Marfey

  2. Tandem MS Analysis of Selenamide-Derivatized Peptide Ions

    PubMed Central

    Zhang, Yun; Zhang, Hao; Cui, Weidong; Chen, Hao

    2013-01-01

    Our previous study showed that selenamide reagents such as ebselen and N-(phenylseleno) phthalimide (NPSP) can be used for selective and rapid derivatization of protein/peptide thiols in high conversion yield. This paper reports the systematic investigation of MS/MS dissociation behaviors of selenamide-derivatized peptide ions upon collision induced dissociation (CID) and electron transfer dissociation (ETD). In the positive ion mode, derivatized peptide ions exhibit tag-dependent CID dissociation pathways. For instance, ebselen-derivatized peptide ions preferentially undergo Se–S bond cleavage upon CID to produce a characteristic fragment ion, the protonated ebselen (m/z 276), which allows selective identification of thiol peptides from protein digest as well as selective detection of thiol proteins from protein mixture using precursor ion scan (PIS). In contrast, NPSP-derivatized peptide ions retain their phenylselenenyl tags during CID, which is useful in sequencing peptides and locating cysteine residues. In the negative ion CID mode, both types of tags are preferentially lost via the Se–S cleavage, analogous to the S–S bond cleavage during CID of disulfide-containing peptide anions. In consideration of the convenience in preparing selenamide-derivatized peptides and the similarity of Se–S of the tag to the S–S bond, we also examined ETD of the derivatized peptide ions to probe the mechanism for electron-based ion dissociation. Interestingly, facile cleavage of Se–S bond occurs to the peptide ions carrying either protons or alkali metal ions, while backbone cleavage to form c/z ions is severely inhibited. These results are in agreement with the Utah-Washington mechanism proposed for depicting electron-based ion dissociation processes. PMID:21953264

  3. Enantioselective Recognition for Many Different Kinds of Chiral Guests by One Chiral Receptor Based on Tetraphenylethylene Cyclohexylbisurea.

    PubMed

    Xiong, Jia-Bin; Xie, Wen-Zhao; Sun, Jian-Ping; Wang, Jin-Hua; Zhu, Zhi-Hua; Feng, Hai-Tao; Guo, Dong; Zhang, Hui; Zheng, Yan-Song

    2016-05-06

    A neutral chiral receptor based on TPE cyclohexylbisurea was synthesized and could discriminate the enantiomers of many different kinds of chiral reagents, including chiral acidic compounds, basic compounds, amino acids, and even neutral alcohols. The (1)H NMR spectra disclosed that the ability of chiral recognition could be ascribed to the multiple hydrogen bonds and CH-π interactions between the TPE urea receptor and the enantiomer of the chiral guest, which led to the selective aggregation of the receptor with one of the two enantiomers. This result exhibited a great potential in enantiomer discernment and high-throughput analysis of enantiomer composition of these chiral analytes by one chiral AIE molecule.

  4. Development and validation of an LC-MS/MS method after chiral derivatization for the simultaneous stereoselective determination of methylenedioxy-methamphetamine (MDMA) and its phase I and II metabolites in human blood plasma.

    PubMed

    Steuer, Andrea E; Schmidhauser, Corina; Liechti, Matthias E; Kraemer, Thomas

    2015-07-01

    3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is a racemic drug of abuse and its two enantiomers are known to differ in their dose-response curves. The S-enantiomer was shown to be eliminated at a higher rate than the R-enantiomer. The most likely explanation for this is a stereoselective metabolism also claimed in in vitro studies. Urinary excretion studies showed that the main metabolites in humans are 4-hydroxy 3-methoxymethamphetamine (HMMA) 4-sulfate, HMMA 4-glucuronide and 3,4-dihydroxymethamphetamine (DHMA) 3-sulfate. For stereoselective pharmacokinetic analysis of phase I and phase II metabolites in human blood plasma useful analytical methods are needed. Therefore the aim of the presented study was the development and validation of a stereoselective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous quantification of MDMA, 3,4-methylenedioxyamphetamine, DHMA, DHMA 3-sulfate, HMMA, HMMA 4-glucuronide, HMMA 4-sulfate, and 4-hydroxy 3-methoxyamphetamine in blood plasma for evaluation of the stereoselective pharmacokinetics in humans. Blood plasma samples were prepared by simple protein precipitation and afterwards all analytes were derivatized using N-(2,4-dinitro-5-fluorophenyl) L-valinamide resulting in the formation of diastereomers which were easily separable on standard reverse phase stationary phases. This simple and fast method was validated according to international guidelines including specificity, recovery, matrix effects, accuracy and precision, stabilities, and limits of quantification. The method proved to be selective, sensitive, accurate and precise for all tested analytes except for DHMA.

  5. Characterization of dicarboxylic naphthenic acid fraction compounds utilizing amide derivatization: proof of concept.

    PubMed

    Kovalchik, Kevin A; MacLennan, Matthew S; Peru, Kerry M; Ajaero, Chukwuemeka; McMartin, Dena W; Headley, John V; Chen, David D Y

    2017-09-25

    The characterization of naphthenic acid fraction compounds (NAFCs) in oil sands process affected water (OSPW) is of interest for both toxicology studies and regulatory reasons. Previous studies utilizing authentic standards have identified dicarboxylic naphthenic acids using two-dimensional gas chromatography hyphenated to time-of-flight mass spectrometry (GCxGC/TOFMS). The selective derivatization of hydroxyl groups has also recently aided in the characterization of oxy-NAFCs, and indirectly the characterization of dicarboxylic NAFCs. However, there has been no previous report of derivatization being used to directly aid in the standard-free characterization of NAFCs with multiple carboxylic acid functional groups. Herein we present proof-of-concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization. Carboxylic acid groups in OSPW extract and in a dicarboxylic acid standard were derivatized to amides using a previously described method. The derivatized extract and derivatized standard were analyzed by direct-injection positive-mode electrospray ionization ((+)ESI) high resolution mass spectrometry (MS), and the underivatized extract was analyzed by (-)ESI MS. Tandem-MS was carried out on selected ions of the derivatized standard and derivatized OSPW. Data analysis was carried out using the Python programming language. The distribution of monocarboxylic NAFCs observed in the amide-derivatized OSPW sample by (+)ESI-MS was generally similar to that seen in underivatized OSPW by (-)ESI-MS. The dicarboxylic acid standard shows evidence of being doubly-derivatized, although the second derivatization appears to be inefficient. Furthermore, a spectrum of potential diacid NAFCs is presented, identified by both charge state and derivatization mass. Interference due to the presence of multiple derivatization products is noted, but can be eliminated using on-line separation or an isotopically labelled derivatization reagent. Proof of concept for the

  6. Heavy-atom derivatization.

    PubMed

    Garman, Elspeth; Murray, James W

    2003-11-01

    Most of the standard methods of solving macromolecular structures involve producing a protein crystal that is derivatized by an anomalous scatterer or heavy atom (MIR, SIRAS, MAD, SAD etc.). The theoretical methodology which underpins the extraction of phase information from such derivatives is widely available in the literature. In addition, there are comprehensive sources of information on the chemistry of heavy-atom compounds and the ligands with which they are known to interact, as well as the Heavy Atom Databank accessible on the World Wide Web. This contribution therefore aims to provide some information on the less well documented practical problems of firstly deciding on an overall strategy for derivatization and secondly performing the physical manipulations involved in producing heavy-atom derivatives from native protein crystals and then cryocooling them. Ways to optimize the chances of isomorphous unit cells are suggested. Methods of determining whether or not the heavy atom is bound are outlined, including the powerful technique of PIXE (particle-induced X-ray emission).

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

    PubMed

    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.

  8. Ultraviolet derivatization of low-molecular-mass thiols for high performance liquid chromatography and capillary electrophoresis analysis.

    PubMed

    Kuśmierek, K; Chwatko, G; Głowacki, R; Kubalczyk, P; Bald, E

    2011-05-15

    Thiols play an important role in metabolic processes of all living creatures and their analytical control is very important in order to understand their physiological and pathological function. Among a variety of methods available to measure thiol concentrations, chemical derivatization utilizing a suitable labeling reagent followed by liquid chromatographic or electrophoretic separation is the most reliable means for sensitive and specific determination of thiol compounds in real world samples. Ultraviolet detection is, for its simplicity, commonly used technique in liquid chromatography and capillary electrophoresis, and consequently many ultraviolet derivatization reagents are in used. This review summarizes HPLC and CE ultraviolet derivatization based methods, including pre-analytical considerations, procedures for sample reduction, derivatization, and separation of the primary biological aminothiols--cysteine, homocysteine, cysteinylglycine and glutathione, and most important thiol-drugs in pharmaceutical formulations and biological samples. Cognizance of the biochemistry involved in the formation of the analytes is taken.

  9. Chiral separation of pharmaceuticals possessing a carboxy moiety.

    PubMed

    Arai, T

    1998-10-09

    The separation of carboxylic enantiomers in the pharmaceutical field using high-performance liquid chromatographic and capillary electrophoretic techniques is reviewed. The techniques used for chiral separation include diastereomer derivatization, a chiral mobile phase, a chiral stationary phase (high-performance liquid chromatography) and chiral additives (capillary electrophoresis). Practical and conventional separation systems for pharmaceutical applications, such as pharmacokinetics, optical purity testing and stability studies, are described. A comprehensive collection of applications to carboxylic drugs and other carboxylic compounds of pharmaceutical interest is listed in the tables. The characteristics of each enantioseparation method are also discussed briefly.

  10. Determination of amphetamines in hair by integrating sample disruption, clean-up and solid phase derivatization.

    PubMed

    Argente-García, A; Moliner-Martínez, Y; Campíns-Falcó, P; Verdú-Andrés, J; Herráez-Hernández, R

    2016-05-20

    The utility of matrix solid phase dispersion (MSPD) for the direct analysis of amphetamines in hair samples has been evaluated, using liquid chromatography (LC) with fluorescence detection and precolumn derivatization. The proposed approach is based on the employment of MSPD for matrix disruption and clean-up, followed by the derivatization of the analytes onto the dispersant-sample blend. The fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) has been used for derivatization. Different conditions for MSPD, analyte purification and solid phase derivatization have been tested, using amphetamine (AMP), methamphetamine (MET), ephedrine (EPE) and 3,4-methylenedioxymethamphetamine (MDMA) as model compounds. The results have been compared with those achieved by using ultrasound-assisted alkaline digestion and by MSPD combined with conventional solution derivatization. On the basis of the results obtained, a methodology is proposed for the analysis of amphetamines in hair which integrates sample disruption, clean-up and derivatization using a C18 phase. Improved sensitivity is achieved with respect to that obtained by the alkaline digestion or by the MSPD followed by solution derivatization methods. The method can be used for the quantification of the tested amphetamines within the 2.0-20.0ng/mg concentration interval, with limits of detection (LODs) of 0.25-0.75ng/mg. The methodology is very simple and rapid (the preparation of the sample takes less than 15min).

  11. Advances in high-throughput and high-efficiency chiral liquid chromatographic separations.

    PubMed

    Patel, Darshan C; Wahab, M Farooq; Armstrong, Daniel W; Breitbach, Zachary S

    2016-10-07

    The need for improved liquid chromatographic chiral separations has led to the advancement of chiral screening techniques as well as the development of new, high efficiency chiral separation methods and stationary phases. This review covers these advancements, which primarily occurred over the last 15 years. High throughput techniques include multi-column screening units, multiple injection sequences, and fast gradient SFC screening. New separation methods and column technologies that aim at high efficiency chiral separations include the use of achiral UHPLC (i.e. sub-2μm) columns for separating derivatized chiral analytes or using chiral additives in the run buffer, UHPLC chiral stationary phases, and superficially porous particle based chiral stationary phases. Finally, the enhancement of chiral separations through these new technologies requires that certain instrumental considerations be made. Future directions in continuing to improve chiral separations are also discussed.

  12. Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

    PubMed Central

    Rong, Jiawei; Collados, Juan F.; Ortiz, Pablo; Jumde, Ravindra P.; Otten, Edwin; Harutyunyan, Syuzanna R.

    2016-01-01

    α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure. PMID:28008909

  13. Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

    NASA Astrophysics Data System (ADS)

    Rong, Jiawei; Collados, Juan F.; Ortiz, Pablo; Jumde, Ravindra P.; Otten, Edwin; Harutyunyan, Syuzanna R.

    2016-12-01

    α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure.

  14. Chiral mixtures

    NASA Astrophysics Data System (ADS)

    Petitjean, Michel

    2002-08-01

    An index evaluating the amount of chirality of a mixture of colored random variables is defined. Properties are established. Extreme chiral mixtures are characterized and examples are given. Connections between chirality, Wasserstein distances, and least squares Procrustes methods are pointed out.

  15. Detecting refractory organic matter on Mars: how derivatization will help

    NASA Astrophysics Data System (ADS)

    Freissinet, C.; Kashyap, S.; Glavin, D. P.; Buch, A.; Brault, A.; Mahaffy, P. R.

    2012-12-01

    The search for organic molecules on Mars can provide important first clues of extinct or extant biota on the planet. Gas Chromatography Mass Spectrometry (GC-MS) is currently the most relevant space-compatible analytical tool for the detection of organics. Nevertheless, GC separation is intrinsically restricted to volatile molecules, and a lot of the molecules of exobiological interest are refractory or polar. To analyze these organics such as amino acids, nucleobases and carboxylic acids, an additional derivatization step is required to transform them into volatile derivatives that are amenable to GC analysis. As part of the Sample Analysis at Mars (SAM) experiment onboard Mars Science Laboratory (MSL) Curiosity rover which successfully landed on Mars on August 5, 2012, a single-step protocol of extraction and chemical derivatization with the silylating reagent N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide MTBSTFA has been developed to reach a wide range of astrobiology-relevant refractory organic molecules. Seven cups on SAM are devoted to MTBSTFA derivatization. However, this chemical reaction adds a protective silyl group in place of each labile hydrogen, which make the molecule non-identifiable in common mass spectra libraries. We thus created an extended library of mass spectra of derivatized compounds of interest, considering their potential occurrence in Mars soils. We then looked specifically at these compounds using the existing and the newly created library, in various Mars analog soils. To enable a more accurate interpretation of the in situ derivatization GC-MS results that will be obtained by SAM, the lab experiments are performed in the restrictive conditions of the SAM flight instrument. First experiments display promising results, the system permitting an extraction and detection of several proteinic amino and carboxylic acids from Martian representative matrices. Preliminary results show a lack of derivatized organic molecules in

  16. Indirect chiral separation of tryptophan enantiomers by high performance liquid chromatography with indirect chemiluminiscence detection.

    PubMed

    Zhou, Jie; Chen, Shanshan; Sun, Fang; Luo, Pei; Du, Qiuzheng; Zhao, Suzhen

    2015-12-01

    In recent years, the study of chiral compounds in vivo has received much attention. In this study, a novel method based on high performance liquid chromatography (HPLC) coupled with chemiluminescence (CL) detection was developed for the separation of tryptophan (Trp) enantiomers. o-Phthalaldehyde and N-acetyl-l-cysteine were used as chiral derivatization reagents for Trp before it can be detected by HPLC-CL method. The separation was carried out on an ODS column using a mobile phase composed of methanol-0.01mol/L phosphate buffer (40/60, v/v). Under the optimum conditions, satisfactory results were obtained, including complete separation, good relative standard deviations and low detection limits. The applicability of the proposed method has been validated by determining Trp in biological samples. Linear responses (r>0.9990) were observed over the range of 2.5×10(-7) to 1.2×10(-5)g/mL of Trp enantiomers, with quantitation limit of 2.5×10(-7)g/mL. The assay method shows good specificity to Trp enantiomers, and thus it will have great potential application in clinical diagnosis. The mean extraction efficiency of Trp enantiomers in mice plasma samples were 98.48% and 97.40%, respectively. The mean relative standard deviation (RSD) of Trp enantiomers were <3%.

  17. A simple protocol for NMR analysis of the enantiomeric purity of chiral hydroxylamines.

    PubMed

    Tickell, David A; Mahon, Mary F; Bull, Steven D; James, Tony D

    2013-02-15

    A practically simple three-component chiral derivatization protocol for determining the enantiopurity of chiral hydroxylamines by (1)H NMR spectroscopic analysis is described, involving their treatment with 2-formylphenylboronic acid and enantiopure BINOL to afford a mixture of diastereomeric nitrono-boronate esters whose ratio is an accurate reflection of the enantiopurity of the parent hydroxylamine.

  18. Simple and rapid determination of hydrogen peroxide using phosphine-based fluorescent reagents with sodium tungstate dihydrate.

    PubMed

    Onoda, Maki; Uchiyama, Takefumi; Mawatari, Ken-Ichi; Kaneko, Kiyoko; Nakagomi, Kazuya

    2006-06-01

    A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 microL sample solution. This method is accurate and has potential for on-line applications.

  19. Handling Pyrophoric Reagents

    SciTech Connect

    Alnajjar, Mikhail S.; Haynie, Todd O.

    2009-08-14

    Pyrophoric reagents are extremely hazardous. Special handling techniques are required to prevent contact with air and the resulting fire. This document provides several methods for working with pyrophoric reagents outside of an inert atmosphere.

  20. Organozinc reagents in DMSO solvent: remarkable promotion of SN2' reaction for allene synthesis.

    PubMed

    Kobayashi, Koji; Naka, Hiroshi; Wheatley, Andrew E H; Kondo, Yoshinori

    2008-08-07

    The S N2' reaction of propragyl mesylates with organozinc reagents was dramatically improved in DMSO solvent, and the stereoselective conversion of chiral substrates was successfully achieved using LiCl-free diorganozinc without the loss of optical purity.

  1. Analysis of flurbiprofen, ketoprofen and etodolac enantiomers by pre-column derivatization RP-HPLC and application to drug-protein binding in human plasma.

    PubMed

    Jin, Yin-Xiu; Tang, Yi-Hong; Zeng, Su

    2008-04-14

    A stereoselective reversed-phase high-performance liquid chromatography (HPLC) assay to determine the enantiomers of flurbiprofen, ketoprofen and etodolac in human plasma was developed. Chiral drug enantiomers were extracted from human plasma with liquid-liquid extraction. Then flurbiprofen and ketoprofen enantiomers reacted with the acylation reagent thionyl chloride and pre-column chiral derivatization reagent (S)-(-)-alpha-(1-naphthyl)ethylamine (S-NEA), and etodolac enantiomers reacted with S-NEA using 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide (EDC) and 1-hydroxybenzotriazole (HOBT) as coupling agents. The derivatized products were separated on an Agilent Zorbax C18 (4.6 mm x 250 mm, 5 microm) column with a mixture of acetonitrile-0.01 mol.L(-1) phosphate buffer (pH 4.5) (70:30, v/v) for flurbiprofen enantiomers, acetonitrile-0.01 mol.L(-1) phosphate buffer (pH 4.5) (60:40, v/v) for ketoprofen enantiomers and methonal-0.01 mol.L(-1) potassium dihydrogen phosphate buffer (pH 4.5) (88:12, v/v) for etodolac enantiomers as mobile phase. The flow of mobile phase was set at 0.8 mL.min(-1) and the detection wavelength of UV detector was set at 250 nm for flurbiprofen and ketoprofen enantiomers and 278 nm for etodolac enantiomers. The assay was linear from 0.5 to 50 microg.mL(-1) for each enantiomer. The inter- and intra-day precision (R.S.D.) was less than 10% and the average extraction recovery was more than 87% for each enantiomer. The limit of quantification for the method was 0.5 microg.mL(-1) (R.S.D.<10%, n=5). The method developed was used to study the drug-protein binding of flurbiprofen, ketoprofen and etodolac enantiomers in human plasma. The results showed that the stereoselective binding of etodolac enantiomer was observed and flurbiprofen and ketoprofen enantiomers were not.

  2. Separation and determination of B vitamins and essential amino acids in health drinks by CE-LIF with simultaneous derivatization.

    PubMed

    Zhao, Danyue; Lu, Minghua; Cai, Zongwei

    2012-08-01

    An efficient and sensitive method for the separation and determination of three essential amino acids and three B vitamins by CE-LIF with a simultaneous derivatization procedure was developed. The conditions for derivatization and separation of these micronutrients were investigated. FITC was used as the reagent for fluorescence tagging of arginine (Arg), valine (Val), tryptophan (Trp), folic acid (FA), and niacinamide (NA). Riboflavin (RF) was detected without derivatization. Derivatization of analytes dissolved in borate solution was performed by successive introduction of fluorescence reagent and analytes followed by water bathing at 43°C. The molar ratio of sample/reagent (S/R), derivatization temperature, and incubation time significantly influenced the efficiency of derivatization. To maximize the fluorescence yield, a high S/R (≥20) was required. The nonderivatized RF and five derivatized analytes were separated in the optimized CE-LIF system with the application of 22 kV voltage and 25 mM borate buffer at pH 9.85. Validation of the method showed good linearity for the corrected peak areas versus standard concentrations for the six analytes. The RSDs (n = 3) of the migration time and the peak area obtained for the analytes ranged from 0.4 to 1.1% and from 1.9 to 4.4%, respectively. The developed method, with the lowest LOD of 0.5 nM, was successfully applied for the efficient derivatization and determination of B vitamins in four health drink samples. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Matrix influence on derivatization and ionization processes during selenoamino acid liquid chromatography electrospray ionization mass spectrometric analysis.

    PubMed

    Rebane, Riin; Oldekop, Maarja-Liisa; Herodes, Koit

    2014-04-01

    Considering the importance of derivatization in LC/ESI/MS analysis, the objective of this work was to develop a method for evaluation of matrix effect that would discriminate between matrix effect due to the derivatization reaction yield and from the ESI. Four derivatization reagents (TAHS, DEEMM, DNS, FMOC-Cl) were studied with respect to matrix effects using two selenoamino acids and onion matrix as model system. A novel method for assessing matrix effects of LC/ESI/MS analyses involving derivatization is proposed, named herein post-derivatization spiking, that allows evaluating effect of matrix on ESI ionization without derivatization reaction yield contribution. The proposed post-derivatization spiking method allowed to demonstrate that the reason of reduced analytical signal can be signal suppression in ESI (as in case of DNS derivatives with matrix effects 38-99%), alteration of derivatization reaction yield (TAHS, matrix effects 92-113%, but reaction yields 20-50%) or both (FMOC-Cl, matrix effects 28-88% and reaction yields 50-70%). In case of DEEMM derivatives, matrix reduces reaction yield but enhances ESI/MS signal. A method for matrix effect evaluation was developed. It was also confirmed that matrix effects can be reduced by dilution.

  4. Application of the Novel 5-chloro-2,2,3,3,4,4,5,5-octafluoro-1-pentyl Chloroformate Derivatizing Agent for the Direct Determination of Highly Polar Water Disinfection Byproducts

    EPA Science Inventory

    A novel derivatizing agent, 5-chloro-2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (ClOFPCF), was synthesized and tested as a reagent for direct water derivatization of highly polar and hydrophilic analytes. Its analytical performance satisfactorily compared to a perfluorinated ...

  5. Application of the Novel 5-chloro-2,2,3,3,4,4,5,5-octafluoro-1-pentyl Chloroformate Derivatizing Agent for the Direct Determination of Highly Polar Water Disinfection Byproducts

    EPA Science Inventory

    A novel derivatizing agent, 5-chloro-2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (ClOFPCF), was synthesized and tested as a reagent for direct water derivatization of highly polar and hydrophilic analytes. Its analytical performance satisfactorily compared to a perfluorinated ...

  6. Microwave-accelerated derivatization prior to GC-MS determination of sex hormones.

    PubMed

    Xu, Xu; Zhao, Xin; Zhang, Yupu; Li, Dan; Su, Rui; Yang, Qiuling; Li, Xueyuan; Zhang, Huihui; Zhang, Hanqi; Wang, Ziming

    2011-06-01

    A new microwave-accelerated derivatization method was developed for rapid determination of 13 natural sex hormones in feeds. Sex hormones were isolated from the sample matrix by ultrasonic extraction, followed by solid-phase extraction, derivatized under microwave irradiation, and then analyzed directly by gas chromatography-mass spectrometry (GC-MS) in selective ion monitoring (SIM) mode. The key parameters affecting derivatization efficiency, including microwave irradiation time, microwave power, and reaction solvent were studied. Under microwave power of 360 W and microwave irradiation for 3 min, 13 natural sex hormones were simultaneously derivatized using heptafluorobutyric acid anhydride (HFBA) as derivatization reagent. This method was applied to the determination of 13 natural sex hormones in different feed samples, and the obtained results were compared with those obtained by the traditional thermal derivatization. The recoveries from 58.1 to 111% were obtained at sex hormone concentrations of 10-300 μg/kg with RSDs ≤12.0%. The results showed that the proposed method was fast, simple, efficient and can be applied to the determination of 13 natural sex hormones in different feed samples.

  7. In-capillary derivatization and laser-induced fluorescence detection for the analysis of organophosphorus pesticides by micellar electrokinetic chromatography.

    PubMed

    Zhou, Lei; Luo, Zhi; Wang, Shumin; Hui, Yang; Hu, Zhide; Chen, Xingguo

    2007-05-18

    We developed a rapid and sensitive method using in-capillary derivatization and laser-induced fluorescence (LIF) detection for the fully automated analysis of organophosphorus pesticides (OPPs), including glufosinate, aminomethylphosphonic acid (AMPA) and glyphosate by micellar electrokinetic chromatography (MEKC). The potential of 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) as in-capillary derivatization reagent is described for the first time. The unique feature of this MEKC method is the capillary being used as a small reaction chamber. In in-capillary derivatization, the sample and reagent solutions were injected directly into the capillary by tandem mode, followed by an electrokinetic step to enhance the mixing efficiency of analytes and reagent plugs in accordance with their different electrophoretic mobilities. Standing a specified time for reaction, the derivatives were then immediately separated and determined. Careful optimization of the derivatization and separation conditions allowed the determination of glufosinate, AMPA and glyphosate with detection limits of 2.8, 3.6 and 32.2 ng/mL, respectively. These detection limits were comparable to those of 1.4, 1.9 and 23.8 ng/mL obtained from conventional pre-capillary derivatization. Furthermore, repeatability better than 0.40% for migration time and 3.4% for peak area, as well as shorter migration time, was obtained. The method was successfully applied to the analysis of spiked river water sample with satisfactory results.

  8. Application of solid-phase microextraction combined with derivatization to the determination of amphetamines by liquid chromatography.

    PubMed

    Cháfer-Pericás, C; Campíns-Falcó, P; Herráez-Hernández, R

    2004-10-15

    This work evaluates the utility of solid-phase microextraction (SPME) in the analysis of amphetamines by liquid chromatography (LC) after chemical derivatization of the analytes. Two approaches have been tested and compared, SPME followed by on-fiber derivatization of the extracted amphetamines, and solution derivatization followed by SPME of the derivatives formed. Both methods have been applied to measure amphetamine (AP), methamphetamine (MA), and 3,4-methylenedioxymethamphetamine (MDMA), using the fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) and carbowax-templated resin (CW-TR)-coated fibers. Data on the application of the proposed methods for the analysis of different kind of samples are presented. When analyzing aqueous solutions of the analytes, both approaches gave similar analytical performance, but the sensitivity attainable with the solution derivatization/SPME method was better. The efficiencies observed when processing spiked urine samples by the SPME/on-fiber derivatization approach were very low. This was because the extraction of matrix components into the fiber coating prevented the extraction of the reagent. In contrast, the efficiencies obtained for spiked urine samples by the solution derivatization/SPME approach were similar to those obtained for aqueous samples. Therefore, the later method would be the method of choice for the quantification of amphetamines in urine.

  9. "Inherently Chiral" Ionic-Liquid Media: Effective Chiral Electroanalysis on Achiral Electrodes.

    PubMed

    Rizzo, Simona; Arnaboldi, Serena; Mihali, Voichita; Cirilli, Roberto; Forni, Alessandra; Gennaro, Armando; Isse, Abdirisak Ahmed; Pierini, Marco; Mussini, Patrizia Romana; Sannicolò, Francesco

    2017-02-13

    To achieve enantioselective electroanalysis either chiral electrodes or chiral media are needed. High enantiodiscrimination properties can be granted by the "inherent chirality" strategy of developing molecular materials in which the stereogenic element responsible for chirality coincides with the molecular portion responsible for their specific properties, an approach recently yielding outstanding performances as electrode surfaces. Inherently chiral ionic liquids (ICILs) have now been prepared starting from atropisomeric 3,3'-bicollidine, synthesized from inexpensive reagents, resolved into antipodes without need of chiral HPLC and converted into long-chain dialkyl salts with melting points below room temperature. Both the new ICILs and shorter family terms, solid at room temperature, employed as low-concentration additives in achiral ILs, afford impressive enantioselection for the enantiomers of different probes on achiral electrodes, regularly increasing with additive concentration.

  10. Selenium Derivatization of Nucleic Acids for Crystallography

    SciTech Connect

    Jiang,J.; Sheng, J.; Carrasco, N.; Huang, Z.

    2007-01-01

    The high-resolution structure of the DNA (5'-GTGTACA-C-3') with the selenium derivatization at the 2'-position of T2 was determined via MAD and SAD phasing. The selenium-derivatized structure (1.28 {angstrom} resolution) with the 2'-Se modification in the minor groove is isomorphorous to the native structure (2.0 {angstrom}). To directly compare with the conventional bromine derivatization, we incorporated bromine into the 5-postion of T4, determined the bromine-derivatized DNA structure at 1.5 {angstrom} resolution, and found that the local backbone torsion angles and solvent hydration patterns were altered in the structure with the Br incorporation in the major groove. Furthermore, while the native and Br-derivatized DNAs needed over a week to form reasonable-size crystals, we observed that the Se-derivatized DNAs grew crystals overnight with high-diffraction quality, suggesting that the Se derivatization facilitated the crystal formation. In addition, the Se-derivatized DNA sequences crystallized under a broader range of buffer conditions, and generally had a faster crystal growth rate. Our experimental results indicate that the selenium derivatization of DNAs may facilitate the determination of nucleic acid X-ray crystal structures in phasing and high-quality crystal growth. In addition, our results suggest that the Se derivatization can be an alternative to the conventional Br derivatization.

  11. Chiral superconductors.

    PubMed

    Kallin, Catherine; Berlinsky, John

    2016-05-01

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

  12. Direct derivatization and rapid GC-MS screening of nerve agent markers in aqueous samples.

    PubMed

    Subramaniam, Raja; Astot, Crister; Juhlin, Lars; Nilsson, Calle; Ostin, Anders

    2010-09-01

    A rapid screening and identification method based on derivatization and gas chromatography mass spectrometry (GC-MS) has been developed for the detection of alkylphosphonic acids (APAs), the degradation products of organophosphorus nerve agents. The novel method described involves rapid (5 min) and direct derivatization of 25 microL aqueous sample using highly fluorinated phenyldiazomethane reagents (e.g., 1-(diazomethyl)-3,5-bis(trifluoromethyl)benzene). The APA derivatives are then screened by GC-MS negative ion chemical ionization (NICI) and identified by electron ionization (EI) mode. The conditions for the derivatization were optimized using statistical experimental design and multivariate data analysis. Method robustness was evaluated using aqueous samples from an official OPCW Proficiency Test and all APAs present in the sample were conclusively identified. Limits of detection for rapid screening using SIM NICI were between 5 and 10 ng/mL APA in aqueous sample, and for identification using full scan EI 100 ng/mL.

  13. Microfluidic lab-on-a-chip derivatization for gaseous carbonyl analysis.

    PubMed

    Pang, Xiaobing; Lewis, Alastair C; Ródenas-García, Milagros

    2013-06-28

    We present a microfluidic lab-on-a-chip derivatization technique for the analysis of gaseous carbonyl compounds using O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) as the derivatizing reagent. The novel microfluidic lab-on-a-chip derivatization technique has been developed to measure nmol per mole (ppbv) mixing ratios of gaseous carbonyl compounds, which are of particular importance to atmospheric chemistry. The technique utilised a planar glass microreactor comprising three inlets and one outlet, gas and fluid splitting and combining channels, mixing junctions, and a 2.0m long, 620μm internal diameter reaction microchannel. The microreactor integrated three functions, providing: (1) a gas and liquid mixer and reactor, (2) reagent heating, and (3) sample pre-concentration. The concentration of derivatization solution, the volumetric flow rates of the incoming gas sample and PFBHA solution, and the temperature of the microreactor were optimised to achieve a near real-time measurement. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the microreactor resulted in a fast and high efficiency derivatization reaction, generating an effluent stream which was ready for direct introduction to GC-MS. Good linearity was observed for eight carbonyl compounds over the measurement ranges of 1-500ppbv when they were derivatized under optimal reaction conditions. The method detection limits (MDLs) were below 0.10nmolmol(-1) for most carbonyls in this study, which is below or close to their typical concentrations in clean ambient air. The performance of the technique was assessed by applying the methodology to the quantification of glyoxal (GLY) and methylglyoxal (MGLY) formed during isoprene photo-oxidation in an outdoor photoreactor chamber (EUPHORE). Good agreements between GLY and MGLY measurements were obtained comparing this new technique with Fourier Transform InfraRed (FTIR), which provides support for the potential effectiveness of

  14. Chemical synthesis of water-soluble, chiral conducting-polymer complexes

    DOEpatents

    Wang, Hsing-Lin; McCarthy, Patrick A.; Yang, Sze Cheng

    2003-01-01

    The template-guided synthesis of water-soluble, chiral conducting polymer complexes is described. Synthesis of water-soluble polyaniline complexes is achieved by carefully controlling the experimental parameters such as; acid concentration, ionic strength, monomer/template ratio, total reagent concentration, and order of reagent addition. Chiral (helical) polyaniline complexes can be synthesized by addition of a chiral inducing agent (chiral acid) prior to polymerization, and the polyaniline helix can be controlled by the addition of the (+) or (-) form of the chiral acid. Moreover the quantity of chiral acid and the salt content has a significant impact on the degree of chirality in the final polymer complexes. The polyaniline and the template have been found to be mixed at the molecular level which results in chiral complexes that are robust through repeated doping and dedoping cycles.

  15. Palladium-Catalyzed Enantioselective C-H Activation of Aliphatic Amines Using Chiral Anionic BINOL-Phosphoric Acid Ligands.

    PubMed

    Smalley, Adam P; Cuthbertson, James D; Gaunt, Matthew J

    2017-02-01

    The design of an enantioselective Pd(II)-catalyzed C-H amination reaction is described. The use of a chiral BINOL phosphoric acid ligand enables the conversion of readily available amines into synthetically valuable aziridines in high enantiomeric ratios. The aziridines can be derivatized to afford a range of chiral amine building blocks incorporating motifs readily encountered in pharmaceutically relevant molecules.

  16. Fast chiral separation of drugs using columns packed with sub-2 microm particles and ultra-high pressure.

    PubMed

    Guillarme, Davy; Bonvin, Gregoire; Badoud, Flavia; Schappler, Julie; Rudaz, Serge; Veuthey, Jean-Luc

    2010-03-01

    The use of columns packed with sub-2 microm particles in liquid chromatography with very high pressure conditions (known as UHPLC) was investigated for the fast enantioseparation of drugs. Two different procedures were evaluated and compared using amphetamine derivatives and beta-blockers as model compounds. In one case, cyclodextrins (CD) were directly added to the mobile phase and chiral separations were carried out in less than 5 min. However, this strategy suffered from several drawbacks linked to column lifetime and low chromatographic efficiencies. In the other case, the analysis of enantiomers was carried out after a derivatization procedure using two different reagents, 2,3,4-tri-O-acetyl-alpha-D-arabinopyranosyl isothiocyanate (AITC) and N-alpha-(2,4-dinitro-5-fluorophenyl)-L-alaninamide (Marfey's reagent). Separation of several amphetamine derivatives contained within the same sample was achieved in 2-5 min with high efficiency and selectivity. The proposed approach was also successfully applied to the enantiomeric purity determination of (+)-(S)-amphetamine and (+)-(S)-methamphetamine. Similar results were obtained with beta-blockers, and the separation of 10 enantiomers was carried out in less than 3 min, whereas the individual separation of several beta-blocker enantiomers was performed in 1 min or less.

  17. p-Tolyl isocyanate derivatization for analysis of CWC-related polar degradation products by mass spectrometry.

    PubMed

    Karthikraj, R; Sridhar, L; Murty, M R V S; Raju, N P; Vairamani, M; Prabhakar, S

    2014-08-01

    Most of the precursors and/or degradation products related to the Chemical Weapons Convention (CWC) are polar. Identification of these molecules in environmental samples provides clues regarding the alleged usage and/or synthesis of the parent toxic chemicals. Such polar compounds need to be derivatized in order to analyze them by gas chromatography-mass spectrometry (GC-MS). In this study, we developed a new derivatizing reagent, para-tolyl isocyanate (PTI), for derivatization of polar CWC-related compounds. The PTI reagent selectively derivatizes the -OH and/or-SH functional groups with high efficiency, but does not react with carboxylic acid (-COOH) or phosphonic acid (-(O)P(OH)2) groups. The PTI derivatives of dialkyl aminoethanols, dialkyl aminoethanol-N-oxides, and 3-quinuclidinol were successfully eluted through GC, and their electron ionization (EI) mass spectra were distinct and provided the structure information by which the isomeric compounds can be easily distinguished. We also calculated the GC-retention index values that can be used for further confirmation of the target compounds. All the studied PTI derivatives can be analyzed by EI-MS with direct insertion probe and/or by direct electrospray ionization mass spectrometry (ESI-MS) together with the MS-MS data; both sets of data provide full structure information. The PTI reagent was found to be better in some respects than the conventional bistrimethylsilyl trifluoroacetamide (BSTFA), a trimethyl silylating reagent. The PTI reagent is commercially available, and the PTI derivatives are highly stable for months and are not sensitive to moisture. The applicability of the PTI derivatization for trace-level determination of the target CWC-related polar compounds in environmental matrices and in human plasma samples is also evaluated.

  18. [Applications of multi-micro-volume pressure-assisted derivatization reaction device for analysis of polar heterocyclic aromatic amines by gas chromatography-mass spectrometry].

    PubMed

    Wang, Yiru; Chen, Fangxiang; Shi, Yamei; Tan, Connieal; Chen, Xi

    2013-01-01

    A multi-micro-volume pressure-assisted derivatization reaction device has been designed and made for the silylation derivatization of polar heterocyclic aromatic amines by N-(tert-butyldimethylsilyl )-N-methyl-trifluoroacetamide (MTBSTFA) with 1% catalyst tert-butyldimethylchlorosilane (TBDMCS) at a high temperature. The tert-butyldimethylsilyl derivatives then could be automatically analyzed by gas chromatography-mass spectrometry. Using the pressure-assisted device, the silylation reaction may occur at a temperature higher than the boiling points of the reagents, and several micro-volume samples can be simultaneously pretreated in the same device to shorten the sample-preparation time and to improve the repeatability. The derivatization conditions including the headspace volume of the vial, the evaporative surface area of the reagent, derivatization temperature and time have been discussed for the use of the pressure-assisted device. The experimental results proved that the device is an effective way for the simultaneous derivatization of several micro-volume samples at a high temperature. Compared with a common device, the derivative amounts were obviously increased when using the pressure-assisted device at 90 degrees C. Quantitative derivatization can be achieved even at 150 degrees C while there was no common device could be applied at such a high temperature due to the heavy losses of reagents by evaporation. However, no obviously higher reaction speed has been observed in such a circumstance with a higher temperature and a higher pressure using the pressure-assisted device.

  19. The Covalent Functionalization of Layered Black Phosphorus by Nucleophilic Reagents.

    PubMed

    Sofer, Zdeněk; Luxa, Jan; Bouša, Daniel; Sedmidubský, David; Lazar, Petr; Hartman, Tomáš; Hardtdegen, Hilde; Pumera, Martin

    2017-08-07

    Layered black phosphorus has been attracting great attention due to its interesting material properties which lead to a plethora of proposed applications. Several approaches are demonstrated here for covalent chemical modifications of layered black phosphorus in order to form P-C and P-O-C bonds. Nucleophilic reagents are highly effective for chemical modification of black phosphorus. Further derivatization approaches investigated were based on radical reactions. These reagents are not as effective as nucleophilic reagents for the surface covalent modification of black phosphorus. The influence of covalent modification on the electronic structure of black phosphorus was investigated using ab initio calculations. Covalent modification exerts a strong effect on the electronic structure including the change of band-gap width and spin polarization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. RNA nucleosides as chiral sensing agents in NMR spectroscopy.

    PubMed

    Lokesh, N; Sachin, S L; Narendra, L V; Arun, K; Suryaprakash, N

    2015-07-14

    The study reports chiral sensing properties of RNA nucleosides. Adenosine, guanosine, uridine and cytidine are used as chiral derivatizing agents to differentiate chiral 1°-amines. A three component protocol has been adopted for complexation of nucleosides and amines. The chiral differentiating ability of nucleosides is examined for different amines based on the (1)H NMR chemical shift differences of diastereomers (Δδ(R,S)). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. Adenosine and guanosine exhibit large chiral differentiation (Δδ(R,S)) due to the presence of a purine ring. The diastereomeric excess (de) measured by using adenosine is in good agreement with the gravimetric values.

  1. High-performance liquid chromatography of histamine and 1-methylhistamine with on-column fluorescence derivatization.

    PubMed

    Saito, K; Horie, M; Nose, N; Nakagomi, K; Nakazawa, H

    1992-03-20

    An on-column fluorometric derivatization method was developed for the determination of histamine and 1-methylhistamine (HMs) by high-performance liquid chromatography. The system for the derivatization consisted only of a commercially available single-plunger pump and a reversed-phase C18 column supported on synthetic polymer with a mobile phase of acetonitrile and alkaline borate buffer solution containing o-phthalaldehyde as a derivatization reagent. It required no additional reaction system as for a post-column derivatization method. Injected HMs might be derivatized to a fluorophore on the inlet site of the high-performance liquid chromatographic column, followed by chromatography on the same column. Optimization of the on-column reaction conditions resulted in a simple and sensitive analytical method for the determination of HMs with excellent reproducibility and linearity of 0.05-5 micrograms/ml of both HMs. Application of this method to the determination of HMs in food samples resulted in a limit of quantification of 0.05 mg/100 g and in a greater than 95% overall mean recovery at a fortification of 0.1 mg/g of both HMs. This method was furthermore applicable to the determination of histamine released from rat peritoneal mast cells.

