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Sample records for chiral amino acid

  1. Amino Acids and Chirality

    Science.gov (United States)

    Cook, Jamie E.

    2012-01-01

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

  2. Supernovae, Neutrinos and the Chirality of Amino Acids

    Directory of Open Access Journals (Sweden)

    Toshitaka Kajino

    2011-05-01

    Full Text Available A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is defined. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth’s proteinaceous amino acids.

  3. Stardust, Supernovae and the Chirality of the Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Boyd, R N; Kajino, T; Onaka, T

    2011-03-09

    A mechanism for creating enantiomerism in the amino acids, the building blocks of the proteins, that involves global selection of one chirality by interactions between the amino acids and neutrinos from core-collapse supernovae is described. The selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's amino acids.

  4. Supernovae, Neutrinos, and the Chirality of the Amino Acids

    CERN Document Server

    Boyd, R N; Onaka, T

    2011-01-01

    A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is described. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's proteinaceous amino acids.

  5. Synthesis of Chiral Amino Cyclic Phosphoric Acids

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Chirai amino cyclic phosphoric acids, 5-amino-2-hydroxy-4- (4-nitrophenyl)-l, 3,2-dioxaphospho- rinane 2-oxide and 2-hydroxy-4- (4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in good over yields (64. 2% and 72. 8% respectively) from 2-amino-l-aryl-l,3-propanediols. The different reaction conditions are necessary in hydrolysis reactions of amino cyclic phosphonyl chlorides.

  6. Supernovae and the Chirality of the Amino Acids

    CERN Document Server

    Boyd, R N; Onaka, T

    2010-01-01

    A mechanism for creating amino acid enantiomerism that always selects the same global chirality is identified, and subsequent chemical replication and galactic mixing that would populate the galaxy with the predominant species is described. This involves: (1) the spin of the 14N in the amino acids, or in precursor molecules from which amino acids might be formed, coupling to the chirality of the molecules; 2) the neutrinos emitted from the supernova, together with magnetic field from the nascent neutron star or black hole formed from the supernova selectively destroying one orientation of the 14N, and thus selecting the chirality associated with the other 14N orientation; (3) chemical evolution, by which the molecules replicate and evolve to more complex forms of a single chirality on a relatively short timescale; and (4) galactic mixing on a longer timescale mixing the selected molecules throughout the galaxy.

  7. Chiral Recognition of Amino Acids by Magnetoelectrodeposited Cu Film Electrodes

    Directory of Open Access Journals (Sweden)

    Iwao Mogi

    2011-01-01

    Full Text Available Chiral behavior of magnetoelectrodeposited (MED Cu film electrodes was investigated for the electrochemical reactions of amino acids. The Cu films were electrodeposited under a magnetic field of 5 T perpendicular to the electrode surface. Such MED Cu films were employed as an electrode, and cyclic voltammograms were measured for the electrochemical reactions of several kinds of amino acids. Chiral behavior was clearly observed as oxidation current difference between the enantiomers of alanine, aspartic acid, and glutamic acid. The MED film electrodes with the thickness of 50~500 nm exhibited such chiral behavior, and their surface morphologies had network structures, which could be induced by the micro-MHD effect.

  8. Synthesis, Characterization and Structure of Chiral Amino Acids and Their Corresponding Amino Alcohols with Camphoric Backbone

    Institute of Scientific and Technical Information of China (English)

    QIAN Hui-Fen; HUANG Wei; LI Hui-Hui; YAO Cheng

    2006-01-01

    Chiral amino acids and their corresponding amino alcohols bearing camphoric backbone were prepared from D-(+)-camphoric imide and characterized by infrared, elemental analysis, ESI-MS, and NMR measurements. Among them, one intermediate (lS,3R)-3-amino-2,2,3-trimethyl cyclopentane-1-carboxylic acid hydrochloride 3 was structurally elucidated by X-ray diffraction techniques. Versatile intermolecular hydrogen bonding interactions observed in its packing structure result in a two-dimensional framework.

  9. Chiral morphology of calcite through selective binding of amino acids

    Science.gov (United States)

    Orme, Christine

    2002-03-01

    Many living organisms contain biominerals and composites with finely tuned properties, reflecting a remarkable level of control over the nucleation, growth and shape of the constituent crystals. Peptides and proteins play an important role in achieving this control. Using in situ AFM we find that site-specific binding of amino acid residues to surface steps changes the step-edge free energies, giving rise to direction-specific binding energies unique to individual amino acid enantiomers and leading to chiral modifications that propagate from atomic length scales to macroscopic length scales. Molecular modeling studies support an energetic basis for the differences in binding. Our results emphasize that the mechanism under-lying crystal modification through organic molecules is best understood by considering both stereochemical recognition as well as the effects of binding on the interfacial energies of the growing crystal.

  10. Deracemization of Racemic Amino Acids Using (R)- and (S)-Alanine Racemase Chiral Analogues as Chiral Converters

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Manjeong [Sunchon National Univ., Suncheon (Korea, Republic of); Jeon, So Hee; Lee, Wonjae [Chosun Univ., Gwangju (Korea, Republic of); Kang, Jong Seong [Chungnam National Univ., Daejeon (Korea, Republic of); Kim, Kwan Mook [Ewha Womans Univ., Seoul (Korea, Republic of)

    2014-07-15

    Our findings show that both (R)- and (S)-ARCA can be practical chiral converters for L- and D-amino acids, respectively, in the deracemization of racemic amino acids. The overall stereoselectivities of both chiral converters are generally greater than 90%. In addition, we developed chiral and achiral HPLC methods for the analysis of stereoselectivity determination. This chromatographic method proved much more accurate and convenient at determining both enantiomer and diastereomer purity than did those previously reported. Deracemization is the stereoselective process of converting a racemate into either a pure enantiomer or a mixture in which one enantiomer is present in excess.1 Previous studies have shown that (S)-alanine racemase chiral analogue (ARCA) [(S)-2-hydroxy-2'-(3-phenyluryl-benzyl)-1,1'-binaphthyl-3-carboxaldehyde], developed as a chiral convertor compound that imitates the function of alanine racemase, plays an essential role in the stereoselective conversion of amino acid. Since (S)-ARCA showed a higher stability with D-amino acids than with L-amino acids, several L-amino acids were preferentially converted to D-amino acids via (S)-ARCA/D-amino acid imine diastereomer formation. For the deracemization process undertaken in this study, we utilized both (R)-ARCA and (S)-ARCA as chiral converters, which were expected to generate L- and D-amino acids, respectively, from the starting racemic mixtures.

  11. Capillary electrophoresis and column chromatography in biomedical chiral amino acid analysis.

    Science.gov (United States)

    Waldhier, Magdalena C; Gruber, Michael A; Dettmer, Katja; Oefner, Peter J

    2009-06-01

    Free amino acids are typically quantified as the sum of their enantiomers, because in terrestrial organisms they mainly exist in the left-handed form. However, with increasing understanding of the biological significance of right-handed amino acids interest in enantioselective quantification of amino acids has steadily increased. Initially, electrophoretic and chromatographic methods using chiral (pseudo)-stationary phases or chiral eluents were applied to the separation of amino acid enantiomers. Later, derivatization of amino acids prior to chromatography with chiral reagents gained in popularity, because the diastereomers formed can be resolved on conventional reversed-phase columns. Novel multi-interaction chiral columns turned attention back to direct chiral chromatographic methods. Hyphenation to mass spectrometry has increasingly replaced optical detection because of superior selectivity, although this has not obviated the need for baseline resolution of amino acid enantiomers. Despite the progress made, enantioselective separation and quantification of amino acids remains an analytical challenge owing to frequently incomplete resolution of all naturally occurring enantiomers and insufficient sensitivity for the determination of the trace amounts of D-amino acids typically found in biological fluids and tissues.

  12. Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Bhushan, Ravi; Dixit, Shuchi

    2012-04-01

    Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

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

    Science.gov (United States)

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

    2015-05-06

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

  14. Chiral selectivity of amino acid adsorption on chiral surfaces—The case of alanine on Pt

    Energy Technology Data Exchange (ETDEWEB)

    Franke, J.-H.; Kosov, D. S. [Department of Physics, Campus Plaine - CP 231, Université Libre de Bruxelles, 1050 Brussels (Belgium)

    2015-02-07

    We study the binding pattern of the amino acid alanine on the naturally chiral Pt surfaces Pt(531), Pt(321), and Pt(643). These surfaces are all vicinal to the (111) direction but have different local environments of their kink sites and are thus a model for realistic roughened Pt surfaces. Alanine has only a single methyl group attached to its chiral center, which makes the number of possible binding conformations computationally tractable. Additionally, only the amine and carboxyl group are expected to interact strongly with the Pt substrate. On Pt(531), we study the molecule in its pristine as well as its deprotonated form and find that the deprotonated one is more stable by 0.47 eV. Therefore, we study the molecule in its deprotonated form on Pt(321) and Pt(643). As expected, the oxygen and nitrogen atoms of the deprotonated molecule provide a local binding “tripod” and the most stable adsorption configurations optimize the interaction of this “tripod” with undercoordinated surface atoms. However, the interaction of the methyl group plays an important role: it induces significant chiral selectivity of about 60 meV on all surfaces. Hereby, the L-enantiomer adsorbs preferentially to the Pt(321){sup S} and Pt(643){sup S} surfaces, while the D-enantiomer is more stable on Pt(531){sup S}. The binding energies increase with increasing surface density of kink sites, i.e., they are largest for Pt(531){sup S} and smallest for Pt(643){sup S}.

  15. The 3-amino-derivative of gamma-cyclodextrin as chiral selector of Dns-amino acids in electrokinetic chromatography.

    Science.gov (United States)

    Giuffrida, A; Contino, A; Maccarrone, G; Messina, M; Cucinotta, V

    2009-04-24

    The enantioseparation of the enantiomeric pairs of 10 Dns derivatives of alpha-amino acids was successfully carried out by using for the first time the 3-amino derivative of the gamma-cyclodextrin. The effects of pH and selector concentration on the migration times and the resolutions of analytes were studied in detail. 3-Deoxy-3-amino-2(S),3(R)-gamma-cyclodextrin (GCD3AM) shows very good chiral recognition ability even at very low concentrations at all the three investigated values of pH, as shown by the very large values of selectivity and resolution towards several pairs of amino acids. The role played by the cavity, the substitution site and the protonation equilibria on the observed properties of chiral selectivity, on varying the specific amino acid involved, is discussed.

  16. Chirality-Discriminated Conductivity of Metal-Amino Acid Biocoordination Polymer Nanowires.

    Science.gov (United States)

    Zheng, Jianzhong; Wu, Yijin; Deng, Ke; He, Meng; He, Liangcan; Cao, Jing; Zhang, Xugang; Liu, Yaling; Li, Shunxing; Tang, Zhiyong

    2016-09-27

    Biocoordination polymer (BCP) nanowires are successfully constructed through self-assembly of chiral cysteine amino acids and Cd cations in solution. The varied chirality of cysteine is explored to demonstrate the difference of BCP nanowires in both morphology and structure. More interestingly and surprisingly, the electrical property measurement reveals that, although all Cd(II)/cysteine BCP nanowires behave as semiconductors, the conductivity of the Cd(II)/dl-cysteine nanowires is 4 times higher than that of the Cd(II)/l-cysteine or Cd(II)/d-cysteine ones. The origin of such chirality-discriminated characteristics registered in BCP nanowires is further elucidated by theoretical calculation. These findings demonstrate that the morphology, structure, and property of BCP nanostructures could be tuned by the chirality of the bridging ligands, which will shed light on the comprehension of chirality transcription as well as construction of chirality-regulated functional materials.

  17. Chiral amino acid metabolomics for novel biomarker screening in the prognosis of chronic kidney disease

    Science.gov (United States)

    Kimura, Tomonori; Hamase, Kenji; Miyoshi, Yurika; Yamamoto, Ryohei; Yasuda, Keiko; Mita, Masashi; Rakugi, Hiromi; Hayashi, Terumasa; Isaka, Yoshitaka

    2016-01-01

    D-Amino acids, the enantiomers of L-amino acids, are increasingly recognized as novel biomarkers. Although the amounts of D-amino acids are usually very trace in human, some of them have sporadically been detected in blood from patients with kidney diseases. This study examined whether multiple chiral amino acids would be associated with kidney functions, comorbidities, and prognosis of chronic kidney disease (CKD) by enantioselective analyses of all chiral amino acids with a micro-two-dimensional high-performance liquid chromatograph (2D-HPLC)-based analytical platform. 16 out of 21 D-amino acids were detected in plasma from 108 CKD patients in a longitudinal cohort. The levels of D-Ser, D-Pro, and D-Asn were strongly associated with kidney function (estimated glomerular filtration ratio), the levels of D-Ala and D-Pro were associated with age, and the level of D-Asp and D-Pro were associated with the presence of diabetes mellitus. D-Ser and D-Asn were significantly associated with the progression of CKD in mutually-adjusted Cox regression analyses; the risk of composite end point (developing to ESKD or death before ESKD) was elevated from 2.7- to 3.8-fold in those with higher levels of plasma D-Ser and D-Asn. These findings identified chiral amino acids as potential biomarkers in kidney diseases. PMID:27188851

  18. Integrated Micro-Chip Amino Acid Chirality Detector for MOD

    Science.gov (United States)

    Glavin, D. P.; Bada, J. L.; Botta, O.; Kminek, G.; Grunthaner, F.; Mathies, R.

    2001-01-01

    Integration of a micro-chip capillary electrophoresis analyzer with a sublimation-based extraction technique, as used in the Mars Organic Detector (MOD), for the in-situ detection of amino acids and their enantiomers on solar system bodies. Additional information is contained in the original extended abstract.

  19. Enantioselective binding of amino acids and amino alcohols by self-assembled chiral basket-shaped receptors

    NARCIS (Netherlands)

    Escuder, B.; Rowan, A.E.; Feiters, M.C.; Nolte, R.J.M.

    2004-01-01

    Amino acid appended diphenylglycoluril-based chiral molecular receptors 2 and 3 have been prepared and their aggregation has been studied in water at various pH's and in chloroform. The binding of several biologically relevant guests with aromatic moieties to these aggregates has been studied with U

  20. Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis.

    Science.gov (United States)

    Paek, Seung-Mann; Jeong, Myeonggyo; Jo, Jeyun; Heo, Yu Mi; Han, Young Taek; Yun, Hwayoung

    2016-07-21

    Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

  1. Chirality, photochemistry and the detection of amino acids in interstellar ice analogues and comets.

    Science.gov (United States)

    Evans, Amanda C; Meinert, Cornelia; Giri, Chaitanya; Goesmann, Fred; Meierhenrich, Uwe J

    2012-08-21

    The primordial appearance of chiral amino acids was an essential component of the asymmetric evolution of life on Earth. In this tutorial review we will explore the original life-generating, symmetry-breaking event and summarise recent thoughts on the origin of enantiomeric excess in the universe. We will then highlight the transfer of asymmetry from chiral photons to racemic amino acids and elucidate current experimental data on the photochemical synthesis of amino and diamino acid structures in simulated interstellar and circumstellar ice environments. The chirality inherent within actual interstellar (cometary) ice environments will be considered in this discussion: in 2014 the Rosetta Lander Philae onboard the Rosetta space probe is planned to detach from the orbiter and soft-land on the surface of the nucleus of comet 67P/Churyumov-Gerasimenko. It is equipped for the in situ enantioselective analysis of chiral prebiotic organic species in cometary ices. The scientific design of this mission will therefore be presented in the context of analysing the formation of amino acid structures within interstellar ice analogues as a means towards furthering understanding of the origin of asymmetric biological molecules.

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

    Science.gov (United States)

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

    2015-03-01

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

  3. Application of modified amino acid as a chiral building block in asymmetric synthesis

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Phenylglycine 1 as a representative of natural resourceful (-amino acid was modified by reduction and protection of functional group to afford the amino alcohol as a chiral building block 3. A new chiral compound, the chiral building block/spiro-cyclopropane derivative containing four stereogenic centers, compound 7, has been obtained in 52% yield with de≥98% via the tandem double Michael addition/internal nucleophilic substitution under mild condition of 5-l-menthyloxy-3-bromo-2-(5H)-furanone 4 with the nucleophilic reagent, the amino alcohol 3. The new chiral compound 7 is identified on the basis of its analytical data and spectroscopic data, such as UV, IR, 1H NMR, 13C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes 7 was established by X-ray crystallography. This result can provide new route and method for the introduction of chiral building block and the important synthetic strategy in synthesis of some complex molecules containing spiro-cyclopropane skeleton with multiple chiral centers and the study of their biological activity.

  4. Metal-organic complex-functionalized protein nanopore sensor for aromatic amino acids chiral recognition.

    Science.gov (United States)

    Guo, Yanli; Niu, Aihua; Jian, Feifei; Wang, Ying; Yao, Fujun; Wei, Yongfeng; Tian, Lei; Kang, Xiaofeng

    2017-03-27

    Chiral recognition at single-molecule level for small active molecules is important, as exhibited by many nanostructures and molecular assemblies in biological systems, but it presents a significant challenge. We report a simple and rapid sensing strategy to discriminate all enantiomers of natural aromatic amino acids (AAA) using a metal-organic complex-functionalized protein nanopore, in which a chiral recognition element and a chiral recognition valve were equipped. A trifunctional molecule, heptakis-(6-deoxy-6-amino)-β-cyclodextrin (am7βCD), was non-covalently lodged within the nanopore of an α-hemolysin (αHL) mutant, (M113R)7-αHL. Copper(ii) ion reversibly bonds to the amino group of am7βCD to form an am7βCD-Cu(II) complex, which allowed chiral recognition for each enantiomer in the mixture of AAA by distinct current signals. The Cu(II) plugging valve plays a crucial rule that holds chiral molecules in the nanocavity for a sufficient registering time. Importantly, six enantiomers of all nature AAA could be simultaneously recognized at one time. Enantiomeric excess (ee) could also be accurately detected by this approach. It should be possible to generalize this approach for sensing of other chiral molecules.

  5. Synthesis of Chiral 1,4-Disubstituted-1,2,3-Triazole Derivatives from Amino Acids

    Directory of Open Access Journals (Sweden)

    Morten Grøtli

    2009-12-01

    Full Text Available A versatile method for the synthesis of chiral 1,4-disubstituted-1,2,3-triazole derivatives starting from easily accessible naturally occurring D-or L-amino acids as chiral synthons is described. The amino acids were converted into azido alcohols, followed by copper catalyzed [3+2] cycloaddition reactions between the azido alcohols and methyl propiolate and subsequent ester aminolysis with primary and secondary amines furnished the target compounds, which were obtained in excellent yields with no racemization. Docking of selected target compounds shows that the chiral 1,4-disubstituted-1,2,3-triazoles derivatives has the potential of mimicking the binding mode of known purine analogues.

  6. Aldolase as a chirality intersection of L-amino acids and D-sugars.

    Science.gov (United States)

    Munegumi, Toratane

    2015-06-01

    Aldolase plays an important role in glycolysis and gluconeogenesis to produce D-fructose-1,6-bisphosphate (D-FBP) from dihydroxyacetone phosphate (DHP) and D-glyceraldehyde-3-phosphate (D-GAP). This reaction is stereoselective and retains the D-GAP 2R configuration and yields D-FBP (with the configuration: 3S, 4S, 5R). The 3- and 4-position carbons are the newly formed chiral carbons because the 5-position carbon of D-FBP comes from the 2-position of D-GAP. Although four diastereomeric products, (3S, 4R, 5R), (3R, 4R, 5R), (3R, 4S, 5R), (3S, 4S, 5R), are expected in the nonenzymatic reaction, only the (3S, 4S, 5R) diastereomer (D-FBP) is obtained. Therefore, the chirality in the 3- and 4-positions is induced by the chirality of the enzyme composed of L-amino acid residues. D-Glucose-6-phosphate (D-G6P), which is generated from D-FBP in the gluconeogenesis pathway, produces D-ribose-5-phosphate (D-R5P) in the pentose phosphate pathway. D-R5P is converted to PRPP (5-phosphoribosyl-α-pyrophosphate), which is used for the de novo synthesis of nucleotides. Ribonucleic acid (RNA) uses the nucleotides as building blocks. The configurations of the 4R-carbon and of the 3S-carbon are retained. The stereochemical structure of RNA is based on 3S as well as 4R (D). The consideration above suggests that aldolase is a key enzyme that determines the 3S configuration in D-R5P. It is thus a chirality intersection between amino acids and sugars, because the sugar chirality is determined by the chiral environment of an L-amino acid protein, aldolase, to produce D-FBP.

  7. Aldolase as a Chirality Intersection of L-Amino Acids and D-Sugars

    Science.gov (United States)

    Munegumi, Toratane

    2015-06-01

    Aldolase plays an important role in glycolysis and gluconeogenesis to produce D-fructose-1,6-bisphosphate (D-FBP) from dihydroxyacetone phosphate (DHP) and D-glyceraldehyde-3-phosphate (D-GAP). This reaction is stereoselective and retains the D-GAP 2R configuration and yields D-FBP (with the configuration: 3S, 4S, 5R). The 3- and 4-position carbons are the newly formed chiral carbons because the 5-position carbon of D-FBP comes from the 2-position of D-GAP. Although four diastereomeric products, ( 3S, 4R, 5R), ( 3R, 4R, 5R), ( 3R, 4S, 5R), ( 3S, 4S, 5R), are expected in the nonenzymatic reaction, only the ( 3S, 4S, 5R) diastereomer (D-FBP) is obtained. Therefore, the chirality in the 3- and 4-positions is induced by the chirality of the enzyme composed of L-amino acid residues. D-Glucose-6-phosphate (D-G6P), which is generated from D-FBP in the gluconeogenesis pathway, produces D-ribose-5-phosphate (D-R5P) in the pentose phosphate pathway. D-R5P is converted to PRPP (5-phosphoribosyl-α-pyrophosphate), which is used for the de novo synthesis of nucleotides. Ribonucleic acid (RNA) uses the nucleotides as building blocks. The configurations of the 4R-carbon and of the 3S-carbon are retained. The stereochemical structure of RNA is based on 3S as well as 4R (D). The consideration above suggests that aldolase is a key enzyme that determines the 3S configuration in D-R5P. It is thus a chirality intersection between amino acids and sugars, because the sugar chirality is determined by the chiral environment of an L-amino acid protein, aldolase, to produce D-FBP.

  8. Chiral MEKC-LIF of amino acids in foods: analysis of vinegars.

    Science.gov (United States)

    Carlavilla, Davinia; Moreno-Arribas, M Victoria; Fanali, Salvatore; Cifuentes, Alejandro

    2006-07-01

    The formation of D-amino acids (D-aa's) in many fermented foods depends, among other factors, on the particular fermentation conditions, the action and autolysis of the microorganisms involved. In this sense, the analysis of chiral amino acids is an interesting analytical strategy for food scientists, since these compounds can be used as bacterial markers and can help, e.g., to detect adulterations, microbiological contaminations, etc. In this work, a fast and sensitive method based on MEKC-LIF has been developed to analyze and quantitate L-amino acid (L-aa) and D-aa in vinegars. The chiral MEKC-LIF procedure uses 100 mM sodium tetraborate, 30 mM SDS, and 20 mM beta-CD at pH 9.7 as running buffer, obtaining a good separation of the main vinegar L-/D-aa previously derivatized with fluorescein isothiocianate. Namely, L/D proline, alanine, arginine, glutamic, and aspartic acid, plus the nonchiral amino acid gamma-aminobutyric acid are separated in less than 20 min with high efficiency (up to 720,000 plates/m) and good sensitivity (LODs lower than 16.6 nM were achieved). Several D-aa's were detected and quantified in balsamic, sherry, white wine, and cider vinegars using this MEKC-LIF procedure, observing interesting differences in their L-aa and D-aa profiles and contents.

  9. Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

    Institute of Scientific and Technical Information of China (English)

    LIU Hai-Yang; TIAN Jun-Chun; YING Xiao; XU Zhi-Guang; LIAO Shi-Jun; CHANG Chi-Kwong

    2005-01-01

    Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipolarizabilities, and they may be ascribed as the "mixture" of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic х (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.

  10. Chiral Recognition for the Two Enantiomers of Phenylalanine and Four Amino Acid Derivatives with (S)-Phenylethylamine Derived Nickel(II) Macrocyclic Complex

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jeong Jae; Ryoo, Jae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

    2013-11-15

    The potency of new chiral selector candidate was assessed by this simple chiral discrimination test. This experiment showed that the macrocyclic molecule can be a powerful candidate as a chiral selector to obtain optically pure amino acid or amino acid derivatives, particularly phenylalanine and N-benzoyl-phenylalanine enantiomers from racemic mixtures. This study attempted to use the chiral metal organic framework (MOF), 1, as a good chiral selector candidate for the chiral discrimination of racemic phenylalanine, N-benzoyl-alanine, N-benzoyl-phenylalanine, N-benzoyl-methionine, N-CBZ-alanine. The chiral recognition ability of the chiral macromolecule, was examined by varying the molar ratio of the macromolecule and racemates.

  11. Efficient optical resolution of amino acid by alanine racemaze chiral analogue supported on mesoporous carbon

    Science.gov (United States)

    Jang, D.; Kim, K.; Park, D.; Kim, G.

    2012-09-01

    Optically pure D-amino acids are industrially important chiral building blocks for the synthesis of pharmaceuticals, food ingredients, and drug intermediates. Chemoenzymatic dynamic kinetic-resolution processes have recently been developed for deracemization of amino acids. S-ARCA would be a good candidate for the selective adsorption of D amino acid through the imine formation reaction. The organic phase containing S-ARCA adsorbent, TPPC or Ionic Liquid (as a phase transfer catalyst) in MC were coated on the surfaces of mesoporous carbon C-SBA-15(CMK). The aqueous solution of racemic D/L-amino acid and NaOH were added to the carbon support coated with ARCA. The D/L ratios on ARCA and in solution were determined with increasing reaction time. S-ARCA has a unique property for the selective adsorption of D- amino acid (up to 90% selcetivity) in the racemic mixture. The fixed bed reactor containing ARCA/carbon support was also adopted successfully for the selective separation of amino acid.

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2014-06-01

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

  14. Amino Acids in Comets and Meteorites: Stability under Gamma Radiation and Preservation of Chirality

    CERN Document Server

    Iglesias-Groth, Susana; Ursini, Ornella; Manchado, Arturo

    2010-01-01

    Amino acids in solar system bodies may have played a key role in the chemistry that led to the origin of life on Earth. We present laboratory studies testing the stability of amino acids against gamma radiation photolysis. All the 20 chiral amino acids in the levo form used in the proteins of the current terrestrial biochemistry have been irradiated in the solid state with gamma radiation to a dose of 3.2 MGy which is the dose equivalent to that derived by radionuclide decay in comets and asteroids in 1.05x109 years. For each amino acid the radiolysis degree and the radioracemization degree was measured by differential scanning calorimetry (DSC) and by optical rotatory dispersion (ORD) spectroscopy. From these measurements a radiolysis rate constant kdsc and a radioracemization rate constant krac have been determined for each amino acid and extrapolated to a dose of 14 MGy which corresponds to the expected total dose delivered by the natural radionuclides decay to all the organic molecules present in comets a...

  15. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    OpenAIRE

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to st...

  16. On the origin of single chirality of amino acids and sugars in biogenesis.

    Science.gov (United States)

    Hein, Jason E; Blackmond, Donna G

    2012-12-18

    The process of delineating the origins of the chemistry of life starts with the consideration of the molecules that might have existed on prebiotic earth and extends to the discussion of potential mechanisms for assembly of these molecules into informational polymers capable of self-replication and transmittance of genetic information. At some point along this pathway, the property of single chirality emerges as the hallmark of the amino acids and sugars present in biological molecules. In the 20th century, researchers developed abstract mathematical theses for the origin of biomolecular homochirality from a presumably racemic collection of prebiotic molecules. Before the end of that century, experimental findings corroborated a number of basic features of these theoretical models, but these studies involved chemical systems without direct prebiotic relevance. Currently researchers are examining prebiotically plausible conditions that couple chemical and physical processes leading to single chirality of sugars and amino acids with subsequent chemical reactions that enhance molecular complexity. While these studies have been conducted for the most part in the context of the RNA World hypothesis, the experimental findings remain relevant to a "metabolism first" model for the origin of life. To many chemists interested in chembiogenesis, the synthesis of activated pyrimidine ribonucleotides under potentially prebiotic conditions by Sutherland's group provided a landmark demonstration of what Eschenmoser has described as "an intrinsic structural propinquity" between certain elementary chemical structures and modern biological molecules. Even while some synthetic issues for plausible prebiotic construction of RNA remain unsolved, our work has focused on coupling these synthetic advances with concepts for the evolution of biomlolecular homochirality. Drawing on our own findings as well as those from others, we present an intriguing "chicken or egg" scenario for the

  17. Development of new chiral ligand exchange capillary electrophoresis system with amino acid ionic liquids ligands and its application in studying the kinetics of L-amino acid oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Bingbing [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); College of Food Sciences and Engineering, Shandong Agricultural University, Tai’an, Shandong 271018 (China); Mu, Xiaoyu [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Qi, Li, E-mail: qili@iccas.ac.cn [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

    2014-04-01

    Highlights: • Novel amino acid ionic liquids with pyridinium as cations and L-lysine as anion were synthesized. • These synthesized AAILs have been explored as the ligands coordinated with Zn(II) in CLE-CE system. • The developed CLE-CE method could be used for the enantioseparation of Dns-D, L-amino acids. • The kinetic contents of L-amino acid oxidase were investigated with the proposed CLE-CE system. - Abstract: New kinds of amino acid ionic liquids (AAILs) with pyridinium as cations and L-lysine (L-Lys) as anion have been developed as the available chiral ligands coordinated with Zn(II) in chiral ligand-exchange capillary electrophoresis (CLE-CE). Four kinds of AAILs, including [1-ethylpyridinium][L-lysine], 1-butylpyridinium][L-lysine], [1-hexylpyridinium][L-lysine] and 1-[octylpyridinium][L-lysine], were successfully synthesized and characterized by nuclear magnetic resonance and mass spectrometry. Compared with other AAILs, the best chiral separation of Dns-D, L-amino acids could be achieved when [1-ethylpyridinium][L-lysine] was chosen as the chiral ligand. It has been found that after investigating the influence of key factors on the separation efficiency, such as pH of buffer solution, the ratio of Zn(II) to ligand and complex concentration, eight pairs of Dns-D, L-AAs enantiomers could be baseline separated and three pairs were partly separated under the optimum conditions. The proposed CLE-CE method also exhibited favorable quantitative analysis property of Dns-D, L-Met with good linearity (r{sup 2} = 0.998) and favorable repeatability (RSD ≤ 1.5%). Furthermore, the CLE-CE system was applied in investigating the kinetic contents of L-amino acid oxidase, which implied that the proposed system has the potential in studying the enzymatic reaction mechanism.

  18. Analysis of chiral amino acids in cerebrospinal fluid samples linked to different stages of Alzheimer disease.

    Science.gov (United States)

    Samakashvili, Shorena; Ibáñez, Clara; Simó, Carolina; Gil-Bea, Francisco J; Winblad, Bengt; Cedazo-Mínguez, Angel; Cifuentes, Alejandro

    2011-10-01

    Chiral micellar electrokinetic chromatography with laser-induced fluorescence detection (chiral-MEKC-LIF) was used to investigate D- and L-amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral-MEKC-LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703,000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L-Arg, L-Leu, L-Gln, γ-aminobutyric acid, L-Ser, D-Ser, L-Ala, Gly, L-Lys, L-Glu and L-Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L-Arg L-Lys, L-Glu and L-Asp compared to the non-AD S1 and S2 samples, showing in the S4 group the lowest amounts of L-Arg L-Lys, L-Glu and L-Asp. Moreover, γ-aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D-Ser. Based on the obtained chiral-MEKC-LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD.

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

    Science.gov (United States)

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

    2012-12-01

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

  20. A universal strategy for visual chiral recognition of α-amino acids with L-tartaric acid-capped gold nanoparticles as colorimetric probes.

    Science.gov (United States)

    Song, Guoxin; Zhou, Fulin; Xu, Chunli; Li, Baoxin

    2016-02-21

    The ability to recognize and quantify the chirality of alpha-amino acids constitutes the basis of many critical areas for specific targeting in drug development and metabolite probing. It is still challenging to conveniently distinguish the enantiomer of amino acids largely due to the lack of a universal and simple strategy. In this work, we report a strategy for the visual recognition of α-amino acids. It is based on the chirality of L-tartaric acid-capped gold nanoparticles (L-TA-capped AuNPs, ca. 13 nm in diameter). All of 19 right-handed α-amino acids can induce a red-to-blue color change of L-TA-capped AuNP solution, whereas all of the left-handed amino acids (except cysteine) cannot. The chiral recognition can be achieved by the naked eye and a simple spectrophotometer. This method does not require complicated chiral modification, and excels through its low-cost, good availability of materials and its simplicity. Another notable feature of this method is its high generality, and this method can discriminate almost all native α-amino acid enantiomers. This versatile method could be potentially used for high-throughput chiral recognition of amino acids.

  1. Chirality Emergence in Thin Solid Films of Amino Acids by Polarized Light from Synchrotron Radiation and Free Electron Laser

    Directory of Open Access Journals (Sweden)

    Mashahiro Adachi

    2009-07-01

    Full Text Available One of the most attractive hypothesis for the origin of homochirality in terrestrial bioorganic compounds is that a kind of “chiral impulse” as an asymmetric excitation source induced asymmetric reactions on the surfaces of such materials such as meteorites or interstellar dusts prior to the existence of terrestrial life (Cosmic Scenario. To experimentally introduce chiral structure into racemic films of amino acids (alanine, phenylalanine, isovaline, etc., we irradiated them with linearly polarized light (LPL from synchrotron radiation and circularly polarized light (CPL from a free electron laser. After the irradiation, we evaluated optical anisotropy by measuring the circular dichroism (CD spectra and verified that new Cotton peaks appeared at almost the same peak position as those of the corresponding non-racemic amino acid films. With LPL irradiation, two-dimensional anisotropic structure expressed as linear dichroism and/or linear birefringence was introduced into the racemic films. With CPL irradiation, the signs of the Cotton peaks exhibit symmetrical structure corresponding to the direction of CPL rotation. This indicates that some kinds of chiral structure were introduced into the racemic film. The CD spectra after CPL irradiation suggest the chiral structure should be derived from not only preferential photolysis but also from photolysis-induced molecular structural change. These results suggest that circularly polarized light sources in space could be associated with the origin of terrestrial homochirality; that is, they would be effective asymmetric exciting sources introducing chiral structures into bio-organic molecules or complex organic compounds.

  2. Decomposition of Alternative Chirality Amino Acids by Alkaliphilic Anaerobe from Owens Lake, California

    Science.gov (United States)

    Townsend, Alisa; Pikuta, Elena V.; Guisler, Melissa; Hoover, Richard B.

    2009-01-01

    The study of alkaliphilic microbial communities from anaerobic sediments of Owens and Mono Lakes in California led to the isolation of a bacterial strain capable of metabolizing amino acids with alternative chirality. According to the phylogenetic analysis, the anaerobic strain BK1 belongs to the genus Tindallia; however, despite the characteristics of other described species of this genus, the strain BK1 was able to grow on D-arginine and Dlysine. Cell morphology of this strain showed straight, motile, non-spore-forming rods with sizes 0.45 x 1.2-3 microns. Physiological characteristics of the strain showed that it is catalase negative, obligately anaerobic, mesophilic, and obligately alkaliphilic. This isolate is unable to grow at pH 7 and requires CO3 (2-) ions for growth. The strain has chemo-heterotrophic metabolism and is able to ferment various proteolysis products and some sugars. It plays the role of a primary anaerobe within the trophic chain of an anaerobic microbial community by the degradation of complex protein molecules to smaller and less energetic molecules. The new isolate requires NaCl for growth, and can grow within the range of 0.5-13 %, with the optimum at 1 % NaCl (w/v). The temperature range for the growth of the new isolate is 12-40 C with optimum at 35 C. The pH range for the growth of strain BK1 occurs between 7.8 and 11.0 with optimum at 9.5. This paper presents detailed physiological characteristics of the novel isolate from Owens Lake, a unique relic ecosystem of Astrobiological significance, and makes an accent on the ability of this strain to utilize L-amino acids.

  3. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    Science.gov (United States)

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-09-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

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

    Science.gov (United States)

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

    1996-09-06

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

  5. Amino Acid Chirality and Ferrocene Conformation Guided Self-Assembly and Gelation of Ferrocene-Peptide Conjugates.

    Science.gov (United States)

    Adhikari, Bimalendu; Singh, Charanpreet; Shah, Afzal; Lough, Alan J; Kraatz, Heinz-Bernhard

    2015-08-03

    The self-assembly and gelation behavior of a series of mono- and disubstituted ferrocene (Fc)-peptide conjugates as a function of ferrocene conformation and amino acid chirality are described. The results reveal that ferrocene-peptide conjugates self-assemble into organogels by controlling the conformation of the central ferrocene core, through inter- versus intramolecular hydrogen bonding in the attached peptide chain(s). The chirality controlled assembling studies showed that two monosubstituted Fc conjugates FcCO-LFLFLA-OMe and FcCO-LFLFDA-OMe form gels with nanofibrillar network structures, whereas the other two diastereomers FcCO-DFLFLA-OMe and FcCO-LFDFLA-OMe exclusively produced straight nanorods and non-interconnected small fibers, respectively. This suggests the potential tuning of gelation behavior and nanoscale morphology by altering the chirality of constituted amino acids. The current study confirms the profound effect of diastereomerism and no influence of enantiomers on gelation. Correspondingly, the diastereomeric and enantiomeric Fc[CO-FFA-OMe]2 were constructed for the study of chirality-organized structures.

  6. Selective adsorption and chiral amplification of amino acids in vermiculite clay-implications for the origin of biochirality.

    Science.gov (United States)

    Fraser, Donald G; Fitz, Daniel; Jakschitz, T; Rode, Bernd M

    2011-01-21

    Smectite clays are hydrated layer silicates that, like micas, occur naturally in abundance. Importantly, they have readily modifiable interlayer spaces that provide excellent sites for nanochemistry. Vermiculite is one such smectite clay and in the presence of small chain-length alkyl-NH(3)Cl ions forms sensitive, 1-D ordered model clay systems with expandable nano-pore inter-layer regions. These inter-layers readily adsorb organic molecules. n-Propyl NH(3)Cl vermiculite clay gels were used to determine the adsorption of alanine, lysine and histidine by chiral HPLC. The results show that during reaction with fresh vermiculite interlayers, significant chiral enrichment of either L- and D-enantiomers occurs depending on the amino acid. Chiral enrichment of the supernatant solutions is up to about 1% per pass. In contrast, addition to clay interlayers already reacted with amino acid solutions resulted in little or no change in D/L ratio during the time of the experiment. Adsorption of small amounts of amphiphilic organic molecules in clay inter-layers is known to produce Layer-by-Layer or Langmuir-Blodgett films. Moreover atomistic simulations show that self-organization of organic species in clay interlayers is important. These non-centrosymmetric, chirally active nanofilms may cause clays to act subsequently as chiral amplifiers, concentrating organic material from dilute solution and having different adsorption energetics for D- and L-enantiomers. The additional role of clays in RNA oligomerization already postulated by Ferris and others, together with the need for the organization of amphiphilic molecules and lipids noted by Szostak and others, suggests that such chiral separation by clays in lagoonal environments at normal biological temperatures might also have played a significant role in the origin of biochirality.

  7. The formation of right-handed and left-handed chiral nanopores within a single domain during amino acid self-assembly on Au(111).

    Science.gov (United States)

    Yang, Sena; Jeon, Aram; Driver, Russell W; Kim, Yeonwoo; Jeon, Eun Hee; Kim, Sehun; Lee, Hee-Seung; Lee, Hangil

    2016-05-25

    We report the formation of both right- and left-handed chiral nanopores within a single domain during the self-assembly of an amino acid derivative on an inert Au(111) surface using STM. DFT calculations employed to rationalize this unusual result identified that intermolecular interactions between chiral, windmill-shaped tetramers are crucial for self-assembly.

  8. New Chiral Calixarene Derivatives: Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.

  9. Selective Adsorption and Chiral Amplification of Amino Acids in Vermiculite Clay -Implications for the origin of biochirality

    CERN Document Server

    Fraser, Donald G; Jakschitz, Thomas; Rode, Bernd M

    2010-01-01

    Smectite clays are hydrated layer silicates that, like micas, occur naturally in abundance. Importantly, they have readily modifiable interlayer spaces that provide excellent sites for nanochemistry. Vermiculite is one such smectite clay and in the presence of small chain-length alkyl-NH3Cl ions, forms sensitive, 1-D ordered model clay systems with expandable nano-pore inter-layer regions. These inter-layers readily adsorb organic molecules. N-propyl NH3Cl vermiculite clay gels were used to determine the adsorption of alanine, lysine and histidine by chiral HPLC. The results show that during reaction with fresh vermiculite interlayers, significant chiral enrichment of either L- and D-enantiomers occurs depending on the amino acid. Chiral enrichment of the supernatant solutions is up to about 1% per pass. In contrast, addition to clay interlayers already reacted with amino acid solutions resulted in little or no change in D/L ratio during the time of the experiment. Adsorption of small amounts of amphiphilic o...

  10. Amino acids

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/002222.htm Amino acids To use the sharing features on this page, please enable JavaScript. Amino acids are organic compounds that combine to form proteins . ...

  11. Indispensable but insufficient role of renal D-amino acid oxidase in chiral inversion of NG-nitro-D-arginine.

    Science.gov (United States)

    Xin, Yan-Fei; Li, Xin; Hao, Bin; Gong, Nian; Sun, Wen-Qiang; Konno, Ryuichi; Wang, Yong-Xiang

    2010-06-01

    Unidirectionally chiral inversion of N(G)-nitro-D-arginine (D-NNA) to its L-enantiomer (L-NNA) occurred in rats, and it was blocked markedly (ca. 80%) by renal vascular ligation, and entirely (100%) by the D-amino acid oxidase (DAO) inhibitor sodium benzoate, suggesting that renal DAO is essential for the inversion. However, the doses of sodium benzoate administrated were extremely high (e.g., 400 mg/kg) due to its low potency. It is thus possible that sodium benzoate-mediated blockade of D-NNA inversion might be due to its nonspecific (or non-DAO-related) effects. In addition, after D-NNA was incubated with the pure enzyme of DAO in vitro without tissue homogenates, L-NNA was not produced, even though D-NNA was disposed. We propose that this occurred because D-NNA was first converted to its corresponding alpha-keto acid by DAO and then to L-NNA by transaminase(s); however, there was no direct evidence for this process. The goal of this study is to further elucidate the process of D-NNA chiral inversion both in vivo and in in vitro tissue homogenates by comparing mutant ddY/DAO(-/-) mice that lack DAO activity entirely compared to normal ddY/DAO(+/+) mice and Swiss mice. Furthermore, the ability to produce L-NNA from D-NNA-corresponding alpha-keto acids (N(G)-nitroguanidino-2-oxopentanoic acid) produced by porcine kidney-derived DAO (pkDAO) was also studied in the DAO inhibitor-pretreated rats. We found that D-NNA chiral inversion occurred in Swiss mice and ddY/DAO(+/+) mice both in vivo and in in vitro kidney homogenates, but not in ddY/DAO(-/-) mice, correlated to their DAO activities. The alpha-keto acid (N(G)-nitro-guanidino-2-oxopentanoic acid) from D-NNA was able to produce L-NNA, and subsequent vasoconstriction and pressor responses. These results indicate that the role of renal DAO is indispensible but insufficient for chiral inversion of D-NNA and other neutral and polar D-amino acids, and unidentified aminotransferase(s) are involved in a subsequent

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

    Science.gov (United States)

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

    2017-03-01

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

  13. Synthesis of variants of Marfey's reagent having d-amino acids as chiral auxiliaries and liquid-chromatographic enantioseparation of (RS)-Mexiletine in spiked plasma: assessment and comparison with L-amino acid analogs.

    Science.gov (United States)

    Bhushan, Ravi; Vashistha, Vinod Kumar

    2015-01-30

    Five d-amino acids have been used for the first time to synthesize chiral derivatizing reagents (as variants of Marfey's reagent) by nucleophilic displacement of one of the fluorine atoms in 1,5-difluoro-2,4-dinitrobenzene as against the literature reports on application of only l-amino acids or their amides as chiral auxiliaries in dinitrobenzene (DNB) moiety. Five other DNB based reagents were also prepared by nucleophilic substitution of fluorine atom with the set of the same amino acids in l-configuration, as chiral auxiliaries. These reagents were characterized and used for synthesis of diastereomers of (RS)-Mexiletine spiked in human plasma. Diastereomers were synthesized employing microwave irradiation and were separated on reversed-phase C18 column. Performance of the two types of chiral derivatizing reagents was compared. The reagents containing d-amino acids provided enhanced separation of diastereomers than those containing l-amino acids. The best resolution was obtained using mobile phase consisting of acetonitrile and 0.1% trifluoroacetic acid in gradient mode. The detection was carried out at 340nm. The method so developed was validated for linearity, accuracy and precision. The limit of quantitation was found to be approximately 25.2ngmL(-1) in human plasma.

  14. Chiral Sensing of Various Amino Acids Using Induced Circularly Polarized Luminescence from Europium(III) Complexes of Phenanthroline Dicarboxylic Acid Derivatives.

    Science.gov (United States)

    Uchida, Taka-Aki; Nozaki, Koichi; Iwamura, Munetaka

    2016-09-06

    Circularly polarized luminescence (CPL) was observed from [Eu(dppda)2 ](-) (dppda=4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid) and [Eu(pzpda)2 ](-) (pzpda=pyrazino[2,3-f][1,10]phenanthroline-7,10-dicarboxylic acid) in aqueous solutions containing various amino acids. The selectivity of these complexes towards amino acids enabled them to be used as chiral sensors and their behavior was compared with that of [Eu(pda)2 ](-) (pda=1,10-phenanthroline-2,9-dicarboxylic acid). As these Eu(III) complexes have achiral D2d structures under ordinary conditions, there were no CPL signals in the emission assigned to f-f transitions. However, when the solutions contained particular amino acids they exhibited detectable CPL signals with glum values of about 0.1 (glum =CPL/2 TL; TL=total luminescence). On examining 13 amino acids with these three Eu(III) complexes, it was found that whether an amino acid induced a detectable CPL depended on the Eu(III) complex ligands. For example, when ornithine was used as a chiral agent, only [Eu(dppda)2 ](-) exhibited intense CPL in aqueous solutions of 10(-2)  mol dm(-3) . Steep amino acid concentration dependence suggested that CPL in [Eu(dppda)2 ](-) and [Eu(pzpda)2 ](-) was induced by the association of four or more amino acid molecules, whereas CPL in [Eu(pda)2 ](-) was induced by association of two arginine molecules.

  15. Amino acid chiral recognition using X-ray diffraction of thin films

    Science.gov (United States)

    Dragoi, D.; Kulleck, J.; Kanik, I.; Beegle, L. W.

    2003-01-01

    The astrobiological search for life, both extinct and extant, on other solar system bodies will take place via several planned lander missions to Mars, Europa and Titan. The detection and identification of organic molecules that have been associated with life is a major technical achievement. Terrestrial life utilizes organic molecules, such as amino acids, as its basic building block. Detection of an entometeric excess of L over D forms of amino acids would be a powerful sign that life had existed on Mars at one time.

  16. Direct chromatographic enantioresolution of fully constrained β-amino acids: exploring the use of high-molecular weight chiral selectors.

    Science.gov (United States)

    Sardella, Roccaldo; Ianni, Federica; Lisanti, Antonella; Scorzoni, Stefania; Marini, Francesca; Sternativo, Silvia; Natalini, Benedetto

    2014-05-01

    To the best of our knowledge enantioselective chromatographic protocols on β-amino acids with polysaccharide-based chiral stationary phases (CSPs) have not yet appeared in the literature. Therefore, the primary objective of this work was the development of chromatographic methods based on the use of an amylose derivative CSP (Lux Amylose-2), enabling the direct normal-phase (NP) enantioresolution of four fully constrained β-amino acids. Also, the results obtained with the glycopeptide-type Chirobiotic T column employed in the usual polar-ionic (PI) mode of elution are compared with those achieved with the polysaccharide-based phase. The Lux Amylose-2 column, in combination with alkyl sulfonic acid containing NP eluent systems, prevailed over the Chirobiotic T one, when used under the PI mode of elution, and hence can be considered as the elective choice for the enantioseparation of this class of rigid β-amino acids. Moreover, the extraordinarily high α (up to 4.60) and R S (up to 10.60) values provided by the polysaccharidic polymer, especially when used with camphor sulfonic acid containing eluent systems, make it also suitable for preparative-scale enantioisolations.

  17. Enantioselective self-assembly of antiferromagnetic hexacopper(II) wheels with chiral amino acid oxamates.

    Science.gov (United States)

    Grancha, Thais; Ferrando-Soria, Jesús; Cano, Joan; Lloret, Francesc; Julve, Miguel; De Munno, Giovanni; Armentano, Donatella; Pardo, Emilio

    2013-07-01

    The Cu(2+)-mediated self-assembly of oxamato-based ligands derived from either the (S)- or (R)-enantiomers of the amino acid valine leads to the formation of two antiferromagnetically coupled homochiral anionic hexacopper(II) wheels in the presence of templating tetramethylammonium countercations.

  18. Specific chiral sensing of amino acids using induced circularly polarized luminescence of bis(diimine)dicarboxylic acid europium(III) complexes.

    Science.gov (United States)

    Okutani, Kazuhiro; Nozaki, Koichi; Iwamura, Munetaka

    2014-06-02

    The circularly polarized luminescence (CPL) from [Eu(pda)2](-) (pda = 1,10-phenanthroline-2,9-dicarboxylic acid) and [Eu(bda)2](-) (bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) in aqueous solutions containing various amino acids was investigated. The europium(III) complexes exhibited bright-red luminescence assignable to the f-f transition of the Eu(III) ion when irradiated with UV light. Although the luminescence was not circularly polarized in the solid state or in aqueous solutions, in accordance with the achiral crystal structure, the complexes exhibited detectable induced CPL (iCPL) in aqueous solutions containing chiral amino acids. In the presence of L-pyrrolidonecarboxylic acid, both [Eu(pda)2](-) and [Eu(bda)2](-) showed similar iCPL intensity (glum ∼ 0.03 for the (5)D0 → (7)F1 transition at 1 mol·dm(-3) of the amino acid). On the other hand, in the presence of L-histidine or L-arginine, [Eu(pda)2](-) exhibited intense CPL (glum ∼ 0.08 for the (5)D0 → (7)F1 transition at 0.10 mol·dm(-3) of the amino acid), whereas quite weak CPL was observed for [Eu(bda)2](-) under the same conditions (glum amino acids, [Eu(pda)2](-) was found to be a good chiral CPL probe with high sensitivity (about 10(-2) mol·dm(-3)) and high selectivity for L-histidine at pH 3 and for L-arginine at pH 7. The mechanism of iCPL was evaluated by analysis of the fine structures in the luminescence spectra and the amino acid concentration dependence of glum. For the [Eu(pda)2](-)-histidine/arginine systems, the europium(III) complexes possess coordination structures similar to that in the crystal with slight distortion to form a chiral structure due to specific interaction with two zwitterionic amino acids. This mechanism was in stark contrast to that of the europium(III) complex-pyrrolidonecarboxylic acid system in which one amino acid coordinates to the Eu(III) ion to yield an achiral coordination structure.