  2. Use of a statistically designed experimental approach to optimize the propylketal derivatization of barbiturates.

    PubMed

    Kushnir, M M; Urry, F M

    2001-04-01

    The derivatization of barbiturates with dimethylformamide dipropylacetal and dimethylformamide diisopropylacetal is studied with respect to the optimization of reaction recovery and reliability. A second-order orthogonal experimental design is utilized in order to obtain regression equations for the reaction recovery dependence on the derivatization solution composition, incubation temperature, and time for amobarbital, butalbital, pentobarbital, phenobarbital, and secobarbital. Regression equations for the effect of incubation temperature and time on the derivative recovery and the optimum conditions for derivatization recoveries are obtained. Differences in the phenomena of the derivative formation are evaluated between the two derivatizing reagents and the barbiturates. Based on the analysis of the obtained equations, it is concluded that the dipropylketal derivative of barbiturates is superior in comparison with diisopropylketal when considering the milder conditions of the reaction, absence of sudden changes in the recovery with a variation in the derivatization parameters, and reliability for the simultaneous testing of the barbiturates. A method for the routine testing of the barbiturates by gas chromatography-mass spectrometry in urine specimens is included.

  3. Sensitive derivatization methods for the determination of genotoxic impurities in drug substances using hyphenated techniques.

    PubMed

    Raman, Nanduri V V S S; Prasad, Adapa V S S; Reddy, Kura Ratnakar

    2014-02-01

    Six sensitive derivatization methods for the determination of genotoxic impurities in selected drug substances were developed using hyphenated techniques. Some of the raw materials, reagents and reaction intermediates of the selected drug substances were identified as genotoxic impurities through DEREK software for windows. The genotoxic impurities which are amenable for derivatization were selected as substrates. Derivatizing agents were selected based on the functional groups of the genotoxic impurities. The chemistry involved in the derivatization was explained with suitable mechanisms. An appropriate hyphenated technique viz. LC-MS and GC-MS was opted based on the sensitivity and aromaticity of the derivatized genotoxic impurities. All the methods were validated as per International Conference on Harmonization guidelines. Correlation coefficient values were found about 0.99. The obtained % R.S.D values from replicate injections in the range of 2.3-4.8 and % recoveries of the added impurities in the range of 83.7-101.7 ensured the precision and accuracy, respectively.

  4. Chiral plasmonics

    PubMed Central

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-01-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes. PMID:28560336

  5. Chiral plasmonics.

    PubMed

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-05-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes.

  6. A microfluidic device for the automated derivatization of free fatty acids to fatty acid methyl esters.

    PubMed

    Duong, Cindy T; Roper, Michael G

    2012-02-21

    Free fatty acid (FFA) compositions are examined in feedstock for biodiesel production, as source-specific markers in soil, and because of their role in cellular signaling. However, sample preparation of FFAs for gas chromatography-mass spectrometry (GC-MS) analysis can be time and labor intensive. Therefore, to increase sample preparation throughput, a glass microfluidic device was developed to automate derivatization of FFAs to fatty acid methyl esters (FAMEs). FFAs were delivered to one input of the device and methanolic-HCl was delivered to a second input. FAME products were produced as the reagents traversed a 29 μL reaction channel held at 55 °C. A Design of Experiment protocol was used to determine the combination of derivatization time (T(der)) and ratio of methanolic-HCl:FFA (R(der)) that maximized the derivatization efficiencies of tridecanoic acid and stearic acid to their methyl ester forms. The combination of T(der) = 0.8 min and R(der) = 4.9 that produced optimal derivatization conditions for both FFAs within a 5 min total sample preparation time was determined. This combination of T(der) and R(der) was used to derivatize 12 FFAs with a range of derivatization efficiencies from 18% to 93% with efficiencies of 61% for tridecanoic acid and 84% for stearic acid. As compared to a conventional macroscale derivatization of FFA to FAME, the microfluidic device decreased the volume of methanolic-HCl and FFA by 20- and 1300-fold, respectively. The developed microfluidic device can be used for automated preparation of FAMEs to analyze the FFA compositions of volume-limited samples.

  7. Evaporative Derivatization of Phenols with 2-Sulfobenzoic Anhydride for Detection by MALDI-MS

    PubMed Central

    Yao, Yuanyuan; Wang, Poguang; Giese, Roger

    2014-01-01

    RATIONALE Phenols are an important class of analytes, for example as bioactive environmental contaminants. Towards a goal of improving their detection by MALDI-TOF-MS or MALDI-TOF/TOF-MS, we studied their derivatization with 2-sulfobenzoic anhydride (SBA). We chose SBA for this purpose since it is commercially available, inexpensive, and forms an anionic derivative. METHODS In selected conditions developed here for phenols, a reaction mixture of one or more of such compounds in acetonitrile containing SBA and 4-dimethylaminopyridine (DMAP) is evaporated to a solid, heated at 60°C for 1 h, redissolved in 50% acetonitrile containing matrix, spotted onto a MALDI target, and subjected to negative ion MALDI-TOF/TOF-MS. RESULTS While conventional (solution-phase) reaction of 4-phenylphenol (model analyte) with SBA and DMAP only gave a 47% yield of SBA-tagged 4-phenylphenol, evaporative derivatization as above gave a 96% yield, and 25 pmol (4.3 ng) of 4-phenylphenol could be detected in this way by MALDI-TOF/TOF-MS at S/N = 260, whereas even 1 nmol of the nonderivatized phenol was not detected in the absence of derivatization. A wide range of responses was observed when a mixture of 15 phenols was derivatized, with the higher responses coming from phenols with a pKa value above 9. Without derivatization, phenols with pKa values below 5 were the most readily detected. CONCLUSION Evaporative derivatization with SBA (a convenient reagent) can improve the detection of phenols with relatively high pKa values (above 9) by negative ion MALDI-TOF-MS, and accomplish this in the absence of post-derivatization reaction cleanup. PMID:24519828

  8. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

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

  9. From analytical methods to large scale chiral supercritical fluid chromatography using chlorinated chiral stationary phases.

    PubMed

    Wu, Dauh-Rurng; Yip, Shiuhang Henry; Li, Peng; Sun, Dawn; Mathur, Arvind

    2016-02-05

    While traditional non-chlorinated Cellulose- and Amylose-derivatized phases have been used successfully in supercritical fluid chromatography (SFC) to resolve a broad variety of chiral compounds, some chiral pharmaceutical compounds are not well resolved on these traditional chiral stationary phases (CSP) due to the lack of chiral selectivity. Since there are no universal CSP to resolve all chiral compounds, chlorinated CSP can be complementary to the non-chlorinated CSP. Chlorinated CSP such as 4-Chloro-3-methylphenyl-carbamatecellulose (Lux-Cellulose-4), 3-Chloro-4-methylphenyl-carbamatecellulose (Lux-Cellulose-2), 5-Chloro-2-methylphenyl-carbamateamylose (Lux-Amylose-2) and immobilized 3,5-dichlorophenyl-carbamatecellulose (Chiralpak IC) have provided a range of chiral recognition mechanisms which have allowed the authors to successfully achieve chiral SFC resolution on several structurally diverse compounds, which are not well resolved in the non-chlorinated CSP. In addition, chlorinated Lux-Cellulose-4, Chiralpak IC and Lux-Amylose-2 have enabled us to utilize non-alcohol solvents as sample diluents and as co-solvents to significantly improve compound solubility and selectivity. This article will discuss the challenges associated with several SFC applications on both coated and immobilized chlorinated CSP to deliver high-quality drug candidates in large quantity. The use of dichloromethane in both sample preparation and as co-solvent in CO2 to increase sample solubility will be presented in preparative example #2 and #3.

  10. A novel derivatization method for the determination of Fosfomycin in human plasma by liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometric detection via phase transfer catalyzed derivatization.

    PubMed

    Papakondyli, Theodora A; Gremilogianni, Aikaterini M; Megoulas, Nikolaos C; Koupparis, Michael A

    2014-03-07

    An analytical method employing novel sample preparation and liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometric detection (LC-APCI/MS) was developed for the determination of fosfomycin in human plasma. Sample preparation involves derivatization through phase transfer catalysis (PTC) which offers multiple advantages due to the simultaneous extraction, preconcentration and derivatization of the analyte. Using a PT catalyst, fosfomycin was extracted from plasma in an organic phase and, then converted to a pentafluorobenzyl ester with the use of pentafluorobenzyl bromide (PFBBr) derivatization reagent. The method was fully optimized by taking into account both PTC and derivatization parameters. Several catalysts, in a wide range of concentrations, with different counter ions and polarities were tested along with different extraction solvents and pH values. Thereafter, the derivatization procedure was optimized by altering the amount of the derivatization reagent, the temperature of the reaction and finally, the derivatization duration. As internal standard (I.S.) ethylphosphonic acid was chosen and underwent the same pretreatment. The derivatives were separated on a pentafluorophenyl (PFP)-C18 analytical column, which provides unique selectivity, using an isocratic elution with acetonitrile-water (70-30, v/v). The method was validated according to US Food and Drug Administration (FDA) guidelines and can be used for a bioequivalence study of fosfomycin in human plasma. The correlation coefficient (r(2)) of the calibration curve of spiked plasma solutions in the range of 50-12000 ng/mL was found greater than 0.999 with a limit of quantitation (LOQ) equal to 50 ng/ml (for 500 μL plasma sample). Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Chemical Derivatization of Peptide Carboxyl Groups for Highly Efficient Electron Transfer Dissociation

    NASA Astrophysics Data System (ADS)

    Frey, Brian L.; Ladror, Daniel T.; Sondalle, Samuel B.; Krusemark, Casey J.; Jue, April L.; Coon, Joshua J.; Smith, Lloyd M.

    2013-11-01

    The carboxyl groups of tryptic peptides were derivatized with a tertiary or quaternary amine labeling reagent to generate more highly charged peptide ions that fragment efficiently by electron transfer dissociation (ETD). All peptide carboxyl groups—aspartic and glutamic acid side-chains as well as C-termini—were derivatized with an average reaction efficiency of 99 %. This nearly complete labeling avoids making complex peptide mixtures even more complex because of partially-labeled products, and it allows the use of static modifications during database searching. Alkyl tertiary amines were found to be the optimal labeling reagent among the four types tested. Charge states are substantially higher for derivatized peptides: a modified tryptic digest of bovine serum albumin (BSA) generates ~90% of its precursor ions with z > 2, compared with less than 40 % for the unmodified sample. The increased charge density of modified peptide ions yields highly efficient ETD fragmentation, leading to many additional peptide identifications and higher sequence coverage (e.g., 70 % for modified versus only 43 % for unmodified BSA). The utility of this labeling strategy was demonstrated on a tryptic digest of ribosomal proteins isolated from yeast cells. Peptide derivatization of this sample produced an increase in the number of identified proteins, a >50 % increase in the sequence coverage of these proteins, and a doubling of the number of peptide spectral matches. This carboxyl derivatization strategy greatly improves proteome coverage obtained from ETD-MS/MS of tryptic digests, and we anticipate that it will also enhance identification and localization of post-translational modifications.

  12. Spectrofluorimetric determination of tetrabenazine after photochemical derivatization in basic medium

    NASA Astrophysics Data System (ADS)

    Osório, Ana C. P.; da Cunha, Alessandra L. M. C.; Khan, Sarzamin; Ponciano, Cássia R.; Aucélio, Ricardo Q.

    Photochemical derivatization is proposed for the spectrofluorimetric determination of tetrabenazine (TBZ). A central composite design was used to adjust experimental conditions (60 min of UV in a 0.45 mol L-1 NaOH solution) enabling the improvement of the analyte signal-to-blank ratio of one order of magnitude, when compared to the TBZ original fluorescence. Limit of quantification was 4.7 × 10-8 mol L-1 but the detection power can be improved at least 10 times using solid phase extraction that also allows the separation of the analyte from matrix components, enabling the analysis of biologic fluids. Linear range covered at least three orders of magnitude. The combined uncertainty of the determination (at a 5 × 10-6 mol L-1) was 16%. Recoveries of TBZ in the analyses of a pharmaceutical formulation were in agreement with the ones obtained using a HPLC method. Recovery in saliva (5 × 10-7 mol L-1 of TBZ) was 90 ± 3% (n = 3). The procedure minimizes the use of toxic chemical derivatization reagents and the generation of hazardous waste.

  13. Detection of methamphetamine in the presence of nicotine using in situ chemical derivatization and ion mobility spectrometry.

    PubMed

    Ochoa, Mariela L; Harrington, Peter B

    2004-02-15

    The detection of methamphetamine in the presence of nicotine has been successfully accomplished using in situ chemical derivatization with propyl chloroformate as the derivatization reagent and ion mobility spectrometry (IMS). The rapid detection of methamphetamine is important for forensic scientists in order to establish a chain of evidence and link criminals to the crime scene. Nicotine is pervasive in clandestine drug laboratories from cigarette smoke residue. It has been demonstrated that nicotine obscures the methamphetamine peaks in ion mobility spectrometers due to their similar charge affinities and ion mobilities, which makes their detection a challenging task. As a consequence, false positive or negative responses may arise. In situ chemical derivatization poses as a sensitive, accurate, and reproducible alternative to remove the nicotine background when detecting nanogram amounts of methamphetamine. The derivatization agent was coated onto the sample disk, and the derivatization product corresponding to propyl methamphetamine carbamate was detected. In the present study, in situ chemical derivatization was demonstrated to be a feasible method to detect methamphetamine hydrochloride as the carbamate derivative, which was baseline-resolved from the nicotine peak. Alternating least squares (ALS) was used to model the datasets. A mixture containing both compounds revealed reduced mobilities of 1.61 cm(2)/V.s and 1.54 cm(2)/V.s for methamphetamine and nicotine, respectively. The reduced mobility of propyl methamphetamine carbamate was found at 1.35 cm(2)/V.s.

  14. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

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

  15. Chiral Polymers.

    DTIC Science & Technology

    1984-10-01

    TITLE (mid Subttlo) 񓂬-JS. TYPE OF REPORT & PERIOD COVERED CHIRAL POLYMERS /~O~~ R E~NNE 7. AUTHOR(e) 11. CONTRACT OR GRANT NUNSIER(e) J. K. Stille...acrylamide monomer containing a chiral 1,3-dioxane unit as well as both racemic and ( R )-6.-methyl ene-vi-methyl -7-butyrol actone were synthesi zed...or ( R )-propylene oxide (10)6. The key step in this synthesis is the palladium catalyzed carbonylation of 4-bromopent-4-en-2-ol. Thus, either racemic or

  16. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    PubMed Central

    Ariga, Katsuhiko; Richards, Gary J.; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P.

    2010-01-01

    Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized. PMID:22163577

  17. Intelligent chiral sensing based on supramolecular and interfacial concepts.

    PubMed

    Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

    2010-01-01

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

  18. Chiral ionic liquids: synthesis, properties, and enantiomeric recognition.

    PubMed

    Yu, Shaofang; Lindeman, Sergey; Tran, Chieu D

    2008-04-04

    We have synthesized a series of structurally novel chiral ionic liquids which have a either chiral cation, chiral anion, or both. Cations are an imidazolium group, while anions are based on a borate ion with spiral structure and chiral substituents. Both (or all) stereoisomeric forms of each compound in the series can be readily synthesized in optically pure form by a simple one-step process from commercially available reagents. In addition to the ease of preparation, most of the chiral ILs in this series are liquid at room temperature with a solid to liquid transformation temperature as low as -70 degrees C and have relatively high thermal stability (up to at least 300 degrees C). Circular dichroism and X-ray crystallographic results confirm that the reaction to form the chiral spiral borate anion is stereospecific, namely, only one of two possible spiral stereoisomers was formed. Results of NMR studies including 1H{15N} heteronuclear single quantum coherence (HSQC) show that these chiral ILs exhibit intramolecular as well as intermolecular enantiomeric recognition. Intramolecularly, the chiral anion of an IL was found to exhibit chiral recognition toward the cation. Specifically, for a chiral IL composing with a chiral anion and a racemic cation, enantiomeric recognition of the chiral anion toward both enantiomers of the cation lead to pronounced differences in the NMR bands of the cation enantiomers. The chiral recognition was found to be dependent on solvent dielectric constant, concentration, and structure of the ILs. Stronger enantiomeric recognition was found in solvent with relatively lower dielectric constants (CDCl3 compared to CD3CN) and at higher concentration of ILs. Also, stronger chiral recognition was found for anions with a relatively larger substituent group (e.g., chiral anion with a phenylmethyl group exhibits stronger chiral recognition compared to that with a phenyl group, and an anion with an isobutyl group has the weakest chiral recognition

  19. Electrophilic, Activation-Free Fluorogenic Reagent for Labeling Bioactive Amines.

    PubMed

    Sintes, Miquel; De Moliner, Fabio; Caballero-Lima, David; Denning, David W; Read, Nick D; Kielland, Nicola; Vendrell, Marc; Lavilla, Rodolfo

    2016-06-15

    Herein we report the preparation of BODIPY mesoionic acid fluorides through a short sequence involving an isocyanide multicomponent reaction as the key synthetic step. These novel BODIPY acid fluorides are water-stable electrophilic reagents that can be used for the fluorescent derivatization of amine-containing biomolecules using mild and activation-free reaction conditions. As a proof of principle, we have labeled the antifungal natamycin and generated a novel fluorogenic probe for imaging a variety of human and plant fungal pathogens, with excellent selectivity over bacterial cells.

  20. Dansyl chloride derivatization of methamphetamine: a method with advantages for screening and analysis of methamphetamine in urine.

    PubMed

    Yamada, Hideyuki; Yamahara, Ayako; Yasuda, Satsuki; Abe, Masamiki; Oguri, Kazuta; Fukushima, Sunao; Ikeda-Wada, Sachiko

    2002-01-01

    The screening and quantitation of methamphetamine (MP) in urine using dansyl chloride (DNC) as the derivatization reagent were studied. Urinary MP derivatized with DNC could be detected by visual observation of the fluorescence in a solid-phase extraction column such as a Sep-Pak C18 cartridge to which the whole reaction solution was applied. The DNC-derivatized MP was eluted from the cartridge and then identified and quantitated by gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC). In the GC-MS analysis with the MS detector in the electron-impact mode, DNC-derivatized MP and amphetamine (AP), exhibited diagnostic molecular ion peaks. The intensities of the molecular ions were 15% (DNC-MP) and 35% (DNC-AP) of the base peak (a fragment ion because of the loss of dimethylnaphthalene from M+), demonstrating that this method of derivatization has a major advantage for confirming APs by GC-MS. MP derivatized with DNC could be determined by HPLC with ultraviolet detection. Because a good correlation (r = 0.95) between the GC-MS and HPLC method for urinary MP was confirmed, both HPLC and GC-MS appear to be useful tools for determining urinary MP. The intensity of the cartridge fluorescence due to DNC-derivatized MP was approximately related to the urinary content of MP determined by HPLC or GC-MS, although a false positive in the visual fluorescence was observed in some urinary specimens from healthy volunteers. From these results, screening and confirmation/determination following DNC derivatization is proposed as a suitable method for the analysis of MP.

  1. Diastereoselective Radical Hydroacylation of Alkylidenemalonates with Aliphatic Aldehydes Initiated by Photolysis of Hypervalent Iodine(III) Reagents.

    PubMed

    Selvakumar, Sermadurai; Sakamoto, Ryu; Maruoka, Keiji

    2016-05-04

    Diastereoselective radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes is realized by the combination of a hypervalent iodine(III) reagent and UV-light irradiation. The reaction is initiated by the photolysis of hypervalent iodine(III) reagents under mild, metal-free conditions, and is the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The obtained optically active ketones are useful chiral synthons, as exemplified by the short formal synthesis of (-)-methyleneolactocin.

  2. Chiral ionic liquids for enantioseparation of pharmaceutical products by capillary electrophoresis.

    PubMed

    Tran, Chieu D; Mejac, Irena

    2008-09-19

    A chiral ionic liquid (IL), S-[3-(chloro-2-hydroxypropyl)trimethylammonium] [bis((trifluoromethyl)sulfonyl)amide] (S-[CHTA](+)[Tf(2)N](-)), which can be easily and readily synthesized in a one-step process from commercially available reagents, can be successfully used both as co-electrolyte and as a chiral selector for CE. A variety of pharmaceutical products including atenolol, propranolol, warfarin, indoprofen, ketoprofen, ibuprofen and flurbiprofen, can be successfully and baseline separated with the use of this IL as electrolyte. Interestingly, while S-[CHTA](+)[Tf(2)N](-) can also serve as a chiral selector, enantioseparation cannot be successfully achieved with S-[CHTA](+)[Tf(2)N](-) as the only chiral selector. In the case of ibuprofen, a second chiral selector, namely a chiral anion (sodium cholate), is needed for the chiral separation. For furbiprofen, in addition to S-[CHTA](+)[Tf(2)N](-) and sodium cholate, a third and neutral chiral selector, 1-S-octyl-beta-d-thioglucopyranoside (OTG), is also needed. Due to the fact that the chirality of this chiral IL resides on the cation (i.e., -[CHTA](+)), and that needed additional chiral selector(s) are either chiral anion (i.e., cholate) or chiral neutral compound (OTG), the results obtained seem to suggest that additional chiral selector(s) are needed to provide the three-point interactions needed for chiral separations.

  3. LC-MS determination of bioactive molecules based upon stable isotope-coded derivatization method.

    PubMed

    Toyo'oka, Toshimasa

    2012-10-01

    Liquid chromatography (LC) coupled with mass spectrometry (MS) has been widely used for the analyses of various molecules in many research fields. The electrospray ionization of MS has contributed to the advancement of the LC-MS and LC-MS/MS methods. However, the detection sensitivity is not always sufficient in biological samples, in spite of the highly sensitive ionization method. To increase the sensitivity, chemical derivatization, providing ionization enhancement and avoiding the matrix effect, is effective for various functional groups in the target molecules. However, the accuracy and precision by the determination is sometimes insufficient, especially in complex matrices. In such a case, stable isotope-labeled analogs are often used as the internal standards for the determination of the analytes. When the target compound in samples is limited, a high accuracy and precision is usually obtained by the isotope dilution method. However, the use of individual isotope standards is very difficult for the analyses of multiple molecules in complex matrices. Instead of the use of an isotope analog of the analytes, the differential isotope labeling method based upon chemical derivatization (stable isotope-coded derivatization) (ICD) by both reagents possessing different isotopes is realized. The ICD technique utilizing mass-different isotope tags is known to be an efficient means for metabolite profiling analyses. Thus, the present paper reviews the ICD method reported in the past 10 years. The species of the ICD reagents, their features and the applications to biological specimens are also described in this review.

  4. Derivatization of hydroxyl functional groups for liquid chromatography and capillary electroseparation.

    PubMed

    Escrig-Doménech, A; Simó-Alfonso, E F; Herrero-Martínez, J M; Ramis-Ramos, G

    2013-06-28

    The derivatization reactions commonly used to enhance the analytical signal in the HPLC and CE determination of compounds with hydroxyl functional groups are revised. Focus is placed on the determination of compounds having aliphatic alcohols and phenols while lacking other reactive functional groups. The derivatization with acyl chlorides, organic anhydrides, isocyanates and a variety of other approaches, including oxidation of primary and secondary alcohols, sulfonation, esterification with carboxylic acids, and the use of azides, sulfonyl chlorides and other reagents having miscellaneous leaving groups, is covered. Reactions mainly addressed to introduce a chromophore or a fluorophore in the analyte molecule, or to introduce a charge to enhance sensitivity in MS detection, or to enable CE separation are included. Applications related to the industrial quality control of raw materials and manufactured products, and to the evaluation of their environmental impact are emphasized. The problem of the different response factors of the derivatives when complex mixtures of oligomers are derivatized, as occurs with non-ionic surfactants (mainly fatty alcohol ethoxylates) and soluble synthetic polymers, is discussed. Other applications related to the biochemical, biomedical, pharmaceutical, nutritional and toxicological fields are also reviewed. The reactions, the criteria to be applied to select the reagent, and the characteristics of the derivatives in relation to separation and detection, are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Lithium Enolates in the Enantioselective Construction of Tetrasubstituted Carbon Centers with Chiral Lithium Amides as Noncovalent Stereodirecting Auxiliaries.

    PubMed

    Yu, Kai; Lu, Ping; Jackson, Jeffrey J; Nguyen, Thuy-Ai D; Alvarado, Joseph; Stivala, Craig E; Ma, Yun; Mack, Kyle A; Hayton, Trevor W; Collum, David B; Zakarian, Armen

    2017-01-11

    Lithium enolates derived from carboxylic acids are ubiquitous intermediates in organic synthesis. Asymmetric transformations with these intermediates, a central goal of organic synthesis, are typically carried out with covalently attached chiral auxiliaries. An alternative approach is to utilize chiral reagents that form discrete, well-defined aggregates with lithium enolates, providing a chiral environment conducive of asymmetric bond formation. These reagents effectively act as noncovalent, or traceless, chiral auxiliaries. Lithium amides are an obvious choice for such reagents as they are known to form mixed aggregates with lithium enolates. We demonstrate here that mixed aggregates can effect highly enantioselective transformations of lithium enolates in several classes of reactions, most notably in transformations forming tetrasubstituted and quaternary carbon centers. Easy recovery of the chiral reagent by aqueous extraction is another practical advantage of this one-step protocol. Crystallographic, spectroscopic, and computational studies of the central reactive aggregate, which provide insight into the origins of selectivity, are also reported.

  6. Amino acids as chiral selectors in enantioresolution by liquid chromatography.

    PubMed

    Bhushan, Ravi; Dixit, Shuchi

    2012-08-01

    Amino acids are unique in terms of their structural features and multidimensional uses. With their simple structures and the ready availability of both enantiomers, amino acids not only serve as a chiral pool for synthesis but also provide an inexpensive pool for resolution studies. There has been no attempt to review the application of amino acids as chiral selectors for chromatographic enantioresolution of pharmaceuticals and other compounds. The present paper deals with application of l-amino acids and complexes of l-amino acids with a metal ion, particularly Cu(II), as an impregnating reagent in thin-layer chromatography or as a chiral ligand exchange reagent or a chiral mobile phase additive in both thin-layer chromatography and high-performance liquid chromatography. Enantiomeric resolution of β-blockers, nonsteroidal anti-inflammatories, amino acids (and their derivatives) and certain other compounds is discussed.

  7. In situ Analysis of Organic Compounds on Mars using Chemical Derivatization and Gas Chromatography Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Glavin, D. P.; Buch, A.; Cabane, M.; Coll, P.; Navarro-Gonzalez, R.; Mahaffy, P. R.

    2005-01-01

    One of the core science objectives of NASA's 2009 Mars Science Laboratory (MSL) mission is to determine the past or present habitability of Mars. The search for key organic compounds relevant to terrestrial life will be an important part of that assessment. We have developed a protocol for the analysis of amino acids and carboxylic acids in Mars analogue materials using gas chromatography mass spectrometry (GCMS). As shown, a variety of carboxylic acids were readily identified in soil collected from the Atacama Desert in Chile at part-per-billion levels by GCMS after extraction and chemical derivatization using the reagent N,N-tert.-butyl (dimethylsilyl) trifluoroacetamide (MTBSTFA). Several derivatized amino acids including glycine and alanine were also detected by GCMS in the Atacama soil at lower concentrations (chromatogram not shown). Lacking derivatization capability, the Viking pyrolysis GCMS instruments could not have detected amino acids and carboxylic acids, since these non-volatile compounds require chemical transformation into volatile species that are stable in a GC column. We are currently optimizing the chemical extraction and derivatization technique for in situ GCMS analysis on Mars. Laboratory results of analyses of Atacama Desert samples and other Mars analogue materials using this protocol will be presented.

  8. Determination of memantine in plasma and vitreous humour by HPLC with precolumn derivatization and fluorescence detection.

    PubMed

    Puente, Belen; Hernandez, Esther; Perez, Susana; Pablo, Luis; Prieto, Esther; Garcia, Maria Angeles; Bregante, Miguel Angel

    2011-01-01

    A new HPLC procedure with precolumn derivatization and rimantadine as the internal standard for determining memantine, a candidate agent for the treatment of glaucoma in plasma and vitreous humour, has been developed and validated. Precolumn derivatization was performed with 9-fluorenylmethyl-chloroformate-chloride (FMOC-Cl) as the derivatization reagent and followed by a liquid-liquid extraction with n-hexane. Optimal conditions for derivatization were an FMOC-Cl concentration of 1.5 mM, a reaction time of 20 min, the temperature at 30°C, the borate buffer pH 8.5, and a borate buffer-acetonitrile ratio of 1:1. The derivatives were analyzed by isocratic HPLC with the fluorescence detector λex 260 nm λem 315 nm on a Novapack C(18) reversed-phase column with a mobile phase of acetonitrile-water (73:27, v/v), 40°C, and a flow rate of 1.2 mL/min. The linear range was 10-1000 ng/mL with a quantification limit of ∼ 10 ng/mL for both types of samples. This analytical method may be suitable for using in ocular availability studies.

  9. Development of a two-step injector for GC-MS with on-column derivatization, and its application to the determination of amphetamine-type stimulants (ATS) in biological specimens.

    PubMed

    Miki, Akihiro; Katagi, Munehiro; Zaitsu, Kei; Nishioka, Hiroshi; Tsuchihashi, Hitoshi

    2008-04-01

    A two-step auto-injector has been developed for the automated on-column derivatization and subsequent GC-MS of amine-type drugs and metabolites. To effectively derivatize such analytes, this injector has been designed to inject the derivatization reagent several seconds after the sample has been injected. Eleven kinds of amphetamine-type stimulants (ATS) and their typical metabolites were examined, using the trifluoroacetylation reagent N-methyl bis(trifluoroacetamide) (MBTFA). Although the quantitative derivatization of the hydroxyl groups was difficult, this technique was successfully applied to the determination of ATS in urine, blood, and hair specimens. The detection limits of methamphetamine and amphetamine in hair were 0.2 and 0.1 ng/mg hair, respectively, in the full-scan mode, when a 10 mg hair sample is analyzed.

  10. Liposomes as signal amplification reagents for bioassays in microfluidic channels.

    PubMed

    Locascio, Laurie E; Hong, Jennifer S; Gaitan, Michael

    2002-03-01

    Liposomes with encapsulated carboxyfluorescein were used in an affinity-based assay to provide signal amplification for small-volume fluorescence measurements. Microfluidic channels were fabricated by imprinting in a plastic substrate material, poly(ethylene terephthalate glycol) (PETG), using a silicon template imprinting tool. Streptavidin was linked to the surface through biotinylated-protein for effective immobilization with minimal nonspecific adsorption of the liposome reagent. Lipids derivatized with biotin were incorporated into the liposome membrane to make the liposomes reactive for affinity assays. Specific binding of the liposomes to microchannel walls, dependence of binding on incubation time, and nonspecific adsorption of the liposome reagent were evaluated. The results of a competitive assay employing liposomes in the microchannels are presented.

  11. Single-drop microextraction followed by in-syringe derivatization and GC-MS detection for the determination of parabens in water and cosmetic products.

    PubMed

    Saraji, Mohammad; Mirmahdieh, Shiva

    2009-04-01

    A single-drop microextraction (SDME) method followed by in-syringe derivatization and GC-MS determination has been developed for analysis of five parabens, including methyl, ethyl, isopropyl, n-propyl and n-butyl paraben in water samples and cosmetic products. N,O-Bis(trimethylsilyl)acetamide (BSA) was used as derivatization reagent. Derivatization reaction was performed inside the syringe barrel using 0.4 microL of BSA. Parameters that affect the derivatization yield such as temperature and time of the reaction were studied. In addition, experimental SDME parameters such as selection of organic solvent, addition of salt, extraction time and extraction temperature were investigated and optimized. The RSD of the method for aqueous samples varied from 8.1 to 13%. The LODs ranged from 0.001 (n-butyl paraben) to 0.015 (methyl paraben) microg/L, and the enrichment factors were between 23 and 150.

  12. Microwave-accelerated derivatization for capillary electrophoresis with laser-induced fluorescence detection: a case study for determination of histidine, 1- and 3-methylhistidine in human urine.

    PubMed

    Zhou, Lei; Yan, Na; Zhang, Huige; Zhou, Ximin; Pu, Qiaosheng; Hu, Zhide

    2010-06-30

    The feasibility of microwave-accelerated derivatization for capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection was evaluated. The derivatization reaction was performed in a domestic microwave oven. Histidine (His), 1-methylhistidine (1-MH) and 3-methylhistidine (3-MH) were selected as test analytes and fluorescein isothiocyanate (FITC) was chosen as a fluorescent derivatizing reagent. Parameters that may affect the derivatization reaction and/or subsequent CE separation were systematically investigated. Under optimized conditions, the microwave-accelerated derivatization reaction was successfully completed within 150 s, compared to 4-24 h in a conventional water-bath derivatization process. This will remarkably reduce the overall analysis time and increase sample throughput of CE-LIF. The detection limits of this method were found to be 0.023 ng/mL for His, 0.023 ng/mL for 1-MH, and 0.034 ng/mL for 3-MH, respectively, comparable to those obtained using traditional derivatization protocols. The proposed method was characterized in terms of precision, linearity, accuracy and successfully applied for rapid and sensitive determination of these analytes in human urine.

  13. Rh(II)-catalyzed Reactions of Diazoesters with Organozinc Reagents

    PubMed Central

    Panish, Robert; Selvaraj, Ramajeyam; Fox, Joseph M.

    2015-01-01

    Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethylacetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed. PMID:26241081

  14. Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents.

    PubMed

    Panish, Robert; Selvaraj, Ramajeyam; Fox, Joseph M

    2015-08-21

    Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethyl acetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed.

  15. On-matrix derivatization extraction of chemical weapons convention relevant alcohols from soil.

    PubMed

    Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Dubey, D K; Pardasani, Deepak

    2013-10-11

    Present study deals with the on-matrix derivatization-extraction of aminoalcohols and thiodiglycols, which are important precursors and/or degradation products of VX analogues and vesicants class of chemical warfare agents (CWAs). The method involved hexamethyldisilazane (HMDS) mediated in situ silylation of analytes on the soil. Subsequent extraction and gas chromatography-mass spectrometry analysis of derivatized analytes offered better recoveries in comparison to the procedure recommended by the Organization for the Prohibition of Chemical Weapons (OPCW). Various experimental conditions such as extraction solvent, reagent and catalyst amount, reaction time and temperature were optimized. Best recoveries of analytes ranging from 45% to 103% were obtained with DCM solvent containing 5%, v/v HMDS and 0.01%, w/v iodine as catalyst. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes ranged from 8 to 277 and 21 to 665ngmL(-1), respectively, in selected ion monitoring mode.

  16. Chiral streamers

    SciTech Connect

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

    2015-10-15

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

  17. Chiral streamers

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  18. Chromatographic profiles of tryptophan and kynurenine enantiomers derivatized with (S)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole using LC-MS/MS on a triazole-bonded column.

    PubMed

    Iizuka, Hideaki; Harashima, Takahiro; Takahashi, Shuhei; Kuwabara, Ryosuke; Naito, Yoko; Sakamoto, Tatsuya; Onozato, Mayu; Ichiba, Hideaki; Fukushima, Takeshi

    2017-10-01

    d- and l-Tryptophan (Trp) and d- and l-kynurenine (KYN) were derivatized with a chiral reagent, (S)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole (DBD-PyNCS), and were separated enantiomerically by high-performance liquid chromatography (HPLC) equipped with a triazole-bonded column (Cosmosil HILIC) using tandem mass spectrometric (MS/MS) detection. Effects of column temperature, salt (HCO2 NH4 ) concentration, and pH of the mobile phase in the enantiomeric separation, followed by MS detection of (S)-DBD-PyNCS-d,l-Trp and -d,l-KYN, were investigated. The mobile phase consisting of CH3 CN/10 mM ammonium formate in H2 O (pH 5.0) (90/10) with a column temperature of 50-60 °C gave satisfactory resolution (Rs) and mass-spectrometric detection. The enantiomeric separation of d,l-Trp and d,l-KYN produced Rs values of 2.22 and 2.13, and separation factors (α) of 1.08 and 1.08, for the Trp and KYN enantiomers, respectively. The proposed LC-MS/MS method provided excellent detection sensitivity of both enantiomers of Trp and KYN (5.1-19 nM). © 2017 Wiley Periodicals, Inc.

  19. Determination of residual arsenic compounds in chicken muscle by ultra-performance liquid chromatography coupled with ultraviolet detection after pre-column derivatization with toluene-3,4-dithiol.

    PubMed

    Eom, Han Young; Yang, Dong-Hyug; Suh, Joon Hyuk; Kim, Unyong; Kim, Junghyun; Cho, Hyun-Deok; Han, Sang Beom

    2015-12-01

    A simple and sensitive derivatization method using toluene-3,4-dithiol as a derivatization reagent for the simultaneous analysis of seven arsenic compounds (roxarsone, nitarsone, p-arsanilic acid, o-arsanilic acid, phenylarsonic acid, phenylarsine oxide, and mono-methylarsonic acid) in chicken muscle was developed and validated by ultra-performance liquid chromatography coupled with ultraviolet detection (UPLC-UV). The structure of the derivatized arsenic compounds was confirmed by liquid chromatography-ion trap mass spectrometry or gas chromatography-mass spectrometry. Optimization of the derivatization reaction conditions was carried out by investigating the influence of reagent concentration, buffer or additive acids, temperature, and time. The optimized conditions were a derivatization reagent concentration of 20mg/mL with 0.05mol/L HCl as an additive acid at 60°C for 15min. In this study, baseline separation of arsenic compounds could be achieved within 13min, except for phenylarsonic acid and phenylarsine oxide whose derivatized products are equal. The developed method was successfully validated and applied to 12 chicken muscle samples from Korean districts and other countries. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Use of Protein Folding Reagents.

    PubMed

    2016-04-01

    The reagents and methods for purification and use of the most commonly used denaturants, guanidine hydrochloride (guanidine-HCl) and urea, are described. Other protein denaturants and reagents used to fold proteins are briefly mentioned. Sulfhydryl reagents (reducing agents) and "oxido-shuffling" (or oxidative regeneration) systems are also described.

  1. Chiral hydroxy phosphonates: synthesis, configuration and biological properties

    NASA Astrophysics Data System (ADS)

    Kolodiazhnyi, Oleg I.

    2006-03-01

    Published data on the synthesis, absolute configurations and biological properties of chiral hydroxy phosphonates are generalised and described systematically. Examples of asymmetric synthesis of hydroxy phosphonates by the phospho-aldol reaction, reduction of keto phosphonates, chemo-enzymatic approach, and so on are discussed. Methods for determination of the optical purity and absolute configuration of hydroxy phosphonates using modification by chiral reagents, NMR, circular dichroism, GLC and HPLC on columns with chiral sorbents are considered. The significance of hydroxy phosphonates as promising compounds for the development of new drugs and bioregulators is demonstrated.

  2. Chemical suppression of contaminant metal ions using a metastable state in precolumn derivatizing HPLC: an ultratrace fluorometric detection of Al(III).

    PubMed

    Saito, Shingo; Anada, Tetsuya; Hoshi, Suwaru; Akatsuka, Kunihiko

    2005-08-15

    The contamination of metal ions from reagents used frequently restricts the practical detection limit of the metal ion, which itself is a source of contamination. We have found a novel solution to this problem, a chemical-suppressing method of contaminant metal ions on a reversed-phase HPLC for Al3+ with a detection limit of 7.6 x 10(-11) mol dm(-3) (2.1 ng dm(-3)) by only adding a certain agent into all stock solutions without any preconcentration or purification steps. This technique decreases the concentration of the contaminant Al3+ originating from the reagents by more than 1 order of magnitude using selective derivatization of sample Al3+ ions to a powerful fluorescent complex at a metastable state in the precolumn chelation processes. Meanwhile, the contaminant Al3+ remains as a nonfluorescent complex with a blocking reagent in order to suppress the contamination. This selective derivatization is achieved by the accumulation of several complexation processes based on the difference of formation, dissociation, and ligand-exchange kinetics and the thermodynamics between the derivatizing reagent, the 4',5'-geometorical isomer of calcein, and the blocking reagent, o,o'-dihydroxyazobenzene. This simple and smart HPLC system was validated through recovery tests of environmental and biological samples.

  3. (RS)-Propranolol: enantioseparation by HPLC using newly synthesized (S)-levofloxacin-based reagent, absolute configuration of diastereomers and recovery of native enantiomers by detagging.

    PubMed

    Alwera, Shiv; Bhushan, Ravi

    2016-08-01

    Diastereomers of (RS)-propranolol were synthesized using (S)-levofloxacin-based new chiral derivatizing reagents (CDRs). Levofloxacin was chosen as the pure (S)-enantiomer for its high molar absorptivity (εo  ∼ 24000) and availability at a low price. Its -COOH group had N-hydroxysuccinimide and N-hydroxybenzotriazole, which acted as good leaving groups during nucleophilic substitution by the amino group of the racemic (RS)-propranolol; the CDRs were characterized by UV, IR, (1) H-NMR, high resolution mass spectrometry (HRMS) and carbon, hydrogen, nitrogen, and sulphur fundamental elemental components analyser (CHNS). Diastereomers were separated quantitatively using open column chromatography; absolute configuration of the diastereomers was established and the reagent moiety was detagged under microwave-assisted acidic conditions. (S)- and (R)-propranolol as pure enantiomers and (S)-levofloxacin were separated, isolated and characterized. Optimized lowest-energy structures of the diastereomers were developed using Gaussian 09 Rev. A.02 program and hybrid density functional B3LYP with 6-31G* basis set (based on density functional theory) for explanation of elution order and configuration. In addition, RP HPLC conditions for separation of diastereomers were optimized with respect to pH, concentration of buffer, flow rate of mobile phase and nature of organic modifier. HPLC separation method was validated as per International Conference on Harmonization guidelines. With the systematic application of various analytical techniques, absolute configuration of the diastereomers (and the native enantiomers) of (RS)-propranolol was established. Copyright © 2016 John Wiley & Sons, Ltd.

  4. Derivatization of haemoglobin with periodate-generated reticulation agents: evaluation of oxidative reactivity for potential blood substitutes.

    PubMed

    Deac, Florina; Iacob, Bianca; Fischer-Fodor, Eva; Damian, Grigore; Silaghi-Dumitrescu, Radu

    2011-01-01

    Periodate modification of the sugar moiety in sugars, including adenosine triphosphate (ATP), has previously been employed in order to prepare dialdehyde-type reagents, which were then utilized in crosslinking reactions on haemoglobin, yielding polymerized material with useful dioxygen-binding properties and hence proposed as possible artificial oxygen carriers ('blood substitutes'). Here, the periodate protocol is shown to be applicable to a wider range of oxygen-containing compounds, illustrated by starch and polyethylene glycol. Derivatization protocols are described for haemoglobin with such periodate-treated crosslinking agents, and the dioxygen-binding properties and redox reactivities are investigated for the derivatized haemoglobins, with emphasis on pro-oxidative properties. There is a general tendency of the derivatization to result in higher autooxidation rates. The peroxide reactivity of the met (ferric) form is also affected by derivatization, as witnessed, among others, by varying yields of ferryl [Fe (IV)-oxo] and free radical generated. In cell, culture tests (human umbilical vein epithelial cells, HUVEC), the derivatization protocols show no toxic effect.

  5. Analysis of steroid estrogens in water using liquid chromatography/tandem mass spectrometry with chemical derivatizations.

    PubMed

    Lin, Ying-Hsuan; Chen, Chia-Yang; Wang, Gen-Shuh

    2007-01-01

    Even in trace amounts, estrogens such as 17beta-estradiol (E2), estrone (E1), estriol (E3), and 17alpha-ethinyl estradiol (EE2) may have adverse effects on humans and the aquatic ecosystem. Therefore, it is essential to be able to measure trace amounts of steroid estrogens in water. To date, most instruments are not sensitive enough to detect these chemicals in small samples of water. Sensitivity, however, may be improved by using appropriate derivatization reagents to modify the structures of these estrogens so that their ionization efficiency is increased, making them more detectable by liquid chromatography/mass spectrometry (LC/MS). This study uses dansyl chloride, 2-fluoro-1-methylpyridinium p-toluenesulfonate (FMPTS), and pentafluorobenzyl bromide (PFBBr) as derivatization reagents to react with the phenolic estrogens to make them more detectable in water. We also test how environmental matrices (wastewater effluent, river water, and drinking water) influence the detectability of these estrogens. Both qualitative and semi-quantitative comparisons of these derivatization methods were made. We found that dansyl chloride derivatives created signal intensities one or two orders of magnitude greater than those normally found in underivatized estrogen standards. The signals derived by FMPTS were analyte-dependent, and the products derived from E1, E2, and EE2 produced 2.19 to 12.1 times the signal intensity of underivatized E1, E2, and EE2. The product derived from E3 produced weaker signals than that produced by underivatized E3. The PFBBr derivatives produced signals that were as much as 5.8 times those found in the underivatized estrogens. When these derivatization methods were applied to river water, drinking water and effluents from a sewage treatment plant (STP), the different matrices were found to significantly suppress the signals if we used electrospray ionization, though this influence became less significant if we used atmospheric pressure chemical

  6. Tagging the Untaggable: A Difluoroalkyl-Sulfinate Ketone-Based Reagent for Direct C-H Functionalization of Bioactive Heteroarenes.

    PubMed

    Gnaim, Samer; Scomparin, Anna; Li, Xiuling; Baran, Phil S; Rader, Christoph; Satchi-Fainaro, Ronit; Shabat, Doron

    2016-09-21

    We have developed a new difluoroalkyl ketal sulfinate salt reagent suitable for direct derivatization of heteroarene C-H bonds. The reagent is capable of introducing a ketone functional group on heteroarene bioactive compounds via a one-pot reaction. Remarkably, in three examples the ketone analog and its parent drug had almost identical cytotoxicity. In a representative example, the ketone analog was bioconjugated with a delivery vehicle via an acid-labile semicarbazone linkage and with a photolabile protecting group to produce the corresponding prodrug. Controlled release of the drug-ketone analog was demonstrated in vitro for both systems. This study provides a general approach to obtain taggable ketone analogs directly from bioactive heteroarene compounds with limited options for conjugation. We anticipate that this sodium ketal-sulfinate reagent will be useful for derivatization of other heteroarene-based drugs to obtain ketone-taggable analogs with retained efficacy.

  7. Gas Phase Chiral Separations By Ion Mobility Spectrometry

    PubMed Central

    Dwivedi, Prabha; Wu, Ching; Hill, Herbert H.

    2013-01-01

    This manuscript introduces the concept of Chiral Ion Mobility Spectrometry (CIMS) and presents examples demonstrating the gas phase separation of enantiomers of a wide range of racemates including pharmaceuticals, amino acids and carbohydrates. CIMS is similar to traditional ion mobility spectrometry (IMS), where gas phase ions, when subjected to a potential gradient are separated at atmospheric pressure due to differences in their shapes and sizes. In addition to size and shape, CIMS separates ions based on their stereospecific interaction with a chiral gas. In order to achieve chiral discrimination by CIMS, an asymmetric environment was provided by doping the drift gas with a volatile chiral reagent. In this study S-(+)-2-butanol was used as a chiral modifier to demonstrate enantiomeric separations of atenolol, serine, methionine, threonine, methyl-α-glucopyranoside, glucose, penicillamine, valinol, phenylalanine, and tryptophan from their respective racemic mixtures. PMID:17165808

  8. Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space

    PubMed Central

    Herbert, Simon A; van Laeren, Laura J; Castell, Dominic C

    2014-01-01

    Summary The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji–Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds. PMID:25550740

  9. Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space.

    PubMed

    Herbert, Simon A; van Laeren, Laura J; Castell, Dominic C; Arnott, Gareth E

    2014-01-01

    The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji-Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds.

  10. Nonisotopic reagents for a cost-effective increase in sample throughput of targeted quantitative proteomics.

    PubMed

    Castillo, Mary Joan; McShane, Adam J; Cai, Min; Shen, Yuanyuan; Wang, Lei; Yao, Xudong

    2015-09-15

    The new technology of ultrathroughput MS (uMS) transforms the intrinsic capability of analyte multiplexing in mass spectrometry (MS) to sample multiplexing. Core technological advantages of uMS rely on the decoupled use of isotopic quantitation reference and nonisotopic mass coding of samples. These advantages include: (1) high sample-throughput potential, (2) utilization of minimal amounts of expensive stable isotopes for the quantitation reference, and (3) unleashing of the open-source exploration of the chemical structure diversity of nonisotopic reagents to significantly enhance the MS detectability of analytes. A particular uMS method, ultrathroughput multiple reaction monitoring (uMRM), is reported for one-experiment quantitation of a surrogate peptide (SVILLGR) of prostate specific antigen (PSA) in multiple serum samples. Following derivatization of the pair of spiked, isotopic reference (SVILLGR*) and endogenous, native peptide in each sample, all samples were pooled for a step of simultaneous enrichment and cleanup of derivatized peptide pairs using immobilized antibody. The MS analysis of the pooled sample reported the quantity and sample origin of the surrogate peptide. Several analyses with different sample throughput were presented, with the highest being 15-in-1. Screening of nonisotopic reagents used combinatorial libraries of peptidyl compounds, and the reagent selection was based on the derivatization effectiveness and the capability of MS signal enhancement for the peptide. The precision, accuracy, and linearity of the uMRM MS technology were found to be comparable with standard isotope dilution MRM MS.

  11. Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases.

    PubMed

    Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

    2012-07-01

    The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Simultaneous determination of eight short-chain aliphatic amines in drug substances by HPLC with diode array detection after derivatization with halonitrobenzenes.

    PubMed

    Han, Lingfei; Hou, Desheng; Ma, Congyu; Fu, Na; Liu, Jing; Feng, Feng; Liu, Wenyuan; Zheng, Feng

    2017-08-01

    Short-chain aliphatic amines are a class of hazardous impurities in drug substances. A simple method, involving derivatization followed by high-performance liquid chromatography with diode array detection, has been developed for residue determination of eight aliphatic amines simultaneously in drug substances. Different halonitrobenzenes derivatization reagents were systematically compared. As a result, 1-fluoro-2-nitro-4-(trifluoromethyl)benzene was selected since the derivatization effectively shifted the absorption wavelength to the visible region (400-450 nm), where most drug substances, impurities and even the derivatization reagent absorb very weakly. Due to the redshift effect, interference was minimized and adequately low limits of quantitation were reached (0.24-0.80 nmol/mL). Moreover, the derivatization reaction was readily carried out in dimethyl sulfoxide at room temperature for 1 h using N,N-diisopropylethylamine as catalyst to achieve the highest yield. Without any pre-treatment, the derivatives were analyzed by high-performance liquid chromatography with diode array detection. The high stability of the derivatives within 24 h at room temperature (RSD<1.04%) further facilitated the simultaneous preparation and consecutive analysis of quantities of samples. Finally, the proposed method was successfully applied for residue determination of eight aliphatic amines simultaneously in eight drug substance samples. This study could be helpful for the routine analysis and residue control of aliphatic amines in drug substances. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma.

    PubMed

    Xu, Xu; Su, Rui; Zhao, Xin; Liu, Zhuang; Zhang, Yupu; Li, Dan; Li, Xueyuan; Zhang, Hanqi; Wang, Ziming

    2011-11-30

    The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n=5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples.

  14. Capillary gas chromatography using a γ-cyclodextrin for enantiomeric separation of methylamphetamine, its precursors and chloro intermediates after optimization of the derivatization reaction.

    PubMed

    Płotka, Justyna M; Simeonov, Vasil; Morrison, Calum; Biziuk, Marek; Namieśnik, Jacek

    2014-06-20

    The enantiomeric ratio of methylamphetamine (MAMP) is closely related to the optical activity of precursors and reagents used for the synthesis and this knowledge can provide useful information concerning the origins and synthetic methods used for illicit manufacture. The information can be utilized for regulation of the precursors and investigation of the manufacturing sources but this requires analytical procedures to determine purity of drug substances, impurity profiling and enantiomeric composition. In this study, a gas chromatography (GC) coupled with mass spectrometry (MS) method using a γ-cyclodextrin chiral stationary phase was developed and optimized for the simultaneous enantiomeric separations of MAMP and its common precursors, ephedrine, and pseudoephedrine, as well as its chlorointermediates formed during MAMP synthesis by the Emde method, after derivatization with trifluoroacetic anhydride. The optimization was performed using multivariate statistics (cluster analysis and principal components analysis) in order to select and compare optimal experimental conditions. Under the optimized experimental conditions, the calculated calibration curves showed good linearity range up to 0.1μg/mL for all tested analytes. The limits of detection were in the range of 0.002-0.008μg/mL and the coefficient of variability was between 1.0 and 3.9%. The method has the advantage of achieving excellent precision under repeatability and reproducibility conditions while detection by MS allows for the identity of analytes to be confirmed in a single analysis. The method was therefore applied satisfactory to MAMP analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Enantioseparation characteristics of the chiral stationary phases based on natural and regenerated chitins.

    PubMed

    Mei, Xiao-Meng; Chen, Wei; Bai, Zheng-Wu

    2017-02-22

    Natural and regenerated chitins were derivatized with 3,5-dimethyphenyl isocyanate. The corresponding chiral stationary phases were prepared by coating the resulting chitin derivatives on 3-aminopropyl silica gel. The swelling capacity of the chitin derivatives, enantioseparation capability, as well as eluents tolerance of the chiral stationary phases were evaluated. The results demonstrated no remarkable difference in enantioseparation capability between natural and regenerated chitins based chiral stationary phases. The similar enantioseparation characteristics of two chiral stationary phases could be understood by comparing the IR spectra of related chitin derivatives. The one of the two chiral stationary phases prepared by coating the chitin derivative with a lower molecular weight generally provided better enantioseparations. All chiral stationary phases can work in 100% chloroform, 100% ethyl acetate, 100% acetone, and the mobile phases containing a certain amount of tetrahydrofuran. The chiral stationary phase prepared from the chitin derivative with the highest swelling capacity exhibited better enantioseparations than others. This chiral stationary phase was damaged by flushing with 100% tetrahydrofuran, however, the enantioseparation capability was recovered again after the column was allowed to stand for 1 month. Furthermore, the recovered chiral stationary phase provided better enantioseparations for some chiral analytes than before.

  16. Chiral mirrors

    SciTech Connect

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

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

  17. Amino acid analysis by high-performance liquid chromatography after derivatization with 9-fluorenylmethyloxycarbonyl chloride Literature overview and further study.

    PubMed

    Jámbor, A; Molnár-Perl, I

    2009-04-10

    A literature overview is given of HPLC methods currently in use to determine amino acids as their 9-fluorenylmethyloxycarbonyl (FMOC) derivatives. On the basis of the detailed literature overview an exhaustive derivatization study was performed with 22 amino acids, applying photodiode array (DAD) and fluorescence (FL) detection simultaneously, in order to clear up the controversial points of FMOC derivatization. Model investigations have been carried out as a function of the reaction time and reaction conditions, such as the molar concentration of the reagent, the molar ratios of the reactants, the pH and the solvent composition of the reaction medium. Special emphasis was put (i) on the evaluation of the blank values of the reagents, as a function of the composition and that of the pH of the reaction medium, (ii) on the unambiguous quantitation of all amino acids, including the less reactive aspartic and glutamic acids, as well as on the formation and transformation of histidine and tyrosine, existing partly, as single (N-FMOC-histidine, N-FMOC-tyrosine), partly as double labeled species (N,NH-FMOC-histidine, N,O-FMOC-tyrosine). Reproducibilities of 22 amino acids, including both histidine and tyrosine derivatives, obtained under optimum derivatization conditions are presented (at 0.5mM FMOC concentration corresponding to the molar ratios of [FMOC]/[amino acids](T)=5.5/1 (note: the superscript 'T' means the total of amino acids), with acetonitrile containing reagents, at pH 9, derivatization time=20 min), and characterized with the relative standard deviation percentages of their responses (

  18. Understanding complex chiral plasmonics.

    PubMed

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-11-07

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the 'host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.

  19. Immobilized strychnine as a new chiral stationary phase for HPLC.

    PubMed

    Sýkora, David; Vozka, Jiří; Tesařová, Eva; Kalíková, Květa; Havlík, Martin; Matějka, Pavel; Král, Vladimír

    2017-08-01

    A new ion-exchanger type chiral stationary phase for high-performance liquid chromatography was prepared. The synthetic protocol is based on derivatization of silica with (3-iodopropyl)trimethoxysilane in the first step followed by immobilization of strychnine via quaternization of nitrogen atom of the alkaloid strychnine. The synthesized chiral stationary phase was chromatographically characterized. The main effort was headed towards the evaluation of the enantioselectivity of the novel sorbent. For that purpose a set of suitable chiral probes, specifically, binaphthyl derivatives, was employed. The influence of methanol content, concentration of aqueous ammonium acetate buffer, and its pH on retention factors, separation selectivity, and resolution of the atropoisomers of the mentioned chiral solutes was studied in detail. It was demonstrated that the new chiral stationary phase was capable to separate atropoisomers of four out of seven testing compounds. Despite the strong influence of the above mentioned variables on retention, their impact on selectivity and resolution was rather moderate. Concerning retention mechanism, it seems that electrostatic interaction between the positively charged quaternary nitrogen of the chiral stationary phase and anionic solute participates significantly in the retention process. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. [Determination of monensin residue in chicken by HPLC with post-column derivatization].

    PubMed

    Chen, X; Shi, X

    1999-01-01

    The monensin residue was extracted from the tissue by homogenization with methanol-water and the extract was filtered and partitioned with dichloromethane. The dichloromethane extract is concentrated and clean up by passing through a silica gel cartridge. The analyte on the cartridge is then eluted with dichloromethane-methanol. The eluate is collected and evaporated to dryness. The residue is dissolved and made to a definite volume with 1 mL methanol and the solution is used for post-column derivatization-HPLC determination. Monensin is separated on mu-Bondapak C18 column (3.9 mm i.d. x 300 mm) with methanol-water-phosphoric acid as a mobile phase and the flow rate was 0.7 mL/min. The eluted monensin was reacted with vaniline under acidic and heated condition in post-column derivatization system then detected at 520 nm and quantitated by external standard method. The derivatization reagent consisted of 20 mL concentrated sulfuric acid, 950 mL methanol and 30 g vaniline. The flow rate was 0.7 mL/min. The reactor was a stainless steel coil (300 cm x 1 mm i.d.) set in a 90 degrees C oven. The response values was linear between 20-200 ng. The recovery was 88.1%-101.3%. The coefficient of variation was 0.1%-0.73%.

  1. Volatile chemical reagent detector

    DOEpatents

    Chen, Liaohai; McBranch, Duncan; Wang, Rong; Whitten, David

    2004-08-24

    A device for detecting volatile chemical reagents based on fluorescence quenching analysis that is capable of detecting neutral electron acceptor molecules. The device includes a fluorescent material, a contact region, a light source, and an optical detector. The fluorescent material includes at least one polymer-surfactant complex. The polymer-surfactant complex is formed by combining a fluorescent ionic conjugated polymer with an oppositely charged surfactant. The polymer-surfactant complex may be formed in a polar solvent and included in the fluorescent material as a solution. Alternatively, the complex may be included in the fluorescent material as a thin film. The use of a polymer-surfactant complex in the fluorescent material allows the device to detect both neutral and ionic acceptor molecules. The use of a polymer-surfactant complex film allows the device and the fluorescent material to be reusable after exposing the fluorescent material to a vacuum for limited time.

  2. Determination of aliphatic alcohols after on-line microwave-assisted derivatization by liquid chromatography-photodiode array detection.

    PubMed

    Chávez, Gerson; Bravo, Bélgica; Piña, Nolberto; Arias, Mónica; Vivas, Eliseo; Ysambertt, Fredy; Márquez, Nelson; Cáceres, Ana

    2004-12-15

    In this study, high-performance liquid chromatography (HPLC) in conjunction with continuous derivatization for the determination of aliphatic and polyethoxylated alcohol is reported. Reaction of alcohol group with phenyl isocyanate or benzyl chloride reagents assisted with microwaves (MW) irradiation is carried out in an on-line system coupled to HPLC with photodiode array detection (PDA). Reactor was placed into a microwave oven at 450W. The flow rate, reagent amounts, irradiation time, and chromatographic conditions were optimized. The continuous analysis using the system MW-HPLC-PDA provided high sensitivity, reduce the amount of reagents and analysis time. This proposed method can be used for the analysis of commercial alcohol polyethoxylated mixture.

  3. Stable Oligomeric Clusters of Gold Nanoparticles: Preparation, Size Distribution, Derivatization, and Physical and Biological Properties

    PubMed Central

    2015-01-01

    Reducing dilute aqueous HAuCl4 with NaSCN under alkaline conditions produces 2–3 nm diameter yellow nanoparticles without the addition of extraneous capping agents. We here describe two very simple methods for producing highly stable oligomeric grape-like clusters (oligoclusters) of these small nanoparticles. The oligoclusters have well-controlled diameters ranging from ∼5 to ∼30 nm, depending mainly on the number of subunits in the cluster. Our first [“delay-time”] method controls the size of the oligoclusters by varying from seconds to hours the delay time between making the HAuCl4 alkaline and adding the reducing agent, NaSCN. Our second [“add-on”] method controls size by using yellow nanoparticles as seeds onto which varying amounts of gold derived from “hydroxylated gold”, Na+[Au(OH4–x)Clx]−, are added-on catalytically in the presence of NaSCN. Possible reaction mechanisms and a simple kinetic model fitting the data are discussed. The crude oligocluster preparations have narrow size distributions, and for most purposes do not require fractionation. The oligoclusters do not aggregate after ∼300-fold centrifugal-filter concentration, and at this high concentration are easily derivatized with a variety of thiol-containing reagents. This allows rare or expensive derivatizing reagents to be used economically. Unlike conventional glutathione-capped nanoparticles of comparable gold content, large oligoclusters derivatized with glutathione do not aggregate at high concentrations in phosphate-buffered saline (PBS) or in the circulation when injected into mice. Mice receiving them intravenously show no visible signs of distress. Their sizes can be made small enough to allow their excretion in the urine or large enough to prevent them from crossing capillary basement membranes. They are directly visible in electron micrographs without enhancement, and can model the biological fate of protein-like macromolecules with controlled sizes and charges

  4. Stable oligomeric clusters of gold nanoparticles: preparation, size distribution, derivatization, and physical and biological properties.

    PubMed

    Smithies, Oliver; Lawrence, Marlon; Testen, Anze; Horne, Lloyd P; Wilder, Jennifer; Altenburg, Michael; Bleasdale, Ben; Maeda, Nobuyo; Koklic, Tilen

    2014-11-11

    Reducing dilute aqueous HAuCl4 with NaSCN under alkaline conditions produces 2-3 nm diameter yellow nanoparticles without the addition of extraneous capping agents. We here describe two very simple methods for producing highly stable oligomeric grape-like clusters (oligoclusters) of these small nanoparticles. The oligoclusters have well-controlled diameters ranging from ∼5 to ∼30 nm, depending mainly on the number of subunits in the cluster. Our first ["delay-time"] method controls the size of the oligoclusters by varying from seconds to hours the delay time between making the HAuCl4 alkaline and adding the reducing agent, NaSCN. Our second ["add-on"] method controls size by using yellow nanoparticles as seeds onto which varying amounts of gold derived from "hydroxylated gold", Na(+)[Au(OH4-x)Clx](-), are added-on catalytically in the presence of NaSCN. Possible reaction mechanisms and a simple kinetic model fitting the data are discussed. The crude oligocluster preparations have narrow size distributions, and for most purposes do not require fractionation. The oligoclusters do not aggregate after ∼300-fold centrifugal-filter concentration, and at this high concentration are easily derivatized with a variety of thiol-containing reagents. This allows rare or expensive derivatizing reagents to be used economically. Unlike conventional glutathione-capped nanoparticles of comparable gold content, large oligoclusters derivatized with glutathione do not aggregate at high concentrations in phosphate-buffered saline (PBS) or in the circulation when injected into mice. Mice receiving them intravenously show no visible signs of distress. Their sizes can be made small enough to allow their excretion in the urine or large enough to prevent them from crossing capillary basement membranes. They are directly visible in electron micrographs without enhancement, and can model the biological fate of protein-like macromolecules with controlled sizes and charges. The ease of

  5. Advanced dress-up chiral columns: New removable chiral stationary phases for enantioseparation of chiral carboxylic acids.

    PubMed

    Todoroki, Kenichiro; Ishii, Yasuhiro; Ide, Takafumi; Min, Jun Zhe; Inoue, Koichi; Huang, Xin; Zhang, Wei; Hamashima, Yoshitaka; Toyo'oka, Toshimasa

    2015-07-02

    This paper describes the preparation of new dress-up columns featuring reproducibly removable and replaceable chiral stationary phases. After synthesizing perfluroalkylated quinine and quinidine derivatives as chiral stationary phase compounds (F-CSPs), we adsorbed them reversibly onto a fluorous LC column through pumping of their solutions. Using this dress-up chiral column and fluorophobic elution of aqueous ammonium formate/MeOH mixtures, we could enantioseparate four racemic N-acetyl amino acids, dichlorprop, and sixteen fluorescent 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC)-derivatized amino acids. Dressing and undressing of the coated F-CSPs could be controlled by varying the fluorophilicity and fluorophobicity of the eluent. The relative standard deviations of the retention times, the retention factors, the number of theoretical plates, the enantioseparation factors, and the resolutions of each of four preparations of such dress-up columns were all less than or equal to 5.26% (from 20 repeated analyses); the reproducibilities from four different preparations were all less than or equal to 10.6%. These columns also facilitated highly sensitive and selective analyses of AQC-amino acids when detected using LC-MS/MS.

  6. Complex amine-based reagents

    NASA Astrophysics Data System (ADS)

    Suslov, S. Yu.; Kirilina, A. V.; Sergeev, I. A.; Zezyulya, T. V.; Sokolova, E. A.; Eremina, E. V.; Timofeev, N. V.

    2017-03-01

    Amines for a long time have been applied to maintaining water chemistry conditions (WCC) at power plants. However, making use of complex reagents that are the mixture of neutralizing and the filmforming amines, which may also contain other organic components, causes many disputes. This is mainly due to lack of reliable information about these components. The protective properties of any amine with regard to metal surfaces depend on several factors, which are considered in this article. The results of applying complex reagents to the protection of heating surfaces in industrial conditions and estimated behavior forecasts for various reagents under maintaining WCC on heat-recovery boilers with different thermal circuits are presented. The case of a two-drum heat-recovery boiler with in-line drums was used as an example, for which we present the calculated pH values for various brands of reagents under the same conditions. Work with different reagent brands and its analysis enabled us to derive a composition best suitable for the conditions of their practical applications in heat-recovery boilers at different pressures. Testing the new amine reagent performed at a CCPP power unit shows that this reagent is an adequate base for further development of reagents based on amine compounds. An example of testing a complex reagent is shown created with the participation of the authors within the framework the program of import substitution and its possible use is demonstrated for maintaining WCC of power-generating units of combined-cycle power plants (CCPP) and TPP. The compliance of the employed reagents with the standards of water chemistry conditions and protection of heating surfaces were assessed. The application of amine-containing reagents at power-generating units of TPP makes it possible to solve complex problems aimed at ensuring the sparing cleaning of heating surfaces from deposits and the implementation of conservation and management of water chemistry condition

  7. Application of INEPT nitrogen-15 and silicon-29 nuclear magnetic resonance spectrometry to derivatized fulvic acids

    USGS Publications Warehouse

    Thorn, K.A.; Folan, D.W.; Arterburn, J.B.; Mikita, M.A.; MacCarthy, P.

    1989-01-01

    Use of the INEPT experiment has been examined in two derivatization studies of the Suwannee River fulvic acid. In the first study, the fulvic acid was derivatized with 15N enriched hydroxylamine. The quantitative 15N NMR spectrum, acquired with a 45° pulse angle, 2.0 second pulse delay and inverse gated decoupling, showed that oximes (390-340 ppm) were the major derivatives, followed by nitriles (270-240 ppm), hydroxamic acids (170-160 ppm), secondary amides (150-115 ppm), and lactams (115-90 ppm). The INEPT 15N NMR spectrum was acquired using refocussing delays and polarization transfer times optimized for signal enhancement of singly protonated nitrogens. INEPT greatly enhanced the amide and lactam resonances, and showed that resonances downfield of 180 ppm in the quantitative spectrum represented nonprotonated nitrogens. In the second study, the fulvic acid was first methylated with diazomethane and then silylated with hexamethyldisilazane. The 29Si NMR spectra exhibited two major peaks, from approximately 33 to 22 ppm, representing silyl esters of carboxylic acids, and from 22 to 13 ppm, representing silyl ethers of alcohols and phenols. The INEPT 29Si NMR spectrum was virtually identical to the quantitative 29Si spectrum, acquired with a 90° pulse angle, 5.0 second pulse delay, inverse gated decoupling, and relaxation reagent. INEPT therefore can be used for quantitative analysis of trimethylsilyl derivatives of the fulvic acid, saving spectrometer time and eliminating the need for relaxation reagents.

  8. Use of cloud point extraction with derivatizing reagent for the extraction and determination of isoniazid.

    PubMed

    Zhao, Wei-jun; Liu, Wei; Chen, Jian-bo; Zhou, Zhi-ming; Yang, Ming-min

    2011-02-01

    A simple and sensitive cloud point extraction high-performance liquid chromatography method is proposed for the determination of isoniazid in blood. The procedure is based on the product of the reaction of isoniazid with benzaldehyde. It can be validated that there is a linear relationship between the signal of isonicotinyl hydrazone and the concentration of isoniazid. A cloud point extraction system of nonionic surfactant Triton X-100 is applied for preconcentration of isonicotinyl hydrazone. Then the analytes in surfactant-rich phase are detected with HPLC-UV system. calibration graph was obtained in the range of 2.0 × 10(-3)-0.5 mg/L, the detection limit was 5.0 × 10(-4) mg/L. Method validation is performed on serum samples spiked at two levels, the recoveries ranging from 82.17-83.81%, with relative standard deviations from 2.45% to 3.89%.

  9. Organic base-promoted enantioselective electrophilic cyanation of β-keto esters by using chiral phase-transfer catalysts.

    PubMed

    Chen, Min; Huang, Zhi-Tang; Zheng, Qi-Yu

    2015-09-07

    Highly enantioselective cyanation of β-keto esters using hypervalent iodine(iii) as the electrophilic cyanating reagent induced by cinchona alkaloid-based chiral quaternary ammonium salt was demonstrated. Organic bases, especially DMAP, in the chiral phase-transfer catalysis were used to obtain high ees.

  10. Chiral gravitational waves from chiral fermions

    NASA Astrophysics Data System (ADS)

    Anber, Mohamed M.; Sabancilar, Eray

    2017-07-01

    We report on a new mechanism that leads to the generation of primordial chiral gravitational waves, and hence, the violation of the parity symmetry in the Universe. We show that nonperturbative production of fermions with a definite helicity is accompanied by the generation of chiral gravitational waves. This is a generic and model-independent phenomenon that can occur during inflation, reheating and radiation eras, and can leave imprints in the cosmic microwave background polarization and may be observed in future ground- and space-based interferometers. We also discuss a specific model where chiral gravitational waves are generated via the production of light chiral fermions during pseudoscalar inflation.

  11. Chiral stationary phases based on chitosan bis(4-methylphenylcarbamate)-(alkoxyformamide).

    PubMed

    Feng, Zi-Wei; Chen, Wei; Bai, Zheng-Wu

    2016-10-01

    Highly N-deacetylated chitosan was chosen as a natural chiral origin for the synthesis of the selectors of chiral stationary phases. Therefore, chitosan was firstly acylated by various alkyl chloroformates yielding chitosan alkoxyformamides, and then these resulting products were further derivatized with 4-methylphenyl isocyanate to afford chitosan bis(4-methylphenylcarbamate)-(alkoxyformamide). A series of chiral stationary phases was prepared by coating these derivatives on 3-aminopropyl silica gel. The content of the derivatives on the chiral stationary phases was nearly 20% by weight. The chiral stationary phases prepared from chitosan bis(4-methylphenylcarbamate)-(ethoxyformamide) and chitosan bis(4-methylphenylcarbamate)-(isopropoxyformamide) comparatively showed better enantioseparation capability than those prepared from chitosan bis(4-methylphenylcarbamate)-(n-pentoxyformamide) and chitosan bis(4-methylphenylcarbamate)-(benzoxyformamide). The tolerance against organic solvents of the chiral stationary phase of chitosan bis(4-methylphenylcarbamate)-(ethoxyformamide) was investigated, and the results revealed that this phase can work in 100% ethyl acetate and 100% chloroform mobile phases. Because as-synthesized chiral selectors did not dissolve in many common organic solvents, the corresponding chiral stationary phases can be utilized in a wider range of mobile phases in comparison with conventional coating type chiral stationary phases of cellulose and amylose derivatives.

  12. Developing an on-line derivatization of FAs by microwave irradiation coupled to HPLC separation with UV detection.

    PubMed

    Bravo, Bélgica; Chávez, Gerson; Piña, Nolberto; Ysambertt, Fredy; Márquez, Nelson; Cáceres, Ana

    2004-12-15

    The development of analytical methods for routine simultaneous identification and quantification of carboxylic fatty acids (CFAs) are required in different fields, such as, pharmaceutical cosmetics, food products and formulations of water-microemulsion-oil systems. Determination of CFAs has been developed mainly by gas chromatography (GC). As an alternative to GC, liquid chromatography (LC) has better sensitivity and selectivity. However, most CFAs show no useful absorption in ultraviolet-violet (UV-Vis) region, one of the more used detection technique in high-performance liquid chromatography (HPLC). In order to allow the use of UV-Vis detection, the use of pre-column derivatization has been reported to increase sensitivity and selectivity. Therefore, establishment of a simpler and faster on-line method with complete separation is needed for the screening of large numbers of samples. 2,4-Dinitrophenylhydrazine (2,4-DNPH.), benzoil chloride (BC), and phenylhydrazine (PH) were used for derivatization of different FAs by microwaves radiation (MW). After the on-line derivatization, products were separated and quantified by HPLC. Reactor coil was placed inside of microwaves oven at 450W. Parameters as flow, amount of reagents, irradiation time, and chromatographic conditions were optimized. The continuous analysis using the MW-HPLC-UV system provided high sensitivity and reduced both the amount of reagent used and the analysis times. This proposed method can be used for the routine analysis of FAs contained in water-microemulsion-oil systems, to quantify the total acid fraction in each phase.

  13. Chirality of Viral Capsids

    NASA Astrophysics Data System (ADS)

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

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

  14. Derivatization reactions of carbamate pesticides in supercritical carbon dioxide.

    PubMed

    King, Jerry W; Zhang, Zhouyao

    2002-09-01

    Supercritical fluid carbon dioxide (SC-CO(2)) has been used to dissolve derivatizing agents (e.g. heptafluorobutyric anhydride, HFBA, and pyridine), which also act as a modifier in the fluid phase, for simultaneous extraction and derivatization of carbamates from the sample matrix. The derivatized carbamate pesticides (carbaryl, 3-hydroxycarbofuran, carbofuran, aldicarb, methiocarb) were then analyzed by GC-ECD or GC-MS with excellent sensitivity. Extraction and conversion of the carbamates was complete, as indicated by HPLC with post-column hydrolysis and o-phthalaldehyde derivatization then fluorescence detection. GC-MS (ion trap) was also used to confirm the formation of the carbamate derivatives. Compared with the same HFBA reaction in an organic solvent the derivatization reaction time was considerably shorter in SC-CO(2.) The described approach, combining both extraction and derivatization, simplifies the analysis of carbamate pesticides and eliminates the use of organic solvents associated with the derivatization step.

  15. Gas-phase reaction products and yields of terpinolene with ozone and nitric oxide using a new derivatization agent

    NASA Astrophysics Data System (ADS)

    Ham, Jason E.; Jackson, Stephen R.; Harrison, Joel C.; Wells, J. R.

    2015-12-01

    The new derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX) was used to investigate the carbonyl reaction products from terpinolene ozonolysis. With ozone (O3) as the limiting reagent, four carbonyl compounds were detected: methylglyoxal (MG), 4-methylcyclohex-3-en-1-one, (4MCH), 6-oxo-3-(propan-2-ylidene) heptanal (6OPH), and 3,6-dioxoheptanal (36DOH). The tricarbonyl 36DOH has not been previously observed. Using cyclohexane as a hydroxyl radical (OHrad) scavenger, the yields of 6OPH and 36DOH were reduced indicating the influence secondary OHrad radicals have on terpinolene ozonolysis products. However, the MG yield increased and the 4MCH yield was unchanged when OHrad radicals were scavenged suggesting they are only made by the terpinolene + O3 reaction. The detection of 36DOH using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The product yields from terpinolene ozonolysis experiments conducted in the presence of 20 ppb nitric oxide (NO) remained unchanged except for MG which decreased. However, in experiments where O3 was kept constant at 50 ppb and NO was varied (20, 50, 100 ppb) MG, 6OPH, 36DOH decreased with increasing NO while 4MCH increased with increasing NO. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

  16. Quantitation of amino acids in plasma by high performance liquid chromatography: simultaneous deproteinization and derivatization with 9-fluorenylmethyloxycarbonyl chloride.

    PubMed

    Jámbor, A; Molnár-Perl, I

    2009-08-21

    This paper, as a novelty to this field, presents the deproteinization and derivatization of plasma's free amino acids (PFAAs), simultaneously, in a single step, with the acetonitrile (ACN) containing 9-fluorenylmethyloxycarbonyl chloride (FMOC) reagent. Deproteinization and derivatization, were studied with 22 amino acids, applying photodiode array (DAD) and fluorescence (FL) detection, simultaneously. Model investigations have been carried out as a function of the FMOC concentration, reaction time and reaction conditions: with standard solutions, with human plasma samples in its initial condition and fortified with standard amino acids (excluding tryptophan because it co-elutes with the hydrolyzed FMOC). Reproducibilities of 22 amino acids, including both histidine and tyrosine derivatives, obtained under optimum derivatization conditions are presented (at 3.0 mM FMOC concentration, at pH 9; derivatization time - 20 min), and characterized with the relative standard deviation percentages of their responses (

  17. 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.

    PubMed

    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.

  18. Chiral Inorganic Nanostructures.

    PubMed

    Ma, Wei; Xu, Liguang; de Moura, André F; Wu, Xiaoling; Kuang, Hua; Xu, Chuanlai; Kotov, Nicholas A

    2017-06-28

    The field of chiral inorganic nanostructures is rapidly expanding. It started from the observation of strong circular dichroism during the synthesis of individual nanoparticles (NPs) and their assemblies and expanded to sophisticated synthetic protocols involving nanostructures from metals, semiconductors, ceramics, and nanocarbons. Besides the well-established chirality transfer from bioorganic molecules, other methods to impart handedness to nanoscale matter specific to inorganic materials were discovered, including three-dimentional lithography, multiphoton chirality transfer, polarization effects in nanoscale assemblies, and others. Multiple chiral geometries were observed with characteristic scales from ångströms to microns. Uniquely high values of chiral anisotropy factors that spurred the development of the field and differentiate it from chiral structures studied before, are now well understood; they originate from strong resonances of incident electromagnetic waves with plasmonic and excitonic states typical for metals and semiconductors. At the same time, distinct similarities with chiral supramolecular and biological systems also emerged. They can be seen in the synthesis and separation methods, chemical properties of individual NPs, geometries of the nanoparticle assemblies, and interactions with biological membranes. Their analysis can help us understand in greater depth the role of chiral asymmetry in nature inclusive of both earth and space. Consideration of both differences and similarities between chiral inorganic, organic, and biological nanostructures will also accelerate the development of technologies based on chiroplasmonic and chiroexcitonic effects. This review will cover both experiment and theory of chiral nanostructures starting with the origin and multiple components of mirror asymmetry of individual NPs and their assemblies. We shall consider four different types of chirality in nanostructures and related physical, chemical, and

  19. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

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

  20. Novel one-step headspace dynamic in-syringe liquid phase derivatization-extraction technique for the determination of aqueous aliphatic amines by liquid chromatography with fluorescence detection.

    PubMed

    Muniraj, Sarangapani; Shih, Hou-Kung; Chen, Ying-Fang; Hsiech, Chunming; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

    2013-06-28

    A novel one-step headspace (HS) dynamic in-syringe (DIS) based liquid-phase derivatization-extraction (LPDE) technique has been developed for the selective determination of two short-chain aliphatic amines (SCAAs) in aqueous samples using high performance liquid chromatography (HPLC) with fluorescence detection (FLD). Methylamine (MA) and dimethylamine (DMA) were selected as model compounds of SCAAs. In this method, a micro-syringe pre-filled with derivatizing reagent solution (9-fluorenylmethyl chloroformate) in the barrel was applied to achieve the simultaneous derivatization and extraction of two methylamines evolved from alkalized aqueous samples through the automated reciprocated movements of syringe plunger. After the derivatization-extraction process, the derivatized phase was directly injected into HPLC-FLD for analysis. Parameters influencing the evolution of methylamines and the HS-DIS-LPDE efficiency, including sample pH and temperature, sampling time, as well as the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger movements, were thoroughly examined and optimized. Under optimal conditions, detections were linear in the range of 25-500μgL(-1) for MA and DMA with correlation coefficients all above 0.995. The limits of detection (based on S/N=3) were 5 and 19ngmL(-1) for MA and DMA, respectively. The applicability of the developed method was demonstrated for the determination of MA and DMA in real water samples without any prior cleanup of the sample. The present method provides a simple, selective, automated, low cost and eco-friendly procedure to determine aliphatic amines in aqueous samples.

  1. Reagent Cluster Anions for Multiple Gas-Phase Covalent Modifications of Peptide and Protein Cations

    NASA Astrophysics Data System (ADS)

    Prentice, Boone M.; Stutzman, John R.; McLuckey, Scott A.

    2013-07-01

    Multiple gas phase ion/ion covalent modifications of peptide and protein ions are demonstrated using cluster-type reagent anions of N-hydroxysulfosuccinimide acetate (sulfo-NHS acetate) and 2-formyl-benzenesulfonic acid (FBMSA). These reagents are used to selectively modify unprotonated primary amine functionalities of peptides and proteins. Multiple reactive reagent molecules can be present in a single cluster ion, which allows for multiple covalent modifications to be achieved in a single ion/ion encounter and at the `cost' of only a single analyte charge. Multiple derivatizations are demonstrated when the number of available reactive sites on the analyte cation exceeds the number of reagent molecules in the anionic cluster (e.g., data shown here for reactions between the polypeptide [K10 + 3H]3+ and the reagent cluster [5R5Na - Na]-). This type of gas-phase ion chemistry is also applicable to whole protein ions. Here, ubiquitin was successfully modified using an FBMSA cluster anion which, upon collisional activation, produced fragment ions with various numbers of modifications. Data for the pentamer cluster are included as illustrative of the results obtained for the clusters comprised of two to six reagent molecules.

  2. Reagent Cluster Anions for Multiple Gas-phase Covalent Modifications of Peptide and Protein Cations

    PubMed Central

    Prentice, Boone M.; Stutzman, John R.; McLuckey, Scott A.

    2013-01-01

    Multiple gas phase ion/ion covalent modifications of peptide and protein ions are demonstrated here using cluster-type reagent anions of N-hydroxysulfosuccinimide acetate (sulfo-NHS acetate) and 2-formyl-benzenesulfonic acid (FBMSA). These reagents are used here to selectively modify unprotonated primary amine functionalities of peptides and proteins. Multiple reactive reagent molecules can be present in a single cluster ion, which allows for multiple covalent modifications to be achieved in a single ion/ion encounter and at the ‘cost’ of only a single analyte charge. Multiple derivatizations are demonstrated when the number of available reactive sites on the analyte cation exceeds the number of reagent molecules in the anionic cluster (e.g., data shown here for reactions between the polypeptide [K10+3H]3+ and the reagent cluster [5R5Na-Na]−). This type of gas phase ion chemistry is also applicable to whole protein ions. Here, ubiquitin was successfully modified using an FBMSA cluster anions which, upon collisional activation, produced fragment ions with various numbers of modifications. Data for the pentamer cluster are included here as illustrative of the results obtained for the clusters comprised of 2–6 reagent molecules. PMID:23702708

  3. Recyclable Trifluoromethylation Reagents from Fluoroform.

    PubMed

    Geri, Jacob B; Szymczak, Nathaniel K

    2017-07-26

    We present a strategy to rationally prepare CF3(-) transfer reagents at ambient temperature from HCF3. We demonstrate that a highly reactive CF3(-) adduct can be synthesized from alkali metal hydride, HCF3, and borazine Lewis acids in quantitative yield at room temperature. These nucleophilic reagents transfer CF3(-) to substrates without additional chemical activation, and after CF3 transfer, the free borazine is quantitatively regenerated. These features enable syntheses of popular nucleophilic, radical, and electrophilic trifluoromethylation reagents with complete recycling of the borazine Lewis acid.