  19. Asymmetric Synthesis of New Chiral Europium N,N'-Disuccinate Complexes : Shift Reagents for Aqueous Solutions and Application in the Enantiomeric Excess Determination of Amino Acids

    NARCIS (Netherlands)

    HULST, R; DEVRIES, NK; FERINGA, BL

    1994-01-01

    The synthesis of new chiral N,N'-disuccinate ligands (R,R)-8, (R,R)-9, and (S,S)-10 from (5R)- or (SS)-(menthyloxy)-2(5H)-furanone is described. These ligands, after complexation with EuCl3.6H(2)O, are highly suitable as chiral shift reagents for the enantiomeric excess determination of amino acids

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

    Science.gov (United States)

    Taujenis, Lukas; Olšauskaitė, Vilma; Padarauskas, Audrius

    2014-11-19

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

  1. Fluorescence turn-on recognition of chiral amino acids using dye incorporated β-CD functionalized AuNPs assembly

    Energy Technology Data Exchange (ETDEWEB)

    Aswathy, B., E-mail: aswathybv@gmail.com; Sony, G., E-mail: emailtosony@gmail.com

    2014-10-15

    An assembly of dye incorporated β-cyclodextrin (βCD) functionalized AuNPs for the fluorescent probing of chiral amino acids is presented. Gold nanoparticles (AuNPs) possessing a high extinction coefficient function can be used as excellent fluorescent quenchers in AuNP–fluorophore system. Inclusion of fluorescein (FL) into β-cyclodextrin (βCD) makes energy transfer to occur through the donor and quencher nearby. This energy transfer switches off by virtue of the analyte induced release of FL from β-CD cavity, which results in the fluorescence recovery of the quenched dye. Analysis suggests that the assembly of AuNPs–βCDs–FL is effective as a turn-on fluorescent probe for the chiroselective optical discrimination between D,L-tryptophan, D,L-phenyl alanine and D,L-tyrosine. The detection limits for analyzing L-tryptophan, L-phenyl alanine and L-tyrosine were found to be 0.59, 1.2 and 1.5 μM respectively. - Highlights: • Fluorescence quenching AuNP–βCD–dye assembly via energy transfer. • Energy transfer from dye to AuNPs is a SET process. • Fluorescence turn-on detection of amino acids by the competitive binding method. • Chiroselective discrimination between enantiomeric amino acids.

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

    Institute of Scientific and Technical Information of China (English)

    MaJianbiao; ChenLi; 等

    1995-01-01

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

  3. Facile Synthesis of N-Methylated Amino Acids from Chiral Aziridine-2-carboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jihye; Ha, Hyun-Joon [Hankuk University of Foreign Studies, Yongin (Korea, Republic of)

    2015-01-15

    Our recent success with the so-called N-methylative aziridine ring-opening reaction of nonactivated aziridines led us to the preparation of N-methylated amino acids. The nucleophilic ring-opening reaction of nonactivated aziridines requires the prerequisite of activation of aziridine as aziridinium ion, as shown in Scheme 1. We activate this nonactivated aziridine by methylation with methyltriflate to methylated aziridinium ion whose counterpart triflate anion is not nucleophilic enough to open the aziridine ring. The following external nucleophiles are applicable to the ringopening reaction, yielding N-methylated aziridine. In conclusion, we described an efficient preparation of Nmethylated α- and β-amino acids by N-methylative aziridine ring-opening reaction of aziridine-2-carboxylate and carboxamide with various nucleophiles.

  4. Chiral Determination of Amino Acids Using X-Ray Diffraction of Thin Films

    Science.gov (United States)

    Dragoi, D.; Kulleck, J.; Kanik, I.; Beegle, L. W.

    2003-01-01

    The astrobiological search for life, both extinct and extant, on other solar system bodies will take place via several planned lander missions to Mars Europa and Titan. The detection and identification of organic molecules that have been associated with life is a major technical challenge. Terrestrial life utilizes organic molecules, such as amino acids, as its basic building block. Amino acids can be synthesized by natural processes as is demonstrated by their detection in meteoritic material. In this process, the organic molecules are produced roughly in a even mixture of D and L forms. Biological process, however, can utilize almost uniquely one form or the other. In terrestrial biology, only the L-amino acids is common in biological processes. If signature of life existed elsewhere in the D form it then be concluded that life had evolutionary beginning on that body. Detection of an enantiomeric excess of L over D would also be a powerful sign that life had existed on that body at one time.

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  6. Synthesis of a chiral amino acid with bicyclo[1.1.1]pentane moiety and its incorporation into linear and cyclic antimicrobial peptides.

    Science.gov (United States)

    Pritz, Stephan; Pätzel, Michael; Szeimies, Günter; Dathe, Margitta; Bienert, Michael

    2007-06-01

    The synthesis of the lipophilic chiral amino acid 1 bearing the bicyclo[1.1.1]pentane moiety is described. Linear and cyclic hexapeptides of the type Arg-Arg-Xaa-Yaa-Arg-Phe containing 1 instead of one or two tryptophan residues are prepared by solid phase peptide synthesis and the antimicrobial and hemolytic activity of the peptides obtained are discussed.

  7. Determination of enantiomeric composition by negative-ion electrospray ionization-mass spectrometry using deprotonated N-(3,5-dinitrobenzoyl)amino acids as chiral selectors.

    Science.gov (United States)

    Brewer, Bobby N; Zu, Chengli; Koscho, Michael E

    2005-10-01

    The ability to use mixtures of deprotonated N-(3,5-dinitrobenzoyl)amino acids as chiral selectors for the determination of enantiomeric composition by electrospray ionization-mass spectrometry is demonstrated. For each experiment, two N-(3,5-dinitrobenzoyl)amino acids were chosen such that each would have opposite selectivity for the enantiomers of the analyte. Electrospray ionization-mass spectrometry, monitored in the negative ion mode, of solutions containing the two N-(3,5-dinitrobenzoyl)amino acids, sodium hydroxide, and the analyte, in a one-to-one mixture of methanol and water, afford peaks in the mass spectrum that correspond to the deprotonated 1:1 analyte-selector complexes. The ratio of the intensities of the complexes in the mass spectrum can be related to the enantiomeric composition of the analyte. Additionally, the sense and extent of chiral recognition is consistent with chromatographic observations, using chiral stationary phases derived from N-(3,5-dinitrobenzoyl)amino acids. Each analysis of enantiomeric composition requires less than 10 s to complete, indicating that this method has great potential for the development of fast-/high-throughput chiral analyses.

  8. Synthesis and Enantioselective Discrimination of Chiral Fluorescence Receptors Bearing Amino Acid Units

    Institute of Scientific and Technical Information of China (English)

    XU Kuo-Xi; HE Yong-Bing; QING Guang-Yan; QIN Hai-duan; LIU Shun-Ying; MENG Ling-Zhi

    2007-01-01

    Two chiral fluorescence receptors (1, 2) were synthesized, and their structures were characterized by IR, 1H NMR, 13C NMR, mass spectra and elemental analysis. The chiral recognition of receptors was studied by 1H NMR and fluorescence spectra. The results demonstrate that receptors and dibenzoyl tartrate anion formed a 1 : 1 complex. The receptor 1 exhibited a good enantioselective recognition ability toward the enantiomers of dibenzoyl tartrate anion.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-17

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

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

    Science.gov (United States)

    Dimitrova, Pepa; Bart, Hans-Jörg

    2010-03-17

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

  11. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids.

    Science.gov (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean

    2014-04-09

    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  12. Microwave-Assisted Synthesis of Chiral β-Amino Acids%微波辅助法合成手性β-氨基酸

    Institute of Scientific and Technical Information of China (English)

    刘发明; 冯柏年

    2014-01-01

    手性β-氨基酸是一类在药物开发和生物研究中具有广泛应用的中间体,尝试了以L-天冬氨酸为手性源合成手性β-氨基酸的研究,其合成方法:首先对天冬氨酸进行氨基保护,然后利用微波,高效地合成( S)-N-保护的丝氨酸-γ-内酯,最后通过傅克反应,合成具有芳香性的手性β氨基酸。具有路线短、操作方便、绿色经济等优点,适合工业化大生产。%Chiral β-amino acids were intermediates , having a wide range of applications in biological research and drug development.Trying to use L-aspartic acid as chiral pool to synthesis β-amino acids , the synthesis method was that protecting the amino group of aspartic acid , then the microwave efficiently synthesized ( S ) -N -protected homoserine γ-lactone , and aromatic chiral βamino acids through Friedel -Crafts reaction was obtained , which had the characteristics of a line short , easy to operate , green economy , suitable for industrial production , etc.

  13. Biocatalytic Synthesis of Chiral Alcohols and Amino Acids for Development of Pharmaceuticals

    Directory of Open Access Journals (Sweden)

    Ramesh N. Patel

    2013-10-01

    Full Text Available Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates and drugs has become increasingly important in the pharmaceutical industry. There has been an increasing awareness of the enormous potential of microorganisms and enzymes derived there from for the transformation of synthetic chemicals with high chemo-, regio- and enatioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral alcohols and unntural aminoacids for pharmaceuticals.

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

    Science.gov (United States)

    Gyllenhaal, Olle; Karlsson, Anders

    2002-12-31

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

  15. Complete chiral symmetry breaking of an amino acid derivative directed by circularly polarized light

    NARCIS (Netherlands)

    Noorduin, Wim L.; Bode, Arno A.C.; Meijden, Maarten van der; Meekes, Hugo; Etteger, Albert F. van; Enckevort, Willem J.P. van; Christianen, Peter C.M.; Kaptein, Bernard; Kellogg, Richard M.; Rasing, Theo; Vlieg, Elias

    2009-01-01

    Circularly polarized light (CPL) emitted from star-forming regions is an attractive candidate as a cause of single chirality in nature. It has remained difficult, however, to translate the relatively small chemical effects observed on irradiation of molecular systems with CPL into high enantiomeric

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

    Science.gov (United States)

    Kotthaus, A F; Altenbach, H-J

    2011-02-01

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

  17. Synthesis of novel nanostructured chiral poly(amide-imide)s containing dopamine and natural amino acids

    Indian Academy of Sciences (India)

    Shadpour Mallakpour; Amin Zadehnazari

    2013-01-01

    Four new thermally stable and optically active poly(amide-imide)s (PAI)s with good inherent viscosities were synthesized from the direct polycondensation reaction of N,N'-(pyromellitoyl)-bis-L--amino acids with 3,5-diamino-N-(3,4-dihydroxy-phen-ethyl)benzamide in a medium consisting of a molten salt, tetrabutylammonium bromide, and triphenyl phosphite as the activator. The polymerization reactions produced a series of novel PAIs containing dopamine segment in the side chain in high yield with inherent viscosities between 0.33 and 0.49 dL/g. The obtained polymers were typically characterized by means of FT-IR, 1HNMR spectroscopy, elemental analyses, powder X-ray diffraction, field emission scanning electronmicroscopy, inherent viscosity, and solubility tests. Thermal properties and flame retardant behaviour of the PAIs were also investigated using thermal gravimetric analysis (TGA and DTG) and limiting oxygen index (LOI). Data obtained by thermal analysis revealed that these polymers showed good thermal stability. Furthermore, high char yield in TGA and good LOI values indicated that the obtained polymers were capable of exhibiting good flame retardant properties.

  18. Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

    Science.gov (United States)

    Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

    2016-12-02

    An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

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

    Science.gov (United States)

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

    2012-11-15

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

  20. An AFM investigation of the interaction of chiral amino acids with the {l_brace}104{r_brace} face of calcite

    Energy Technology Data Exchange (ETDEWEB)

    Orme, C A; Noy, A; McBride, M T; DeYoreo, J J

    2000-10-01

    In biomineralized tissue, Nature often uses a single crystal system to form tools with widely varied form and functionality. To accomplish this, organisms have developed methods to deterministically modify and control crystal habit, commonly creating shapes with lower symmetry than is possessed by the pure crystal. In this paper we use atomic force microscopy to investigate the effect of chiral amino acids on calcite growth. We show that the atomic steps and resultant macroscopic shape exhibit a lower symmetry that reflects the chirality of the amino acid. We use this result to constrain the possible stereospecific binding sites. We argue that the change in morphology is not due to the incorporation of the amino acid, but rather that it acts like a surfactant changing the energetics of the interface. These results suggest that the conventional paradigm for understanding the geometrical and chemical aspects of biomineralization in terms of stereochemical recognition should be expanded to capture the energetic controls that determine the mechanisms of mineral modification by biomolecules.

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

    Science.gov (United States)

    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.

  2. Saponification of esters of chiral alpha-amino acids anchored through their amine function on solid support.

    Science.gov (United States)

    Cantel, Sonia; Desgranges, Stéphane; Martinez, Jean; Fehrentz, Jean-Alain

    2004-06-01

    Anchoring an alpha-amino acid residue by its amine function onto a solid support is an alternative to develop chemistry on its carboxylic function. This strategy can involve the use of amino-acid esters as precursors of the carboxylic function. A complete study on the Wang-resin was performed to determine the non racemizing saponification conditions of anchored alpha-amino esters. The use of LiOH, NaOH, NaOSi(Me)3, various solvents and temperatures were tested for this reaction. After saponification and cleavage from the support, samples were examined through their Marfey's derivatives by reversed phase HPLC to evaluate the percentage of racemization.

  3. Molecular recognition on supramolecular systems (XXXV)-- Synthesis of novel b-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel b-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-b-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol·L-1) at 25 ℃ by using spectrofluormetric titrations. The stoichiometry is 1︰1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral isomer. As com-pared with mono-[6-(1-pyridinio)-6-deoxy]-b-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. The-se results are discussed from the viewpoints of geometric compensation, induced-fit concept and cooperation of several weak interactions.

  4. Molecular recognition on supramolecular systems (XXXV)——Synthesis of novel β-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    刘育; 康诗钊

    2001-01-01

    A novel p-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-p-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol ?L-1) at 25℃by using spectrofluorometric titrations. The stoichiometry is 1 : 1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral iso-mer. As compared with mono-[6-(1-pyridinio)-6-deoxy]-p-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. These results are discussed from the viewpoints of ge

  5. Analysis of Chiral Carboxylic Acids in Meteorites

    Science.gov (United States)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe

  6. Plasma amino acids

    Science.gov (United States)

    Amino acids blood test ... types of methods used to determine the individual amino acid levels in the blood. ... test is done to measure the level of amino acids in the blood. An increased level of a ...

  7. Replacement of two amino acids of 9R-dioxygenase-allene oxide synthase of Aspergillus niger inverts the chirality of the hydroperoxide and the allene oxide.

    Science.gov (United States)

    Sooman, Linda; Wennman, Anneli; Hamberg, Mats; Hoffmann, Inga; Oliw, Ernst H

    2016-02-01

    The genome of Aspergillus niger codes for a fusion protein (EHA25900), which can be aligned with ~50% sequence identity to 9S-dioxygenase (DOX)-allene oxide synthase (AOS) of Fusarium oxysporum, homologues of the Fusarium and Colletotrichum complexes and with over 62% sequence identity to homologues of Aspergilli, including (DOX)-9R-AOS of Aspergillus terreus. The aims were to characterize the enzymatic activities of EHA25900 and to identify crucial amino acids for the stereospecificity. Recombinant EHA25900 oxidized 18:2n-6 sequentially to 9R-hydroperoxy-10(E),12(Z)-octadecadienoic acid (9R-HPODE) and to a 9R(10)-allene oxide. 9S- and 9R-DOX-AOS catalyze abstraction of the pro-R hydrogen at C-11, but the direction of oxygen insertion differs. A comparison between twelve 9-DOX domains of 9S- and 9R-DOX-AOS revealed conserved amino acid differences, which could contribute to the chirality of products. The Gly616Ile replacement of 9R-DOX-AOS (A. niger) increased the biosynthesis of 9S-HPODE and the 9S(10)-allene oxide, whereas the Phe627Leu replacement led to biosynthesis of 9S-HPODE and the 9S(10)-allene oxide as main products. The double mutant (Gly616Ile, Phe627Leu) formed over 90% of the 9S stereoisomer of HPODE. 9S-HPODE was formed by antarafacial hydrogen abstraction and oxygen insertion, i.e., the original H-abstraction was retained but the product chirality was altered. We conclude that 9R-DOX-AOS can be altered to 9S-DOX-AOS by replacement of two amino acids (Gly616Ile, Phe627Leu) in the DOX domain.

  8. ASYMMETRIC-SYNTHESIS OF NEW CHIRAL EUROPIUM N,N'-DISUCCINATE COMPLEXES - SHIFT-REAGENTS FOR AQUEOUS-SOLUTIONS AND APPLICATION IN THE ENANTIOMERIC EXCESS DETERMINATION OF AMINO-ACIDS

    NARCIS (Netherlands)

    HULST, R; DEVRIES, NK; FERINGA, BL

    1994-01-01

    The synthesis of new chiral N,N'-disuccinate ligands (R,R)-8, (R,R)-9, and (S,S)-10 from (5R)- or (SS)-(menthyloxy)-2(5H)-furanone is described. These ligands, after complexation with EuCl3.6H(2)O, are highly suitable as chiral shift reagents for the enantiomeric excess determination of amino acids

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2005-05-01

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

  11. Ab initio study of the circular intensity difference in electric-field-induced second harmonic generation of chiral natural amino acids.

    Science.gov (United States)

    Rizzo, Antonio; Agren, Hans

    2013-01-28

    We present a systematic computational study of circular intensity difference (CID) in electric-field-induced second harmonic generation (EFISHG) of some representative chiral natural amino acids (Alanine, Arginine, Aspartic Acid, Cysteine and Tryptophan), taking into account the electric-dipole, electric-quadrupole and magnetic-dipole interactions. The calculations are performed by applying cubic response theory at both Hartree-Fock and Density Functional theory levels, the latter with the popular Becke-three parameters, Lee, Yang and Parr (B3LYP) functional. Special focus is given to the basis set, electron correlation and origin dependence of the properties. The full set of molecular parameters defined by Lam and Thirunamachandran in their reference theoretical paper published in 1982 [J. Chem. Phys., 1982, 77, 3810] is obtained and discussed. This permits the prediction of the CID observable for different possible experimental setups.

  12. Racemization of Meteoritic Amino Acids

    Science.gov (United States)

    Cohen, Barbara A.; Chyba, Christopher F.

    2000-05-01

    Meteorites may have contributed amino acids to the prebiotic Earth, affecting the global ratio of right-handed to left-handed (D/L) molecules. We calculate D/L ratios for seven biological, α-hydrogen, protein amino acids over a variety of plausible parent body thermal histories, based on meteorite evidence and asteroid modeling. We show that amino acids in meteorites do not necessarily undergo complete racemization by the time they are recovered on Earth. If the mechanism of amino acid formation imposes some enantiomeric preference on the amino acids, a chiral signature can be retained through the entire history of the meteorite. Original enantiomeric excesses in meteorites such as Murchison, which have undergone apparently short and cool alteration scenarios, should have persisted to the present time. Of the seven amino acids for which relevant data are available, we expect glutamic acid, isoleucine, and valine, respectively, to be the most likely to retain an initial enantiomeric excess, and phenylalanine, aspartic acid, and alanine the least. Were the D/L ratio initially identical in each amino acid, final D/L ratios could be used to constrain the initial ratio and the thermal history experienced by the whole suite.

  13. Characterization of chiral amino acids from different milk origins using ultra-performance liquid chromatography coupled to ion-mobility mass spectrometry

    Science.gov (United States)

    Tian, He; Zheng, Nan; Li, Songli; Zhang, Yangdong; Zhao, Shengguo; Wen, Fang; Wang, Jiaqi

    2017-01-01

    Milk contains free amino acids (AAs) that play essential roles in maintaining the growth and health of infants, and D-AA isomers are increasingly being recognized as important signalling molecules. However, there are no studies of the different characteristics of chiral AA (C-AA) from different milk origins. Here, UPLC coupled to ion-mobility high-resolution MS (IM-HRMS) was employed to characterize 18 pairs of C-AAs in human, cow, yak, buffalo, goat, and camel milk. The results proved that milk origins can be differentiated based on the D- to L- AA ratio-based projection scores by principal component analysis. The present study gives a deeper understanding of the D- to L- AA ratio underlying the biological functions of different animal milks, and provide a new strategy for the study of AA metabolic pathways. PMID:28393862

  14. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Solution Self-Aggregation and Recognition.

    Science.gov (United States)

    Sorrenti, Alessandro; Illa, Ona; Pons, Ramon; Ortuño, Rosa M

    2015-09-08

    Novel diastereomeric anionic amphiphiles based on the rigid cyclobutane β-amino acid scaffold have been synthesized and deeply investigated with the aim of generating new functional supramolecular architectures on the basis of the rational design of original amphiphilic molecules and the control of their self-assembly. The main interest has been focused on the effect that cis/trans stereochemistry exerts on their molecular organization and recognition. In diluted solutions, the relative stereochemistry mainly influences the headgroup solvation and anionic-charge stabilization, i.e., better stabilized in the cis diastereoisomer due to intramolecular hydrogen-bonding and/or charge-dipole interactions. This provokes differences in their physicochemical behavior (pKa, cmc, conductivity) as well as in the structural parameters of the spherical micelles formed. Although both diastereoisomers form fibers that evolve with time from the spherical micelles, they display markedly different morphology and kinetics of formation. In the lyotropic liquid crystal domain, the greatest differences are observed at the highest concentrations and can be ascribed to different hydrogen-bonding and molecular packing imposed by the stereochemical constraints. Remarkably, the spherical micelles of the two anionic surfactants show dramatically diverse enantioselection ability for bilirubin enantiomers. In addition, both the surfactants form heteroaggregates with bilirubin at submicellar concentrations but with a different expression of supramolecular chirality. This points out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates. All these differential features can be appropriate and useful for the design and development of new soft materials with

  15. Chiral bio-nanocomposites based on thermally stable poly(amide-imide) having phenylalanine linkages and reactive organoclay containing tyrosine amino acid.

    Science.gov (United States)

    Mallakpour, Shadpour; Dinari, Mohammad

    2013-03-01

    Montmorillonite clay modified with the bio-active trifunctional L-tyrosine amino acid salt was used as a reactive organoclay (OC) for the preparation of poly(amide-imide) (PAI)/OC hybrid films. One of the functional groups of the L-tyrosine as the swelling agent formed an ionic bond with the negatively charged silicates, whereas the remaining functional groups were available for further reaction with polymer matrix. The soluble PAI with amine end groups including phenylalanine amino acid was synthesised under green condition using molten tetra-butylammonium bromide by direct polymerization reaction of chiral diacid and 2-(3,5-diaminophenyl)benzimidazole. PAI/OC bio-nanocomposites films containing different contents of OC were prepared via solution intercalation method through blending of OC with the PAI solution. X-ray diffraction and transmission electron microscopy revealed that the dispersion of silicate layers in the PAI created an exfoliated structure as a result of using the trifunctional groups of the swelling agent. The structure and thermal behavior of the synthesised materials were characterized by a range of methods, including X-ray diffraction, Fourier transform infrared spectroscopy, (1)H-NMR, electron microscopy, elemental and thermogravimetric analysis techniques. Thermogravimetric analysis results indicated that the addition of OC into the PAI matrix was increased in the thermal decomposition temperatures of the resulted bio-nanocomposites.

  16. Amino Acid Metabolism Disorders

    Science.gov (United States)

    ... this process. One group of these disorders is amino acid metabolism disorders. They include phenylketonuria (PKU) and maple syrup urine disease. Amino acids are "building blocks" that join together to form ...

  17. Noncovalent chirality sensing ensembles for the detection and reaction monitoring of amino acids, peptides, proteins, and aromatic drugs.

    Science.gov (United States)

    Biedermann, Frank; Nau, Werner M

    2014-05-26

    Ternary complexes between the macrocyclic host cucurbit[8]uril, dicationic dyes, and chiral aromatic analytes afford strong induced circular dichroism (ICD) signals in the near-UV and visible regions. This allows for chirality sensing and peptide-sequence recognition in water at low micromolar analyte concentrations. The reversible and noncovalent mode of binding ensures an immediate response to concentration changes, which allows the real-time monitoring of chemical reactions. The introduced supramolecular method is likely to find applications in bioanalytical chemistry, especially enzyme assays, for drug-related analytical applications, and for continuous monitoring of enantioselective reactions, particularly asymmetric catalysis.

  18. Chiral mobile phase in ligand-exchange chromatography of amino acids: exploring the copper(II) salt anion effect with a computational approach.

    Science.gov (United States)

    Sardella, Roccaldo; Macchiarulo, Antonio; Carotti, Andrea; Ianni, Federica; Rubiño, Maria Eugenia García; Natalini, Benedetto

    2012-12-21

    With the use of a chiral ligand-exchange chromatography (CLEC) system operating with the O-benzyl-(S)-serine [(S)-OBS] [1,2] as the chiral mobile phase (CMP) additive to the eluent, the effect of the copper(II) anion type on retention (k) and separation (α) factors was evaluated, by rationally changing the following experimental conditions: salt concentration and temperature. The CLEC-CMP analysis was carried out on ten amino acidic racemates and with nine different cupric salts. While the group of analytes comprised both aliphatic (leucine, isoleucine, nor-leucine, proline, valine, nor-valine, and α-methyl-valine) and aromatic (1-aminoindan-1,5-dicarboxylic acid, phenylglycine, and tyrosine) species, representative organic (formate, methanesulfonate, and trifluoroacetate) and inorganic (bromide, chloride, fluoride, nitrate, perchlorate, and sulfate) Cu(II) salts were selected as the metal source into the eluent. This route of investigation was pursued with the aim of identifying analogies among the employed Cu(II) salts, by observing the variation profile of the selected chromatographic parameters, upon a change of the above experimental conditions. All the data were collected and analyzed through a statistical approach (PCA and k-means clustering) that revealed the presence of two behavioral classes of cupric salts, sharing the same variation profile for k and α values. Interestingly, this clustering can be explained in terms of ESP (electrostatic surface potential) balance (ESP(bal)) values, obtained by an ab initio calculation operated on the cupric salts. The results of this appraisal could aid the rational choice of the most suitable eluent system, to succeed in the enantioseparation of difficult-to-resolve compounds, along with the eventual scale-up to a semi-preparative level.

  19. Left or Right: How Does Amino Acid Chirality Affect the Handedness of Nanostructures Self-Assembled from Short Amphiphilic Peptides?

    Science.gov (United States)

    Wang, Meng; Zhou, Peng; Wang, Jiqian; Zhao, Yurong; Ma, Hongchao; Lu, Jian R; Xu, Hai

    2017-03-22

    Peptide and protein fibrils have attracted an enormous amount of interests due to their relevance to many neurodegenerative diseases and their potential applications in nanotechnology. Although twisted fibrils are regarded as the key intermediate structures of thick fibrils or bundles of fibrils, the factors determining their twisting tendency and their handedness development from the molecular to the supramolecular level are still poorly understood. In this study, we have designed three pairs of enantiomeric short amphiphilic peptides: (L)I3(L)K and (D)I3(D)K, (L)I3(D)K and (D)I3(L)K, and (La)I3(L)K and (Da)I3(D)K, and investigated the chirality of their self-assembled nanofibrils through the combined use of atomic force microscopy (AFM), circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), and molecular dynamic (MD) simulations. The results indicated that the twisted handedness of the supramolecular nanofibrils was dictated by the chirality of the hydrophilic Lys head at the C-terminal, while their characteristic CD signals were determined by the chirality of hydrophobic Ile residues. MD simulations delineated the handedness development from molecular chirality to supramolecular handedness by showing that the β-sheets formed by (L)I3(L)K, (La)I3(L)K, and (D)I3(L)K exhibited a propensity to twist in a left-handed direction, while the ones of (D)I3(D)K, (Da)I3(D)K, and (L)I3(D)K in a right-handed twisting orientation.

  20. Parenteral Nutrition: Amino Acids

    Science.gov (United States)

    Hoffer, Leonard John

    2017-01-01

    There is growing interest in nutrition therapies that deliver a generous amount of protein, but not a toxic amount of energy, to protein-catabolic critically ill patients. Parenteral amino acids can achieve this goal. This article summarizes the biochemical and nutritional principles that guide parenteral amino acid therapy, explains how parenteral amino acid solutions are formulated, and compares the advantages and disadvantages of different parenteral amino acid products with enterally-delivered whole protein products in the context of protein-catabolic critical illness. PMID:28287411

  1. Parenteral Nutrition: Amino Acids.

    Science.gov (United States)

    Hoffer, Leonard John

    2017-03-10

    There is growing interest in nutrition therapies that deliver a generous amount of protein, but not a toxic amount of energy, to protein-catabolic critically ill patients. Parenteral amino acids can achieve this goal. This article summarizes the biochemical and nutritional principles that guide parenteral amino acid therapy, explains how parenteral amino acid solutions are formulated, and compares the advantages and disadvantages of different parenteral amino acid products with enterally-delivered whole protein products in the context of protein-catabolic critical illness.

  2. Free D-amino acids determination in ready-to-eat cooked ham irradiated with electron-beam by indirect chiral HPLC.

    Science.gov (United States)

    Gil-Díaz, M; Santos-Delgado, M J; Rubio-Barroso, S; Polo-Díez, L M

    2009-05-01

    Potential racemization of L-amino acids (AA) in ready-to-eat (RTE) cooked ham after hygienization by electron-beam irradiation between 1 and 8kGy was studied. An indirect chiral method based on the derivatization reaction of AA with o-phthaldialdehyde and N-acetyl-L-cysteine followed by reversed-phase HPLC and fluorimetric detection was applied to detect ten enantiomeric pairs of free AA (Asp, Ser, Thr, Ala, Tyr, Val, Trp, Phe and Leu). Five of the D-AA were not found in any of the samples analyzed; the other five remaining D-AA (D-Asp, D-Ser, D-Ala, D-Val and D-Leu) were detected both in irradiated and non-irradiated cooked ham samples, their content being in the range 1.25-13.79μg/g. Although significant differences appeared for a few of the samples and doses, no positive correlation between the D-AA content and the irradiation doses was observed. Therefore, the electron-beam irradiation technique could be useful for sanitation of packed RTE cooked ham at doses allowed by WHO and EU, since it remains chemically safe to eat.

  3. Amino Acid Crossword Puzzle

    Science.gov (United States)

    Sims, Paul A.

    2011-01-01

    Learning the 20 standard amino acids is an essential component of an introductory course in biochemistry. Later in the course, the students study metabolism and learn about various catabolic and anabolic pathways involving amino acids. Learning new material or concepts often is easier if one can connect the new material to what one already knows;…

  4. Catalytic Enantioselective Reduction of Prochiral Ketones with Chiral Ferrocenyl Amino Alcohols

    Institute of Scientific and Technical Information of China (English)

    CHEN, Wei-Yi(陈维一); LU, Jun(陆军); SHEN, Zong-Xuan(沈宗旋); ZHANG, Ya-Wen(张雅文)

    2004-01-01

    The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in high chemical yields and moderate to good enantiomeric excesses.

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

    Science.gov (United States)

    Bhushan, Ravi; Nagar, Hariom

    2015-03-01

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

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

    Science.gov (United States)

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

    2017-04-14

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

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

    Science.gov (United States)

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

    2015-05-22

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

  8. Amino acid racemisation dating

    Energy Technology Data Exchange (ETDEWEB)

    Murray-Wallace, C.V. [University of Wollongong, Wollongong, NSW (Australia). School of Geosciences

    1999-11-01

    The potential of the time-dependent amino acid racemisation reaction as a method of age assessment was first reported by Hare and Abelson (1968). They noted that in specimens of the bivalve mollusc Mercenaria sp., greater concentrations of amino acids in the D-configuration with increasing fossil age. Hare and Abelson (1968) also reported negligible racemisation in a modern specimen of Mecanaria sp. On this basis they suggested that the extent of amino acid racemisation (epimerisation in the case of isoleucine) may be used to assess the age of materials within and beyond the range of radiocarbon dating. For the past thirty years amino acid racemisation has been extensively applied in Quaternary research as a method of relative and numeric dating, and a particularly large literature has emerged on the subject 12 refs.

  9. Chiral resolution of derivatized amino acids using uniformly sized molecularly imprinted polymers in hydro-organic mobile phases.

    Science.gov (United States)

    Haginaka, Jun; Kagawa, Chino

    2004-04-01

    Uniformly sized molecularly imprinted polymers (MIPs) for Boc-L-Trp were prepared using ethylene glycol dimethacrylate (EDMA) as the cross-linker, and methacylic acid (MAA) and/or 4-vinylpyridine (4-VPY) as the functional monomers or without use of a functional monomer. The MIPs prepared were evaluated using acetonitrile or a mixture of phosphate buffer and acetonitrile as the mobile phase. The Boc-L-Trp-imprinted EDMA polymers can recognize Boc-L-Trp by its molecular shape, and can thus afford the enantioseparation of Boc-Trp. Besides the molecular shape recognition, the hydrophobic interactions with the polymer backbones as well as the hydrogen-bonding interactions of Boc-L-Trp with carboxyl and pyridyl groups in the polymers should work for the retention and recognition of Boc-L-Trp on the imprinted MAA- co-EDMA and 4-VPY- co-EDMA polymers, respectively, in the hydro-organic mobile phase. The hydrogen-bonding interactions seem to become dominant when only acetonitrile is used as the mobile phase. The Boc-L-Trp-imprinted 4-VPY- co-EDMA polymers gave the highest retentivity and enantioselectivity for Boc-Trp among the MIPs prepared. However, the simultaneous use of MAA and 4-VPY was not effective for the enantioseparation of Boc-Trp in a hydro-organic mobile phase. Furthermore, the baseline separation of Boc-Trp enantiomers was attained within 10 min on the Boc-L-Trp-imprinted 4-VPY- co-EDMA polymers under the optimized HPLC conditions.

  10. X-ray studies of crystalline complexes involving amino acids and peptides. XLIV. Invariant features of supramolecular association and chiral effects in the complexes of arginine and lysine with tartaric acid.

    Science.gov (United States)

    Selvaraj, M; Thamotharan, S; Roy, Siddhartha; Vijayan, M

    2007-06-01

    The tartaric acid complexes with arginine and lysine exhibit two stoichiometries depending upon the ionization state of the anion. The structures reported here are DL-argininium DL-hydrogen tartrate, bis(L-argininium) L-tartrate, bis(DL-lysinium) DL-tartrate monohydrate, L-lysinium D-hydrogen tartrate and L-lysinium L-hydrogen tartrate. During crystallization, L-lysine preferentially interacts with D-tartaric acid to form a complex when DL-tartaric acid is used in the experiment. The anions and the cations aggregate into separate alternating layers in four of the five complexes. In bis(L-argininium) L-tartrate, the amino acid layers are interconnected by individual tartrate ions which do not interact among themselves. The aggregation of argininium ions in the DL- and the L-arginine complexes is remarkably similar, which is in turn similar to those observed in other dicarboxylic acid complexes of arginine. Thus, argininium ions have a tendency to assume similar patterns of aggregation, which are largely unaffected by a change in the chemistry of partner molecules such as the introduction of hydroxyl groups or a change in chirality or stoichiometry. On the contrary, the lysinium ions exhibit fundamentally different aggregation patterns in the DL-DL complexes on the one hand and L-D and L-L complexes on the other. Interestingly, the pattern in the L-D complex is similar to that in the L-L complex. The lysinium ions in the DL-DL complex exhibit an aggregation pattern similar to those observed in the DL-lysine complexes involving other dicarboxylic acids. Thus, the effect of change in the chirality of a subset of the component complexes could be profound or marginal, in an unpredictable manner. The relevant crystal structures appear to indicate that the preference of L-lysine for D-tartaric acid is perhaps caused by chiral discrimination resulting from the amplification of a small energy difference.

  11. Stereoselective synthesis of unsaturated α-amino acids.

    Science.gov (United States)

    Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

    2015-06-01

    Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-22

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

  13. Physiological and biochemical studies of bacterial amino acid amide metabolism

    NARCIS (Netherlands)

    Hermes, Hubertus Franciscus Maria

    2008-01-01

    Amino acids represent a class of versatile chiral building blocks for a whole range of fine chemicals, used in the pharmaceutical and agro-chemical industry. Considerable experience currently is available with a wide variety of chemo-enzymatic processes for the synthesis of amino acids, which is app

  14. Recent developments in the catalytic asymmetric synthesis of alpha- and beta-amino acids.

    Science.gov (United States)

    Ma, Jun-An

    2003-09-22

    The stereoselective synthesis of amino acids is of great importance for the construction of optically active natural products and pharmaceuticals. Apart from enzymes, a broad repertoire of chiral reagents, auxiliaries, and catalysts can be used for the formation of amino acids. Asymmetric reactions using catalytic amounts of chiral molecules provide efficient methods for the generation of optically active proteinogenic and nonproteinogenic amino acids. This minireview collects recent work on catalytic asymmetric synthesis of alpha- and beta-amino acids.

  15. Azetidinic amino acids

    DEFF Research Database (Denmark)

    Bräuner-Osborne, Hans; Bunch, Lennart; Chopin, Nathalie

    2005-01-01

    of two diastereoisomers that were easily separated and converted in two steps into azetidinic amino acids. Azetidines 35-44 were characterized in binding studies on native ionotropic Glu receptors and in functional assays at cloned metabotropic receptors mGluR1, 2 and 4, representing group I, II and III...

  16. Enantioseparation of Amino Acids by Micelle-Enhanced Ultrafiltration : Experimental and Theoretical Studies of Copper(II) Amino Acid Interactions

    NARCIS (Netherlands)

    Bruin, de T.J.M.

    2000-01-01

    A micelle-enhanced ultrafiltration system, which can potentially be used for large scale separations, has been used to investigate the resolution of amino acid enantiomers. For this purpose amino acid derivatives were synthesized, which in combination with copper(II) ions were used as chiral selecto

  17. Distribution of Amino Acids in Lunar Regolith

    Science.gov (United States)

    Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Dworkin, J. P.; Noble, S. K.; Gibson, E. K., Jr.

    2014-01-01

    One of the most eagerly studied questions upon initial return of lunar samples was whether significant amounts of organic compounds, including amino acids, were present. Analyses during the 1970s produced only tentative and inconclusive identifications of indigenous amino acids. Those analyses were hampered by analytical difficulties including relative insensitivity to certain compounds, the inability to separate chiral enantiomers, and the lack of compound-specific isotopic measurements, which made it impossible to determine whether the detected amino acids were indigenous to the lunar samples or the results of contamination. Numerous advances have been made in instrumentation and methodology for amino acid characterization in extraterrestrial samples in the intervening years, yet the origin of amino acids in lunar regolith samples has been revisited only once for a single lunar sample, (3) and remains unclear. Here, we present initial data from the analyses of amino acid abundances in 12 lunar regolith samples. We discuss these abundances in the context of four potential amino acid sources: (1) terrestrial biological contamination; (2) contamination from lunar module (LM) exhaust; (3) derivation from solar windimplanted precursors; and (4) exogenous delivery from meteorites.

  18. De novo design, synthesis and spectroscopic characterization of chiral benzimidazole-derived amino acid Zn(II) complexes: Development of tryptophan-derived specific hydrolytic DNA artificial nuclease agent

    Science.gov (United States)

    Parveen, Shazia; Arjmand, Farukh

    2012-01-01

    Novel ternary dizinc(II) complexes 1- 3, derived from 1,2-bis(1H-benzimidazol-2-yl)ethane-1,2-diol and L-form of amino acids (viz., tryptophan, leucine and valine) were synthesized and characterized by spectroscopic (IR, 1H NMR, UV-vis, ESI-MS) and other analytical methods. To evaluate the biological preference of chiral drugs for inherently chiral target DNA, interaction of 1- 3 with calf thymus DNA in Tris-HCl buffer was studied by various biophysical techniques which reveal that all these complexes bind to CT DNA non-covalently via electrostatic interaction. The higher Kb value of L-tryptophan complex 1 suggested greater DNA binding propensity. Further, to evaluate the mode of action at the molecular level, interaction studies of complexes 1 and 2 with nucleotides (5'-GMP and 5'-TMP) were carried out by UV-vis titrations, 1H and 31P NMR which implicates the preferential selectivity of these complexes to N3 of thymine rather than N7 of guanine. Furthermore, complex 1 exhibits efficient DNA cleavage with supercoiled pBR322. The complex 1 cleaves DNA efficiently involving hydrolytic cleavage pathway. Such chiral synthetic hydrolytic nucleases with asymmetric centers are gaining considerable attention owing to their importance in biotechnology and drug design, in particular to cleave DNA with sequence selectivity different from that of the natural enzymes.

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

    Science.gov (United States)

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

    2007-08-01

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

  20. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Condensed Phase and Monolayer Structure.

    Science.gov (United States)

    Sorrenti, Alessandro; Illa, Ona; Ortuño, Rosa M; Pons, Ramon

    2016-07-12

    New diastereomeric nonionic amphiphiles, cis- and trans-1, based on an optically pure cyclobutane β-amino ester moiety have been investigated to gain insight into the influence exerted by cis/trans stereochemistry and stereochemical constraints on the physicochemical behavior, molecular organization, and morphology of their Langmuir monolayers and dry solid states. All these features are relevant to the rational design of functional materials. trans-1 showed a higher thermal stability than cis-1. For the latter, a higher fluidity of its monolayers was observed when compared with the films formed by trans-1 whose BAM images revealed the formation of condensed phase domains with a dendritic shape, which are chiral, and all of them feature the same chiral sign. Although the formation of LC phase domains was not observed by BAM for cis-1, compact dendritic crystals floating on a fluid subphase were observed beyond the collapse, which are attributable to multilayered 3D structures. These differences can be explained by the formation of hydrogen bonds between the amide groups of consecutive molecules allowing the formation of extended chains for trans-1 giving ordered arrangements. However, for cis-1, this alignment coexists with another one that allows the simultaneous formation of two hydrogen bonds between the amide and the ester groups of adjacent molecules. In addition, the propensity to form intramolecular hydrogen bonds must be considered to justify the formation of different patterns of hydrogen bonding and, consequently, the formation of less ordered phases. Those characteristics are congruent also with the results obtained from SAXS-WAXS experiments which suggest a more bent configuration for cis-1 than for trans-1.

  1. Amino acid-functionalized multi-walled carbon nanotubes for improving compatibility with chiral poly(amide-ester-imide) containing L-phenylalanine and L-tyrosine linkages

    Energy Technology Data Exchange (ETDEWEB)

    Abdolmaleki, Amir, E-mail: abdolmaleki@cc.iut.ac.ir [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Mallakpour, Shadpour, E-mail: mallakpour84@alumni.ufl.edu [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Borandeh, Sedigheh [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of)

    2013-12-15

    Amino acid functionalized multi-walled carbon nanotubes (f-MWCNTs)/poly(amide-ester-imide) (PAEI) composites were fabricated by solution mixing method. Proper functionalization and mixing strategy of MWCNTs provides the best opportunity for better distribution and bonding of nanoparticles to the polymer matrix. MWCNTs have been chemically modified with L-phenylalanine to improve their compatibility with L-phenylalanine based PAEI. Field emission scanning electron microscopy micrographs of composite revealed that f-MWCNTs made a good interaction with polymer chains by wrapping the polymer around them, and transmission electron microscopy results confirmed well dispersion with nano size of f-MWCNTs in the polymer matrix. In addition, thermal analysis showed good enhancement in thermal properties of composites compared to pure polymer. Thermal stability of the composites containing f-MWCNTs was enhanced due to their good dispersion and improved interfacial interaction between the amino acid based PAEI matrix and f-MWCNTs.

  2. Amino acid-functionalized multi-walled carbon nanotubes for improving compatibility with chiral poly(amide-ester-imide) containing L-phenylalanine and L-tyrosine linkages

    Science.gov (United States)

    Abdolmaleki, Amir; Mallakpour, Shadpour; Borandeh, Sedigheh

    2013-12-01

    Amino acid functionalized multi-walled carbon nanotubes (f-MWCNTs)/poly(amide-ester-imide) (PAEI) composites were fabricated by solution mixing method. Proper functionalization and mixing strategy of MWCNTs provides the best opportunity for better distribution and bonding of nanoparticles to the polymer matrix. MWCNTs have been chemically modified with L-phenylalanine to improve their compatibility with L-phenylalanine based PAEI. Field emission scanning electron microscopy micrographs of composite revealed that f-MWCNTs made a good interaction with polymer chains by wrapping the polymer around them, and transmission electron microscopy results confirmed well dispersion with nano size of f-MWCNTs in the polymer matrix. In addition, thermal analysis showed good enhancement in thermal properties of composites compared to pure polymer. Thermal stability of the composites containing f-MWCNTs was enhanced due to their good dispersion and improved interfacial interaction between the amino acid based PAEI matrix and f-MWCNTs.

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

  4. Amino Acid Catabolism in Plants.

    Science.gov (United States)

    Hildebrandt, Tatjana M; Nunes Nesi, Adriano; Araújo, Wagner L; Braun, Hans-Peter

    2015-11-02

    Amino acids have various prominent functions in plants. Besides their usage during protein biosynthesis, they also represent building blocks for several other biosynthesis pathways and play pivotal roles during signaling processes as well as in plant stress response. In general, pool sizes of the 20 amino acids differ strongly and change dynamically depending on the developmental and physiological state of the plant cell. Besides amino acid biosynthesis, which has already been investigated in great detail, the catabolism of amino acids is of central importance for adjusting their pool sizes but so far has drawn much less attention. The degradation of amino acids can also contribute substantially to the energy state of plant cells under certain physiological conditions, e.g. carbon starvation. In this review, we discuss the biological role of amino acid catabolism and summarize current knowledge on amino acid degradation pathways and their regulation in the context of plant cell physiology.

  5. Nucleic acids, proteins, and chirality

    Science.gov (United States)

    Usher, D. A.; Profy, A. T.; Walstrum, S. A.; Needels, M. C.; Bulack, S. C.; Lo, K. M.

    1984-01-01

    The present investigation is concerned with experimental results related, in one case, to the chirality of nucleotides, and, in another case, to the possibility of a link between the chirality of nucleic acids, and that of peptides. It has been found that aminoacylation of the 'internal' hydroxyl group of a dinucleoside monophosphate can occur stereoselectively. However, this reaction has not yet been made a part of a working peptide synthesis scheme. The formation and cleavage of oligonucleotides is considered. In the event of the formation of a helical complex between the oligonucleotide and the polymer, 1-prime,5-prime-bonds in the oligomer are found to become more resistant towards cleavage. The conditions required for peptide bond formation are examined, taking into account the known structures of RNA and possible mechanisms for prebiotic peptide bond formation. The possibility is considered that the 2-prime,5-prime-internucleotide linkage could have played an important part in the early days of biological peptide synthesis.

  6. Synthesis and properties of optically active nanostructured polymers bearing amino acid moieties by direct polycondensation of 4,4'-thiobis(2-tert-butyl-5-methylphenol) with chiral diacids.

    Science.gov (United States)

    Mallakpour, Shadpour; Soltanian, Samaneh

    2012-06-01

    Four derivatives of N-trimellitylimido-L-amino acid (4a-4d) were prepared by the reaction of trimellitic anhydride (1) with the L-amino acids (2a-2d) in acetic acid as diacid monomers and were used with the aim to obtain a new family of amino acid based poly(ester-imide)s (PEI)s. The polymerization was performed by direct polycondensation of chiral diacids (4a-4d) with 4,4'-thiobis(2-tert-butyl-5-methylphenol) (5) in the presence of tosyl chloride (TsCl), pyridine and N,N-dimethyl formamide (DMF). Step-growth polymerization was carried out by varying the time of heating and the molar ratio of TsCl/diacid and the optimum conditions were achieved. The synthesized polymers were characterized by means of specific rotation experiments, FT-IR, 1H-NMR, X-ray diffraction techniques and elemental analysis. The surface morphology of the obtained polymers was studied by field emission scanning electron microscopy. The result showed nanostructure morphology of the resulting polymers. The obtained PEIs were soluble in polar aprotic solvents such as DMF, N,N-dimethyl acetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and protic solvents such as sulfuric acid. Thermal stability and the weight-loss behavior of the PEIs were studied by thermal gravimetric analysis (TGA) techniques. TGA showed that the 10% weight loss temperature in a nitrogen atmosphere was more than 402°C, therefore they had useful levels of thermal stability associated with excellent solubility.

  7. Amino Trans-position through the Chiral Aziridine

    Institute of Scientific and Technical Information of China (English)

    FENG Xi-Chun; LIANG Shu-Cai; SU Jiang-Tao; QIU Quo-Fu; HU Xian-Ming

    2003-01-01

    @@ Aziridines are valuable synthetic reagents and intermediates.[1~3] The highly strained three membered ring readily opens with excellent stereo- and regio-control to afford a wide variety of more stable ring opened chiral amines. (1 S, 2S)-1-Phenyl-2-amino-1,3-propanediol (1) is sulphonated at amino group and the hydroxyl group. Obtainning two kinds of sulphonated 1. Then it reacts in the conditions of Mitsunobu reagents (DEAD/PPh3) and alkaline, get α-phenyl-1-p-toluensulfonyl-aziridinemethanol (4). The chiral aziridine intermediate can aza-payne rearrange and ring opened with the reagent of LiAlH4 to get the N-tosyl-norephedrine (5) and 3-sulphurylamino-1aryl-propanol (7). The structure of these products was detected by IR, 1H NMR and MS spectra.

  8. Chiral trans-1,2-diaminocyclohexane derivatives as chiral solvating agents for carboxylic acids

    Indian Academy of Sciences (India)

    Mariappan Periasamy; Manasi Dalai; Meduri Padmaja

    2010-07-01

    Efficient use of the readily accessible chiral 2-symmetric acyclic diamines (1-2) as well as macrocyclic amines (3-5) containing trans-1,2-diaminocyclohexyl moiety as chiral solvating agents (CSA) for the determination of enantiomeric excess of representative carboxylic acids (6-7) and an amino acid derivative (8) is illustrated. The enantiomeric composition of different carboxylic acids estimated here by the 1H NMR method, based on the integration of the corresponding methine proton signals are in good correlation with that determined using HPLC method. The data are in accordance with the formation of multimolecular diastereomeric complexes in solution, which render good splitting of NMR signals for the enantiomers of representative carboxylic acids as well as for -Ts-phenylglycine (up to = 0.295 ppm, 118 Hz).

  9. Stereoselective synthesis of stable-isotope-labeled amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Unkefer, C.J.; Martinez, R.A.; Silks, L.A. III [Los Alamos National Laboratory, NM (United States); Lodwig, S.N. [Centralia College, WA (United States)

    1994-12-01

    For magnetic resonance and vibrational spectroscopies to reach their full potential, they must be used in combination with sophisticated site-specific stable isotope labeling of biological macromolecules. Labeled amino acids are required for the study of the structure and function of enzymes and proteins. Because there are 20 common amino acids, each with its own distinguishing chemistry, they remain a synthetic challenge. The Oppolzer chiral auxiliary provides a general tool with which to approach the synthesis of labeled amino acids. By using the Oppolzer auxiliary, amino acids can be constructed from several small molecules, which is ideal for stable isotope labeling. In addition to directing the stereochemistry at the {alpha}-carbon, the camphorsultam can be used for stereo-specific isotope labeling at prochiral centers in amino acids. By using the camphorsultam auxiliary we have the potential to synthesize virtually any isotopomer of all of the common amino acids.

  10. Use of neutral capillaries for the enantioseparation of N-benzoylated amino acids by capillary electrophoresis with bromobalhimycin as chiral selector.

    Science.gov (United States)

    Peng, Yongbo; Zhang, Tingting; Wang, Tingting; Liu, Zhenghua; Crommen, Jacques; Jiang, Zhengjin

    2013-05-01

    In this study, the partial filling technique on both polycationic polymer hexadimethrine bromide (HDB) modified capillary and eCAP neutral capillary were systematically compared in order to enhance the enantioseparation ability of bromobalhimycin as CE additive. The separation conditions, such as pH, the plug length, and the concentration of bromobalhimycin, etc., were optimized in order to obtain satisfactory separations. As expected, for all tested 28 N-benzoylated amino acids, up to five times higher enantioresolutions were obtained on the eCAP neutral capillary compared to that on the polycationic polymer hexadimethrine bromide modified capillary. Moreover, 26 of 28 tested racemic compounds were almost baseline- resolved without observing any interference from the front of the plug of bromobalhimycin. Although the limitation of longer running time on the neutral capillary, it allows the use of higher content of bromobalhimycin in the running buffer without any interference on the detection of analytes when enantioseparations are more difficult to obtain.

  11. Amino acids in Arctic aerosols

    Directory of Open Access Journals (Sweden)

    E. Scalabrin

    2012-07-01

    Full Text Available Amino acids are significant components of atmospheric aerosols, affecting organic nitrogen input to marine ecosystems, atmospheric radiation balance, and the global water cycle. The wide range of amino acid reactivities suggest that amino acids may serve as markers of atmospheric transport and deposition of particles. Despite this potential, few measurements have been conducted in remote areas to assess amino acid concentrations and potential sources. Polar regions offer a unique opportunity to investigate atmospheric processes and to conduct source apportionment studies of such compounds. In order to better understand the importance of amino acid compounds in the global atmosphere, we determined free amino acids (FAAs in seventeen size-segregated aerosol samples collected in a polar station in the Svalbard Islands from 19 April until 14 September 2010. We used an HPLC coupled with a tandem mass spectrometer (ESI-MS/MS to analyze 20 amino acids to quantify compounds at fmol m−3 levels. Mean total FAA concentration was 1070 fmol m−3 where serine and glycine were the most abundant compounds in almost all samples and accounted for 45–60% of the total amino acid relative abundance. The other eighteen compounds had average concentrations between 0.3 and 98 fmol m−3. The higher amino acid concentrations were present in the ultrafine aerosol fraction (<0.49 μm and accounted for the majority of the total amino acid content. Local marine sources dominate the boreal summer amino acid concentrations, with the exception of the regional input from Icelandic volcanics.