  4. Baryons and chiral symmetry

    NASA Astrophysics Data System (ADS)

    Liu, Keh-Fei

    The relevance of chiral symmetry in baryons is highlighted in three examples in the nucleon spectroscopy and structure. The first one is the importance of chiral dynamics in understanding the Roper resonance. The second one is the role of chiral symmetry in the lattice calculation of πNσ term and strangeness. The third one is the role of chiral U(1) anomaly in the anomalous Ward identity in evaluating the quark spin and the quark orbital angular momentum. Finally, the chiral effective theory for baryons is discussed.

  5. Chiral separation of acidic compounds using an O-9-(tert-butylcarbamoyl)quinidine functionalized monolith in micro-liquid chromatography.

    PubMed

    Wang, Qiqin; Zhu, Peijie; Ruan, Meng; Wu, Huihui; Peng, Kun; Han, Hai; Somsen, Govert W; Crommen, Jacques; Jiang, Zhengjin

    2016-04-29

    An O-9-(tert-butylcarbamoyl) quinidine (t-BuCQD) functionalized polymeric monolithic capillary column was prepared by the in situ copolymerization method. The physicochemical properties of the optimized monolithic column were characterized by scanning electron microscopy and micro-LC. Satisfactory column permeability, efficiency, stability and reproducibility were obtained for this monolithic column. The chiral recognition ability of the resulting monolith was also evaluated using 47 N-derivatized amino acids, eight N-derivatized dipeptides, and two herbicides. Under the selected conditions, the enantiomers of all chiral analytes were baseline separated with exceptionally high selectivity and resolution using micro-LC. It is worth noting that this chiral stationary phase (CSP) containing quinidine with a tert-butyl carbamate residue as chiral selector exhibits much higher enantioselectivity and diastereoselectivity than the previously developed O-9-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroquinidine (MQD) based CSP for N-derivatized amino acids and dipeptides. These results indicate that this novel quinidine-based polymeric monolith can be used as an effective tool for the enantioseparation of chiral acidic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Mass spectrometric analysis of free fatty acids in infant milk powders by frozen pretreatment coupled with isotope-labeling derivatization.

    PubMed

    Zhou, Tianxiao; Leng, Jiapeng; Peng, Yaoshan; Zhang, Lei; Guo, Yinlong

    2016-03-01

    In combination with frozen pretreatment and carboxyl group derivatization, a novel workflow was developed for the determination of free fatty acids in milk powder. The workflow showed a significantly enhanced performance for comprehensive free fatty acid analysis owing to a highly efficient frozen extraction method. In addition, the advantages of the workflow also involved high sensitivity and great tolerance to a complex matrix. Characteristic fragment ions of derivatization reagents also provide clear evidence for the qualitative analysis of free fatty acids. Fourteen types of free fatty acids in a number of domestic and overseas infant milk powders have been successfully detected. The content of free fatty acids in the different samples was different, which probably indicates the diverse quality of infant milk powder. The workflow is expected to be a pragmatic tool for the analysis of free fatty acids in intricate matrices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Sequencing and characterization of oligosaccharides using infrared multiphoton dissociation and boronic acid derivatization in a quadrupole ion trap.

    PubMed

    Pikulski, Michael; Hargrove, Amanda; Shabbir, Shagufta H; Anslyn, Eric V; Brodbelt, Jennifer S

    2007-12-01

    A simplified method for determining the sequence and branching of oligosaccharides using infrared multiphoton dissociation (IRMPD) in a quadrupole ion trap (QIT) is described. An IR-active boronic acid (IRABA) reagent is used to derivatize the oligosaccharides before IRMPD analysis. The IRABA ligand is designed to both enhance the efficiency of the derivatization reaction and to facilitate the photon absorption process. The resulting IRMPD spectra display oligosaccharide fragments that are formed from primarily one type of diagnostic cleavage, thus making sequencing straightforward. The presence of sequential fragment ions, a phenomenon of IRMPD, permit the comprehensive sequencing of the oligosaccharides studied in a single stage of activation. We demonstrate this approach for two series of oligosaccharides, the lacto-N-fucopentaoses (LNFPs) and the lacto-N-difucohexaoses (LNDFHs).

  8. Nontargeted detection and identification of (aromatic) amines in environmental samples based on diagnostic derivatization and LC-high resolution mass spectrometry.

    PubMed

    Muz, Melis; Ost, Norbert; Kühne, Ralph; Schüürmann, Gerrit; Brack, Werner; Krauss, Martin

    2017-01-01

    The presence of aromatic amines in the environment has been in the focus of research, as many of these compounds are known or suspected mutagens and carcinogens. To facilitate the detection of aromatic amines in complex environmental samples by LC-high resolution mass spectrometry, an on-line-post-column and a pre-column derivatization method to label (in an ideal case) all aromatic amines was evaluated by applying different derivatization reagents. 4-Fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) was found to be the most promising labeling reagent due to its high reactivity with both primary and secondary amines and its low signal in positive mode electrospray ionization (ESI+). Post-column on-line derivatization did not result in sufficient signal intensities of derivatives. With pre-column derivatization most of the selected aromatic amines resulted in a derivative that shows common fragments of diagnostic value. The selectivity of NBD-F was studied in depth with a data set of 220 compounds with different functional groups showing that also aliphatic amines and some thiols yield a derivative. The developed method was successfully applied to wastewater effluent samples and several derivatives were confirmed by diagnostic neutral losses. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Derivatization of the tricarboxylic acid cycle intermediates and analysis by online solid-phase extraction-liquid chromatography-mass spectrometry with positive-ion electrospray ionization.

    PubMed

    Kloos, D; Derks, R J E; Wijtmans, M; Lingeman, H; Mayboroda, O A; Deelder, A M; Niessen, W M A; Giera, M

    2012-04-06

    The analysis of cellular metabolic processes is of fundamental biological interest. Cellular metabolites, such as the intermediates of the tricarboxylic acid (TCA) cycle, provide essential information about the metabolic state of the cell. Not only is the TCA cycle a key factor in the energy regulation within aerobic cells, it possibly also plays a role in cell signaling. This paper describes a novel derivatization strategy, using the empirically selected N-methyl-2-phenylethanamine as derivatization reagent with a carbodiimide as co-reagent, for the selective derivatization of carboxylic acids, such as the di- and tri-carboxylic acids of the TCA cycle. Optimization of the derivatization protocol is described. This procedure enables analysis of the derivatives using on-line solid-phase extraction and reversed-phase liquid chromatography in combination with sensitive positive-ion electrospray ionization mass spectrometry. The complete procedure, involving the use of core-shell silica column material, allows the rapid analysis of TCA cycle intermediates in sample matrices, here shown for pig heart tissue extracts, with a good linearity over 3-4 orders of magnitude. Detection limits range from 12 to 1000 nM, depending on the analyte. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Determination of atranol and chloroatranol in perfumes using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    López-Nogueroles, Marina; Chisvert, Alberto; Salvador, Amparo

    2014-05-15

    A new analytical method based on simultaneous derivatization and dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS), for the determination of the allergenic compounds atranol and chloroatranol in perfumes, is presented. Derivatization of the target analytes by means of acetylation with anhydride acetic in carbonate buffer was carried out. Thereby volatility and detectability were increased for improved GC-MS sensitivity. In addition, extractability by DLLME was also enhanced due to a less polar character of the solutes. A liquid-liquid extraction was performed before DLLME to clean up the sample and to obtain an aqueous sample solution, free of the low polar matrix from the essential oils, as donor phase. Different parameters, such as the nature and volume of both the extraction and disperser solvents, the ionic strength of the aqueous donor phase or the effect of the derivatization reagent volume, were optimized. Under the selected conditions (injection of a mixture of 750μL of acetone as disperser solvent, 100μL of chloroform as extraction solvent and 100μL of anhydride acetic as derivatization reagent) the figures of merit of the proposed method were evaluated. Limits of detection in the low ngmL(-1) range were obtained. Matrix effect was observed in real perfume samples and thus, standard addition calibration is recommended.

  11. Quantitative analysis of ripasudil hydrochloride hydrate and its impurities by reversed-phase high-performance liquid chromatography after precolumn derivatization: Identification of four impurities.

    PubMed

    Hui, Wenkai; Sun, Lili; Zhang, Hui; Zou, Liang; Zou, Qiaogen; Ouyang, Pingkai

    2016-09-01

    We report the development and validation of a stability-indicating reversed-phase high-performance liquid chromatography method with precolumn derivatization for the separation and identification of the impurities of ripasudil hydrochloride hydrate, a novel protein kinase inhibitor. 2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl isothiocyanate was chosen as the derivatizing reagent and triethylamine was added as catalyst. 200 μL sample solution (1 mg/mL), 600 μL derivatizing reagent (1 mg/mL), and 200 μL triethylamine solution (1%, v/v) were mixed and reacted at 40°C for 30 min. The separation was achieved on an Inertsil C18 ODS-3 (250 mm × 4.6 mm, 5 μm) column using mobile phases including 10 mmol monopotassium phosphate buffer (pH 3.0) and methanol in gradient mode. The column temperature was adjusted at 25°C and the flow rate at 1 mL/min. The detection was carried out at 220 nm. Different precolumn derivatization conditions as well as the high-performance liquid chromatography conditions were optimized. Ripasudil hydrochloride hydrate and its four impurities were detected and quantitated, among which two new compounds were characterized. The proposed method was validated and proven to be selective, accurate, and precise and suitable for the quantitative analysis of ripasudil hydrochloride hydrate.

  12. Chiral HPLC for a study of the optical purity of new liquid crystalline materials derived from lactic acid

    NASA Astrophysics Data System (ADS)

    Vojtylová, T.; Kašpar, M.; Hamplová, V.; Novotná, V.; Sýkora, D.

    2014-08-01

    New liquid crystalline (LC) materials were prepared by derivatization of lactic acid. First compound possesses the lactic acid unit as the only chiral center and the second group of LC materials contains two chiral centers. Mesomorphic properties of both the newly synthesized LC materials were studied and the presence of the SmA*-SmC* or exhibit the twist grain boundary (TGB) phases, namely TGBA and TGBC, in a wide range of temperatures down to the room temperature was established. The potential of high-performance liquid chromatography (HPLC) applying chiral stationary phases to separate enantiomers or diastereoisomers of the synthesized LC compounds was evaluated. Two different brands of commercial chiral sorbents, Lux Amylose-2 and Chiralpak AD-3, both based on modified silica with derivatized polysaccharide, were employed in the development of separation procedures. The optimized chiral HPLC method provided a baseline separation of the individual enantiomers for the LC material containing one chiral center. In the case of the more complex compound with two asymmetric carbon atoms, where four isomers exist, partial separation was reached only using the current chiral HPLC.

  13. Development of a polydimethylsiloxane-thymol/nitroprusside composite based sensor involving thymol derivatization for ammonium monitoring in water samples.

    PubMed

    Prieto-Blanco, M C; Jornet-Martínez, N; Moliner-Martínez, Y; Molins-Legua, C; Herráez-Hernández, R; Verdú Andrés, J; Campins-Falcó, P

    2015-01-15

    This report describes a polydimethylsiloxane (PDMS)-thymol/nitroprusside delivery composite sensor for direct monitoring of ammonium in environmental water samples. The sensor is based on a PDMS support that contains the Berthelot's reaction reagents. To prepare the PDMS-thymol/nitroprusside composite discs, thymol and nitroprusside have been encapsulated in the PDMS matrix, forming a reagent release support which significantly simplifies the analytical measurements, since it avoids the need to prepare derivatizing reagents and sample handling is reduced to the sampling step. When, the PDMS-thymol/nitroprusside composite was introduced in water samples spontaneous release of the chromophore and catalyst was produced, and the derivatization reaction took place to form the indothymol blue. Thus, qualitative analysis of NH4(+) could be carried out by visual inspection, but also, it can be quantified by measuring the absorbance at 690 nm. These portable devices provided good sensitivity (LOD<0.4 mg L(-1)) and reproducibility (RSD <10%) for the rapid detection of ammonium. The PDMS-NH4(+) sensor has been successfully applied to determine ammonium in water samples and in the aqueous extracts of particulate matter PM10 samples. Moreover, the reliability of the method for qualitative analysis has been demonstrated. Finally, the advantages of the PDMS-NH4(+) sensor have been examined by comparing some analytical and complementary characteristics with the properties of well-established ammonium determination methods.

  14. Separation of amino acids and antibiotics by narrow-bore and normal-bore high-performance liquid chromatography with pre-column derivatization.

    PubMed

    Fiedler, H P; Plaga, A

    1987-01-16

    The selectivity, efficiency and lifetime of normal- and narrow-bore columns for high-performance liquid chromatography were investigated for the separation and quantification of amino acids and the amino acid-like antibiotics phosphinothricin and phosphinothricylalanylalanine in biological samples. These compounds were determined by an automated pre-column derivatization with o-phthalaldehyde-2-mercaptoethanol reagent and UV detection at 338 nm.

  15. /sup 125/I-labeled crosslinking reagent that is hydrophilic, photoactivatable, and cleavable through an azo linkage

    SciTech Connect

    Denny, J.B.; Blobel, G.

    1984-09-01

    A radioactive crosslinking reagent, N-(4-(p-azido-m-(/sup 125/I)iodophenylazo)benzoyl)-3-aminopropyl-N'-oxysulfosuccinimide ester, has been synthesized. The reagent is photoactivatable, water-soluble, cleavable through an azo linkage, and labeled with /sup 125/I at the carrier-free specific activity of 2000 Ci/mmol. Any protein derivatized with the reagent is thus converted into an /sup 125/I-labeled photoaffinity probe. Crosslinks are formed following photolysis with 366-nm light, and cleavage by sodium dithionite results in the donation of radioactivity to the distal partner in crosslinked complexes. The newly labeled proteins are then analyzed by gel electrophoresis and autoradiography. The compound was prepared by iodination of N-(4-(p-aminophenylazo)benzoyl)-3-aminopropionic acid using carrier-free Na/sup 125/I and chloramine-T, followed by azide formation and conversion to the water-soluble sulfosuccinimide ester. As a model system, protein A-Sepharose was derivatized with the reagent under subdued light. Each derivatized protein A molecule contained only one crosslinker. The derivatized protein A-Sepharose was then photolyzed in the presence of human serum and subsequently treated with sodium dithionite. Analysis of the serum by gel electrophoresis revealed that 1.1% of the radioactive label originally present on the protein A-Sepharose was transferred to the heavy chain of IgG, which was the most intensely labeled protein in the gel. The next most intensely labeled protein was IgG light chain, which incorporated radioactivity that was lower by a factor of 3.6 than that of the heavy chain. 36 references, 3 figures.

  16. Simultaneous chiral analyses of multiple analytes: case studies, implications and method development considerations.

    PubMed

    Srinivas, Nuggehally R

    2004-12-01

    The field of chiral separations had a modest beginning some two decades ago. However, due to rapid technological advancement coupled with simultaneous availability of innovative chiral stationary phases and novel chiral derivatization agents, the field of chiral separations has now totally outpaced many other separation fields. Keeping pace with rapid changes in the field of chiral separations, investigators continue to add stereoselective pharmacokinetic, pharmacodynamic, pharmacologic and toxicological data of new and/or marketed racemic compounds to the literature. Examination of the evolution of chiral separations suggests that in the beginning many investigators attempted to separate and quantify a single pair of enantiomers, adopting either direct (separation made on a chiral stationary phase) or indirect (separation made following precolumn conversion of enantiomers to corresponding diastereomers) approaches. However, more recent trends in chiral separations suggest that investigators are attempting to separate and quantify multiple pairs of enantiomers with available technologies. Added to this, some interesting trends have been observed in many of the recently reported chiral applications, including preferences regarding internal standard selection, mobile phase contents and composition, sorting out issues with mass spectrometric detection, determination of elution order, analytical manipulations of metabolite(s) without reference standards and addressing some specificity-related issues. This review mainly focuses on chiral separations involving multiple chiral analytes and attempts to justify the need for such chiral separations involving multiple analytes. In this context, several cases studies are described on the utility and applicability of such chiral separations under discrete headings to provide an account to the readership on the implications of such tasks. The topics of case studies covered in this review include: (a) therapy markers

  17. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

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

  18. Synthesis of novel chiral imidazolium stationary phases and their enantioseparation evaluation by high-performance liquid chromatography.

    PubMed

    Wang, Tao; Yang, Haiyan; Qiu, Ruchen; Huang, Shaohua

    2016-11-09

    Two novel chiral stationary phases (CSPs) were prepared by bonding chiral imidazoliums on the surface of silica gel. The chiral imidazoles were derivatized from chiral amines, 1-phenylethylamine and 1-(1-naphthyl)ethylamine. The obtained CSPs were characterized by Fourier Transform Infrared (FT-IR) spectroscopy and elemental analysis (EA), demonstrating the bonding densities of CSP 1 and CSP 2 were 0.43 mmol g(-1) and 0.40 mmol g(-1), respectively. These two CSPs could be used to availably separate 8 pharmaceuticals, 7 mandelic acid/its derivatives, 2 1-phenylethylamine derivatives, 1 1,1'-bi-2-naphthol, and 1 camphorsulfonic acid in high-performance liquid chromatography (HPLC). It is found that CSP 1 could effectively enantioseparate most chiral analytes, especially the acidic components, while CSP 2 could enantiorecognize all chiral analytes, although a number of components did not achieve baseline separation. Additionally, the effects of mobile phase composition, mobile phase pH and salt content, chiral selector structures, and analyte structures on the enantiorecognitions of the two CSPs were investigated. It is found that high acetonitrile content in mobile phases was conducive to enantiorecognition. Mobile phase pH and salt content could alter the retention behaviors of different enantiomers of the same chiral compound, resulting in better enantioresolution. Moreover, both chiral selector structures and substituted groups of analytes played a significant role in the separation of chiral solutes.

  19. Determination of phenols in water samples by single-drop microextraction followed by in-syringe derivatization and gas chromatography-mass spectrometric detection.

    PubMed

    Saraji, Mohammad; Bakhshi, Mohsen

    2005-12-09

    Trace analysis of phenolic compounds in water was performed by coupling single-drop microextraction (SDME) with in-syringe derivatization of the analytes and GC-MS analysis. The analytes were extracted from a 3ml sample solution using 2.5microl of hexyl acetate. After extraction, derivatization was carried out in syringe barrel using 0.5microl of N,O-bis(trimethylsilyl)acetamide. The influence of derivatizing reagent volume, derivatization time and temperature on the yield of the in-syringe silylation was investigated. Derivatization reaction is completed in 5min at 50 degrees C. Experimental SDME parameters, such as selection of organic solvent, sample pH, addition of salt, extraction time and temperature of extraction were studied. Analytical parameters, such as enrichment factor, precision, linearity and detection limits were also determined. The limits of detection were in the range of 4-61ng/l (S/N=3). The relative standard deviations obtained were between 4.8 and 12% (n=5).

  20. Application of single-drop microextraction combined with in-microvial derivatization for determination of acidic herbicides in water samples by gas chromatography-mass spectrometry.

    PubMed

    Saraji, Mohammad; Farajmand, Bahman

    2008-01-18

    A single-drop microextraction (SDME) method and gas chromatography with mass spectrometry detection have been developed for the determination of acidic herbicides in water. The analytes were extracted from a 3 mL sample solution using 4 microL of hexyl acetate. After extraction, derivatization was carried out inside a glass microvial (1.1mm i.d.) using pentafluorobenzyl bromide (PFBBr). Triethylamine (TEA) was used as the reaction catalyst. The influence of derivatization reagent volume, catalyst amount, derivatization time and temperature on the yield of the in-microvial derivatization was investigated. Derivatization reaction was performed using 0.3 microL of PFBBr and 0.4 microL of TEA (10%, v/v in toluene) at 100 degrees C during 5 min. Also, the effects of different experimental SDME parameters such as selection of organic solvent, sample pH, addition of salt, extraction time and temperature of extraction were studied. Analytical parameters such as enrichment factor, precision, linearity and detection limits were also determined. The enrichment factors were between 83 and 157. The limits of detection (LOD) were in the range 1.2-7 ng/L (S/N=3). The relative standard deviations obtained were below 10.1% (n=5).

  1. Microwave-assisted one-step extraction-derivatization for rapid analysis of fatty acids profile in herbal medicine by gas chromatography-mass spectrometry.

    PubMed

    Liu, Rui-Lin; Zhang, Jing; Mou, Zhao-Li; Hao, Shuang-Li; Zhang, Zhi-Qi

    2012-11-07

    A rapid and practical microwave-assisted one-step extraction-derivatization (MAED) method was developed for gas chromatography-mass spectrometry analysis of fatty acids profile in herbal medicine. Several critical experimental parameters for MAED, including reaction temperature, microwave power and the amount of derivatization reagent (methanol), were optimized with response surface methodology. The results showed that the chromatographic peak areas of total fatty acids and total unsaturated fatty acids content obtained with MAED were markedly higher than those obtained by the conventional Soxhlet or microwave extraction and then derivatization method. The investigation of kinetics and thermodynamics of the derivatization reaction revealed that microwave assistance could reduce activation energy and increase the Arrhenius pre-exponential factor. The MAED method simplified the sample preparation procedure, shortened the reaction time, but improved the extraction and derivatization efficiency of lipids and reduced ingredient losses, especially for the oxidization and isomerization of unsaturated fatty acids. The simplicity, speed and practicality of this method indicates great potential for high throughput analysis of fatty acids in natural medicinal samples.

  2. Understanding complex chiral plasmonics

    NASA Astrophysics Data System (ADS)

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-10-01

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant

  3. Microwave-assisted on-spot derivatization for gas chromatography-mass spectrometry based determination of polar low molecular weight compounds in dried blood spots.

    PubMed

    Sadones, Nele; Van Bever, Elien; Archer, John R H; Wood, David M; Dargan, Paul I; Van Bortel, Luc; Lambert, Willy E; Stove, Christophe P

    2016-09-23

    Dried blood spot (DBS) sampling and analysis is increasingly being applied in bioanalysis. Although the use of DBS has many advantages, it is also associated with some challenges. E.g. given the limited amount of available material, highly sensitive detection techniques are often required to attain sufficient sensitivity. In gas chromatography coupled to mass spectrometry (GC-MS), derivatization can be helpful to achieve adequate sensitivity. Because this additional sample preparation step is considered as time-consuming, we introduce a new derivatization procedure, i.e. "microwave-assisted on-spot derivatization", to minimize sample preparation of DBS. In this approach the derivatization reagents are directly applied onto the DBS and derivatization takes place in a microwave instead of via conventional heating. In this manuscript we evaluated the applicability of this new concept of derivatization for the determination of two polar low molecular weight molecules, gamma-hydroxybutyric acid (GHB) and gabapentin, in DBS using a standard GC-MS configuration. The method was successfully validated for both compounds, with imprecision and bias values within acceptance criteria (<20% at LLOQ, <15% at 3 other QC levels). Calibration lines were linear over the 10-100μg/mL and 1-30μg/mL range for GHB and gabapentin, respectively. Stability studies revealed no significant decrease of gabapentin and GHB in DBS upon storage at room temperature for at least 84 days. Furthermore, DBS-specific parameters, including hematocrit and volume spotted, were evaluated. As demonstrated by the analysis of GHB and gabapentin positive samples, "microwave-assisted on-spot derivatization" proved to be reliable, fast and applicable in routine toxicology. Moreover, other polar low molecular weight compounds of interest in clinical and/or forensic toxicology, including vigabatrin, beta-hydroxybutyric acid, propylene glycol, diethylene glycol, 1,4-butanediol and 1,2-butanediol, can also be

  4. A smog chamber comparison of a microfluidic derivatization measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques

    NASA Astrophysics Data System (ADS)

    Pang, X.; Lewis, A. C.; Richard, A.; Baeza-Romero, M. T.; Adams, T. J.; Ball, S. M.; Daniels, M. J. S.; Goodall, I. C. A.; Monks, P. S.; Peppe, S.; Ródenas García, M.; Sánchez, P.; Muñoz, A.

    2013-06-01

    A microfluidic lab-on-a-chip derivatization technique has been developed to measure part per billion volume (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method compared with other techniques in a smog chamber experiment. The method uses o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatization reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor result in a fast and highly efficient derivatization reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatized under optimal reaction conditions. The method detection limits (MDLs) were 80 pptV and 200 pptV for GLY and MGLY respectively, calculated as 3 times the standard deviation of the S/N of the blank sample chromatograms. These MDLs are below or close to typical concentrations in clean ambient air. The feasibility of the technique was assessed by applying the methodology under controlled conditions to quantify of α-dicarbonyls formed during the photo-oxidation of isoprene in a large scale outdoor atmospheric simulation chamber (EUPHORE). Good general agreement was seen between microfluidic measurements and Fourier Transform Infra Red (FTIR), Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) and a detailed photochemical chamber box modelling calculation for both GLY and MGLY. Less good agreement was found with Proton-Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) and Solid Phase Microextraction (SPME) derivatization methods for MGLY measurement.

  5. Hydrazide and hydrazine reagents as reactive matrices for MALDI-MS to detect gaseous aldehydes.

    PubMed

    Shigeri, Yasushi; Ikeda, Shinya; Yasuda, Akikazu; Ando, Masanori; Sato, Hiroaki; Kinumi, Tomoya

    2014-08-01

    The reagents 19 hydrazide and 14 hydrazine were examined to function as reactive matrices for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to detect gaseous aldehydes. Among them, two hydrazide (2-hydroxybenzohydrazide and 3-hydroxy-2-naphthoic acid hydrazide) and two hydrazine reagents [2-hydrazinoquinoline and 2,4-dinitrophenylhydrazine (DNPH)] were found to react efficiently with carbonyl groups of gaseous aldehydes (formaldehyde, acetaldehyde and propionaldehyde); these are the main factors for sick building syndrome and operate as reactive matrices for MALDI-MS. Results from accurate mass measurements by JMS-S3000 Spiral-TOF suggested that protonated ion peaks corresponding to [M + H](+) from the resulting derivatives were observed in all cases with the gaseous aldehydes in an incubation, time-dependent manner. The two hydrazide and two hydrazine reagents all possessed absorbances at 337 nm (wavelength of MALDI nitrogen laser), with, significant electrical conductivity of the matrix crystal and functional groups, such as hydroxy group and amino group, being important for desorption/ionization efficiency in MALDI-MS. To our knowledge, this is the first report that gaseous molecules could be derivatized and detected directly in a single step by MALDI-MS using novel reactive matrices that were derivatizing agents with the ability to enhance desorption/ionization efficiency.

  6. Gelation induced supramolecular chirality: chirality transfer, amplification and application.

    PubMed

    Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

    2014-08-14

    Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

  7. Another side of the oxazaphospholidine oxide chiral ortho-directing group.

    PubMed

    Martins, Nelson; Mateus, Nuno; Vinci, Daniele; Saidi, Ourida; Brigas, Amadeu; Bacsa, John; Xiao, Jianliang

    2012-05-28

    A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring. The X-ray structures of the compounds 2 and 3 as well as those of the new 1,2-ferrocenes 4 and 7 have been determined.

  8. Metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates: construction of chiral nonracemic allylic isocyanates.

    PubMed

    Grange, Rebecca L; Evans, P Andrew

    2014-08-27

    We report the facile and efficient metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates. This process facilitates the room temperature construction of an array of chiral nonracemic allylic isocyanates, which are versatile intermediates for the construction of unsymmetrical ureas, carbamates, thiocarbamates and amides. Furthermore, the sulfilimine/isocyanate metathesis reaction with 4,4'-methylene diphenyl diisocyanate (4,4'-MDI) circumvents harsh reaction conditions and/or hazardous reagents employed with more classical methods for the preparation of this important functional group.

  9. Cu-catalyzed enantioselective allylic alkylation with organolithium reagents.

    PubMed

    Hornillos, Valentín; Guduguntla, Sureshbabu; Fañanás-Mastral, Martín; Pérez, Manuel; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L

    2017-03-01

    This protocol describes a method for the catalytic enantioselective synthesis of tertiary and quaternary carbon stereogenic centers, which are widely present in pharmaceutical and natural products. The method is based on the direct reaction between organolithium compounds, which are cheap, readily available and broadly used in chemical synthesis, and allylic electrophiles, using chiral copper catalysts. The methodology involves the asymmetric allylic alkylation (AAA) of allyl bromides, chlorides and ethers with organolithium compounds using catalyst systems based on Cu-Taniaphos and Cu-phosphoramidites. The protocol contains a complete description of the reaction setup, a method based on (1)H-NMR, gas chromatography-mass spectrometry (GC-MS) and chiral HPLC for assaying the regioselectivity and enantioselectivity of the product, and isolation, purification and characterization procedures. Six Cu-catalyzed AAA reactions between different organolithium reagents and allylic systems are detailed in the text as representative examples of these procedures. These reactions proceed within 1-10 h, depending on the nature of the allylic substrate (bromide, chloride, or ether and disubstituted or trisubstituted) or the chiral ligand used (Taniaphos or phosphoramidite). However, the entire protocol, including workup and purification, generally requires an additional 4-7 h to complete.

  10. Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

    PubMed

    Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

    2015-01-21

    Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

  11. Chiral separation of lipoxygenase metabolites utilizing high-performance liquid chromatography.

    PubMed

    Myrdal, Paul B; Angersbach, B Steven; Karlage, Kelly; Kuehl, Philip J

    2006-11-03

    An isocratic, reversed-phase HPLC assay has been developed for the separation of the enantiomers of four lipoxygenase metabolites, without the need for a derivatization step. Separation of the enantiomers was studied on a polysaccharide type chiral stationary phase column. Upon determination of suitable mobile phase composition, the assay was evaluated at various temperatures. In all cases the R enantiomer eluted before the S enantiomer. The best separations were observed at 0 degrees C.

  12. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

    Cameron, Robert P.; Götte, Jörg B.; Barnett, Stephen M.

    2016-09-01

    We introduce chiral rotational spectroscopy, a technique that enables the determination of the orientated optical activity pseudotensor components BX X, BY Y, and BZ Z of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centers. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarizability components αX X, αY Y, and αZ Z as by-products, which could see it find use even for achiral molecules.

  13. Emerging chirality in nanoscience.

    PubMed

    Wang, Yong; Xu, Jun; Wang, Yawen; Chen, Hongyu

    2013-04-07

    Chirality in nanoscience may offer new opportunities for applications beyond the traditional fields of chirality, such as the asymmetric catalysts in the molecular world and the chiral propellers in the macroscopic world. In the last two decades, there has been an amazing array of chiral nanostructures reported in the literature. This review aims to explore and categorize the common mechanisms underlying these systems. We start by analyzing the origin of chirality in simple systems such as the helical spring and hair vortex. Then, the chiral nanostructures in the literature were categorized according to their material composition and underlying mechanism. Special attention is paid to highlight systems with original discoveries, exceptional structural characteristics, or unique mechanisms.

  14. Chiral fluctuations in achiral systems

    NASA Astrophysics Data System (ADS)

    Harris, Robert A.

    2001-12-01

    "Chiral fluctuations" are defined, and their relation to "dynamic chirality" is discussed. Simple experiments to measure chiral fluctuations are proposed. The unique aspects of these measurements for systems such as atomic clusters and gases are outlined.

  15. Densitometric determination of (+)-catechin and (-)-epicatechin by 4-dimethylaminocinnamaldehyde reagent.

    PubMed

    Glavnik, Vesna; Simonovska, Breda; Vovk, Irena

    2009-05-15

    We report the optimization of a sensitive, selective and robust derivatization method using 4-dimethylaminocinnamaldehyde (DMACA) for densitometric determination of (+)-catechin and (-)-epicatechin. The separation of these compounds was achieved by thin-layer chromatography (TLC) on cellulose plates developed with water. With DMACA in HCl, both compounds gave blue bands, while under the same conditions, vanillin produced a fast fading red coloration of bands. Quantitation at 655nm showed that for both compounds the calibration curve was linear from 2 to 12ng and polynomial from 2 to 30ng, and the repeatability of chromatography of 20ng was 3.5% (RSD, n=6). The visible limit of detection of both standards was 1ng, but the densitometric limit of detection was lower (0.2ng). The optimized DMACA reagent is superior to the more frequently used vanillin reagent and is applicable also for determination of mixtures containing other catechins ((-)-catechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, procyanidin A2, procyanidin B1 and procyanidin B2).

  16. Palladium(II)-catalyzed enantioselective C(sp³)-H activation using a chiral hydroxamic acid ligand.

    PubMed

    Xiao, Kai-Jiong; Lin, David W; Miura, Motofumi; Zhu, Ru-Yi; Gong, Wei; Wasa, Masayuki; Yu, Jin-Quan

    2014-06-04

    An enantioselective method for Pd(II)-catalyzed cross-coupling of methylene β-C(sp(3))-H bonds in cyclobutanecarboxylic acid derivatives with arylboron reagents is described. High yields and enantioselectivities were achieved through the development of chiral mono-N-protected α-amino-O-methylhydroxamic acid (MPAHA) ligands, which form a chiral complex with the Pd(II) center. This reaction provides an alternative approach to the enantioselective synthesis of cyclobutanecarboxylates containing α-chiral quaternary stereocenters. This new class of chiral catalysts also show promises for enantioselective β-C(sp(3))-H activation of acyclic amides.

  17. Periodic chiral structures

    NASA Technical Reports Server (NTRS)

    Jaggard, Dwight L.; Engheta, Nader; Pelet, Philippe; Liu, John C.; Kowarz, Marek W.; Kim, Yunjin

    1989-01-01

    The electromagnetic properties of a structure that is both chiral and periodic are investigated using coupled-mode equations. The periodicity is described by a sinusoidal perturbation of the permittivity, permeability, and chiral admittance. The coupled-mode equations are derived from physical considerations and used to examine bandgap structure and reflected and transmitted fields. Chirality is observed predominantly in transmission, whereas periodicity is present in both reflection and transmission.

  18. Planar plasmonic chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-01

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

  19. Absolute structure determination of compounds with axial and planar chirality using the crystalline sponge method† †Electronic supplementary information (ESI) available: Details of sample preparation and crystallographic analysis. CCDC 1051799, 1051800, 1051618, 1051619, 1043948 and 1043949. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01681a Click here for additional data file. Click here for additional data file.

    PubMed Central

    Yoshioka, Shota; Inokuma, Yasuhide; Hoshino, Manabu; Sato, Takashi

    2015-01-01

    The absolute stereochemistry of compounds with axial and planar chirality is successfully determined by the crystalline sponge method without crystallization or derivatization of the compounds. This method is applied to absolute structure determination in the asymmetric synthesis of unique compounds with axial and planar chirality. PMID:28706719

  20. Characterizing optical chirality

    SciTech Connect

    Bliokh, Konstantin Y.; Nori, Franco

    2011-02-15

    We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

  1. Chiral atomically thin films.

    PubMed

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

    2016-06-01

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

  2. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. Catalytic wateroxidation on derivatized nanoITO

    SciTech Connect

    Chen, Zuofeng; Concepcion, Javier J; Hull, Jonathan F; Hoertz, Paul G.; Meyer, Thomas J.

    2010-06-22

    Electrocatalytic water oxidation occurs on high surface area, nanocrystalline ITO (nanoITO) surface-derivatized by phosphonate-binding of the catalyst [Ru(Mebimpy)(4,4'-((HO)2OPCH2)2bpy)(OH2)]2+ (Mebimpy is 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy is 2,2'-bipyridine). With nanoITO, spectral data can be acquired on electrochemically generated intermediates and voltammograms monitored spectrophotometrically.

  4. Highly diastereoselective dioxetane formation in the photooxygenation of enecarbamates with an oxazolidinone chiral auxiliary: steric control in the [2 + 2] cycloaddition of singlet oxygen through conformational alignment.

    PubMed

    Adam, Waldemar; Bosio, Sara G; Turro, Nicholas J

    2002-07-31

    The photooxygenation of oxazolidinone-substituted enecarbamates leads to diastereomerically pure dioxetanes. The high diastereoselectivity is rationalized in terms of effective pi-facial control achieved by shielding one side of the double bond with the chiral auxiliary. The absolute configuration of the dioxetanes is assigned by derivatization to diols.

  5. 21 CFR 1271.210 - Supplies and reagents.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... supply or reagent, or by the vendor of the supply or reagent. (b) Reagents. Reagents used in processing... supply or reagent, including the type, quantity, manufacturer, lot number, date of receipt, and...

  6. Chemical Amplification with Encapsulated Reagents

    NASA Technical Reports Server (NTRS)

    Chen, Jian; Koemer, Steffi; Craig, Stephen; Lin, Shirley; Rudkevich, Dmitry M.; Rebek, Julius, Jr.

    2002-01-01

    Autocatalysis and chemical amplification are characteristic properties of living systems, and they give rise to behaviors such as increased sensitivity, responsiveness, and self-replication. Here we report a synthetic system in which a unique form of compartmentalization leads to nonlinear, autocatalytic behavior. The compartment is a reversibly formed capsule in which a reagent is sequestered. Reaction products displace the reagent from the capsule into solution and the reaction rate is accelerated. The resulting self-regulation is sensitive to the highly selective molecular recognition properties of the capsule.

  7. Chemical Amplification with Encapsulated Reagents

    NASA Technical Reports Server (NTRS)

    Chen, Jian; Koemer, Steffi; Craig, Stephen; Lin, Shirley; Rudkevich, Dmitry M.; Rebek, Julius, Jr.

    2002-01-01

    Autocatalysis and chemical amplification are characteristic properties of living systems, and they give rise to behaviors such as increased sensitivity, responsiveness, and self-replication. Here we report a synthetic system in which a unique form of compartmentalization leads to nonlinear, autocatalytic behavior. The compartment is a reversibly formed capsule in which a reagent is sequestered. Reaction products displace the reagent from the capsule into solution and the reaction rate is accelerated. The resulting self-regulation is sensitive to the highly selective molecular recognition properties of the capsule.

  8. Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

    PubMed

    Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

    2006-01-01

    Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented.

  9. SITS Derivatization of Peptides to Enhance 266 nm Ultraviolet Photodissociation (UVPD)

    NASA Astrophysics Data System (ADS)

    Quick, M. Montana; Mehaffey, M. Rachel; Johns, Robert W.; Parker, W. Ryan; Brodbelt, Jennifer S.

    2017-07-01

    N-terminal derivatization of peptides with the chromogenic reagent 4-acetamido-4-isothiocyanatostilbene-2,2-disulfonic acid (SITS) is demonstrated to enhance the efficiency of 266 nm ultraviolet photodissociation (UVPD). Attachment of the chromophore results in a mass shift of 454 Da and provides significant gains in the number and abundances of diagnostic fragment ions upon UVPD. Activation of SITS-tagged peptides with 266 nm UVPD leads to many fragment ions akin to the a/b/y ions commonly produced by CID, along with other sequence ions ( c, x, and z) typically accessed through higher energy pathways. Extreme bias towards C-terminal fragment ions is observed upon activation of SITS-tagged peptides using multiple 266 nm laser pulses. Due to the high reaction efficiency of the isothiocyanate coupling to the N-terminus of peptides, we demonstrate the ability to adapt this strategy to a high-throughput LC-MS/MS workflow with 266 nm UVPD.

  10. SITS Derivatization of Peptides to Enhance 266 nm Ultraviolet Photodissociation (UVPD)

    NASA Astrophysics Data System (ADS)

    Quick, M. Montana; Mehaffey, M. Rachel; Johns, Robert W.; Parker, W. Ryan; Brodbelt, Jennifer S.

    2017-03-01

    N-terminal derivatization of peptides with the chromogenic reagent 4-acetamido-4-isothiocyanatostilbene-2,2-disulfonic acid (SITS) is demonstrated to enhance the efficiency of 266 nm ultraviolet photodissociation (UVPD). Attachment of the chromophore results in a mass shift of 454 Da and provides significant gains in the number and abundances of diagnostic fragment ions upon UVPD. Activation of SITS-tagged peptides with 266 nm UVPD leads to many fragment ions akin to the a/b/y ions commonly produced by CID, along with other sequence ions (c, x, and z) typically accessed through higher energy pathways. Extreme bias towards C-terminal fragment ions is observed upon activation of SITS-tagged peptides using multiple 266 nm laser pulses. Due to the high reaction efficiency of the isothiocyanate coupling to the N-terminus of peptides, we demonstrate the ability to adapt this strategy to a high-throughput LC-MS/MS workflow with 266 nm UVPD.

  11. Residue determination of glyphosate in environmental water samples with high-performance liquid chromatography and UV detection after derivatization with 4-chloro-3,5-dinitrobenzotrifluoride.

    PubMed

    Qian, Kun; Tang, Tao; Shi, Tianyu; Wang, Fang; Li, Jianqiang; Cao, Yongsong

    2009-03-09

    A pre-column derivatization high-performance liquid chromatographic method for glyphosate analysis has been developed. Derivatization of glyphosate was performed with 4-chloro-3,5-dinitrobenzotrifluoride (CNBF). In pH 9.5 H(3)BO(3)-Na(2)B(4)O(7) media, the reaction of glyphosate with CNBF completed at 60 degrees C for 30min. The labeled glyphosate was separated on a Kromasil C18 column (250mmx4.6mm, 5microm) at room temperature and UV detection was applied at 360nm. The separation of labeled glyphosate was achieved within 15min by gradient elution mode. Compared to other pre-column derivatization, this derivatization was performed more mildly, the derivative was more stable, and the detection limits of a few reagents were higher than CNBF, except 9-fluorenylmethyl chloroformate (FMOC-Cl) using fluorescence and mass spectrometry, however, this reagent avoid to be removed after derivatization like FMOC-Cl. The detection limit of glyphosate was 0.009mgL(-1) (S/N=3) without preconcentration and reach MRL, which is set at the level of 0.1mgL(-1) in China. The method linearity correlation coefficient was 0.9999, in concentrations ranging from 0.3 to 48.5mgL(-1). The proposed method has been applied to the quantitative determination of glyphosate in environmental water with recoveries of 91.80-100.20% and R.S.D. of 2.27-6.80, depending on the sample investigated.

  12. [Determination of fumonisins B1 and B2 in corn by high performance liquid chromatography with post-column derivatization method].

    PubMed

    Zhang, Xiaoxu; Xiao, Zhiyong; Zhang, Hongyan; Yang, Lili; Ma, Liyan

    2012-08-01

    A high performance liquid chromatography-fluorescence detection with post-column derivatization method was developed to detect fumonisin B1 (FB1) and fumonisin B2 (FB2) in corn. Several factors, such as the pH of derivatization buffer, concentration and flow rate of derivatization reagents, excitation wavelength, emission wavelength, which affected the detection of fumonisins were optimized. The separation was performed on a ZORBAX SB C18 column operated at 40 degrees C with the gradient elution by two mobile phases of 0.1 mol/L sodium dihydrogen phosphate solution (pH 3.3) and methanol at a flow rate of 0.8 mL/min. The derivatization was performed at ambient temperature. The o-phthalaldehyde (OPA) flow rate was 0.4 mL/min. The results showed that the optimum conditions were pH 10.5 of the derivatization reagent, OPA concentration at 2 g/L, and excitation wavelength of 335 nm, emission wavelength of 440 nm. The linear plots of FB1 and FB2 were obtained between 0.2 to 20 mg/L, with the correlation coefficients above 0.999 for both FB1 and FB2. The limits of detection of fumonisins B1 and B2 were 0.02 mg/kg. The mean recoveries at the three spiked levels of 0.1 - 4.0 mg/kg were 82.5% - 89.8%. This method is accurate, simple, rapid and suitable for the determination of fumonisins B1 and B2 in corn.

  13. Photorefractive effect in ferroelectric liquid crystal blends containing terthiophene photoconductive chiral dopants

    NASA Astrophysics Data System (ADS)

    Sasaki, Takeo; Yoshino, Masanori

    2016-04-01

    Ferroelectric liquid crystalline mixtures composed of a smectic liquid crystal, a photoconductive chiral dopant, and an electron trap reagent exhibit a large photorefractivity with a rapid response. It is expected that the photorefractive FLC blends can be utilized in dynamic amplification of moving optical signals. In the present study, the photorefractive properties of the ferroelectric liquid crystal blends containing different photoconductive chiral dopants were examined. The durability of the photoconductive chiral dopants during laser irradiation was investigated. Tthe effect of the conduction of photogenerated ionic species on the photorefractivity decay was clarified.

  14. A method for the measurement of atmospheric HONO based on DNPH derivatization and HPLC analysis

    SciTech Connect

    Zhou, X.; Qiao, H.; Deng, G.; Civerolo, K.

    1999-10-15

    A simple measurement technique was developed for atmospheric HONO based on aqueous scrubbing using a coil sampler followed by 2,4-dinitrophenylhydrazine (DNPH) derivatization and high-performance liquid chromatographic (HPLC) analysis. Quantitative sampling efficiency was obtained using a 1 mM phosphate buffer, pH 7.0, as the scrubbing solution at a gas sampling flow rate of 2 L min{sup {minus}1} and a liquid flow rate of 0.24 mL min{sup {minus}1}. Derivation of the scrubbed nitrous acid by DNPH was fast and was completed within 5 min in a derivatization medium containing 300 {micro}M DNPH and 8 mM HCI at 45 C. The azide derivative was separated from DNPH reagent and carbonyl derivatives by reverse-phase HPLC and was detected with an UV detector at 309 nm. The detection limit is {le}5 pptv and may be lowered to 1 pptv with further DNPH purification. Interferences from NO, NO{sub 2} PAN, O{sub 3}, HNO{sub 3}, and HCHO were studied and found to be negligible. Ambient HONO concentration was measured simultaneously in downtown Albany, NY, by this method and by an ion chromatographic technique after sampling using a fritted bubbler. The results, from 70 pptv during the day to 1.7 ppbv in the early morning, were in very good agreement from the two techniques, within {+-} 20%.

  15. Fixed bed reactor for solid-phase surface derivatization of superparamagnetic nanoparticles.

    PubMed

    Steitz, Benedikt; Salaklang, Jatuporn; Finka, Andrija; O'Neil, Conlin; Hofmann, Heinrich; Petri-Fink, Alke

    2007-01-01

    The functionalization of nanoparticles is conditio sine qua non in studies of specific interaction with a biological target. Often, their biological functionality is achieved by covalent binding of bioactive molecules on a preexisting single surface coating. The yield and quality of the resulting coated and functionalized superparamagnetic iron oxide nanoparticles (SPIONs) can be significantly improved and reaction times reduced by using solid-phase synthesis strategies. In this study, a fixed bed reactor with a quadrupole repulsive arrangement of permanent magnets was assayed for SPION surface derivatization. The magnet array around the fixed bed reactor creates very high magnetic field gradients that enables the immobilization of SPIONs with a diameter as low as 9 nm. The functionalization on the surface of immobilized 25 nm 3-(aminopropyl)trimethoxysilane-coated SPIONs (APS-SPIONs) was performed using fluorescein-isothiocyanate directly, and by the SV40 large T-antigen nuclear localization signal peptide (PKKKRKVGC) conjugated to acryloylpoly(ethylene glycol)-N-hydroxysuccinimide, where the PEG reagent is conjugated first to create a functionalized nanoparticle and the peptide is added to the acryloyl group. We show that the yield of reactant grafted on the surface of the APS-coated SPIONs was higher in solid-phase within the fixed bed reactor compared to conventional liquid-phase chemistry. In summary, the functionalization of SPIONs using a magnetically fixed bed reactor was superior to the liquid-phase reaction in terms of the yield, reaction times required for derivatization, size distribution, and scalability.

  16. Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane.

    PubMed

    Nyholm, Jenny Rattfelt; Gustafsson, Tomas; Östin, Anders

    2013-07-01

    Nerve agents are a class of organophosphorous chemicals that are prohibited under the Chemical Weapons Convention. Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non-volatile and very polar, their identification by GC-MS requires a derivatization step prior to analysis. Standard derivatization methods for gas-chromatography electron-impact mass-spectrometry analysis give very similar spectra for many alkyl phosphonic acid isomers, which complicates the identification process. We present a new reagent, 3-pyridyldiazomethane, for preparing picolinyl ester derivatives of alkyl methylphosphonic acids facilitating the determination of their structure by enhancing predictable fragmentation of the O-alkyl chain. This fragmentation is directed by the nitrogen nucleus of the pyridyl moiety that abstracts hydrogen from the O-alkyl chain, inducing radical cleavage of the carbon-carbon bonds and thereby causing extensive fragmentation that can be used for detailed structure elucidation of the O-alkyl moiety. The separability of related isomers was tested by comparing the spectra of the picolinyl esters formed from twelve hexyl methylphosphonic acid isomers. Spectral library matches and principal component analysis showed that the picolinyl esters were more effectively separated than the corresponding trimethylsilyl derivatives used in the standard operating procedures. The suggested method will improve the unambiguous structural determination process for phosphonic acids. Copyright © 2013 John Wiley & Sons, Ltd.

  17. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds.

    PubMed

    Silva, Márcio S

    2017-02-07

    Nuclear magnetic resonance (NMR) is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to ¹H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear ((19)F, (31)P, (13)C, and (77)Se) NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

  18. Chiral magnetic superconductivity

    NASA Astrophysics Data System (ADS)

    Kharzeev, Dmitri E.

    2017-03-01

    Materials with charged chiral quasiparticles in external parallel electric and magnetic fields can support an electric current that grows linearly in time, corresponding to diverging DC conductivity. From experimental viewpoint, this "Chiral Magnetic Superconductivity" (CMS) is thus analogous to conventional superconductivity. However the underlying physics is entirely different - the CMS does not require a condensate of Cooper pairs breaking the gauge degeneracy, and is thus not accompanied by Meissner effect. Instead, it owes its existence to the (temperature-independent) quantum chiral anomaly and the conservation of chirality. As a result, this phenomenon can be expected to survive to much higher temperatures. Even though the chirality of quasiparticles is not strictly conserved in real materials, the chiral magnetic superconductivity should still exhibit itself in AC measurements at frequencies larger than the chirality-flipping rate, and in microstructures of Dirac and Weyl semimetals with thickness below the mean chirality-flipping length that is about 1 - 100 μm. In nuclear physics, the CMS should contribute to the charge-dependent elliptic flow in heavy ion collisions.

  19. Superenantioselective chiral surface explosions.

    PubMed

    Gellman, Andrew J; Huang, Ye; Feng, Xu; Pushkarev, Vladimir V; Holsclaw, Brian; Mhatre, Bharat S

    2013-12-26

    Chiral inorganic materials predated life on Earth, and their enantiospecific surface chemistry may have played a role in the origins of biomolecular homochirality. However, enantiospecific differences in the interaction energies of chiral molecules with chiral surfaces are small and typically lead to modest enantioselectivities in adsorption, catalysis, and chemistry on chiral surfaces. To yield high enantioselectivities, small energy differences must be amplified by reaction mechanisms such as autocatalytic surface explosions which have nonlinear kinetics. Herein, we report the first observations of superenantiospecificity resulting from an autocatalytic surface explosion reaction of a chiral molecule on a naturally chiral surface. R,R- and S,S-tartaric acid decompose via a vacancy-mediated surface explosion mechanism on Cu single crystal surfaces. When coupled with surface chirality, this leads to decomposition rates that exhibit extraordinarily high enantiospecificity. On the enantiomorphs of naturally chiral Cu(643)(R&S), Cu(17,5,1)(R&S), Cu(531)(R&S) and Cu(651)(R&S) single crystal surfaces, R,R- and S,S-tartaric acid exhibit enantiospecific decomposition rates that differ by as much as 2 orders of magnitude, despite the fact that the effective rates constants for decomposition differ by less than a factor of 2.

  20. [Supplies: inventory control and reagents].

    PubMed

    Szymanowicz, A

    2013-06-01

    The main relevant features useful for the management of reagents and consumables as well as documents to be developed to meet the requirements of the accreditation standard ISO/FDIS 15189-2012 are listed. This article is intended to help the medical laboratory to get mandatory accreditation.

  1. RESEARCH NOTE: INTERFERENCES DUE TO OZONE-SCAVENGING REAGENTS IN THE GC-ECD DETERMINATION OF ALDEHYDES AND KETONS AS THE O-(2,3,4,5,6-PENTAFLUOROBENZYL)OXIMES

    EPA Science Inventory

    Six potential ozone-scavenging reagents were tested for possible interference in the GC-ECD determination of aldehydes and ketones after derivatization with O-(2,3,4,5,6-pentafluorobenzyl)oxylamine (PFBOA). All six-nitrite, cynaide, methanoate (formate), indigo-55'-disulfonate d...

  2. Self-replication and amplification of enantiomeric excess of chiral multifunctionalized large molecules by asymmetric autocatalysis.

    PubMed

    Kawasaki, Tsuneomi; Nakaoda, Mai; Takahashi, Yutaro; Kanto, Yusuke; Kuruhara, Nanako; Hosoi, Kenji; Sato, Itaru; Matsumoto, Arimasa; Soai, Kenso

    2014-10-13

    Self-replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self-replicating and self-improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction.

  3. On-Line Derivatization Gas Chromatography Ion Trap Mass Spectrometry for Determination of Endocrine Disruptors in Surface Water

    SciTech Connect

    Tzing, Shin-Hwa; Chang, Jia-Yaw; Ling, Yong-Chien

    2004-03-31

    A method has been developed for the determination of endocrine disruptors (EDs) (containing hydroxyl groups) in surface water from different sources. The surface water samples from different sites including school and local dormitory sewage effluents, lake water and river water were collected and analyzed. In this method, the pretreated sample is directly analyzed by GC-MS using on-line derivatization, where tetramethylammonium hydroxide (TMA-OH) was used as the derivatizing agent. Use of large-volume direct sample introduction (DSI) and co-injection of the sample and TMAOH avoids external contaminations as observed in conventional derivatization protocols. Additionally, the use of chemical ionization (CI) and CI-MS/MS could enable detection of EDs at lower concentrations and reduce the matrices' interference thereby enhancing detection sensitivity of EDs for quantification. In this work, the use of dichloromethane as CI reagent for EDs is reported for the first time and could detect EDs to concentrations as low as 0.5 pg/mL. The recovery ranged from 74 to 112 % and the relative standard derivations for replicate analyses ranged from 5 to 17 %. We hope that this method will be applicable for routine analysis of EDs with hydroxyl functional groups.

  4. Simultaneous determination of HFBA-derivatized amphetamines and ketamines in urine by gas chromatography-mass spectrometry.

    PubMed

    Lee, Hei Hwa; Lee, Jong Feng; Lin, Sin Yu; Chen, Ping Ho; Chen, Bai Hsiun

    2011-04-01

    To facilitate the analysis of targeted drugs under high sample volume testing environment, an extraction, derivatization and gas chromatographic-mass spectrometric analysis method was developed for simultaneously determination of amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDEA), ketamine, and norketamine in urine. This method utilized solid-phase extraction in conjunction with derivatization using heptafluorobutyric anhydride (HFBA) as the derivatization reagent. Using a 1-mL sample, the limits of quantitation achieved for the analysis of AMP, MAMP, MDA, MDMA, MDEA, ketamine, and norketamine were 25, 15, 60, 60, 70, 25, and 30 ng/mL, respectively. Upper limits of quantitation were 8000 ng/mL for all amphetamines and 6000 ng/mL for ketamine and norketamine. Except for dehydronorketamine (DHNK), within-day and between-day precisions (as expressed in CV%) for quality control samples were ≤ 3.1% and ≤ 4.95%, respectively. Except DHNK, the within-day accuracy ranged between 96.0% and 110.7% and the between-day accuracy ranged between 96.9% and 108.7%. A group of 107 urine samples previously determined to contain the target analytes were analyzed by this new approach. Quantitative data produced by both methods agreed well. With this new approach, we were able to use a single analytical protocol to conduct the confirmation test for samples that preliminarily tested positive (by immunoassay) for amphetamines, ketamine, or both.

  5. [Determination of bisphenol A from toys and food contact materials by derivatization and gas chromatography-mass spectrometry].

    PubMed

    Gao, Yonggang; Zhang, Yanyan; Gao, Jianguo; Zhang, Huiling; Zheng, Lisha; Chen, Jing

    2012-10-01

    A method was developed for the determination of bisphenol A (BPA) in toys and food contact materials. The BPA was extracted with Soxhlet extraction method from the sample and reacted with acetic anhydride. The final product was determined by gas chromatography-mass spectrometry (GC-MS). To achieve the optimum derivatization performance, the derivatization time and dosage of derivatization reagent etc. were investigated. Under the optimized experimental conditions, the final product was stable and the peak shape was good. The linearity of the derivative was good in the range of 0.05 to 50 mg/L with the correlation coefficient (r2) above 0.999. The recoveries ranged from 80% to 93% at the spiked levels of 0.05, 1.00, 10.00 mg/kg with the relative standard deviations (RSDs) less than 3.7%. The limit of detection (S/N = 3) was 10 microg/kg. The method is accurate and has high recovery. The method is suitable for the inspection of bisphenol A in toys and food contact materials.

  6. Direct derivatization and gas chromatography-tandem mass spectrometry identification of nerve agent biomarkers in urine samples.

    PubMed

    Subramaniam, Raja; Östin, Anders; Nilsson, Calle; Åstot, Crister

    2013-06-01

    Rapid determination of nerve agent biomarkers at low-ppb levels in urine samples was achieved by direct derivatization and sample analysis using gas chromatography-tandem mass spectrometry. The studied biomarkers were alkylphosphonic acids (APAs), as they are specific hydrolysis products of organophosphorus nerve agents that can be used to verify nerve agent exposure. The sample preparation technique employed involves rapid direct derivatization (5min) of acidified urine samples (25μL) using a highly fluorinated phenyldiazomethane reagent [1-(diazomethyl)-3,5-bis(trifluoromethyl)benzene]. The derivatization conditions were optimized using statistical experimental design and multivariate data analysis. The APA derivatives were analyzed by GC-MS and MS/MS using negative ion chemical ionization. The selectivity and sensitivity of analyses performed by low and high resolution single ion monitoring MS-mode were compared with those performed by multiple reaction monitoring MS/MS-mode. The MS/MS technique offered the greatest sensitivity and selectivity of the tested mass spectrometric techniques, with limits of detection ranging from 0.5 to 1ng APAs/mL of urine. The method's robustness was evaluated using urine samples from the OPCW 2nd biomedical confidence building exercise and all APAs present in the samples were conclusively identified. The method thus offers excellent performance and is viable for the simultaneous trace determination of a wide range of nerve agent markers.

  7. Pentafluorobenzyl bromide-A versatile derivatization agent in chromatography and mass spectrometry: I. Analysis of inorganic anions and organophosphates.

    PubMed

    Tsikas, Dimitrios

    2017-02-01

    Pentafluorobenzyl bromide (PFB-Br) is a versatile derivatization agent. It is widely used in chromatography and mass spectrometry since several decades. The bromide atom is largely the single leaving group of PFB-Br. It is substituted by wide a spectrum of nucleophiles in aqueous and non-aqueous systems to form electrically neutral, in most organic solvents soluble, generally thermally stable, volatile, strongly electron-capturing and ultraviolet light-absorbing derivatives. Because of these greatly favoured physicochemical properties, PFB-Br emerged an ideal derivatization agent for highly sensitive analysis of endogenous and exogenous substances including various inorganic and organic anions by electron capture detection or after electron-capture negative-ion chemical ionization in GC-MS. The present article attempts an appraisal of the utility of PFB-Br in analytical chemistry. It reviews and discusses papers dealing with the use of PFB-Br as the derivatization reagent in the qualitative and quantitative analysis of endogenous and exogenous inorganic anions in various biological samples, notably plasma, urine and saliva. These analytes include nitrite, nitrate, cyanide and dialkyl organophosphates. Special emphasis is given to mass spectrometry-based approaches and stable-isotope dilution techniques.

  8. A sensitive and selective determination method of histamine by HPLC with intramolecular excimer-forming derivatization and fluorescence detection.

    PubMed

    Yoshitake, Takashi; Ichinose, Fumio; Yoshida, Hideyuki; Todoroki, Ken-ichiro; Kehr, Jan; Inoue, Osamu; Nohta, Hitoshi; Yamaguchi, Masatoshi

    2003-12-01

    A highly sensitive, selective and simple method is described for the determination of histamine by high-performance liquid chromatography (HPLC) with fluorescence detection. The method is based on an intramolecular excimer-forming fluorescence derivatization of histamine with 4-(1-pyrene)butyric acid N-hydroxysuccinimide ester (PSE), followed by reversed-phase HPLC. Histamine, having two amino moieties in a molecule, was converted to the dipyrene-labeled derivative by reaction with PSE. The derivative afforded intramolecular excimer fluorescence (450-540 nm), which can clearly be discriminated from the monomer fluorescence (370-420 nm) emitted from PSE. Typically, a 10 micro L sample solution was mixed with 100 micro L of derivatization reagent solution, which was a mixture of 0.5 mm PSE in acetonitrile and 0.5 mm potassium carbonate in water (8:2, v/v). The derivatization was carried out at 100 degrees C for 90 min. The PSE derivative of histamine could be separated by reversed-phase ODS column with isocratic elution using acetonitrile:water (82:18, v/v) containing 0.03% triethylamine. The detection limit (singnal-to-noise ratio = 3) of histamine was 0.5 fmol for a 30 micro L injection. The method was successfully applied to the determination of histamine in human urine, and had enough selectivity and sensitivity for urinary histamine quantification.

  9. Asymmetric conjugate addition of Grignard reagents to 3-silyl unsaturated esters for the facile preparation of enantioenriched β-silylcarbonyl compounds and allylic silanes.

    PubMed

    Zhao, Kai; Loh, Teck-Peng

    2014-12-08

    A highly enantioselective conjugate addition of Grignard reagents to 3-silyl unsaturated esters to deliver synthetically useful chiral β-silylcarbonyl compounds was developed. The synthetic value of this methodology was further illustrated by the synthesis of enantioenriched β-hydroxyl esters and the facile access granted to various α-chiral allylic silanes. A plethora of diastereoselective transformations of β-silylenolates were also investigated and afforded manifold organosilanes that contained contiguous stereogenic centers with excellent enantioselectivity.

  10. Determination of trace amino acids in human serum by a selective and sensitive pre-column derivatization method using HPLC-FLD-MS/MS and derivatization optimization by response surface methodology.

    PubMed

    Li, Guoliang; Cui, Yanyan; You, Jinmao; Zhao, Xianen; Sun, Zhiwei; Xia, Lian; Suo, Yourui; Wang, Xiao

    2011-04-01

    Analysis of trace amino acids (AA) in physiological fluids has received more attention, because the analysis of these compounds could provide fundamental and important information for medical, biological, and clinical researches. More accurate method for the determination of those compounds is highly desirable and valuable. In the present study, we developed a selective and sensitive method for trace AA determination in biological samples using 2-[2-(7H-dibenzo [a,g]carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEC) as labeling reagent by HPLC-FLD-MS/MS. Response surface methodology (RSM) was first employed to optimize the derivatization reaction between DBCEC and AA. Compared with traditional single-factor design, RSM was capable of lessening laborious, time and reagents consumption. The complete derivatization can be achieved within 6.3 min at room temperature. In conjunction with a gradient elution, a baseline resolution of 20 AA containing acidic, neutral, and basic AA was achieved on a reversed-phase Hypersil BDS C(18) column. This method showed excellent reproducibility and correlation coefficient, and offered the exciting detection limits of 0.19-1.17 fmol/μL. The developed method was successfully applied to determinate AA in human serum. The sensitive and prognostic index of serum AA for liver diseases has also been discussed.

  11. Design of Selenium-Based Chiral Chemical Probes for Simultaneous Enantio- and Chemosensing of Chiral Carboxylic Acids with Remote Stereogenic Centers by NMR Spectroscopy.

    PubMed

    Shyshkanov, Sergey A; Orlov, Nikolai V

    2016-10-17

    Selenium-based enantiopure chiral chemical probes have been designed in a modular way starting from available amino alcohols. The probes developed were found to be efficient in chemoselective interaction with carboxylic functions of chiral substrates leading to diastereomeric amide formation and in sensing α-, β-, and remote (up to seven bonds away from the carboxylic group) chiral centers by using (77) Se NMR spectroscopy. As a result, it was possible to determine the enantiomeric ratio of structurally diverse individual chiral acids including polyfunctional compounds and drugs with high accuracy. An approach to analyzing the crude reaction mixtures has been successfully developed by using bifunctional selenium- and fluorine-containing chiral probes. More importantly, it was revealed that, based on the (77) Se NMR data obtained, it is possible to obtain primary information about the location and nature of the substituents at the chiral center (chemo- and enantiosensing), which can simplify the structural elucidation of complex compounds. The derivatization procedure takes as little as 5 min and can be performed directly in an NMR tube followed by NMR measurements without any isolation and purification steps.

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

    PubMed

    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.

  13. Spot indole test: evaluation of four reagents.

    PubMed Central

    Miller, J M; Wright, J W

    1982-01-01

    Kovacs indole reagent, p-dimethylaminobenzaldehyde, Ehrlich indole reagent and p-dimethylaminocinnamaldehyde were used as spot indole reagents to test 359 strains of gram-negative rods growing on 5% sheep blood agar, Trypticase soy agar (BBL Microbiology Systems), and MacConkey agar. The p-dimethylaminocinnamaldehyde reagent was the most sensitive of those tested and provided results that were easiest to interpret. The p-dimethylaminocinnamaldehyde reagent was able to detect providencia alcalifaciens indole production because of the red-violet color unique to that organism. All reagents tested were accurate in detecting indole produced by members of the Enterobacteriaceae family, with the exception of P. alcalifaciens. PMID:7040458

  14. Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC.

    PubMed

    Maeda, Katsuhiro; Maruta, Miyuki; Sakai, Yuki; Ikai, Tomoyuki; Kanoh, Shigeyoshi

    2016-11-07

    A series of optically active poly(diphenylacetylene) derivatives bearing a chiral substituent (poly-2S) or chiral and achiral substituents (poly-(2Sx-co-31-x)) on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenyl)acetylene) with (S)-1-phenylethylamine ((S)-2) or benzylamine (3) in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) were investigated. Poly-2S and poly-(2Sx-co-31-x) (0.06 < x < 0.71) formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2S and h-poly-(2Sx-co-31-x)). Furthermore, h-poly-2S and h-poly-(2S0.36-co-30.64) emitted circularly polarized luminescence with opposite signs. h-Poly-2S showed higher chiral recognition abilities toward a larger number of racemates than poly-2S without a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene) derivative bearing the same chiral substituent on half of its pendant phenyl rings. h-Poly-(2S0.36-co-30.64) also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared with h-poly-2S.

  15. Foodomics platform for the assay of thiols in wines with fluorescence derivatization and ultra performance liquid chromatography mass spectrometry using multivariate statistical analysis.

    PubMed

    Inoue, Koichi; Nishimura, Maiko; Tsutsui, Haruhito; Min, Jun Zhe; Todoroki, Kenichiro; Kauffmann, Jean-Michel; Toyo'oka, Toshimasa

    2013-02-13

    The presence of specific volatile and aminothiols in wine is associated with quality, worth, price, and taste. The identification of specific thiol-containing compounds in various wines has been reported in many valuable and interesting works. In this study, a novel foodomics assay of thiol-containing compounds, such as free aminothiols and related conjugates, was developed using ultra performance liquid chromatography (UPLC) with fluorescence (FL) and electrospray (ESI) time-of-flight mass spectrometric (TOF/MS) detections. FL specific derivatization was applied along with multivariate statistical analysis. First, the optimal experimental conditions were studied using representative thiols, such as l-cysteine, N-acetyl-l-cysteine, cysteamine, and l-glutathione, and then the UPLC-FL derivatization and separation steps were fixed for the subsequent screening of unknown thiol-containing compounds. The screening assay consisted of monitoring the UPLC-TOF/MS peaks of unknown thiols, which decreased due to the derivatization as compared to the nonderivatized thiols. The principal component analysis of the UPLC-TOF/MS data could be well-differentiated and categorized into two groups. The orthogonal signal correction partial least-squares discriminant analysis, the so-called S-plot, showed that the quality differentiation is directly related to the decrease of native thiols and increase of derivatized thiols. With this strategy, the mass difference from the derivatization reagent (+m/z 198) could be utilized for the identification of these thiols using the FL peaks retention time and metabolomics-databases. The presence of l-glutathione in rice wine was for the first time reported on the basis of the available metabolomics-databases and standard matching. This novel concept based on foodomics could be applied in food analysis for the ready screening of specific functional compounds by exploiting the various derivatization modes available.

  16. XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach

    NASA Astrophysics Data System (ADS)

    Manakhov, Anton; Michlíček, Miroslav; Felten, Alexandre; Pireaux, Jean-Jacques; Nečas, David; Zajíčková, Lenka

    2017-02-01

    The quantitative analysis of the chemistry at the surface of functional plasma polymers is highly important for the optimization of their deposition conditions and, therefore, for their subsequent applications. The chemical derivatization of amine and carboxyl-anhydride layers is a well-known technique already applied by many researchers, notwithstanding the known drawback of the derivatization procedures like side or uncomplete reactions that could lead to "unreliable" results. In this work, X-ray photoelectron spectroscopy (XPS) combined with depth profiling with argon clusters is applied for the first time to study derivatized amine and carboxyl-anhydride plasma polymer layers. It revealed an additional important parameter affecting the derivatization reliability, namely the permeation of the derivatizing molecule through the target analysed layer, i.e. the composite effect of the probe molecule size and the layer porosity. Amine-rich films prepared by RF low pressure plasma polymerization of cyclopropylamine were derivatized with trifluoromethyl benzaldehide (TFBA) and it was observed by that the XPS-determined NH2 concentration depth profile is rapidly decreasing over top ten nanometers of the layer. The anhydride-rich films prepared by atmospheric plasma co-polymerization of maleic anhydride and C2H2 have been reacted with, parafluoroaniline and trifluoroethyl amine. The decrease of the F signal in top surface layer of the anhydride films derivatized by the "large" parafluoroaniline was observed similarly as for the amine films but the derivatization with the smaller trifluoroethylamine (TFEA) led to a more homogenous depth profile. The data analysis suggests that the size of the derivatizing molecule is the main factor, showing that the very limited permeation of the TFBA molecule can lead to underestimated densities of primary amines if the XPS analysis is solely carried out at a low take-off angle. In contrast, TFEA is found to be an efficient

  17. Molecular model for chirality phenomena.

    PubMed

    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.

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

    PubMed

    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.

  19. Applications of chiral symmetry

    SciTech Connect

    Pisarski, R.D.

    1995-03-01

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

  20. Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry.

    PubMed

    Hsu, Ching-Lin; Ding, Wang-Hsien

    2009-12-15

    A rapid and environmental-friendly injection-port derivatization with gas chromatography-mass spectrometry (GC-MS) method was developed to determine selected low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) 20 mM in methanol gave excellent yield for di-butyl ester dicarboxylate derivatives at injection-port temperature at 300 degrees C. Solid-phase extraction (SPE) method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 78 to 95% with relative standard deviation (RSD) less than 12%. Limits of quantitation (LOQs) ranged from 25 to 250 pg/m(3). The concentrations of di-carboxylated C2-C5 and total C6-C10 in particles of atmospheric aerosols ranged from 91.9 to 240, 11.3 to 56.7, 9.2 to 49.2, 8.7 to 35.3 and n.d. to 37.8 ng/m(3), respectively. Oxalic acid (C2) was the dominant LMW-dicarboxylic acids detected in aerosol samples. The quantitative results were comparable to the results obtained by the off-line derivatization.

  1. Determination of atrazine and its major degradation products in soil pore water by solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Carter, D.S.

    1996-01-01

    This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.

  2. Dispersive liquid-liquid microextraction and injection-port derivatization for the determination of free lipophilic compounds in fruit juices by gas chromatography-mass spectrometry.

    PubMed

    Marsol-Vall, Alexis; Balcells, Mercè; Eras, Jordi; Canela-Garayoa, Ramon

    2017-04-28

    A method consisting of dispersive liquid-liquid microextraction (DLLME) followed by injection-port derivatization and gas chromatography-mass spectrometry (GC-MS) for the analysis of free lipophilic compounds in fruit juices is described. The method allows the analysis of several classes of lipophilic compounds, such as fatty acids, fatty alcohols, phytosterols and triterpenes. The chromatographic separation of the compounds was achieved in a chromatographic run of 25.5min. The best conditions for the dispersive liquid-liquid microextraction were 100μL of CHCl3 in 1mL of acetone. For the injection-port derivatization, the best conditions were at 280°C, 1min purge-off, and a 1:1 sample:derivatization reagent ratio (v/v) using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA):pyridine (1:1) as reagent. Quality parameters were assessed for the target compounds, giving a limits of detection (LODs) ranging from 1.1 to 5.7ng/mL and limits of quantification (LOQs) from 3.4 to 18.7ng/mL for linoleic and stearic acid, respectively. Repeatability (%RSD, n=5) was below 11.51% in all cases. In addition, the method linearity presented an r(2) ≥0.990 for all ranges applied. Finally, the method was used to test the lipophilic fraction of various samples of commercial fruit juice.

  3. Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n-butyl ester.

    PubMed

    Wang, Zhifeng; Cui, Zhaojie

    2016-12-01

    A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples.

  4. A highly sensitive quantification of phytosterols through an inexpensive derivatization.

    PubMed

    Liu, Songbai; Ruan, Huina

    2013-01-01

    A highly sensitive method for quantification of phytosterols based on HPLC has been developed by derivatization with the benzoyl chromophore. Introduction of the chromophore, benzoyl group, to phytosterols via simple and inexpensive derivatization greatly improved the UV response at 254 nm. Quantification of phytosterols was effectively performed by HPLC analysis with methyl benzoate as the internal standard after derivatization. This new method demonstrated outstanding yield of recovery (> 95%) and excellent sensitivity (ng level) and was applicable for sterols from either plant or animal sources. This method is generally useful in phytosterol studies.

  5. Thionation using fluorous Lawesson's reagent.

    PubMed

    Kaleta, Zoltán; Makowski, Brian T; Soós, Tibor; Dembinski, Roman

    2006-04-13

    [reaction: see text] Thionation of amides, 1,4-diketones, N-(2-oxoalkyl)amides, N,N'-acylhydrazines, and acyl-protected uridines with the use of a fluorous analogue of the Lawesson's reagent leads to thioamides, thiophenes, 1,3-thiazoles, 1,3,4-thiadiazoles, and acyl-protected 4-thiouridines. The isolation of the final products in high yields is achieved in most cases by a simple filtration (fluorous solid-phase extraction).

  6. Development of single-drop microextraction and simultaneous derivatization followed by GC-MS for the determination of aliphatic amines in tobacco.

    PubMed

    Sha, Yunfei; Meng, Jiaoran; Lin, Huaqing; Deng, Chunhui; Liu, Baizhan

    2010-05-01

    In this work, for the first time, headspace (HS) single-drop microextraction and simultaneous derivatization followed by GC-MS was developed to determine the aliphatic amines in tobacco samples. In the HS extraction procedure, the mixture of derivatization reagent and organic solvent was employed as the extraction solvent for HS single-drop microextraction and in situ derivatization of aliphatic amine in the samples. Fast extraction and simultaneous derivatization of the analytes were performed in a single step, and the obtained derivatives in the microdrop extraction solvent were analyzed by GC-MS. The optimized experiment conditions were: sample preparation temperature of 80 degrees C and time of 30 min, HS extraction solvent (the mixture of benzyl alcohol and 2,3,4,5,6-pentafluorobenzaldehyde) volume of 2.0 microL, extraction time of 90 s. With the optimal conditions, the method validations were also studied. The method has good linearity (R(2) more than 0.99), accepted precision (RSD less than 13%), good recovery (98-104%) and low limit of detection (0.11-0.97 microg/g). Finally, the proposed technique was successfully applied to the analyses of aliphatic amines in tobacco samples of seven different brands. It was further demonstrated that the proposed method offered a simple, low-cost and reliable approach to determine aliphatic amines in tobacco samples.

  7. Automated on-line in-tube solid-phase microextraction-assisted derivatization coupled to liquid chromatography for quantifying residual dimethylamine in cationic polymers.

    PubMed

    Prieto-Blanco, M C; Cháfer-Pericás, C; López-Mahía, P; Campíns-Falcó, P

    2008-04-25

    A method for the analysis of dimethylamine (DMA) by automated in-tube solid-phase microextraction (IT-SPME)-supported chemical derivatization coupled with high-performance liquid chromatography was developed. Extraction, derivatization and desorption were studied by using a capillary coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane. Solution derivatization and automated IT-SPME derivatization using 9-fluorenylmethyl chloroformate (FMOC) were compared. The proposed procedure provided adequate linearity, accuracy and precision in the 0.2-2.0 microg/mL concentration interval, and the limit of detection (LOD) was 50 ng/mL. The main advantages of the proposed procedure are: (i) no off-line sample manipulation, (ii) rapidity, as the total analysis time is about 10 min, (iii) specificity for the samples assayed, (iv) minimal consumption of FMOC reagent and (v) minimal residues. Therefore, the proposed method is an environmental-friendly and cost-effective alternative for the control of residual DMA in polymeric cationic surfactants used like flocculants in water treatment.

  8. A Derivatization and Validation Strategy for Determining the Spatial Localization of Endogenous Amine Metabolites in Tissues using MALDI Imaging Mass Spectrometry

    PubMed Central

    Manier, M. Lisa; Spraggins, Jeffrey M.; Reyzer, Michelle L.; Norris, Jeremy L.; Caprioli, Richard M.

    2014-01-01

    Imaging mass spectrometry (IMS) studies increasingly focus on endogenous small molecular weight metabolites and consequently bring special analytical challenges. Since analytical tissue blanks do not exist for endogenous metabolites, careful consideration must be given to confirm molecular identity. Here we present approaches for the improvement in detection of endogenous amine metabolites such as amino acids and neurotransmitters in tissues through chemical derivatization and matrix-assisted laser desorption/ionization (MALDI) IMS. Chemical derivatization with 4-hydroxy-3-methoxycinnamaldehyde (CA) was used to improve sensitivity and specificity. CA was applied to the tissue via MALDI sample targets precoated with a mixture of derivatization reagent and ferulic acid (FA) as a MALDI matrix. Spatial distributions of chemically derivatized endogenous metabolites in tissue were determined by high-mass resolution and MSn imaging mass spectrometry. We highlight an analytical strategy for metabolite validation whereby tissue extracts are analyzed by high-performance liquid chromatography (HPLC)-MS/MS to unambiguously identify metabolites and distinguish them from isobaric compounds. PMID:25044893

  9. A facile and fully automated on-fiber derivatization protocol for direct analysis of short-chain aliphatic amines using a matrix compatible solid-phase microextraction coating.

    PubMed

    Gionfriddo, Emanuela; Passarini, Alice; Pawliszyn, Janusz

    2016-07-29

    Solid-phase microextraction (SPME) analysis of short-chain aliphatic amines (C3-C6) in aqueous solutions was investigated using pentafluorobenzaldehyde (PFBAY) as on-fiber derivatization reagent. A standard gas generating vial agent was used for on-fiber loading of the derivatization agent so as to avoid the need for its regeneration at each derivatization cycle. Several parameters such as loading time, reaction temperature, and reaction/extraction time were optimized for headspace and direct sampling in aqueous solutions. Three different coating chemistries were tested and their performances compared in order to achieve the best compromise between sensitivity and analysis throughput. The newly developed PDMS/DVB/PDMS coating showed superior performance in terms of extraction efficiency while the capability to prevent on-fiber degradation of the derivatizing products. The optimized method was used for quantitation of short-chain aliphatic amines in aqueous samples and provided detection limits in the low ppb range for all the amines tested with accuracy values between 79 and 120%. The method was applied towards the analysis of environmental water samples and the accuracy of the results was evaluated by different calibration approaches. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Rapid determination of bisphenol A in drinking water using dispersive liquid-phase microextraction with in situ derivatization prior to GC-MS.

    PubMed

    Wang, Xia; Diao, Chun-Peng; Zhao, Ru-Song

    2009-01-01

    This paper described a novel approach for the determination of bisphenol A by dispersive liquid-phase microextraction with in situ acetylation prior to GC-MS. In this derivatization/extraction method, 500 microL acetone (disperser solvent) containing 30.0 microL chlorobenzene (extraction solvent) and 30.0 microL acetic anhydride (derivatization reagent) was rapidly injected into 5.00 mL aqueous sample containing bisphenol A and K2CO3 (0.5% w/v). Within a few seconds the analyte was derivatized and extracted at the same time. After centrifugation, 1.0 microL of sedimented phase containing enriched analyte was determined by GC-MS. Some important parameters, such as type and volume of extraction and disperser solvent, volume of acetic anhydride, derivatization and extraction time, amount of K2CO3, and salt addition were studied and optimized. Under the optimum conditions, the LOD and the LOQ were 0.01, 0.1 microg/L, respectively. The experimental results indicated that there was linearity over the range 0.1-50 microg/L with coefficient of correlation 0.9997, and good reproducibility with RSD 3.8% (n = 5). The proposed method has been applied for the analysis of drinking water samples, and satisfactory results were achieved.

  11. Development and validation of an LC-ESI/MS/MS method with precolumn derivatization for the determination of betulin in rat plasma.

    PubMed

    Hu, Zhiwei; Guo, Na; Wang, Ziming; Liu, Yong; Wang, Yu; Ding, Weimin; Zhang, Dehui; Wang, Yang; Yan, Xiufeng

    2013-11-15

    Neutral pentacyclic triterpenes with only one or two hydroxyl groups, such as betulin, are not easily ionized by electrospray ionization (ESI). However, because betulin is reactive and neutral, derivatization may improve ionization efficiency. In the present study, the potency of different derivatization reagents was evaluated and p-toluenesulfonyl isocyanate (PTSI) was proven to be the optimal. The derivative generated by the reaction of betulin with PTSI was ionizable and fragmentable in the negative mode by liquid chromatography-electrospray ionization/tandem mass spectrometry (LC-ESI/MS/MS). Based on this chemical derivatization, an LC-ESI/MS/MS method was developed and validated for the quantification of betulin in rat plasma. The sample was extracted with ethyl acetate, derivatized with PTSI, separated on an ACQ UPLC BEH phenyl column, and analyzed in negative multiple reaction monitoring (MRM) mode. The calibration curve was linear over the betulin concentration range 2.5-200ng/mL. The lower limit of quantification was 2.5ng/mL. The inter- and intra-day accuracy and precision were within ±15%. Betulin recoveries were 86.7% or higher at three quality control levels (5, 50, and 160ng/mL). This validated method was subsequently applied to a pharmacokinetic study of betulin in rat plasma after oral administration.

  12. Simultaneous determination of individual isothiocyanates in plant samples by HPLC-DAD-MS following SPE and derivatization with N-acetyl-l-cysteine.

    PubMed

    Pilipczuk, Tadeusz; Kusznierewicz, Barbara; Chmiel, Tomasz; Przychodzeń, Witold; Bartoszek, Agnieszka

    2017-01-01

    The procedure for the isothiocyanates (ITCs) determination that involves derivatization with N-acetyl-l-cysteine (NAC) and separation by HPLC was developed. Prior to derivatization, plant ITCs were isolated and purified using solid-phase extraction (SPE). The optimum conditions of derivatization are: 500μL of isopropanolic eluate obtained by SPE combined with 500μL of derivatizing reagent (0.2M NAC and 0.2M NaHCO3 in water) and reaction time of 1h at 50°C. The formed dithiocarbamates are directly analyzed by HPLC coupled with diode array detector and mass spectrometer if required. The method was validated for nine common natural ITCs. Calibration curves were linear (R(2)⩾0.991) within a wide range of concentrations and limits of detection were below 4.9nmol/mL. The recoveries were in the range of 83.3-103.7%, with relative standard deviations <5.4%. The developed method has been successfully applied to determine ITCs in broccoli, white cabbage, garden cress, radish, horseradish and papaya. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Catalysis of dynamical chiral symmetry breaking by chiral chemical potential

    NASA Astrophysics Data System (ADS)

    Braguta, V. V.; Kotov, A. Yu.

    2016-05-01

    In this paper, we study the properties of media with chiral imbalance parametrized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus, the chiral chemical potential plays the role of the catalyst of dynamical chiral symmetry breaking. Physically, this effect results from the appearance of the Fermi surface and additional fermion states on this surface, which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  14. Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Jiang, Jinghua; Yang, Deng-Ke

    2017-01-01

    Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

  15. ESA mission ROSETTA will probe for chirality of cometary amino acids.

    PubMed

    Thiemann, W H; Meierhenrich, U

    2001-01-01

    New crucial theoretical investigations on the origin of biomolecular chirality are reviewed briefly. With the goal to investigate these theories our team is going to perform the 'chirality-experiment' in the near future with cometary matter. In 2012 the robotical lander RoLand will detach from the orbiter of the ROSETTA spacecraft and set down on the surface of comet 46P/Wirtanen in order to separate and identify cometary organic compounds via GC-MS in situ. Chiral organics will be separated into their enantiomers by application of 3 capillary columns coated with different kinds of stationary phases. Non-volatile compounds like amino acids will be derivatized in especially developed gas phase alkylation steps avoiding reactions in the liquid phase. The results of these preliminary gas phase reactions are presented in this article.