  12. Protein and amino acid nutrition

    Science.gov (United States)

    Dairy cow protein and amino acid nutrition have a significant role in sustainable dairying. Protein, amino acids, and nitrogen are inextricably linked through effects in the rumen, metabolism of the cow, and environmental nutrient management. Feeding systems have been making progress toward emphasiz...

  13. Amino Acid Formation on Interstellar Dust Particles

    Science.gov (United States)

    Meierhenrich, U. J.; Munoz Caro, G. M.; Barbier, B.; Brack, A.; Thiemann, W.; Goesmann, F.; Rosenbauer, H.

    2003-04-01

    In the dense interstellar medium dust particles accrete ice layers of known molecular composition. In the diffuse interstellar medium these ice layers are subjected to energetic UV-irradiation. Here, photoreactions form complex organic molecules. The interstellar processes were recently successfully simulated in two laboratories. At NASA Ames Research Center three amino acids were detected in interstellar ice analogues [1], contemporaneously, our European team reported on the identification of 16 amino acids therein [2]. Amino acids are the molecular building blocks of proteins in living organisms. The identification of amino acids on the simulated icy surface of interstellar dust particles strongly supports the assumption that the precursor molecules of life were delivered from interstellar and interplanetary space via (micro-) meteorites and/or comets to the earyl Earth. The results shall be verified by the COSAC experiment onboard the ESA cometary mission Rosetta [3]. [1] M.P. Bernstein, J.P. Dworkin, S.A. Sandford, G.W. Cooper, L.J. Allamandola: itshape Nature \\upshape 416 (2002), 401-403. [2] G.M. Muñoz Caro, U.J. Meierhenrich, W.A. Schutte, B. Barbier, A. Arcones Sergovia, H. Rosenbauer, W.H.-P. Thiemann, A. Brack, J.M. Greenberg: itshape Nature \\upshape 416 (2002), 403-406. [3] U. Meierhenrich, W.H.-P. Thiemann, H. Rosenbauer: itshape Chirality \\upshape 11 (1999), 575-582.

  14. Chromatographic determination of amino acid enantiomers in beers and raw materials used for their manufacture.

    Science.gov (United States)

    Erbe, T; Brückner, H

    2000-06-09

    Using gas chromatography (GC) on a chiral stationary phase, accompanied by high-performance liquid chromatography, beers and raw materials used for manufacturing (hops, barley grains, malts) were investigated for the pattern and quantities of amino acid enantiomers. Although L-amino acids were most abundant, certain D-amino acids were detected in all beers and most of the raw materials. Highest amounts of D-amino acids were detected in special beers such as Berliner Weisse that underwent bottle-conditioning with lactic cultures, and Belgian fruit beers produced by spontaneous fermentation. It is demonstrated that GC on chiral stationary phases is highly suitable for the quantitative determination of amino acid enantiomers in beers and raw materials used for their manufacture. Quantities, relative amounts and pattern of amino acid enantiomers can serve in particular as chiral markers for the authenticity of special beers.

  15. Using the Chiral Organophosphorus Derivatizing Agents for Determination of the Enantiomeric Composition of Chiral Carboxylic Acids by 31PNMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Chao CHE; Zhong Ning ZHANG; Gui Lan HUANG; Xin Xing WANG; Zhao Hai QIN

    2004-01-01

    The use of chiral organophosphorus derivatizing agents prepared in situ from chiral tartrate or chiral diamine for the 31PNMR determination of the enantiomeric composition of chiral carboxylic acids is described. The method is accurate, reliable and convenient.

  16. Amino Acids from a Comet

    Science.gov (United States)

    Cook, Jamie Elisla

    2009-01-01

    NASA's Stardust spacecraft returned samples from comet 81P/Wild 2 to Earth in January 2006. Examinations of the organic compounds in cometary samples can reveal information about the prebiotic organic inventory present on the early Earth and within the early Solar System, which may have contributed to the origin of life. Preliminary studies of Stardust material revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds (cometary- vs. terrestrial contamination) could not be identified. We have recently measured the carbon isotopic ratios of these amino acids to determine their origin, leading to the first detection of a coetary amino acid.

  17. Sonochemical-assisted fabrication of biologically active chiral poly(ester-imide/TiO2 bionanocomposites derived from L-methionine and L-tyrosine amino acids

    Directory of Open Access Journals (Sweden)

    2011-09-01

    Full Text Available A new chiral poly(ester-imide (PEI was prepared via direct polyesterification of N,N'-(pyromellitoyl-bis-(Ltyrosine dimethyl ester and N-trimellitylimido-L-methionine using tosyl chloride/pyridine/N,N'-dimethylformamide system as a condensing agent. The resulting new chiral polymer was obtained in good yield and had good thermal stability as well as good solubility in common organic solvents. After that, PEI/titanium bionanocomposites (PEI/TiO2 BNCs were prepared using the modified nanosized TiO2 via sonochemical reaction that can accelerate hydrolysis, increase collision chance for the reactive system and improve the dispersion of the nanoparticles in polymer matrix. The scanning electron microscopy (SEM, field emission scanning electron microscopy (FE-SEM and transmission electron microscopy (TEM results indicated that there is no aggregation of a large quantity of particles. Thermogravimetric analysis (TGA confirmed that the heat stability of the BNC polymers in the temperature range of 400–800ºC was enhanced by addition of TiO2 nanoparticles. Furthermore, in vitro toxicity test was employed for assessing the sensitivity of these compounds to microbial degradation. To this purpose, polymer and PEI/TiO2 BNCs were investigated under soil burial conditions. The results of this study revealed that polymer and its BNCs are biologically active and non-toxic in the natural environment although some antimicrobial properties were found for BNCs.

  18. CATALYTIC HYDROGENATION OF ACRYLATE ASMMETRIC Dd(Ⅱ)—CHELATING RESINS CONTAINING AMINO ACID LIGANDS

    Institute of Scientific and Technical Information of China (English)

    Wangying; WangHongzuo; 等

    1995-01-01

    The catalytic hydrogenation of palladium chelating resins containing chiral amino acid ligands based on lower crosslinked poly(chloroethyl acrylate) and some effects on the rate of hydrogenation were studied.

  19. A new theoretical model for the origin of amino acid homochirality

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Amino acid homochirality, as a unique behavior of life, could have originated synchronously with the genetic code. In this paper, phosphoryl amino-acid -5'-nucleosides with P-N bond are postulated to be a chiral origin model in prebiotic molecular evolution. The enthalpy change in the intramolecular interaction between the nucleotide base and the amino-acid side-chain determines the stability of the particular complex, resulting in a preferred conformation associated with the chirality of amino acids. Based on the theoretical model, our experiments and calculations show that the chiral selection of the earliest amino acids for L-enantiomers seems to be a strict stereochemical/physicochemical determinism. As other amino acids developed biosynthetically from the earliest amino acids, we infer that the chirality of the later amino acids was inherited from the precursor amino acids. This idea probably goes far back in history, but it is hoped that it will be a guide for further experiments in this area.

  20. Intermolecular Vibrations of Hydrophobic Amino Acids

    Science.gov (United States)

    Williams, Michael Roy Casselman

    Hydrophobic amino acids interact with their chemical environment through a combination of electrostatic, hydrogen bonding, dipole, induced dipole, and dispersion forces. These interactions all have their own characteristic energy scale and distance dependence. The low-frequency (0.1-5 THz, 5-150 cm-1) vibrational modes of amino acids in the solid state are a direct indicator of the interactions between the molecules, which include interactions between an amino acid functional group and its surroundings. This information is central to understanding the dynamics and morphology of proteins. The alpha-carbon is a chiral center for all of the hydrophobic amino acids, meaning that they exist in two forms, traditionally referred to as L- and D-enantiomers. This nomenclature indicates which direction the molecule rotates plane-polarized visible light (levorotory and dextrorotory). Chiral a-amino acids in proteins are exclusively the L-variety In the solid state, the crystal lattice of the pure L-enantiomer is the mirror image of the D-enantiomer crystal lattice. These solids are energetically identical. Enantiomers also have identical spectroscopic properties except when the measurement is polarization sensitive. A mixture of equal amounts D- and L-amino acid enantiomers can crystallize into a racemic (DL-) structure that is different from that of the pure enantiomers. Whether a solution of both enantiomers will crystallize into a racemic form or spontaneously resolve into a mixture of separate D- and L-crystals largely depends on the interactions between molecules available in the various possible configurations. This is an active area of research. Low-frequency vibrations with intermolecular character are very sensitive to changes in lattice geometry, and consequently the vibrational spectra of racemic crystals are usually quite distinct from the spectra of the crystals of the corresponding pure enantiomers in the far-infrared (far-IR). THz time-domain spectroscopy (THz

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

    Directory of Open Access Journals (Sweden)

    Rajalingam Agneeswari

    2016-08-01

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

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

    Science.gov (United States)

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

    2016-08-12

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

  3. Stereoselective assembly of amino acid-based metal-biomolecule nanofibers.

    Science.gov (United States)

    Wu, Hong; Tian, Chunyong; Zhang, Yufei; Yang, Chen; Zhang, Songping; Jiang, Zhongyi

    2015-04-14

    A series of amino acid-based metal-biomolecule nanofibers are fabricated through a coordination-directed assembly process. The chirality and carbon chain length of the amino acids exert a pronounced influence on the assembly process. This study may be extended to design diverse kinds of 1-D metal-biomolecule frameworks (MBioFs).

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

    Science.gov (United States)

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

    2013-09-01

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

  5. Combinatorics of aliphatic amino acids.

    Science.gov (United States)

    Grützmann, Konrad; Böcker, Sebastian; Schuster, Stefan

    2011-01-01

    This study combines biology and mathematics, showing that a relatively simple question from molecular biology can lead to complicated mathematics. The question is how to calculate the number of theoretically possible aliphatic amino acids as a function of the number of carbon atoms in the side chain. The presented calculation is based on earlier results from theoretical chemistry concerning alkyl compounds. Mathematical properties of this number series are highlighted. We discuss which of the theoretically possible structures really occur in living organisms, such as leucine and isoleucine with a chain length of four. This is done both for a strict definition of aliphatic amino acids only involving carbon and hydrogen atoms in their side chain and for a less strict definition allowing sulphur, nitrogen and oxygen atoms. While the main focus is on proteinogenic amino acids, we also give several examples of non-proteinogenic aliphatic amino acids, playing a role, for instance, in signalling. The results are in agreement with a general phenomenon found in biology: Usually, only a small number of molecules are chosen as building blocks to assemble an inconceivable number of different macromolecules as proteins. Thus, natural biological complexity arises from the multifarious combination of building blocks.

  6. Excitatory amino acid receptor antagonists

    DEFF Research Database (Denmark)

    Johansen, T N; Frydenvang, Karla Andrea; Ebert, B

    1997-01-01

    We have previously shown that (RS)-2-amino-2-(5-tert-butyl-3-hydroxyisoxazol-4-yl)acetic acid (ATAA) is an antagonist at N-methyl-D-aspartic acid (NMDA) and (RS)-2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl)propionic acid (AMPA) receptors. We have now resolved ATAA via diastereomeric salt formation......)-phenylethylamine salt of N-BOC-(R)-ATAA. Like ATAA, neither (R)- nor (S)-ATAA significantly affected (IC50 > 100 microM) the receptor binding of tritiated AMPA, kainic acid, or (RS)-3-(2-carboxypiperazin-4-yl)propyl-1-phosphonic acid, the latter being a competitive NMDA antagonist. Electrophysiological experiments......, using the rat cortical wedge preparation, showed the NMDA antagonist effect as well as the AMPA antagonist effect of ATAA to reside exclusively in the (R)-enantiomer (Ki = 75 +/- 5 microM and 57 +/- 1 microM, respectively). Neither (R)- nor (S)-ATAA significantly reduced kainic acid-induced excitation...

  7. Preparation and Reactions of Amino Acid Ester Sulfones as New Remote Asymmetrical Induced Reagents

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Cheng-He; BAI,Xue; LI,Tan-Qing; WU,Jun; Alfred Hassner

    2004-01-01

    @@ The development of chiral auxiliary-controlled asymmetric synthesis has been receiving increasing interest in recent yearsfi,2] Various chiral auxiliary reagents have been observed[3] and a lot of results showed that variation of the chiral auxiliary could influence asymmetric induction. Recently, it has been reported the reaction of the aminated sulfones as a remote chiral auxiliary with α,β-unsaturated carbonyl compounds.[4] Here we would like to report the preparation of amino acid ester sulfones as new remote asymmetrical induced reagents and their reactions with α,β-unsaturated esters.

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

    Science.gov (United States)

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

    2006-10-06

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

  9. Unnatural reactive amino acid genetic code additions

    Science.gov (United States)

    Deiters, Alexander; Cropp, Ashton T; Chin, Jason W; Anderson, Christopher J; Schultz, Peter G

    2013-05-21

    This invention provides compositions and methods for producing translational components that expand the number of genetically encoded amino acids in eukaryotic cells. The components include orthogonal tRNAs, orthogonal aminoacyl-tRNA synthetases, pairs of tRNAs/synthetases and unnatural amino acids. Proteins and methods of producing proteins with unnatural amino acids in eukaryotic cells are also provided.

  10. Unnatural reactive amino acid genetic code additions

    Science.gov (United States)

    Deiters, Alexander; Cropp, T. Ashton; Chin, Jason W.; Anderson, J. Christopher; Schultz, Peter G.

    2014-08-26

    This invention provides compositions and methods for producing translational components that expand the number of genetically encoded amino acids in eukaryotic cells. The components include orthogonal tRNAs, orthogonal aminoacyl-tRNA synthetases, orthogonal pairs of tRNAs/synthetases and unnatural amino acids. Proteins and methods of producing proteins with unnatural amino acids in eukaryotic cells are also provided.

  11. Amino acids as antioxidants for frying oil

    Science.gov (United States)

    Amino acids, proteins and hydrolysates of proteins have been known to protect edible oils from oxidation. While amino acids and related materials have high potential as antioxidants for frying oil, effectiveness of each amino acid and mechanisms of their activities are not well understood yet. Propo...

  12. Current topics in the biotechnological production of essential amino acids, functional amino acids, and dipeptides.

    Science.gov (United States)

    Mitsuhashi, Satoshi

    2014-04-01

    Amino acids play important roles in both human and animal nutrition and in the maintenance of health. Here, amino acids are classified into three groups: first, essential amino acids, which are essential to nutrition; second, functional amino acids, recently found to be important in the promotion of physiological functions; and third, dipeptides, which are used to resolve problematic features of specific free amino acids, such as their instability or insolubility. This review focusses on recent researches concerning the microbial production of essential amino acids (lysine and methionine), functional amino acids (histidine and ornithine), and a dipeptide (L-alanyl-L-glutamine).

  13. Pseudoephedrine-Directed Asymmetric α-Arylation of α-Amino Acid Derivatives.

    Science.gov (United States)

    Atkinson, Rachel C; Fernández-Nieto, Fernando; Mas Roselló, Josep; Clayden, Jonathan

    2015-07-27

    Available α-amino acids undergo arylation at their α position in an enantioselective manner on treatment with base of N'-aryl urea derivatives ligated to pseudoephedrine as a chiral auxiliary. In situ silylation and enolization induces diastereoselective migration of the N'-aryl group to the α position of the amino acid, followed by ring closure to a hydantoin with concomitant explulsion of the recyclable auxiliary. The hydrolysis of the hydantoin products provides derivatives of quaternary amino acids. The arylation avoids the use of heavy-metal additives, and is successful with a range of amino acids and with aryl rings of varying electronic character.

  14. Amino acid properties conserved in molecular evolution.

    Directory of Open Access Journals (Sweden)

    Witold R Rudnicki

    Full Text Available That amino acid properties are responsible for the way protein molecules evolve is natural and is also reasonably well supported both by the structure of the genetic code and, to a large extent, by the experimental measures of the amino acid similarity. Nevertheless, there remains a significant gap between observed similarity matrices and their reconstructions from amino acid properties. Therefore, we introduce a simple theoretical model of amino acid similarity matrices, which allows splitting the matrix into two parts - one that depends only on mutabilities of amino acids and another that depends on pairwise similarities between them. Then the new synthetic amino acid properties are derived from the pairwise similarities and used to reconstruct similarity matrices covering a wide range of information entropies. Our model allows us to explain up to 94% of the variability in the BLOSUM family of the amino acids similarity matrices in terms of amino acid properties. The new properties derived from amino acid similarity matrices correlate highly with properties known to be important for molecular evolution such as hydrophobicity, size, shape and charge of amino acids. This result closes the gap in our understanding of the influence of amino acids on evolution at the molecular level. The methods were applied to the single family of similarity matrices used often in general sequence homology searches, but it is general and can be used also for more specific matrices. The new synthetic properties can be used in analyzes of protein sequences in various biological applications.

  15. Microbial production of amino acids in Japan.

    Science.gov (United States)

    Kumagai, H

    2000-01-01

    The microbial biotechnology of amino acids production which was developed and industrialized in Japan have been summarized. The amino acids include L-glutamic acid, L-lysine, L-threonine, L-aspartic acid, L-alanine, L-cysteine, L-dihydroxyphenylalanine, D-p-hydroxyphenyl-glycine, and hydroxy-L-proline.

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

    Institute of Scientific and Technical Information of China (English)

    吴海霞; 王东强; 赵见超; 柯燕雄; 梁鑫淼

    2016-01-01

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

  17. Stardust and the Molecules of Life (Why are the Amino Acids Left-Handed?)

    Energy Technology Data Exchange (ETDEWEB)

    Boyd, R N; Kajino, T; Onaka, T

    2010-04-02

    A mechanism for creating and selecting amino acid chirality is identified, and subsequent chemical replication and galactic mixing that would populate the galaxy with the predominant species will be described. This involves: (1) the spin of the {sup 14}N in the amino acids, or in precursor molecules from which amino acids might be formed, coupling to the chirality of the molecules; (2) the neutrinos emitted from the supernova, together with magnetic field from the nascent neutron star or black hole from the supernova selectively destroying one orientation of the {sup 14}N, thereby selecting the chirality associated with the other {sup 14}N orientation; (3) amplification by chemical evolution, by which the molecules replicate on a relatively short timescale; and (4) galactic mixing on a longer timescale mixing the selected molecules throughout the galaxy.

  18. Indigenous amino acids in primitive CR meteorites

    CERN Document Server

    Martins, Z; Orzechowska, G E; Fogel, M L; Ehrenfreund, P

    2008-01-01

    CR meteorites are among the most primitive meteorites. In this paper, we report the first measurements of amino acids in Antarctic CR meteorites, two of which show the highest amino acid concentrations ever found in a chondrite. EET92042, GRA95229 and GRO95577 were analyzed for their amino acid content using high performance liquid chromatography with UV fluorescence detection (HPLC-FD) and gas chromatographymass spectrometry (GC-MS). Our data show that EET92042 and GRA95229 are the most amino acid-rich chondrites ever analyzed, with total amino acid concentrations ranging from 180 parts-per-million (ppm) to 249 ppm. GRO95577, however, is depleted in amino acids. The most abundant amino acids present in the EET92042 and GRA95229 meteorites are the alpha-amino acids glycine, isovaline, alpha-aminoisobutyric acid (alpha-AIB), and alanine, with delta13C values ranging from +31.6per mil to +50.5per mil. The carbon isotope results together with racemic enantiomeric ratios determined for most amino acids strongly i...

  19. Rigid nonproteinogenic cyclic amino acids as ligands for glutamate receptors: trans-tris(homoglutamic) acids

    DEFF Research Database (Denmark)

    Meyer, Udo; Bisel, Philippe; Bräuner-Osborne, Hans;

    2005-01-01

    The second-generation asymmetric synthesis of the trans-tris(homoglutamic) acids reported herein proceeds via Strecker reaction of chiral ketimines, obtained from condensation of racemic 2-ethoxycarbonylmethylcyclopentanone and commercially available (S)- and (R)-1-phenylethylamine, respectively......) yielded diastereomeric mixtures of secondary alpha-amino amido-esters, which after separation were hydrogenolyzed and hydrolyzed each to the enantiomeric trans-1-amino-2-carboxymethylcyclopentanecarboxylic acids. Their configuration was completely established by NMR methods, CD spectra, and X-ray analysis...... of the trans-1S,2R-configured secondary alpha-amino amido-ester. In receptor binding assays and functional tests, trans-1S,2R-1-amino-2-carboxymethylcyclopentanecarboxylic acid hydrochloride was found to behave as a selective mGluR(2)-antagonist without relevant binding properties at iGluRs....

  20. Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

    Science.gov (United States)

    Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

    2014-06-01

    A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates.

  1. Amino acid composition of some Mexican foods.

    Science.gov (United States)

    Morales de León, Josefina; Camacho, M Elena; Bourges, Héctor

    2005-06-01

    Knowledge of the amino acid composition of foods is essential to calculate their chemical score, which is used to predict protein quality of foods and diets. Though amino acid composition of many foods is reasonably well established, better knowledge is needed on native foods consumed in different regions and countries. This paper presents the amino acid composition of different presentations of raw and processed foods produced and consumed in Mexico. The amino acid composition was determined using Beckman amino acid analyzers (models 116 and 6300). Tryptophan was determined using the Spies and Chambers method. Of the different foods analyzed, some comments are made on native or basic foods in Mexico: Spirulin, where lysine is the limiting amino acid, with a chemical score of 67%, is a good source of tryptophan (1.16g/16 gN); amaranth contains high levels of sulphur amino acids (4.09 to 5.34 g/16gN), with a protein content of 15 g/100g; and pulque, a Pre-Hispanic beverage that contains high levels of tryptophan (2.58 g/16 gN) and sulphur amino acids (2.72 g/16 gN). Finally, insects are good sources of sulphur amino acids and lysine.

  2. Effect of domoic acid on brain amino acid levels.

    Science.gov (United States)

    Durán, R; Arufe, M C; Arias, B; Alfonso, M

    1995-03-01

    The administration of Domoic Acid (Dom) in a 0.2 mg/kg i.p. dose induces changes in the levels of amino acids of neurochemical interest (Asp, Glu, Gly, Tau, Ala, GABA) in different rat brain regions (hypothalamus, hippocampus, amygdala, striatum, cortex and midbrain). The most affected amino acid is the GABA, the main inhibitory amino acid neurotransmitter, whereas glutamate, the main excitatory amino acid, is not affected. The rat brain regions that seem to be the main target of the Dom action belong to the limbic system (hippocampus, amygdala). The possible implication of the amino acids in the actions of Dom is also discussed.

  3. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

    Science.gov (United States)

    Hazen, R. M.; Filley, T. R.; Goodfriend, G. A.

    2001-01-01

    The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

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

    Science.gov (United States)

    Bozkurt, Selahattin

    2013-09-01

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

  5. Plasma amino acid relationships during parenteral nutrition.

    Science.gov (United States)

    Wells, F E; Smits, B J

    1980-01-01

    The plasma amino acidfs of 17 patients were studied before and during total parenteral nutrition (TPN). The amino acid (AA) pattern changed similarly for all patients. The AA concentration changes relative to preinfusion (PAER) were the most informative index of change. Two groups of AA were defined, the "branched chain" group (five amino acids) and the "hepatic" group (four amino acids) based on the correlation of PAER values. Comparison of PAER values with the ratio of AA intake to requirement indicated that the requirements of the sick patients were more similar to those of children than those of healthy adults.

  6. A quantitative measure of chirality inside nucleic acid databank.

    Science.gov (United States)

    Pietropaolo, Adriana; Parrinello, Michele

    2011-08-01

    We show the capability of a chirality index (Pietropaolo et al., Proteins 2008;70:667-677) to investigate nucleic acid structures because of its high sensitivity to helical conformations. By analyzing selected structures of DNA and RNA, we have found that sequences rich in cytosine and guanine have a tendency to left-handed chirality, in contrast to regions rich in adenine or thymine which show strong negative, right-handed, chirality values. We also analyze RNA structures, where specific loops and hairpin motifs are characterized by a well-defined chirality value. We find that in nucleosome the chirality is exalted, whereas in ribosome it is reduced. Our results illustrate the sensitivity of this descriptor for nucleic acid conformations.

  7. Nutritional value of D-amino acids, D-peptides, and amino acid derivatives in mice.

    Science.gov (United States)

    Friedman, Mendel; Levin, Carol E

    2012-01-01

    This paper describes a method for determining the nutritional value of D-amino acids, D-peptides, and amino acid derivatives using a growth assay in mice fed a synthetic all-amino acid diet. A large number of experiments were carried out in which a molar equivalent of the test compound replaced a nutritionally essential amino acid such as L-lysine (L-Lys), L-methionine (L-Met), L -phenylalanine (L-Phe), and L-tryptophan (L-Trp) as well as the semi-essential amino acids L-cysteine (L-Cys) and L-tyrosine (L-Tyr). The results show wide-ranging variations in the biological utilization of test substances. The method is generally applicable to the determination of the biological utilization and safety of any amino acid derivative as a potential nutritional source of the corresponding L-amino acid. Because the organism is forced to use the D-amino acid or amino acid derivative as the sole source of the essential or semi-essential amino acid being replaced, and because a free amino acid diet allows better control of composition, the use of all-amino acid for such determinations may be preferable to protein-based diets.

  8. Microbial production of natural poly amino acid

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three kinds of poly amino acids, poly-γ-glutamic acid, poly(ε-L-lysine) and multi-L-arginyl-poly (L-aspartic acid) can be synthesized by enzymatic process independently from ribosomal protein biosynthesis pathways in microorganism. These biosynthesized polymers have attracted more and more attentions because of their unique properties and various applications. In this review, the current knowledge on the biosynthesis, biodegradations and applications of these three poly amino acids are summarized.

  9. The Apollo Program and Amino Acids

    Science.gov (United States)

    Fox, Sidney W.

    1973-01-01

    Discusses the determination of hydrolyzable amino acid precursors and a group of six amino acids in the returned lunar samples of the Apollo programs. Indicates that molecular evolution is arrested at the precursor stage on the Moon because of lack of water. (CC)

  10. Crystalline amino acids and nitrogen emission

    NARCIS (Netherlands)

    Verstegen, M.W.A.; Jongbloed, A.W.

    2003-01-01

    Reductions in dietary protein level and supplementation with certain crystalline amino acids is a well-established method of formulating diets to achieve a more ideal amino acid pattern and to reduce nitrogen excretion. Up to 35% reduction in nitrogen excretion may be achieved by supplementing pig d

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

    Science.gov (United States)

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

    2010-07-23

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

  12. Synthesis of β-Amino Acid Derivatives

    Institute of Scientific and Technical Information of China (English)

    Zhao Yonghua; Ma Zhihua; Jiang Nan; Wang Jianbo

    2004-01-01

    In recent years, β-amino acids and their derivatives have attracted considerable attention due to their occurrence in biologically active natural products, such as dolastatins,cyclohexylnorstatine and Taxol. β-Amino acids also find application in the synthesis of β-lactams,piperidines, indolizidines. Moreover, the peptides consisting of β-amino acids, the so-called β-peptides, have been extensively studied recently. Consequently, considerable efforts have been directed to the synthesis of β-amino acids and their derivatives1. In particular, stereoselective synthesis of β-amino acids has been a challenging project, and there are only limited methods available. In this presentation, we report our efforts in this area.

  13. Differential distribution of amino acids in plants.

    Science.gov (United States)

    Kumar, Vinod; Sharma, Anket; Kaur, Ravdeep; Thukral, Ashwani Kumar; Bhardwaj, Renu; Ahmad, Parvaiz

    2017-03-15

    Plants are a rich source of amino acids and their individual abundance in plants is of great significance especially in terms of food. Therefore, it is of utmost necessity to create a database of the relative amino acid contents in plants as reported in literature. Since in most of the cases complete analysis of profiles of amino acids in plants was not reported, the units used and the methods applied and the plant parts used were different, amino acid contents were converted into relative units with respect to lysine for statistical analysis. The most abundant amino acids in plants are glutamic acid and aspartic acid. Pearson's correlation analysis among different amino acids showed that there were no negative correlations between the amino acids. Cluster analysis (CA) applied to relative amino acid contents of different families. Alismataceae, Cyperaceae, Capparaceae and Cactaceae families had close proximity with each other on the basis of their relative amino acid contents. First three components of principal component analysis (PCA) explained 79.5% of the total variance. Factor analysis (FA) explained four main underlying factors for amino acid analysis. Factor-1 accounted for 29.4% of the total variance and had maximum loadings on glycine, isoleucine, leucine, threonine and valine. Factor-2 explained 25.8% of the total variance and had maximum loadings on alanine, aspartic acid, serine and tyrosine. 14.2% of the total variance was explained by factor-3 and had maximum loadings on arginine and histidine. Factor-4 accounted 8.3% of the total variance and had maximum loading on the proline amino acid. The relative content of different amino acids presented in this paper is alanine (1.4), arginine (1.8), asparagine (0.7), aspartic acid (2.4), cysteine (0.5), glutamic acid (2.8), glutamine (0.6), glycine (1.0), histidine (0.5), isoleucine (0.9), leucine (1.7), lysine (1.0), methionine (0.4), phenylalanine (0.9), proline (1.1), serine (1.0), threonine (1

  14. Molecular pharmacology of 4-substituted glutamic acid analogues at ionotropic and metabotropic excitatory amino acid receptors

    DEFF Research Database (Denmark)

    Bräuner-Osborne, Hans; Nielsen, B; Stensbøl, T B;

    1997-01-01

    using rat brain ionotropic glutamate receptors, and in functional assays using cloned metabotropic glutamate (mGlu) receptors. As a notable result of these studies, (2S,4R)-4-methylglutamic acid and (2S,4S)-4-methylglutamic acid were shown to be selective for kainic acid receptors and mGlu receptors......The pharmacology of (2S,4R)-4-methylglutamic acid, (2S,4S)-4-methylglutamic acid and (S)- and (R)-4-methyleneglutamic acids (obtained in high chemical and enantiomeric purity from racemic 4-methyleneglutamic acid by chiral HPLC using a Crownpak CR(+) column), was examined in binding experiments...... (subtypes 1alpha and 2), respectively, whereas (S)-4-methyleneglutamic acid showed high but rather non-selective affinity for the (RS)-2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl)propionic acid (AMPA), kainic acid, NMDA and mGlu receptors (subtypes 1alpha and 2). Although none of the compounds were specific...

  15. Synthesis and anticonvulsant activity of novel bicyclic acidic amino acids

    DEFF Research Database (Denmark)

    Conti, Paola; De Amici, Marco; Joppolo Di Ventimiglia, Samuele

    2003-01-01

    Bicyclic acidic amino acids (+/-)-6 and (+/-)-7, which are conformationally constrained homologues of glutamic acid, were prepared via a strategy based on a 1,3-dipolar cycloaddition. The new amino acids were tested toward ionotropic and metabotropic glutamate receptor subtypes; both of them...

  16. Gemini surfactants from natural amino acids.

    Science.gov (United States)

    Pérez, Lourdes; Pinazo, Aurora; Pons, Ramon; Infante, Mrosa

    2014-03-01

    In this review, we report the most important contributions in the structure, synthesis, physicochemical (surface adsorption, aggregation and phase behaviour) and biological properties (toxicity, antimicrobial activity and biodegradation) of Gemini natural amino acid-based surfactants, and some potential applications, with an emphasis on the use of these surfactants as non-viral delivery system agents. Gemini surfactants derived from basic (Arg, Lys), neutral (Ser, Ala, Sar), acid (Asp) and sulphur containing amino acids (Cys) as polar head groups, and Geminis with amino acids/peptides in the spacer chain are reviewed.

  17. THE ASYMMETRIC SYNTHESIS OF AMINO ACIDS UNDER POLYMER-SUPPORTED PHASE TRANSFER CATALYTIC CONDITION

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    The optical α-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical α-amino acids. This is a new method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.

  18. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  19. Amino acid analogs for tumor imaging

    Energy Technology Data Exchange (ETDEWEB)

    Goodman, Mark M. (Atlanta, GA); Shoup, Timothy (Decatur, GA)

    1998-09-15

    The invention provides novel amino acid compounds of use in detecting and evaluating brain and body tumors. These compounds combine the advantageous properties of 1-amino-cycloalkyl-1-carboxylic acids, namely, their rapid uptake and prolonged retention in tumors with the properties of halogen substituents, including certain useful halogen isotopes including fluorine-18, iodine-123, iodine-125, iodine-131, bromine-75, bromine-76, bromine-77 and bromine-82. In one aspect, the invention features amino acid compounds that have a high specificity for target sites when administered to a subject in vivo. Preferred amino acid compounds show a target to non-target ratio of at least 5:1, are stable in vivo and substantially localized to target within 1 hour after administration. An especially preferred amino acid compound is ›.sup.18 F!-1-amino-3-fluorocyclobutane-1-carboxylic acid (FACBC). In another aspect, the invention features pharmaceutical compositions comprised of an .alpha.-amino acid moiety attached to either a four, five, or a six member carbon-chain ring. In addition, the invention features analogs of .alpha.-aminoisobutyric acid.

  20. Amino acid analogs for tumor imaging

    Energy Technology Data Exchange (ETDEWEB)

    Goodman, Mark M. (Atlanta, GA); Shoup, Timothy (Decatur, GA)

    1998-10-06

    The invention provides novel amino acid compounds of use in detecting and evaluating brain and body tumors. These compounds combine the advantageous properties of 1-amino-cycloalkyl-1-carboxylic acids, namely, their rapid uptake and prolonged retention in tumors with the properties of halogen substituents, including certain useful halogen isotopes including fluorine-18, iodine-123, iodine-125, iodine-131, bromine-75, bromine-76, bromine-77 and bromine-82. In one aspect, the invention features amino acid compounds that have a high specificity for target sites when administered to a subject in vivo. Preferred amino acid compounds show a target to non-target ratio of at least 5:1, are stable in vivo and substantially localized to target within 1 hour after administration. An especially preferred amino acid compound is ›.sup.18 F!-1-amino-3-fluorocyclobutane-1-carboxylic acid (FACBC). In another aspect, the invention features pharmaceutical compositions comprised of an .alpha.-amino acid moiety attached to either a four, five, or a six member carbon-chain ring. In addition, the invention features analogs of .alpha.-aminoisobutyric acid.

  1. Amino acid analogs for tumor imaging

    Energy Technology Data Exchange (ETDEWEB)

    Goodman, M.M.; Shoup, T.

    1998-10-06

    The invention provides novel amino acid compounds of use in detecting and evaluating brain and body tumors. These compounds combine the advantageous properties of 1-amino-cycloalkyl-1-carboxylic acids, namely, their rapid uptake and prolonged retention in tumors with the properties of halogen substituents, including certain useful halogen isotopes including fluorine-18, iodine-123, iodine-125, iodine-131, bromine-75, bromine-76, bromine-77 and bromine-82. In one aspect, the invention features amino acid compounds that have a high specificity for target sites when administered to a subject in vivo. Preferred amino acid compounds show a target to non-target ratio of at least 5:1, are stable in vivo and substantially localized to target within 1 hour after administration. An especially preferred amino acid compound is [{sup 18}F]-1-amino-3-fluorocyclobutane-1-carboxylic acid (FACBC). In another aspect, the invention features pharmaceutical compositions comprised of an {alpha}-amino acid moiety attached to either a four, five, or a six member carbon-chain ring. In addition, the invention features analogs of {alpha}-aminoisobutyric acid.

  2. Amino acid analogs for tumor imaging

    Science.gov (United States)

    Goodman, M.M.; Shoup, T.

    1998-09-15

    The invention provides novel amino acid compounds of use in detecting and evaluating brain and body tumors. These compounds combine the advantageous properties of 1-amino-cycloalkyl-1-carboxylic acids, namely, their rapid uptake and prolonged retention in tumors with the properties of halogen substituents, including certain useful halogen isotopes including fluorine-18, iodine-123, iodine-125, iodine-131, bromine-75, bromine-76, bromine-77 and bromine-82. In one aspect, the invention features amino acid compounds that have a high specificity for target sites when administered to a subject in vivo. Preferred amino acid compounds show a target to non-target ratio of at least 5:1, are stable in vivo and substantially localized to target within 1 hour after administration. An especially preferred amino acid compound is [{sup 18}F]-1-amino-3-fluorocyclobutane-1-carboxylic acid (FACBC). In another aspect, the invention features pharmaceutical compositions comprised of an {alpha}-amino acid moiety attached to either a four, five, or a six member carbon-chain ring. In addition, the invention features analogs of {alpha}-aminoisobutyric acid.

  3. Amino Acids in the Martian Meteorite Nakhla

    Science.gov (United States)

    Glavin, Daniel P.; Bada, Jeffrey L.; Brinton, Karen L. F.; McDonald, Gene D.

    1999-08-01

    A suite of protein and nonprotein amino acids were detected with high-performance liquid chromatography in the water- and acid-soluble components of an interior fragment of the Martian meteorite Nakhla, which fell in Egypt in 1911. Aspartic and glutamic acids, glycine, alanine, β -alanine, and γ -amino-n-butyric acid (γ -ABA) were the most abundant amino acids detected and were found primarily in the 6 M HCl-hydrolyzed, hot water extract. The concentrations ranged from 20 to 330 parts per billion of bulk meteorite. The amino acid distribution in Nakhla, including the D/L ratios (values range from contamination of Martian meteorites after direct exposure to the terrestrial environment has important implications for Mars sample-return missions and the curation of the samples from the time of their delivery to Earth.

  4. Amino Acid Stability in the Early Oceans

    Science.gov (United States)

    Parker, E. T.; Brinton, K. L.; Burton, A. S.; Glavin, D. P.; Dworkin, J. P.; Bada, J. L.

    2015-01-01

    It is likely that a variety of amino acids existed in the early oceans of the Earth at the time of the origin and early evolution of life. "Primordial soup", hydrothermal vent, and meteorite based processes could have contributed to such an inventory. Several "protein" amino acids were likely present, however, based on prebiotic synthesis experiments and carbonaceous meteorite studies, non-protein amino acids, which are rare on Earth today, were likely the most abundant. An important uncertainty is the length of time these amino acids could have persisted before their destruction by abiotic and biotic processes. Prior to life, amino acid concentrations in the oceans were likely regulated by circulation through hydro-thermal vents. Today, the entire ocean circulates through vent systems every 10(exp 7) years. On the early Earth, this value was likely smaller due to higher heat flow and thus marine amino acid life-time would have been shorter. After life, amino acids in the oceans could have been assimilated by primitive organisms.

  5. Enantiomer-specific selection of amino acids.

    Science.gov (United States)

    Ren, Xueying; Tellez, Luis A; de Araujo, Ivan E

    2013-12-01

    Dietary intake of L-amino acids impacts on several physiological functions, including the control of gastrointestinal motility, pancreatic secretion, and appetite. However, the biological mechanisms regulating behavioral predilections for certain amino acid types remain poorly understood. We tested the hypothesis that, in mice, the potency with which a given glucogenic amino acid increases glucose utilization reflects its rewarding properties. We have found that: (1) during long-, but not short-, term preference tests, L-alanine and L-serine were preferred over their D-enantiomer counterparts, while no such effect was observed for L-threonine vs. D-threonine; (2) these behavioral patterns were closely associated with the ability of L-amino acids to promote increases in respiratory exchange ratios such that those, and only those, L-amino acids able to promote increases in respiratory exchange ratios were preferred over their D-isomers; (3) these behavioral preferences were independent of gustatory influences, since taste-deficient Trpm5 knockout mice displayed ingestive responses very similar to those of their wild-type counterparts. We conclude that the ability to promote increases in respiratory exchange ratios enhances the reward value of nutritionally relevant amino acids and suggest a mechanistic link between substrate utilization and amino acid preferences.

  6. Enantioselective conjugate additions of α-amino radicals via cooperative photoredox and Lewis acid catalysis.

    Science.gov (United States)

    Ruiz Espelt, Laura; McPherson, Iain S; Wiensch, Eric M; Yoon, Tehshik P

    2015-02-25

    We report the highly enantioselective addition of photogenerated α-amino radicals to Michael acceptors. This method features a dual-catalyst protocol that combines transition metal photoredox catalysis with chiral Lewis acid catalysis. The combination of these two powerful modes of catalysis provides an effective, general strategy to generate and control the reactivity of photogenerated reactive intermediates.

  7. Amino Acid Degradation after Meteoritic Impact Simulation

    Science.gov (United States)

    Bertrand, M.; Westall, F.; vanderGaast, S.; Vilas, F.; Hoerz, F.; Barnes, G.; Chabin, A.; Brack, A.

    2008-01-01

    Amino acids are among the most important prebiotic molecules as it is from these precursors that the building blocks of life were formed [1]. Although organic molecules were among the components of the planetesimals making up the terrestrial planets, large amounts of primitive organic precursor molecules are believed to be exogenous in origin and to have been imported to the Earth via micrometeorites, carbonaceous meteorites and comets, especially during the early stages of the formation of the Solar System [1,2]. Our study concerns the hypothesis that prebiotic organic matter, present on Earth, was synthesized in the interstellar environment, and then imported to Earth by meteorites or micrometeorites. We are particularly concerned with the formation and fate of amino acids. We have already shown that amino acid synthesis is possible inside cometary grains under interstellar environment conditions [3]. We are now interested in the effects of space conditions and meteoritic impact on these amino acids [4-6]. Most of the extraterrestrial organic molecules known today have been identified in carbonaceous chondrite meteorites [7]. One of the components of these meteorites is a clay with a composition close to that of saponite, used in our experiments. Two American teams have studied the effects of impact on various amino acids [8,9]. [8] investigated amino acids in saturated solution in water with pressure ranges between 5.1 and 21 GPa and temperature ranges between 412 and 870 K. [9] studied amino acids in solid form associated with and without minerals (Murchison and Allende meteorite extracts) and pressure ranges between 3 and 30 GPa. In these two experiments, the amino acids survived up to 15 GPa. At higher pressure, the quantity of preserved amino acids decreases quickly. Some secondary products such as dipeptides and diketopiperazins were identified in the [8] experiment.

  8. A study of aliphatic amino acids using simulated vibrational circular dichroism and Raman optical activity spectra

    CERN Document Server

    Ganesan, Aravindhan; Wang, Feng

    2013-01-01

    Vibrational optical activity (VOA) spectra, such as vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra, of aliphatic amino acids are simulated using density functional theory (DFT) methods in both gas phase (neutral form) and solution (zwitterionic form), together with their respective infrared (IR) and Raman spectra of the amino acids. The DFT models, which are validated by excellent agreements with the available experimental Raman and ROA spectra of alanine in solution, are employed to study other aliphatic amino acids. The inferred (IR) intensive region (below 2000 cm-1) reveals the signature of alkyl side chains, whereas the Raman intensive region (above 3000 cm-1) contains the information of the functional groups in the amino acids. Furthermore, the chiral carbons of the amino acids (except for glycine) dominate the VCD and ROA spectra in the gas phase, but the methyl group vibrations produce stronger VCD and ROA signals in solution. The C-H related asymmetric vibrations domina...

  9. Amino acids in the Martian meteorite Nakhla.

    Science.gov (United States)

    Glavin, D P; Bada, J L; Brinton, K L; McDonald, G D

    1999-08-03

    A suite of protein and nonprotein amino acids were detected with high-performance liquid chromatography in the water- and acid-soluble components of an interior fragment of the Martian meteorite Nakhla, which fell in Egypt in 1911. Aspartic and glutamic acids, glycine, alanine, beta-alanine, and gamma-amino-n-butyric acid (gamma-ABA) were the most abundant amino acids detected and were found primarily in the 6 M HCl-hydrolyzed, hot water extract. The concentrations ranged from 20 to 330 parts per billion of bulk meteorite. The amino acid distribution in Nakhla, including the D/L ratios (values range from meteorite soon after its fall to Earth, although it is possible that some of the amino acids are endogenous to the meteorite. The rapid amino acid contamination of Martian meteorites after direct exposure to the terrestrial environment has important implications for Mars sample-return missions and the curation of the samples from the time of their delivery to Earth.

  10. Oxidative diversification of amino acids and peptides by small-molecule iron catalysis

    Science.gov (United States)

    Osberger, Thomas J.; Rogness, Donald C.; Kohrt, Jeffrey T.; Stepan, Antonia F.; White, M. Christina

    2016-09-01

    Secondary metabolites synthesized by non-ribosomal peptide synthetases display diverse and complex topologies and possess a range of biological activities. Much of this diversity derives from a synthetic strategy that entails pre- and post-assembly oxidation of both the chiral amino acid building blocks and the assembled peptide scaffolds. The vancomycin biosynthetic pathway is an excellent example of the range of oxidative transformations that can be performed by the iron-containing enzymes involved in its biosynthesis. However, because of the challenges associated with using such oxidative enzymes to carry out chemical transformations in vitro, chemical syntheses guided by these principles have not been fully realized in the laboratory. Here we report that two small-molecule iron catalysts are capable of facilitating the targeted C-H oxidative modification of amino acids and peptides with preservation of α-centre chirality. Oxidation of proline to 5-hydroxyproline furnishes a versatile intermediate that can be transformed to rigid arylated derivatives or flexible linear carboxylic acids, alcohols, olefins and amines in both monomer and peptide settings. The value of this C-H oxidation strategy is demonstrated in its capacity for generating diversity: four ‘chiral pool’ amino acids are transformed to twenty-one chiral unnatural amino acids representing seven distinct functional group arrays; late-stage C-H functionalizations of a single proline-containing tripeptide furnish eight tripeptides, each having different unnatural amino acids. Additionally, a macrocyclic peptide containing a proline turn element is transformed via late-stage C-H oxidation to one containing a linear unnatural amino acid.

  11. An astrophysically-relevant mechanism for amino acid enantiomer enrichment

    NARCIS (Netherlands)

    P. Fletcher, S.; B. C. Jagt, R.; Feringa, B.L.

    2007-01-01

    The sublimation of low ee amino acids was examined while exploring simple mechanisms by which high ee amino acids can be generated under conditions that exist in space; significant enantioenrichment of a variety of amino acids by sublimation was achieved.

  12. Side Chain Cyclized Aromatic Amino Acids

    DEFF Research Database (Denmark)

    Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel

    2016-01-01

    Constraining the conformation of flexible peptides is a proven strategy to increase potency, selectivity, and metabolic stability. The focus has mostly been on constraining the backbone dihedral angles; however, the correct orientation of the amino acid side chains (χ-space) that constitute...... the peptide pharmacophore is equally important. Control of χ-space utilizes conformationally constrained amino acids that favor, disfavor, or exclude the gauche (-), the gauche (+), or the trans conformation. In this review we focus on cyclic aromatic amino acids in which the side chain is connected...... to the peptide backbone to provide control of χ(1)- and χ(2)-space. The manifold applications for cyclized analogues of the aromatic amino acids Phe, Tyr, Trp, and His within peptide medicinal chemistry are showcased herein with examples of enzyme inhibitors and ligands for G protein-coupled receptors....

  13. Genetically encoded fluorescent coumarin amino acids

    Science.gov (United States)

    Wang, Jiangyun; Xie, Jianming; Schultz, Peter G.

    2010-10-05

    The invention relates to orthogonal pairs of tRNAs and aminoacyl-tRNA synthetases that can incorporate the coumarin unnatural amino acid L-(7-hydroxycoumarin-4-yl) ethylglycine into proteins produced in eubacterial host cells such as E. coli. The invention provides, for example but not limited to, novel orthogonal synthetases, methods for identifying and making the novel synthetases, methods for producing proteins containing the unnatural amino acid L-(7-hydroxycoumarin-4-yl)ethylglycine and related translation systems.

  14. Genetically encoded fluorescent coumarin amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiangyun [San Diego, CA; Xie, Jianming [San Diego, CA; Schultz, Peter G [La Jolla, CA

    2012-06-05

    The invention relates to orthogonal pairs of tRNAs and aminoacyl-tRNA synthetases that can incorporate the coumarin unnatural amino acid L-(7-hydroxycoumarin-4-yl)ethylglycine into proteins produced in eubacterial host cells such as E. coli. The invention provides, for example but not limited to, novel orthogonal synthetases, methods for identifying and making the novel synthetases, methods for producing proteins containing the unnatural amino acid L-(7-hydroxycoumarin-4-yl)ethylglycine and related translation systems.

  15. Evaluation of amino acids as turfgrass nematicides.

    Science.gov (United States)

    Zhang, Yun; Luc, John E; Crow, William T

    2010-12-01

    Laboratory experiments revealed that DL-methionine, sodium methionate, potassium methionate, and methionine hydroxyl analog at rates of 224 and 448 kg amino acid/ha reduced the number of Belonolaimus longicaudatus mixed life-stages and Meloidogyne incognita J2 in soil, whereas L-threonine and lysine were not effective in reducing the number of either nematode. Futhermore, greenhouse experiments demonstrated that DL-methionine, sodium methionate, potassium methionate, and methionine hydroxyl analog were equally effective against B. longicaudatus at rates of 112, 224, and 448 kg amino acid/ha, and the highest rate (448 kg amino acid/ha) of all amino acids was more effective in reducing the number of B. longicaudatus than the lower rate. However, phytotoxicity was observed on creeping bentgrass (Agrostis palustris) treated with 448 kg amino acid/ha of methionine hydroxyl analog and DL methionine. In addition, in one of two field experiments on bermudagrass (Cynodon dactylon × C. transvaalensis) turf percentage green cover was increased and the number of B. longicaudatus was reduced by 224 kg amino acid/ha of DL-methionine and potassium methionate compared to untreated controls in one of two trials.

  16. Effects of Exogenous Amino Acids on the Contents of Amino Acids in Tobacco Leaves

    Institute of Scientific and Technical Information of China (English)

    WU Xue-ping; LIU Guo-shun; ZHU Kai; PENG Sa; GUO Qiao-yan

    2005-01-01

    The effect of three amino acids on the growth of flue-cured tobacco was studied with water culture. The results showed that the three amino acids improved the growth of flue-cured tobacco and increased the contents of chlorophyll a,chlorophyll b and carotenoid in tobacco. At the same time, the activities of NR (nitrate reductase), INV(invertase) and root growth activity were also significantly enhanced. The exogenous glutamic, aspartate and phenylalanine all increased the amino acid contents of tobacco leaves. Of these three amino acids, glutamic had the greatest effect, the next was aspartate,and phenylalanine had the least effect. These three amino acids all had significantly increased the accumulation of amino acids in the leaves of individual plants of tobacco; and the magnitude of accumulation indicated aspartate > glutamic >phenylalanine.

  17. Highly enantioselective aza-Diels-Alder reaction of 1-azadienes with enecarbamates catalyzed by chiral phosphoric acids.

    Science.gov (United States)

    He, Long; Laurent, Gregory; Retailleau, Pascal; Folléas, Benoît; Brayer, Jean-Louis; Masson, Géraldine

    2013-10-11

    On demand: A highly enantio- and diastereoselective synthesis of 6-amino- trisubstituted tetrahydropyridine compounds has been developed through the inverse-electron-demand aza-Diels-Alder reaction of N-aryl α,β-unsaturated ketimines with enecarbamates (E)-1. Chiral phosphoric acid catalysts achieve simultaneous activation of both the 1-azadiene and dienophile partners.

  18. Synthesis of L-2-amino-8-oxodecanoic acid: an amino acid component of apicidins

    OpenAIRE

    Linares de la Morena, María Lourdes; Agejas Chicharro, Francisco Javier; Alajarín Ferrández, Ramón; Vaquero López, Juan José; Álvarez-Builla Gómez, Julio

    2001-01-01

    The synthesis Of L-2-amino-8-oxodecanoic acid (Aoda) is described. This is a rare amino acid component of apicidins, a family of new cyclic tetrapeptides, inhibitors of histone deacetylase. Aoda was synthesised in seven steps from L-glutamic acid along with some derivatives. Universidad de Alcalá Fundación General de la Universidad de Alcalá FEDER

  19. Detection of D-amino acids in purified proteins synthesized in Escherichia coli.

    Science.gov (United States)

    Miyamoto, Tetsuya; Sekine, Masae; Ogawa, Tetsuhiro; Hidaka, Makoto; Homma, Hiroshi; Masaki, Haruhiko

    2010-05-01

    It has long been believed that amino acids comprising proteins of all living organisms are only of the L-configuration, except for Gly. However, peptidyl D-amino acids were observed in hydrolysates of soluble high molecular weight fractions extracted from cells or tissues of various organisms. This strongly suggests that significant amounts of D-amino acids are naturally present in usual proteins. Thus we analyzed the D-amino acid contents of His-tag-purified beta-galactosidase and human urocortin, which were synthesized by Escherichia coli grown in controlled synthetic media. After acidic hydrolysis for various times at 110 degrees C, samples were derivatized with 4-fluoro-7-nitro-2, 1, 3-benzoxadiazole (NBD-F) and separated on a reverse-phase column followed by a chiral column into D- and L-enantiomers. The contents of D-enantiomers of Ala, Leu, Phe, Val, Asp, and Glu were determined by plotting index D/(D + L) against the incubation time for hydrolysis and extrapolating the linear regression line to 0 h to eliminate the effect of racemization of amino acids during the incubation. Significant contents of D-amino acids were reproducibly detected, the D-amino acid profile being specific to an individual protein. This finding indicated the likelihood that D-amino acids are in fact present in the purified proteins. On the other hand, the D-amino acid contents of proteins were hardly influenced by the addition of D- or L-amino acids to the cultivation medium, whereas intracellular free D-amino acids sensitively varied according to the extracellular conditions. The origin of these D-amino acids detected in proteins was discussed.