  16. Determination of chiral pharmaceutical compounds, terbutaline, ketamine and propranolol, by on-line capillary electrophoresis-electrospray ionization mass spectrometry.

    PubMed

    Lu, W; Cole, R B

    1998-08-28

    On-line capillary electrophoresis-electrospray ionization mass spectrometry (CE-ESI-MS) has been employed for the determination of racemic mixtures of the chiral drugs, terbutaline, ketamine, and propranolol. Separation of the different chiral forms has been achieved by introducing cyclodextrins (CDs), which act as chiral selectors, into the CE operating electrolytes. Cyclodextrins function as chiral selectors in CE because of their ability to form host-guest complexes (inclusion complexes) of varying stability with an array of chiral drugs and other compounds. Derivatized forms of beta-CD (i.e., dimethyl-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin) were used in this study due to their higher solubilities in the aqueous methanolic operating electrolyte than native beta-CD. Addition of minor quantities of methanol to the aqueous-based CE operating electrolytes improved the stability of electrospray ionization conditions and further enhanced CE resolution of the enantiomeric pairs relative to purely aqueous systems. Introduction of the CDs into the CE operating electrolytes caused suppression of analyte signals in ESI-MS, and the dependence of analyte signal intensities on the solution concentrations of the derivatized beta-CDs was examined. Under optimized conditions, the different enantiomeric forms of the compounds under investigation were successfully separated and detected by CE-ESI-MS.

  17. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

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

  18. Chiral magnetic wave

    SciTech Connect

    Kharzeev, Dmitri E.; Yee, Ho-Ung

    2011-04-15

    We consider a relativistic plasma containing charged chiral fermions in an external magnetic field, e.g. a chirally symmetric quark-gluon plasma created in relativistic heavy ion collisions. We show that triangle anomalies imply the existence of a new type of collective gapless excitation in this system that stems from the coupling between the density waves of the electric and chiral charges; we call it ''the chiral magnetic wave'' (CMW). The CMW exists even in a neutral plasma, i.e. in the absence of the axial and vector chemical potentials. We demonstrate the existence of CMW and study its properties using three different approaches: i) relativistic magnetohydrodynamics; ii) dimensional reduction to (1+1) Sine-Gordon model, appropriate in a strong magnetic field; and iii) holographic QCD (Sakai-Sugimoto model), appropriate at strong coupling. We also briefly discuss the phenomenological implications of the CMW for heavy ion collisions.

  19. Relativistic Chiral Kinetic Theory

    NASA Astrophysics Data System (ADS)

    Stephanov, Mikhail

    2016-12-01

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi:10.1103/PhysRevLett.113.182302; J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: 10.1103/PhysRevLett.115.021601; M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: 10.1103/PhysRevLett.116.122302].

  20. Chiral Hypervalent, Pentacoordinated Phosphoranes.

    PubMed

    Krasowska, Dorota; Chrzanowski, Jacek; Kiełbasiński, Piotr; Drabowicz, Józef

    2016-11-21

    This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

  1. Biocatalysis: Chiral cascades

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Bo; Reetz, Manfred T.

    2015-12-01

    Racemic or enantiomerically pure alcohols can be converted with high yield into enantiopure chiral amines in a one-pot redox-neutral cascade process by the clever combination of an alcohol dehydrogenase and an appropriate amine dehydrogenase.

  2. Fragmentation behavior of a thiourea-based reagent for protein structure analysis by collision-induced dissociative chemical cross-linking.

    PubMed

    Müller, Mathias Q; Dreiocker, Frank; Ihling, Christian H; Schäfer, Mathias; Sinz, Andrea

    2010-08-01

    The fragmentation behavior of a novel thiourea-based cross-linker molecule specifically designed for collision-induced dissociation (CID) MS/MS experiments is described. The development of this cross-linker is part of our ongoing efforts to synthesize novel reagents, which create either characteristic fragment ions or indicative constant neutral losses (CNLs) during tandem mass spectrometry allowing a selective and sensitive analysis of cross-linked products. The new derivatizing reagent for chemical cross-linking solely contains a thiourea moiety that is flanked by two amine-reactive N-hydroxy succinimide (NHS) ester moieties for reaction with lysines or free N-termini in proteins. The new reagent offers simple synthetic access and easy structural variation of either length or functionalities at both ends. The thiourea moiety exhibits specifically tailored CID fragmentation capabilities--a characteristic CNL of 85 u--ensuring a reliable detection of derivatized peptides by both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) tandem mass spectrometry and as such possesses a versatile applicability for chemical cross-linking studies. A detailed examination of the CID behavior of the presented thiourea-based reagent reveals that slight structural variations of the reagent will be necessary to ensure its comprehensive and efficient application for chemical cross-linking of proteins.

  3. A sensitive fluorescence reagent for the determination of aldehydes from alcoholic beverage using high-performance liquid chromatography with fluorescence detection and mass spectrometric identification.

    PubMed

    You, Jinmao; Yan, Tao; Zhao, Huaixin; Sun, Zhiwei; Xia, Lian; Suo, Yourui; Li, Yulin

    2009-03-16

    A pre-column derivatization method for the sensitive determination of aldehydes using the tagging reagent 2-[2-(7H-dibenzo[a,g] carbazol-7-yl)-ethoxy] ethyl carbonylhydrazine (DBCEEC) followed by high-performance liquid chromatography with fluorescence detection and APCI-MS identification has been developed. The chromophore of fluoren-9-methoxy-carbonylhydrazine (Fmoc-hydrazine) reagent was replaced by 2-[2-(7H-dibenzo[a,g] carbazol-7-yl)-ethoxy] ethyl functional group, which resulted in a sensitive fluorescence tagging reagent DBCEEC. DBCEEC could easily and quickly labeled aldehydes. The maximum excitation (300nm) and emission (400nm) wavelengths did not essentially change for all the aldehyde derivatives. Derivatives were sufficiently stable to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z [M+(CH(2))(n)](+) in positive-ion mode (M: molecular weight of DBCEEC, n: corresponding aldehyde carbon atom numbers). The collision-induced dissociation of protonated molecular ion formed fragment ions at m/z 294.6, m/z 338.6 and m/z 356.5. Studies on derivatization demonstrated excellent derivative yields in the presence of trichloroacetic acid (TCA) catalyst. Maximal yields close to 100% were observed with a 10 to 15-fold molar reagent excess. Separation of the derivatized aldehydes had been optimized on ZORBAX Eclipse XDB-C(8) column with aqueous acetonitrile as mobile phase in conjunction with a binary gradient elution. Excellent linear responses were observed at the concentration range of 0.01-10nmolmL(-1) with coefficients of >0.9991. Detection limits obtained by the analysis of a derivatized standard containing 0.01nmolmL(-1) of each aldehyde, were from 0.2 to 1.78nmolL(-1) (at a signal-to-noise ratio of 3).

  4. Chirality and protein biosynthesis.

    PubMed

    Banik, Sindrila Dutta; Nandi, Nilashis

    2013-01-01

    Chirality is present at all levels of structural hierarchy of protein and plays a significant role in protein biosynthesis. The macromolecules involved in protein biosynthesis such as aminoacyl tRNA synthetase and ribosome have chiral subunits. Despite the omnipresence of chirality in the biosynthetic pathway, its origin, role in current pathway, and importance is far from understood. In this review we first present an introduction to biochirality and its relevance to protein biosynthesis. Major propositions about the prebiotic origin of biomolecules are presented with particular reference to proteins and nucleic acids. The problem of the origin of homochirality is unresolved at present. The chiral discrimination by enzymes involved in protein synthesis is essential for keeping the life process going. However, questions remained pertaining to the mechanism of chiral discrimination and concomitant retention of biochirality. We discuss the experimental evidence which shows that it is virtually impossible to incorporate D-amino acids in protein structures in present biosynthetic pathways via any of the two major steps of protein synthesis, namely aminoacylation and peptide bond formation reactions. Molecular level explanations of the stringent chiral specificity in each step are extended based on computational analysis. A detailed account of the current state of understanding of the mechanism of chiral discrimination during aminoacylation in the active site of aminoacyl tRNA synthetase and peptide bond formation in ribosomal peptidyl transferase center is presented. Finally, it is pointed out that the understanding of the mechanism of retention of enantiopurity has implications in developing novel enzyme mimetic systems and biocatalysts and might be useful in chiral drug design.

  5. The quest for chirality

    SciTech Connect

    Bonner, W.A.

    1996-07-01

    The indispensable role played by homochirality and chiral homogeneity in the self-replication of crucial biomolecules is stressed, with the conclusion that life could neither exist nor originate without these chiral molecular attributes. Hypotheses historically proposed for the origin of chiral molecules on Earth are reviewed, including biogenic theories as well as abiotic theories embracing both indeterminate and determinate mechanisms. Indeterminate mechanisms, including autocatalytic symmetry breaking, asymmetric adsorption on quartz and clay minerals, and asymmetric syntheses in chiral crystals, are discussed and evaluated in the context of the prebiotic environment. Abiotic determinate mechanisms based on electric, magnetic and gravitational fields, on circularly polarized light (CPL), and on parity violation effects are summarized, with the emphasis that only CPL has proved practicable experimentally, but that it would be implausible on the primitive Earth. Mechanisms for the amplification of small, indigenous enantiomeric excesses are discussed, with one involving the partial polymerization of amino acids and the partial hydrolysis of polypeptides suggested as potentially viable prebiotically. Aspects of the turbulent, chirality-destructive primeval environment are described, with the conclusion that all of the above mechanisms for the {ital terrestrial} prebiotic origin of chirality would be non-viable, and that an alternative extraterrestrial source for the accumulation of chiral molecules on primitive Earth must have been operative. A scenario for this is outlined, in which we postulate that asymmetric photolysis of the organic mantles on interstellar grains in molecular clouds by circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae produces chiral molecules in the grain mantles. (Abstract Truncated)

  6. Electrodynamics of chiral matter

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  7. A Robust, Recyclable Resin for Decagram Scale Resolution of (±)-Mefloquine and Other Chiral N-Heterocycles.

    PubMed

    Kreituss, Imants; Chen, Kuang-Yen; Eitel, Simon H; Adam, Jean-Michel; Wuitschik, Georg; Fettes, Alec; Bode, Jeffrey W

    2016-01-22

    Decagram quantities of enantiopure (+)-mefloquine have been produced via kinetic resolution of racemic mefloquine using a ROMP-gel supported chiral acyl hydroxamic acid resolving agent. The requisite monomer was prepared in a few synthetic steps without chromatography and polymerization was safely performed on a >30 gram scale under ambient conditions. The reagent was readily regenerated and reused multiple times for the resolution of 150 grams of (±)-mefloquine and other chiral N-heterocylces.

  8. Mass spectrometer having a derivatized sample presentation apparatus

    DOEpatents

    Nelson, Randall W.

    2000-07-25

    A mass spectrometer having a derivatized sample presentation apparatus is provided. The sample presentation apparatus has a complex bound to the surface of the sample presentation apparatus. This complex includes a molecule which may chemically modify a biomolecule.

  9. Quantification of cyclamate and cyclohexylamine in urine samples using high-performance liquid chromatography with trinitrobenzenesulfonic acid pre-column derivatization.

    PubMed

    Casals, I; Reixach, M; Amat, J; Fuentes, M; Serra-Majem, L

    1996-10-25

    An HPLC isocratic method with pre-column derivatization and UV detection for the quantification of cyclamate and cyclohexylamine in urine samples is described. The method requires very little sample preparation. Free cyclohexylamine is analysed in a first run and subsequently cyclamate is analysed as cyclohexylamine, after the simple process of oxidation of the sample by means of hydrogen peroxide. Cycloheptylamine is used as internal standard. Trinitrobenzenesulfonic acid (TNBS) appears to be a good reagent for the pre-column derivatization. The time per run is 15 min; the coefficients of variation of the assays range from 1.1 to 5.5%; the limits of detection are 0.09 and 0.11 ppm for cyclohexylamine and cyclamate anion, respectively. The system described has always performed efficiently, with a high degree of stability, in daily routine work.

  10. Liquid chromatography coupled to on-line post column derivatization for the determination of organic compounds: a review on instrumentation and chemistries.

    PubMed

    Zacharis, Constantinos K; Tzanavaras, Paraskevas D

    2013-10-10

    Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular "chemistries" that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables.

  11. Analysis of cysteine-containing proteins using precolumn derivatization with N-(2-ferroceneethyl)maleimide and liquid chromatography/electrochemistry/mass spectrometry.

    PubMed

    Seiwert, Bettina; Karst, Uwe

    2007-08-01

    N-(2-ferroceneethyl)maleimide (FEM) is introduced as an electroactive derivatizing agent for thiol functionalities in proteins. Using appropriate reaction conditions, the derivatization is completed within five minutes and no unspecific labeling of free amino functions is observed. Liquid chromatography/electrochemistry/mass spectrometry was used to detect the reaction products. The reagent is a useful tool for determining the number of free thiol groups or the total number of free and disulfide-bound thiol groups in proteins. The electrochemical cell provides additional information, because the increase in mass spectrometric response upon electrochemical oxidation of the neutral ferrocene to the charged ferrocinium groups is monitored. The method was successfully applied to the analysis of native proteins and their tryptic digests.

  12. Liquid chromatography-tandem mass spectrometric determination of propofol in rat serum and hair at attogram level after derivatization with 3-bromomethyl-propyphenazone.

    PubMed

    Khedr, Alaa; El-Hay, Soad S Abd; Kammoun, Ahmed K

    2017-02-05

    A sensitive, selective and precise liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for determination of propofol (PRO) in rat serum and hair has been developed. 3-Bromomethyl-propyphenazone was used as derivatization reagent forming propofol-methyl-propyphenazone compound. The derivatization reaction was optimized and validated for maximum MS sensitivity. The MS instrumental sensitivity reached to 10 attogram. The serum samples were extracted by using Chromabond C8 columns, while hair samples extracted with methanol. The tendency of volatility of PRO was minimized by adding triethylamine to the extract before the use of nitrogen gas for evaporation of solvent. The limit of quantitation (LLOQ) was 0.01pg/mL and the assay was linear to 10000pg/mL. The intra-and inter-day precision (RSD%) ranged from 0.33 to 3.44% while the accuracy (Er%, relative error) were -6.4 to 1.1%. The ionization suppression, due to reagent, was minimized by reacting the excess reagent with methanol, and eluting to waste before MS ionization source (2-4.5min). The method was successfully applied for detection and determination of PRO in rat serum and hair after 7-28days from administration of only one dose of propofol (10mg/kg).

  13. Chiral nihility effects on energy flow in chiral materials.

    PubMed

    Qiu, Cheng-Wei; Burokur, Nawaz; Zouhd, Saïd; Li, Le-Wei

    2008-01-01

    The propagation of electromagnetic plane waves in an isotropic chiral medium is characterized, and a special interest is shown in chiral nihility and the effects of chirality on energy transmission. In particular, the wave impedance is matched to that of free space. Moreover, the refractive index n is also matched in impedance to that of free space when an appropriate value of the chirality is chosen. A "chiral nihility" medium is explored in which both the permittivity and the permeability tend to zero. Some specific case studies of chiral nihility are presented, and Brewster angles are found to cover an extremely wide range. The E-field distributions in these different cases where the chiral slab is placed in free space are analyzed by using the appropriate constitutive relations. It is shown from numerical calculations that one can obtain some critical characteristics of the effects of chirality on energy transmission and reflection, such as transparency and power tunneling.

  14. Enantioselective synthesis of chiral sulfinates using chiral diamines.

    PubMed

    Nakamura, Shuichi; Tateyama, Motoaki; Sugimoto, Hideki; Nakagawa, Masaya; Watanabe, Yoshihiko; Shibata, Norio; Toru, Takeshi

    2005-02-01

    The reaction of p-toluenesulfinyl chloride with alcohols in the presence of chiral diamines was examined. Chiral sulfinates were obtained in good yields with enantioselectivity up to 76% ee. Copyright 2005 Wiley-Liss, Inc.

  15. Renewable-reagent electrochemical sensor

    DOEpatents

    Wang, Joseph; Olsen, Khris B.

    1999-01-01

    A new electrochemical probe(s) design allowing for continuous (renewable) reagent delivery. The probe comprises an integrated membrane-sampling/electrochemical sensor that prevents interferences from surface-active materials and greatly extends the linear range. The probe(s) is useful for remote or laboratory-based monitoring in connection with microdialysis sampling and electrochemical measurements of metals and organic compounds that are not readily detected in the absence of reacting with the compound. Also disclosed is a method of using the probe(s).

  16. Renewable-reagent electrochemical sensor

    DOEpatents

    Wang, J.; Olsen, K.B.

    1999-08-24

    A new electrochemical probe(s) design allowing for continuous (renewable) reagent delivery is described. The probe comprises an integrated membrane sampling/electrochemical sensor that prevents interferences from surface-active materials and greatly extends the linear range. The probe(s) is useful for remote or laboratory-based monitoring in connection with microdialysis sampling and electrochemical measurements of metals and organic compounds that are not readily detected in the absence of reacting with the compound. Also disclosed is a method of using the probe(s). 19 figs.

  17. A convenient and validated enantiomer separation of chiral aliphatic amines as nitrobenzoxadiazole derivatives on polysaccharide-derived chiral stationary phases under simultaneous ultraviolet and fluorescence detection.

    PubMed

    Adhikari, Suraj; Kang, Jong Seong; Lee, Wonjae

    2016-12-01

    A convenient method using a fluorogenic agent, 4-chloro-7-nitro-1,2,3-benzoxadiazole (NBD-Cl), was developed for enantiomer separation of chiral aliphatic amines including amino alcohols by normal high-performance liquid chromatography. The enantiomer separation of chiral aliphatic amines as NBD derivatives was performed on six covalently bonded and four coated-type polysaccharide-derived chiral stationary phases (CSPs) under simultaneous ultraviolet (UV) and fluorescence detection (FLD). Among the covalently bonded CSPs, Chiralpak IE showed the best enantiomer separation for most analytes. The other CSPs also showed good enantioselectivity except for Chiralpak IB. On the other hand, Chiralpak AD-H and Amylose-1 generally exhibited better enantiomer separation of NBD derivatized chiral amines among the coated CSPs. The developed analytical technique was also applied to determine the optical purity of commercially available (R)- and (S)-leucinol; the impurity was found to be 0.06%. The developed method was validated and proved to be an accurate, precise, sensitive, and selective method suitable for separation of chiral aliphatic amines as NBD derivatives under simultaneous UV and FLD.

  18. New aniline-containing amino alcohols from trans-(R,R)-2-(2-nitrophenyl)-3-phenyloxirane as useful intermediates for the synthesis of chiral ligands, bases, and benzoxazine nucleus.

    PubMed

    Solladié-Cavallo, Arlette; Lupattelli, Paolo; Bonini, Carlo; Ostuni, Valeria; Blasio, Nadia Di

    2006-12-22

    New enantiopure aniline-containing amino alcohols are directly derived from trans-(R,R)-2-(2-nitrophenyl)-3-phenyloxirane, by alternative regioselective double reductions. Subsequent selective alkylation procedures and derivatizations provide a rapid and high-yielding access to different chiral ligands, bases, and benzoxazines, without loss of optical purity.

  19. Chirality of light and its interaction with chiral matter

    NASA Astrophysics Data System (ADS)

    Tang, Yiqiao

    This thesis conducts a systematic study on the chirality of light and its interaction with chiral matter. In the theory section, we introduce a measure of local density of chirality, applying to arbitrary electromagnetic fields. This optical chirality suggests the existence of superchiral modes, which are more selective than circularly polarized light (CPL) in preferentially exciting single enantiomers in certain regions of space. Experimentally, we demonstrate an 11-fold enhancement over CPL in discriminating chiral fluorophores of single handedness in a precisely sculpted superchiral field. This result agrees to within 15% with theoretical predictions. Any chiral configuration of point charges is beyond the scope of our theory on optical chirality. To address chiroptical excitations at nanoscale, we develop a model of twisted dipolar oscillators. We design a simple tunable chiral nanostructure and observe localized chiroptical "hot spots" with dramatically enhanced circular differential scattering. Our work on superchiral light and 3D chiral metamaterials establishes optical chirality as a fundamental and tunable property of light, with implications ranging from plasmonic sensors, absolute asymmetric synthesis to new strategies for fabricating three-dimensional chiral metamaterials. This thesis is organized as such: Chapter 1 provides a background on previous studies of chiroptical phenomena, and recent efforts in preparing chiral metamaterials. Chapter 2 derives theory on optical chirality, superchiral modes and coupled-dipolar oscillators at nanoscale. Chapter 3 introduces material, apparatus, and pitfalls in chiroptical experiments. Chapter 4 is an overview of the experimental procedure and results on generating and observing superchiral enhancement. Chapter 5 describes the experiments on using spectroscopic polarization microscopy to study chiral 3D chiral metamaterials. Finally in Chapter 6, I discuss quantization of optical chirality and perspectives on

  20. Chiral Graphene Quantum Dots.

    PubMed

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

    2016-02-23

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

  1. Reactions between Grignard reagents and heterocyclic N-oxides: stereoselective synthesis of substituted pyridines, piperidines, and piperazines.

    PubMed

    Andersson, Hans; Olsson, Roger; Almqvist, Fredrik

    2011-01-21

    In this perspective we discuss the recent developments of stereoselective synthesis of substituted pyridines, piperidines, and piperazines from cheap and commercially readily available starting materials. Pyridine N-oxides and pyrazine N-oxides are reacted with alkyl, aryl, alkynyl and vinyl Grignard reagents to give a diverse set of heterocycles in high yields. Optically active substituted piperazines are obtained by an asymmetric reaction from pyrazine N-oxides using sparteine as chiral ligand. In addition, a stereoselective synthesis of dienal-oximes from the reaction between pyridine N-oxides and Grignard reagents is presented, which results in a useful intermediate for the synthesis of a diverse set of compounds.

  2. 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.

    PubMed

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

    2013-09-06

    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.

  3. Microcalibrator system for chemical signature and reagent delivery.

    SciTech Connect

    Staton, Alan W.; Simonson, Robert Joseph; Adkins, Douglas Ray; Rawlinson, Kim Scott; Robinson, Alex Lockwood; Hance, Bradley G.; Manginell, Ronald Paul; Sanchez, Lawrence James; Ellison, Jennifer Anne; Sokolowski, Sara Suzette

    2005-03-01

    Networked systems of low-cost, small, integrable chemical sensors will enable monitoring of Nonproliferation and Materials Control targets and chemical weapons threats. Sandia-designed prototype chemical sensor systems are undergoing extended field testing supported by DOE and other government agencies. A required surety component will be verification of microanalytical system performance, which can be achieved by providing a programmable source of chemical signature(s) for autonomous calibration of analytical systems. In addition, such a controlled chemical source could be used to dispense microaliquots of derivatization reagents, extending the analysis capability of chemical sensors to a wider range of targets. We have developed a microfabricated system for controlled release of selected compounds (calibrants) into the analytical stream of microsensor systems. To minimize pumping and valve requirements of microfluidic systems, and to avoid degradation issues associated with storage of dilute solutions, we have utilized thermally labile organic salts as solid-phase reservoir materials. Reproducible deposition of tetrapropyl ammonium hydroxide onto arrays of microfabricated heating elements can provide a pair of calibration marker compounds (one fast and one slow-eluting compound) for GC analyses. The use of this microaliquot gas source array for hydrogen generation is currently under further development. The goal of the latter effort will be to provide a source of high-pressure, low viscosity GC carrier gas for Sandia's next-generation microfabricated gas-phase chemical analysis systems.

  4. Superconductivity in a chiral nanotube

    NASA Astrophysics Data System (ADS)

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-02-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity--unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  5. Chiral anomalies and differential geometry

    SciTech Connect

    Zumino, B.

    1983-10-01

    Some properties of chiral anomalies are described from a geometric point of view. Topics include chiral anomalies and differential forms, transformation properties of the anomalies, identification and use of the anomalies, and normalization of the anomalies. 22 references. (WHK)

  6. Superconductivity in a chiral nanotube

    PubMed Central

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-01-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity—unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures. PMID:28205518

  7. Superconductivity in a chiral nanotube.

    PubMed

    Qin, F; Shi, W; Ideue, T; Yoshida, M; Zak, A; Tenne, R; Kikitsu, T; Inoue, D; Hashizume, D; Iwasa, Y

    2017-02-16

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity-unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  8. Sulfonium Ion Derivatization, Isobaric Stable Isotope Labeling and Data Dependent CID- and ETD-MS/MS for Enhanced Phosphopeptide Quantitation, Identification and Phosphorylation Site Characterization

    PubMed Central

    Lu, Yali; Zhou, Xiao; Stemmer, Paul M.; Reid, Gavin E.

    2014-01-01

    An amine specific peptide derivatization strategy involving the use of novel isobaric stable isotope encoded ‘fixed charge’ sulfonium ion reagents, coupled with an analysis strategy employing capillary HPLC, ESI-MS, and automated data dependent ion trap CID-MS/MS, -MS3, and/or ETD-MS/MS, has been developed for the improved quantitative analysis of protein phosphorylation, and for identification and characterization of their site(s) of modification. Derivatization of 50 synthetic phosphopeptides with S,S′-dimethylthiobutanoylhydroxysuccinimide ester iodide (DMBNHS), followed by analysis using capillary HPLC-ESI-MS, yielded an average 2.5-fold increase in ionization efficiencies and a significant increase in the presence and/or abundance of higher charge state precursor ions compared to the non-derivatized phosphopeptides. Notably, 44% of the phosphopeptides (22 of 50) in their underivatized states yielded precursor ions whose maximum charge states corresponded to +2, while only 8% (4 of 50) remained at this maximum charge state following DMBNHS derivatization. Quantitative analysis was achieved by measuring the abundances of the diagnostic product ions corresponding to the neutral losses of ‘light’ (S(CH3)2) and ‘heavy’ (S(CD3)2) dimethylsulfide exclusively formed upon CID-MS/MS of isobaric stable isotope labeled forms of the DMBNHS derivatized phosphopeptides. Under these conditions, the phosphate group stayed intact. Access for a greater number of peptides to provide enhanced phosphopeptide sequence identification and phosphorylation site characterization was achieved via automated data-dependent CID-MS3 or ETD-MS/MS analysis due to the formation of the higher charge state precursor ions. Importantly, improved sequence coverage was observed using ETD-MS/MS following introduction of the sulfonium ion fixed charge, but with no detrimental effects on ETD fragmentation efficiency. PMID:21952753

  9. Determination of lignin in marine sediment using alkaline cupric oxide oxidation-solid phase extraction-on-column derivatization-gas chromatography

    NASA Astrophysics Data System (ADS)

    Zhang, Ting; Li, Xianguo; Sun, Shuwen; Lan, Haiqing; Du, Peirui; Wang, Min

    2013-03-01

    Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters (TOMs) in marine environment. Extraction and derivatization of lignin oxidation products (LOPs) are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide (CuO) oxidation method, the modification consisting in a solid phase extraction (SPE) and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations (RSDs) ranging from 0.57% to 8.04% ( n=3), while those with traditional liquid-liquid extraction (LLE) are from 44.52% to 86.16% with RSDs being from 0.53% to 13.14% ( n=3). Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8% ± 0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents. Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxyben-zaldehyde. The lignin content Σ8 (produced from 10 g dry sediment) in the research area is between 0.231 and 0.587 mg. S/V and C/V ratios (1.028 ± 0.433 and 0.192 ± 0.066, respectively) indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values of (Ad/Al)v suggest that the TOMs has been highly degraded.

  10. Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts.

    PubMed

    Avila, Carolina M; Patel, Jigar S; Reddi, Yernaidu; Saito, Masato; Nelson, Hosea M; Shunatona, Hunter P; Sigman, Matthew S; Sunoj, Raghavan B; Toste, F Dean

    2017-05-15

    A mild, asymmetric Heck-Matsuda reaction of five-, six- and seven-membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd(0) and chiral anion co-catalysts, the latter functioning as a chiral anion phase-transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by-products. More specifically, BINAM-derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP-D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Chiral electroweak currents in nuclei

    DOE PAGES

    Riska, D. O.; Schiavilla, R.

    2017-01-10

    Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

  12. A novel mass spectrometric method for formaldehyde in children's personal-care products and water via derivatization with acetylacetone.

    PubMed

    Backe, Will J

    2017-06-30

    New legislation in the state of Minnesota prohibits the sale of children's personal-care products (PCPs) that contain more than 500 ng/mg formaldehyde. Previous attempts to quantify formaldehyde in PCPs use nonspecific derivatization procedures that employ harsh reagents and/or nonspecific detection. Derivatization of formaldehyde by acetylacetone occurs under mild conditions and is specific for formaldehyde but it has not been investigated using high-performance liquid chromatography/tandem mass-spectrometry (HPLC/MS/MS). To determine formaldehyde, PCPs were dissolved and then interferences were minimized by graphitized-carbon solid-phase extraction. Formaldehyde was derivatized to 3,5-diacetyl-1,4-dihydrolutidine (DDL) using an acetylacetone solution. Post-derivatization, samples were diluted and analyzed by HPLC/MS/MS. Quantification was performed by isotopic dilution. Product-ion spectra were acquired for DDL and D12 -DDL. The mass shifts between the two product-ion spectra were used to assign fragment structures. To confirm molecular formulas, high-resolution accurate-mass analysis of the DDL product ions was performed by quadrupole time-of-flight MS. Structures were proposed for all product ions of DDL above 10% relative intensity. Method accuracy ranged between 96-104% for all matrices at all concentrations tested. Method precision was less than 4% relative standard deviation. The reporting limit was 10 ng/mg in PCPs and 100 μg/L in water. Twenty children's PCPs were tested to demonstrate the method and formaldehyde was reported in five from 23-1500 ng/mg. Of those five, two samples contained formaldehyde above the Minnesota regulatory limit. The developed method allows for the accurate quantification of formaldehyde in PCPs at levels below those required by a new regulation on children's products in Minnesota. The method includes a derivatization procedure that is newly adapted to HPLC/MS/MS; therefore, structures were proposed for the product ions of

  13. Improved sensitivity of serum/plasma 1α,25-dihydroxyvitamin D quantification by DAPTAD derivatization.

    PubMed

    Ishige, Takayuki; Satoh, Mamoru; Ogawa, Shoujiro; Nishimura, Motoi; Matsushita, Kazuyuki; Higashi, Tatsuya; Nomura, Fumio

    2017-10-01

    Although immunoassays have several limitations such as the cross-reactivities of antibodies, such techniques are widely used for serum/plasma 1,25(OH)2D quantification. An accurate method is required for the determination of the 1,25(OH)2D status. We designed a serum/plasma 1,25(OH)2D quantification method using LC-MS/MS. Immunoaffinity extraction (IE) and the recently developed Cookson-type reagent 4-(4'-dimethylaminophenyl)-1,2,4-triazoline-3,5-dione (DAPTAD) were used for sample preparation and derivatization, respectively. Analytical and pre-analytical validations were performed. Serum 1,25(OH)2D3 concentrations were determined in 232 healthy Japanese individuals. The intra- and inter-assay CVs for 1,25(OH)2D3 were 5.2% and 7.0%, respectively. The limit of quantification for 1,25(OH)2D3 was 7.1pg/ml. Rheumatoid factor (RF) at concentrations below 517IU/ml did not affect serum 1,25(OH)2D analysis. No significant differences were observed for various blood collection tubes, repeated freeze-thaw cycles, whole blood standing time, or serum storage time. A strong correlation between LC-MS/MS and radioimmunoassay (RIA) was observed (r=0.786), but serum 1,25(OH)2D concentrations obtained from RIA were 2-fold higher than those obtained from LC-MS/MS. Serum 1,25(OH)2D3 concentrations by LC-MS/MS were 18.7-53.9pg/ml. A highly sensitive and selective LC-MS/MS-based serum/plasma 1,25(OH)2D quantification method was developed using IE and DAPTAD derivatization. This method will enable the accurate determination of serum/plasma 1,25(OH)2D concentrations in the clinical setting. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. The Interchangeability of Viscoelastographic Instruments and Reagents

    DTIC Science & Technology

    2014-01-01

    each manufacturer. METHODS: We tested three sets of reagents as follows: (1) in-tem and ex-tem (Tem International GmbH); (2) kaolin and RapidTEG...parameter. Significant differences between the instruments were found in the > angle and maximum firmness of the clot for ex-tem and kaolin reagents as well... kaolin and RapidTEG (Haemonetics); (3) a well-characterized control recombinant tissue factorYphospholipid reagent. Blood was drawn from six healthy donors

  15. Supramolecular chirality in self-assembled soft materials: regulation of chiral nanostructures and chiral functions.

    PubMed

    Zhang, Li; Qin, Long; Wang, Xiufeng; Cao, Hai; Liu, Minghua

    2014-10-29

    Supramolecular chirality, which arises from the nonsymmetric spatial arrangement of components in the self-assembly systems, has gained great attention owing to its relation to the natural biological structures and the possible new functions in advanced materials. During the self-assembling process, both chiral and achiral components are possible to form chiral nanostructures. Therefore, it becomes an important issue how to fabricate these molecular components into chiral nanostructures. Furthermore, once the chiral nanostructure is obtained, will it show new functions that simple component molecule could not? In this research news, we report our recent development in the regulation of chiral nanostructures in soft gels or vesicle materials. We have further developed several new functions pertaining to the soft gel materials, which single chiral molecules could not perform, such as the chiroptical switch, chiral recognition and the asymmetry catalysis.

  16. Doped Chiral Polymer Metamaterials

    NASA Technical Reports Server (NTRS)

    Park, Cheol (Inventor); Kang, Jin Ho (Inventor); Gordon, Keith L. (Inventor); Sauti, Godfrey (Inventor); Lowther, Sharon E. (Inventor); Bryant, Robert G. (Inventor)

    2017-01-01

    Some implementations provide a composite material that includes a first material and a second material. In some implementations, the composite material is a metamaterial. The first material includes a chiral polymer (e.g., crystalline chiral helical polymer, poly-.gamma.-benzyl-L-glutamate (PBLG), poly-L-lactic acid (PLA), polypeptide, and/or polyacetylene). The second material is within the chiral polymer. The first material and the second material are configured to provide an effective index of refraction value for the composite material of 1 or less. In some implementations, the effective index of refraction value for the composite material is negative. In some implementations, the effective index of refraction value for the composite material of 1 or less is at least in a wavelength of one of at least a visible spectrum, an infrared spectrum, a microwave spectrum, and/or an ultraviolet spectrum.

  17. Creating chiral anomalies

    NASA Astrophysics Data System (ADS)

    Bradlyn, Barry; Cano, Jennifer; Wang, Zhijun; Hirschberger, Max; Ong, N. Phuan; Bernevig, B. Andrei

    Materials with intrinsic Weyl points should present exotic magnetotransport phenomena due to spectral flow between Weyl nodes of opposite chirality - the so-called ``chiral anomaly''. However, to date, the most definitive transport data showing the presence of a chiral anomaly comes from Dirac (not Weyl) materials. These semimetals develop Weyl fermions only in the presence of an externally applied magnetic field, when the four-fold degeneracy is lifted. In this talk we examine Berry phase effects on transport due to the emergence of these field-induced Weyl point and (in some cases) line nodes. We pay particular attention to the differences between intrinsic and field-induced Weyl fermions, from the point of view of kinetic theory. Finally, we apply our analysis to a particular material relevant to current experiments performed at Princeton.

  18. [Chirality and drugs].

    PubMed

    Testa, B; Reist, M; Carrupt, P A

    2000-07-01

    The two enantiomers of a chiral drug may have vastly different pharmacodynamic and pharmacokinetic properties. As a result, the research and development of chiral drugs raises specific problems some of which are discussed here. Thus, various pharmacokinetic interactions may involve two enantiomers, as seen for example when one enantiomer inhibits the metabolism of the other and modifies its effects. A different situation occurs when a third compound stereoselectively inhibits the metabolism of one of the two enantiomers. Another problem examined here results from the lack of configurational stability of some chiral drugs, a little known phenomenon whose consequences can be of pharmacological or pharmaceutical significance depending on the rate of the reaction of racemization or epimerisation. In-depth investigations are needed before choosing between a eutomer or a racemate.

  19. Nonmicrobial alternative to reagent quality control testing.

    PubMed Central

    Reynolds, S M

    1982-01-01

    The traditional approach to quality control in microbiology involves the routine testing of both media and reagents with live microbial cultures. This is expensive, time consuming, and subject to the variables associated with the use of live organisms. A system of reagent quality control based on the pure chemical form of the metabolic end products important to the identification of the Enterobacteriaceae was evaluated. The metabolite reagent control system is simple, reliable, and extremely cost effective, and it eliminates the need for live microbial cultures and media for reagent quality control. PMID:6759528

  20. Renewable Reagent Fiber Optic Based Ammonia Sensor

    NASA Astrophysics Data System (ADS)

    Berman, Richard J.; Burgess, Lloyd W.

    1990-02-01

    Many fiber optic based chemical sensors have been described which rely on a reagent chemistry fixed at the fiber endface to provide analyte specificity. In such systems, problems involving probe-to-probe reproducibility, reagent photolability and reagent leaching are frequently encountered. As a result, calibration and standardization of these sensors becomes difficult or impossible and thus inhibits their application for long term in situ chemical monitoring. Many of these problems can be addressed and several additional advantages gained by continuously renewing the reagent chemistry. To illustrate this concept, a fiber optic ammonia sensor is described in which the reagent is delivered under direct control to a sensing volume of approximately 400 nanoliters located at the probe tip. Using an acid-base indicator (bromothymol blue) as the reagent, the sample ammonia concentrations are related to modulations in light intensity with a lower limit of detection of 10 ppb. The sensor performance was studied with respect to reagent pH, concentration and reagent delivery rate. Compared with previous fiber optic ammonia sensors, the ability to reproducibly renew the reagent has resulted in improvements with respect to response and return times, probe-to-probe reproducibility, probe lifetime and flexibility of use.

  1. Catalytic Synthesis of N-Unprotected Piperazines, Morpholines, and Thiomorpholines from Aldehydes and SnAP Reagents.

    PubMed

    Luescher, Michael U; Bode, Jeffrey W

    2015-09-07

    Commercially available SnAP (stannyl amine protocol) reagents allow the transformation of aldehydes and ketones into a variety of N-unprotected heterocycles. By identifying new ligands and reaction conditions, a robust catalytic variant that expands the substrate scope to previously inaccessible heteroaromatic substrates and new substitution patterns was realized. It also establishes the basis for a catalytic enantioselective process through the use of chiral ligands.

  2. Chiral Liouville gravity

    NASA Astrophysics Data System (ADS)

    Compère, Geoffrey; Song, Wei; Strominger, Andrew

    2013-05-01

    Classical two-dimensional Liouville gravity is often considered in conformal gauge which has a residual left and right Virasoro symmetry algebra. We consider an alternate, chiral, gauge which has a residual right Virasoro Kac-Moody algebra, and no left Virasoro algebra. The Kac-Moody zero mode is the left-moving energy. Dirac brackets of the constrained Hamiltonian theory are derived, and the residual symmetries are shown to be generated by integrals of the conserved chiral currents. The central charge and Kac-Moody level are computed. The possible existence of a corresponding quantum theory is discussed.

  3. Single-step enantioselective amino acid flux analysis by capillary electrophoresis using on-line sample preconcentration with chemical derivatization.

    PubMed

    Ptolemy, Adam S; Tran, Lara; Britz-McKibbin, Philip

    2006-07-15

    Capillary electrophoresis (CE) represents a versatile platform for integrating sample pretreatment with chemical analysis because of its ability to tune analyte electromigration and band dispersion properties in discontinuous electrolyte systems. In this article, a single-step method that combines on-line sample preconcentration with in-capillary chemical derivatization is developed for rapid, sensitive, and enantioselective analysis of micromolar levels of amino acids that lack intrinsic chromophores by CE with UV detection. Time-resolved electrophoretic studies revealed two distinct stages of amino acid band narrowing within the original long sample injection plug occurring both prior to and after in-capillary labeling via zone passing by ortho-phthalaldehyde/N-acetyl l-cysteine (OPA/NAC). This technique enabled direct analysis of d-amino acids in a 95% enantiomeric excess mixture with sub-micromolar detection limits and minimal sample handling, where the capillary functions as a preconcentrator, microreactor, and chiral selector. On-line sample preconcentration with chemical derivatization CE (SPCD-CE) was applied to study the enantioselective amino acid flux in Escherichia coli bacteria cultures, which demonstrated a unique l-Ala efflux into the extracellular medium. New strategies for high-throughput analyses of low-abundance metabolites are important for understanding fundamental physiological processes in bacteria required for screening the efficacy of new classes of antibiotics as well as altered metabolism in genetically modified mutant strains.

  4. Chiral symmetry in quarkyonic matter

    SciTech Connect

    Kojo, T.

    2012-05-15

    The 1/N{sub c} expansion classifies nuclear matter, deconfined quark matter, and Quarkyonic matter in low temperature region. We investigate the realization of chiral symmetry in Quarkyonic matter by taking into account condensations of chiral particle-hole pairs. It is argued that chiral symmetry and parity are locally violated by the formation of chiral spirals, <{psi}-bar exp (2i{mu}{sub q} z{gamma}{sup 0} {gamma}{sup z}){psi}> . An extension to multiple chiral spirals is also briefly discussed.

  5. Interchangeability of rotational elastographic instruments and reagents.

    PubMed

    Aleshnick, Maya; Orfeo, Thomas; Brummel-Ziedins, Kathleen; Gissel, Matthew; Mann, Kenneth

    2014-01-01

    Viscoelastic measurements are frequently being used in clinical and research settings for a rapid assessment of the hemostatic processes of blood clot formation and degradation. These measurements are being performed on either of two instruments (TEG and ROTEM) using their proprietary reagents. Standardization between the instruments and the reagents has been lacking but is necessary to compare results across instruments. In this study, we perform a crossover analysis between the TEG and ROTEM instruments using proprietary reagents from each manufacturer. We tested three sets of reagents as follows: (1) in-tem and ex-tem (Tem International GmbH); (2) kaolin and RapidTEG (Haemonetics); (3) a well-characterized control recombinant tissue factor-phospholipid reagent. Blood was drawn from six healthy donors, and each reagent was run concurrently in the TEG and ROTEM instruments. The volume of commercial reagent and calcium used was adjusted for crossover measurements to maintain the same concentration of each reagent in the blood. The outputs of clot time, rate of clot formation, and maximum firmness of the clot of the ROTEM and the TEG tracings were evaluated. The in-tem and RapidTEG reagents showed no disparity between instruments for any parameter. Significant differences between the instruments were found in the α angle and maximum firmness of the clot for ex-tem and kaolin reagents as well as in the clot time and maximum firmness of the clot for the recombinant tissue factor-phospholipid reagent. Although significant differences were observed for some parameters, the magnitudes were small compared with the differences between tests or the normal range variation in parameter values observed for these tests. These findings indicate that the instruments are more interchangeable than previously reported.

  6. The role of EDTA in malonaldehyde formation from DNA oxidized by Fenton reagent systems.

    PubMed

    Matsufuji, Hiroshi; Shibamoto, Takayuki

    2004-05-19

    Calf thymus DNA was oxidized by various Fenton reagent systems [Fe(II)/H(2)O(2)] with or without ethylenediamine tetraacetic acid (EDTA) under different reaction conditions. Calf DNA was also oxidized by a modified Fenton reagent (Fe(III)/H(2)O(2)/ascorbic acid) with EDTA. Malonaldehyde (MA) formed from DNA was derivatized into 1-methyl hydrazine, which was subsequently analyzed by gas chromatography with a nitrogen-phosphorus detector. MA formation increased linearly with an increase of Fe(II) concentration. MA formation reached a plateau at nearly 2 mmol/L of Fe(II) with 0.5 mmol/L of H(2)O(2). Addition of EDTA increased MA formation from DNA nearly 5 times. When DNA was oxidized with various amount of ethanol, MA formation decreased with an increase of ethanol concentration, either with or without EDTA. The rate of inhibition was greater without EDTA than with EDTA. When DNA was oxidized by a modified Fenton reagent, MA formation linearly increased with the increase of DNA. Ascorbic acid alone produced some MA upon oxidation.

  7. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    NASA Astrophysics Data System (ADS)

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-09-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base.

  8. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    PubMed Central

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-01-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base. PMID:27625043

  9. U. S. Veterinary Immune Reagents Network: Progress with poultry immune reagents development

    USDA-ARS?s Scientific Manuscript database

    A major obstacle to advances in veterinary immunology and disease research is the lack of sufficient immunological reagents specific for veterinary animal species. In 2006, U. S. Veterinary Immune Reagent Network (VIRN) Consortium (www.vetimm.org) was developed to develop immune reagents against ma...

  10. On-line sample preconcentration with chemical derivatization of bacterial biomarkers by capillary electrophoresis: a dual strategy for integrating sample pretreatment with chemical analysis.

    PubMed

    Ptolemy, Adam S; Le Bihan, Marianne; Britz-McKibbin, Philip

    2005-11-01

    Simple, selective yet sensitive methods to quantify low-abundance bacterial biomarkers derived from complex samples are required in clinical, biological, and environmental applications. In this report, a new strategy to integrate sample pretreatment with chemical analysis is investigated using on-line preconcentration with chemical derivatization by CE and UV detection. Single-step enantioselective analysis of muramic acid (MA) and diaminopimelic acid (DAP) was achieved by CE via sample enrichment by dynamic pH junction with ortho-phthalaldehyde/N-acetyl-L-cysteine labeling directly in-capillary. The optimized method resulted in up to a 100-fold enhancement in concentration sensitivity compared to conventional off-line derivatization procedures. The method was also applied toward the detection of micromolar levels of MA and DAP excreted in the extracellular medium of Escherichia coli bacterial cell cultures. On-line preconcentration with chemical derivatization by CE represents a unique approach for conducting rapid, sensitive, and high-throughput analyses of other classes of amino acid and amino sugar metabolites with reduced sample handling, where the capillary functions simultaneously as a concentrator, microreactor, and chiral selector.

  11. Chiral fiber sensors

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Churikov, Victor M.; Singer, Jonathan; Neugroschl, Daniel; Genack, Azriel Z.

    2010-04-01

    We have fabricated a variety of chiral fiber sensors by twisting one or more standard or custom optical fibers with noncircular or nonconcentric core as they pass though a miniature oven. The resulting structures are as stable as the glass material and can be produced with helical pitch ranging from microns to hundreds of microns. The polarization selectivity of the chiral gratings is determined by the geometry of the fiber cross section. Single helix structures are polarization insensitive, while double helix gratings interact only with a single optical polarization component. Both single and double helix gratings may function as a fiber long period grating, coupling core and cladding modes or as a diffraction grating scattering light from the fiber core out of the fiber. The resulting dips in the transmission spectrum are sensitive to fiber elongation, twist and temperature, and (in the case of the long period gratings) to the refractive index of the surrounding medium. The suitability of chiral gratings for sensing temperature, elongation, twist and liquid levels will be discussed. Gratings made of radiation sensitive glass can be used to measure the cumulative radiation dose, while gratings made of radiation-hardened glass are suitable for stable sensing of the environment in nuclear power plants. Excellent temperature stability up to 900°C is found in pure silica chiral diffraction grating sensors.

  12. 21 CFR 866.4100 - Complement reagent.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Complement reagent. 866.4100 Section 866.4100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Immunology Laboratory Equipment and Reagents § 866.4100...

  13. 21 CFR 866.4100 - Complement reagent.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Complement reagent. 866.4100 Section 866.4100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Immunology Laboratory Equipment and Reagents § 866.4100...

  14. 21 CFR 866.4100 - Complement reagent.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Complement reagent. 866.4100 Section 866.4100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Immunology Laboratory Equipment and Reagents § 866.4100...

  15. 21 CFR 866.4100 - Complement reagent.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Complement reagent. 866.4100 Section 866.4100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Immunology Laboratory Equipment and Reagents § 866.4100...

  16. 21 CFR 866.4100 - Complement reagent.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Complement reagent. 866.4100 Section 866.4100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Immunology Laboratory Equipment and Reagents § 866.4100...

  17. [Determination of 14 sulfonamide residues in shrimps by high performance liquid chromatography coupled with post-column derivatization].

    PubMed

    Huang, Dongmei; Huang, Xuanyun; Gu, Runrun; Hui, Yunhua; Tian, Liangliang; Feng, Bing; Zhang, Xuan; Yu, Huijuan

    2014-08-01

    A method for the determination of 14 sulfonamide residues in shrimps by high performance liquid chromatography coupled with post-column derivatization was established. The sulfonamide residues were extracted with ethyl acetate after adding sulfapyridine as internal standard. The extracts were vacuum-concentrated and reverse-extracted by 2 mol/L hydrochloric acid solution for clean-up, and then the hydrochloric acid solution was defatted with n-hex- ane. The solution after filtration was blended with a mixed solution of methanol, acetonitrile and 3. 5 mol/L sodium acetate solution (5:5:20, v/v/v). The sulfonamides were separated on a C18 column by RP-HPLC and on-line derivatized with a fluorescamine and detected with a fluorescence detector. The standard addition method was used for quantitative analysis. The parameters of post-column derivatization system, such as concentration of fluorescamine solution, velocity of reagent solution and reaction temperature, were optimized. The calibration curves of the method showed good linearity in the range of 5 - 200 μg/L. The limits of quantification (LOQ, S/N= 10) were 1.0-5.0 μg/kg for the 14 sulfonamides. The recoveries were 77.8%- 103. 6% in the spiked range of 1. 0-100.0 μg/kg in shrimps with the relative standard deviations of 2.9%-9.1% (n= 6). The results indicated that the method is sensitive, efficient and more accurate. It is suitable for the simultaneous determination of the 14 sulfonamide residues in shrimps.

  18. Determination of theanine and gamma-aminobutyric acid in tea by high performance- liquid chromatography with precolumn derivatization.

    PubMed

    Tu, Yunfei; Yang, Xiufang; Zhang, Shikang; Zhu, Yuejin

    2012-02-01

    A method of precolumn derivatization-high performance liquid chromatography (HPLC) for the determination of theanine and gamma-aminobutyric acid (GABA) in tea was established. o-Phthalaldehyde (OPA) and N-acetyl-L-cysteine (NAC) were chosen as the derivatization reagents. The effects of teapolyphenol (Tp), proline (Pro) and Vitamin C (Vc) on derivatization yields were investigated. The results indicated that Vc not only stabilized the stock solution of OPA, but also enhanced the yield of GABA derivative. However, the yield of theanine derivative was less affected. The HPLC separation system was also optimized. The resolution of the derivatives was improved by adjusting the pH value and phosphate-citric buffer concentration of the mobile phase. The limits of detection (LODs) for GABA and theanine were 3.01 x 10(-5) mmol/L and 7.98 x 10(-5) mmol/L, and the limits of quantification (LOQs) were 9.99 x 10(-5) mmol/L and 2.658 x 10(-4) mmol/L, respectively. The linear ranges of GABA and theanine were 0.01 - 0.4 mmol/L with the correlation coefficient of 0.996 and 0.05 - 0.8 mmol/L with the correlation coefficient of 0.995, respectively. The main recoveries for GABA and theanine in green tea, Oolong tea, and black tea, ranged from 99.29% to 119.60% and from 62.88% to 141.06% respectively. The method with simple procedure and efficient separation was proved to be suitable for the determination of GABA and theanine in tea.

  19. Tuning spontaneous radiation of chiral molecules by asymmetric chiral nanoparticles.

    PubMed

    Guzatov, Dmitry V; Klimov, Vasily V; Chan, Hsun-Chi; Guo, Guang-Yu

    2017-03-20

    We have obtained analytical expressions for the radiative decay rate of the spontaneous emission of a chiral molecule located near a dielectric spherical particle with a chiral nonconcentric spherical shell made of a bi-isotropic material. Our numerical and graphical analyses show that material composition, thickness and degree of non-concentricity of the shell can influence significantly the spontaneous radiation of the chiral molecule. In particular, the radiative decay rates can differ in orders of magnitude for a chiral molecule located near the thin and thick parts of a nonconcentric shell as well as near a concentric shell made of chiral metamaterial. We also find that the radiative decay rates of the "right" and "left" chiral molecule enantiomers located near a nanoparticle with a chiral metamaterial shell can differ pronouncedly from each other. Our findings therefore suggest a way to tune the spontaneous emission of chiral molecules by varying the material composition, thickness and degree of non-concentricity of the shell in the nearby composite nanoparticle and also to enhance the chirality selection of chiral molecules in racemic mixtures.

  20. Synthesis of a C1-C11 fragment of Zincophorin using planar chiral, neutral π-allyl iron complexes.

    PubMed

    Cooksey, John P

    2013-08-21

    A key step in the synthesis of a C1-C11 fragment of the ionophore antibiotic Zincophorin involves the addition of an α-alkoxyalkylcopper(I) reagent to a planar chiral, neutral π-allyl iron complex. The key allylic alkylation reaction is highly regio- and stereoselective with addition taking place at the γ-position anti to the metal centre.

  1. Ynamides as Racemization-Free Coupling Reagents for Amide and Peptide Synthesis.

    PubMed

    Hu, Long; Xu, Silin; Zhao, Zhenguang; Yang, Yang; Peng, Zhiyuan; Yang, Ming; Wang, Changliu; Zhao, Junfeng

    2016-10-04

    A highly efficient, two-step, one-pot synthetic strategy for amides and peptides was developed by employing ynamides as novel coupling reagents under extremely mild reaction conditions. The ynamides not only are effective for simple amide and dipeptide synthesis but can also be used for peptide segment condensation. Importantly, no racemization was detected during the activation of chiral carboxylic acids. Excellent amidation selectivity toward amino groups in the presence of -OH, -SH, -CONH2, ArNH2, and the NH of indole was observed, making the protection of these functional groups unnecessary in amide and peptide synthesis.

  2. Interweaving chiral spirals

    NASA Astrophysics Data System (ADS)

    Kojo, Toru; Hidaka, Yoshimasa; Fukushima, Kenji; McLerran, Larry D.; Pisarski, Robert D.

    2012-02-01

    We elaborate how to construct interweaving chiral spirals in (2+1) dimensions, defined as a superposition of chiral spirals oriented in different directions. We divide a two-dimensional Fermi sea into distinct wedges, characterized by the opening angle 2 Θ and depth Q≃p, where p is the Fermi momentum. In each wedge, the energy is lowered by forming a single chiral spiral. The optimal values for Θ and Q are chosen by balancing this gain in energy versus the cost of deforming the Fermi surface (which dominates at large Θ) and patch-patch interactions (dominant at small Θ). Using a non-local four-Fermi interaction model, we estimate the gain and cost in energy by expanding in terms of 1/N (where N is the number of colors), Λ/Q, and Θ. Due to a form factor in our non-local model, at small 1/N the mass gap (chiral condensate) is large, and the interaction among quarks and the condensate local in momentum space. Consequently, interactions between different patches are localized near their boundaries, and it is simple to embed many chiral spirals. We identify the dominant and subdominant terms at high density and categorize formulate an expansion in terms of Λ/Q or Θ. The kinetic term in the transverse directions is subdominant, so that techniques from (1+1)-dimensional systems can be utilized. To leading order in 1/N and Λ/Q, the total gain in energy is ˜pΛQCD2 with Θ˜(. Since Θ decreases with increasing p, there should be phase transitions associated with the change in the wedge number. We also argue the effects of subdominant terms at lower density where the large- N approximation is more reliable.

  3. How To Expoit Chirality As A Biomarker; GC-MS Analysis Of The Martian Soil In The Moma Experiment

    NASA Astrophysics Data System (ADS)

    Freissinet, Caroline; Buch, A.; Sternberg, R.; Szopa, C.; Coll, P.; Rodier, C.; Stambouli, M.; Raulin, F.; Goesmann, F.; MOMA GC-team

    2009-09-01

    One of the goal of the next European Martian mission Exomars 2016 will be to find traces of life. In this aim the MOMA experiment will be dedicated to the search of organic compounds such as amino acids and possible presence of chiral compounds. Then, this work deals with the development of a space compatible analysis technique of chiral organic molecules using dimethyl-formamide dimethylacetal (DMF-DMA). This study involves three steps, extraction, derivatization and GC-MS analysis, which are firstly considered one by one, and then studied as a whole. This work shows that as well as its intrinsic qualities such as light weight derivatives and great resistance to drastic operating conditions, DMF-DMA allows simple and fast derivatization suitable with in situ analysis within the constraints of a space mission. It allows the identification of 19 out of the 20 proteogenic amino acids, and the enantiomeric separation of 10. Moreover, other amino and carboxylic acids, found on meteorites, and nucleic bases are also detected with the same parameters. Racemization of the molecules has been studied within the different conditions of derivatization. Measurement of the limit of detection show that the proposed method is suitable for a quantitative determination of enantiomers of several amino acids as the limit of detection is lower than the ppb level of organic molecules already detected in Martian meteorites. The extraction-derivatization-analysis combined in one pot raises more issues, as it added the constraints of each step to the whole. A single pot is used as the extraction reactor of the organic molecules from complex soils, the derivatization reactor with DMF-DMA and the injection tool to the gas chromatograph. Preliminary results let us very optimistic since from different soils, in a one-step one-pot reaction, one can detect and identify amino and carboxylic acids, as well as nucleic bases.

  4. Double-helix micro-channels on microfluidic chips for enhanced continuous on-chip derivatization followed by electrophoretic separation.

    PubMed

    Peng, Xianglu; Zhao, Lei; Guo, Jinxiu; Yang, Shenghong; Ding, Hui; Wang, Xiayan; Pu, Qiaosheng

    2015-10-15

    Micro-channels that contain a special inner structure are critical for efficient mixing and chemical reactions. In this paper, we described the facile fabrication of an integrated microchip with double-helix type micro-channels to improve mixing efficiency and to facilitate multi-step derivatization reactions prior to electrophoretic separation. With a prepared microchip, reagents, samples and reaction products could be driven through micro-channels by siphon, and no other pumping device was necessary. To test its performance, reductive amination of aldehydes with 8-aminonaphthalene-1,3,6-trisulfonate acid disodium (ANTS) was attempted via microchip electrophoresis with laser induced fluorescence (LIF). The effect of the geometry of the reaction micro-channel on the reaction's efficiency was evaluated. Under the selected conditions, successful derivatization of five aldehydes was realized for highly reproducible analysis. The relative standard deviations of the peak areas for 30 consecutive injections were in the range of 0.28-1.61%. The method was applied for the determination of aldehydes in real samples with standard addition recoveries of 87.8-102.8%. Good tolerance of organic solvents was achieved, and the proposed method can potentially be employed for rapid screening of excessively added aldehyde food flavoring. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Chiral separation of 2-hydroxyglutaric acid on cinchonan carbamate based weak chiral anion exchangers by high-performance liquid chromatography.

    PubMed

    Calderón, Carlos; Horak, Jeannie; Lämmerhofer, Michael

    2016-10-07

    d- and l-2-Hydroxyglutaric acid (d- and l-2-HG, respectively) are metabolites related to some diseases (2-hydroxyglutaric aciduria, cancer), which make their identification and analysis crucially important for diagnostic purposes. Chiral stationary phases (CSP) based on tert-butylcarbamoyl-quinine and -quinidine (Chiralpak QN-AX and QD-AX), and the corresponding zwitterionic derivatives (Chiralpak ZWIX(+) and Chiralpak ZWIX(-)) were employed in a weak anion-exchange mechanism to perform the enantiomer separation of d- and l-2-HG without derivatization. QD-AX CSP showed the most promising separation and therefore optimization of eluent, additives, and temperature, required for the baseline separation of solutes was carried out. Depending on experimental conditions resolution values ranged up to 2.0 with run times <20min and MS-compatible conditions. Inversion on the elution order of d- and l-2-HG was possible by using the pseudo-enantiomeric QN-AX CSP.

  6. Chiral high-performance liquid chromatographic studies of 2-(4-chloro-2-methylphenoxy)propanoic acid.

    PubMed

    Blessington, B; Crabb, N; O'Sullivan, J

    1987-06-19

    The direct enantiomeric resolution of the racemic herbicide 2-(4-chloro-2-methylphenoxy)propanoic acid (CMPP) was demonstrated on an Enantiopac (alpha 1-acid glycoprotein) chiral high-performance liquid chromatographic (HPLC) column. The HPLC separation of various amide derivatives of CMPP on a chiral "Ionic Pirkle" column comprising of N-(3,5-dinitrobenzoyl) (R)-(-)phenylglycine as chiral ligand, was also accomplished. These amides and racemic ibuprofen, however could not be separated on the Enantiopac system. The performance, stability and cost of the two systems were compared. Using optically pure CMPP enantiomers the elution order was determined and shown to reverse between the two systems. It was also shown that negligible racemisation occurred during derivatization.

  7. Enantioseparation of α-amino acids by means of Cinchona alkaloids as selectors in chiral ligand-exchange chromatography.

    PubMed

    Keunchkarian, Sonia; Franca, Carlos A; Gagliardi, Leonardo G; Castells, Cecilia B

    2013-07-12

    A conventional nonchiral column was used for the enantioseparation of several racemic α-amino acids (native and derivatized) through the use of Cinchona alkaloids as chiral selectors along with Cu(II) ions in chiral ligand-exchange chromatography. The mobile phase composition (i.e., the organic modifier content and pH) was studied in order to modulate retention and enantioselectivity. Good enantioseparation of many amino acids was obtained using equimolar amounts of Cu(II) and either cinchonidine, quinine or quinidine as chiral selectors in the mobile phase. The molecular geometry of the diastereomeric complexes formed was modeled and energetic differences between both compounds were calculated by methods based on semi-empirical force-field. Good correlations were obtained between experimental enantioselectivity factors and calculated energetic differences. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Enhancement of Drug Detection and Identification by Use of Various Derivatizing Reagents on GC-FTIR Analysis.

    DTIC Science & Technology

    1992-07-01

    retention time within 4 minutes ofphenylpropanolamine .a-i under the conditions used. The resulting doxylamine solution has a concentration of 2.97 mg/mL...5.08 mg/mL. sample of this solution was then injected into the GC- FTIR and the sample was chromatographed using the Next, a doxylamine succinate...solution was prepared method described above. While the GC-FTIR analysis by placing 0.2134 grams of doxylamine succinate into a was in progress, a I ul

  9. Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C-H Bond Functionalization.

    PubMed

    Gao, De-Wei; Gu, Qing; Zheng, Chao; You, Shu-Li

    2017-02-21

    Ferrocenes are of great interest in the fields of materials science, organic synthesis, and biomedical research. Of particular significance is the fact that ferrocenes bearing planar chirality have been demonstrated to be highly efficient ligands or catalysts in asymmetric catalysis, some of which have been employed in the industrial synthesis of pharmaceuticals and agrochemicals. So far, the main methods for the synthesis of planar chiral ferrocenes involve diastereoselective directed ortho-metalation (DoM), enantioselective DoM, and chiral resolution. Despite the fact that these approaches are well developed and widely applied, the use of chiral auxiliaries or external stoichiometric chiral bases is required in most cases. Additionally, the practicality of these processes is hampered by the requirement of sensitive organometallic reagents, the poor compatibility with functional groups, and the low atom economy in some cases. Therefore, the development of highly efficient strategies to introduce planar chirality on the backbone of ferrocene that do not possess these limitations is highly desirable. Meanwhile, transition-metal-catalyzed asymmetric C-H bond functionalization reactions have attracted much attention over the past few years owing to their emerging potential for providing a straightforward approach for the preparation of chiral molecules. In addition to the majority of the work focusing on the installation of central chirality, methods for the catalytic asymmetric synthesis of planar chiral compounds via C-H bond functionalization have also been explored. In this Account, we summarize our recent efforts aimed at the development of novel methods to synthesize planar chiral compounds via asymmetric C-H bond functionalization and also highlight related achievements by other groups. First, we briefly introduce the precedent examples of diastereoselective and enantioselective synthesis of planar chiral ferrocenes. Subsequently, asymmetric syntheses of

  10. Use of a macrocyclic antibiotic as the chiral selector for enantiomeric separations by TLC

    SciTech Connect

    Armstrong, D.W.; Zhou, Y. . Dept. of Chemistry)

    1994-01-01

    The macrocyclic antibiotic, vancomycin, was used as a chiral mobile phase additive for the thin layer chromatographic (TLC) resolution of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatized amino acids, racemic drugs and dansyl-amino acids. Excellent separations were achieved for most of these compounds in the reversed phase mode. Both the nature of the stationary phase and the composition of the mobile phase strongly influenced enantiomeric resolution. The best results were obtained using diphenyl stationary phases. Acetonitrile was the organic modifier that produced the most effective separations with the shortest development times. It is highly likely that macrocyclic antibiotics will play a major role in future enantiomeric separations.

  11. Critical ligand binding reagent preparation/selection: when specificity depends on reagents.

    PubMed

    Rup, Bonita; O'Hara, Denise

    2007-05-11

    Throughout the life cycle of biopharmaceutical products, bioanalytical support is provided using ligand binding assays to measure the drug product for pharmacokinetic, pharmacodynamic, and immunogenicity studies. The specificity and selectivity of these ligand binding assays are highly dependent on the ligand binding reagents. Thus the selection, characterization, and management processes for ligand binding reagents are crucial to successful assay development and application. This report describes process considerations for selection and characterization of ligand binding reagents that are integral parts of the different phases of assay development. Changes in expression, purification, modification, and storage of the ligand binding reagents may have a profound effect on the ligand binding assay performance. Thus long-term management of the critical ligand binding assay reagents is addressed including suggested characterization criteria that allow ligand binding reagents to be used in as consistent a manner as possible. Examples of challenges related to the selection, modification, and characterization of ligand binding reagents are included.

  12. Development and validation of a simple and sensitive method for quantification of levodopa and carbidopa in rat and monkey plasma using derivatization and UPLC-MS/MS.

    PubMed

    Junnotula, Venkatraman; Licea-Perez, Hermes

    2013-05-01

    A simple, selective, and sensitive quantitative method has been developed for the simultaneous determination of levodopa and carbidopa in rat and monkey plasma by protein precipitation using acetonitrile containing the derivatizing reagent, flourescamine. Derivatized products of levodopa and carbidopa were separated on a BEH C18 column (2.1 mm × 50 mm; 1.7 μm particle size) using ultra high performance liquid chromatography (UHPLC) without any further purification. Tandem mass spectrometry (MS/MS) was used for detection. The method was validated over the concentration range of 5-5000 ng/mL and 3-3000 ng/mL for levodopa and carbidopa, respectively in rat and monkey plasma. Due to the poor stability of the investigated analytes in biological matrices, a mixture of sodium metabisulfite and hydrazine dihydrochloride was used as a stabilizer. This method was successfully utilized to support pharmacokinetic studies in both species. The results from assay validations and incurred samples re-analysis show that the method is selective, sensitive and robust. To our knowledge, this is the first UHPLC-MS/MS based method that utilizes derivatization with fluorescamine and provides adequate sensitivity for both levodopa and carbidopa with 50 μL of sample and a run time of 3.5 min. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Simultaneous analysis of apolar phytohormones and 1-aminocyclopropan-1-carboxylic acid by high performance liquid chromatography/electrospray negative ion tandem mass spectrometry via 9-fluorenylmethoxycarbonyl chloride derivatization.

    PubMed

    Ziegler, Jörg; Qwegwer, Jakob; Schubert, Melvin; Erickson, Jessica L; Schattat, Martin; Bürstenbinder, Katharina; Grubb, C Douglas; Abel, Steffen

    2014-10-03

    A strategy to detect and quantify the polar ethylene precursor 1-aminocyclopropan-1-carboxylic acid (ACC) along with the more apolar phytohormones abscisic acid (ABA), indole-3-acetic acid (IAA), jasmonic acid (JA), jasmonic acid-isoleucine conjugate (JA-Ile), 12-oxo-phytodienoic acid (OPDA), trans-zeatin, and trans-zeatin 9-riboside using a single extraction is presented. Solid phase resins commonly employed for extraction of phytohormones do not allow the recovery of ACC. We circumvent this problem by attaching an apolar group to ACC via derivatization with the amino group specific reagent 9-fluorenylmethoxycarbonyl chloride (Fmoc-Cl). Derivatization in the methanolic crude extract does not modify other phytohormones. The derivatized ACC could be purified and detected together with the more apolar phytohormones using common solid phase extraction resins and reverse phase HPLC/electrospray negative ion tandem mass spectrometry. The limit of detection was in the low nanomolar range for all phytohormones, a sensitivity sufficient to accurately determine the phytohormone levels from less than 50mg (fresh weight) of Arabidopsis thaliana and Nicotiana benthamiana tissues. Comparison with previously published phytohormone levels and the reported changes in phytohormone levels after stress treatments confirmed the accuracy of the method.

  14. [Determination of netilmicin in rat plasma by reversed-phase high performance liquid chromatography with fluorescence detection and pre-column derivatization].

    PubMed

    Chang, Xiaojuan; Peng, Jingdong; Liu, Shaopu; Liu, Limin; Dai, Yongkuang

    2009-11-01

    A new, simple and sensitive method based on pre-column derivatization by reversed-phase high performance liquid chromatography (HPLC) is described for the separation and quantification of netilmicin in plasma, using 9-fluorenylmethyl chloroformate (FMOC-Cl) as the derivatization reagent. Its pharmacokinetics is also presented. The derivatization modes and chromatographic conditions were optimized. The separation was performed on an Agilent ZORBAX Eclipse XDB-C8 column (150 mm x 4.6 mm, 5 microm) with a mixture of water-acetonitrile (15:85, v/v) as mobile phase and the flow rate was 1.0 mL/min. The excitation wavelength was 265 nm and the emission wavelength was 315 nm. The linear range was 0.045-8.88 mg/L and the correlation coefficient (r) was 0.9993. The limit of detection (LOD) (S/N = 3) was about 0.01 mg/L, and the limit of quantification was 0.03 mg/L (3LOD) for netilmicin. The relative standard deviation was less than 3% for intra-day assay (n = 5) and 3.5% for inter-day assay (n = 5) and the relative recovery was in the range of 96.62%-100.84% (n = 3). The plasma volume of 30 microL was sufficient for the determination of netilmicin. The method provides a reliable bioanalytical methodology to carry out netilmicin pharmacokinetics in rat plasma.

  15. Determination of herbicides and its metabolite in soil and water samples by capillary electrophoresis-laser induced fluorescence detection using microwave-assisted derivatization.

    PubMed

    Cao, Liwei; Deng, Tao; Liang, Siliu; Tan, Xiaofang; Meng, Jianxin

    2014-01-01

    Methods were developed to determine glufosinate (GLUF), glyphosate (GLYP) and its metabolite, aminomethylphosphonic acid (AMPA) by capillary electrophoresis-laser induced fluorescence detection using 5-(4,6-dichlorotriazinylamino) fluorescein (DTAF) and fluorescein isothiocyanate (FITC) as the derivatizing reagents. To accelerate the labeling speed, a microwave-assisted derivatization method was adopted. The derivatizing reaction time was reduced to 180 and 150 s for DTAF and FITC, whose reaction time for conventional labeling was 50 min and 5 h, respectively. The optimum separation conditions for derivatives were as follows: a back ground electrolyte (BGE) of 30 mmol L(-1) sodium tetraborate containing 15 mmol L(-1) brij-35, hydrodynamic injection 15 s and a 10 kV separation voltage. Under these conditions, the LODs (S/N = 3) for DTAF derivatives were 0.32, 0.19 and 0.15 nmol L(-1) for GLUF, GLYP, and AMPA, respectively. The LODs (S/N = 3) for FITC derivatives were 2.60, 3.88 and 2.42 nmol L(-1) for GLUF, GLYP, and AMPA, respectively. The applicability of the developed method was demonstrated by the detection of the above herbicides and metabolite in water and soil samples.

  16. Ion-pairing high-performance liquid chromatography determination of amitrole in apple after solid-phase extraction and precolumn derivatization.

    PubMed

    Sun, Yan; Luo, Laixin; Wang, Fang; Li, Jianqiang; Cao, Yongsong

    2009-09-01

    A novel method based on solid-phase extraction was studied for the extraction of amitrole (3-amino-1,2,4-triazole), and its residue determination in apples has been developed. The samples were derivatized with 4-chloro-3,5-dinitrobenzotrifluoride (CNBF). The derivatization conditions and the influence of elution composition on the separation were investigated. In pH 9.5 H(3)BO(3)-Na(2)B(4)O(7) media, the reaction of amitrole with CNBF was complete at 60 degrees C after 30 min. The separation of derivatized amitrole was achieved at room temperature within 13 min by gradient elution mode with cetyltrimethylammonium bromide in mobile phase as ion-pair reagent. The method correlation coefficient was 0.9996, in concentrations ranging from 1.66 to 415 mg L(-1). The calculated recoveries of the proposed method were from 94.17% to 105.67%, and relative standard deviations were 1.57% to 6.44% in the application to the quantitative determination of amitrole in apples. The detection limit of amitrole was 0.10 mg L(-1) with a signal-to-noise ratio of 3.

  17. Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization.

    PubMed

    Lin, Yi-Liang; Wang, Po-Yen; Hsieh, Ling-Ling; Ku, Kuan-Hsuan; Yeh, Yun-Tai; Wu, Chien-Hou

    2009-09-04

    A simple and sensitive method is described for the determination of picomolar amounts of C(1)-C(9) linear aliphatic aldehydes in waters containing heavy metal ions. In this method, aldehydes were first derivatized with 2,4-dinitrophenylhydrazine (DNPH) at optimized pH 1.8 for 30 min and analyzed by HPLC with UV detector at 365 nm. Factors affecting the derivatization reaction of aldehydes and DNPH were investigated. Cupric ion, an example of heavy metals, is a common oxidative reagent, which may oxidize DNPH and greatly interfere with the determination of aldehydes. EDTA was used to effectively mask the interferences by heavy metal ions. The method detection limits for direct injection of derivatized most aldehydes except formaldehyde were of the order of 7-28 nM. The detection limit can be further lowered by using off-line C(18) adsorption cartridge enrichment. The recoveries of C(1)-C(9) aldehydes were 93-115% with a relative standard deviation of 3.6-8.1% at the 0.1 microM level for aldehydes. The HPLC-DNPH method has been applied for determining aldehyde photoproducts from Cu(II)-amino acid complex systems.

  18. Ionic liquid-based microwave-assisted surfactant-improved dispersive liquid-liquid microextraction and derivatization of aminoglycosides in milk samples.

    PubMed

    Xu, Xu; Liu, Zhuang; Zhao, Xin; Su, Rui; Zhang, Yupu; Shi, Jiayuan; Zhao, Yajing; Wu, Lijie; Ma, Qiang; Zhou, Xin; Zhang, Hanqi; Wang, Ziming

    2013-02-01

    A green and simple method, ionic liquid-based microwave-assisted surfactant-improved dispersive liquid-liquid microextraction and derivatization was developed for the determination of aminoglycosides in milk samples. Nonionic surfactant Triton X-100 and ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate were used as the disperser and extraction solvent, respectively. Extraction, preconcentration, and derivatization of aminoglycosides were carried out in a single step. Several experimental parameters, including type and volume of extraction solvent, type and concentration of surfactant, microwave power and irradiation time, concentration of derivatization reagent, and pH value and volume of buffer were investigated and optimized. Under the optimum experimental conditions, the linearities for determining the analytes were in the range 0.4-10.0 ng/mL for tobramycin, 1.0-25.0 ng/mL for neomycin, and 2.0-50.0 ng/mL for gentamicin, with the correlation coefficients ranging from 0.9991 to 0.9998. The LODs for the analytes were between 0.11 and 0.50 ng/mL. The present method was applied to the analysis of different milk samples, and the recoveries of aminoglycosides obtained were in the range 96.4-105.4% with the RSDs lower than 5.5%. The results showed that the present method was a rapid, convenient, and environmentally friendly method for the determination of aminoglycosides in milk samples.

  19. GC-MS analysis of multiply derivatized opioids in urine.

    PubMed

    Chen, Bud-Gen; Wang, Sheng-Meng; Liu, Ray H

    2007-08-01

    Opiates such as hydrocodone, hydromorphone, oxycodone, noroxycodone, and oxymorphone reportedly may interfere with the analysis of morphine and codeine. The analysis of these compounds themselves also is an important issue. Thus, double derivatization approaches utilizing methoxyamine and hydroxylamine to first form oxime products with keto-opiates, followed by the derivatization with trimethylsilyl (TMS) or propionyl groups, have been developed for the simultaneous analysis of these compounds. However, these studies have not included all compounds of interest and resulted in inadequate chromatographic resolution or significant intensity cross-contribution between the ions designating the analyte and its deuterated internal standard for certain compounds. By exploring three-step derivatization approaches with the combination of various derivatization groups and orders, this study concluded that application of methoxyimino/propionyl/TMS groups, in the order listed, facilitated the simultaneous analysis of eight opiates (morphine, 6-acetylmorphine, hydromorphone, oxymorphone, codeine, hydrocodone, oxycodone and noroxycodone) in urine samples, achieving satisfactory limits of quantitation and detection. In addition, the adapted approach resulted in two usable products for morphine and codeine providing alternatives, should interferences render any of these products non-usable.

  20. Process for derivatizing carbon nanotubes with diazonium species

    NASA Technical Reports Server (NTRS)

    Tour, James M. (Inventor); Bahr, Jeffrey L. (Inventor); Yang, Jiping (Inventor)

    2007-01-01

    The invention incorporates new processes for the chemical modification of carbon nanotubes. Such processes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications and sensor devices. The methods of derivatization include electrochemical induced reactions thermally induced reactions (via in-situ generation of diazonium compounds or pre-formed diazonium compounds), and photochemically induced reactions. The derivatization causes significant changes in the spectroscopic properties of the nanotubes. The estimated degree of functionality is ca. 1 out of every 20 to 30 carbons in a nanotube bearing a functionality moiety. Such electrochemical reduction processes can be adapted to apply site-selective chemical functionalization of nanotubes. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes ##STR00001##.

  1. Optical properties of chiral nanotubes

    NASA Astrophysics Data System (ADS)

    Cecilia, Noguez; Román-Velázquez Carlos, E.; Ariadna, Sánchez; Montes Lilia, Meza

    2004-03-01

    A recent theoretical model [1] is applied to study the optical properties chiral nanostructures like carbon nanotubes. We calculate the Circular Dichroism (CD) spectra for carbon nanotubes with different chirality. The calculated CD spectra show features that allow us to distinguish between nanotubes with different indexes of chirality. Other nanostructures, like chiral fullerenes are also investigated.These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral. This work has been partly financed by CONACyT grant No. 36651-E and by DGAPA-UNAM grants No. IN104201. [1] C. E. Roman-Velazquez, et al., J. of Phys. Chem. B (Letter) 107, 12035 (2003)

  2. Modes of structurally chiral lasers

    NASA Astrophysics Data System (ADS)

    Topf, René D. M.; McCall, Martin W.

    2014-11-01

    We employ coupled wave theory to enumerate the lasing modes of structurally chiral lasers. The elliptical modes are shown to be fundamentally distinct from those of a scalar distributed feedback laser. High threshold modes are shown to lase with the opposite chirality as the active medium, in contrast to their low-threshold counterparts that lase with the same chirality as the active medium. The lasing mode structure suggests the intriguing possibility of dynamically changing the polarization handedness of a chiral laser, as well as the possibility of lasing within the forbidden band-gap region. These observations arise from the fundamental interplay between the distributed chirality-preserving reflections within the active medium and the localized chirality-reversing reflections at the medium's boundaries.

  3. ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

    EPA Science Inventory

    Enantiomers, the mirror image isomers of chiral pollutants, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. Considerable research has shown, for example, that chiral pesticides are degraded selectively by micr...

  4. Inactivation of rabies diagnostic reagents by gamma radiation

    SciTech Connect

    Gamble, W.C.; Chappell, W.A.; George, E.H.

    1980-11-01

    Treatment of CVS-11 rabies adsorbing suspensions and street rabies infected mouse brains with gamma radiation resulted in inactivated reagents that are safer to distribute and use. These irradiated reagents were as sensitive and reactive as the nonirradiated control reagents.

  5. 21 CFR 866.3740 - Streptococcus spp. serological reagents.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... (CONTINUED) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Serological Reagents § 866.3740 Streptococcus spp. serological reagents. (a) Identification. Streptococcus spp. serological reagents are devices... streptococci are associated with infections, such as sore throat, impetigo (an infection characterized by...

  6. Fluorescence derivatization method for sensitive chromatographic determination of zidovudine based on the Huisgen reaction.

    PubMed

    Maeda, Yuki; Kishikawa, Naoya; Ohyama, Kaname; Wada, Mitsuhiro; Ikeda, Rie; Kuroda, Naotaka

    2014-08-15

    A novel pre-column fluorescence derivatization method for chromatographic analysis of azide compounds was developed based on the Huisgen reaction, which is a specific cycloaddition reaction between an alkyne and an azide. We designed and synthesized a fluorescent alkyne, 2-(4-ethynylphenyl)-4,5-diphenyl-1H-imidazole (DIB-ET) as a reagent. DIB-ET has a lophine skeleton carrying an alkyne acting as fluorophore and reactive center, respectively. In order to evaluate the practicality of DIB-ET, a high-performance liquid chromatography with fluorescence detection method was developed for the determination of zidovudine as a model of azide compound. Zidovudine could be reacted with DIB-ET in the presence of copper(II) sulfate and L-ascorbic acid as catalysts, and the formed derivative was detected fluorometrically. The proposed method allows sensitive and selective determination of zidovudine in plasma samples with the detection limit of 0.28ngmL(-1) at a S/N=3. Finally, the proposed method could be applied to determine the zidovudine concentration in rat plasma after administration of zidovudine without interference from biological components.

  7. Amylose and amylopectin branch chain reactivity in a model derivatization system.

    PubMed

    Hong, Jung Sun; Huber, Kerry C

    2015-05-20

    The impact of starch granule structure on amylose (AM) and amylopectin (AP) chain reactivities was investigated over a 24h period in a model reaction system utilizing a fluorescent probe [DTAF, 5-(4,6-dichlorotriazinyl)aminofluorescein] as a reagent. For various reaction time intervals (0.5, 4, 12, or 24h), molecular reactivities of debranched starch derivatives were assessed via size-exclusion chromatography equipped with refractive index and fluorescence detection. For all starch chain fractions, the initial rate of derivatization (0-0.5h) was rapid, but decreased thereafter. Starch chain reactivities followed the general order: AP long chains ≫ AM, AP medium chains>AP short chains, though both AM and AP long chain reactivities were somewhat impacted by the high relative reactivity of starch chains eluting in the AM/AP long chain boundary region. Varied starch chain reactivities were attributed to their relative locale within the granule, corroborating the impact of granule architecture on molecular-level reaction patterns of starch chains.

  8. Girard derivatization for LC-MS/MS profiling of endogenous ecdysteroids in Drosophila[S

    PubMed Central

    Lavrynenko, Oksana; Nedielkov, Ruslan; Möller, Heiko M.; Shevchenko, Andrej

    2013-01-01

    Ecdysteroids are potent developmental regulators that control molting, reproduction, and stress response in arthropods. In developing larvae, picogram quantities of individual ecdysteroids and their conjugated forms are present along with milligrams of structural and energy storage lipids. To enhance the specificity and sensitivity of ecdysteroid detection, we targeted the 6-ketone group, which is common to all ecdysteroids, with Girard reagents. Unlike other ketosteroids, during the reaction, Girard hydrazones of ecdysteroids eliminated the C14-hydroxyl group, creating an additional C14-C15 double bond. Dehydrated hydrazones of endogenous ecdysteroids were detected by LC-MS/MS in the multiple reaction monitoring (MRM) mode using two mass transitions: one relied upon neutral loss of a quaternary amine from the Girard T moiety; another complementary transition followed neutral loss of the hydrocarbon chain upon C20-C27 cleavage. We further demonstrated that a combination of Girard derivatization and LC-MS/MS enabled unequivocal detection of three major endogenous hormones at the picogram level in an extract from a single Drosophila pupa. PMID:23843360

  9. [Preparation of chiral monolithic column with covalently bonded cellulose and their application to rapid enantioseparation].

    PubMed

    Wang, Jiabin; Wang, Xiao; Li, Jianhua; Lü, Haixia; Lin, Xucong; Xie, Zenghong; Zhang, Qiqing

    2011-12-01

    A chiral monolithic capillary column for rapid enantioseparation was prepared by covalently bonding of cellulose tris(4-methylbenzoate) (CTMB) on N-acryloxysuccinimide-based monolith. The preparation and derivatization conditions of the monolithic column were optimized. The successful grafting of CTMB was confirmed on the characterizations of the infrared spectrum and the cathodic electroosmotic flow (EOF). The effects of acetic acid concentration and methanol content on the enantioseparation were studied. The solvent resistance, reproducibility and stability of the monolithic column have also been investigated. The rapid enantioseparation of the five solutes (phenylalanine, tyrosine, tryptophan, propranolol and phenylethanol) with resolution (R(s)) values up to 1.31 was achieved within 1.2 min on the prepared chiral capillary monolithic column by capillary electrochromatography.