  20. The first proton sponge-based amino acids: synthesis, acid-base properties and some reactivity.

    Science.gov (United States)

    Ozeryanskii, Valery A; Gorbacheva, Anastasia Yu; Pozharskii, Alexander F; Vlasenko, Marina P; Tereznikov, Alexander Yu; Chernov'yants, Margarita S

    2015-08-21

    The first hybrid base constructed from 1,8-bis(dimethylamino)naphthalene (proton sponge or DMAN) and glycine, N-methyl-N-(8-dimethylamino-1-naphthyl)aminoacetic acid, was synthesised in high yield and its hydrobromide was structurally characterised and used to determine the acid-base properties via potentiometric titration. It was found that the basic strength of the DMAN-glycine base (pKa = 11.57, H2O) is on the level of amidine amino acids like arginine and creatine and its structure, zwitterionic vs. neutral, based on the spectroscopic (IR, NMR, mass) and theoretical (DFT) approaches has a strong preference to the zwitterionic form. Unlike glycine, the DMAN-glycine zwitterion is N-chiral and is hydrolytically cleaved with the loss of glycolic acid on heating in DMSO. This reaction together with the mild decarboxylative conversion of proton sponge-based amino acids into 2,3-dihydroperimidinium salts under air-oxygen was monitored with the help of the DMAN-alanine amino acid. The newly devised amino acids are unique as they combine fluorescence, strongly basic and redox-active properties.

  1. Hybrid gold single crystals incorporating amino acids

    CERN Document Server

    Chen, Linfeng; Weber, Eva; Fitch, Andy N; Pokroy, Boaz

    2016-01-01

    Composite hybrid gold crystals are of profound interest in various research areas ranging from materials science to biology. Their importance is due to their unique properties and potential implementation, for example in sensing or in bio-nanomedicine. Here we report on the formation of hybrid organic-metal composites via the incorporation of selected amino acids histidine, aspartic acid, serine, glutamine, alanine, cysteine, and selenocystine into the crystal lattice of single crystals of gold. We used electron microscopy, chemical analysis and high-resolution synchrotron powder X ray diffraction to examine these composites. Crystal shape, as well as atomic concentrations of occluded amino acids and their impact on the crystal structure of gold, were determined. Concentration of the incorporated amino acid was highest for cysteine, followed by serine and aspartic acid. Our results indicate that the incorporation process probably occurs through a complex interaction of their individual functional groups with ...

  2. A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde.

    Science.gov (United States)

    Liu, Lijia; Long, Qing; Aoki, Toshiki; Zhang, Geng; Kaneko, Takashi; Teraguchi, Masahiro; Zhang, Chunhong; Wang, Yudan

    2015-08-01

    One-handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix-sense-selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main-chain chirality based on the one-handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands. In addition, the polymer ligands could be easily recovered by precipitation after the reaction.

  3. Amino acid survival in large cometary impacts

    Science.gov (United States)

    Pierazzo, E.; Chyba, C. F.

    1999-11-01

    A significant fraction of the Earth's prebiotic volatile inventory may have been delivered by asteroidal and cometary impacts during the period of heavy bombardment. The realization that comets are particularly rich in organic material seemed to strengthen this suggestion. Previous modeling studies, however, indicated that most organics would be entirely destroyed in large comet and asteroid impacts. The availability of new kinetic parameters for the thermal degradation of amino acids in the solid phase made it possible to readdress this question. We present the results of new high-resolution hydrocode simulations of asteroid and comet impact coupled with recent experimental data for amino acid pyrolysis in the solid phase. Differences due to impact velocity as well as projectile material have been investigated. Effects of angle of impacts were also addressed. The results suggest that some amino acids would survive the shock heating of large (kilometer-radius) cometary impacts. At the time of the origins of life on Earth, the steady-state oceanic concentration of certain amino acids (like aspartic and glutamic acid) delivered by comets could have equaled or substantially exceeded that due to Miller-Urey synthesis in a carbon dioxide-rich atmosphere. Furthermore, in the unlikely case of a grazing impact (impact angle around 5 degrees from the horizontal) an amount of some amino acids comparable to that due to the background steady-state production or delivery would be delivered to the early Earth.

  4. Gustatory sensation of (L)- and (D)-amino acids in humans.

    Science.gov (United States)

    Kawai, Misako; Sekine-Hayakawa, Yuki; Okiyama, Atsushi; Ninomiya, Yuzo

    2012-12-01

    Amino acids are known to elicit complex taste, but most human psychophysical studies on the taste of amino acids have focused on a single basic taste, such as umami (savory) taste, sweetness, or bitterness. In this study, we addressed the potential relationship between the structure and the taste properties of amino acids by measuring the human gustatory intensity and quality in response to aqueous solutions of proteogenic amino acids in comparison to D-enantiomers. Trained subjects tasted aqueous solution of each amino acid and evaluated the intensities of total taste and each basic taste using a category-ratio scale. Each basic taste of amino acids showed the dependency on its hydrophobicity, size, charge, functional groups on the side chain, and chirality of the alpha carbon. In addition, the overall taste of amino acid was found to be the combination of basic tastes according to the partial structure. For example, hydrophilic non-charged middle-sized amino acids elicited sweetness, and L-enantiomeric hydrophilic middle-sized structure was necessary for umami taste. For example, L-serine had mainly sweet and minor umami taste, and D-serine was sweet. We further applied Stevens' psychophysical function to relate the total-taste intensity and the concentration, and found that the slope values depended on the major quality of taste (e.g., bitter large, sour small).

  5. Convenient Syntheses of Some C4 Chiral Building Blocks Starting From (S)-Malic Acid

    Institute of Scientific and Technical Information of China (English)

    WU TianJun; YU XianYong; ZHENG Xiao; HUANG PeiQiang

    2001-01-01

    @@ In the field of chiral technology, the synthesis of chiral intermediates and chiral building blocks occupies an important position. Chiral building blocks bearing double and / or multiple functionalities is particularly useful for the synthesis of chiral pharmaceuticals and chiral agrochemicals. In the recent years, we have been engaged in the development of synthetic methodology based on (S)-malic acid1-s. In these studies, malimide 2, easily accessible from (S)-malic acid, was shown to be a useful multifunctional building block in the asymmetric synthesis of natural products and chiral drugs (Scheme 1).

  6. Convenient Syntheses of Some C4 Chiral Building Blocks Starting From (S)-Malic Acid

    Institute of Scientific and Technical Information of China (English)

    WU; TianJun

    2001-01-01

    In the field of chiral technology, the synthesis of chiral intermediates and chiral building blocks occupies an important position. Chiral building blocks bearing double and / or multiple functionalities is particularly useful for the synthesis of chiral pharmaceuticals and chiral agrochemicals.  In the recent years, we have been engaged in the development of synthetic methodology based on (S)-malic acid1-s. In these studies, malimide 2, easily accessible from (S)-malic acid, was shown to be a useful multifunctional building block in the asymmetric synthesis of natural products and chiral drugs (Scheme 1).  ……

  7. [Asymmetric synthesis of aromatic L-amino acids catalyzed by transaminase].

    Science.gov (United States)

    Xia, Wenna; Sun, Yu; Min, Cong; Han, Wei; Wu, Sheng

    2012-11-01

    Aromatic L-Amino acids are important chiral building blocks for the synthesis of many drugs, pesticides, fine chemicals and food additives. Due to the high activity and steroselectivity, enzymatic synthesis of chiral building blocks has become the main research direction in asymmetric synthesis field. Guided by the phylogenetic analysis of transaminases from different sources, two representative aromatic transaminases TyrB and Aro8 in type I subfamily, from the prokaryote Escherichia coli and eukaryote Saccharomyces cerevisia, respectively, were applied for the comparative study of asymmetric transamination reaction process and catalytic efficiency of reversely converting keto acids to the corresponding aromatic L-amino acid. Both TyrB and Aro8 could efficiently synthesize the natural aromatic amino acids phenylalanine and tyrosine as well as non-natural amino acid phenylglycine. The chiral HPLC analysis showed the produced amino acids were L-configuration and the e.e value was 100%. L-alanine was the optimal amino donor, and the transaminase TyrB and Aro8 could not use D-amino acids as amino donor. The optimal molar ratio of amino donor (L-alanine) and amino acceptor (aromatic alpha-keto acids) was 4:1. Both of the substituted group on the aromatic ring and the length of fatty acid carbon chain part in the molecular structure of aromatic substrate alpha-keto acid have the significant impact on the enzyme-catalyzed transamination efficiency. In the experiments of preparative-scale transamination synthesis of L-phenylglycine, L-phenylalanine and L-tyrosine, the specific production rate catalyzed by TryB were 0.28 g/(g x h), 0.31 g/(g x h) and 0.60 g/(g x h) and the specific production rate catalyzed by Aro8 were 0.61 g/(g x h), 0.48 g/(g x h) and 0.59 g/(g x h). The results obtained here were useful for applying the transaminases to asymmetric synthesis of L-amino acids by reversing the reaction balance in industry.

  8. Amino acids in the sedimentary humic and fulvic acids

    Digital Repository Service at National Institute of Oceanography (India)

    Sardessai, S.

    Humic and fulvic acids isolated from a few sediment samples from Arabian Sea and Bay of Bengal were analysed for total hydrolysable amino acids concentration and their composition. The amono acids content of fulvic acids was higher than in the humic...

  9. Amino acid "little Big Bang": Representing amino acid substitution matrices as dot products of Euclidian vectors

    Directory of Open Access Journals (Sweden)

    Zimmermann Karel

    2010-01-01

    Full Text Available Abstract Background Sequence comparisons make use of a one-letter representation for amino acids, the necessary quantitative information being supplied by the substitution matrices. This paper deals with the problem of finding a representation that provides a comprehensive description of amino acid intrinsic properties consistent with the substitution matrices. Results We present a Euclidian vector representation of the amino acids, obtained by the singular value decomposition of the substitution matrices. The substitution matrix entries correspond to the dot product of amino acid vectors. We apply this vector encoding to the study of the relative importance of various amino acid physicochemical properties upon the substitution matrices. We also characterize and compare the PAM and BLOSUM series substitution matrices. Conclusions This vector encoding introduces a Euclidian metric in the amino acid space, consistent with substitution matrices. Such a numerical description of the amino acid is useful when intrinsic properties of amino acids are necessary, for instance, building sequence profiles or finding consensus sequences, using machine learning algorithms such as Support Vector Machine and Neural Networks algorithms.

  10. Economic aspects of amino acids production.

    Science.gov (United States)

    Mueller, Udo; Huebner, Susanna

    2003-01-01

    Amino acids represent basic elements of proteins, which as a main source of nutrition themselves serve as a major reserve for maintaining essential functions of humans as well as animals. Taking the recent state of scientific knowledge into account, the industrial sector of amino acids is a priori "suitable" to a specific kind of an ecologically sound way of production, which is based on biotechnology. The following article may point out characteristics of this particular industrial sector and illustrates the applicability of the latest economic methods, founded on development of the discipline of bionics in order to describe economic aspects of amino acids markets. The several biochemical and technological fields of application of amino acids lead to specific market structures in high developed and permanently evolving systems. The Harvard tradition of industrial economics explains how market structures mould the behaviour of the participants and influences market results beyond that. A global increase in intensity of competition confirms the notion that the supply-side is characterised by asymmetric information in contrast to Kantzenbachs concept of "narrow oligopoly" with symmetrical shared knowledge about market information. Departing from this point, certain strategies of companies in this market form shall be derived. The importance of Research and Development increases rapidly and leads to innovative manufacturing methods which replace more polluting manufacturing processes like acid hydrolysis. In addition to these modifications within the production processes the article deals furthermore with the pricing based on product life cycle concept and introduces specific applications of tools like activity based costing and target costing to the field of amino acid production. The authors come to the conclusion that based on a good transferability of latest findings in bionics and ecological compatibility competitors in amino acids manufacturing are well advised

  11. Ionotropic excitatory amino acid receptor ligands. Synthesis and pharmacology of a new amino acid AMPA antagonist

    DEFF Research Database (Denmark)

    Madsen, U; Sløk, F A; Stensbøl, T B;

    2000-01-01

    We have previously described the potent and selective (RS)-2-amino-3-(3-hydroxy-5-methyl-4-isoxazolyl)propionic acid (AMPA) receptor agonist, (RS)-2-amino-3-(3-carboxy-5-methyl-4-isoxazolyl)propionic acid (ACPA), and the AMPA receptor antagonist (RS)-2-amino-3-[3-(carboxymethoxy)-5-methyl-4......-isoxazolyl]propionic acid (AMOA). Using these AMPA receptor ligands as leads, a series of compounds have been developed as tools for further elucidation of the structural requirements for activation and blockade of AMPA receptors. The synthesized compounds have been tested for activity at ionotropic...... excitatory amino acid (EAA) receptors using receptor binding and electrophysiological techniques, and for activity at metabotropic EAA receptors using second messenger assays. Compounds 1 and 4 were essentially inactive. (RS)-2-Amino-3-[3-(2-carboxyethyl)-5-methyl-4-isoxazolyl]propionic acid (ACMP, 2...

  12. Enantiomer labelling, a method for the quantitative analysis of amino acids.

    Science.gov (United States)

    Frank, H; Nicholson, G J; Bayer, E

    1978-12-21

    Enantiomer labelling a method for the quntitative analysis of optically active natural compounds by gas chromatography, involves the use of the unnatural enantiomer as an internal standard. With Chirasil-Val, a chiral stationary phase that is thermally stable up to up to 240 degrees, the enantiomers of amino acids and a variety of other compounds can be separated and quantitated. Incomplete recovery from the sample, incomplete derivatization, hydrolysis and thermal decomposition of the derivative and shifting response factors can be compensated for by adding the unnatural enantiomer. The accuracy of amino acid analysis by enantiomer labelling is equal or superior to that of hitherto known methods. The procedure affords a complete analysis of peptides with respect to both amino acid composition and the optical purity of each amino acid.

  13. Deracemization of amino acids by partial sublimation and via homochiral self-organization.

    Science.gov (United States)

    Tarasevych, Arkadii V; Sorochinsky, Alexander E; Kukhar, Valery P; Guillemin, Jean-Claude

    2013-04-01

    Deracemization of a 50/50 mixture of enantiomers of aliphatic amino acids (Ala, Leu, Pro, Val) can be achieved by a simple sublimation of a pre-solubilized solid mixture of the racemates with a huge amount of a less-volatile optically active amino acid (Asn, Asp, Glu, Ser, Thr). The choice of chirality correlates with the handedness of the enantiopure amino acids--Asn, Asp, Glu, Ser, and Thr. The deracemization, enantioenrichment and enantiodepletion observed in these experiments clearly demonstrate the preferential homochiral interactions and a tendency of natural amino acids to homochiral self-organization. These data may contribute toward an ultimate understanding of the pathways by which prebiological homochirality might have emerged.

  14. Structure and property of multiple amino acids assembled on the surface of a CNT

    Science.gov (United States)

    Wang, Cuihong; Yang, Guangwu; Jiang, Yue

    2017-01-01

    Amino acids were placed with maximal filling on the surface of a CNT via hydrogen bonding and H/π interactions. The interaction structures and properties of assembled complexes were investigated via the density functional tight-binding method. The structural parameters and interaction energies were analyzed to identify the weak interaction strengths. We found that the H/π interactions between amino acids and CNTs play more important roles than the hydrogen bonds between amino acids in stabilizing the complex structures. The effect of CNT chirality and amino acid type were also studied. Furthermore, the HOMOs and LUMOs of the representative complexes were also studied to illustrate the interactions. Our data is helpful in the modification of CNTs by biomolecules.

  15. Cytokines: muscle protein and amino acid metabolism

    DEFF Research Database (Denmark)

    van Hall, Gerrit

    2012-01-01

    raises TNF-α and IL-6 to moderate levels, has only identified IL-6 as a potent cytokine, decreasing systemic amino acid levels and muscle protein metabolism. The marked decrease in circulatory and muscle amino acid concentrations was observed with a concomitant reduction in both the rates of muscle...... protein synthesis and breakdown, that is, reduced turnover with a minor increase in net muscle degradation. Very similar observations have been made in models of acute inflammation, induced by high-dose endotoxin injection. However, these changes were suggested not to be attributed to a direct effect...... of IL-6 on the regulation of muscle protein metabolism but indirectly via IL-6 reducing amino acid availability. SUMMARY: Recent studies suggest that the best described cytokines TNF-α and IL-6 are unlikely to be the major direct mediators of muscle protein loss in inflammatory diseases. However...

  16. Cometary Amino Acids from the STARDUST Mission

    Science.gov (United States)

    Cook, Jamie Elsila

    2009-01-01

    NASA's Stardust spacecraft returned samples from comet 81 P/WiId 2 to Earth in January 2006. Examinations of the organic compounds in cometary samples can reveal information about the prebiotic organic inventory present on the early Earth and within the early Solar System, which may have contributed to the origin of life. Preliminary studies of Stardust material revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds (cometary vs. terrestrial contamination) could not be identified. We have recently measured the carbon isotopic ratios of these amino acids to determine their origin, leading to the first detection of a cometary amino acid.

  17. Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

    Directory of Open Access Journals (Sweden)

    Tor E. Kristensen

    2015-04-01

    Full Text Available Amino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA, many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of

  18. Metal induced amino acid adsorption on nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Chia M., E-mail: abinitio@dragon.nchu.edu.t [Research Center for the Remediation of Soil and Ground Water Pollution, Department of Soil and Environmental Sciences, National Chung Hsing University, Taichung 402, Taiwan (China); Jalbout, Abraham F. [Departamento de Investigacion en Fisica, Universidad de Sonora, Hermosillo, Sonora C.P., 83000 Mexico (Mexico)

    2010-02-01

    In this work we detail the mechanism by which alkali metal encapsulation inside an armchair (9,9) single walled carbon nanotube (SWNT) can affect external amino acid interactions. Based on our analysis, several configurations revealed that the physical properties of the SWNT systems are modified by using an internally situated Li atom. Density-functional theory calculations reveal that the most favorable interactions of the SWNT system is with tryptophan, threonine and proline that can be directly correlated to the backbone geometry of the amino acid species.

  19. Large neutral amino acids in daily practice

    DEFF Research Database (Denmark)

    Ahring, Kirsten Kiær

    2010-01-01

    At the Kennedy Centre for Phenylketonuria, Denmark, large neutral amino acids (LNAAs) are being used to treat adult and adolescent patients who are nonadherent to dietary treatment for phenylketonuria (PKU). At the start of treatment, a patient must undergo dietary analysis and regular blood...... sampling to measure plasma amino acid (AA) concentrations. The aim of this analysis and treatment is that the patient receives 25-30% of the daily protein requirement from LNAA supplementation and the remaining 70-75% from natural, low-phenylalanine proteins (although some patients have difficulties...

  20. Microbial degradation of poly(amino acid)s.

    Science.gov (United States)

    Obst, Martin; Steinbüchel, Alexander

    2004-01-01

    Natural poly(amino acid)s are a group of poly(ionic) molecules (ionomers) with various biological functions and putative technical applications and play, therefore, an important role both in nature and in human life. Because of their biocompatibility and their synthesis from renewable resources, poly(amino acid)s may be employed for many different purposes covering a broad spectrum of medical, pharmaceutical, and personal care applications as well as the domains of agriculture and of environmental applications. Biodegradability is one important advantage of naturally occurring poly(amino acid)s over many synthetic polymers. The intention of this review is to give an overview about the enzyme systems catalyzing the initial steps in poly(amino acid) degradation. The focus is on the naturally occurring poly(amino acid)s cyanophycin, poly(epsilon-L-lysine) and poly(gamma-glutamic acid); but biodegradation of structurally related synthetic polyamides such as poly(aspartic acid) and nylons, which are known from various technical applications, is also included.

  1. Dual stereoselectivity in the dialkylzinc reaction using (-)-beta-pinene derived amino alcohol chiral auxiliaries.

    Science.gov (United States)

    Binder, Caitlin M; Bautista, April; Zaidlewicz, Marek; Krzemiński, Marek P; Oliver, Allen; Singaram, Bakthan

    2009-03-20

    (+)-Nopinone, prepared from naturally occurring (-)-beta-pinene, was converted to the two regioisomeric amino alcohols 3-MAP and 2-MAP in very good yield and excellent isomeric purity. Amino alcohol 3-MAP was synthesized by converting (+)-nopinone to the corresponding alpha-ketooxime. This was reduced to the primary amino alcohol and was converted to the morpholino group through a simple substitution reaction. 3-MAP was characterized by X-ray crystallography, which displayed the rigidity of the pinane framework. Amino alcohol 2-MAP was prepared from its trans isomer 2, which in turn was synthesized via hydroboration/oxidation of the morpholine enamine of (+)-nopinone. Two-dimensional NMR was used to characterize amino alcohol 2-MAP, and NOE was used to confirm its relative stereochemistry. These amino alcohols were employed as chiral auxiliaries in the addition of diethylzinc to benzaldehyde to obtain near-quantitative asymmetric induction in the products. The use of 3-MAP yielded (S)-phenylpropanol in 99% ee, and its regioisomer 2-MAP gave the opposite enantiomer, (R)-phenylpropanol, also in 99% ee. Other aromatic, aliphatic, and alpha,beta-unsaturated aldehydes were implemented in this method, affording secondary alcohols in high yield and enantiomeric excess. Amino alcohols 2-MAP and 3-MAP were also found to be useful in the dimethylzinc addition reaction, both catalyzing the addition to benzaldehyde with nearly quantitative ee. Regioisomeric amino alcohols 2-MAP and 3-MAP, even though they were prepared from one enantiomer of nopinone, provide antipodal enantiofacial selectivity in the dialkylzinc addition reaction. This circumvents the necessity to synthesize amino alcohols derived from (-)-nopinone, which in turn requires the unnatural (+)-beta-pinene. Possible mechanistic insights are offered to explain the dual stereoselectivity observed in the diethylzinc addition reaction involving regioisomeric, pseudo-enantiomeric amino alcohols 3-MAP and 2-MAP.

  2. Enantioselective Crystallization of Sodium Chlorate in the Presence of Racemic Hydrophobic Amino Acids and Static Magnetic Fields

    Directory of Open Access Journals (Sweden)

    María-Paz Zorzano

    2014-06-01

    Full Text Available We study the bias induced by a weak (200 mT external magnetic field on the preferred handedness of sodium chlorate crystals obtained by slow evaporation at ambient conditions of its saturated saline solution with 20 ppm of added racemic (dl hydrophobic amino acids. By applying the Fisher test to pairs of experiments with opposing magnetic field orientation we conclude, with a confidence level of 99.7%, that at the water-air interface of this saline solution there is an enantioselective magnetic interaction that acts upon racemic mixtures of hydrophobic chiral amino acids. This interaction has been observed with the three tested racemic hydrophobic amino acids: dl-Phe, dl-Try and dl-Trp, at ambient conditions and in spite of the ubiquitous chiral organic contamination. This enantioselective magnetic dependence is not observed when there is only one handedness of added chiral amino-acid, if the added amino acid is not chiral or if there is no additive. This effect has been confirmed with a double blind test. This novel experimental observation may have implications for our view of plausible initial prebiotic scenarios and of the roles of the geomagnetic field in homochirality in the biosphere.

  3. Amino acid derived 1,4-dialkyl substituted imidazolones

    DEFF Research Database (Denmark)

    Diness, Frederik; Meldal, Morten Peter

    2010-01-01

    A general method for synthesis of 1,4-substituted imidazolones from amino acids on solid support or in solution has been developed. Amino acid derived 3-Boc-(1,3)-oxazinane (Box) protected amino aldehyde building blocks were coupled through urea bonds to the amino terminal of dipeptides or amino...

  4. Novel cinchona carbamate selectors with complementary enantioseparation characteristics for N-acylated amino acids.

    Science.gov (United States)

    Krawinkler, Karl Heinz; Maier, Norbert M; Ungaro, Rocco; Sansone, Francesco; Casnati, Alessandro; Lindner, Wolfgang

    2003-01-01

    The synthesis and chromatographic evaluation of the enantiomer separation capabilities of covalently immobilized calix[4]arene-cinchona carbamate hybrid type receptors derived from quinine (QN) and its corresponding C9-epimer (eQN) in different solvents are reported. The receptors display complementary enantiomer separation profiles in terms of elution order, chiral substrate specificity, and mobile phase characteristics, indicating the existence of two distinct chiral recognition mechanisms. The QN-derived receptor binds the (S)-enantiomers of N-acylated amino acids more strongly, shows preferential recognition of open-chained amino acids, and superior enantioselectivity in polar media such as methanol/acetic acid. In contrast, the eQN congener preferentially recognizes the corresponding (R)-enantiomers, displays good enantioselectivity (alpha up to 1.74) for cyclic amino acids, and enhanced stereodiscriminating properties in apolar mobile phases, e.g., chloroform/acetic acid. A comparison of the enantiomer separation profiles with those of the corresponding QN and eQN tert-butyl carbamate congeners indicates no significant level of cooperativity between the calix[4]arene module and the cinchona units in terms of overall chiral recognition, most probably as a consequence of residual conformational flexibility of the calixarene module and the carbamate linkage.

  5. Chiral Integrated Catalysts Composed of Bifunctional Thiourea and Arylboronic Acid: Asymmetric Aza-Michael Addition of α,β-Unsaturated Carboxylic Acids.

    Science.gov (United States)

    Hayama, Noboru; Azuma, Takumi; Kobayashi, Yusuke; Takemoto, Yoshiji

    2016-01-01

    The first intermolecular asymmetric Michael addition of nitrogen-nucleophiles to α,β-unsaturated carboxylic acids was achieved through a new type of arylboronic acid equipped with chiral aminothiourea. The use of BnONH2 as a nucleophile gives a range of enantioenriched β-(benzyloxy)amino acid derivatives in good yields and with high enantioselectivity (up to 90% yield, 97% enantiomeric excess (ee)). The obtained products are efficiently converted to optically active β-amino acid and 1,2-diamine derivatives.

  6. Practical synthesis of enantiomerically pure beta2-amino acids via proline-catalyzed diastereoselective aminomethylation of aldehydes.

    Science.gov (United States)

    Chi, Yonggui; English, Emily P; Pomerantz, William C; Horne, W Seth; Joyce, Leo A; Alexander, Lane R; Fleming, William S; Hopkins, Elizabeth A; Gellman, Samuel H

    2007-05-01

    Proline-catalyzed diastereoselective aminomethylation of aldehydes using a chiral iminium ion, generated from a readily prepared precursor, provides alpha-substituted-beta-amino aldehydes with 85:15 to 90:10 dr. The alpha-substituted-beta-amino aldehydes can be reduced to beta-substituted-gamma-amino alcohols, the major diastereomer of which can be isolated via crystallization or column chromatography. The amino alcohols are efficiently transformed to protected beta2-amino acids, which are valuable building blocks for beta-peptides, natural products, and other interesting molecules. Because conditions for the aminomethylation and subsequent reactions are mild, beta2-amino acid derivatives with protected functional groups in the side chain, such as beta2-homoglutamic acid, beta2-homotyrosine, and beta2-homolysine, can be prepared in this way. The synthetic route is short, and purifications are simple; therefore, this method enables the preparation of protected beta2-amino acids in useful quantities.

  7. Chiral and structural discrimination in binding of polypeptides with condensed nucleic acid structures.

    Science.gov (United States)

    Reich, Z; Ittah, Y; Weinberger, S; Minsky, A

    1990-04-05

    In biological systems nucleic acids are invariably found in highly compact forms. These rather intricate forms raise questions of basic importance which are related to the various factors involved in the condensation processes, the chemical, physical, and structural features revealed by the packed species, and the effects of the extremely tight packaging upon interactions of the DNA molecules with proteins and drugs. A means for addressing these questions on a molecular level is provided by various procedures known to induce in vitro condensation of DNA molecules into highly compact species which, in turn, may serve as a model for the in vivo physical organization of nucleic acids. A study of the optical properties of the tightly packed DNA molecules indicates that the interactions of these species with polypeptides are characterized by distinct, hitherto unobserved, chiral and structural discrimination. Specifically, the polypeptides found to be selected against are composed of those amino acids that are not normally used in protein biosynthesis, such as D-lysine or ornithine. These findings provide new clues to long debated topics such as the specific universal chirality of amino acids in proteins or the correlation between conformational flexibility of polypeptides and their ability to form stable compact complexes with nucleic acids.

  8. Sugar-assisted kinetic resolution of amino acids and amplification of enantiomeric excess of organic molecules.

    Science.gov (United States)

    Córdova, Armando; Sundén, Henrik; Xu, Yongmei; Ibrahem, Ismail; Zou, Weibiao; Engqvist, Magnus

    2006-07-17

    The origins of biological homochirality have intrigued researchers since Pasteur's discovery of the optical activity of biomolecules. Herein, we propose and demonstrate a novel alternative for the evolution of homochirality that is not based on autocatalysis and forges a direct relationship between the chirality of sugars and amino acids. This process provides a mechanism in which a racemic mixture of an amino acid can catalyze the formation of an optically active organic molecule in the presence of a sugar product of low enantiomeric excess.

  9. Photochirogenesis: Photochemical models on the absolute asymmetric formation of amino acids in interstellar space

    DEFF Research Database (Denmark)

    Meinert, Cornelia; de Marcellus, Pierre; Le Sergeant d'Hendecourt, Louis

    2011-01-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which...... interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b...

  10. Amino acid modifications on tRNA

    Institute of Scientific and Technical Information of China (English)

    Jing Yuan; Kelly Sheppard; Dieter S(o)ll

    2008-01-01

    The accurate formation of cognate aminoacyl-transfer RNAs (aa-tRNAs) is essential for the fidelity of translation.Most amino acids are esterified onto their cognate tRNA isoacceptors directly by aa.tRNA synthetases.However,in the case of four amino acids (Gin,Asn,Cys and Sec),aminoacyl-tRNAs are made through indirect pathways in many organisms across all three domains of life.The process begins with the charging ofnoncognate amino acids to tRNAs by a specialized synthetase in the case of Cys-tRNAcys formation or by synthetases with relaxed specificity,such as the non-discriminating glutamyl-tRNA,non-discriminating aspartyl-tRNA and seryl-tRNA synthetases.The resulting misacylated tRNAs are then converted to cognate pairs through transformation of the amino acids on the tRNA,which is catalyzed by a group of tRNA-dependent modifying enzymes,such as tRNA-dependent amidotransferases,Sep-tRNA:Cys-tRNA synthase,O-phosphoseryi-tRNA kinase and Sep-tRNA:Sec-tRNA synthase.The majority of these indirect pathways are widely spread in all domains of life and thought to be part of the evolutionary process.

  11. Dietary Supplements and Sports Performance: Amino Acids

    Directory of Open Access Journals (Sweden)

    Williams Melvin

    2005-12-01

    Full Text Available Abstract This is the third in a series of six articles to discuss the major classes of dietary supplements (vitamins; minerals; amino acids; herbs or botanicals; metabolites, constituents/extracts, or combinations. The major focus is on efficacy of such dietary supplements to enhance exercise or sport performance.

  12. [Sublicons containing amino acids and nucleotides].

    Science.gov (United States)

    Kaĭmakov, E A

    1979-01-01

    Sublicons have been obtained. Sublicons are threadlike structures appearing during sublimation of frozen solutions of small concentrations, containing racemate mixture of amino acids and nucleotides. It is suggested that close location of chains and their zonal distribution by the section of helix spire forming sublicon wall, should provide the formation of stereohomogenous and complementary successions of biomonomers of different clases.

  13. Estimate of Amino Acid Balance in Nutrition

    Institute of Scientific and Technical Information of China (English)

    SunWenzhi

    1995-01-01

    A new chemical index-imbalance degree(IBD),was proposed on the basis of cluster analysis in multivariate statistical analysis to estimate the extent of amino acid balance in protein.The range of IBD is between 0 and 1,successively corresponding to complete baance and entire imbalance for the amino acid profile of a sample.The amino acid increment model of IBD belongs to an asymmetrical maximum-type,and there is a high correlation between IBD and coefficient of variation(CV),The nutritional Value of individual feed can be ranked and clustered according to its IBD;and by calculating the IBD of amixed sample with two or more feedstuffs,it is possible theoretically to predict whether a synergetic phenomenon exists and when an optimal mutual complement can happen.If the conceptive frame of IBD extended,it can be used to study the balance of plement can happen.If the conceptive frame of IBD extended,it can be used to study the balance of nutrients besides amino acids,and is helpful to realize the automatic distinction and selection in diet formulating.

  14. 21 CFR 172.320 - Amino acids.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Amino acids. 172.320 Section 172.320 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Special Dietary and Nutritional Additives §...

  15. Non-racemic amino acids in the Murray and Murchison meteorites.

    Science.gov (United States)

    Pizzarello, S; Cronin, J R

    2000-01-01

    Small (1.0-9.2%) L-enantiomer excesses were found in six alpha-methyl-alpha-amino alkanoic acids from the Murchison (2.8-9.2%) and Murray (1.0-6.0%) carbonaceous chondrites by gas chromatography-mass spectroscopy of their N-trifluoroacetyl or N-pentafluoropropyl isopropyl esters. These amino acids [2-amino-2,3-dimethylpentanoic acid (both diastereomers), isovaline, alpha-methyl norvaline, alpha-methyl valine, and alpha-methyl norleucine] are either unknown or rare in the terrestrial biosphere. Enantiomeric excesses were either not observed in the four alpha-H-alpha-amino alkanoic acids analyzed (alpha-amino-n-butyric acid, norvaline, alanine, and valine) or were attributed to terrestrial contamination. The substantial excess of L-alanine reported by others was not found in the alanine in fractionated extracts of either meteorite. The enantiomeric excesses reported for the alpha-methyl amino acids may be the result of partial photoresolution of racemic mixtures caused by ultraviolet circularly polarized light in the presolar cloud. The alpha-methyl-alpha-amino alkanoic acids could have been significant in the origin of terrestrial homochirality given their resistance to racemization and the possibility for amplification of their enantiomeric excesses suggested by the strong tendency of their polymers to form chiral secondary structure.

  16. Searching for Amino Acids in Meteorites and Comet Samples

    Science.gov (United States)

    Cook, Jamie Elsila

    2010-01-01

    Chemistry plays an important role in the interdisciplinary field of astrobiology, which strives to understand the origin, distribution, and evolution of life throughout the universe. Chemical techniques are used to search for and characterize the basic ingredients for life, from the elements through simple molecules and up to the more complex compounds that may serve as the ingredients for life. The Astrobiology Analytical Laboratory at NASA Goddard uses state-of-the-art laboratory analytical instrumentation in unconventional ways to examine extraterrestrial materials and tackle some of the big questions in astrobiology. This talk will discuss some of the instrumentation and techniques used for these unique samples, as well as some of our most interesting results. The talk will present two areas of particular interest in our laboratory: (1) the search for chiral excesses in meteoritic amino acids, which may help to explain the origin of homochirality in life on Earth; and (2) the detection of amino acids and amines in material returned by NASA's Stardust mission, which rendevouzed with a cornet and brought back cometary particles to the Earth.

  17. Amino acid quality indices of the leaves of Clerodendrum volubile

    Directory of Open Access Journals (Sweden)

    Ochuko Lucky Erukainure

    2016-04-01

    Full Text Available Objective: To evaluate the amino acid profile and quality indices of Clerodendrum volubile (C. volubile leaves. Methods: Dried leaves of C. volubile were blended, defatted and subjected to amino acid analysis using the technicon sequential multi-sample amino acid analyzer. The amino acid quality indices which covers for chemical score, essential amino acid index, nutritional index, true digestibility, protein digestibility corrected amino acid score, and digestible indispensable amino acid score were evaluated using standard formulas. Results: Amino acid analysis revealed glutamic acid to have the highest concentration, with cysteine having the least. Aspartic acid had the highest chemical score, this was followed by glycine, histidine and arginine, respectively. The least scores were observed in serine and methionine. Glutamic acid had the highest value for true digestibility and protein digestibility corrected amino acid score, with the least observed in cysteine. Digestible indispensable amino acid score evaluation showed histidine to have the highest value for infants (birth to 6 months, threonine for children (6 months to 3 years, while isoleucine was observed to have the highest value for older children, adolescents and adults. The essential amino acid index value was less than 4, while nutritional index value was less than 0.5. Conclusions: These results indicated the leaves of C. volubile as a potential source of amino acids in the human diet as portrayed by its amino acids profile and qualities.

  18. Biosynthesis of natural products containing β-amino acids.

    Science.gov (United States)

    Kudo, Fumitaka; Miyanaga, Akimasa; Eguchi, Tadashi

    2014-08-01

    Covering: up to January, 2014. We focus here on β-amino acids as components of complex natural products because the presence of β-amino acids produces structural diversity in natural products and provides characteristic architectures beyond those of ordinary α-L-amino acids, thus generating significant and unique biological functions in nature. In this review, we first survey the known bioactive β-amino acid-containing natural products including nonribosomal peptides, macrolactam polyketides, and nucleoside-β-amino acid hybrids. Next, the biosynthetic enzymes that form β-amino acids from α-amino acids and the de novo synthesis of β-amino acids are summarized. Then, the mechanisms of β-amino acid incorporation into natural products are reviewed. Because it is anticipated that the rational swapping of the β-amino acid moieties with various side chains and stereochemistries by biosynthetic engineering should lead to the creation of novel architectures and bioactive compounds, the accumulation of knowledge regarding β-amino acid-containing natural product biosynthetic machinery could have a significant impact in this field. In addition, genome mining of characteristic β-amino acid biosynthetic genes and unique β-amino acid incorporation machinery could lead to the discovery of new β-amino acid-containing natural products.

  19. Chiral magnesium BINOL phosphate-catalyzed phosphination of imines: access to enantioenriched α-amino phosphine oxides.

    Science.gov (United States)

    Ingle, Gajendrasingh K; Liang, Yuxue; Mormino, Michael G; Li, Guilong; Fronczek, Frank R; Antilla, Jon C

    2011-04-15

    A new method to synthesize chiral α-amino phosphine oxides is reported. The reaction combines N-substituted imines and diphenylphosphine oxide and is catalyzed by a chiral magnesium phosphate salt. A wide variety of aliphatic and aromatic aldimines substituted by electron-neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The dibenzocycloheptene protected imines afforded improved enantioselectivity in the resulting products. Substituted diphenylphosphine oxide nucleophiles also showed good reactivity.

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

    Science.gov (United States)

    Tran, Le Ngoc; Park, Jung Hag

    2015-05-29

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

  1. Microbial Production of Amino Acid-Related Compounds.

    Science.gov (United States)

    Wendisch, Volker F

    2016-11-22

    Corynebacterium glutamicum is the workhorse of the production of proteinogenic amino acids used in food and feed biotechnology. After more than 50 years of safe amino acid production, C. glutamicum has recently also been engineered for the production of amino acid-derived compounds, which find various applications, e.g., as synthons for the chemical industry in several markets including the polymer market. The amino acid-derived compounds such as non-proteinogenic ω-amino acids, α,ω-diamines, and cyclic or hydroxylated amino acids have similar carbon backbones and functional groups as their amino acid precursors. Decarboxylation of amino acids may yield ω-amino acids such as β-alanine, γ-aminobutyrate, and δ-aminovalerate as well as α,ω-diamines such as putrescine and cadaverine. Since transamination is the final step in several amino acid biosynthesis pathways, 2-keto acids as immediate amino acid precursors are also amenable to production using recombinant C. glutamicum strains. Approaches for metabolic engineering of C. glutamicum for production of amino acid-derived compounds will be described, and where applicable, production from alternative carbon sources or use of genome streamline will be referred to. The excellent large-scale fermentation experience with C. glutamicum offers the possibility that these amino acid-derived speciality products may enter large-volume markets.

  2. Detection of DBD-carbamoyl amino acids in amino acid sequence and D/L configuration determination of peptides with fluorogenic Edman reagent 7-[(N,N-dimethylamino)sulfonyl]-2,1,3-benzoxadiazol-4-yl isothiocyanate.

    Science.gov (United States)

    Huang, Y; Matsunaga, H; Toriba, A; Santa, T; Fukushima, T; Imai, K

    1999-06-01

    A method for amino acid sequence and D/L configuration identification of peptides by using fluorogenic Edman reagent 7-[(N, N-dimethylamino)sulfonyl]-2,1,3-benzoxadiazol-4-yl isothiocyanate (DBD-NCS) has been developed. This method was based on the Edman degradation principle with some modifications. A peptide or protein was coupled with DBD-NCS under basic conditions and then cyclized/cleaved to produce DBD-thiazolinone (TZ) derivative by BF3, a Lewis acid, which could significantly suppress the amino acid racemization. The liberated DBD-TZ amino acid was hydrolyzed to DBD-thiocarbamoyl (TC) amino acid under a weakly acidic condition and then oxidized by NaNO2/H+ to DBD-carbamoyl (CA) amino acid which was a stable and had a strong fluorescence intensity. The individual DBD-CA amino acids were separated on a reversed-phase high-performance liquid chromatography (RP-HPLC) for amino acid sequencing and their enantiomers were resolved on a chiral stationary-phase HPLC for identifying their D/L configurations. Combination of the two HPLC systems, the amino acid sequence and D/L configuration of peptides could be determined. This method will be useful for searching D-amino-acid-containing peptides in animals.

  3. 手性氨基酸酰胺催化二乙基锌与芳香醛不对称加成反应%Enantioselective Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by Modular Amino Acids and Phenylethanamine Based Chiral Ligands

    Institute of Scientific and Technical Information of China (English)

    苟绍华; 叶仲斌; 蔡潇潇; 刘曼; 蒋文超

    2012-01-01

    Enantioselective addition of diethylzinc to a series of aromatic aldehydes was developed by chiral ligand (5)-N-(4-methoxyphenethyl)-3-phenyl-2-(tosylamino)propanamide (Id), which was derivatived from a modular amino acids and long chain amine containg OMe. The catalytic system employing 15 mol% of Id without using titanium complex was found to promote the addition of diethylzinc (ZnEt2) to a wide range of aromatic aldehydes with electron-donating and electron-withdrawing substituents, giving up to 87% ee of the corresponding secondary alcohol under mild conditions.%将由磺酰化氨基酸和长链的含甲氧基官能团的胺制备的(S)-N-(4-甲氧基苯乙基)-3-苯基-2-(对甲基苯磺酰胺)丙酰胺(1d)手性配体用于催化二乙基锌与系列芳香醛对映选择性加成反应.15mol%该催化剂能够对含有吸电子基团、供电子基团及不同位阻的芳香醛均有较好的效果,能够在比较温和的条件下获得高达87%ee和中等程度的产率.

  4. Amino acids regulate the intracellular trafficking of the general amino acid permease of Saccharomycescerevisiae.

    Science.gov (United States)

    Chen, Esther J; Kaiser, Chris A

    2002-11-12

    The delivery to the plasma membrane of the general amino acid permease, Gap1p, of Saccharomyces cerevisiae is regulated by the quality of the nitrogen source in the growth medium. In an effort to define how different nitrogen sources control Gap1p sorting, we find that mutations in GDH1 and GLN1 that decrease the flux through the glutamate and glutamine synthesis pathways result in increased Gap1p sorting to the plasma membrane. Conversely, deletion of MKS1, which increases glutamate and glutamine synthesis, decreases Gap1p sorting to the plasma membrane. Glutamate and glutamine are not unusual in their ability to regulate Gap1p sorting, because the addition of all natural amino acids and many amino acid analogs to the growth medium results in increased Gap1p sorting to the vacuole. Importantly, amino acids have the capacity to signal Gap1p sorting to the vacuole regardless of whether they can be used as a source of nitrogen. Finally, we show that rapamycin does not affect Gap1p sorting, indicating that Gap1p sorting is not directly influenced by the TOR pathway. Together, these data show that amino acids are a signal for sorting Gap1p to the vacuole and imply that the nitrogen-regulated Gap1p sorting machinery responds to amino acid-like compounds rather than to the overall nutritional status associated with growth on a particular nitrogen source.

  5. Recent advances in amino acid production by microbial cells.

    Science.gov (United States)

    Hirasawa, Takashi; Shimizu, Hiroshi

    2016-12-01

    Amino acids have been utilized for the production of foods, animal feeds and pharmaceuticals. After the discovery of the glutamic acid-producing bacterium Corynebacterium glutamicum by Japanese researchers, the production of amino acids, which are primary metabolites, has been achieved using various microbial cells as hosts. Recently, metabolic engineering studies on the rational design of amino acid-producing microbial cells have been successfully conducted. Moreover, the technology of systems biology has been applied to metabolic engineering for the creation of amino acid-producing microbial cells. Currently, new technologies including synthetic biology, single-cell analysis, and evolutionary engineering have been utilized to create amino acid-producing microbial cells. In addition, useful compounds from amino acids have been produced by microbial cells. Here, current researches into the metabolic engineering of microbial cells toward production of amino acids and amino acid-related compounds are reviewed.

  6. Biosynthesis of 'essential' amino acids by scleractinian corals.

    Science.gov (United States)

    Fitzgerald, L M; Szmant, A M

    1997-02-15

    Animals rely on their diet for amino acids that they are incapable either of synthesizing or of synthesizing in sufficient quantities to meet metabolic needs. These are the so-called 'essential amino acids'. This set of amino acids is similar among the vertebrates and many of the invertebrates. Previously, no information was available for amino acid synthesis by the most primitive invertebrates, the Cnidaria. The purpose of this study was to examine amino acid synthesis by representative cnidarians within the Order Scleractinia. Three species of zooxanthellate reef coral, Montastraea faveolata, Acropora cervicornis and Porites divaricata, and two species of non-zooxanthellate coral, Tubastrea coccinea and Astrangia poculata, were incubated with 14C-labelled glucose or with the 14C-labelled amino acids glutamic acid, lysine or valine. Radiolabel tracer was followed into protein amino acids. A total of 17 amino acids, including hydroxyproline, were distinguishable by the techniques used. Of these, only threonine was not found radiolabelled in any of the samples. We could not detect tryptophan or cysteine, nor distinguish between the amino acid pairs glutamic acid and glutamine, or aspartic acid and asparagine. Eight amino acids normally considered essential for animals were made by the five corals tested, although some of them were made only in small quantities. These eight amino acids are valine, isoleucine, leucine, tyrosine, phenylalanine histidine, methionine and lysine. The ability of cnidarians to synthesize these amino acids could be yet another indicator of a separate evolutionary history of the cnidarians from the rest of the Metazoa.

  7. Amino acid-based surfactants – do they deserve more attention?

    Science.gov (United States)

    Bordes, Romain; Holmberg, Krister

    2015-08-01

    The 20 standard amino acids (together with a few more that are not used in the biosynthesis of proteins) constitute a versatile tool box for synthesis of surfactants. Anionic, cationic and zwitterionic amphiphiles can be prepared and surfactants with several functional groups can be obtained by the proper choice of starting amino acid. This review gives examples of procedures used for preparation and discusses important physicochemical properties of the amphiphiles and how these can be taken advantage of for various applications. Micelles with a chiral surface can be obtained by self-assembly of enantiomerically pure surfactants and such supramolecular chirality can be utilized for asymmetric organic synthesis and for preparation of mesoporous materials with chiral pores. Surfactants based on amino acids with two carboxyl groups are effective chelating agents and can be used as collectors in mineral ore flotation. A surfactant based on cysteine readily oxidizes into the corresponding cystine compound, which can be regarded as a gemini surfactant. The facile and reversible cysteine-cystine transformation has been taken advantage of in the design of a switchable surfactant. A very attractive aspect of surfactants based on amino acids is that the polar head-group is entirely natural and that the linkage to the hydrophobic tail, which is often an ester or an amide bond, is easily cleaved. The rate of degradation can be tailored by the structure of the amphiphile. The ester linkage in betaine ester surfactants is particularly susceptible to alkaline hydrolysis and this surfactant type can be used as a biocide with short-lived action. This paper is not intended as a full review on the topic. Instead it highlights concepts that are unique to amino acid-based surfactants and that we believe can have practical implications.

  8. Direct amino acid analyses of mozzarella cheese.

    Science.gov (United States)

    Hoskins, M N

    1985-12-01

    The amino acid content of mozzarella (low moisture, part skim milk) and asadero cheeses was determined by the column chromatographic method. Data from the direct analyses of the mozzarella cheeses were compared with the calculated amino acid composition reported in tables in Agriculture Handbook No. 8-1. Phenylalanine and tyrosine contents were found to be higher in the direct analyses than in the calculated data in Handbook No. 8-1 (1.390 gm and 1.127 gm for phenylalanine, and 1.493 gm and 1.249 gm for tyrosine per 100 gm edible portion, respectively). That is of particular concern in the dietary management of phenylketonuria, in which accuracy in computing levels of phenylalanine and tyrosine is essential.

  9. Rotational Study of Natural Amino Acid Glutamine

    Science.gov (United States)

    Varela, Marcelino; Cabezas, Carlos; Alonso, José L.

    2014-06-01

    Recent improvements in laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW) have allowed the investigation of glutamine (COOH-CH(NH2)-CH2-CH2-CONH2), a natural amino acid with a long polar side chain. One dominant structure has been detected in the rotational spectrum. The nuclear quadrupole hyperfine structure of two 14N nuclei has been totally resolved allowing the conclusive identification of the observed species.

  10. Alimentary proteins, amino acids and cholesterolemia.

    Science.gov (United States)

    Blachier, François; Lancha, Antonio H; Boutry, Claire; Tomé, Daniel

    2010-01-01

    Numerous data from both epidemiological and experimental origins indicate that some alimentary proteins and amino acids in supplements can modify the blood LDL cholesterol, HDL cholesterol and total cholesterol. After an initial approval of the health claim for soy protein consumption for the prevention of coronary heart disease, more recently it has been concluded from an overall analysis of literature that isolated soy protein with isoflavones only slightly decrease LDL and total cholesterol. Other plant extracts and also some proteins from animal origin have been reported to exert a lowering effect on blood cholesterol when compared with a reference protein (often casein). The underlying mechanisms are still little understood. Individual amino acids and mixture of amino acids have also been tested (mostly in animal studies) for their effects on cholesterol parameters and on cholesterol metabolism. Methionine, lysine, cystine, leucine, aspartate and glutamate have been tested individually and in combination in different models of either normo or hypercholesterolemic animals and found to be able to modify blood cholesterol and/or LDL cholesterol and/or HDL cholesterol. It is however not known if these results are relevant to human nutrition.

  11. A Green Synthesis of Diisopropyl Phosphoryl Amino Acid

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    In this paper, we report that diisopropyl phosphoryl amino acid could be prepared with reasonable yields under solvent-free condition by adding amino acid to the mixture of diisopropyl phosphite and N-chlorodiisopropylamine.

  12. Is Amino-Acid Homochirality Due To Asymmetric Photolysis In Space?

    CERN Document Server

    Cerf, C

    1999-01-01

    Amino acids occurring in proteins are, with rare exceptions, exclusively of the L-configuration. Among the many scenarios put forward to explain the origin of this chiral homogeneity (i.e., homochirality), one involves the asymmetric photolysis of amino acids present in space, triggered by circularly polarized UV radiation. The recent observation of circularly polarized light (CPL) in the Orion OMC-1 star-forming region (Bailey et al. 1998, Science 281, 672) has been presented as providing a strong validation of this scenario. The present paper reviews the situation. It is stressed for example that one important condition for the asymmetric photolysis by CPL to be at the origin of the terrestrial homochirality of natural amino acids is generally overlooked, namely, the asymmetric photolysis should favour the L-enantiomer for ALL the primordial amino acids involved in the genesis of life (i.e., biogenic amino acids). Although this condition is probably satisfied for aliphatic amino acids, some non-aliphatic am...