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

    PubMed

    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.

  11. Chiral conical diffraction

    NASA Astrophysics Data System (ADS)

    Berry, M. V.; Jeffrey, M. R.

    2006-05-01

    The geometrical and wave optics are explored for light emerging from a slab of transparent biaxial crystal with optical activity (chirality), for an incident beam directed along the optic axis. The geometrical optics, here derived from Hamilton's principle, is dominated by a circularly symmetric cusped caustic surface ('spun cusp') threaded by an axial focal line. In wave optics, formulated exactly in the paraxial approximation in terms of integrals previously obtained by Belsky and Stepanov and here derived using a unitary evolution operator, the field is determined by two dimensionless parameters. The geometrical features are decorated by interference, here explored in the focal image plane (where the Poggendorff rings of the non-chiral case are in sharpest focus) and along the axis. Asymptotic approximations are derived in terms of the geometrical optics rays (including interference and evanescent waves), near the spun cusp, and uniformly across the caustic surface far from the cusp.

  12. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

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

  13. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

  14. [Chirality and drugs].

    PubMed

    Husson, H P

    1997-01-01

    Following a brief historical review of the notion of chirality, the importance of the relationship between pharmacological activity and the enantiomeric forms of drugs is indicated. Different approaches for the preparation of optically-pure molecules are discussed, and an original strategy, known as the "CN(R,S) method", is described. To conclude, an application of this method in the synthesis of a pharmacologically-active molecule is presented.

  15. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

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

  16. Application of Cookson-type reagents for biomedical HPLC and LC/MS analyses: a brief overview.

    PubMed

    Higashi, Tatsuya; Shimada, Kazutake

    2017-01-01

    High-performance liquid chromatography (HPLC), LC/mass spectrometry (MS) and LC/tandem mass spectrometry (MS/MS) have been widely used for biomedical analyses, in which chemical derivatization is one of the most important methods to increase the sensitivity and selectivity. A Cookson-type reagent [4-substituted-1,2,4-triazoline-3,5-dione (4-substituted-TAD)] reacts with the compound bearing a conjugated diene, such as the vitamin D compound, to quantitatively form the stable Diels-Alder adduct. The reagent with a chromophore or fluorophore at the 4-position of TAD yields a highly responsive adduct for the UV or fluorescence detection, respectively. The Diels-Alder adduct with a Cookson-type reagent having a permanently charged, proton-affinitive or electron-affinitive moiety is sensitively detected by a specific MS analyzer. This paper is a brief overview of the applications of the reagents for biomedical analyses mainly using HPLC or LC/MS(/MS).

  17. Generalized simplicial chiral models

    NASA Astrophysics Data System (ADS)

    Alimohammadi, Masoud

    2000-02-01

    Using the auxiliary field representation of the simplicial chiral models on a ( d-1)-dimensional simplex, the simplicial chiral models are generalized through replacing the term Tr (AA †) in the Lagrangian of these models by an arbitrary class function of AA †; V(AA †) . This is the same method used in defining the generalized two-dimensional Yang-Mills theories (gYM 2) from ordinary YM 2. We call these models the "generalized simplicial chiral models". Using the results of the one-link integral over a U( N) matrix, the large- N saddle-point equations for eigenvalue density function ρ( z) in the weak ( β> βc) and strong ( β< βc) regions are computed. In d=2, where the model is in some sense related to the gYM 2 theory, the saddle-point equations are solved for ρ( z) in the two regions, and the explicit value of critical point βc is calculated for V(B)= Tr B n(B=AA †) . For V(B)= Tr B 2, Tr B 3, and Tr B4, the critical behaviour of the model at d=2 is studied, and by calculating the internal energy, it is shown that these models have a third order phase transition.

  18. Chiral magnetohydrodynamic turbulence

    NASA Astrophysics Data System (ADS)

    Pavlović, Petar; Leite, Natacha; Sigl, Günter

    2017-07-01

    In this work the influence of the chiral anomaly effect on the evolution of magnetohydrodynamic turbulence was studied. We argue that before the electroweak symmetry breaking and for temperatures high enough such that the electron mass can be ignored, the description of a charged plasma in general needs to take into account the interplay between turbulence and the anomaly effects. It was demonstrated that this generalization can have important consequences on the evolution of turbulence, leading to the creation of maximally-helical fields from initially nonhelical ones. Therefore, chiral effects can strongly support turbulent inverse cascade, and lead to a slower decrease of the magnetic field with time, and also to a faster growth of the correlation length, when compared to the evolution predicted by the standard magnetohydrodynamics description. Using the weak anomaly approximation, and treating the anomaly contributions to magnetic energy and helicity as a small perturbation, we derive the specific solutions for the inverse cascade regime that demonstrate how chiral effects support the inverse cascade.

  19. Collective Hamiltonian for chiral modes

    NASA Astrophysics Data System (ADS)

    Chen, Q. B.; Zhang, S. Q.; Zhao, P. W.; Jolos, R. V.; Meng, J.

    2013-02-01

    A collective model is proposed to describe the chiral rotation and vibration and applied to a system with one h11/2 proton particle and one h11/2 neutron hole coupled to a triaxial rigid rotor. The collective Hamiltonian is constructed from the potential energy and mass parameter obtained in the tilted axis cranking approach. By diagonalizing the collective Hamiltonian with a box boundary condition, it is found that for the chiral rotation, the partner states become more degenerate with the increase of the cranking frequency, and for the chiral vibrations, their important roles for the collective excitation are revealed at the beginning of the chiral rotation region.

  20. Microchip electrophoresis for chiral separations.

    PubMed

    Belder, Detlev; Ludwig, Martin

    2003-08-01

    Microchip electrophoresis (MCE) is a promising new technique for the separation of enantiomers. This recently introduced technique enables chiral separations to be performed in seconds on tiny micromachined devices. This review is intended to give a brief introduction into the principles of chiral separations with MCE with regard to methodology and instrumentation. Different approaches to realize chiral separations in microfluidic devices are described and discussed. This review gives an overview of original work done in this field with emphasis on approaches to improve detection and resolution in chiral MCE.

  1. Free-standing chiral plasmonics

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  2. Highly selective detection of histidine using o-phthaldialdehyde derivatization after the removal of aminothiols through Tween 20-capped gold nanoparticles.

    PubMed

    Huang, Chia-Chi; Tseng, Wei-Lung

    2009-08-01

    In this paper, we describe a simple and sensitive method for the selective detection of histidine by combining Tween 20-capped gold nanoparticles (Tween 20-AuNPs) as aminothiol removers and o-phthaldialdehyde (OPA) as the derivatization reagent. We have shown that Tween 20-AuNPs are capable of removing homocysteine (HCys), glutathione (GSH), and gamma-glutamylcysteine (Glu-Cys) at low pH conditions, but they are ineffective in the case of removal of histidine. In contrast, at high pH, Tween 20-AuNPs have strong hydrophobic interactions with the unprotonated imidazole group of histidine. It is observed that 48.0 nM Tween 20-AuNPs can remove 95.7% of HCys, 99.7% of GSH, and 99.5% of Glu-Cys from 40 mM phosphate solution at pH 2.0 in the presence of 0.1 mM cetyltrimethylammonium bromide, whereas only 2.1% of histidine was removed under identical conditions. In addition, OPA is a highly selective fluorogenic reagent for GSH, HCys, Glu-Cys, and histidine. Thus, after the centrifugation of a solution containing Tween 20-AuNPs, histidine, HCys GSH, Glu-Cys, and other amino acids, the selectivity of this method is remarkably high for histidine through OPA derivatization. Under optimum derivatization conditions, the lowest detectable concentration of histidine detected with this method was 5.2 nM. This method has been successfully applied to detect the presence of histidine in urine and serum samples.

  3. Comparison of five derivatizing agents for the determination of amphetamine-type stimulants in human urine by extractive acylation and gas chromatography-mass spectrometry.

    PubMed

    Dobos, Adrienn; Hidvégi, Elod; Somogyi, Gábor Pál

    2012-06-01

    Five acylation reagents have been compared for use as derivatizing agents for the analysis of amphetamine-type stimulants (ATS) in urine by gas chromatography-mass spectrometry (GC-MS). The evaluated reagents were heptafluorobutyric anhydride, pentafluoropropionic anhydride, trifluoroacetic anhydride, acetic anhydride (AA) and N-methyl-bis(trifluoroacetamide). The ATS included amphetamine, methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA). A mixture of the ATS was added to urine (1 mL) followed by KOH solution and saturated NaHCO(3) solution. The sample was then extracted with dichloromethane and the derivatizing agent and 2 µL were injected into the GC-MS instrument. The derivatizing agents were compared with reference to the signal-to-noise (S/N) ratios, peak area values, relative standard deviations (RSDs), linearities, limits of detection (LODs) and selectivities. The acetic anhydride proved to be the best according to the S/N ratio and peak area results for amphetamine, MA, MDMA and MDEA. The best RSD values of peak areas and of S/N ratios at 3 µg/mL were also given by AA in cases of MDA, MDMA and MDEA. At 20 µg/mL, the lowest RSD values of peak areas for MDA and the lowest RSD values of S/N ratios for MA, MDA, MDMA and MDEA were again given by AA. Additionally, the highest correlation coefficients for MA, MDA, MDMA and MDEA and the lowest LOD results for MA, MDMA and MDEA were produced by AA.

  4. PREPARATION AND EVALUATION OF HPLC CHIRAL STATIONARY PHASES BASED ON CATIONIC/BASIC DERIVATIVES OF CYCLOFRUCTAN 6

    PubMed Central

    Padivitage, Nilusha L.; Smuts, Jonathan P.; Breitbach, Zachary S.; Armstrong, Daniel W.; Berthod, Alain

    2014-01-01

    The cyclofructan 6 (CF6) macrocyclic-oligosaccharide was derivatized with five different substituents able to bear positive charges: propyl imidazole (IM) methyl benzimidazole (BIM), dimethyl aminopropyl (AP), pyridine (PY) and dimethyl aminophenyl (DMAP). The derivatized cyclofructans were reacted with triethoxysilyl-propylisocyanate as a linker to bond them to 5 μm spherical silica gel particles and then used to prepare HPLC columns. The bonded silica particles were analyzed to establish the bonding densities. A set of 34 chiral compounds including acids, neutral compounds and bases was tested with nine different mobile phase compositions including two reverse phase (RP) acetonitrile/pH 4 buffer, three polar organic (PO) acetonitrile/methanol and four normal phase (NP) heptane/ethanol mobile phases. No compounds could be separated in the RP mode. Eight compounds only could be enantioseparated in the PO mode and 21 compounds in the NP mode. The most effective chiral stationary phase was the propyl imidazole derivatized CF6 phase, provided that no more than six imidazole substituents and two linkers are attached per CF6 unit. PMID:25663797

  5. PREPARATION AND EVALUATION OF HPLC CHIRAL STATIONARY PHASES BASED ON CATIONIC/BASIC DERIVATIVES OF CYCLOFRUCTAN 6.

    PubMed

    Padivitage, Nilusha L; Smuts, Jonathan P; Breitbach, Zachary S; Armstrong, Daniel W; Berthod, Alain

    2015-03-01

    The cyclofructan 6 (CF6) macrocyclic-oligosaccharide was derivatized with five different substituents able to bear positive charges: propyl imidazole (IM) methyl benzimidazole (BIM), dimethyl aminopropyl (AP), pyridine (PY) and dimethyl aminophenyl (DMAP). The derivatized cyclofructans were reacted with triethoxysilyl-propylisocyanate as a linker to bond them to 5 μm spherical silica gel particles and then used to prepare HPLC columns. The bonded silica particles were analyzed to establish the bonding densities. A set of 34 chiral compounds including acids, neutral compounds and bases was tested with nine different mobile phase compositions including two reverse phase (RP) acetonitrile/pH 4 buffer, three polar organic (PO) acetonitrile/methanol and four normal phase (NP) heptane/ethanol mobile phases. No compounds could be separated in the RP mode. Eight compounds only could be enantioseparated in the PO mode and 21 compounds in the NP mode. The most effective chiral stationary phase was the propyl imidazole derivatized CF6 phase, provided that no more than six imidazole substituents and two linkers are attached per CF6 unit.

  6. Rapid and sensitive determination of phytosterols in functional foods and medicinal herbs by using UHPLC-MS/MS with microwave-assisted derivatization combined with dual ultrasound-assisted dispersive liquid-liquid microextraction.

    PubMed

    Sun, Jing; Zhao, Xian-En; Dang, Jun; Sun, Xiaoyan; Zheng, Longfang; You, Jinmao; Wang, Xiao

    2017-02-01

    In this work, a hyphenated technique of dual ultrasound-assisted dispersive liquid-liquid microextraction combined with microwave-assisted derivatization followed by ultra high performance liquid chromatography tandem mass spectrometry has been developed for the determination of phytosterols in functional foods and medicinal herbs. Multiple reaction monitoring mode was used for the tandem mass spectrometry detection. A mass spectrometry sensitive reagent, 4'-carboxy-substituted rosamine, has been used as the derivatization reagent for five phytosterols, and internal standard diosgenin was used for the first time. Parameters for the dual microextraction, microwave-assisted derivatization, and ultra high performance liquid chromatography tandem mass spectrometry were all optimized in detail. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect, extremely low limits of detection (0.005-0.015 ng/mL) and limits of quantification (0.030-0.10 ng/mL) were achieved. The proposed method was compared with previously reported methods. It showed better sensitivity, selectivity, and accuracy. The matrix effect was also significantly reduced. The proposed method was successfully applied to the determination of five phytosterols in vegetable oil (sunflower oil, olive oil, corn oil, peanut oil), milk and orange juice (soymilk, peanut milk, orange juice), and medicinal herbs (Ginseng, Ganoderma lucidum, Cordyceps, Polygonum multiflorum) for the quality control of functional foods and medicinal herbs.

  7. Evaluation of Two Spot-Indole Reagents

    PubMed Central

    Lowrance, B. L.; Reich, P.; Traub, W. H.

    1969-01-01

    Two spot-indole reagents, p-dimethylaminobenzaldehyde (DMABA) and p-dimethylaminocinnamaldehyde, were evaluated quantitatively. Although fourfold less sensitive, DMABA proved to be more stable and economical. PMID:4894726

  8. Iodine(III) Reagents in Radical Chemistry

    PubMed Central

    2017-01-01

    Conspectus The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF3, X–CF3 (X = heteroatom), C–Rf (Rf = perfluoroalkyl), X–Rf, C–N3, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF3+”, “Rf+”, “N3+”, “Ar+”, “CN+”, and “X+” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, aryliodonium ylides, aryl(cyano)iodonium triflates, and aryl(perfluoroalkyl)iodonium triflates. Radical generation starting with I(III) reagents can also occur via thermal or light mediated homolysis of the weak hypervalent bond in such reagents. This reactivity can be used for alkane C–H functionalization. We will address important pioneering work in the area but will mainly focus on studies that have been conducted by our group over the last 5 years. We entered the field by investigating transition metal free single electron reduction of Togni type reagents using the readily available sodium 2,2,6,6-tetramethylpiperidine-1-oxyl salt (TEMPONa) as an organic one electron reductant for clean generation of the trifluoromethyl radical and perfluoroalkyl radicals. That valuable approach was later successfully also applied to the generation of azidyl and aryl radicals starting with the corresponding benziodoxole (Zhdankin reagent

  9. A simultaneous derivatization of 3-monochloropropanediol and 1,3-dichloropropane with hexamethyldisilazane-trimethylsilyl trifluoromethanesulfonate at room temperature for efficient analysis of food sample analysis.

    PubMed

    Lee, Bai Qin; Wan Mohamed Radzi, Che Wan Jasimah Bt; Khor, Sook Mei

    2016-02-05

    This paper reports the application of hexamethyldisilazane-trimethylsilyl trifluoromethanesulfonate (HMDS-TMSOTf) for the simultaneous silylation of 3-monochloro-1,2-propanediol (3-MCPD) and 1,3-dicholoropropanol (1,3-DCP) in solid and liquid food samples. 3-MCPD and 1,3-DCP are chloropropanols that have been established as Group 2B carcinogens in clinical testing. They can be found in heat-processed food, especially when an extended high-temperature treatment is required. However, the current AOAC detection method is time-consuming and expensive. Thus, HMDS-TMSOTf was used in this study to provide a safer, and cost-effective alternative to the HFBI method. Three important steps are involved in the quantification of 3-MCPD and 1,3-DCP: extraction, derivatization and quantification. The optimization of the derivatization process, which involved focusing on the catalyst volume, derivatization temperature, and derivatization time was performed based on the findings obtained from both the Box-Behnken modeling and a real experimental set up. With the optimized conditions, the newly developed method was used for actual food sample quantification and the results were compared with those obtained via the standard AOAC method. The developed method required less samples and reagents but it could be used to achieve lower limits of quantification (0.0043mgL(-1) for 1,3-DCP and 0.0011mgL(-1) for 3-MCPD) and detection (0.0028mgL(-1) for 1,3-DCP and 0.0008mgL(-1) for 3-MCPD). All the detected concentrations are below the maximum tolerable limit of 0.02mgL(-1). The percentage of recovery obtained from food sample analysis was between 83% and 96%. The new procedure was validated with the AOAC method and showed a comparable performance. The HMDS-TMSOTf derivatization strategy is capable of simultaneously derivatizing 1,3-DCP and 3-MCPD at room temperature, and it also serves as a rapid, sensitive, and accurate analytical method for food samples analysis.

  10. [Rapid determination of fatty acids in Ranunculus ternatus Thunb by microwave-ultrasonic synergistic one-step extraction-derivatization and gas chromatography-mass spectrometry].

    PubMed

    Zhan, Hanying; Liu, Ruilin; Wang, Dejin; Yuan, Jing; Xu, Shengjie; Zhang, Zhiqi

    2013-03-01

    A rapid and simple microwave-ultrasonic synergistic one-step extraction-derivatization (MUED) method and gas chromatography-mass spectrometry was established for the determination of low content fatty acids (FAs) profile in Ranunculus ternatus Thunb. The critical experimental parameters for MUED method were optimized with response surface methodology by taking the chromatographic peak areas of total FAs as a major response index. The best technological parameters were determined as 5.0 g of Ranunculus ternatus Thunb. powder, 50.0 mL of n-hexane, 500 W of microwave power, 50 degree C of reaction temperature, 0.30 g of catalyst (KOH), 4.0 mL of derivatization reagent (methanol) and the time of extraction-derivatization of 8 min. The contents of individual FAs were quantified by internal standard method. The results showed that the chromatographic peak areas of the total FAs and the total unsaturated FAs contents obtained with MUED were (3.327 +/- 0.023) x 10(7) (n = 3) and (13.59 +/- 0.30) mg/g (n = 3) respectively. They were markedly higher than those obtained by the conventional method which were (2.410 +/- 0.036) x 10(7) (n = 3) and (12.05 +/- 0.34) mg/g (n = 3) respectively. The MUED method simplified the complicated sample handling steps, shortened the sample preparation time, reduced the cost of analysis, and improved the extraction and derivatization efficiency of the lipids, especially weakened the oxidization and decomposition of the unsaturated FAs. The simplicity, speed and practicability suggest the proposed method has significant potential for the determination of lowcontent FAs in herbal medicines.

  11. Implementation and evaluation of an analytical method for a novel derivatizing agent to measure 4,4'-methylene diphenyl diisocyanate atmospheres.

    PubMed

    Puscasu, Silvia; Aubin, Simon; Spence, Mark; Gagné, Sébastien

    2016-08-01

    Accurate measurement of 4,4'-methylene diphenyl diisocyanate (MDI) atmospheres is a challenge since the molecule is both chemically reactive and likely to be present in aerosol form when heated and sprayed because of its low vapor pressure. Meeting this challenge requires optimizing both the sampling device used and the derivatization agent employed to stabilize the isocyanate functional group. This study describes the use of a novel derivatization reagent for isocyanate sampling to address the challenge of MDI aerosol exposure sampling. Like most conventional derivatizing agents for isocyanates, 1,8-diaminonapthalene (DAN) reacts with isocyanate functional groups to form a urea. However, unlike other isocyanate derivatizing agents, the sample workup procedure with DAN includes a second step which yields a single analyte molecule, perimidone, for each isocyanate group. This feature gives DAN the unique ability to assess exposure to "total reactive isocyanate group" (TRIG). The analytical method implemented to quantitate the perimidone uses liquid chromatography coupled with tandem mass spectrometry. Positive mode ionization led to LOD and LOQ of 10 ng/mL and 34 ng/mL, respectively. The dynamic range was from 50-2000 ng/mL (with R(2) ≥ 0.990), which corresponds to TRIG concentrations in air from 0.07-3.04 µg/m(3), assuming 60 min of sampling at 10 L/min (based on use of the CIP-10M sampler). The intra-day and inter-day analytical precisions were <4% for all of the concentration levels tested, and the accuracy was within an appropriate range of 98 ± 2%. Minimal matrix effect was observed, and a total recovery of 109% was obtained. The approach seems to be promising for TRIG measurements and further work is planned to establish DAN method behavior in samplers used for workplace monitoring.

  12. Rapid determination of trans-resveratrol in red wine by solid-phase microextraction with on-fiber derivatization and multidimensional gas chromatography-mass spectrometry.

    PubMed

    Cai, Lingshuang; Koziel, Jacek A; Dharmadhikari, Murli; Hans van Leeuwen, J

    2009-01-09

    There has been considerable public interest and a growing number of scientific studies linking certain phenolic compounds in grapes and wines, particularly trans-resveratrol (trans-3,5,4'-trihydroxystilbene, TRA), to human health benefits. Typical TRA concentrations in wine are very low. It is a polar compound with very low volatility, which makes it difficult to extract and to separate on a gas chromatography (GC) column without derivatization. In this study, a new method for trace analysis of TRA was developed using solid-phase microextraction (SPME) with on-fiber silylation derivatization. Multidimensional GC equipped with a heartcut valve and cryogenic focusing was coupled with a mass-selective detector and used for improved separations and analysis. The effects of SPME fiber selection, extraction time, temperature, and desorption time were investigated. The derivatization conditions, time/temperature and the volume of derivatization reagent were also optimized. The calibration curve was linear over the concentration range from 10 ng L(-1) to 5 mg L(-1), with a correlation coefficient of 0.9996. The average recovery of TRA in red wine was 83.6+/-5.6%. The method detection limit (MDL) for TRA in ethanol:water (12.5:87.5, v/v) solution in this study was 7.08 ng L(-1) whereas the MDL for TRA in pure water was 2.85 ng L(-1). The new method was used to test the TRA content in six selected Iowa red wine samples. Measured concentrations varied from 12.72 to 851.9 microg L(-1).

  13. [Comparison between the post-column derivatization with bromine by HPLC and the fluorometric analysis for determination of aflatoxins in medicinal herbs and plant extracts].

    PubMed

    Zhang, Xue-hui; Chen, Jian-min

    2004-12-01

    To compare the post-column derivatization technique (IAC-PCD-HPLC) for the determination of aflatoxins B1, B2, G1 and G2 and the rapid procedure with fluorometric analysis (SFB) for the determination of total aflatoxins. The method of post-column derivatization with bromine by HPLC consisted of extraction of the sample with MeOH-H2O (70:30) followed by clean-up of the extracts with immunoaffinity columns and finally, HPLC determination with fluorescence detection. Aflatoxins B1 and G1 were determined as their bromine derivatives, produced in an on-line post-column derivatization system. In SFB method, samples were ground and extracted with methanol-water (70:30). A portion of the extract was cleaned up by passage through a immunoaffinity column, One mL of purified extract was derivatized with a bromine reagent, and fluorescence of the solution was immediately quantified with a calibrated fluorometer containing a broad wavelength pulsed xenon light source. In IAC-HPLC method, the overall average recoveries for three different medicinal herbs spiked at levels of 1.3 and 2.6 ng x g(-1) of total aflatoxins ranged from 93% to 97%. The detection limit was 0. 06 microg x kg(-1) for both G2 and B2 and 0.20 microg x kg(-1) for both G1 and B1, based on a signal/noise 3:1 and the precision (within-laboratory relative standard deviation) ranged from 0.8% to 1.4%. Each of aflatoxins B1, B2, G1 and G2 in 39 kind medicinal materials were determined by IAC-PCD-HPLC, and the total aflatoxins were determined by SFB. The SFB method is not the suitable method for the determination of total aflatoxins in medicinal herbs and plant extracts.

  14. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

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

  15. Chiral Recognition of Amino Acids by Use of a Fluorescent Resorcinarene

    PubMed Central

    RICHARD, GERALD I.; MARWANI, HADI M.; JIANG, SHAN; FAKAYODE, SAYO O.; LOWRY, MARK; STRONGIN, ROBERT M.; WARNER, ISIAH M.

    2009-01-01

    The spectroscopic properties of a chiral boronic acid based resorcinarene macrocycle employed for chiral analysis were investigated. Specifically, the emission and excitation characteristics of tetraarylboronate resorcinarene macrocycle (TBRM) and its quantum yield were evaluated. The chiral selector TBRM was investigated as a chiral reagent for the enantiomeric discrimination of amino acids using steady-state fluorescence spectroscopy. Chiral recognition of amino acids in the presence of the macrocycle was based on diastereomeric complexes. Results demonstrated that TBRM had better chiral discrimination ability for lysine as compared to the other amino acids. Partial least squares regression modeling (PLS-1) of spectral data for macrocycle-lysine guest-host complexes was used to correlate the changes in the fluorescence emission for a set of calibration samples consisting of TBRM in the presence of varying enantiomeric compositions of lysine. In addition, validation studies were performed using an independently prepared set of samples with different enantiomeric compositions of lysine. The results of multivariate regression modeling indicated good prediction ability of lysine, which was confirmed by a root mean square percent relative error (RMS%RE) of 5.8%. PMID:18498687

  16. Enantioselective Trifluoromethylthiolating Lactonization Catalyzed by an Indane-Based Chiral Sulfide.

    PubMed

    Liu, Xiang; An, Rui; Zhang, Xuelin; Luo, Jie; Zhao, Xiaodan

    2016-05-04

    Enantioselective trifluoromethylthiolation, especially of alkenes, is a challenging task. In this work, we have developed an efficient approach for enantioselective trifluoromethylthiolating lactonization by designing an indane-based bifunctional chiral sulfide catalyst and a shelf-stable electrophilic SCF3 reagent. The desired products were formed with diastereoselectivities of >99:1 and good to excellent enantioselectivities. The transformation represents the first enantioselective trifluoromethylthiolation of alkenes and the first enantioselective trifluoromethylthiolation that is enabled by a catalyst with a Lewis basic sulfur center.

  17. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

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

    2015-09-01

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

  18. Green synthesis of a typical chiral stationary phase of cellulose-tris(3, 5-dimethylphenylcarbamate)

    PubMed Central

    2013-01-01

    Background At present, the study on the homogeneous-phase derivatization of cellulose in ionic liquid is mainly focused on its acetylation. To the best of our knowledge, there has been no such report on the preparation of cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) with ionic liquid 1-allyl-3-methyl-imidazolium chloride (AmimCl) so far. Results With ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction solvent, cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) was synthesized by the reaction of 3,5-dimethylphenyl isocyanate and soluble microcrystalline cellulose in a homogeneous phase. The synthesized CDMPC was then coated onto the surfaces of aminopropyl silica gel to prepare a chiral stationary phase (CSP). The prepared CSP was successfully used in chiral separation of seven racemic pesticides by high performance liquid chromatography (HPLC). Good chiral separation was obtained using n-hexane and different modifiers as the mobile phases under the optimal percentage and column temperature, with the resolution of metalaxyl, diniconazole, flutriafol, paclobutrazol, hexaconazole, myclobutanil and hexythiazox of 1.73, 1.56, 1.26, 1.00, 1.18, 1.14 and 1.51, respectively. The experimental results suggested it was a good choice using a green solvent of AmimCl for cellulose functionalization. Conclusion CDMPC was successfully synthesized as the chiral selector by reacting 3, 5-dimethylphenyl isocyanate with dissolved microcrystalline cellulose in a green ionic liquid of AmimCl. PMID:23890199

  19. Detection of carbohydrates using new labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone by capillary zone electrophoresis with absorbance (UV).

    PubMed

    You, Jinmao; Sheng, Xiao; Ding, Chenxu; Sun, Zhiwei; Suo, Yourui; Wang, Honglun; Li, Yulin

    2008-02-18

    A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupled with capillary electrophoresis (CE) with DAD detection for the determination of carbohydrates has been developed. The chromophore in the 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent is replaced by naphthyl functional group, which results in a reagent with very high molar absorptivity (epsilon251 nm = 5.58 x 10(4) L mol(-1) cm(-1)). This permits NMP-labeled carbohydrates to be detected with UV absorbance in standard 50-mum-i.d. fused silica capillaries by zone electrophoresis. In this mode, nanomolar concentrations of detection limits are obtained. The method for the derivatization of carbohydrates with NMP is simplified. The derivatization reaction is rapid and mild in the presence of ammonia catalyst without further transfer steps. Nine monosaccharide derivatives such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected in CE mode. Good reproducibility can be obtained with relative standard deviation (R.S.D.) values of the migration times and peak area, respectively, from 0.44 to 0.48 and from 3.2 to 4.8. Furthermore, the developed method has been successfully applied to the analysis of carbohydrates in the hydrolyzed rape bee pollen samples.

  20. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

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

    2005-01-01

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

  1. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

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

    2005-01-01

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

  2. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

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

  3. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

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

  4. Empirical description of chiral autocatalysis.

    PubMed

    Micskei, Karoly; Póta, György; Caglioti, Luciano; Palyi, Gyula

    2006-05-11

    The only known example of chiral autocatalysis is the alkylation of N-heterocyclic aldehydes with iPr(2)Zn (Soai reaction). The mechanism and some details of this reaction are not yet clear. An empirical formula is proposed here for the description of this chiral autocatalytic reaction. This formula allows the calculation of some very informative parameters.

  5. Light amplification by photorefractive ferroelectric liquid crystal blends containing quarter-thiophene photoconductive chiral dopant

    NASA Astrophysics Data System (ADS)

    Sasaki, T.; Hara, T.; Yamamoto, Y.; Naka, Y.; Le, K. V.

    2017-05-01

    The photorefractive effect is a phenomenon that forms a rewritable hologram in a material. This phenomenon can be utilized in devices including 3D displays, optical tomography, novelty filters, phase conjugate wave generators, and optical amplification. Ferroelectric liquid crystal blends composed of a smectic liquid crystalline mixture, a photoconductive chiral dopant, and an electron trap reagent exhibit significant photorefractivity together with rapid responses. As such, they allow the dynamic amplification of moving optical signals. The photoconductive chiral dopants used in the previous study are ter-thiphene derivatives so that the photorefractive effect was examined at 488 nm. In the present work, chiral dopants possessing quarter-thiphene chromophore were synthesized and the photorefractive effect of the FLC blends at longer wavelength was demonstrated.

  6. Monitoring interconversion between stereochemical states in single chirality-transfer complexes on a platinum surface

    NASA Astrophysics Data System (ADS)

    Goubert, Guillaume; Dong, Yi; Groves, Michael N.; Lemay, J.-C.; Hammer, Bjørk; McBreen, Peter H.

    2017-06-01

    Elementary steps in enantioselective heterogeneous catalysis take place on the catalyst surface and the targeted synthesis of a desired enantiomer requires the implantation of chiral information at the surface, which can be achieved—for example—by adsorbing chiral molecules. Studies of the structures of complexes formed between adsorbed prochiral reagents and chiral molecules yield information on the forces exerting stereocontrol, but further insight could be gained by studying the dynamics of their interactions. Here, using time-lapsed scanning tunnelling microscopy and density functional theory, we observe coupling between multiple stereochemical states within individual non-covalently bonded chirality-transfer complexes on a metal surface. We identify two modes of transformation between stereochemical states and find that the prochiral reagent can sample several complexation geometries during the lifetime of a complex, switching between states of opposing prochirality in the process. These results provide insight on the contribution of individual stereochemical states to the overall enantioselectivity of reactions occurring on catalyst surfaces.

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

    PubMed

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

    2016-05-01

    To determine the true enantiomeric composition of methamphetamine urine drug testing results, chiral separation of dextro (D) and levo (L) enantiomers is necessary. While enantiomeric separation of methamphetamine has traditionally been accomplished using gas chromatography-mass spectrometry (GC-MS), chiral separation of D- and L-methamphetamine by chiral stationary phase (CSP) liquid chromatography-mass spectrometry/mass spectrometry (LC-MS-MS) has proved more reliable. Chirally selective detection of methamphetamine by GC-MS is often performed using L-N-trifluoroacetyl-prolyl chloride (TPC). L-TPC, a chiral compound, is known to have impurities that can affect the chiral composition percentages of the methamphetamine sample, potentially leading to inaccurate patient results. The comparative analysis of the samples run by GC and LC methods showed preferential bias of the GC method for producing error rates, consistent with previous research, of 8-19%. The CSP-LC-MS-MS method produces percent deviation errors of <2%. Additionally, the GC method failed to produce results that were 100% D- or L-isomer even for enantiomerically pure standards. A higher rate of D- and L-methamphetamine isomer racemization is seen in samples when analyzed by GC-MS using L-TPC-derivatizing agent. This racemization is not seen when these samples are tested with CSP-LC-MS-MS. Thus, a more accurate method of enantiomeric analysis is provided by CSP-LC-MS-MS. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  8. Enantiodifferentiation of whisky and cognac lactones using gas chromatography with different cyclodextrin chiral stationary phases.

    PubMed

    Schmarr, Hans-Georg; Mathes, Maximilian; Wall, Kristina; Metzner, Frank; Fraefel, Marius

    2017-09-22

    The chiral lactone 5-butyl-4-methyloxolan-2-one or 5-butyl-4-methyldihydro-2(3H)-furanone, often named whisky lactone, is found in oak wood, then contributing to the appreciated flavor of beverages stored in such wooden barrels. Its next higher homologue is named cognac lactone (5-pentyl-4-methyloxolan-2-one or 5-pentyl-4-methyldihydro-2(3H)-furanone), however is much less known, probably due to its minor concentration level. In order to study the direct enantioseparation of both lactones by gas chromatography on chiral stationary phases, individual enantiomers, particularly for cognac lactone were made available. This was achieved by baker's yeast reduction of synthesized ethyl 3-methyl-4-oxononanoate or, after hydrolysis, of the corresponding 4-ketoacid, that gave access to individual enantiomers of cognac lactone. Good enantioseparation was achieved for both whisky and cognac lactone with high values for the chiral resolution with 6-O-tert. butyl dimethylsilyl-2,3-dialkylated or 6-O-tert. butyl dimethylsilyl-2,3-diacylated cyclodextrin derivatives as chiral selectors. The influence of the nature and position of derivatization of the cyclodextrin moiety revealed a strong impact on the chiral recognition mechanism, as the investigated alkylated derivatives heptakis-(2,6-di-O-iso-pentyl-3-O-allyl)-β-cyclodextrin and octakis-(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin did not provide any or only minor chiral selectivity for the two lactones. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Mass-Selective Chiral Analysis

    NASA Astrophysics Data System (ADS)

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-01

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

  10. Quark structure of chiral solitons

    SciTech Connect

    Dmitri Diakonov

    2004-05-01

    There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ''chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ''soliton'', however, with computable relativistic corrections and additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.

  11. Controlling Chirality of Entropic Crystals.

    PubMed

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

    2015-10-09

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

  12. Chiral models: Geometrical aspects

    NASA Astrophysics Data System (ADS)

    Perelomov, A. M.

    1987-02-01

    Two-dimensional classical chiral models of field theory are considered, the main attention being paid on geometrical aspects of such theories. A characteristic feature of these models is that the interaction is inserted not by adding the interaction Lagrangian to the free field Lagrangian, but has a purely geometrical origin and is related to the inner curvature of the manifold. These models are in many respects analogous to non-Abelian gauge theories and as became clear recently, they are also important for the superstring theory which nowadays is the most probable candidate for a truly unified theory of all interactions including gravitation.

  13. Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction.

    PubMed

    Davis, William E; Li, Yongtao

    2008-07-15

    A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.

  14. Novel and cost-effective 6-plex isobaric tagging reagent, DiART, is effective for identification and relative quantification of complex protein mixtures using PQD fragmentation.

    PubMed

    Ramsubramaniam, Nikhil; Tao, Feng; Li, Shuwei; Marten, Mark R

    2013-09-01

    Deuterium isobaric Amine Reactive Tag (DiART) reagents facilitate relative quantification during proteomic analysis in a functionally similar manner to commercially available isobaric tag for relative and absolute quantitation (iTRAQ) and tandem mass tag (TMT) reagents. In contrast to iTRAQ and TMT, DiART reagents incorporate deuterium isotopes which significantly reduce the number of required synthesis steps and hence have potential to significantly reduce reagent production cost. We examined the capability of DiART for performing quantitative proteomic experiments using a linear ion-trap mass spectrometer with Pulsed Q Dissociation (PQD) fragmentation. Using a synthetic peptide tagged with DiART reagent, we observed a precise mass shift of 144.79 Da on the triply charged precursor ion, which shows complete derivatization of the N-terminus and ε-amino group of lysine. A DiART tagged tryptic digest of bovine serum albumin showed a sequence coverage of 57.99% which was very comparable to that showed by iTRAQ, 54.77%. Furthermore, a ten protein mixture tagged with DiART reagents and mixed in 1:1:1:1:1:1 exhibited < 15% error, whereas a linear trend (slope of 1.085) was observed when tagged proteins were mixed in the ratio 2:1:2:4:10:14 and plotted against theoretical ratios. Finally, when complex cell-wall protein mixtures from the model fungus A. nidulans were tagged with DiART reagents and mixed in different ratios, they exhibited similar trends. We conclude that DiART reagents are capable of performing quantitative proteomic experiments using PQD on a linear ion trap mass spectrometer. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Planar chiral organoborane Lewis acids derived from naphthylferrocene.

    PubMed

    Chen, Jiawei; Venkatasubbaiah, Krishnan; Pakkirisamy, Thilagar; Doshi, Ami; Yusupov, Andrej; Patel, Yesha; Lalancette, Roger A; Jäkle, Frieder

    2010-08-02

    Enantiomerically pure metalated 2-(1-naphthyl)ferrocene (NpFc) derivatives NpFcM (M=SnMe(3), HgCl) were prepared and characterized by multinuclear NMR and UV/Vis spectroscopy, cyclic voltammetry, and elemental analysis. Optical rotation measurements were performed and the absolute configuration of the new planar chiral ferrocene species was confirmed by single-crystal X-ray diffraction analysis. The mercuriated species NpFcHgCl proved suitable as a reagent for the preparation of the chiral organoborane Lewis acid NpFcBCl(2), which can in turn be converted to other ferrocenylboranes by replacement of Cl with nucleophiles. The highly Lewis acidic perfluoroarylborane derivatives NpFcB(C(6)F(5))Cl and NpFcB(C(6)F(5))(2) were successfully prepared by treatment with CuC(6)F(5). The structures were studied by single-crystal X-ray diffraction and variable-temperature (19)F NMR spectroscopy, which suggested that pi stacking of a C(6)F(5) group on boron with the adjacent naphthyl group is energetically favorable. UV/Vis absorption spectroscopy and cyclic voltammetry measurements were performed to examine the electronic properties of these novel redox-active chiral Lewis acids.

  16. Analysis of Theanine in Tea (Camellia sinensis) Dietary Ingredients and Supplements by High-Performance Liquid Chromatography with Postcolumn Derivatization: Single-Laboratory Validation, First Action 2016.10.

    PubMed

    Ofitserova, Maria; Nerkar, Sareeta

    2016-11-01

    An HPLC method with postcolumn derivatization was developed and validated for the determination of theanine content in tea dietary ingredients and supplements. A variety of common commercially available supplement forms such as powders, liquid tinctures, tablets, softgels, and gelcaps, as well as three National Institute of Standards and Technology Camellia sinensis Standard Reference Materials were investigated in the study. A simple extraction procedure using citrate buffer at pH 2.2 allowed for the analysis of theanine without additional cleanup or concentration steps, even at low ppm levels. Theanine was separated from other naturally occurring amino acids using a cation-exchange column and detected using a UV-Vis detector after derivatization with ninhydrin reagent. A single-laboratory validation demonstrated that specificity, accuracy, precision, and other method performance parameters have met the requirements set for theanine analysis by the AOAC Stakeholder Panel on Dietary Supplements.

  17. An overview of heavy-atom derivatization of protein crystals

    PubMed Central

    Pike, Ashley C. W.; Garman, Elspeth F.; Krojer, Tobias; von Delft, Frank; Carpenter, Elisabeth P.

    2016-01-01

    Heavy-atom derivatization is one of the oldest techniques for obtaining phase information for protein crystals and, although it is no longer the first choice, it remains a useful technique for obtaining phases for unknown structures and for low-resolution data sets. It is also valuable for confirming the chain trace in low-resolution electron-density maps. This overview provides a summary of the technique and is aimed at first-time users of the method. It includes guidelines on when to use it, which heavy atoms are most likely to work, how to prepare heavy-atom solutions, how to derivatize crystals and how to determine whether a crystal is in fact a derivative. PMID:26960118

  18. An overview of heavy-atom derivatization of protein crystals.

    PubMed

    Pike, Ashley C W; Garman, Elspeth F; Krojer, Tobias; von Delft, Frank; Carpenter, Elisabeth P

    2016-03-01

    Heavy-atom derivatization is one of the oldest techniques for obtaining phase information for protein crystals and, although it is no longer the first choice, it remains a useful technique for obtaining phases for unknown structures and for low-resolution data sets. It is also valuable for confirming the chain trace in low-resolution electron-density maps. This overview provides a summary of the technique and is aimed at first-time users of the method. It includes guidelines on when to use it, which heavy atoms are most likely to work, how to prepare heavy-atom solutions, how to derivatize crystals and how to determine whether a crystal is in fact a derivative.

  19. Chemical derivatization of compact disc polycarbonate surfaces for SNPs detection.

    PubMed

    Bañuls, María-José; García-Piñón, Francisco; Puchades, Rosa; Maquieira, Angel

    2008-03-01

    Compact discs have been proposed as an efficient analytical platform, with potential to develop high-throughput affinity assays for genomics, proteomics, clinics, and health monitoring. Chemical derivatization of CD surfaces is one