  13. A Review of Salam Phase Transition in Protein Amino Acids Implication for Biomolecular Homochirality

    CERN Document Server

    Bai, F; Bai, Fan; Wang, Wenqing

    2002-01-01

    The origin of chirality, closely related to the evolution of life on the earth, has long been debated. In 1991, Abdus Salam suggested a novel approach to achieve biomolecular homochirality by a phase transition. In his subsequent publication, he predicted that this phase transition could eventually change D-amino acids to L-amino acids as C -H bond would break and H atom became a superconductive atom. Since many experiments denied the configuration change in amino acids, Salam hypothesis aroused suspicion. This paper is aimed to provide direct experimental evidence of a phase transition in alanine, valine single crystals but deny the configuration change of D- to L- enantiomers. New views on Salam phase transition are presented to revalidate its great importance in the origin of homochirality.

  14. Adsorption and properties of aromatic amino acids on single-walled carbon nanotubes

    Science.gov (United States)

    Wang, Cuihong; Li, Shuang; Zhang, Ruiqin; Lin, Zijing

    2012-02-01

    We investigated the adsorption of three aromatic amino acids--phenylalanine, tyrosine, and tryptophan--on the sidewalls of a number of representative single-walled carbon nanotubes (SWNTs) using density-functional tight-binding calculations, complemented by an empirical dispersion correction. The armchair (n, n) SWNTs (n = 3-12) and zigzag (n, 0) SWNTs (n = 4-12) were thoroughly examined. We found that the most stable amino acid/SWNT complexes for different SWNTs have similar local structures, and that the distance between the amino acid and SWNT is about 3 Å. Owing to the π-π and H-π stacking interactions, the benzene and indole rings are not exactly parallel to the SWNTs but instead lie at a small angle. We also investigated the diameter and chirality dependences of binding energies and found that SWNT (5, 0) has an especially large binding energy that can be used for SWNT identification or selection.

  15. Origin, Microbiology, Nutrition, and Pharmacology of D-Amino Acids

    Science.gov (United States)

    Exposure of food proteins to certain processing conditions induces two major chemical changes: racemization of all L-amino acids (LAA) to D-amino acids (DAA) and concurrent formation of crosslinked amino acids such as lysinoalanine (LAL). The diet contains both processing-induced and naturally-form...

  16. A Convenient Synthesis of Amino Acid Methyl Esters

    Directory of Open Access Journals (Sweden)

    Yaowu Sha

    2008-05-01

    Full Text Available A series of amino acid methyl ester hydrochlorides were prepared in good toexcellent yields by the room temperature reaction of amino acids with methanol in thepresence of trimethylchlorosilane. This method is not only compatible with natural aminoacids, but also with other aromatic and aliphatic amino acids.

  17. Metabolism of amino acid amides in Pseudomonas putida ATCC 12633

    NARCIS (Netherlands)

    Hermes, H.F.M.; Croes, L.M.; Peeters, W.P.H.; Peters, P.J.H.; Dijkhuizen, L.

    1993-01-01

    The metabolism of the natural amino acid L-valine, the unnatural amino acids D-valine, and D-, L-phenylglycine (D-, L-PG), and the unnatural amino acid amides D-, L-phenylglycine amide (D, L-PG-NH2) and L-valine amide (L-Val-NH2) was studied in Pseudomonas putida ATCC 12633. The organism possessed c

  18. Differential diagnosis of (inherited) amino acid metabolism or transport disorders

    NARCIS (Netherlands)

    W. Blom (W.); J.G.M. Huijmans (Jan)

    1992-01-01

    markdownabstract__Abstract__ Disorders of amino acid metabolism or transport are most clearly expressed in urine. Nevertheless the interpretation of abnormalities in urinary amino acid excretion remains difficult. An increase or decrease of almost every amino acid in urine can be due to various eti

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

    Institute of Scientific and Technical Information of China (English)

    Zhi Gang Zhao; Xing Li Liu; Yi Zhong

    2008-01-01

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

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

    Science.gov (United States)

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

    2007-01-05

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

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

    NARCIS (Netherlands)

    Bechtold, M; Heinemann, M; Panke, S

    2006-01-01

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

  2. Teicoplanin bonded sub-2 μm superficially porous particles for enantioseparation of native amino acids.

    Science.gov (United States)

    Min, Yi; Sui, Zhigang; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

    2015-10-10

    Superficially porous particles (SPPs) demonstrate superior efficiency than totally porous particles in chiral separations. In order to obtain high efficiency and fast separation, sub-2 μm SPPs with high surface area are synthesized, and with teicoplanin bonded, such materials are successfully applied into the rapid enantioseparation of native amino acids. In brief, 1.27 ± 0.06 μm nonporous silica particles are prepared by a modified seeded growth method, followed by mesoporous shell fabrication via one-pot templated dissolution and redeposition strategy, and pore size expansion via acid-refluxing. The diameter of the formed SPPs is 1.49 ± 0.04 μm, with the shell thickness as 206 nm. Nitrogen physisorption experiments show that the Brunauer-Emmett-Teller (BET) specific surface area is 213.6 m(2)/g and pore size is 9 nm. After teicoplanin derivatization with bonding capacity as 83.3 μmol/g, the prepared chiral stationary phase is packed into a stainless steel tube with the geometry of 50 mm × 2.1 mm i.d.. In less than 6.4 min, six native amino acids (norleucine, alanine, valine, methionine, leucine, norvaline) are enantioseparated with resolution factors ranging from 1.9 to 5.0. Besides, the resolution for chiral separation is improved with ethanol-water instead of methanol-water as the mobile phase. Moreover, the low temperature gives higher resolution, but longer retention time and higher backpressure. Finally, the effect of flow rate on enantiomeric separation is studied and fast chiral separation within 1 min is obtained with flow rate of 0.4 mL/min. All these results show that the synthesized teicoplanin bonded sub-2 μm SPPs have great potential to achieve the enantioseparation of native amino acids with high resolution and rapid speed.

  3. 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.

    Science.gov (United States)

    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).

  4. Computational model of abiogenic amino acid condensation to obtain a polar amino acid profile.

    Science.gov (United States)

    Polanco, Carlos; Buhse, Thomas; Samaniego, José Lino; Castañón González, Jorge Alberto; Arias Estrada, Miguel

    2014-01-01

    In accordance with the second law of thermodynamics, the Universe as a whole tends to higher entropy. However, the sequence of far-from-equilibrium events that led to the emergence of life on Earth could have imposed order and complexity during the course of chemical reactions in the so-called primordial soup of life. Hence, we may expect to find characteristic profiles or biases in the prebiotic product mixtures, as for instance among the first amino acids. Seeking to shed light on this hypothesis, we have designed a high performance computer program that simulates the spontaneous formation of the amino acid monomers in closed environments. The program was designed in reference to a prebiotic scenario proposed by Sydney W. Fox. The amino acid abundances and their polarities as the two principal biases were also taken into consideration. We regarded the computational model as exhaustive since 200,000 amino acid dimers were formed by simulation, subsequently expressed in a vector and compared with the corresponding amino acid dimers that were experimentally obtained by Fox. We found a very high similarity between the experimental results and our simulations.

  5. Chiral Discrimination of Tryptophan Enantiomers via (1R, 2R-2-Amino-1, 2-Diphenyl Ethanol Modified Interface

    Directory of Open Access Journals (Sweden)

    Juan Zhou

    2011-01-01

    Full Text Available The paper reported that a simple chiral selective interface constructed by (1R, 2R-2-amino-1, 2-diphenyl ethanol had been developed to discriminate tryptophan enantiomers. Cyclic voltammetry (CV and electrochemical impedance spectroscopy (EIS were used for the characteristic analysis of the electrode. The results indicated that the interface showed stable and sensitive property to determine the tryptophan enantiomers. Moreover, it exhibited the better stereoselectivity for L-tryptophan than that for D-tryptophan. The discrimination characteristics of the chiral selective interface for discriminating tryptophan enantiomers, including the response time, the effect of tryptophan enantiomers concentration, and the stability, were investigated in detail. In addition, the chiral selective interface was used to determine the enantiomeric composition of L- and D-tryptophan enantiomer mixtures by measuring the relative change of the peak current as well as in pure enantiomeric solutions. These results suggested that the chiral selective interface has the potential for enantiomeric discrimination of tryptophan enantiomers.

  6. Determination and stereochemistry of proteinogenic and non-proteinogenic amino acids in Saudi Arabian date fruits.

    Science.gov (United States)

    Ali, Hatem Salama Mohamed; Alhaj, Omar Amin; Al-Khalifa, Abdulrahman Saleh; Brückner, Hans

    2014-09-01

    Whereas an abundance of literature is available on the occurrence of common proteinogenic amino acids (AAs) in edible fruits of the date palm (Phoenix dactylifera L.), recent reports on non-proteinogenic (non-coded) AAs and amino components are scarce. With emphasis on these components we have analyzed total hydrolysates of twelve cultivars of date fruits using automated ion-exchange chromatography, HPLC employing a fluorescent aminoquinolyl label, and GC-MS of total hydrolysates using the chiral stationary phases Chirasil(®)-L-Val and Lipodex(®) E. Besides common proteinogenic AAs, relatively large amounts of the following non-proteinogenic amino acids were detected: (2S,5R)-5-hydroxypipecolic acid (1.4-4.0 g/kg dry matter, DM), 1-aminocyclopropane-1-carboxylic acid (1.3-2.6 g/kg DM), γ-amino-n-butyric acid (0.5-1.2 g/kg DM), (2S,4R)-4-hydroxyproline (130-230 mg/kg DM), L-pipecolic acid (40-140 mg/kg DM), and 2-aminoethanol (40-160 mg/kg DM) as well as low or trace amounts (amino acids in date fruits is briefly addressed.

  7. Nutritional and medicinal aspects of D-amino acids.

    Science.gov (United States)

    Friedman, Mendel; Levin, Carol E

    2012-05-01

    This paper reviews and interprets a method for determining the nutritional value of D-amino acids, D-peptides, and amino acid derivatives using a growth assay in mice fed a synthetic all-amino acid diet. A large number of experiments were carried out in which a molar equivalent of the test compound replaced a nutritionally essential amino acid such as L-lysine (L-Lys), L-methionine (L-Met), L-phenylalanine (L-Phe), and L-tryptophan (L-Trp) as well as the semi-essential amino acids L-cysteine (L-Cys) and L-tyrosine (L-Tyr). The results show wide-ranging variations in the biological utilization of test substances. The method is generally applicable to the determination of the biological utilization and safety of any amino acid derivative as a potential nutritional source of the corresponding L-amino acid. Because the organism is forced to use the D-amino acid or amino acid derivative as the sole source of the essential or semi-essential amino acid being replaced, and because a free amino acid diet allows better control of composition, the use of all-amino-acid diets for such determinations may be preferable to protein-based diets. Also covered are brief summaries of the widely scattered literature on dietary and pharmacological aspects of 27 individual D-amino acids, D-peptides, and isomeric amino acid derivatives and suggested research needs in each of these areas. The described results provide a valuable record and resource for further progress on the multifaceted aspects of D-amino acids in food and biological samples.

  8. Neighbor preferences of amino acids and context-dependent effects of amino acid substitutions in human, mouse, and dog.

    Science.gov (United States)

    Fu, Mingchuan; Huang, Zhuoran; Mao, Yuanhui; Tao, Shiheng

    2014-09-10

    Amino acids show apparent propensities toward their neighbors. In addition to preferences of amino acids for their neighborhood context, amino acid substitutions are also considered to be context-dependent. However, context-dependence patterns of amino acid substitutions still remain poorly understood. Using relative entropy, we investigated the neighbor preferences of 20 amino acids and the context-dependent effects of amino acid substitutions with protein sequences in human, mouse, and dog. For 20 amino acids, the highest relative entropy was mostly observed at the nearest adjacent site of either N- or C-terminus except C and G. C showed the highest relative entropy at the third flanking site and periodic pattern was detected at G flanking sites. Furthermore, neighbor preference patterns of amino acids varied greatly in different secondary structures. We then comprehensively investigated the context-dependent effects of amino acid substitutions. Our results showed that nearly half of 380 substitution types were evidently context dependent, and the context-dependent patterns relied on protein secondary structures. Among 20 amino acids, P elicited the greatest effect on amino acid substitutions. The underlying mechanisms of context-dependent effects of amino acid substitutions were possibly mutation bias at a DNA level and natural selection. Our findings may improve secondary structure prediction algorithms and protein design; moreover, this study provided useful information to develop empirical models of protein evolution that consider dependence between residues.

  9. Neighbor Preferences of Amino Acids and Context-Dependent Effects of Amino Acid Substitutions in Human, Mouse, and Dog

    Directory of Open Access Journals (Sweden)

    Mingchuan Fu

    2014-09-01

    Full Text Available Amino acids show apparent propensities toward their neighbors. In addition to preferences of amino acids for their neighborhood context, amino acid substitutions are also considered to be context-dependent. However, context-dependence patterns of amino acid substitutions still remain poorly understood. Using relative entropy, we investigated the neighbor preferences of 20 amino acids and the context-dependent effects of amino acid substitutions with protein sequences in human, mouse, and dog. For 20 amino acids, the highest relative entropy was mostly observed at the nearest adjacent site of either N- or C-terminus except C and G. C showed the highest relative entropy at the third flanking site and periodic pattern was detected at G flanking sites. Furthermore, neighbor preference patterns of amino acids varied greatly in different secondary structures. We then comprehensively investigated the context-dependent effects of amino acid substitutions. Our results showed that nearly half of 380 substitution types were evidently context dependent, and the context-dependent patterns relied on protein secondary structures. Among 20 amino acids, P elicited the greatest effect on amino acid substitutions. The underlying mechanisms of context-dependent effects of amino acid substitutions were possibly mutation bias at a DNA level and natural selection. Our findings may improve secondary structure prediction algorithms and protein design; moreover, this study provided useful information to develop empirical models of protein evolution that consider dependence between residues.

  10. [Bound amino acids in local strains of Trichomonas vaginalis].

    Science.gov (United States)

    Tsvetkova, A; Osinovski, E; Vasilevska, M

    1990-01-01

    Amino acid composition of water-soluble and water-insoluble proteins of 8 strains of Tr. vaginalis is studied. 17 amino acids are found in both protein hydrolyzates. Despite the complete coincidence of their qualitative compositions there are reliable differences in the quantitative contents of some amino acids. Differences in the contents of main amino acids of water-soluble proteins of different strains reflect the belonging of the latter to different sero-groups. No reliable differences in the quantitative contents of amino acids of both water-soluble and water-insoluble proteins in strains belonging to one sero-group are recognised.

  11. Deracemization of Axially Chiral Nicotinamides by Dynamic Salt Formation with Enantiopure Dibenzoyltartaric Acid (DBTA

    Directory of Open Access Journals (Sweden)

    Fumitoshi Yagishita

    2013-11-01

    Full Text Available Dynamic atroposelective resolution of chiral salts derived from oily racemic nicotinamides and enantiopure dibenzoyltartaric acid (DBTA was achieved by crystallization. The absolute structures of the axial chiral nicotinamides were determined by X-ray structural analysis. The chirality could be controlled by the selection of enantiopure DBTA as a chiral auxiliary. The axial chirality generated by dynamic salt formation was retained for a long period after dissolving the chiral salt in solution even after removal of the chiral acid. The rate of racemization of nicotinamides could be controlled based on the temperature and solvent properties, and that of the salts was prolonged compared to free nicotinamides, as the molecular structure of the pyridinium ion in the salts was different from that of acid-free nicotinamides.

  12. Characterization of amino acids using Raman spectroscopy

    Science.gov (United States)

    Jenkins, Amanda L.; Larsen, Richard A.; Williams, Timothy B.

    2005-05-01

    A key process in the development of new drugs is elucidation of the interaction between the drug molecule and the target protein. Such knowledge then makes it possible to make systematic structural modifications of the drug molecule to optimize the interaction. Many analytical techniques can be applied to proteins in solution such as circular dichroism, ultraviolet, and fluorescence spectroscopy but these all have limitations. In this paper, we investigate the feasibility of using relatively simple, visible light Raman spectroscopic methods to investigate amino acids and related biopolymers.

  13. Photoinduced dynamics in protonated aromatic amino acid

    CERN Document Server

    Grégoire, Gilles; Barat, Michel; Fayeton, Jacqueline; Dedonder-Lardeux, Claude; Jouvet, Christophe

    2008-01-01

    UV photoinduced fragmentation of protonated aromatics amino acids have emerged the last few years, coming from a situation where nothing was known to what we think a good understanding of the optical properties. We will mainly focus this review on the tryptophan case. Three groups have mostly done spectroscopic studies and one has mainly been involved in dynamics studies of the excited states in the femtosecond/picosecond range and also in the fragmentation kinetics from nanosecond to millisecond. All these data, along with high level ab initio calculations, have shed light on the role of the different electronic states of the protonated molecules upon the fragmentation mechanisms.

  14. Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

    Science.gov (United States)

    Glavin, Daniel P.; Aubrey, Andrew D.; Callahan, Michael P.; Dworkin, Jason P.; Elsila, Jamie E.; Parker, Eric T.; Bada, Jeffrey L.

    2010-01-01

    Amino acid analysis of a meteorite fragment of asteroid 2008 TC3 called Almahata Sitta was carried out using reverse-phase liquid chromatography coupled with UV fluorescence detection and time-of-flight mass spectrometry (LC-FD/ToF-MS) as part of a sample analysis consortium. LC-FD/ToF-MS analyses of hot-water extracts from the meteorite revealed a complex distribution of two- to seven-carbon aliphatic amino acids and one- to three-carbon amines with abundances ranging from 0.5 to 149 parts-per-billion (ppb). The enantiomeric ratios of the amino acids alanine, R-amino-n-butyric acid (beta-ABA), 2-amino-2-methylbutanoic acid (isovaline), and 2-aminopentanoic acid (norvaline) in the meteorite were racemic (D/L approximately 1), indicating that these amino acids are indigenous to the meteorite and not terrestrial contaminants. Several other non-protein amino acids were also identified in the meteorite above background levels including alpha-aminoisobutyric acid (alpha-AIB), 4-amino-2- methylbutanoic acid, 4-amino-3-methylbutanoic acid, and 3-, 4-, and 5-aminopentanoic acid. The total abundances of isovaline and alpha-AIB in Almahata Sitta are 1000 times lower than the abundances of these amino acids found in the CM carbonaceous chondrite Murchison. The extremely low abundances and unusual distribution of five carbon amino acids in Almahata Sitta compared to Cl, CM, and CR carbonaceous chondrites may reflect extensive thermal alteration of amino acids on the parent asteroid by partial melting during formation or subsequent impact shock heating. It is also possible that amino acids were synthesized by catalytic reactions on the parent body after asteroid 2008 TC3 cooled to lower temperatures.

  15. Ribosomal Synthesis of Peptides with Multiple β-Amino Acids.

    Science.gov (United States)

    Fujino, Tomoshige; Goto, Yuki; Suga, Hiroaki; Murakami, Hiroshi

    2016-02-17

    The compatibility of β-amino acids with ribosomal translation was studied for decades, but it has been still unclear whether the ribosome can accept various β-amino acids, and whether the ribosome can introduce multiple β-amino acids in a peptide. In the present study, by using the Escherichia coli reconstituted cell-free translation system with a reprogramed genetic code, we screened β-amino acids that give high single incorporation efficiency and used them to synthesize peptides containing multiple β-amino acids. The experiments of single β-amino acid incorporation into a peptide revealed that 13 β-amino acids are compatible with ribosomal translation. Six of the tested β-amino acids (βhGly, l-βhAla, l-βhGln, l-βhPhg, l-βhMet, and d-βhPhg) showed high incorporation efficiencies, and seven (l-βhLeu, l-βhIle, l-βhAsn, l-βhPhe, l-βhLys, d-βhAla, and d-βhLeu) showed moderate incorporation efficiencies; whereas no full-length peptide was produced using other β-amino acids (l-βhPro, l-βhTrp, and l-βhGlu). Subsequent double-incorporation experiments using β-amino acids with high single incorporation efficiency revealed that elongation of peptides with successive β-amino acids is prohibited. Efficiency of the double-incorporation of the β-amino acids was restored by the insertion of Tyr or Ile between the two β-amino acids. On the basis of these experiments, we also designed mRNA sequences of peptides, and demonstrated the ribosomal synthesis of peptides containing different types of β-amino acids at multiple positions.

  16. Evolutionary systems biology of amino acid biosynthetic cost in yeast.

    Directory of Open Access Journals (Sweden)

    Michael D Barton

    Full Text Available Every protein has a biosynthetic cost to the cell based on the synthesis of its constituent amino acids. In order to optimise growth and reproduction, natural selection is expected, where possible, to favour the use of proteins whose constituents are cheaper to produce, as reduced biosynthetic cost may confer a fitness advantage to the organism. Quantifying the cost of amino acid biosynthesis presents challenges, since energetic requirements may change across different cellular and environmental conditions. We developed a systems biology approach to estimate the cost of amino acid synthesis based on genome-scale metabolic models and investigated the effects of the cost of amino acid synthesis on Saccharomyces cerevisiae gene expression and protein evolution. First, we used our two new and six previously reported measures of amino acid cost in conjunction with codon usage bias, tRNA gene number and atomic composition to identify which of these factors best predict transcript and protein levels. Second, we compared amino acid cost with rates of amino acid substitution across four species in the genus Saccharomyces. Regardless of which cost measure is used, amino acid biosynthetic cost is weakly associated with transcript and protein levels. In contrast, we find that biosynthetic cost and amino acid substitution rates show a negative correlation, but for only a subset of cost measures. In the economy of the yeast cell, we find that the cost of amino acid synthesis plays a limited role in shaping transcript and protein expression levels compared to that of translational optimisation. Biosynthetic cost does, however, appear to affect rates of amino acid evolution in Saccharomyces, suggesting that expensive amino acids may only be used when they have specific structural or functional roles in protein sequences. However, as there appears to be no single currency to compute the cost of amino acid synthesis across all cellular and environmental

  17. EFFECT OF MICROORGANISMS ON FREE AMINO ACID AND FREE D-AMINO ACID CONTENTS OF VARIOUS DAIRY PRODUCTS

    OpenAIRE

    Csilla Albert; Gabriella Pohn; Katalin Lóki; Szidónia Salamon; Beáta Albert; P. Sára; Z. Mándoki; Jánosné Csapó; Csapó, J.

    2007-01-01

    Free amino acid and free D-amino acid contents of milk samples with different microorganism numbers and composition of dairy products produced from them were examined. Total microorganism number of milk samples examined varied from 1.25x106 to 2.95x106. It was established that concentration of both free D-amino acids and free L-amino acids increased with an increase in microorganism number. However, increase in D-amino acid contents was higher considering its proportion. There was a particula...

  18. Effects of alkali or acid treatment on the isomerization of amino acids.

    Science.gov (United States)

    Ohmori, Taketo; Mutaguchi, Yuta; Doi, Katsumi; Ohshima, Toshihisa

    2012-10-01

    The effect of alkali treatment on the isomerization of amino acids was investigated. The 100×D/(D+L) values of amino acids from peptide increased with increase in the number of constituent amino acid residues. Furthermore, the N-terminal amino acid of a dipeptide was isomerized to a greater extent than the C-terminal residue.

  19. Conformational properties of oxazoline-amino acids

    Science.gov (United States)

    Staś, Monika; Broda, Małgorzata A.; Siodłak, Dawid

    2016-04-01

    Oxazoline-amino acids (Xaa-Ozn) occur in natural peptides of potentially important bioactivity. The conformations of the model compounds: Ac-(S)-Ala-Ozn(4R-Me), Ac-(S)-Ala-Ozn(4S-Me), and (gauche+, gauche-, anti) Ac-(S)-Val-Ozn(4R-Me) were studied at meta-hybrid M06-2X/6-311++G(d,p) method including solvent effect. Boc-L-Ala-L-Ozn-4-COOMe and Boc-L-Val-L-Ozn-4-COOMe were synthesized and studied by FT-IR and NMR-NOE methods. The conformations in crystal state were gathered from the Cambridge Structural Data Base. The main conformational feature of the oxazoline amino acids is the conformation β2 (ϕ,ψ ∼ -161°, -6°), which predominates in weakly polar environment and still is accessible in polar surrounding. The changes of the conformational preferences towards the conformations αR (ϕ,ψ ∼ -70°, -15°) and then β (ϕ,ψ ∼ -57°, -155°) are observed with increase of the environment polarity.

  20. Formation and transformation of amino acids and amino acid precursors by high-velocity impacts

    Science.gov (United States)

    Kaneko, T.; Kobayashi, K.; Yamori, A.

    A wide variety of organic compounds have been found in extraterrestrial bodies such as comets and carbonaceous chondrites. It is plausible that these extraterrestrial bodies carried organic compounds such as amino acids or their precursors to the early Earth. It is claimed, however, that these extraterrestrial organics were destroyed during impacts to the Earth. We therefore examined possible transformation of amino acids and their precursors during high-velocity impacts by using a rail gun "HYPAC" in ISAS. Starting materials used in the impact experiments were (i) aqueous solution of glycine (10 mM or 1.0 M), and (ii) a mixture of ammonia, methanol and water. The target materials were sealed in stainless steel capsules, and shocked by impact with a polycarbonate projectile accelerated with "HYPAC" to the velocities of 2.5 - 7.0 km/s. A part of the products was acid-hydrolyzed. Both hydrolyzed an unhydrolyzed products were analyzed by mass spectrometry, high performance liquid chromatography and capillary electrophoresis and chromatography. When an aqueous solution containing ammonia, methanol and water was shocked by impact at the velocity of 6.4 km/s, a number of amino acids (e.g., serine and glycine) were detected after hydrolysis. The present results suggest that amino acid precursors could be formed during cometary impacts. When glycine solution was used as a starting material, about 40 % of glycine was recovered even after 6 km/s impact. Methylamine and ammonia, which are known as pyrolytic products of glycine, were detected, besides them, diketopiperazine and an unidentified product whose molecular weight was 134, were detected, while no glycine peptides were identified in them. It was shown that the impact processes resulted in the formation of amino acid condensates. Thermal stability of glycine precursor is comparable with glycine. The present results suggest that organic material could survive and/or formed during an impact process. Most of organic

  1. Inadequacy of prebiotic synthesis as origin of proteinous amino acids.

    Science.gov (United States)

    Wong, J T; Bronskill, P M

    1979-07-18

    The production of some nonproteinous, and lack of production of other proteinous, amino acids in model prebiotic synthesis, along with the instability of glutamine and asparagine, suggest that not all of the 20 present day proteinous amino acids gained entry into proteins directly from the primordial soup. Instead, a process of active co-evolution of the genetic code and its constituent amino acids would have to precede the final selection of these proteinous amono acids.

  2. Determining important regulatory relations of amino acids from dynamic network analysis of plasma amino acids.

    Science.gov (United States)

    Shikata, Nahoko; Maki, Yukihiro; Nakatsui, Masahiko; Mori, Masato; Noguchi, Yasushi; Yoshida, Shintaro; Takahashi, Michio; Kondo, Nobuo; Okamoto, Masahiro

    2010-01-01

    The changes in the concentrations of plasma amino acids do not always follow the flow-based metabolic pathway network. We have previously shown that there is a control-based network structure among plasma amino acids besides the metabolic pathway map. Based on this network structure, in this study, we performed dynamic analysis using time-course data of the plasma samples of rats fed single essential amino acid deficient diet. Using S-system model (conceptual mathematical model represented by power-law formalism), we inferred the dynamic network structure which reproduces the actual time-courses within the error allowance of 13.17%. By performing sensitivity analysis, three of the most dominant relations in this network were selected; the control paths from leucine to valine, from methionine to threonine, and from leucine to isoleucine. This result is in good agreement with the biological knowledge regarding branched-chain amino acids, and suggests the biological importance of the effect from methionine to threonine.

  3. A one-pot procedure for the preparation of N-9-fluorenylmethyloxycarbonyl-α-amino diazoketones from α-amino acids.

    Science.gov (United States)

    Siciliano, Carlo; De Marco, Rosaria; Guidi, Ludovica Evelin; Spinella, Mariagiovanna; Liguori, Angelo

    2012-12-07

    The study describes a new "one-pot" route to the synthesis of N-9-fluorenylmethyloxycarbonyl (Fmoc) α-amino diazoketones. The procedure was tested on a series of commercially available free or side-chain protected α-amino acids employed as precursors. The conversion into the title compounds was achieved by masking and activating the α-amino acids with a single reagent, namely, 9-fluorenylmethyl chloroformate (Fmoc-Cl). The resulting N-protected mixed anhydrides were reacted with diazomethane to lead to the α-amino diazoketones, which were isolated by flash column chromatography in very good to excellent overall yields. The versatility of the procedure was verified on lipophilic α-amino acids and further demonstrated by the preparation of N-Fmoc-α-amino diazoketones also from α-amino acids containing side-chain masking groups, which are orthogonal to the Fmoc one. The results confirmed that tert-butyloxycarbonyl (Boc), tert-butyl ((t)Bu), and 2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl (Pbf), three acid-labile protecting groups mostly adopted in the solution and solid-phase peptide synthesis, are compatible to the adopted reaction conditions. In all cases, the formation of the corresponding C-methyl ester of the starting amino acid was not observed. Moreover, the proposed method respects the chirality of the starting α-amino acids. No racemization occurred when the procedure was applied to the synthesis of the respective N-Fmoc-protected α-amino diazoketones from L-isoleucine and L-threonine and to the preparation of a diastereomeric pair of N-Fmoc-protected dipeptidyl diazoketones.

  4. Asymmetric autocatalysis induced by meteoritic amino acids with hydrogen isotope chirality† †This article is part of a ChemComm ‘Catalysis in Organic Synthesis’ web-theme issue showcasing high quality research in organic chemistry. Please see our website (http://www.rsc.org/chemcomm/organicwebtheme2009) to access the other papers in this issue. ‡ ‡Electronic supplementary information (ESI) available: Procedures for the asymmetric autocatalysis in the presence of 1 and 2, the preparation of enantiomers of 1 and 2, and the determination of the enantiomeric purity of 1 and 2. See DOI: 10.1039/b908754k Click here for additional data file.

    Science.gov (United States)

    Kawasaki, Tsuneomi; Shimizu, Masako; Nishiyama, Daisuke; Ito, Masateru; Ozawa, Hitomi

    2009-01-01

    Achiral meteoritic amino acids, glycine and α-methylalanine, with hydrogen isotope (D/H) chirality, acted as the source of chirality in asymmetric autocatalysis with amplification of ee to afford highly enantioenriched 5-pyrimidyl alkanols. PMID:19597604

  5. Meteoritic Input of Amino Acids and Nucleobases: Methodology and Implications for the Origins of Life

    Science.gov (United States)

    Burton, Aaron S.; Stern, Jennifer C.; Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    The discoveries of amino acids of extraterrestrial origin in many meteorites over the last 40 years have revolutionized the Astrobiology field. A variety of non-terrestrial amino acids similar to those found in life on Earth have been detected in meteorites. A few amino acids have even been found with chiral excesses, suggesting that meteorites could have contributed to the origin of homochirality in life on Earth. In addition to amino acids, which have been productively studied for years, sugar-like molecules, activated phosphates, and nucleobases have also been determined to be indigenous to numerous meteorites. Because these molecules are essential for life as we know it, and meteorites have been delivering them to the Earth since accretion, it is plausible that the origin(s) of life on Earth were aided by extraterrestrially-synthesized molecules. Understanding the origins of life on Earth guides our search for life elsewhere, helping to answer the question of whether biology is unique to Earth. This tutorial review focuses on meteoritic amino acids and nucleobases, exploring modern analytical methods and possible formation mechanisms. We will also discuss the unique window that meteorites provide into the chemistry that preceded life on Earth, a chemical record we do not have access to on Earth due to geologic recycling of rocks and the pervasiveness of biology across the planet. Finally, we will address the future of meteorite research, including asteroid sample return mIssIons.

  6. Understanding Prebiotic Chemistry Through the Analysis of Extraterrestrial Amino Acids and Nucleobases in Meteorites

    Science.gov (United States)

    Burton, Aaron S.; Stern, Jennifer C.; Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    The discoveries of amino acids of extraterrestrial origin in many meteorites over the last 50 years have revolutionized the Astrobiology field. A variety of non-terrestrial amino acids similar to those found in life on Earth have been detected in meteorites. A few amino acids have even been found with chiral excesses, suggesting that meteorites could have contributed to the origin of homochirality in life on Earth. In addition to amino acids, which have been productively studied for years, sugar-like molecules, activated phosphates, and nucleobases have also been determined to be indigenous to numerous meteorites. Because these molecules are essential for life as we know it, and meteorites have been delivering them to the Earth since accretion, it is plausible that the origines) of life on Earth were aided by extrataterrestrially-synthesized molecules. Understanding the origins of life on Earth guides our search for life elsewhere, helping to answer the question of whether biology is unique to Earth. This tutorial focuses on meteoritic amino acids and nucleobases, exploring modern analytical methods and possible formation mechanisms. We will also discuss the unique window that meteorites provide into the chemistry that preceded life on Earth, a chemical record we do not have access to on Earth due to geologic recycling of rocks and the pervasiveness of biology across the planet. Finally. we will address the future of meteorite research, including asteroid sample return missions.

  7. Understanding prebiotic chemistry through the analysis of extraterrestrial amino acids and nucleobases in meteorites.

    Science.gov (United States)

    Burton, Aaron S; Stern, Jennifer C; Elsila, Jamie E; Glavin, Daniel P; Dworkin, Jason P

    2012-08-21

    The discoveries of amino acids of extraterrestrial origin in many meteorites over the last 50 years have revolutionized the Astrobiology field. A variety of non-terrestrial amino acids similar to those found in life on Earth have been detected in meteorites. A few amino acids have even been found with chiral excesses, suggesting that meteorites could have contributed to the origin of homochirality in life on Earth. In addition to amino acids, which have been productively studied for years, sugar-like molecules, activated phosphates, and nucleobases have also been determined to be indigenous to numerous meteorites. Because these molecules are essential for life as we know it, and meteorites have been delivering them to the Earth since accretion, it is plausible that the origin(s) of life on Earth were aided by extraterrestrially-synthesized molecules. Understanding the origins of life on Earth guides our search for life elsewhere, helping to answer the question of whether biology is unique to Earth. This tutorial review focuses on meteoritic amino acids and nucleobases, exploring modern analytical methods and possible formation mechanisms. We will also discuss the unique window that meteorites provide into the chemistry that preceded life on Earth, a chemical record we do not have access to on Earth due to geologic recycling of rocks and the pervasiveness of biology across the planet. Finally, we will address the future of meteorite research, including asteroid sample return missions.

  8. The prebiotic synthesis of amino acids - interstellar vs. atmospheric mechanisms

    Science.gov (United States)

    Meierhenrich, U. J.; Muñoz Caro, G. M.; Schutte, W. A.; Barbier, B.; Arcones Segovia, A.; Rosenbauer, H.; Thiemann, W. H.-P.; Brack, A.

    2002-11-01

    Until very recently, prebiotic amino acids were believed to have been generated in the atmosphere of the early Earth, as successfully simulated by the Urey-Miller experiments. Two independent studies now identified ice photochemistry in the interstellar medium as a possible source of prebiotic amino acids. Ultraviolet irradiation of ice mixtures containing identified interstellar molecules (such as H2O, CO2, CO, CH3OH, and NH3) in the conditions of vacuum and low temperature found in the interstellar medium generated amino acid structures including glycine, alanine, serine, valine, proline, and aspartic acid. After warmup, hydrolysis and derivatization, our team was able to identify 16 amino acids as well as furans and pyrroles. Enantioselective analyses of the amino acids showed racemic mixtures. A prebiotic interstellar origin of amino acid structures is now discussed to be a plausible alternative to the Urey-Miller mechanism.

  9. Transfer of Asymmetry between Proteinogenic Amino Acids under Harsh Conditions.

    Science.gov (United States)

    Tarasevych, Arkadii V; Vives, Thomas; Snytnikov, Valeriy N; Guillemin, Jean-Claude

    2017-03-31

    The heating above 400 °C of serine, cysteine, selenocysteine and threonine leads to a complete decomposition of the amino acids and to the formation in low yields of alanine for the three formers and of 2-aminobutyric acid for the latter. At higher temperature, this amino acid is observed only when sublimable α-alkyl-α-amino acids are present, and with an enantiomeric excess dependent on several parameters. Enantiopure or enantioenriched Ser, Cys, Sel or Thr is not able to transmit its enantiomeric excess to the amino acid formed during its decomposition. The presence during the sublimation-decomposition of enantioenriched valine or isoleucine leads to the enantioenrichment of all sublimable amino acids independently of the presence of many decomposition products coming from the unstable derivative. All these studies give information on a potentially prebiotic key-reaction of abiotic transformations between α-amino acids and their evolution to homochirality.

  10. Fast mass spectrometry-based enantiomeric excess determination of proteinogenic amino acids.

    Science.gov (United States)

    Fleischer, Heidi; Thurow, Kerstin

    2013-03-01

    A rapid determination of the enantiomeric excess of proteinogenic amino acids is of great importance in various fields of chemical and biologic research and industries. Owing to their different biologic effects, enantiomers are interesting research subjects in drug development for the design of new and more efficient pharmaceuticals. Usually, the enantiomeric composition of amino acids is determined by conventional analytical methods such as liquid or gas chromatography or capillary electrophoresis. These analytical techniques do not fulfill the requirements of high-throughput screening due to their relative long analysis times. The method presented allows a fast analysis of chiral amino acids without previous time consuming chromatographic separation. The analytical measurements base on parallel kinetic resolution with pseudoenantiomeric mass tagged auxiliaries and were carried out by mass spectrometry with electrospray ionization. All 19 chiral proteinogenic amino acids were tested and Pro, Ser, Trp, His, and Glu were selected as model substrates for verification measurements. The enantiomeric excesses of amino acids with non-polar and aliphatic side chains as well as Trp and Phe (aromatic side chains) were determined with maximum deviations of the expected value less than or equal to 10ee%. Ser, Cys, His, Glu, and Asp were determined with deviations lower or equal to 14ee% and the enantiomeric excess of Tyr were calculated with 17ee% deviation. The total screening process is fully automated from the sample pretreatment to the data processing. The method presented enables fast measurement times about 1.38 min per sample and is applicable in the scope of high-throughput screenings.

  11. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  12. Chiral Building Blocks: Enantioselective Syntheses of Benzyloxymethyl Phenyl Propionic Acids

    Directory of Open Access Journals (Sweden)

    Rustum S. Boyce

    2004-05-01

    Full Text Available The synthesis of (2S-2-benzyloxymethyl-3-(2-fluoro-4-methoxyphenyl- propionic acid, (2S-2-benzyloxymethyl-3-(2-fluoro-4-methylphenylpropionic acid and (2S-2-benzyl-oxymethyl-3-(2,4-dimethylphenylpropionic acid has been achieved by TiCl4 mediated alkylation of the corresponding (4R-4-benzyl-3-[3-(2-fluoro-4-methoxyphenyl-, 2-fluoro-4-methylphenyl-, 2,4- dimethylphenyl-propionyl]-2-oxazolidinones, followed by hydrolysis of the chiral auxiliary. The stereochemistry of the alkylation reaction was confirmed by an X-ray crystal structure of (4R-4-benzyl-3-[(2S-2-benzyloxymethyl-3-(2- fluoro-4-methylphenylpropionyl]-2-oxazolidinone.

  13. 2-Amino-3-(3-hydroxy-1,2,5-thiadiazol-4-yl)propionic acid

    DEFF Research Database (Denmark)

    Johansen, Tommy N; Janin, Yves L; Nielsen, Birgitte

    2002-01-01

    In order to identify new subtype-selective (S)-glutamate (Glu) receptor ligands we have synthesized (RS)-2-amino-3-(3-hydroxy-1,2,5-thiadiazol-4-yl)propionic acid [(RS)-TDPA]. Resolution of (RS)-TDPA by chiral chromatography was performed using a Crownpac CR(+) column affording (R)- and (S......)-TDPA of high enantiomeric purity (enantiomeric excess=99.9%). An X-ray crystallographic analysis revealed that the early eluting enantiomer has R-configuration. Both enantiomers showed high affinity as well as high agonist activity at (RS)-2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl)propionic acid (AMPA...... a remarkably low AMPA receptor stereoselectivity, (S)-TDPA showing the highest affinity and (R)-TDPA the most potent agonist activity. In addition, (S)-TDPA was shown to interact with synaptosomal Glu uptake sites displacing [(3)H](R)-aspartic acid (IC(50 ) approximately 390 microM). An enantiospecific...

  14. Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

    Science.gov (United States)

    Glavin, Daniel P.; Aubrey, Andrew D.; Callahan, Michael P.; Dworkin, Jason P.; Elsila, Jamie E.; Parker, Eric T.; Bada, Jeffrey L.

    2009-01-01

    Amino acid analysis of a meteorite fragment of asteroid 2008 TC(sub 3) called Almahata Sitta was carried out using reverse-phase high-perfo rmance liquid chromatography coupled with UV fluorescence detection a nd time-of-flight mass spectrometry (HPLC-FD/ToF-MS) as part of a sam ple analysis consortium. HPLC analyses of hot-water extracts from the meteorite revealed a complex distribution of two- to six-carbon aliph atic amino acids and one- to three carbon amines with abundances rang ing from 0.5 to 149 parts-per-billion (ppb). The enantiomeric ratios of the amino acids alanine, Beta-amino-n-butyric acid (Beta-ABA), 2-amino-2- methylbutanoic acid (isovaline), and 2-aminopentanoic acid (no rvaline) in the meteorite were racemic (D/L approximately 1), indicat ing that these amino acids are indigenous to the meteorite and not te rrestrial contaminants. Several other non-protein amino acids were also identified in the meteorite above background levels including alpha -aminoisobutyric acid (alpha-AIB), 4-amino-2- methybutanoic acid, 4-a mino-3-methylbutanoic acid, and 3-, 4-, and 5-aminopentanoic acid. Th e total abundances of isovaline and AlB in Almahata Sitta are approximately 1000 times lower than the abundances of these amino acids found in the CM carbonaceous meteorite Murchison. The extremely love abund ances and unusual distribution of five carbon amino acids in Almahata Sitta compared to Cl, CM, and CR carbonaceous meteorites and may be due to extensive thermal alteration of amino acids on the parent aster oid by partial melting during formation or impact shock heating.

  15. Potential of vancomycin for the enantiomeric resolution of FMOC-amino acids by capillary electrophoresis-ion-trap-mass spectrometry.

    Science.gov (United States)

    Sánchez-Hernández, Laura; Domínguez-Vega, Elena; Montealegre, Cristina; Castro-Puyana, María; Marina, María Luisa; Crego, Antonio L

    2014-05-01

    The potential of the antibiotic vancomycin (VC) as chiral selector for the enantiomeric separation of amino acids by CE-ESI-MS/MS² was investigated for the first time in this work. Derivatization of amino acids with FMOC-Cl was carried out to enable their interaction with VC as well as the formation of precursor ions with larger m/z which were employed in MS² experiments. The partial filling of a coated capillary was employed to avoid the loss in MS sensitivity originated by the introduction of VC in the ionization source. Under optimized conditions, the simultaneous enantiomeric separation and unequivocal identification of 17 amino acids (two of them being nonprotein amino acids) took place in about 20 min with LODs in the micromolar range.

  16. Bacterial utilization of L-sugars and D-amino acids

    Science.gov (United States)

    Pikuta, Elena V.; Hoover, Richard B.; Klyce, Brig; Davies, Paul C. W.; Davies, Pauline

    2006-08-01

    The fact that organotrophic organisms on Earth use L-amino acids and D-sugars as an energy source is recognized as one of the universal features of life. The chirality of organic molecules with asymmetric location of group-radicals was described a relatively long time ago. Louis Pasteur observed that abiotic (chemical) processes produced mixtures with equal numbers (racemic) of the two forms but that living organisms possessed a molecular asymmetry that included only one of the enantiomers (homochirality). He speculated that the origin of the asymmetry of chiral biomolecules might hold the key to the nature of life. All of the amino acids in proteins (except for Glycine which is symmetrical) exhibit the same absolute steric configuration as L-glyceraldehyde. D-amino acids are never found in proteins, although they do exist in nature and are often found in polypeptide antibiotics. Constitutional sugars of cells, opposite to the amino acids, are the D-enantiomers, and the appearance of L-sugars in Nature is extremely rare. Notwithstanding this fact, the metabolism of some bacteria does have the capability to use amino acids and sugars with alternative chirality. This property may be caused by the function of specific enzymes belonging to the class of isomerases (racemases, epimerases, isomerases, tautomerases). In our laboratory, we have investigated several anaerobic bacterial strains, and have found that some of these bacteria are capable of using D-amino acids and L-sugars. Strain BK1 is capable of growth on D-arginine, but its growth characteristics on L-arginine are approximately twice as high. Another alkaliphilic strain SCA T (= ATCC BAA-1084 T = JCM 12857 T = DSM 17722 T = CIP 107910 T) was found to be capable of growth on L-ribose and L-arabinose. It is interesting that this strain was incapable of growth on D-arabinose, which suggests the involvement of some alternative mechanism of enzyme activity. In this paper, we describe the preliminary results of

  17. Twenty natural amino acids identification by a photochromic sensor chip.

    Science.gov (United States)

    Qin, Meng; Li, Fengyu; Huang, Yu; Ran, Wei; Han, Dong; Song, Yanlin

    2015-01-20

    All 20 natural amino acids identification shows crucial importance in biochemistry and clinical application while it is still a challenge due to highly similarity in molecular configuration of the amino acids. Low efficiency, complicated sensing molecules and environment hindered the successful identification. Here, we developed a facile sensor chip composed of one photochromic molecule with metal ions spotted to form spirooxazine-metallic complexes, and successfully recognized all the 20 natural amino acids as well as their mixtures. The sensor chip gives distinct fluorescent fingerprint pattern of each amino acid, based on multistate of spirooxazine under different light stimulations and discriminated interaction between various metal ions and amino acids. The sensor chip demonstrates powerful capability of amino acids identification, which promotes sensing of biomolecules.

  18. Modulatory Effects of Dietary Amino Acids on Neurodegenerative Diseases.

    Science.gov (United States)

    Rajagopal, Senthilkumar; Sangam, Supraj Raja; Singh, Shubham; Joginapally, Venkateswara Rao

    2016-01-01

    Proteins are playing a vital role in maintaining the cellular integrity and function, as well as for brain cells. Protein intake and supplementation of individual amino acids can affect the brain functioning and mental health, and many of the neurotransmitters in the brain are made from amino acids. The amino acid supplementation has been found to reduce symptoms, as they are converted into neurotransmitters which in turn extenuate the mental disorders. The biosynthesis of amino acids in the brain is regulated by the concentration of amino acids in plasma. The brain diseases such as depression, bipolar disorder, schizophrenia, obsessive-compulsive disorder (OCD), and Alzheimer's (AD), Parkinson's (PD), and Huntington's diseases (HD) are the most common mental disorders that are currently widespread in numerous countries. The intricate biochemical and molecular machinery contributing to the neurological disorders is still unknown, and in this chapter, we revealed the involvement of dietary amino acids on neurological diseases.

  19. Surface Propensity of Atmospherically Relevant Amino Acids Studied by XPS.

    Science.gov (United States)

    Mocellin, Alexandra; Gomes, Anderson Herbert de Abreu; Araújo, Oscar Cardoso; de Brito, Arnaldo Naves; Bjorneholm, Olle

    2017-03-30

    Amino acids constitute an important fraction of the water-soluble organic nitrogen (WSON) compounds in aerosols and are involved in many processes in the atmosphere. In this work, we applied XPS to study aqueous solutions of four amino acids: glycine, alanine, valine and methionine, in their zwitterionic forms. We found that amino acids with hydrophilic side chains and smaller size, GLY and ALA, tend to stay in the bulk of the liquid, while the hydrophobic and bigger amino acids, VAL and MET, are found to concentrate more on the surface. We found experimental evidences that the amino acids have preferential orientation relative to the surface, with the hydrophobic side chain being closer to the surface than the hydrophilic carboxylate group. The observed amino acid surface propensity has implications in atmospheric science as the surface interaction play a central role in cloud droplet formation, and they should be considered in climate models.

  20. Distribution and Origin of Amino Acids in Lunar Regolith Samples

    Science.gov (United States)

    Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Dworkin, J. P.; McLain, H. L.; Noble, S. K.; Gibson, E. K., Jr.

    2015-01-01

    The existence of organic compounds on the lunar surface has been a question of interest from the Apollo era to the present. Investigations of amino acids immediately after collection of lunar samples yielded inconclusive identifications, in part due to analytical limitations including insensitivity to certain compounds, an inability to separate enantiomers, and lack of compound-specific isotopic measurements. It was not possible to determine if the detected amino acids were indigenous to the lunar samples or the result of terrestrial contamination. Recently, we presented initial data from the analysis of amino acid abundances in 12 lunar regolith samples and discussed those results in the context of four potential amino acid sources [5]. Here, we expand on our previous work, focusing on amino acid abundances and distributions in seven regolith samples and presenting the first compound-specific carbon isotopic ratios measured for amino acids in a lunar sample.

  1. Diversity of amino acids in a typical chernozem of Moldova

    Science.gov (United States)

    Frunze, N. I.

    2014-12-01

    The content and composition of the amino acids in typical chernozems were studied. The objects of the study included a reference soil under an old fallow and three variants under fodder crop rotations: not fertilized, with mineral fertilizers, and with organic fertilizers. The contents of 18 amino acids were determined in these soils. The amino acids were extracted by the method of acid hydrolysis and identified by the method of ion-exchange chromatography. The total content of most of the amino acids was maximal in the reference soil; it was much lower in the cultivated soils and decreased in the following sequence: organic background > mineral background > no fertilization. The diversity of amino acids was evaluated quantitatively using different parameters applied in ecology for estimating various aspects of the species composition of communities (Simpson, Margalef, Menhinick, and Shannon's indices). The diversity and contribution of different amino acids to the total pool of amino acids also varied significantly in the studied variants. The maximum diversity of amino acids and maximum evenness of their relative abundance indices were typical of the reference chernozem; these parameters were lower in the cultivated soils. It was concluded that the changes in the structure of the amino acids under the impact of agricultural loads are similar to those that are usually observed under stress conditions.

  2. Preference for and learning of amino acids in larval Drosophila

    Directory of Open Access Journals (Sweden)

    Nana Kudow

    2017-03-01

    Full Text Available Relative to other nutrients, less is known about how animals sense amino acids and how behaviour is organized accordingly. This is a significant gap in our knowledge because amino acids are required for protein synthesis − and hence for life as we know it. Choosing Drosophila larvae as a case study, we provide the first systematic analysis of both the preference behaviour for, and the learning of, all 20 canonical amino acids in Drosophila. We report that preference for individual amino acids differs according to the kind of amino acid, both in first-instar and in third-instar larvae. Our data suggest that this preference profile changes across larval instars, and that starvation during the third instar also alters this profile. Only aspartic acid turns out to be robustly attractive across all our experiments. The essentiality of amino acids does not appear to be a determinant of preference. Interestingly, although amino acids thus differ in their innate attractiveness, we find that all amino acids are equally rewarding. Similar discrepancies between innate attractiveness and reinforcing effect have previously been reported for other tastants, including sugars, bitter substances and salt. The present analyses will facilitate the ongoing search for the receptors, sensory neurons, and internal, homeostatic amino acid sensors in Drosophila.

  3. Preference for and learning of amino acids in larval Drosophila.

    Science.gov (United States)

    Kudow, Nana; Miura, Daisuke; Schleyer, Michael; Toshima, Naoko; Gerber, Bertram; Tanimura, Teiichi

    2017-03-15

    Relative to other nutrients, less is known about how animals sense amino acids and how behaviour is organized accordingly. This is a significant gap in our knowledge because amino acids are required for protein synthesis - and hence for life as we know it. Choosing Drosophila larvae as a case study, we provide the first systematic analysis of both the preference behaviour for, and the learning of, all 20 canonical amino acids in Drosophila We report that preference for individual amino acids differs according to the kind of amino acid, both in first-instar and in third-instar larvae. Our data suggest that this preference profile changes across larval instars, and that starvation during the third instar also alters this profile. Only aspartic acid turns out to be robustly attractive across all our experiments. The essentiality of amino acids does not appear to be a determinant of preference. Interestingly, although amino acids thus differ in their innate attractiveness, we find that all amino acids are equally rewarding. Similar discrepancies between innate attractiveness and reinforcing effect have previously been reported for other tastants, including sugars, bitter substances and salt. The present analyses will facilitate the ongoing search for the receptors, sensory neurons, and internal, homeostatic amino acid sensors in Drosophila.

  4. The Origin of Amino Acids in Lunar Regolith Samples

    Science.gov (United States)

    Cook, Jamie E.; Callahan, Michael P.; Dworkin, Jason P.; Glavin, Daniel P.; McLain, Hannah L.; Noble, Sarah K.; Gibson, Everett K., Jr.

    2016-01-01

    We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5 ppb to 651.1 ppb in 6M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D- and L-alanine, D- and L-aspartic acid, D- and L-glutamic acid, D- and L-serine, L-threonine, and L-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: -aminoisobutyric acid (AIB), D-and L-amino-n-butyric acid (-ABA), DL-amino-n-butyric acid, -amino-n-butyric acid, -alanine, and -amino-n-caproic acid. We observed an excess of the L enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic -ABA were present in some samples.

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

    Institute of Scientific and Technical Information of China (English)

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

    2002-01-01

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

  6. Self-assembly of amino acids on noble metal surfaces: universality of the amino acid bonding scheme

    Energy Technology Data Exchange (ETDEWEB)

    Reichert, Joachim; Auwaerter, Willi; Marschall, Matthias; Barth, Johannes V. [Physik Department, TU Muenchen (Germany); Schiffrin, Agustin [Physik Department, TU Muenchen (Germany); Chemistry Department, University of British Columbia, Vancouver (Canada); Pennec, Yan; Weber-Bargioni, Alexander [Chemistry Department, University of British Columbia, Vancouver (Canada); Cvetko, Dean; Cossaro, Albano; Morgante, Alberto [INFM/TASC, Trieste (Italy)

    2009-07-01

    We investigated the molecular self-assemblies of L-methionine on Cu(111) and L-tyrosine on Ag(111) by means of STM, HAS, XPS and NEXAFS in UHV. The self-assembly of L-methionine on Cu(111) is strongly influenced by the substrate reactivity and reveals a temperature dependent structural transformation involving a chiral orientational switch and the emergence of an ordered 1D high temperature phase. XPS data show that this transformation is triggered by a thermally activated deprotonation of the NH{sub 3}{sup +} group. The ordered phase shows noncovalent molecular dimerization and alignment into chains which are commensurate with the underlying substrate. L-tyrosine on Ag(111) self-assembles into linear nanoribbons primarily following the substrate crystalline symmetry. A zwitterionic noncovalent molecular dimerization is observed, and NEXAFS data provide evidence of a non-flat adsorption of the phenol ring. This dimerization scheme is reminiscent of methionine on Cu(111) and Ag(111), and supports a universal self-assembling trend for amino acids on close-packed noble metal surfaces.

  7. PHARMACOLOGICAL EFFECTS OF SNAKE VENOM L- AMINO ACID OXIDASES

    OpenAIRE

    Joseph Baby; Rajan Sheeja S; M.V Jeevitha; S.U Ajisha

    2011-01-01

    L-Amino acid oxidases are flavoenzymes which catalyze the stereospecific oxidative deamination of an L-amino acid substrate to a corresponding a-ketoacid with hydrogen peroxide and ammonia production. These enzymes, which are widely distributed in many different organisms, exhibit a marked affinity for hydrophobic amino acids, including phenylalanine, tryptophan, tyrosine, and leucine. Snake venom LAAO induces platelet aggregation and cytotoxicity in various cancer cell lines. The enzyme has ...

  8. SIFT: predicting amino acid changes that affect protein function

    OpenAIRE

    Ng, Pauline C.; Henikoff, Steven

    2003-01-01

    Single nucleotide polymorphism (SNP) studies and random mutagenesis projects identify amino acid substitutions in protein-coding regions. Each substitution has the potential to affect protein function. SIFT (Sorting Intolerant From Tolerant) is a program that predicts whether an amino acid substitution affects protein function so that users can prioritize substitutions for further study. We have shown that SIFT can distinguish between functionally neutral and deleterious amino acid changes in...

  9. A new synthetic protocol for coumarin amino acid

    Directory of Open Access Journals (Sweden)

    Xinyi Xu

    2013-02-01

    Full Text Available The hydrochloride of the racemic amino acid (2-(7-hydroxycoumarin-4-ylethylglycine, which can serve as a fluorescent probe in proteins, and two halogen derivatives of it, were synthesized by using a new synthetic protocol in five steps. It is less costly and relatively easy to prepare this kind of fluorescent amino acid with the new synthetic method. Furthermore, it can be applied to synthesize other derivatives of the coumarin amino acid with some specific properties.

  10. A Novel Synthesis of β-Hydroxy-α-amino Acids

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhi-Hui; LI Shuo; XU Pen-gFei

    2003-01-01

    @@ β-hydroxy-α-amino acids constitute an important class of compounds as naturally occurring amino acids and as components of many complex natural products possessing a wide range of biological activities. [1] As a consequence of the essential role played by these amino acids in the biological systems and their utility as synthetic building blocks, a number of useful strategies have been devised for their preparation. [2

  11. Amino Acid transport in protoplasts isolated from soybean leaves.

    Science.gov (United States)

    Vernooy, C D; Lin, W

    1986-05-01

    We isolated large quantities of mesophyll protoplasts from source and sink leaves of soybean plants and examined them for amino acid uptake. Accumulation of amino acids in isolated protoplasts was linear for at least 40 minutes. Uptake kinetics revealed the presence of both saturable and linear components. Increasing external pH decreases the uptake. The uncoupler, carbonyl cyanide p-trifluoromethoxyphenylhydrazone at 15 micromolar inhibited and fusicoccin at 10 micromolar stimulated amino acid uptake. Our data are consistent with a proton-cotransport mechanism for the uptake of l-glutamine and alpha-amino isobutyric acid into soybean mesophyll cells.

  12. Amino acids in the cultivation of mammalian cells.

    Science.gov (United States)

    Salazar, Andrew; Keusgen, Michael; von Hagen, Jörg

    2016-05-01

    Amino acids are crucial for the cultivation of mammalian cells. This importance of amino acids was realized soon after the development of the first cell lines, and a solution of a mixture of amino acids has been supplied to cultured cells ever since. The importance of amino acids is further pronounced in chemically defined mammalian cell culture media, making the consideration of their biological and chemical properties necessary. Amino acids concentrations have been traditionally adjusted to their cellular consumption rates. However, since changes in the metabolic equilibrium of amino acids can be caused by changes in extracellular concentrations, metabolomics in conjunction with flux balance analysis is being used in the development of culture media. The study of amino acid transporters is also gaining importance since they control the intracellular concentrations of these molecules and are influenced by conditions in cell culture media. A better understanding of the solubility, stability, dissolution kinetics, and interactions of these molecules is needed for an exploitation of these properties in the development of dry powdered chemically defined media for mammalian cells. Due to the complexity of these mixtures however, this has proven to be challenging. Studying amino acids in mammalian cell culture media will help provide a better understanding of how mammalian cells in culture interact with their environment. It would also provide insight into the chemical behavior of these molecules in solutions of complex mixtures, which is important in the understanding of the contribution of individual amino acids to protein structure.

  13. Design and characterization of auxotrophy-based amino acid biosensors.

    Directory of Open Access Journals (Sweden)

    Felix Bertels

    Full Text Available Efficient and inexpensive methods are required for the high-throughput quantification of amino acids in physiological fluids or microbial cell cultures. Here we develop an array of Escherichia coli biosensors to sensitively quantify eleven different amino acids. By using online databases, genes involved in amino acid biosynthesis were identified that - upon deletion - should render the corresponding mutant auxotrophic for one particular amino acid. This rational design strategy suggested genes involved in the biosynthesis of arginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, threonine, tryptophan, and tyrosine as potential genetic targets. A detailed phenotypic characterization of the corresponding single-gene deletion mutants indeed confirmed that these strains could neither grow on a minimal medium lacking amino acids nor transform any other proteinogenic amino acid into the focal one. Site-specific integration of the egfp gene into the chromosome of each biosensor decreased the detection limit of the GFP-labeled cells by 30% relative to turbidometric measurements. Finally, using the biosensors to determine the amino acid concentration in the supernatants of two amino acid overproducing E. coli strains (i.e. ΔhisL and ΔtdcC both turbidometrically and via GFP fluorescence emission and comparing the results to conventional HPLC measurements confirmed the utility of the developed biosensor system. Taken together, our study provides not only a genotypically and phenotypically well-characterized set of publicly available amino acid biosensors, but also demonstrates the feasibility of the rational design strategy used.

  14. Abiotic racemization kinetics of amino acids in marine sediments

    DEFF Research Database (Denmark)

    Steen, Andrew; Jørgensen, Bo Barker; Lomstein, Bente Aagaard

    2013-01-01

    Enantiomeric ratios of amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic racemize abiotically. Based on a heating experiment, we report Arrhenius parameters...... between different amino acids or depths. These results can be used in conjunction with measurements of sediment age to predict the ratio of D:L amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial...

  15. Synthesis of novel fullerene α-amino acid conjugates

    Institute of Scientific and Technical Information of China (English)

    Jing Zhang; Yan Xia Wang; Feng Kang; Ying Ya Shao; Zong Jie Li; Xin Lin Yang

    2008-01-01

    Aspartie acid and glutamic acid with protected α-amino and α-carboxyl groups had been used to react with the activated hydroxyl group of N-substituted 3,4-fuUero pyrrolidine.The products were deprotected,affording two monofullerene α-amino acids,monofullerene aspartic acid(mFas)and monofullerene glutamic acid(mFgu).Then a bifullerene glutamic acid conjugate (bFguC)was synthesized by reaction of mFgu containing protected amino group with N-subsfimted 3,4-fullero pyrrolidine.

  16. Amino Acid Transporters and Release of Hydrophobic Amino Acids in the Heterocyst-Forming Cyanobacterium Anabaena sp. Strain PCC 7120

    Directory of Open Access Journals (Sweden)

    Rafael Pernil

    2015-04-01

    Full Text Available Anabaena sp. strain PCC 7120 is a filamentous cyanobacterium that can use inorganic compounds such as nitrate or ammonium as nitrogen sources. In the absence of combined nitrogen, it can fix N2 in differentiated cells called heterocysts. Anabaena also shows substantial activities of amino acid uptake, and three ABC-type transporters for amino acids have been previously characterized. Seven new loci encoding predicted amino acid transporters were identified in the Anabaena genomic sequence and inactivated. Two of them were involved in amino acid uptake. Locus alr2535-alr2541 encodes the elements of a hydrophobic amino acid ABC-type transporter that is mainly involved in the uptake of glycine. ORF all0342 encodes a putative transporter from the dicarboxylate/amino acid:cation symporter (DAACS family whose inactivation resulted in an increased uptake of a broad range of amino acids. An assay to study amino acid release from Anabaena filaments to the external medium was set up. Net release of the alanine analogue α-aminoisobutyric acid (AIB was observed when transport system N-I (a hydrophobic amino acid ABC-type transporter was engaged in the uptake of a specific substrate. The rate of AIB release was directly proportional to the intracellular AIB concentration, suggesting leakage from the cells by diffusion.

  17. Novel urea-linked cinchona-calixarene hybrid-type receptors for efficient chromatographic enantiomer separation of carbamate-protected cyclic amino acids.

    Science.gov (United States)

    Krawinkler, Karl Heinz; Maier, Norbert M; Sajovic, Elisabeth; Lindner, Wolfgang

    2004-10-22

    Two novel diastereomeric cinchona-calixarene hybrid-type receptors (SOs) were synthesized by inter-linking 9-amino(9-deoxy)-quinine (AQN)/9-amino(9-deoxy)-epiquinine (eAQN) and a calix[4]arene scaffold via an urea functional unit. Silica-supported chiral stationary phases (CSPs) derived from these SOs revealed, for N-protected amino acids, complementary chiral recognition profiles in terms of elution order and substrate specificity. The AQN-derived CSP showed narrow-scoped enantioselectivity for open-chained amino acids bearing pi-acidic aromatic protecting groups, preferentially binding the (S)-enantiomers. In contrast, the eAQN congener exhibited broad chiral recognition capacity for open-chained as well as cyclic amino acids, and preferential binding of the (R)-enantiomers. Exceedingly strong retention due to nonenantioselective hydrophobic analyte-calixarene interactions observed with hydro-organic mobile phases could be largely suppressed with organic mobile phases containing small amounts of acetic acid as acidic modifier. With the eAQN-calixarene hybrid-type CSP particularly high levels of enantioselectivity could be achieved for tert-butoxycarbonyl (Boc)-, benzyloxycarbonyl (Z)- and fluorenylmethoxycarbonyl (Fmoc)-protected cyclic amino acids using chloroform as mobile phase, e.g. an enantioselectivty factor alpha >5.0 for Boc-proline. Increasing amounts of acetic acid compromised enantioselectivity, indicating the crucial contributions of hydrogen bonding to chiral recognition. Comparison of the performance characteristics of the urea-linked eAQN-calixarene hybrid-type CSP with those of structurally closely related mutants provided evidence for the active involvement of the urea and calixarene units in the chiral recognition process. The urea linker motif was shown to contribute to analyte binding via multiple hydrogen bonding interactions, while the calixarene module is believed to support stereodiscrimination by enhancing the shape complementarity of the

  18. Searching for amino-acid homochirality on Mars with the Mars Organic Molecule Analyzer (MOMA) onboard ExoMars

    Science.gov (United States)

    Buch, A.; Freissinet, C.; Sternberg, R.; Brault, A.; Szopa, C.; Claude-Geffroy, C.; Coll, P. J.; Grand, N.; Raulin, F.; Pinick, V.; Goesmann, F.

    2012-12-01

    The joint ESA-Roscosmos Exo-Mars-2018 rover mission plans to seek the signs of a past or a present life on Mars. The Mars Organic Molecule Analyzer (MOMA) experiment onboard theExoMars rover will be a key analytical tool in providing molecular information from Mars solid samples, with a specific focus on the characterization of their organic content. In this purpose, one of MOMA's main instruments is a gas chromatograph-mass spectrometer (GC-MS), which provides a unique ability to characterize a broad range of compounds and allow chemical analyses on volatile and refractory species. The challenge with the analysis of this refractory matter embedded in soil is their primary extraction before their analysis by GC-MS. Since the extraction of organic matter is not possible by liquid solvent extraction, we have developed a method based on the thermodesorption and subsequent derivatization of the organic molecules. The goal of the thermodesorption is to extract the organic matter by heating the sample quickly enough not to degrade its organic content. One of the main focuses is to determine the chirality of this organic matter, notably amino acids. Indeed, on Earth, homochirality of molecules is an indicator for the presence of life. Amino acids appear to bear only the left-handed form (L) in living system. However, other refractory compounds can raise interest: nucleobases, carboxylic acids and PAHs are among molecules supported by life as we know it, and all of them can display chirality. The intrinsic chirality of molecules being thermosensitive, the thermodesorption parameters have been adjusted to occur within a range of temperatures from 150 °C to 300 °C over a period of 30 s to 10 min, depending on the chemical compound. Under these conditions, we have shown that amino acids are not degraded and that their chirality is preserved. Once extracted, refractory molecules with labile hydrogens (e.g. amino acids, nucleobases, carboxylic acids, etc.) are derivatized

  19. Chiroptical study of α-aliphatic amino acid films in the vacuum ultraviolet region.

    Science.gov (United States)

    Tanaka, Masahito; Yagi-Watanabe, Kazutoshi; Kaneko, Fusae; Nakagawa, Kazumichi

    2010-11-11

    A series of natural circular dichroism (CD) and absorption spectra for films of α-aliphatic amino acids--such as alanine, aminobutyric acid, norvaline, norleucine, valine, leucine, and isoleucine--in the vacuum ultraviolet (VUV) region were observed with the absolute values of optical constants at the undulator-based CD beamline TERAS BL5. Preliminary predictions of some CD spectra were also performed, based on quantum-chemical calculations using the crystal structure. Although the absorption spectra show similar features to each other, significant differences between the CD spectra were found, especially in the 7-8 eV region. The CD spectra of aliphatic amino acids with branched alkyl groups in the side-chain--such as valine, leucine, and isoleucine--exhibit strong negative CD peaks in this energy region. In contrast, the corresponding CD peaks were weak or absent in the spectra of amino acids with straight alkyl groups. Our simple calculation, and the absorption spectra of alkanes, suggest that this difference partly originates from the contribution of the alkyl group. Clear discrepancies between the CD spectra of these amino acids in solutions and those in the solid state were also observed; this is probably caused by the different molecular structures in each state. Our results clearly indicated that CD spectra in the VUV region were very sensitive to the conformations of chiral molecules.

  20. 2-Phenyl-tetrahydropyrimidine-4(1H-ones – cyclic benzaldehyde aminals as precursors for functionalised β2-amino acids

    Directory of Open Access Journals (Sweden)

    Markus Nahrwold

    2009-09-01

    Full Text Available Novel procedures have been developed to condense benzaldehyde effectively with β-amino acid amides to cyclic benzyl aminals. Double carbamate protection of the heterocycle resulted in fully protected chiral β-alanine derivatives. These serve as universal precursors for the asymmetric synthesis of functionalised β2-amino acids containing acid-labile protected side chains. Diastereoselective alkylation of the tetrahydropyrimidinone is followed by a chemoselective two step degradation of the heterocycle to release the free β2-amino acid. In the course of this study, an L-asparagine derivative was condensed with benzaldehyde and subsequently converted to orthogonally protected (R-β2-homoaspartate.

  1. Abc Amino Acids: Design, Synthesis, and Properties of New Photoelastic Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Standaert, Robert F [ORNL; Park, Dr Seung Bum [Seoul National University

    2006-01-01

    Photoisomerizable amino acids provide a direct avenue to the experimental manipulation of bioactive polypeptides, potentially allowing real-time, remote control of biological systems and enabling useful applications in nanobiotechnology. Herein, we report a new class of photoisomerizable amino acids intended to cause pronounced expansion and contraction in the polypeptide backbone, i.e., to be photoelastic. These compounds, termed Abc amino acids, employ a photoisomerizable azobiphenyl chromophore to control the relative disposition of aminomethyl and carboxyl substituents. Molecular modeling of nine Abc isomers led to the identification of one with particularly attractive properties, including the ability to induce contractions up to 13A in the backbone upon transa?cis photoisomerization. This isomer, designated mpAbc, has substituents at meta and para positions on the inner (azo-linked) and outer rings, respectively. An efficient synthesis of Fmoc-protected mpAbc was executed in which the biaryl components were formed via Suzuki couplings and the azo linkage was formed via amine/nitroso condensation; protected forms of three other Abc isomers were prepared similarly. A decapeptide incorporating mpAbc was synthesized by conventional solid-phase methods and displayed characteristic azobenzene photochemical behavior with optimal conversion to the cis isomer at 360 nm and a thermal cisa?trans half life of 100 min. at 80 AoC.

  2. EFFECT OF MICROORGANISMS ON FREE AMINO ACID AND FREE D-AMINO ACID CONTENTS OF VARIOUS DAIRY PRODUCTS

    Directory of Open Access Journals (Sweden)

    Csilla Albert

    2007-06-01

    Full Text Available Free amino acid and free D-amino acid contents of milk samples with different microorganism numbers and composition of dairy products produced from them were examined. Total microorganism number of milk samples examined varied from 1.25x106 to 2.95x106. It was established that concentration of both free D-amino acids and free L-amino acids increased with an increase in microorganism number. However, increase in D-amino acid contents was higher considering its proportion. There was a particularly significant growth in the microorganism number range from 1.5x106 to 2.9x106. Based on analysis of curds and cheese samples produced using different technologies we have come to the conclusion that for fresh dairy products and for those matured over a short time there was a close relation between total microorganism number and free D-amino acid and free L-amino acid contents. At the same time it was found that the ratio of the enantiomers was not affected by the total microorganism number. For dairy products, however, where amino acid production capability of the microbial cultures considerably exceeds, production of microorganisms originally present in the milk raw material, free amino acid contents of the milk product (both D- and L-enantiomers seem to be independent of the composition of milk raw material.

  3. Gas-phase Acidities of Aspartic Acid, Glutamic Acid, and their Amino Acid Amides.

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhong; Matus, Myrna H; Velazquez, Hector A; Dixon, David A; Cassady, Carolyn J

    2007-02-14

    Gas-phase acidities (GA or ΔGacid) for the two most acidic common amino acids, aspartic acid and glutamic acid, have been determined for the first time. Because of the amide linkage’s importance in peptides and as an aid in studying side chain versus main chain deprotonation, aspartic acid amide and glutamic acid amide were also studied. Experimental GA values were measured by proton transfer reactions in an electrospray ionization/Fourier transform ion cyclotron resonance mass spectrometer. Calculated GAs were obtained by density functional and molecular orbital theory approaches. The best agreement with experiment was found at the G3MP2 level; the MP2/CBS and B3LYP/aug-cc-pVDZ results are 3–4 kcal/mol more acidic than the G3MP2 results. Experiment shows that aspartic acid is more acidic than glutamic acid by ca. 3 kcal/mol whereas the G3MP2 results show a smaller acidity difference of 0.2 kcal/mol. Similarly, aspartic acid amide is experimentally observed to be ca. 2 kcal/mol more acidic than glutamic acid amide whereas the G3MP2 results show a correspondingly smaller energy difference of 0.7 kcal/mol. The computational results clearly show that the anions are all ring-like structures with strong hydrogen bonds between the OH or NH2 groups and the CO2- group from which the proton is removed. The two amino acids are main-chain deprotonated. In addition, use of the COSMO model for the prediction of the free energy differences in aqueous solution gave values in excellent agreement with the most recent experimental values for pKa. Glutamic acid is predicted to be more acidic than aspartic acid in aqueous solution due to differential solvation effects.

  4. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-04-22

    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  5. Vibrational and photoionization spectroscopy of biomolecules: aliphatic amino acid structures.

    Science.gov (United States)

    Hu, Yongjun; Bernstein, Elliot R

    2008-04-28

    The aliphatic amino acids glycine, valine, leucine, and isoleucine are thermally placed into the gas phase and expanded into a vacuum system for access by time of flight mass spectroscopy and infrared (IR) spectroscopy in the energy range of 2500-4000 cm(-1) (CH, NH, OH, and stretching vibrations). The isolated neutral amino acids are ionized by a single photon of 10.5 eV energy (118 nm), which exceeds by less than 2 eV their reported ionization thresholds. As has been reported for many hydrogen bonded acid-base systems (e.g., water, ammonia, alcohol, acid clusters, and acid molecules), the amino acids undergo a structural rearrangement in the ion state (e.g., in simplest form, a proton transfer) that imparts sufficient excess vibrational energy to the ion to completely fragment it. No parent ions are observed. If the neutral ground state amino acids are exposed to IR radiation prior to ionization, an IR spectrum of the individual isomers for each amino acid can be determined by observation of the ion intensity of the different fragment mass channels. Both the IR spectrum and fragmentation patterns for individual isomers can be qualitatively identified and related to a particular isomer in each instance. Thus, each fragment ion detected presents an IR spectrum of its particular parent amino acid isomer. In some instances, the absorption of IR radiation by the neutral amino acid parent isomer increases a particular fragmentation mass channel intensity, while other fragmentation mass channel intensities decrease. This phenomenon can be rationalized by considering that with added energy in the molecule, the fragmentation channel populations can be modulated by the added vibrational energy in the rearranged ions. This observation also suggests that the IR absorption does not induce isomerization in the ground electronic state of these amino acids. These data are consistent with theoretical predictions for isolated amino acid secondary structures and can be related to

  6. Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

    Science.gov (United States)

    Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto

    2014-05-16

    Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

  7. Amino acid adsorption on mesoporous materials: influence of types of amino acids, modification of mesoporous materials, and solution conditions.

    Science.gov (United States)

    Gao, Qiang; Xu, Wujun; Xu, Yao; Wu, Dong; Sun, Yuhan; Deng, Feng; Shen, Wanling

    2008-02-21

    In order to disclose the dominant interfacial interaction between amino acids and ordered mesoporous materials, the adsorption behaviors of five amino acids on four mesoporous materials were investigated in aqueous solutions with adjustable amino acid concentration, ion strength, and pH. The selected amino acids were acidic amino acid glutamic acid (Glu), basic amino acid arginine (Arg), and neutral amino acids phenylalanine (Phe), leucine (Leu), and alanine (Ala), and the selected mesoporous materials were SBA-15, Al-SBA-15, CH3(10%)-SBA-15, and CH3(20%)-SBA-15. The adsorption capacities of Glu and Arg were strongly dependent on pH and surface charge of the mesoporous adsorbent. The adsorption of Phe showed pH insensitivity but depended on the surface organic functionalization of mesoporous adsorbent. On the basis of the theoretical analysis about the interaction between amino acid and adsorbent, such a remarkable difference was attributed to the different nature of the interaction between amino acid and adsorbent. Arg could be readily adsorbed on the surface of SBA-15, especially Al-SBA-15, under appropriate pH in which the electrostatic interaction was predominant. The driving force of Phe adsorption on mesoporous adsorbent mainly came from the hydrophobic interaction. Therefore, the adsorption capability of Arg decreased with increasing ion strength of solution, while the adsorption capability of Phe increased with the increasing degree of CH3 functionalization on SBA-15. For neutral amino acid Phe, Ala, and Leu, the adsorption capability increased with the increase of the length of their side chains, which was another evidence of hydrophobic effect. Thus, all the adsorption of amino acids on mesoporous silica materials can be decided by the combined influence of two fundamental interactions: electrostatic attraction and hydrophobic effect.

  8. Polysulfone affinity membranes for the treatment of amino acid mixtures.

    Science.gov (United States)

    Rodemann, K; Staude, E

    1995-06-20

    Affinity membranes for the treatment of solutions containing amino acids were obtained via lithiating polysulfone that was subsequently converted with glycidylether. From this polymer asymmetric ultrafiltration membranes were cast. The membranes were reacted with iminodiacetic acid yielding membranes fitted out with bidentate chelates. The same reaction path was applied to commercially available symmetric microfiltration membranes. The chelate-bearing membranes were complexed with Cu, Ni, and Zn ions. For the experiments with amino acids only the Cu-complexed membranes were used. The complexation constants for histidine and tryptophan for six different membranes were determined. Because of the affinity of these two amino acids for the complexed Cu ions, they could easily be separated from solutions containing amino acids such as alanine, glycine, and valine. Also, concentrating very dilute amino acid solutions was carried out successfully.

  9. Synthesis of gold nanoparticles using various amino acids.

    Science.gov (United States)

    Maruyama, Tatsuo; Fujimoto, Yuhei; Maekawa, Tetsuya

    2015-06-01

    Gold nanoparticles (4-7nm) were synthesized from tetraauric acid using various amino acids as reducing and capping agents. The gold nanoparticles were produced from the incubation of a AuCl4(-) solution with an amino acid at 80°C for 20min. Among the twenty amino acids tested, several amino acids produced gold nanoparticles. The color of the nanoparticle solutions varied with the amino acids used for the reduction. We adopted l-histidine as a reducing agent and investigated the effects of the synthesis conditions on the gold nanoparticles. The His and AuCl4(-) concentrations affected the size of the gold nanoparticles and their aggregates. The pH of the reaction solution also affected the reaction yields and the shape of the gold nanoparticles.

  10. Free amino acids in botanicals and botanical preparations.

    Science.gov (United States)

    Carratù, B; Boniglia, C; Giammarioli, S; Mosca, M; Sanzini, E

    2008-06-01

    Numerous studies were carried out about aminoacidic composition of vegetable proteins, but information about the free amino acid pool and the role of these substances is very incomplete. The aim of this paper was to contribute to the scarce knowledge concerning the composition of free amino acids in botanicals and botanical preparations widely used as food, in dietary supplements, and in pharmaceutical products. This work studied the composition of free amino acids, identified the major components of 19 species of plants, and evaluated the influence of different types of extraction on the amino acid profile. Amino acids were determined using an automatic precolumn derivatization with fluorenylmethyl-chloroformate and reversed-phase liquid chromatography with fluorescence and ultraviolet detection. The amounts of total free amino acids varied widely between plants, from approximately 12 g in 100 g of Echinacea pallida extract to less than 60 mg in the same amount of Coleus forskohlii, Garcinia cambogia, and Glycine max. In 13 plants arginine, asparagine, glutamine, proline, and gamma-aminobutyric acid were the free amino acids found in preponderant quantities. The levels of free amino acids above the quantification limit in 36 assayed samples of botanicals, extracts, and supplements are shown.

  11. Polycarboxylate derivative of -amino acid as growth modifier of sulphide minerals

    Indian Academy of Sciences (India)

    Harjyoti Thakuria; Gopal Das

    2011-02-01

    Construction of modified inorganic mineral with controlled mineralization analogues of those produced by nature is now of current interest for understanding the mechanism of the in vivo biomineralization processes, as well as looking for fresh industrial and technological applications. Low-molecular-weight chiral polycarboxylate ligands derived fromnaturally occurring -\\alpha-amino acids have been used asmodel systems to study the effect of small organic matrix on crystal growth modification. The sulphide minerals are characterized by PXRD, FT–IR and SEM. Furthermore, the optical properties of these minerals have been characterized by UV-Vis and photoluminescence (PL) spectra.

  12. Asymmetric synthesis of vinylogous β-amino acids and their incorporation into mixed backbone oligomers.

    Science.gov (United States)

    Wu, Hao; An, Hongchan; Mo, Shuting Cynthia; Kodadek, Thomas

    2017-03-27

    Chiral vinylogous β-amino acids (VBAA) were synthesized using enantioselective Mannich reactions of aldehydes with in situ generated N-carbamoyl imines followed by a Horner-Wadsworth-Emmons reaction. The efficiency with which these units could be incorporated into oligomers with different moieties on the C- and N-terminal sides was established, as was the feasibility of sequencing oligomers containing VBAAs by tandem mass spectrometry. The data show that VBAAs will be useful building blocks for the construction of combinatorial libraries of peptidomimetic compounds.

  13. Synthesis and conformational analysis of hybrid α/β-dipeptides incorporating S-glycosyl-β(2,2)-amino acids.

    Science.gov (United States)

    García-González, Iván; Mata, Lara; Corzana, Francisco; Jiménez-Osés, Gonzalo; Avenoza, Alberto; Busto, Jesús H; Peregrina, Jesús M

    2015-01-12

    We synthesized and carried out the conformational analysis of several hybrid dipeptides consisting of an α-amino acid attached to a quaternary glyco-β-amino acid. In particular, we combined a S-glycosylated β(2,2)-amino acid and two different types of α-amino acid, namely, aliphatic (alanine) and aromatic (phenylalanine and tryptophan) in the sequence of hybrid α/β-dipeptides. The key step in the synthesis involved the ring-opening reaction of a chiral cyclic sulfamidate, inserted in the peptidic sequence, with a sulfur-containing nucleophile by using 1-thio-β-D-glucopyranose derivatives. This reaction of glycosylation occurred with inversion of configuration at the quaternary center. The conformational behavior in aqueous solution of the peptide backbone and the glycosidic linkage for all synthesized hybrid glycopeptides was analyzed by using a protocol that combined NMR experiments and molecular dynamics with time-averaged restraints (MD-tar). Interestingly, the presence of the sulfur heteroatom at the quaternary center of the β-amino acid induced θ torsional angles close to 180° (anti). Notably, this value changed to 60° (gauche) when the peptidic sequence displayed aromatic α-amino acids due to the presence of CH-π interactions between the phenyl or indole ring and the methyl groups of the β-amino acid unit.

  14. Enzymatic tRNA acylation by acid and alpha-hydroxy acid analogues of amino acids.

    Science.gov (United States)

    Owczarek, Alina; Safro, Mark; Wolfson, Alexey D

    2008-01-08

    Incorporation of unnatural amino acids with unique chemical functionalities has proven to be a valuable tool for expansion of the functional repertoire and properties of proteins as well as for structure-function analysis. Incorporation of alpha-hydroxy acids (primary amino group is substituted with hydroxyl) leads to the synthesis of proteins with peptide bonds being substituted by ester bonds. Practical application of this modification is limited by the necessity to prepare corresponding acylated tRNA by chemical synthesis. We investigated the possibility of enzymatic incorporation of alpha-hydroxy acid and acid analogues (lacking amino group) of amino acids into tRNA using aminoacyl-tRNA synthetases (aaRSs). We studied direct acylation of tRNAs by alpha-hydroxy acid and acid analogues of amino acids and corresponding chemically synthesized analogues of aminoacyl-adenylates. Using adenylate analogues we were able to enzymatically acylate tRNA with amino acid analogues which were otherwise completely inactive in direct aminoacylation reaction, thus bypassing the natural mechanisms ensuring the selectivity of tRNA aminoacylation. Our results are the first demonstration that the use of synthetic aminoacyl-adenylates as substrates in tRNA aminoacylation reaction may provide a way for incorporation of unnatural amino acids into tRNA, and consequently into proteins.

  15. Chiral discrimination of secondary alcohols and carboxylic acids by NMR spectroscopy.

    Science.gov (United States)

    Pal, Indrani; Chaudhari, Sachin R; Suryaprakash, Nagaraja Rao

    2015-02-01

    The manuscript reports two novel ternary ion-pair complexes, which serve as chiral solvating agents, for enantiodiscrimination of secondary alcohols and carboxylic acids. The protocol for discrimination of secondary alcohols is designed by using one equivalent mixture each of enantiopure mandelic acid, 4-dimethylaminopyridine (DMAP) and a chiral alcohol. For discrimination of carboxylic acids, the ternary complex is obtained by one equivalent mixture each of enantiopure chiral alcohol, DMAP and a carboxylic acid. The designed protocols also permit accurate measurement of enantiomeric composition.

  16. Synthèse de mono et diphosphines dérivées d'amino acides ou de peptides, appliquées en chimie de coordination et pour le greffage de fullerène C60

    OpenAIRE

    Minois, Pauline,

    2013-01-01

    The synthesis of secondary phosphine borane amino acids or dipeptides and their applications for the preparation of chiral ligands or for the grafting of fullerene, is described. These compounds were synthesized in good yield (up to 98%) without racemization. The principle of the synthesis is based on the alkylation of primary phosphine borane with a γ-iodo amino acid using phase transfer conditions. Tertiary diphosphine amino acids are obtained with 70% yield after a second alkylation. These...

  17. Gas-phase acidities of aspartic acid, glutamic acid, and their amino acid amides

    Science.gov (United States)

    Li, Zhong; Matus, Myrna H.; Velazquez, Hector Adam; Dixon, David A.; Cassady, Carolyn J.

    2007-09-01

    Gas-phase acidities (GA or [Delta]Gacid) for the two most acidic common amino acids, aspartic acid and glutamic acid, have been determined for the first time. Because of the amide linkage's importance in peptides and as an aid in studying side chain versus main chain deprotonation, aspartic acid amide and glutamic acid amide were also studied. Experimental GA values were measured by proton transfer reactions in an electrospray ionization/Fourier transform ion cyclotron resonance mass spectrometer. Calculated GAs were obtained by density functional and molecular orbital theory approaches. The best agreement with experiment was found at the G3MP2 level; the MP2/CBS and B3LYP/aug-cc-pVDZ results are 3-4 kcal/mol more acidic than the G3MP2 results. Experiment shows that aspartic acid is more acidic than glutamic acid by ca. 3 kcal/mol whereas the G3MP2 results show a smaller acidity difference of 0.2 kcal/mol. Similarly, aspartic acid amide is experimentally observed to be ca. 2 kcal/mol more acidic than glutamic acid amide whereas the G3MP2 results show a correspondingly smaller energy difference of 0.7 kcal/mol. The computational results clearly show that the anions are all ring-like structures with strong hydrogen bonds between the OH or NH2 groups and the CO2- group from which the proton is removed. The two amino acids are main-chain deprotonated. In addition, use of the COSMO model for the prediction of the free energy differences in aqueous solution gave values in excellent agreement with the most recent experimental values for pKa. Glutamic acid is predicted to be more acidic than aspartic acid in aqueous solution due to differential solvation effects.

  18. The Path of Carbon in Photosynthesis II. Amino Acids

    Science.gov (United States)

    Stepka, W.; Benson, A. A.; Calvin, M.

    1948-05-25

    The radioactive amino acid's synthesized from C{sup 14}O{sub 2} by green algae both in the light and in the dark after CO{sub 2}-free preillumination have been separated and identified using paper chromatography and radioautography. The radioactive amino acids identified were aspartic acid, alanine and smaller amounts of 3- and 4-carbon amino acids. This finding as well as the total absence of radioactive glutamic acid substantiates the mechanism for reduction of CO{sub 2} previously postulated by members of this laboratory.

  19. Natural toxins that affect plant amino acid metabolism

    Science.gov (United States)

    A diverse range of natural compounds interfere with the synthesis and other aspects of amino acid metabolism. Some are amino acid analogues, but most are not. This review covers a number of specific natural phytotoxic compounds by molecular target site. Inhibition of glutamine synthetase is of part...

  20. CO2 sorption by supported amino acid ionic liquids

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns the absorption and desorption behaviour of carbon dioxide (CO2) using ionic liquids derived from amino acids adsorbed on porous carrier materials.......The present invention concerns the absorption and desorption behaviour of carbon dioxide (CO2) using ionic liquids derived from amino acids adsorbed on porous carrier materials....

  1. Representation of protein-sequence information by amino acid subalphabets

    DEFF Research Database (Denmark)

    Andersen, C.A.F.; Brunak, Søren

    2004-01-01

    -sequence information, using machine learning strategies, where the primary goal is the discovery of novel powerful representations for use in AI techniques. In the case of proteins and the 20 different amino acids they typically contain, it is also a secondary goal to discover how the current selection of amino acids...

  2. Origin of Homochirality of Amino Acids in the Biosphere

    Directory of Open Access Journals (Sweden)

    Shosuke Kojo

    2010-05-01

    Full Text Available Discussions are made concerning realistic mechanisms for the origin of L-amino acids in the biosphere. As the most plausible mechanism, it is proposed that a mixture of racemic amino acids in the prebiotic sea caused spontaneous and effective optical resolution through self crystallization, even if asymmetric synthesis of a single amino acid has never occurred without the aid of an optically active molecule. This hypothesis is based on recrystallization of a mixture of D,L-amino acids in the presence of excess of D,L-asparagine (Asn. The enantiomeric excess (ee of each amino acid in the resulting crystals indicates that crystallization of co-existing amino acids with the configuration same as that of Asn took place, although it was incidental whether the enrichment occurred in L- or D-amino acids. In addition, the resulting ee was sufficiently high (up to 100% to account for the predominance of L-amino acids on the earth.

  3. Nitrogen and amino acid metabolism in dairy cows

    NARCIS (Netherlands)

    Tamminga, S.

    1981-01-01

    For the process of milk production, the dairy cow requires nutrients of which energy supplying nutrients and protein or amino acid supplying nutrients are the most important. Amino acid supplying nutrients have to be absorbed from the small intestine and the research reported in this thesis mainly c

  4. Amino acid determination in some edible Mexican insects.

    Science.gov (United States)

    Ladrón de Guevara, O; Padilla, P; García, L; Pino, J M; Ramos-Elorduy, J

    1995-06-01

    The amino acid contents of edible insects from different provinces of Mexico and reference proteins were analysed by reversed-phase high-performance liquid chromatography and ion exchange chromatography. The insect amino acid contents were higher than the adult requirements indicated by the WHO/FAO pattern.

  5. A plasma membrane association module in yeast amino acid transporters

    NARCIS (Netherlands)

    Popov-Čeleketić, Dušan; Bianchi, Frans; Ruiz, Stephanie J; Meutiawati, Febrina; Poolman, Bert

    2016-01-01

    Amino acid permeases (AAPs) in the plasma membrane (PM) of Saccharomyces cerevisiae are responsible for the uptake of amino acids and involved in regulation of their cellular levels. Here, we report on a strong and complex module for PM association found in the C-terminal tail of AAPs. Using in sili

  6. Site specific incorporation of keto amino acids into proteins

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Peter G [La Jolla, CA; Wang, Lei [San Diego, CA

    2012-02-14

    Compositions and methods of producing components of protein biosynthetic machinery that include orthogonal tRNAs, orthogonal aminoacyl-tRNA synthetases, and orthogonal pairs of tRNAs/synthetases, which incorporate keto amino acids into proteins are provided. Methods for identifying these orthogonal pairs are also provided along with methods of producing proteins with keto amino acids using these orthogonal pairs.

  7. Site specific incorporation of keto amino acids into proteins

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Peter G. (La Jolla, CA); Wang, Lei (San Diego, CA)

    2011-03-22

    Compositions and methods of producing components of protein biosynthetic machinery that include orthogonal tRNAs, orthogonal aminoacyl-tRNA synthetases, and orthogonal pairs of tRNAs/synthetases, which incorporate keto amino acids into proteins are provided. Methods for identifying these orthogonal pairs are also provided along with methods of producing proteins with keto amino acids using these orthogonal pairs.

  8. Site specific incorporation of keto amino acids into proteins

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Peter G [La Jolla, CA; Wang, Lei [San Diego, CA

    2011-12-06

    Compositions and methods of producing components of protein biosynthetic machinery that include orthogonal tRNAs, orthogonal aminoacyl-tRNA synthetases, and orthogonal pairs of tRNAs/synthetases, which incorporate keto amino acids into proteins are provided. Methods for identifying these orthogonal pairs are also provided along with methods of producing proteins with keto amino acids using these orthogonal pairs.

  9. Ab initio Calculations of the Linear and Nonlinear Optical Properties of Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Tokarz, D; Tuer, A; Cisek, R; Krouglov, S; Barzda, V, E-mail: virgis.barzda@utoronto.ca [Department of Chemical and Physical Sciences, Department of Chemistry, Department of Physics, and Institute for Optical Sciences, University of Toronto, 3359 Mississauga Road North, Mississauga, ON L5L 1C6 (Canada)

    2010-11-01

    A number of proteins can assemble into chiral structures that display strong nonlinear optical activity. For instance, proteins such as myosin and collagen exhibit intense second harmonic generation (SHG). A large number of experimental studies on the SHG of proteins have been conducted; however few predictive models have been proposed that reliably relate the macroscopic SHG properties to the amino acids present in the peptidic chain. In this study, the linear polarizability ({alpha}), first ({beta}) and second hyperpolarizability ({gamma}) of all twenty amino acids was investigated by time-dependent Hartree-Fock calculations under physiological conditions. Ab initio calculations were performed using the GAMESSUS computational chemistry package. We have found that the aromatic amino acids give rise to the largest mean {alpha}, {beta} and {gamma} values. With this finding, we hope to apply this method to protein structures in order to understand how second harmonic signal is generated from individual amino acids, as well as, recognize how manipulation of the secondary structure of proteins might enhance SHG and third harmonic generation (THG).

  10. Amino acids: metabolism, functions, and nutrition.

    Science.gov (United States)

    Wu, Guoyao

    2009-05-01

    Recent years have witnessed the discovery that amino acids (AA) are not only cell signaling molecules but are also regulators of gene expression and the protein phosphorylation cascade. Additionally, AA are key precursors for syntheses of hormones and low-molecular weight nitrogenous substances with each having enormous biological importance. Physiological concentrations of AA and their metabolites (e.g., nitric oxide, polyamines, glutathione, taurine, thyroid hormones, and serotonin) are required for the functions. However, elevated levels of AA and their products (e.g., ammonia, homocysteine, and asymmetric dimethylarginine) are pathogenic factors for neurological disorders, oxidative stress, and cardiovascular disease. Thus, an optimal balance among AA in the diet and circulation is crucial for whole body homeostasis. There is growing recognition that besides their role as building blocks of proteins and polypeptides, some AA regulate key metabolic pathways that are necessary for maintenance, growth, reproduction, and immunity. They are called functional AA, which include arginine, cysteine, glutamine, leucine, proline, and tryptophan. Dietary supplementation with one or a mixture of these AA may be beneficial for (1) ameliorating health problems at various stages of the life cycle (e.g., fetal growth restriction, neonatal morbidity and mortality, weaning-associated intestinal dysfunction and wasting syndrome, obesity, diabetes, cardiovascular disease, the metabolic syndrome, and infertility); (2) optimizing efficiency of metabolic transformations to enhance muscle growth, milk production, egg and meat quality and athletic performance, while preventing excess fat deposition and reducing adiposity. Thus, AA have important functions in both nutrition and health.

  11. Functional amino acids in nutrition and health.

    Science.gov (United States)

    Wu, Guoyao

    2013-09-01

    The recent years have witnessed growing interest in biochemistry, physiology and nutrition of amino acids (AA) in growth, health and disease of humans and other animals. This results from the discoveries of AA in cell signaling involving protein kinases, G protein-coupled receptors, and gaseous molecules (i.e., NO, CO and H2S). In addition, nutritional studies have shown that dietary supplementation with several AA (e.g., arginine, glutamine, glutamate, leucine, and proline) modulates gene expression, enhances growth of the small intestine and skeletal muscle, or reduces excessive body fat. These seminal findings led to the new concept of functional AA, which are defined as those AA that participate in and regulate key metabolic pathways to improve health, survival, growth, development, lactation, and reproduction of the organisms. Functional AA hold great promise in prevention and treatment of metabolic diseases (e.g., obesity, diabetes, and cardiovascular disorders), intrauterine growth restriction, infertility, intestinal and neurological dysfunction, and infectious disease (including viral infections).

  12. Electronic coupling through natural amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Berstis, Laura; Beckham, Gregg T., E-mail: michael.crowley@nrel.gov, E-mail: gregg.beckham@nrel.gov; Crowley, Michael F., E-mail: michael.crowley@nrel.gov, E-mail: gregg.beckham@nrel.gov [National Renewable Energy Laboratory, National Bioenergy Center, 15013 Denver West Pkwy, Golden, Colorado 80401 (United States)

    2015-12-14

    Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For both motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. The unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green’s function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges. The distinct sensitivities of tunneling pathways to sequence and conformation revealed in this electronic coupling database help improve our fundamental understanding of the broad diversity of ET reactivity and provide guiding principles for peptide design.

  13. Amino Acid Analyses of Acid Hydrolysates in Desert Varnish

    Science.gov (United States)

    Perry, Randall S.; Staley, James T.; Dworkin, Jason P.; Engel, Mike

    2001-01-01

    There has long been a debate as to whether rock varnish deposits are microbially mediated or are deposited by inorganic processes. Varnished rocks are found throughout the world primarily in arid and semi-arid regions. The varnish coats are typically up to 200 microns thick and are composed of clays and alternating layers enriched in manganese and iron oxides. The individual layers range in thickness from 1 micron to greater than 10 microns and may continue laterally for more than a 100 microns. Overlapping botryoidal structures are visible in thin section and scanning electron micrographs. The coatings also include small amounts of organic mater and detrital grains. Amino-acid hydrolysates offer a means of assessing the organic composition of rock varnish collected from the Sonoran Desert, near Phoenix, AZ. Chromatographic analyses of hydrolysates from powdered samples of rock varnish suggest that the interior of rock varnish is relatively enriched in amino acids and specifically in d-alanine and glutamic acid. Peptidoglycan (murein) is the main structural component of gram-positive bacterial cell walls. The d-enantiomer of alanine and glutamic acid are specific to peptidoglycan and are consequently an indicator for the presence of bacteria. D-alanine is also found in teichoic acid which is only found in gram-positive bacteria. Several researchers have cultured bacteria from the surface of rock varnish and most have been gram-positive, suggesting that gram-positive bacteria are intimately associated with varnish coatings and may play a role in the formation of varnish coatings.

  14. Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

    Science.gov (United States)

    Gupta, A.; Loew, G. H.; Lawless, J.

    1983-01-01

    A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

  15. Adaptive amino acid composition in collagens of parasitic nematodes.

    Science.gov (United States)

    Hughes, Austin L

    2015-04-01

    Amino acid composition was analyzed in the glycine-rich repeat region of 306 collagens belonging to three major families of collagens from both parasitic and free-living nematodes. The collagens of parasitic species showed a tendency toward decreased usage of the hydrophilic residues A, D, and Q and increased usage of the hydrophobic resides I, L, and M; and this trend was seen in parasitic species of both the order Rhabdita and the order Spirurida. The amino acid composition of collagens of parasitic Rhabdita thus tended to resemble those of Spirurida more than that of free-living Rhabdita, suggesting an association between amino acid composition and a parasitic lifestyle. Computer predictions suggested that the more hydrophobic amino acid composition was associated with a reduction of the propensity towards B-cell epitope formation, suggesting that evasion of host immune responses may be a major selective factor responsible for the parasite-specific trend in collagen amino acid composition.

  16. Amino acid biogeo- and stereochemistry in coastal Chilean sediments

    DEFF Research Database (Denmark)

    Lomstein, Bente Aagaard; Jørgensen, Bo Barker; Schubert, Carsten J.;

    2006-01-01

    The spatial distribution of total hydrolysable amino acids (THAA) and amino acid enantiomers (D- and L-forms) was investigated in sediments underlying two contrasting Chilean upwelling regions,: at ~23°S off Antofagasta and at ~36°S off Concepcion. The contribution of amino acids to total organic...... carbon (%TAAC: 7-14%) and total nitrogen (%TAAN: 23-38%) in surface sediments decreased with increasing water depth (from 126 to 1350 m) indicating that organic matter becomes increasingly decomposed in surface sediments at greater water depth. Changes in the ratio between the protein amino acid...... aspartate and its non-protein degradation product β-alanine confirmed this observation. Furthermore, estimates of THAA mineralization showed that sedimentary amino acid reactivity decreased with both increasing water depth as well as progressive degradation status of the organic matter that was incorporated...

  17. Independence divergence-generated binary trees of amino acids.

    Science.gov (United States)

    Tusnády, G E; Tusnády, G; Simon, I

    1995-05-01

    The discovery of the relationship between amino acids is important in terms of the replacement ability, as used in protein engineering homology studies, and gaining a better understanding of the roles which various properties of the residues play in the creation of a unique, stable, 3-D protein structure. Amino acid sequences of proteins edited by evolution are anything but random. The measure of nonrandomness, i.e. the level of editing, can be characterized by an independence divergence value. This parameter is used to generate binary tree relationships between amino acids. The relationships of residues presented in this paper are based on protein building features and not on the physico-chemical characteristics of amino acids. This approach is not biased by the tautology present in all sequence similarity-based relationship studies. The roles which various physico-chemical characteristics play in the determination of the relationships between amino acids are also discussed.

  18. Regulation of intestinal protein metabolism by amino acids.

    Science.gov (United States)

    Bertrand, Julien; Goichon, Alexis; Déchelotte, Pierre; Coëffier, Moïse

    2013-09-01

    Gut homeostasis plays a major role in health and may be regulated by quantitative and qualitative food intake. In the intestinal mucosa, an intense renewal of proteins occurs, at approximately 50% per day in humans. In some pathophysiological conditions, protein turnover is altered and may contribute to intestinal or systemic diseases. Amino acids are key effectors of gut protein turnover, both as constituents of proteins and as regulatory molecules limiting intestinal injury and maintaining intestinal functions. Many studies have focused on two amino acids: glutamine, known as the preferential substrate of rapidly dividing cells, and arginine, another conditionally essential amino acid. The effects of glutamine and arginine on protein synthesis appear to be model and condition dependent, as are the involved signaling pathways. The regulation of gut protein degradation by amino acids has been minimally documented until now. This review will examine recent data, helping to better understand how amino acids regulate intestinal protein metabolism, and will explore perspectives for future studies.

  19. Amino Acids in Asteroids and Comets: Implications for the Origin of Life on Earth and Possibly Elsewhere

    Science.gov (United States)

    Glavin, Daniel

    2012-01-01

    Meteorites provide a record of the chemical processes that occurred in the early solar system before life began on Earth. The delivery of organic matter by asteroids, comets, and their fragments to the Earth and other planetary bodies in our solar system could have been an important source of the prebiotic organic inventory needed for the emergence of life. Amino acids are essential components of proteins and enzymes in life on Earth and these prebiotic organic compounds have been detected in a wide variety of carbon-rich meteorites, the majority of which have been determined to be extraterrestrial in origin. In addition, many amino acids are structurally chiral (they possess handedness) and with a few very rare exceptions, only left handed (L) amino acids are found in biology, while all known abiotic syntheses of amino acids result in equal mixtures of left and right handed (LD) amino acids. The discovery of a significant left handed amino acid imbalance of up to 20% in several different carbonaceous meteorites, could point toward a possible prebiotic contribution to the origin of biological homochirality by the exogenous delivery of extraterrestrial organic material to the early Earth. In this talk, I will focus on recent state-of-the-art measurements of the distribution, chirality, and isotopic composition of amino acids in meteorites and cometary samples carried out at the Goddard Astrobiology Analytical Laboratory. Results from the analyses of a variety of Antarctic meteorites, samples from comet Wild 2 returned by the STARDUST mission, and meteorite fragments of asteroid 2008 TC3 called Almahata Sitta recovered from northern Sudan will be discussed

  20. Cooperative catalysis by palladium and a chiral phosphoric acid: enantioselective amination of racemic allylic alcohols.

    Science.gov (United States)

    Banerjee, Debasis; Junge, Kathrin; Beller, Matthias

    2014-11-24

    Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This catalytic protocol is highly regio- and stereoselective (up to e.r. 96:4) and furnishes valuable chiral amines in almost quantitative yield.

  1. Synthesis of (R)-3-Methylpyrrolidine Alkaloids Using (S)-Malic Acid as a Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    ZHENG; Xiao

    2001-01-01

    Previous work in our laboratory was around the development of chiral 2-pyrrolidinone synthon A. Malimides 1 and 2, which can be easily prepared from (S)-malic acid, have been shown to be versatile chiral synthetic intermediates. All the reactivities showed in synthon A have been exploited.1  ……

  2. Amino Acid Profile of Some New Vartieties of Oil Seeds

    Directory of Open Access Journals (Sweden)

    Satish Ingale and S.K. Shrivastava

    2011-04-01

    Full Text Available There are large varieties of oil seeds and legumes in India, which are part of traditional food system but whose nutritional and economic values have not been completely determine and are far less exploited for both human and livestock utilization. The objective of this study was to evaluate Sunflower (Helianths annuus LSF-11, Sunflower (Helianths annuus LSF-8, Safflower (Carthamus tinctorius PBNS-12, Safflower (Carthamus tinctorius PBNS-40, and Ground nut (Arachis hypogaea JL-24 seeds with the aim of qualifying and quantifying chemical information that might serve as a guide to exploit its potentials and benefits for human and animal nutrition. The amino acid profile of these oil seed were carried out using standard methods. Amino acid analysis using technical sequential multisampling amino acid analyzer detected all essential and non essential amino acids. The seeds are rich in four amino acids (EAA and NEAA (g/16g N Glutamic acid (5.083, Aspartic acid (3.459, Proline (6.412 and Methionine (3.001%, respectively. The other amino acids compared well with the FAO reference protein, Serine appeared to be the most limiting amino acid percent. Based on results of this study, the lesser known and under-utilized oil seeds, they can be a potential source and energy supplements in livestock feed.

  3. Elevated amniotic fluid amino acid levels in fetuses with gastroschisis

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    A. Kale

    2006-08-01

    Full Text Available Our objective was to measure maternal plasma and amniotic fluid amino acid concentrations in pregnant women diagnosed as having fetuses with gastroschisis in the second trimester of pregnancy. Twenty-one pregnant women who had fetuses with gastroschisis detected by ultrasonography (gastroschisis group in the second trimester and 32 women who had abnormal triple screenings indicating an increased risk for Down syndrome but had healthy fetuses (control group were enrolled in the study. Amniotic fluid was obtained by amniocentesis, and maternal plasma samples were taken simultaneously. The chromosomal analysis of the study and control groups was normal. Levels of free amino acids and non-essential amino acids were measured in plasma and amniotic fluid samples using EZ:fast kits (EZ:fast GC/FID free (physiological amino acid kit by gas chromatography (Focus GC AI 3000 Thermo Finnigan analyzer. The mean levels of essential amino acids (histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, and valine and non-essential amino acids (alanine, glycine, proline, and tyrosine in amniotic fluid were found to be significantly higher in fetuses with gastroschisis than in the control group (P < 0.05. A significant positive correlation between maternal plasma and amniotic fluid concentrations of essential and nonessential amino acids was found only in the gastroschisis group (P < 0.05. The detection of significantly higher amino acid concentrations in the amniotic fluid of fetuses with a gastroschisis defect than in healthy fetuses suggests the occurrence of amino acid malabsorption or of amino acid leakage from the fetus into amniotic fluid.

  4. Hydration of amino acids: FTIR spectra and molecular dynamics studies.

    Science.gov (United States)

    Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

    2015-11-01

    The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

  5. Excretion of amino acids by humans during space flight

    Science.gov (United States)

    Stein, T. P.; Schluter, M. D.

    1998-01-01

    We measured the urine amino acid distribution patterns before, during and after space flight on the Space Shuttle. The urine samples were collected on two separate flights of the space shuttle. The first flight lasted 9.5 days and the second flight 15 days. Urine was collected continuously on 8 subjects for the period beginning 10 d before launch to 6 d after landing. Results: In contrast to the earlier Skylab missions where a pronounced amino aciduria was found, on shuttle the urinary amino acids showed little change with spaceflight except for a marked decrease in all of the amino acids on FD (flight day) 1 (pvaline on FD3 and FD4 (p<0.05). Conclusions: (i) Amino aciduria is not an inevitable consequence of space flight. (ii) The occurrence of amino aciduria, like muscle protein breakdown is a mission specific effect rather than part of the general human response to microgravity.

  6. Non-protein amino acids in peptide design

    Indian Academy of Sciences (India)

    S Aravinda; N Shamala; Rituparna S Roy; P Balaram

    2003-10-01

    An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the use -aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and DPro-Xxx segments for nucleating of -hairpin structures. - and -amino acid residues have been used to expand the range of designed polypeptide structures.

  7. D-Amino acids in the brain and mutant rodents lacking D-amino-acid oxidase activity.

    Science.gov (United States)

    Yamanaka, Masahiro; Miyoshi, Yurika; Ohide, Hiroko; Hamase, Kenji; Konno, Ryuichi

    2012-11-01

    D-Amino acids are stereoisomers of L-amino acids. They are often called unnatural amino acids, but several D-amino acids have been found in mammalian brains. Among them, D-serine is abundant in the forebrain and functions as a co-agonist of NMDA receptors to enhance neurotransmission. D-Amino-acid oxidase (DAO), which degrades neutral and basic D-amino acids, is mainly present in the hindbrain. DAO catabolizes D-serine and, therefore, modulates neurotransmission. In the brains of mutant mice and rats lacking DAO activity, the amounts of D-serine and other D-amino acids are markedly increased. Mutant mice manifested behavioral changes characteristic of altered NMDA receptor activity, likely due to increased levels of D-serine. D-Serine and DAO have been demonstrated to play important roles in cerebellar development and synaptic plasticity. They have also implicated in amyotrophic lateral sclerosis and pain response. There have also been several lines of evidence correlating DAO with schizophrenia. Taken together, the experiments indicate that D-amino acids and DAO have pivotal functions in the central nervous system.

  8. Quantitative analysis of 17 amino acids in tobacco leaves using an amino acid analyzer and chemometric resolution.

    Science.gov (United States)

    Zeng, Yihang; Cai, Wensheng; Shao, Xueguang

    2015-06-01

    A method was developed for quantifying 17 amino acids in tobacco leaves by using an A300 amino acid analyzer and chemometric resolution. In the method, amino acids were eluted by the buffer solution on an ion-exchange column. After reacting with ninhydrin, the derivatives of amino acids were detected by ultraviolet detection. Most amino acids are separated by the elution program. However, five peaks of the derivatives are still overlapping. A non-negative immune algorithm was employed to extract the profiles of the derivatives from the overlapping signals, and then peak areas were adopted for quantitative analysis of the amino acids. The method was validated by the determination of amino acids in tobacco leaves. The relative standard deviations (n = 5) are all less than 2.54% and the recoveries of the spiked samples are in a range of 94.62-108.21%. The feasibility of the method was proved by analyzing the 17 amino acids in 30 tobacco leaf samples.

  9. Organometallic and Bioorganometallic Chemistry – Ferrocene Amino Acids

    Directory of Open Access Journals (Sweden)

    Barišić, L.

    2012-01-01

    Full Text Available This article is the second part of a series dealing with organometallic and bioorganometallic chemistry. In the first part of this series a short review on the history and development of these disciplines was given, emphasizing the importance and scope of bioorganometallic chemistry as a new field dealing with conjugates of organometallics and biomolecules (DNA, PNA, amino acids, peptides.... From the variety of biorganometallics, syntheses and properties of simple conjugates of ferrocene with natural amino acids/peptides were elaborated inter alia. This material is the basis for the second part in which ferrocene amino acids are described. The introduction presents nonproteinogenic alicyclic and aromatic amino acids as the models for the title compounds. Naturally occurring amino acids labelled with ferrocene moiety mostly retain properties of the biomolecules included. Contrary to these ω-ferrocenylamino acids, one could imagine specific amino acids with inserted ferrocene core belonging to either homo- or heterodisubstituted type. The central part of this article is devoted to our investigations of the second type - H2N-(CH2m-Fn-(CH2n-COOH. The general rational procedure for synthesis of these compounds and of their N- and/or C-protected derivatives via the azide intermediates N3-CO-(CH2m- Fn-(CH2n-COOMe has been described. In the solid state derivatives of ferrocene amino acids contain intermolecular hydrogen bonds giving dimeric structures, three-dimensional networks or endless helical chains. The solutions of homologues Ac-NH-(CH2m-Fn-(CH2n-COOMe in nonpolar solvents are dominated by open form conformers. Compounds containing 2–3 ferrocene cores connected by amide, imide and oxalamide spacers were prepared by oligomerization of 1'-aminoferrocene-1-carboxylic acid (Fca or by its condensation with the appropriate reagents. Similar to natural amino acids, ferrocene amino acids are water-soluble substances with high melting points

  10. Subcritical Water Extraction of Amino Acids from Atacama Desert Soils

    Science.gov (United States)

    Amashukeli, Xenia; Pelletier, Christine C.; Kirby, James P.; Grunthaner, Frank J.

    2007-01-01

    Amino acids are considered organic molecular indicators in the search for extant and extinct life in the Solar System. Extraction of these molecules from a particulate solid matrix, such as Martian regolith, will be critical to their in situ detection and analysis. The goals of this study were to optimize a laboratory amino acid extraction protocol by quantitatively measuring the yields of extracted amino acids as a function of liquid water temperature and sample extraction time and to compare the results to the standard HCl vapor- phase hydrolysis yields for the same soil samples. Soil samples from the Yungay region of the Atacama Desert ( Martian regolith analog) were collected during a field study in the summer of 2005. The amino acids ( alanine, aspartic acid, glutamic acid, glycine, serine, and valine) chosen for analysis were present in the samples at concentrations of 1 - 70 parts- per- billion. Subcritical water extraction efficiency was examined over the temperature range of 30 - 325 degrees C, at pressures of 17.2 or 20.0 MPa, and for water- sample contact equilibration times of 0 - 30 min. None of the amino acids were extracted in detectable amounts at 30 degrees C ( at 17.2 MPa), suggesting that amino acids are too strongly bound by the soil matrix to be extracted at such a low temperature. Between 150 degrees C and 250 degrees C ( at 17.2 MPa), the extraction efficiencies of glycine, alanine, and valine were observed to increase with increasing water temperature, consistent with higher solubility at higher temperatures, perhaps due to the decreasing dielectric constant of water. Amino acids were not detected in extracts collected at 325 degrees C ( at 20.0 MPa), probably due to amino acid decomposition at this temperature. The optimal subcritical water extraction conditions for these amino acids from Atacama Desert soils were achieved at 200 degrees C, 17.2 MPa, and a water- sample contact equilibration time of 10 min.

  11. Amino acid profiles and digestible indispensable amino acid scores of proteins from the prioritized key foods in Bangladesh.

    Science.gov (United States)

    Shaheen, Nazma; Islam, Saiful; Munmun, Sarah; Mohiduzzaman, Md; Longvah, Thingnganing

    2016-12-15

    Concentrations of standard amino acids were determined in the composite samples (representing 30 agro-ecological zones of Bangladesh) of six prioritized key dietary protein sources: Oryza sativa (rice), Triticum aestivum (wheat flour), Lens culinaris (lentils), Pangusius pangusius (pangas), Labeo rohita (rohu) and Oreochromis mossambicus (tilapia). Digestible indispensable amino acid scores (DIAAS) was calculated using published data on amino acids' digestibility to evaluate the protein quality of these foods. Indispensable amino acid (IAA) contents (mg IAA/g protein), found to be highest in pangas (430) and lowest in wheat (336), of all these analyzed foods exceeded the FAO recommended daily allowance (277mg IAA/g protein) and contributed on average 40% to total amino acid contents. Untruncated DIAAS values ranged from 51% (lysine) in wheat to 106% (histidine) in pangas and distinguished pangas, rohu, and tilapia containing 'excellent quality' protein (DIAAS>100%) with potential to complement lower quality protein of cereals, fruits, and vegetables.

  12. Evaluation of methods to estimate the essential amino acids requirements of fish from the muscle amino acid profile

    Directory of Open Access Journals (Sweden)

    Álvaro José de Almeida Bicudo

    2014-03-01

    Full Text Available Many methods to estimate amino acid requirement based on amino acid profile of fish have been proposed. This study evaluates the methodology proposed by Meyer & Fracalossi (2005 and by Tacon (1989 to estimate amino acids requirement of fish, which do exempt knowledge on previous nutritional requirement of reference amino acid. Data on amino acid requirement of pacu, Piaractus mesopotamicus, were used to validate de accuracy of those methods. Meyer & Fracalossi's and Tacon's methodology estimated the lysine requirement of pacu, respectively, at 13 and 23% above requirement determined using dose-response method. The values estimated by both methods lie within the range of requirements determined for other omnivorous fish species, the Meyer & Fracalossi (2005 method showing better accuracy.

  13. Amino Acid Synthesis in a Supercritical Carbon Dioxide - Water System

    Directory of Open Access Journals (Sweden)

    Akiyoshi Hoshino

    2009-06-01

    Full Text Available Mars is a CO2-abundant planet, whereas early Earth is thought to be also CO2-abundant. In addition, water was also discovered on Mars in 2008. From the facts and theory, we assumed that soda fountains were present on both planets, and this affected amino acid synthesis. Here, using a supercritical CO2/liquid H2O (10:1 system which mimicked crust soda fountains, we demonstrate production of amino acids from hydroxylamine (nitrogen source and keto acids (oxylic acid sources. In this research, several amino acids were detected with an amino acid analyzer. Moreover, alanine polymers were detected with LC-MS. Our research lights up a new pathway in the study of life’s origin.

  14. Amino Acid and Peptide Immobilization on Oxidized Nanocellulose: Spectroscopic Characterization

    Directory of Open Access Journals (Sweden)

    Claude Daneault

    2012-06-01

    Full Text Available In this work, oxidized nanocellulose (ONC was synthesized and chemically coupled with amino acids and peptides using a two step coupling method at room temperature. First, ONC was activated by N-ethyl-N’-(3-dimethylaminopropyl carbodiimide hydrochloride, forming a stable active ester in the presence of N-hydroxysuccinimide. Second, the active ester was reacted with the amino group of the amino acid or peptide, forming an amide bond between ONC and the grafted molecule. Using this method, the intermolecular interaction of amino acids and peptides was avoided and uniform coupling of these molecules on ONC was achieved. The coupling reaction was very fast in mild conditions and without alteration of the polysaccharide. The coupling products (ONC-amino acids and ONC-peptides were characterized by transmission electron microscopy and by the absorption, emission, Fourier transform infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS spectroscopic techniques.

  15. Prolonged maternal amino acid infusion in late-gestation pregnant sheep increases fetal amino acid oxidation.

    Science.gov (United States)

    Rozance, Paul J; Crispo, Michelle M; Barry, James S; O'Meara, Meghan C; Frost, Mackenzie S; Hansen, Kent C; Hay, William W; Brown, Laura D

    2009-09-01

    Protein supplementation during human pregnancy does not improve fetal growth and may increase small-for-gestational-age birth rates and mortality. To define possible mechanisms, sheep with twin pregnancies were infused with amino acids (AA group, n = 7) or saline (C group, n = 4) for 4 days during late gestation. In the AA group, fetal plasma leucine, isoleucine, valine, and lysine concentrations were increased (P < 0.05), and threonine was decreased (P < 0.05). In the AA group, fetal arterial pH (7.365 +/- 0.007 day 0 vs. 7.336 +/- 0.012 day 4, P < 0.005), hemoglobin-oxygen saturation (46.2 +/- 2.6 vs. 37.8 +/- 3.6%, P < 0.005), and total oxygen content (3.17 +/- 0.17 vs. 2.49 +/- 0.20 mmol/l, P < 0.0001) were decreased on day 4 compared with day 0. Fetal leucine disposal did not change (9.22 +/- 0.73 vs. 8.09 +/- 0.63 micromol x min(-1) x kg(-1), AA vs. C), but the rate of leucine oxidation increased 43% in the AA group (2.63 +/- 0.16 vs. 1.84 +/- 0.24 micromol x min(-1) x kg(-1), P < 0.05). Fetal oxygen utilization tended to be increased in the AA group (327 +/- 23 vs. 250 +/- 29 micromol x min(-1) x kg(-1), P = 0.06). Rates of leucine incorporation into fetal protein (5.19 +/- 0.97 vs. 5.47 +/- 0.89 micromol x min(-1) x kg(-1), AA vs. C), release from protein breakdown (4.20 +/- 0.95 vs. 4.62 +/- 0.74 micromol x min(-1) x kg(-1)), and protein accretion (1.00 +/- 0.30 vs. 0.85 +/- 0.25 micromol x min(-1) x kg(-1)) did not change. Consistent with these data, there was no change in the fetal skeletal muscle ubiquitin ligases MaFBx1 or MuRF1 or in the protein synthesis regulators 4E-BP1, eEF2, eIF2alpha, and p70(S6K). Decreased concentrations of certain essential amino acids, increased amino acid oxidation, fetal acidosis, and fetal hypoxia are possible mechanisms to explain fetal toxicity during maternal amino acid supplementation.

  16. Solubility of xenon in amino-acid solutions. II. Nine less-soluble amino acids

    Science.gov (United States)

    Kennan, Richard P.; Himm, Jeffrey F.; Pollack, Gerald L.

    1988-05-01

    Ostwald solubility (L) of xenon gas, as the radioisotope 133Xe, has been measured as a function of solute concentration, at 25.0 °C, in aqueous solutions of nine amino acids. The amino-acid concentrations investigated covered much of their solubility ranges in water, viz., asparagine monohydrate (0-0.19 M), cysteine (0-1.16 M), glutamine (0-0.22 M), histidine (0-0.26 M), isoleucine (0-0.19 M), methionine (0-0.22 M), serine (0-0.38 M), threonine (0-1.4 M), and valine (0-0.34 M). We have previously reported solubility results for aqueous solutions of six other, generally more soluble, amino acids (alanine, arginine, glycine, hydroxyproline, lysine, and proline), of sucrose and sodium chloride. In general, L decreases approximately linearly with increasing solute concentration in these solutions. If we postulate that the observed decreases in gas solubility are due to hydration, the results under some assumptions can be used to calculate hydration numbers (H), i.e., the number of H2O molecules associated with each amino-acid solute molecule. The average values of hydration number (H¯) obtained at 25.0 °C are 15.3±1.5 for asparagine, 6.8±0.3 for cysteine, 11.5±1.1 for glutamine, 7.3±0.7 for histidine, 5.9±0.4 for isoleucine, 10.6±0.8 for methionine, 11.2±1.3 for serine, 7.7± 1.0 for threonine, and 6.6±0.6 for valine. We have also measured the temperature dependence of solubility L(T) from 5-40 °C for arginine, glycine, and proline, and obtained hydration numbers H¯(T) in this range. Between 25-40 °C, arginine has an H¯ near zero. This may be evidence for an attractive interaction between xenon and arginine molecules in aqueous solution.

  17. Production of non-proteinogenic amino acids from α-keto acid precursors with recombinant Corynebacterium glutamicum.

    Science.gov (United States)

    Kim, Ju-Yeon; Lee, Young-A; Wittmann, Christoph; Park, Jin-Byung

    2013-11-01

    In the present work, Corynebacterium glutamicum was metabolically engineered for the enantioselective synthesis of non-proteinogenic amino acids as valuable building blocks for pharmaceuticals and agrochemicals. The novel bio-catalytic activity of C. glutamicum was obtained by heterologous expression of the branched chain aminotransferase IlvE from Escherichia coli. Upon this modification, the recombinant cells converted the α-keto acid precursor 2-(3-hydroxy-1-adamantyl)-2-oxoethanoic acid (HOAE) into the corresponding amino acid 2-(3-hydroxy-1-adamantyl)-(2S)-amino ethanoic acid (HAAE). Similarly, also L-tert-leucine could be obtained from trimethyl pyruvate indicating a broader applicability of the novel strategy. In both cases, the amino group donor glutamate was supplied from the endogenous metabolism of the recombinant producer. Hereby, the uptake of the precursor and secretion of the product was supported by an enhanced cell permeability through treatment of ethambutol, which inhibits arabinosyl transferases involved in cell wall biosynthesis. The excretion of HAAE into the reaction medium was linked to the secretion of glutamate, indicating a similar mechanism for the export of both compounds. On the other hand, the efflux of L-tert-leucine appeared to be driven by active transport. Subsequent bioprocess engineering enabled HAAE and L-tert-leucine to be produced at a rate of 0.21 and 0.42 mmol (g dry cells)⁻¹  h⁻¹, respectively up to a final product titer of 40 mM. Beyond the given examples, integrated metabolic and cell envelop engineering might extend the production of a variety of other non-proteinogenic amino acids as well as chiral amines by C. glutamicum.

  18. Enantiopure cyclic O-substituted phenylphosphonothioic acid: synthesis and chirality-recognition ability.

    Science.gov (United States)

    Ribeiro, Nigel; Kobayashi, Yuka; Maeda, Jin; Saigo, Kazuhiko

    2011-07-01

    As a new acidic selector (resolving agent), we synthesized an enantiopure O-alkyl phenylphosphonothioic acid with a seven-membered ring ((R)-5), which was designed on the basis of the results for the enantioseparation of 1-arylethylamine derivatives with acyclic O-ethyl phenylphosphonothioic acid (I). The phosphonothioic acid (R)-5 showed unique chirality-recognition ability in the enantioseparation of 1-naphthylethylamine derivatives, aliphatic secondary amines, and amino alcohols; the ability was complementary to that of I. The X-ray crystallographic analyses of the less- and more-soluble diastereomeric salts showed that hydrogen-bonding networks in the salt crystals are 2(1) -column-type with a single exception which is cluster-type. In the cases of the 2(1) -column-type crystals, stability of the crystals is firstly governed by hydrogen bonds to form a 2(1) -column and secondly determined by intra-columnar T-shaped CH/π interaction(s), intra-columnar hydrogen bond(s), inter-columnar van der Waals interaction and/or inter-columnar T-shaped CH/π interaction(s). In contrast, the cluster-type salt crystal is stabilized by the assistance of inter-cluster T-shaped CH/π and van der Waals interactions. To realize still more numbers of intra- and inter-columnar and -cluster T-shaped CH/π interactions, the seven-membered ring of (R)-5 plays a considerable role.

  19. Aromatic amino acids in high selectivity bismuth(III) recognition.

    Science.gov (United States)

    Ghatak, Sumanta Kumar; Dey, Debarati; Sen, Souvik; Sen, Kamalika

    2013-04-21

    The three aromatic amino acids, tyrosine, tryptophan and phenylalanine, play different physiological roles in life processes. Metal ions capable of binding these amino acids may aid in the reduction of effective concentration of these amino acids in any physiological system. Here we have studied the efficacy of some heavy metals for their complexation with these three amino acids. Bismuth has been found to bind selectively with these aromatic amino acids and this was confirmed using spectrofluorimetric, spectrophotometric and cyclic voltammetric studies. The series of heavy metals has been chosen because each of these metals remains associated with the others at very low concentration levels and Bi(III) is the least toxic amongst the other elements. So, selective recognition for Bi(III) would also mean no response for the other heavy elements if contaminants are present even at low concentration levels. The affinity towards these amino acids has been found to be in the order tryptophan phenylalanine amino acids have been calculated using Benesi-Hildebrand equations and the corresponding free energy change has also been calculated. The values of the association constants obtained from BH equations using absorbance values corroborate with the Stern-Volmer constants obtained from fluorimetric studies. The evidence for complexation is also supported by the results of cyclic voltammetry.

  20. Metabolism of amino acids, dipeptides and tetrapeptides by Lactobacillus sakei.

    Science.gov (United States)

    Sinz, Quirin; Schwab, Wilfried

    2012-04-01

    The microbial degradation of proteins, peptides and amino acids generates volatiles involved in the typical flavor of dry fermented sausage. The ability of three Lactobacillus sakei strains to form aroma compounds was investigated. Whole resting cells were fermented in phosphate buffer with equimolar amounts of substrates consisting of dipeptides, tetrapeptides and free amino acids, respectively. Dipeptides disappeared quickly from the solutions whereas tetrapeptides were only partially degraded. In both approaches the concentration of free amino acids increased in the reaction mixture but did not reach the equimolar amount of the initial substrates. When free amino acids were fed to the bacteria their levels decreased only slightly. Although peptides were more rapidly degraded and/or transported into the cells, free amino acids produced higher amounts of volatiles. It is suggested, that after transport into the cell peptides are only partially hydrolyzed to their amino acids, while the rest is metabolized via alternative metabolic pathways. The three L. sakei strains differed to some extend in their ability to metabolize the substrates to volatile compounds. In a few cases this was due to the position of the amino acids within the peptides. Compared to other starter cultures used for the production of dry fermented sausages, the metabolic impact of the L. sakei strains on the formation of volatiles was very low.

  1. Amino Acid Catabolism in Alzheimer's Disease Brain: Friend or Foe?

    Science.gov (United States)

    2017-01-01

    There is a dire need to discover new targets for Alzheimer's disease (AD) drug development. Decreased neuronal glucose metabolism that occurs in AD brain could play a central role in disease progression. Little is known about the compensatory neuronal changes that occur to attempt to maintain energy homeostasis. In this review using the PubMed literature database, we summarize evidence that amino acid oxidation can temporarily compensate for the decreased glucose metabolism, but eventually altered amino acid and amino acid catabolite levels likely lead to toxicities contributing to AD progression. Because amino acids are involved in so many cellular metabolic and signaling pathways, the effects of altered amino acid metabolism in AD brain are far-reaching. Possible pathological results from changes in the levels of several important amino acids are discussed. Urea cycle function may be induced in endothelial cells of AD patient brains, possibly to remove excess ammonia produced from increased amino acid catabolism. Studying AD from a metabolic perspective provides new insights into AD pathogenesis and may lead to the discovery of dietary metabolite supplements that can partially compensate for alterations of enzymatic function to delay AD or alleviate some of the suffering caused by the disease. PMID:28261376

  2. Differential diagnosis of (inherited) amino acid metabolism or transport disorders.

    Science.gov (United States)

    Blom, W; Huijmans, J G

    1992-02-01

    Disorders of amino acid metabolism or transport are most clearly expressed in urine. Nevertheless the interpretation of abnormalities in urinary amino acid excretion remains difficult. An increase or decrease of almost every amino acid in urine can be due to various etiology. To differentiate between primary and secondary aminoacido-pathies systematic laboratory investigation is necessary. Early diagnosis of disorders of amino acid metabolism or transport is very important, because most of them can be treated, leading to the prevention of (further) clinical abnormalities. In those disorders, which cannot be treated, early diagnosis in an index-patient may prevent the birth of other siblings by means of genetic counseling and prenatal diagnosis.Primary aminoacidopathies can be due to genetically determined transport disorders and enzyme deficiencies in amino acid metabolism or degradation. Secondary aminoacidopathies are the result of abnormal or deficient nutrition, intestinal dysfunction, organ pathology or other metabolic diseases like organic acidurias.A survey of amino acid metabolism and transport abnormalities will be given, illustrated with metabolic pathways and characteristic abnormal amino acid chromatograms.

  3. Distribution of soluble amino acids in maize endosperm mutants

    Directory of Open Access Journals (Sweden)

    Toro Alejandro Alberto

    2003-01-01

    Full Text Available For human nutrition the main source of vegetable proteins are cereal and legume seeds. The content of total soluble amino acids in mature endosperm of wild-type, opaque and floury maize (Zea mays L. mutants were determined by HPLC. The total absolute concentration of soluble amino acids among the mutants varied depending on the mutant. The o11 and o13 mutants exhibited the highest average content, whereas o10, fl3 and fl1 exhibited the lowest average content. In general, the mutants exhibited similar concentrations of total soluble amino acids when compared to the wild-type lines, with the clear exception of mutants o11 and fl1, with the o11 mutant exhibiting a higher concentration of total soluble amino acids when compared to its wild-type counterpart W22 and the fl1 mutant a lower concentration when compared to its wild-type counterpart Oh43. For methionine, the mutants o2 and o11 and wild-type Oh43 exhibited the highest concentrations of this amino acid. Significant differences were not observed between mutants for other amino acids such as lysine and threonine. The high lysine concentrations obtained originally for these mutants may be due to the amino acids incorporated into storage proteins, but not those present in the soluble form.

  4. Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

    Directory of Open Access Journals (Sweden)

    Yann Garcia

    2011-10-01

    Full Text Available The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs and metal-organic frameworks (MOFs are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

  5. The origin of amino acids in lunar regolith samples

    Science.gov (United States)

    Elsila, Jamie E.; Callahan, Michael P.; Dworkin, Jason P.; Glavin, Daniel P.; McLain, Hannah L.; Noble, Sarah K.; Gibson, Everett K.

    2016-01-01

    We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5-651.1 ppb in 6 M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D- and L-alanine, D- and L-aspartic acid, D- and L-glutamic acid, D- and L-serine, L-threonine, and L-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: α-aminoisobutyric acid (AIB), D- and L-β-amino-n-butyric acid (β-ABA), DL-α-amino-n-butyric acid, γ-amino-n-butyric acid, β-alanine, and ε-amino-n-caproic acid. We observed an excess of the L enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic β-ABA were present in some samples. We also examined seven samples from Apollo 15, 16, and 17 that had been previously allocated to a non-curation laboratory, as well as two samples of terrestrial dunite from studies of lunar module engine exhaust that had been stored in the same laboratory. The amino acid content of these samples suggested that contamination had occurred during non-curatorial storage. We measured the compound-specific carbon isotopic ratios of glycine, β-alanine, and L-alanine in Apollo regolith sample 70011 and found values of -21‰ to -33‰. These values are consistent with those seen in terrestrial biology and, together with the enantiomeric compositions of the proteinogenic amino acids, suggest that terrestrial biological contamination is a primary source of the

  6. Exhaustive Database Searching for Amino Acid Mutations in Proteomes

    Energy Technology Data Exchange (ETDEWEB)

    Hyatt, Philip Douglas [ORNL; Pan, Chongle [ORNL

    2012-01-01

    Amino acid mutations in proteins can be found by searching tandem mass spectra acquired in shotgun proteomics experiments against protein sequences predicted from genomes. Traditionally, unconstrained searches for amino acid mutations have been accomplished by using a sequence tagging approach that combines de novo sequencing with database searching. However, this approach is limited by the performance of de novo sequencing. The Sipros algorithm v2.0 was developed to perform unconstrained database searching using high-resolution tandem mass spectra by exhaustively enumerating all single non-isobaric mutations for every residue in a protein database. The performance of Sipros for amino acid mutation identification exceeded that of an established sequence tagging algorithm, Inspect, based on benchmarking results from a Rhodopseudomonas palustris proteomics dataset. To demonstrate the viability of the algorithm for meta-proteomics, Sipros was used to identify amino acid mutations in a natural microbial community in acid mine drainage.

  7. A common periodic table of codons and amino acids.

    Science.gov (United States)

    Biro, J C; Benyó, B; Sansom, C; Szlávecz, A; Fördös, G; Micsik, T; Benyó, Z

    2003-06-27

    A periodic table of codons has been designed where the codons are in regular locations. The table has four fields (16 places in each) one with each of the four nucleotides (A, U, G, C) in the central codon position. Thus, AAA (lysine), UUU (phenylalanine), GGG (glycine), and CCC (proline) were placed into the corners of the fields as the main codons (and amino acids) of the fields. They were connected to each other by six axes. The resulting nucleic acid periodic table showed perfect axial symmetry for codons. The corresponding amino acid table also displaced periodicity regarding the biochemical properties (charge and hydropathy) of the 20 amino acids and the position of the stop signals. The table emphasizes the importance of the central nucleotide in the codons and predicts that purines control the charge while pyrimidines determine the polarity of the amino acids. This prediction was experimentally tested.

  8. Metabolic Response of Pakchoi Leaves to Amino Acid Nitrogen

    Institute of Scientific and Technical Information of China (English)

    WANG Xiao-li; YU Wen-juan; ZHOU Qian; HAN Rui-feng; HUANG Dan-feng

    2014-01-01

    Different nitrogen (N) forms may cause changes in the metabolic profiles of plants. However, few studies have been conducted on the effects of amino acid-N on plant metabolic proifles. The main objective of this study was to identify primary metabolites associated with amino acid-N (Gly, Gln and Ala) through metabolic proifle analysis using gas chromatography-mass spectrometry (GC-MS). Plants of pakchoi (Brassica campestris L. ssp. chinensis L.), Huawang and Wuyueman cultivars, were grown with different nitrogen forms (i.e., Gly, Gln, Ala, NO3--N, and N starvation) applied under sterile hydroponic conditions. The fresh weight and plant N accumulation of Huawang were greater than those of Wuyueman, which indicates that the former exhibited better N-use efficiency than the latter. The physiological performances of the applied N forms were generally in the order of NO3--N>Gln>Gly>Ala. The metabolic analysis of leaf polar extracts revealed 30 amino acid N-responsive metabolites in the two pakchoi cultivars, mainly consisting of sugars, amino acids, and organic acids. Changes in the carbon metabolism of pakchoi leaves under amino acid treatments occurred via the accumulation of fructose, glucose, xylose, and arabinose. Disruption of amino acid metabolism resulted in accumulation of endogenous Gly in Gly treatment, Pro in Ala treatment, and Asn in three amino acid (Gly, Gln and Ala) treatments. By contrast, the levels of endogenous Gln and Leu decreased. However, this reduction varied among cultivars and amino acid types. Amino acid-N supply also affected the citric acid cycle, namely, the second stage of respiration, where leaves in Gly, Gln and Ala treatments contained low levels of malic, citric and succinic acids compared with leaves in NO3--N treatments. No signiifcant difference in the metabolic responses was observed between the two cultivars which differed in their capability to use N. The response of primary metabolites in pakchoi leaves to amino acid-N supply

  9. PROTEINS, PEPTIDES AND AMINO ACIDS AS MARKERS OF BRONCHOPULMONARY DISEASES

    Directory of Open Access Journals (Sweden)

    V. I. Fyodorov

    2013-01-01

    Full Text Available The article is a review of current literature on a content of proteins, peptides and amino acids in human exhaled breath. The results of proteomics and metabolomics applying for selective detection of individual proteins, peptides and amino acids are described. The study of exhaled breath condensate and exhaled endogenous particles contained lung proteins are considered. The peculiarities of protein, peptide and amino acid content in exhaled breath at various respiratory diseases are described. It is shown that the detectable substances may be specific markers of individual diseases.

  10. Hybride magnetic nanostructure based on amino acids functionalized polypyrrole

    Science.gov (United States)

    Nan, Alexandrina; Bunge, Alexander; Turcu, Rodica

    2015-12-01

    Conducting polypyrrole is especially promising for many commercial applications because of its unique optical, electric, thermal and mechanical properties. We report the synthesis and characterization of novel pyrrole functionalized monomers and core-shell hybrid nanostructures, consisting of a conjugated polymer layer (amino acids functionalized pyrrole copolymers) and a magnetic nanoparticle core. For functionalization of the pyrrole monomer we used several amino acids: tryptophan, leucine, phenylalanine, serine and tyrosine. These amino acids were linked via different types of hydrophobic linkers to the nitrogen atom of the pyrrole monomer. The magnetic core-shell hybrid nanostructures are characterized by various methods such as FTIR spectroscopy, transmission electron microscopy (TEM) and magnetic measurements.

  11. SIFT: Predicting amino acid changes that affect protein function.

    Science.gov (United States)

    Ng, Pauline C; Henikoff, Steven

    2003-07-01

    Single nucleotide polymorphism (SNP) studies and random mutagenesis projects identify amino acid substitutions in protein-coding regions. Each substitution has the potential to affect protein function. SIFT (Sorting Intolerant From Tolerant) is a program that predicts whether an amino acid substitution affects protein function so that users can prioritize substitutions for further study. We have shown that SIFT can distinguish between functionally neutral and deleterious amino acid changes in mutagenesis studies and on human polymorphisms. SIFT is available at http://blocks.fhcrc.org/sift/SIFT.html.

  12. Hybride magnetic nanostructure based on amino acids functionalized polypyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Nan, Alexandrina, E-mail: alexandrina.nan@itim-cj.ro; Bunge, Alexander; Turcu, Rodica [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, 400293 Cluj-Napoca (Romania)

    2015-12-23

    Conducting polypyrrole is especially promising for many commercial applications because of its unique optical, electric, thermal and mechanical properties. We report the synthesis and characterization of novel pyrrole functionalized monomers and core-shell hybrid nanostructures, consisting of a conjugated polymer layer (amino acids functionalized pyrrole copolymers) and a magnetic nanoparticle core. For functionalization of the pyrrole monomer we used several amino acids: tryptophan, leucine, phenylalanine, serine and tyrosine. These amino acids were linked via different types of hydrophobic linkers to the nitrogen atom of the pyrrole monomer. The magnetic core-shell hybrid nanostructures are characterized by various methods such as FTIR spectroscopy, transmission electron microscopy (TEM) and magnetic measurements.

  13. Enantiomeric separation of free L- and D-amino acids in hydrolyzed protein fertilizers by capillary electrophoresis tandem mass spectrometry.

    Science.gov (United States)

    Sánchez-Hernández, Laura; Serra, Nuria Sierras; Marina, María Luisa; Crego, Antonio L

    2013-05-29

    Two capillary electrophoresis-tandem mass spectrometry (CE-MS(2)) methods were optimized in this work using cyclodextrins (CDs) as chiral selectors in order to determine the degree of racemization of the free amino acids contained in different hydrolyzed protein fertilizers used as plant biostimulants. The methodologies developed were characterized by the specificity of MS(2) experiments enabling the identification of all protein amino acids, except for cysteine. The enantiomeric separation of up to 14 amino acids was achieved with resolutions above 1.0 and limits of detection between 0.02 and 0.8 μM. The methods were applied to the analysis of complex samples such as hydrolyzed protein fertilizers to evaluate the presence of d-amino acids after different kinds of hydrolysis treatments. The results corroborated the absence or almost negligible presence of enantiomeric conversions of the L-amino acids into D-amino acids in the case of fertilizers obtained by enzymatic hydrolysis, as well as the high racemization rate for those obtained through a chemical hydrolysis.

  14. Transport of amino acids and GABA analogues via the human proton-coupled amino acid transporter, hPAT1

    DEFF Research Database (Denmark)

    Larsen, Mie; Larsen, Birger Brodin; Frølund, Bente;

    2008-01-01

    The objective of this study was to investigate transepithelial amino acid transport as a function of Caco-2 cell culture time. Furthermore, the objective was to investigate apical uptake characteristics of hPAT1-mediated transport under various experimental conditions. Apical amino acid uptake......, which has been shown to function as a carboxylic acid bioisostere for substrates of the GABA receptor and transport systems....

  15. Method Development for Efficient Incorporation of Unnatural Amino Acids

    KAUST Repository

    Harris, Paul D.

    2014-04-01

    The synthesis of proteins bearing unnatural amino acids has the potential to enhance and elucidate many processes in biochemistry and molecular biology. There are two primary methods for site specific unnatural amino acid incorporation, both of which use the cell’s native protein translating machinery: in vitro chemical acylation of suppressor tRNAs and the use of orthogonal amino acyl tRNA synthetases. Total chemical synthesis is theoretically possible, but current methods severely limit the maximum size of the product protein. In vivo orthogonal synthetase methods suffer from the high cost of the unnatural amino acid. In this thesis I sought to address this limitation by increasing cell density, first in shake flasks and then in a bioreactor in order to increase the yield of protein per amount of unnatural amino acid used. In a parallel project, I used the in vitro chemical acylation system to incorporate several unnatural amino acids, key among them the fluorophore BODIPYFL, with the aim of producing site specifically fluorescently labeled protein for single molecule FRET studies. I demonstrated successful incorporation of these amino acids into the trial protein GFP, although incorporation was not demonstrated in the final target, FEN1. This also served to confirm the effectiveness of a new procedure developed for chemical acylation.

  16. Bolus ingestion of individual branched-chain amino acids alters plasma amino acid profiles in young healthy men.

    Science.gov (United States)

    Matsumoto, Takuya; Nakamura, Koichi; Matsumoto, Hideki; Sakai, Ryosei; Kuwahara, Tomomi; Kadota, Yoshihiro; Kitaura, Yasuyuki; Sato, Juichi; Shimomura, Yoshiharu

    2014-01-01

    Physiological conditions in humans affect plasma amino acid profiles that might have potential for medical use. Because the branched-chain amino acids (BCAAs) leucine, isoleucine and valine are used as medicines and supplements, we investigated the acute effects of individual BCAAs (10-90 mg/kg body weight) or mixed BCAAs ingested as a bolus on plasma amino acid profiles in young healthy men. Plasma leucine levels rapidly increased and peaked around 30 min after leucine ingestion. Concentrations of plasma isoleucine, valine and phenylalanine subsequently decreased after ingestion, and those of methionine and tyrosine tended to decrease. The effects of ingested leucine on other plasma amino acids were biphasic, being higher at lower doses (10-20 mg/kg body weight). Isoleucine or valine intake also caused corresponding plasma amino acid concentrations to rapidly elevate, and peaks at 30-40 min after ingestion were much higher than that of plasma leucine after leucine ingestion. However, the increase in plasma isoleucine and valine concentrations essentially did not affect those of other plasma amino acids. The rate of decline among peak plasma BCAA concentrations was the highest for leucine, followed by isoleucine and valine. Oral mixed BCAAs promoted the decline in plasma isoleucine and valine concentrations. These results suggest that plasma leucine is a regulator of the plasma concentrations of BCAAs, methionine and aromatic amino acids.

  17. Searching for Extraterrestrial Amino Acids in a Contaminated Meteorite: Amino Acid Analyses of the Canakkale L6 Chondrite

    Science.gov (United States)

    Burton, A. S.; Elsila, J. E.; Glavin, D. P.; Dworkin, J. P.; Ornek, C. Y.; Esenoglu, H. H.; Unsalan, O.; Ozturk, B.

    2016-01-01

    Amino acids can serve as important markers of cosmochemistry, as their abundances and isomeric and isotopic compositions have been found to vary predictably with changes in parent body chemistry and alteration processes. Amino acids are also of astrobiological interest because they are essential for life on Earth. Analyses of a range of meteorites, including all groups of carbonaceous chondrites, along with H, R, and LL chondrites, ureilites, and a martian shergottite, have revealed that amino acids of plausible extraterrestrial origin can be formed in and persist after a wide range of parent body conditions. However, amino acid analyses of L6 chondrites to date have not provided evidence for indigenous amino acids. In the present study, we performed amino acid analysis on larger samples of a different L6 chondite, Canakkale, to determine whether or not trace levels of indigenous amino acids could be found. The Canakkale meteor was an observed fall in late July, 1964, near Canakkale, Turkey. The meteorite samples (1.36 and 1.09 g) analyzed in this study were allocated by C. Y. Ornek, along with a soil sample (1.5 g) collected near the Canakkale recovery site.

  18. The Amino Acid Composition of the Sutter's Mill Carbonaceous Chondrite

    Science.gov (United States)

    Glavin, D. P.; Burton, A. S.; Elsila, J. E.; Dworkin, J. P.; Yin, Q. Z.; Cooper, G.; Jenniskens, P.

    2012-01-01

    In contrast to the Murchison meteorite which had a complex distribution of amino acids with a total C2 to Cs amino acid abundance of approx.14,000 parts-per-billion (ppb) [2], the Sutters Mill meteorite was found to be highly depleted in amino acids. Much lower abundances (approx.30 to 180 ppb) of glycine, beta-alanine, L-alanine and L-serine were detected in SM2 above procedural blank levels indicating that this meteorite sample experienced only minimal terrestrial amino acid contamination after its fall to Earth. Carbon isotope measurements will be necessary to establish the origin of glycine and beta-alanine in SM2. Other non-protein amino acids that are rare on Earth, yet commonly found in other CM meteorites such as aaminoisobutyric acid (alpha-AIB) and isovaline, were not identified in SM2. However, traces of beta-AIB (approx.1 ppb) were detected in SM2 and could be" extraterrestrial in origin. The low abundances of amino acids in the Sutter's Mill meteorite is consistent with mineralogical evidence that at least some parts of the Sutter's Mill meteorite parent body experienced extensive aqueous and/or thermal alteration.

  19. Updates on industrial production of amino acids using Corynebacterium glutamicum.

    Science.gov (United States)

    Wendisch, Volker F; Jorge, João M P; Pérez-García, Fernando; Sgobba, Elvira

    2016-06-01

    L-Amino acids find various applications in biotechnology. L-Glutamic acid and its salts are used as flavor enhancers. Other L-amino acids are used as food or feed additives, in parenteral nutrition or as building blocks for the chemical and pharmaceutical industries. L-amino acids are synthesized from precursors of central carbon metabolism. Based on the knowledge of the biochemical pathways microbial fermentation processes of food, feed and pharma amino acids have been developed. Production strains of Corynebacterium glutamicum, which has been used safely for more than 50 years in food biotechnology, and Escherichia coli are constantly improved using metabolic engineering approaches. Research towards new processes is ongoing. Fermentative production of L-amino acids in the million-ton-scale has shaped modern biotechnology and its markets continue to grow steadily. This review focusses on recent achievements in strain development for amino acid production including the use of CRISPRi/dCas9, genome-reduced strains, biosensors and synthetic pathways to enable utilization of alternative carbon sources.

  20. Covalently functionalized graphene sheets with biocompatible natural amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Mallakpour, Shadpour, E-mail: mallak@cc.iut.ac.ir [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Abdolmaleki, Amir, E-mail: abdolmaleki@cc.iut.ac.ir [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of); Borandeh, Sedigheh [Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Islamic Republic of Iran (Iran, Islamic Republic of)

    2014-07-01

    Graphene sheets were covalently functionalized with aromatic–aliphatic amino acids (phenylalanine and tyrosine) and aliphatic amino acids (alanine, isoleucine, leucine, methionine and valine) by simple and green procedure. For this aim, at first natural graphite was converted into graphene oxide (GO) through strong oxidation procedure; then, based on the surface-exposed epoxy and carboxylic acid groups in GO solid, its surface modification with naturally occurring amino acids, occurred easily throughout the corresponding nucleophilic substitution and condensation reactions. Amino acid functionalized graphene demonstrates stable dispersion in water and common organic solvents. Fourier transform infrared, Raman and X-ray photoelectron spectroscopies, X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy were used to investigate the nanostructures and properties of prepared materials. Each amino acid has different considerable effects on the structure and morphology of the pure graphite, from increasing the layer spacing to layer scrolling, based on their structures, functional groups and chain length. In addition, therogravimetric analysis was used for demonstrating a successful grafting of amino acid molecules to the surface of graphene.

  1. Profile of Fatty Acids, Amino Acids, Carotenoid Total, and α-Tocopherol from Flying Fish Eggs

    Directory of Open Access Journals (Sweden)

    Aulia Azka

    2015-12-01

    Full Text Available Flying fish are found in waters of eastern Indonesia, which until now is still limited information about nutritional content. The purpose of this research was determine the composition of fatty acids, amino acids, total carotenoids, α-tocopherol flying fish eggs (Hyrundicthys sp.. The composition of fatty acid was measured by gas chromatography (GC, while amino acids, total carotenoids, α-tocopherol was measured by High performanced Liquid Chromatography (HPLC. Egg contained 22 fatty acids such as saturated fatty acid 29.71%, monounsaturated fatty acid 7.86%, and polysaturated fatty acid 13.64%. The result showed that eggs flying fish contained 17 amino acids, such as essential amino acid 14.96% and non-essential amino acids 20.27%. Eggs contained a total carotenoid of 245.37 ppm. α-tocopherol content of flying fish eggs by 1.06 ppm.

  2. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1–S3) at neutral pH indicated that the “back-to-back” bisCD complex CuL1 favoured higher catalytic efficiency and more pronounced enantioselectivity than the “face-to-face” complex CuL2. The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL1, which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL1, even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  3. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes.

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-26

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  4. The Practical Asymmetric Syntheses of Key Chiral Intermediates of Chiral Drug from Four-Carbon Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    MI AiQiao; LIN WenQin; HE Zhe; JIN Yi; JIANG YaoZhong

    2001-01-01

    @@ (S)-or (R)-2-Amino-4-phenylbutyric acid and (S)-or (R)-2-hydroxy-4-phenylbutyric acid and their ethyl esters are key chiral intermediates for the preparation of angiotensin converting enzyme inhibitors (ACEI) and other chiral drugs. Their practically asymmetric synthetic methods in large scale from four-carbon chiral pool, commercially available L-aspartic acid and L-malic acid, will be presented (as scheme). (S)-2-Amino-4-phenylbutyric acid and its ethyl ester hydrochloride were prepared from the easily available L-aspartic acid via activation by forming anhydride hydrochloride, Friedel-Crafts reaction with benzene, hydrogenolysis and esterification with ethanol in the presence of thionyl chloride in overall yield of 80% and 73.6% respectively with 99% ee. We first used amino acid anhydride hydrochloride as the acylating agent in Friedel-Crafts reaction without racemization. [1

  5. The Practical Asymmetric Syntheses of Key Chiral Intermediates of Chiral Drug from Four-Carbon Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    MI; AiQiao

    2001-01-01

    (S)-or (R)-2-Amino-4-phenylbutyric acid and (S)-or (R)-2-hydroxy-4-phenylbutyric acid and their ethyl esters are key chiral intermediates for the preparation of angiotensin converting enzyme inhibitors (ACEI) and other chiral drugs. Their practically asymmetric synthetic methods in large scale from four-carbon chiral pool, commercially available L-aspartic acid and L-malic acid, will be presented (as scheme).  (S)-2-Amino-4-phenylbutyric acid and its ethyl ester hydrochloride were prepared from the easily available L-aspartic acid via activation by forming anhydride hydrochloride, Friedel-Crafts reaction with benzene, hydrogenolysis and esterification with ethanol in the presence of thionyl chloride in overall yield of 80% and 73.6% respectively with 99% ee. We first used amino acid anhydride hydrochloride as the acylating agent in Friedel-Crafts reaction without racemization. [1]……

  6. Sugar amino acids and related molecules: Some recent developments

    Indian Academy of Sciences (India)

    Tushar Kanti Chakraborty; Pothukanuri Srinivasu; Subhasish Tapadar; Bajjuri Krishna Mohan

    2004-06-01

    To meet the growing demands for the development of new molecular entities for discovering new drugs and materials, organic chemists have started working on many new concepts that can help to assimilate knowledge-based structural diversities more efficiently than ever before. Emulating the basic principles followed by Nature to build its vast repertoire of biomolecules, organic chemists are developing many novel multifunctional building blocks and using them to create `nature-like’ and yet unnatural organic molecules. Sugar amino acids constitute an important class of such polyfunctional scaffolds where the carboxyl, amino and hydroxyl termini provide an excellent opportunity to organic chemists to create structural diversities akin to Nature’s molecular arsenal. In recent years, sugar amino acids have been used extensively in the area of peptidomimetic studies. Advances made in the area of combinatorial chemistry can provide the necessary technological support for rapid compilations of sugar amino acidbased libraries exploiting the diversities of their carbohydrate frameworks and well-developed solidphase peptide synthesis methods. This perspective article chronicles some of the recent applications of various sugar amino acids, furan amino acids, pyrrole amino acids etc. and many other related building blocks in wide-ranging peptidomimetic studies.

  7. Protein evolution via amino acid and codon elimination

    DEFF Research Database (Denmark)

    Goltermann, Lise; Larsen, Marie Sofie Yoo; Banerjee, Rajat;

    2010-01-01

    BACKGROUND: Global residue-specific amino acid mutagenesis can provide important biological insight and generate proteins with altered properties, but at the risk of protein misfolding. Further, targeted libraries are usually restricted to a handful of amino acids because there is an exponential...... correlation between the number of residues randomized and the size of the resulting ensemble. Using GFP as the model protein, we present a strategy, termed protein evolution via amino acid and codon elimination, through which simplified, native-like polypeptides encoded by a reduced genetic code were obtained...... simultaneously), while retaining varying levels of activity. Combination of these substitutions to generate a Phe-free variant of GFP abolished fluorescence. Combinatorial re-introduction of five Phe residues, based on the activities of the respective single amino acid replacements, was sufficient to restore GFP...

  8. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    Science.gov (United States)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  9. Excitatory amino acid transporters as potential drug targets

    DEFF Research Database (Denmark)

    Bunch, Lennart; Erichsen, Mette Navy; Jensen, Anders Asbjørn

    2009-01-01

    BACKGROUND: Excitatory amino acid transporters (EAATs) are transmembrane proteins responsible for the uptake of (S)-glutamate (Glu) from the synaptic cleft, thereby terminating the glutamatergic neurotransmitter signal. Today five subtypes have been identified. Except for EAAT2, their individual...

  10. Detection of COL III in Parchment by Amino Acid Analysis

    DEFF Research Database (Denmark)

    Vestergaard Poulsen Sommer, Dorte; Larsen, René

    2016-01-01

    Cultural heritage parchments made from the reticular dermis of animals have been subject to studies of deterioration and conservation by amino acid analysis. The reticular dermis contains a varying mixture of collagen I and III (COL I and III). When dealing with the results of the amino acid...... analyses, till now the COL III content has not been taken into account. Based on the available amino acid sequences we present a method for determining the amount of COL III in the reticular dermis of new and historical parchments calculated from the ratio of Ile/Val. We find COL III contents between 7...... and 32 % in new parchments and between 0.2 and 40 % in the historical parchments. This is consistent with results in the literature. The varying content of COL III has a significant influence on the uncertainty of the amino acid analysis. Although we have not found a simple correlation between the COL...

  11. Synthesis and catalytic application of amino acid based dendritic macromolecules

    NARCIS (Netherlands)

    Koten, G. van; Gossage, R.A.; Jastrzebski, J.T.B.H.; Ameijde, J. van; Mulders, S.J.E.; Brouwer, Arwin J.; Liskamp, R.M.J.

    1999-01-01

    The use of amino acid based dendrimers as molecular scaffolds for the attachment of catalytically active organometallic Ni ''pincer'' complexes, via a urea functionality, is described; the dendrimer catalysts have comparable activity to their mononuclear (NCN)NiX analogues.

  12. Chemical Approaches to Studying Labile Amino Acid Phosphorylation.

    Science.gov (United States)

    Marmelstein, Alan M; Moreno, Javier; Fiedler, Dorothea

    2017-04-01

    Phosphorylation of serine, threonine, and tyrosine residues is the archetypal posttranslational modification of proteins. While phosphorylation of these residues has become standard textbook knowledge, phosphorylation of other amino acid side chains is underappreciated and minimally characterized by comparison. This disparity is rooted in the relative instability of these chemically distinct amino acid side chain moieties, namely phosphoramidates, acyl phosphates, thiophosphates, and phosphoanhydrides. In the case of the O-phosphorylated amino acids, synthetic constructs were critical to assessing their stability and developing tools for their study. As the chemical biology community has become more aware of these alternative phosphorylation sites, methodology has been developed for the synthesis of well-characterized standards and close mimics of these phosphorylated amino acids as well. In this article, we review the synthetic chemistry that is a prerequisite to progress in this field.

  13. Disturbed amino acid metabolism in HIV: association with neuropsychiatric symptoms

    Directory of Open Access Journals (Sweden)

    Johanna M Gostner

    2015-07-01

    Full Text Available Blood levels of the amino acid phenylalanine, as well as of the tryptophan breakdown product kynurenine, are found to be elevated in human immunodeficiency virus type 1 (HIV-1-infected patients. Both essential amino acids, tryptophan and phenylalanine are important precursor molecules for neurotransmitter biosynthesis. Thus, dysregulated amino acid metabolism may be related to disease-associated neuropsychiatric symptoms such as development of depression, fatigue, and cognitive impairment.Increased phenylalanine/tyrosine and kynurenine/tryptophan ratios are associated with immune activation in patients with HIV-1 infection and decrease upon effective antiretroviral therapy. Recent large-scale metabolic studies have confirmed the crucial involvement of tryptophan and phenylalanine metabolism in HIV-associated disease. Herein, we summarize the current status of the role of tryptophan and phenylalanine metabolism in HIV disease and discuss how inflammatory stress-associated dysregulation of amino acid metabolism may be part of the pathophysiology of common HIV-associated neuropsychiatric conditions.

  14. Amyloid Aggregates Arise from Amino Acid Condensations under Prebiotic Conditions.

    Science.gov (United States)

    Greenwald, Jason; Friedmann, Michael P; Riek, Roland

    2016-09-12

    Current theories on the origin of life reveal significant gaps in our understanding of the mechanisms that allowed simple chemical precursors to coalesce into the complex polymers that are needed to sustain life. The volcanic gas carbonyl sulfide (COS) is known to catalyze the condensation of amino acids under aqueous conditions, but the reported di-, tri-, and tetra-peptides are too short to support a regular tertiary structure. Here, we demonstrate that alanine and valine, two of the proteinogenic amino acids believed to have been among the most abundant on a prebiotic earth, can polymerize into peptides and subsequently assemble into ordered amyloid fibers comprising a cross-β-sheet quaternary structure following COS-activated continuous polymerization of as little as 1 mm amino acid. Furthermore, this spontaneous assembly is not limited to pure amino acids, since mixtures of glycine, alanine, aspartate, and valine yield similar structures.

  15. Comparison of amino acids interaction with gold nanoparticle.

    Science.gov (United States)

    Ramezani, Fatemeh; Amanlou, Massoud; Rafii-Tabar, Hashem

    2014-04-01

    The study of nanomaterial/biomolecule interface is an important emerging field in bionanoscience, and additionally in many biological processes such as hard-tissue growth and cell-surface adhesion. To have a deeper understanding of the amino acids/gold nanoparticle assemblies, the adsorption of these amino acids on the gold nanoparticles (GNPs) has been investigated via molecular dynamics simulation. In these simulations, all the constituent atoms of the nanoparticles were considered to be dynamic. The geometries of amino acids, when adsorbed on the nanoparticle, were studied and their flexibilities were compared with one another. The interaction of each of 20 amino acids was considered with 3 and 8 nm gold GNPs.

  16. Inhibitors of amino acids biosynthesis as antifungal agents.

    Science.gov (United States)

    Jastrzębowska, Kamila; Gabriel, Iwona

    2015-02-01

    Fungal microorganisms, including the human pathogenic yeast and filamentous fungi, are able to synthesize all proteinogenic amino acids, including nine that are essential for humans. A number of enzymes catalyzing particular steps of human-essential amino acid biosynthesis are fungi specific. Numerous studies have shown that auxotrophic mutants of human pathogenic fungi impaired in biosynthesis of particular amino acids exhibit growth defect or at least reduced virulence under in vivo conditions. Several chemical compounds inhibiting activity of one of these enzymes exhibit good antifungal in vitro activity in minimal growth media, which is not always confirmed under in vivo conditions. This article provides a comprehensive overview of the present knowledge on pathways of amino acids biosynthesis in fungi, with a special emphasis put on enzymes catalyzing particular steps of these pathways as potential targets for antifungal chemotherapy.

  17. Astrobionibbler: In Situ Microfluidic Subcritical Water Extraction of Amino Acids

    Science.gov (United States)

    Noell, A. C.; Fisher, A. M.; Takano, N.; Fors-Francis, K.; Sherrit, S.; Grunthaner, F.

    2016-10-01

    A fluidic-chip based instrument for subcritical water extraction (SCWE) of amino acids and other organics from powder samples has been developed. A variety of soil analog extractions have been performed to better understand SCWE capabilities.

  18. AMINO ACID BLOOD POOL OF CHILDREN WITH ALLERGIC DISEASES

    Directory of Open Access Journals (Sweden)

    Shmulich O. V.

    2014-01-01

    Full Text Available The amino acid blood pool of children with atopic dermatitis, bronchial asthma, urticaria, angioedema was investigated. The variability of blood plasma amino acid content (tryptophan, histidine, tyrosine, cysteine, methionine was observed. The changes of histidine and tryptophan levels might be connected with the formation of biogenic amines, such as histamine, serotonine, with take part in the development of allergic reactions and inflammatory processes in organism.

  19. Expression of heteromeric amino acid transporters along the murine intestine.

    Science.gov (United States)

    Dave, Mital H; Schulz, Nicole; Zecevic, Marija; Wagner, Carsten A; Verrey, Francois

    2004-07-15

    Members of the new heterodimeric amino acid transporter family are composed of two subunits, a catalytic multitransmembrane spanning protein (light chain) and a type II glycoprotein (heavy chain). These transporters function as exchangers and thereby extend the transmembrane amino acid transport selectivity to specific amino acids. The heavy chain rBAT associates with the light chain b degrees (,+)AT to form a cystine and cationic amino acid transporter. The other heavy chain, 4F2hc, can interact with seven different light chains to form various transporters corresponding to systems L, y(+)L, asc or x(-)(c). The importance of some of these transporters in intestinal and renal (re)absorption of amino acids is highlighted by the fact that mutations in either the rBAT or b degrees (,+)AT subunit result in cystinuria whereas a defect in the y(+)-LAT1 light chain causes lysinuric protein intolerance. Here we investigated the localization of these transporters in intestine since both diseases are also characterized by altered intestinal amino acid absorption. Real time PCR showed organ-specific expression patterns for all transporter subunit mRNAs along the intestine and Western blotting confirmed these findings on the protein level. Immunohistochemistry demonstrated basolateral coexpression of 4F2hc, LAT2 and y(+)-LAT1 in stomach and small intestine, whereas rBAT and b degrees (,+)AT were found colocalizing on the apical side of small intestine epithelium. In stomach, 4F2hc and LAT2 were localized in H(+)/K(+)-ATPase-expressing parietal cells. The abundant expression of several members of the heterodimeric transporter family along the murine small intestine suggests their involvement in amino acids absorption. Furthermore, strong expression of rBAT, b degrees (,+)AT and y(+)-LAT1 in the small intestine explains the reduced intestinal absorption of some amino acid in patients with cystinuria or lysinuric protein intolerance.

  20. Co2 chemosorption by functionalized amino acid derivatives

    DEFF Research Database (Denmark)

    2015-01-01

    The absorption and desorption behaviour of carbon dioxide (CO2) using a composition comprising an ionic compound comprising a cation [A+] and an anion [B-] is described, wherein the anion [B-] is a mono-amine functionalized amino acid.......The absorption and desorption behaviour of carbon dioxide (CO2) using a composition comprising an ionic compound comprising a cation [A+] and an anion [B-] is described, wherein the anion [B-] is a mono-amine functionalized amino acid....

  1. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    Science.gov (United States)

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  2. Asymmetric synthesis of α-amino-1,3-dithianes via chiral N-phosphonyl imine-based Umpolung reaction without using chromatography and recrystallization.

    Science.gov (United States)

    Kattamuri, Padmanabha V; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-04-15

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane-ethyl acetate.

  3. Determination of (alpha)-dialkylamino acids and their Enantiomers in Geological Samples by High-Performance Liquid Chromatography after Dervatization with a Chiral Adduct of (omicron)-Phthaldialdehyde

    Science.gov (United States)

    Zhoa, Meixun; Bada, Jeffrey L.

    1995-01-01

    Derivatization with (omicron)-phthaldialdehyde (OPA) and the chiral thiol N-acetyl-L-cysteine (NAC) is a convenient and sensitive technique for the HPLC detection and resolution of protein amino acid enantiomers. The kinetics of the reaction of OPA-NAC with (alpha)-dialkylamino acids was investigated. The fluorescence yield of (alpha)-dialkylamino acids was only about 10% of that of protein amino acids when the derivatization was carried out at room temperature for 1-2 min, which is the procedure generally used for protein amino acid analyses. The fluorescence yield of (alpha)-dialkylamino acids can be enhanced by up to ten-fold when the derivatization reaction time is increased to 15 min at room temperature. The OPA-NAC technique was optimized for the detection and enantiomeric resolution of a-dialkylamino acids in geological samples which contain a large excess of protein amino acids. The estimated detection limit for a-dialkylamino acids is 1-2 pmol, comparable to that for protein amino acids.

  4. Amino acid modifiers in guayule rubber compounds

    Science.gov (United States)

    Tire producers are increasingly interested in biobased materials, including rubber but also as compounding chemicals. An alternative natural rubber for tire use is produced by guayule, a woody desert shrub native to North America. Alternative compounding chemicals include naturally-occurring amino a...

  5. Release of selected amino acids from zinc carriers

    Directory of Open Access Journals (Sweden)

    Dyja Renata

    2016-06-01

    Full Text Available The paper deals with the results of an investigation of the release of selected amino acids (histidine, tryptophan, tyrosine from model suspensions prepared by co-precipitation with zinc chloride. It has been proven that the influence of the Zn(II/amino acid molar ratio on dissolution profiles of the tested amino acids and dissolution half-life (t1/2 of histidine or tryptophan is significant. The amount of amino acid in the dispersed phase (supporting dose is a determinant of the amino acid release profile. There is a minimal supporting dose (30.0 μmol of histidine or 17.4 μmol of tryptophan that provides release of similar amounts of amino acid (4.1–4.6 μmol of histidine or 8.7–9.9 μmol of tryptophan after the same time intervals. The tyrosine release profiles follow first order kinetics since the supporting dose (0.9–11.2 μmol is limited by the tyrosine low solubility in water.

  6. Computational protein design quantifies structural constraints on amino acid covariation.

    Directory of Open Access Journals (Sweden)

    Noah Ollikainen

    Full Text Available Amino acid covariation, where the identities of amino acids at different sequence positions are correlated, is a hallmark of naturally occurring proteins. This covariation can arise from multiple factors, including selective pressures for maintaining protein structure, requirements imposed by a specific function, or from phylogenetic sampling bias. Here we employed flexible backbone computational protein design to quantify the extent to which protein structure has constrained amino acid covariation for 40 diverse protein domains. We find significant similarities between the amino acid covariation in alignments of natural protein sequences and sequences optimized for their structures by computational protein design methods. These results indicate that the structural constraints imposed by protein architecture play a dominant role in shaping amino acid covariation and that computational protein design methods can capture these effects. We also find that the similarity between natural and designed covariation is sensitive to the magnitude and mechanism of backbone flexibility used in computational protein design. Our results thus highlight the necessity of including backbone flexibility to correctly model precise details of correlated amino acid changes and give insights into the pressures underlying these correlations.

  7. D-Amino Acids in the Nervous and Endocrine Systems

    Directory of Open Access Journals (Sweden)

    Yoshimitsu Kiriyama

    2016-01-01

    Full Text Available Amino acids are important components for peptides and proteins and act as signal transmitters. Only L-amino acids have been considered necessary in mammals, including humans. However, diverse D-amino acids, such as D-serine, D-aspartate, D-alanine, and D-cysteine, are found in mammals. Physiological roles of these D-amino acids not only in the nervous system but also in the endocrine system are being gradually revealed. N-Methyl-D-aspartate (NMDA receptors are associated with learning and memory. D-Serine, D-aspartate, and D-alanine can all bind to NMDA receptors. H2S generated from D-cysteine reduces disulfide bonds in receptors and potentiates their activity. Aberrant receptor activity is related to diseases of the central nervous system (CNS, such as Alzheimer’s disease, amyotrophic lateral sclerosis, and schizophrenia. Furthermore, D-amino acids are detected in parts of the endocrine system, such as the pineal gland, hypothalamus, pituitary gland, pancreas, adrenal gland, and testis. D-Aspartate is being investigated for the regulation of hormone release from various endocrine organs. Here we focused on recent findings regarding the synthesis and physiological functions of D-amino acids in the nervous and endocrine systems.

  8. Cytokinin producing bacteria stimulate amino acid deposition by wheat roots.

    Science.gov (United States)

    Kudoyarova, Guzel R; Melentiev, Alexander I; Martynenko, Elena V; Timergalina, Leila N; Arkhipova, Tatiana N; Shendel, Galina V; Kuz'mina, Ludmila Yu; Dodd, Ian C; Veselov, Stanislav Yu

    2014-10-01

    Phytohormone production is one mechanism by which rhizobacteria can stimulate plant growth, but it is not clear whether the bacteria gain from this mechanism. The hypothesis that microbial-derived cytokinin phytohormones stimulate root exudation of amino acids was tested. The rhizosphere of wheat plants was drenched with the synthetic cytokinin trans-zeatin or inoculated with Bacillus subtilis IB-22 (which produces zeatin type cytokinins) or B. subtilis IB-21 (which failed to accumulate cytokinins). Growing plants in a split root system allowed spatial separation of zeatin application or rhizobacterial inoculation to one compartment and analyses of amino acid release from roots (rhizodeposition) into the other compartment (without either microbial inoculation or treatment with exogenous hormone). Supplying B. subtilis IB-22 or zeatin to either the whole root system or half of the roots increased concentrations of amino acids in the soil solution although the magnitude of the increase was greater when whole roots were treated. There was some similarity in amino acid concentrations induced by either bacterial or zeatin treatment. Thus B. subtilis IB-22 increased amino acid rhizodeposition, likely due to its ability to produce cytokinins. Furthermore, B. subtilis strain IB-21, which failed to accumulate cytokinins in culture media, did not significantly affect amino acid concentrations in the wheat rhizosphere. The ability of rhizobacteria to produce cytokinins and thereby stimulate rhizodeposition may be important in enhancing rhizobacterial colonization of the rhizoplane.

  9. The preferences of orientations between the Pairs of amino acids

    Institute of Scientific and Technical Information of China (English)

    Chen Ying; Wang Jun; Wang Wei

    2007-01-01

    In this work,we make an investigation on the preferences of orientations between amino acids using the orientation defined based on the local geometry of the amino acids concerned.It is found that there are common preferences of orientations (70°,30°,140°) and (110°,340°,100°) for various pairs of amino acids.Different side chains may strengthen or weaken the common preferences,which is related to the effect of packing.Some amino acids having specific local flexibility may possess some preferences of orientations besides the common ones,such as (10°,280°,210°) .Another analysis on the pairs of the amino acids with different secondary-structure preferences shows that the directional interaction may affect the distribution of orientation more effectively than the packing or local flexibility.All these results provide us some insight of the organization of amino acids in protein,and their relation with some related interactions.

  10. Extraterrestrial Amino Acids in Ureilites Including Almahata Sitta

    Science.gov (United States)

    Burton, A. S.; Glavin, D. P.; Callahan, M. P.; Dworkin, J. P.

    2011-01-01

    Ureilites are a class of meteorites that lack chondrules (achondrites) but have relatively high carbon abundances, averaging approx.3 wt %. Using highly sensitive liquid chromatography coupled with UV fluorescence and time-of-flight mass spectrometry (LC-FD/ToF-MS), it was recently determined that there are amino acids in. fragment 94 of the Almahata Sitta ureilite[l]. Based on the presence of amino acids that are rare in the Earth's biosphere, as well as the near-racemic enantiomeric ratios of marry of the more common amino acids, it was concluded that most of the detected amino acids were indigenous to the meteorite. Although the composition of the Almahata Sitta ureilite appears to be unlike other recovered ureilites, the discovery of amino acids in this meteorite raises the question of whether other ureilites rnav also contain amino acids. Herein we present the results of LC-FDlTo.F-MS analyses of: a sand sample from the Almahata Sitta strewn held, Almahata Sitta fragments 425 (an ordinary H5 chondrite) and 427 (ureilite), as well as an Antarctic ureilite (Allan lulls, ALHA 77257).

  11. Theoretical study on the acidities of chiral phosphoric acids in dimethyl sulfoxide: hints for organocatalysis.

    Science.gov (United States)

    Yang, Chen; Xue, Xiao-Song; Jin, Jia-Lu; Li, Xin; Cheng, Jin-Pei

    2013-07-19

    The pKa values of 41 chiral phosphoric acid-family catalysts in DMSO were predicted using the SMD/M06-2x/6-311++G(2df,2p)//B3LYP/6-31+G(d) method for the first time. The study showed that the calculated pKa's range from -4.23 to 6.16 for absolute pKa values and from -4.21 to 6.38 for relative pKa values. Excellent agreement between the calculated and experimental pKa's was achieved for the few available cases (to a precision of around 0.4 pKa unit), indicating that this strategy may be suitable for calculating highly accurate pKa's. A good linear correlation between the pKa's for 3 and 3' disubstituted phenyl BINOL phosphoric acids and the Hammett constants was obtained. The relationship between the acidities of phosphoric acid catalysts and their reaction activity and selectivity was also discussed. Knowledge of the pKa values of phosphoric acids should be of great value for the understanding of chiral Brønsted acid-catalyzed reactions and may aid in future catalyst design.

  12. 77 FR 65537 - Requirements for Patent Applications Containing Nucleotide Sequence and/or Amino Acid Sequence...

    Science.gov (United States)

    2012-10-29

    ... Amino Acid Sequence Disclosures ACTION: Proposed collection; comment request. SUMMARY: The United States....'' SUPPLEMENTARY INFORMATION: I. Abstract Patent applications that contain nucleotide and/or amino acid...

  13. Amino Acid Synthesis in a Supercritical Carbon Dioxide - Water System

    OpenAIRE

    2009-01-01

    Mars is a CO2-abundant planet, whereas early Earth is thought to be also CO2-abundant. In addition, water was also discovered on Mars in 2008. From the facts and theory, we assumed that soda fountains were present on both planets, and this affected amino acid synthesis. Here, using a supercritical CO2/liquid H2O (10:1) system which mimicked crust soda fountains, we demonstrate production of amino acids from hydroxylamine (nitrogen source) and keto acids (oxylic acid sources). In this research...

  14. Abiotic Racemization Kinetics of Amino Acids in Marine Sediments

    OpenAIRE

    Steen, Andrew D.; Bo Barker Jørgensen; Bente Aa Lomstein

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth be...

  15. Digestible indispensable amino acid score and digestible amino acids in eight cereal grains.

    Science.gov (United States)

    Cervantes-Pahm, Sarah K; Liu, Yanhong; Stein, Hans H

    2014-05-01

    To determine values for the digestible indispensable amino acid score (DIAAS), it is recommended that ileal amino acid (AA) digestibility values obtained in growing pigs are used to characterise protein quality in different foods. Therefore, an experiment was conducted to determine the standardised ileal digestibility (SID) of AA in eight cereal grains (yellow dent maize, Nutridense maize, dehulled barley, dehulled oats, polished white rice, rye, sorghum and wheat) fed to pigs, where SID values in pigs can be used to calculate approximate DIAAS values in humans. In the present experiment, twenty-four barrows with a T-cannula inserted in the distal ileum were allotted to eight diets and fed for three periods to give a total of nine replicate pigs per diet. Each period lasted 14 d, and ileal digesta samples were collected on days 13 and 14. Among the SID values obtained for all cereal grains, values for total indispensable AA were greatest (P< 0·05) in rice and lowest (P< 0·05) in rye and sorghum. The concentrations of SID indispensable AA in rice were less (P< 0·05) than in dehulled oats, but greater (P< 0·05) than in the other cereal grains, and the concentrations of SID indispensable AA in Nutridense maize were greater (P< 0·05) than in yellow dent maize and sorghum, but less (P< 0·05) than in the other cereal grains, except rye. In conclusion, results indicate that to meet dietary requirements for AA in humans, diets based on yellow dent maize or sorghum require more AA supplementation than diets based on other cereal grains.

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

    Directory of Open Access Journals (Sweden)

    Yogesh K. Choughule

    2016-05-01

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

  17. Abiotic racemization kinetics of amino acids in marine sediments.

    Science.gov (United States)

    Steen, Andrew D; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5)-11×10(-5) yr(-1). These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  18. Primordial Synthesis of Amines and Amino Acids in a 1958 Miller H2S-Rich Spark Discharge Experiment

    Science.gov (United States)

    Parker, Eric T.; Cleaves, Henderson J.; Dworkin, Jason P.; Glavin, Daniel P.; Callahan, Michael; Aubrey, Andrew; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordia! environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

  19. Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Amino Acids.

    Science.gov (United States)

    Sanchez-Sanchez, Ana; Rivilla, Ivan; Agirre, Maddalen; Basterretxea, Andere; Etxeberria, Agustin; Veloso, Antonio; Sardon, Haritz; Mecerreyes, David; Cossío, Fernando P

    2017-03-22

    Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac-lactide (rac-LA). We have polymerized rac-LA using the diastereomeric densely substituted amino acids (2S,3R,4S,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (endo-6) and (2S,3S,4R,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (exo-6), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a Pm higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers (l or d) with respect to the other. Thus, exo-6 preferentially polymerized l-lactide, whereas endo-6 preferred d-lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.

  20. The interaction of amino acids, peptides, and proteins with DNA.

    Science.gov (United States)

    Solovyev, Andrey Y; Tarnovskaya, Svetlana I; Chernova, Irina A; Shataeva, Larisa K; Skorik, Yury A

    2015-01-01

    Amino acids that carry charges on their side groups can bind to double stranded DNA (dsDNA) and change the strength of the double helix. Measurement of the DNA melting temperature (Tm) confirmed that acidic amino acids (Glu, Asp) weaken the H-bonds between DNA strands, whereas basic amino acids (Arg, Lys) strengthen the interaction between the strands. A rank correlation exists between the amino acid isoelectric points and the observed changes in Tm. A similar dependence of the hyperchromic effect on the isoelectric point of a protein (pepsin, insulin, cortexin, and protamine) was observed for DNA-protein complexes at room temperature. Short peptides (KE, AEDG, and KEDP) containing a mixture of acidic and basic amino acid residues also affect Tm and the stability of the double helix. A model for binding Glu and Lys to dsDNA was explored by a docking simulation. The model shows that Glu, in an untwisted shape, binds to dsDNA in its major groove and disrupts three H-bonds between the strands, thereby destabilizing the double helix. Lys, in an untwisted shape, binds to the external side of the dsDNA and forms two bonds with O atoms of neighboring phosphodiester groups, thereby strengthening the DNA helix.

  1. Raman spectra of amino acids and their aqueous solutions

    Science.gov (United States)

    Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

    2011-03-01

    Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

  2. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    Science.gov (United States)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  3. Chiral Phosphoric Acid Catalyzed Enantioselective Allylation of Aldehydes with Allyltrichlorosilane%Chiral Phosphoric Acid Catalyzed Enantioselective Allylation of Aldehydes with Allyltrichlorosilane

    Institute of Scientific and Technical Information of China (English)

    程柯; 范甜甜; 孙健

    2011-01-01

    Easily accessible chiral phosphoric acid lb has been applied as efficient organocatalyst for the asymmetric al- lylation of aldehydes with allyltrichlorosilane. In the presence of 20 mol% of lb, the allylation of a broad range of aldehydes proceeded smoothly to give the corresponding homoallylic alcohol with up to 87% ee and 97% yield.

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

    Institute of Scientific and Technical Information of China (English)

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

    2007-01-01

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

  5. Synthesis and Biological Activity of Novel Amino Acid-(N'-Benzoyl Hydrazide and Amino Acid-(N'-Nicotinoyl Hydrazide Derivatives

    Directory of Open Access Journals (Sweden)

    Sherine N. Khattab

    2005-09-01

    Full Text Available The coupling reaction of benzoic acid and nicotinic acid hydrazides with N- protected L-amino acids including valine, leucine, phenylalanine, glutamic acid and tyrosine is reported. The target compounds, N-Boc-amino acid-(N`-benzoyl- and N- Boc-amino acid-(N`-nicotinoyl hydrazides 5a-5e and 6a-6e were prepared in very high yields and purity using N-[(dimethylamino-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl- methylene]-N-methyl-methanaminium hexafluorophosphate N-oxide (HATU as coupling reagent. The antimicrobial activity of the Cu and Cd complexes of the designed compounds was tested. The products were deprotected affording the corresponding amino acid-(N`-benzoyl hydrazide hydrochloride salts (7a-7e and amino acid-(N`- nicotinoyl hydrazide hydrochloride salts (8a-8e. These compounds and their Cu and Cd complexes were also tested for their antimicrobial activity. Several compounds showed comparable activity to that of ampicillin against S. aureus and E. coli.

  6. Supramolecular chiral host-guest nanoarchitecture induced by the selective assembly of barbituric acid derivative enantiomers

    Science.gov (United States)

    Sun, Xiaonan; Silly, Fabien; Maurel, Francois; Dong, Changzhi

    2016-10-01

    Barbituric acid derivatives are prochiral molecules, i.e. they are chiral upon adsorption on surfaces. Scanning tunneling microscopy reveals that barbituric acid derivatives self-assemble into a chiral guest-host supramolecular architecture at the solid-liquid interface on graphite. The host nanoarchitecture has a sophisticated wavy shape pattern and paired guest molecules are nested insides the cavities of the host structure. Each unit cell of the host structure is composed of both enantiomers with a ratio of 1:1. Furthermore, the wavy patterns of the nanoarchitecture are formed from alternative appearance of left- and right-handed chiral building blocks, which makes the network heterochiral. The functional guest-host nanoarchitecture is the result of two-dimensional chiral amplification from single enantiomers to organizational heterochiral supramolecular self-assembly.

  7. Amino acids in dew - origin and seasonal variation

    Science.gov (United States)

    Scheller, Edwin

    At two sites in the Armenhof district, 10 km east of Fulda, Germany, dew samples were collected from June 1996 to June 1997 and investigated for free and protein-bound amino acids. On account of the high pollen content, at the beginning of June 1996 and in May 1997 total amino acid concentrations were 53-390 μmol l -1, in one sample 922 μmol l -1. At other times the concentration in dew was 8-164 μmol l -1. On 4 and 5 June 1996 the diluted free amino acid fraction (DFAA) of the total hydrolysed amino acids (THAA) at both sites amounted to 35-44% and was predominantly arginine, proline and glutamine/glutamate. Likewise on 11 March 1997 the fraction of DFAA was found to be 39.5% with extremely high arginine and proline fractions. At other times the DFAA-fraction was in the range 14-26%. From July 1996 to June 1997 the amino acid concentrations in the vapours rising from a meadow were also measured and it ranged from 8 to 51 μmol l -1. From July to October 1996 the amino acid composition in the hydrolysates of dew samples and meadow vapours collected overnight were almost identical. The DFAA fraction in the condensation water collected overnight from the meadow varied from 18 to 40%. From 4 to 6 June 1996, on 11 and 13 March 1997 and in the period 16-20 May 1997, the amino acid distribution in dew showed much variation. The percentage fraction of arginine and proline in the hydrolysate increased greatly, whereas that of glycine and serine decreased. The large increase in proline and arginine in hydrolysate is attributable solely to the large amounts of free arginine and proline. This effect occurred in both 1996 and 1997 over several days at both sites at any one time and therefore appears confirmed.

  8. Alterations in amino acid status in cats with feline dysautonomia

    Science.gov (United States)

    Symonds, Herb W.; Knottenbelt, Clare; Cave, Tom A.; MacDonald, Susan J.; Stratton, Joanna; Leon, Irene; Turner, Judith A.; Pirie, R. Scott

    2017-01-01

    Feline dysautonomia (FD) is a multiple system neuropathy of unknown aetiology. An apparently identical disease occurs in horses (equine grass sickness, EGS), dogs, rabbits, hares, sheep, alpacas and llamas. Horses with acute EGS have a marked reduction in plasma concentrations of the sulphur amino acids (SAA) cyst(e)ine and methionine, which may reflect exposure to a neurotoxic xenobiotic. The aim of this study was to determine whether FD cats have alterations in amino acid profiles similar to those of EGS horses. Amino acids were quantified in plasma/serum from 14 FD cats, 5 healthy in-contact cats which shared housing and diet with the FD cats, and 6 healthy control cats which were housed separately from FD cats and which received a different diet. The adequacy of amino acids in the cats’ diet was assessed by determining the amino acid content of tinned and dry pelleted foods collected immediately after occurrences of FD. Compared with controls, FD cats had increased concentrations of many essential amino acids, with the exception of methionine which was significantly reduced, and reductions in most non-essential amino acids. In-contact cats also had inadequate methionine status. Artefactual loss of cysteine during analysis precluded assessment of the cyst(e)ine status. Food analysis indicated that the low methionine status was unlikely to be attributable to dietary inadequacy of methionine or cystine. Multi-mycotoxin screening identified low concentrations of several mycotoxins in dry food from all 3 premises. While this indicates fungal contamination of the food, none of these mycotoxins appears to induce the specific clinico-pathologic features which characterise FD and equivalent multiple system neuropathies in other species. Instead, we hypothesise that ingestion of another, as yet unidentified, dietary neurotoxic mycotoxin or xenobiotic, may cause both the characteristic disease pathology and the plasma SAA depletion. PMID:28333983

  9. Thyroid peroxidase activity is inhibited by amino acids

    Directory of Open Access Journals (Sweden)

    D.P. Carvalho

    2000-03-01

    Full Text Available Normal in vitro thyroid peroxidase (TPO iodide oxidation activity was completely inhibited by a hydrolyzed TPO preparation (0.15 mg/ml or hydrolyzed bovine serum albumin (BSA, 0.2 mg/ml. A pancreatic hydrolysate of casein (trypticase peptone, 0.1 mg/ml and some amino acids (cysteine, tryptophan and methionine, 50 µM each also inhibited the TPO iodide oxidation reaction completely, whereas casamino acids (0.1 mg/ml, and tyrosine, phenylalanine and histidine (50 µM each inhibited the TPO reaction by 54% or less. A pancreatic digest of gelatin (0.1 mg/ml or any other amino acid (50 µM tested did not significantly decrease TPO activity. The amino acids that impair iodide oxidation also inhibit the TPO albumin iodination activity. The inhibitory amino acids contain side chains with either sulfur atoms (cysteine and methionine or aromatic rings (tyrosine, tryptophan, histidine and phenylalanine. Among the amino acids tested, only cysteine affected the TPO guaiacol oxidation reaction, producing a transient inhibition at 25 or 50 µM. The iodide oxidation inhibitory activity of cysteine, methionine and tryptophan was reversed by increasing iodide concentrations from 12 to 18 mM, while no such effect was observed when the cofactor (H2O2 concentration was increased. The inhibitory substances might interfere with the enzyme activity by competing with its normal substrates for their binding sites, binding to the free substrates or reducing their oxidized form.

  10. A set of amino acids found to occur more frequently in human and fly than in plant and yeast proteomes consists of non-essential amino acids

    OpenAIRE

    2007-01-01

    We investigated the hypothesis that essential amino acids are being replaced in proteins by non-essential amino acids.We compared the amino acid composition in human, worm and fly proteomes, organisms that cannot synthesize all amino acids, with the amino acids of the proteomes of plant, bakers yeast and budding yeast, which are capable of synthesizing them. The analysis covered 460,737 proteins (212,197,907 amino acids). The data suggest a bias towards the usage of non-essential ami...

  11. Chiral amide from (1, 2)-(+)-norephedrine and furoic acid: An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    Nallamuthu Ananthi; Sivan Velmathi

    2014-01-01

    Chiral amide derived from (1, 2)-(+)-norephedrine and 2-furoic acid was found to catalyse the asymmetric Reformatsky reaction between prochiral aldehydes and α-bromo ethylacetate with diethylzinc as zinc source. The corresponding chiral -hydroxy esters were formed in 99% yield with over 80% enantiomeric excess. The presence of air was found to be essential for the effective C-C bond formation. The mechanism for the catalytic reaction was proposed.

  12. (-)-Hydroxycitric Acid Nourishes Protein Synthesis via Altering Metabolic Directions of Amino Acids in Male Rats.

    Science.gov (United States)

    Han, Ningning; Li, Longlong; Peng, Mengling; Ma, Haitian

    2016-08-01

    (-)-Hydroxycitric acid (HCA), a major active ingredient of Garcinia Cambogia extracts, had shown to suppress body weight gain and fat accumulation in animals and humans. While, the underlying mechanism of (-)-HCA has not fully understood. Thus, this study was aimed to investigate the effects of long-term supplement with (-)-HCA on body weight gain and variances of amino acid content in rats. Results showed that (-)-HCA treatment reduced body weight gain and increased feed conversion ratio in rats. The content of hepatic glycogen, muscle glycogen, and serum T4 , T3 , insulin, and Leptin were increased in (-)-HCA treatment groups. Protein content in liver and muscle were significantly increased in (-)-HCA treatment groups. Amino acid profile analysis indicated that most of amino acid contents in serum and liver, especially aromatic amino acid and branched amino acid, were higher in (-)-HCA treatment groups. However, most of the amino acid contents in muscle, especially aromatic amino acid and branched amino acid, were reduced in (-)-HCA treatment groups. These results indicated that (-)-HCA treatment could reduce body weight gain through promoting energy expenditure via regulation of thyroid hormone levels. In addition, (-)-HCA treatment could promote protein synthesis by altering the metabolic directions of amino acids. Copyright © 2016 John Wiley & Sons, Ltd.

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

    Science.gov (United States)

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

    2015-01-01

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

  14. Absolute quantitation of proteins by Acid hydrolysis combined with amino Acid detection by mass spectrometry

    DEFF Research Database (Denmark)

    Mirgorodskaya, Olga A; Körner, Roman; Kozmin, Yuri P;

    2012-01-01

    Amino acid analysis is among the most accurate methods for absolute quantification of proteins and peptides. Here, we combine acid hydrolysis with the addition of isotopically labeled standard amino acids and analysis by mass spectrometry for accurate and sensitive protein quantitation...

  15. Facile synthesis of α-hydroxy carboxylic acids from the corresponding α-amino acids

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Padrah, Shahrokh; Strømgaard, Kristian

    2014-01-01

    An effective and improved procedure is developed for the synthesis of α-hydroxy carboxylic acids by treatment of the corresponding protonated α-amino acid with tert-butyl nitrite in 1,4-dioxane-water. The amino moiety must be protonated and located α to a carboxylic acid function in order...

  16. Valuable biomolecules from nine North Atlantic red macroalgae: Amino acids, fatty acids, carotenoids, minerals and metals

    DEFF Research Database (Denmark)

    Razi Parjikolaei, Behnaz; Bruhn, Annette; Eybye, Karin Loft

    2016-01-01

    , glutamic acid, and arginine, respectively. The amino acid score of the nine algae varied from 44% to 92%, the most commonly first limiting amino acid being histidine. Lutein, β-carotene, and zeaxanthin were the identified carotenoids. Contents of all macro and trace minerals, with the exception...

  17. Effects of amino acid additives during hemodialysis of children.

    Science.gov (United States)

    Abitbol, C L; Mrozinska, K; Mandel, S; McVicar, M; Wapnir, R A

    1984-01-01

    The intradialytic losses into the dialysate of free amino acids (AA) and alpha-amino nitrogen were determined during the dialysis of three children. Variations in plasma AA were determined pre- and postdialysis. The effect of these losses with the addition of an Abbott General Amino Acid Mixture to the dialysate in concentrations of 8.5, 17, and 34 mg/100 ml was studied. The major determinant of AA losses was the plasma concentration of the AA before beginning the dialysis treatment. Dialysance of individual AA varied inversely with their molecular weights. A zero flux of alpha-amino nitrogen occurred at a derived concentration of 22 mg/100 ml of the AA additive in the dialysate. Plasma concentrations of nonessential amino acids were little affected by the dialysate additive. In contrast, total essential amino acid nitrogen which fell during baseline dialyses showed significant improvement when the AA solution was added to the dialysate. This study suggests that the addition of AA to the dialysate bath may be effective in decreasing AA nitrogen losses during dialysis.

  18. 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.

    Science.gov (United States)

    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.

  19. RESEARCH ON THE POLYCONDENSATION KINETICS OF ω-AMINO-ACIDS

    Institute of Scientific and Technical Information of China (English)

    WANG Baoren; SHI Manli; QIAN Chunqing

    1983-01-01

    In our previous report, it was discovered that the polycondensation of 9-amino-nonanoic acid follows second order from the beginning up to the extent of reaction, p, around 99%, and after which the reaction changes rapidly to third order. In this paper, we wish to report that this change of the reaction order from second to third occurred also in the polycondensation of 6aminocaproic acid and 11-amino-undecanoic acid. The transition region lay again at p around 99%.It may be concluded that this is a general rule in the polycondensation of the ω-amino-acids (monomers of the A-B type), and the controversial results that appeared in the literature may be cleared up by our experiments.

  20. Fungal Peptaibiotics: Assessing Potential Meteoritic Amino Acid Contamination

    Science.gov (United States)

    Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Dworkin, J. P.; Bruckner, H.

    2010-01-01

    The presence of non-protein alpha-dialkyl-amino acids such as alpha-aminoisobutyric acid (alpha-A1B) and isovaline (Iva), which are relatively rare in the terrestrial biosphere, has long been used as an indication of the indigeneity of meteoritic amino acids, however, the discovery of alpha-AIB in peptides producers by a widespread group of filamentous fungi indicates the possibility of a terrestrial biotic source for the alpha-AIB observed in some meteorites. The alpha-AIB-containing peptides produced by these fungi are dubbed peptaibiotics. We measured the molecular distribution and stable carbon and nitrogen isotopic ratios for amino acids found in the total hydrolysates of four biologically synthesized peptaibiotics. We compared these aneasurenetts with those from the CM2 carbonaceous chondrite Murchison and from three Antarctic CR2 carbonaceous chondrites in order to understand the peptaibiotics as a potential source of meteoritic contamination.

  1. Amino acid catabolism by Lactobacillus helveticus in cheese

    DEFF Research Database (Denmark)

    Kananen, Soila Kaarina

    Amino acid catabolism is the final step in the conversion of caseins to flavour compounds and a part of a complex combination of biochemical pathways in cheese flavour formation. Lactobacillus helveticus is a thermophilic lactic acid bacterium that is used in cheese manufacture as a primary starter...... culture or as an adjunct culture. It has shown high proteolytic activities in conversion of caseins to peptides and further to amino acids and flavour compounds. Better understanding of the enzyme activity properties and the influence of different properties on final cheese flavour is favourable...... for developing new cheese products with enhanced flavour. The aim of this Ph.D. study was to investigate the importance of strain variation of Lb. helveticus in relation flavour formation in cheese related to amino acid catabolism. Aspects of using Lb. helveticus as starter as well as adjunct culture in cheese...

  2. Complete amino acid sequence of the Aspergillus cytotoxin mitogillin

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Luna, J.L.; Lopez-Otin, C.; Soriano, F.; Mendez, E.

    1985-02-12

    The complete amino acid sequence of the cytotoxin mitogillin has been determined by sequencing the intact chain and peptide fragments produced by cleavage at methionyl, arginyl, lysyl, and tryptophanyl residues and at one aspartic acid-proline bond. The protein consists of 149 amino acid residues with alanine at the NH/sub 2/ terminus and histidine at the COOH terminus. The calculated Mr of the native mitogillin was 16,867. The native molecule presents two disulfide bridges, one between cysteine residues at positions 5 and 147 and another one between cysteine residues at positions 75 and 131. The amino acid sequence of mitogillin shows 86% homology with another cytotoxic protein called alpha-sarcin.

  3. Amino acid analogs IV:4-fluoroisoleucine.

    Science.gov (United States)

    Gershon, H; Shanks, L; Clarke, D D

    1978-05-01

    4-Fluoroisoleucine was produced by ammonolysis of 2-bromo-4-fluoro-3-methylpentanoic acid, which resulted from the bromofluorination of 4-methyl-2-pentenoic acid. It did not inhibit Plasmodium berghei in mice at 640 mg/kg and was not toxic to the animals. The fluoroamino acid inhibited Aspergillus niger, Trichoderma viride, Myrothecium verrucaria, Trichophyton mentagrophytes, and Mucor mucedo in Czapek solution agar at a concentration between 10(4) and 10(3) microgram/ml. Growth of Escherichia coli was inhibited 25% at 900 microgram/ml in a defined medium.

  4. How Amino Acids and Peptides Shaped the RNA World

    Directory of Open Access Journals (Sweden)

    Peter T.S. van der Gulik

    2015-01-01

    Full Text Available The “RNA world” hypothesis is seen as one of the main contenders for a viable theory on the origin of life. Relatively small RNAs have catalytic power, RNA is everywhere in present-day life, the ribosome is seen as a ribozyme, and rRNA and tRNA are crucial for modern protein synthesis. However, this view is incomplete at best. The modern protein-RNA ribosome most probably is not a distorted form of a “pure RNA ribosome” evolution started out with. Though the oldest center of the ribosome seems “RNA only”, we cannot conclude from this that it ever functioned in an environment without amino acids and/or peptides. Very small RNAs (versatile and stable due to basepairing and amino acids, as well as dipeptides, coevolved. Remember, it is the amino group of aminoacylated tRNA that attacks peptidyl-tRNA, destroying the bond between peptide and tRNA. This activity of the amino acid part of aminoacyl-tRNA illustrates the centrality of amino acids in life. With the rise of the “RNA world” view of early life, the pendulum seems to have swung too much towards the ribozymatic part of early biochemistry. The necessary presence and activity of amino acids and peptides is in need of highlighting. In this article, we try to bring the role of the peptide component of early life back into focus. We argue that an RNA world completely independent of amino acids never existed.

  5. Differential regulation of placental amino acid transport by saturated and unsaturated fatty acids.

    Science.gov (United States)

    Lager, Susanne; Jansson, Thomas; Powell, Theresa L

    2014-10-15

    Fatty acids are critical for normal fetal development but may also influence placental function. We have previously reported that oleic acid (OA) stimulates amino acid transport in primary human trophoblasts (PHTs). In other tissues, saturated and unsaturated fatty acids have distinct effects on cellular signaling, for instance, palmitic acid (PA) but not OA reduces IκBα expression. We hypothesized that saturated and unsaturated fatty acids differentially affect trophoblast amino acid transport and cellular signaling. To test this hypothesis, PHTs were cultured in docosahexaenoic acid (DHA; 50 μM), OA (100 μM), or PA (100 μM). DHA and OA were also combined to test whether DHA could counteract the OA stimulatory effect on amino acid transport. The effects of fatty acids were compared against a vehicle control. Amino acid transport was measured by isotope-labeled tracers. Activation of inflammatory-related signaling pathways and the mechanistic target of rapamycin (mTOR) pathway were determined by Western blot analysis. Exposure of PHTs to DHA for 24 h reduced amino acid transport and phosphorylation of p38 MAPK, STAT3, mTOR, eukaryotic initiation factor 4E-binding protein 1, and ribosomal protein (rp)S6. In contrast, OA increased amino acid transport and phosphorylation of ERK, mTOR, S6 kinase 1, and rpS6. The combination of DHA with OA increased amino acid transport and rpS6 phosphorylation. PA did not affect amino acid transport but reduced IκBα expression. In conclusion, these fatty acids differentially regulated placental amino acid transport and cellular signaling. Taken together, these findings suggest that dietary fatty acids could alter the intrauterine environment by modifying placental function, thereby having long-lasting effects on the developing fetus.

  6. New optically active poly(amide-imide)s based on N,N '-(pyromellitoyl)-bis-L-amino acid and methylene diphenyl-4,4 '-diisocyanate

    DEFF Research Database (Denmark)

    Tian, Xiaoyu; Yao, Jinshui; Zhang, Xian;

    2014-01-01

    Five new optically active poly(amide-imide)s were synthesized through the direct polycondensation reaction between chiral N,N-(pyromellitoyl)-bis-L-amino acids and methylene diphenyl-4,4-diisocyanate in a medium consisting of N-methyl-2-pyrrolidone (NMP) and xylene. The resulted polymers were fully......,N-dimethyl formamide, dimethyl sulfoxide (DMSO), NMP, sulfuric acid, and para-methyl phenol. Same specific rotations of these polymers in these different solvents were obtained....

  7. Amino acid containing glass-ionomer cement for orthopedic applications

    Science.gov (United States)

    Wu, Wei

    Amino acid containing glass-ionomer cements were synthesized, formulated, and evaluated for orthopedic application. The formulation of different amino acid containing glass-ionomer bone cements was optimized, and conventional and resin-modified glass-ionomer bone cements were compared. Properties of interest included handling characteristics, physical and chemical properties, and mechanical strength of the bone cement. The study was based on the synthesis of different vinyl containing amino acids, different polyelectrolytes containing these amino acid residues, and different resin-modified polyelectrolytes, as well as formulation and evaluation of conventional and resin-modified glass-ionomer bone cements using these polyelectrolytes. Systematic preparation of polyelectrolytes and formulation of glass-ionomer bone cements were essential features of this work, since we anticipated that the mechanical properties of the glass-ionomer bone cements could be strongly affected by the nature of the polyelectrolytes and formulation. Mechanical properties were evaluated in a screw driven mechanical testing machine, and structure-property relationships were determined by scanning electron microscopic (SEM) observation of the fracture surface of the specimens. How the structure of polyelectrolytes, such as different amino acid residues, molecular weight, different modifying resin, and formulation of glass-ionomer bone cement, affected the mechanical properties was also studied.

  8. Impact of dietary aromatic amino acids on osteoclastic activity.

    Science.gov (United States)

    Refaey, Mona El; Zhong, Qing; Ding, Ke-Hong; Shi, Xing-Ming; Xu, Jianrui; Bollag, Wendy B; Hill, William D; Chutkan, Norman; Robbins, Richard; Nadeau, Hugh; Johnson, Maribeth; Hamrick, Mark W; Isales, Carlos M

    2014-08-01

    We had shown that aromatic amino acid (phenylalanine, tyrosine, and tryptophan) supplementation prevented bone loss in an aging C57BL/6 mice model. In vivo results from the markers of bone breakdown suggested an inhibition of osteoclastic activity or differentiation. To assess osteoclastic differentiation, we examined the effects of aromatic amino acids on early /structural markers as vitronectin receptor, calcitonin receptor, and carbonic anhydrase II as well as, late/functional differentiation markers; cathepsin K and matrix metalloproteinase 9 (MMP-9). Our data demonstrate that the aromatic amino acids down-regulated early and late osteoclastic differentiation markers as measured by real time PCR. Our data also suggest a link between the vitronectin receptor and the secreted cathepsin K that both showed consistent effects to the aromatic amino acid treatment. However, the non-attachment related proteins, calcitonin receptor, and carbonic anhydrase II, demonstrated less consistent effects in response to treatment. Our data are consistent with aromatic amino acids down-regulating osteoclastic differentiation by suppressing remodeling gene expression thus contributing initially to the net increase in bone mass seen in vivo.

  9. Detection of COL III in parchment by amino acid analysis.

    Science.gov (United States)

    Sommer, Dorte V P; Larsen, René

    2016-01-01

    Cultural heritage parchments made from the reticular dermis of animals have been subject to studies of deterioration and conservation by amino acid analysis. The reticular dermis contains a varying mixture of collagen I and III (COL I and III). When dealing with the results of the amino acid analyses, till now the COL III content has not been taken into account. Based on the available amino acid sequences, we present a method for determining the amount of COL III in the reticular dermis of new and historical parchments calculated from the ratio of Ile/Val. We find COL III contents between 7 and 32 % in new parchments and between 0.2 and 40 % in the historical parchments. This is consistent with results in the literature. The varying content of COL III has a significant influence on the uncertainty of the amino acid analysis. Although we have not found a simple correlation between the COL III content and the degree of deterioration, our results show that this question must be taken into consideration in future studies of the chemical and physical deterioration of parchment measured by amino acid analysis and other analytical methods.

  10. An amino acid depleted cell-free protein synthesis system for the incorporation of non-canonical amino acid analogs into proteins.

    Science.gov (United States)

    Singh-Blom, Amrita; Hughes, Randall A; Ellington, Andrew D

    2014-05-20

    Residue-specific incorporation of non-canonical amino acids into proteins is usually performed in vivo using amino acid auxotrophic strains and replacing the natural amino acid with an unnatural amino acid analog. Herein, we present an efficient amino acid depleted cell-free protein synthesis system that can be used to study residue-specific replacement of a natural amino acid by an unnatural amino acid analog. This system combines a simple methodology and high protein expression titers with a high-efficiency analog substitution into a target protein. To demonstrate the productivity and efficacy of a cell-free synthesis system for residue-specific incorporation of unnatural amino acids in vitro, we use this system to show that 5-fluorotryptophan and 6-fluorotryptophan substituted streptavidin retain the ability to bind biotin despite protein-wide replacement of a natural amino acid for the amino acid analog. We envisage this amino acid depleted cell-free synthesis system being an economical and convenient format for the high-throughput screening of a myriad of amino acid analogs with a variety of protein targets for the study and functional characterization of proteins substituted with unnatural amino acids when compared to the currently employed in vivo methodologies.

  11. Industrial production of amino acids by coryneform bacteria.

    Science.gov (United States)

    Hermann, Thomas

    2003-09-04

    In the 1950s Corynebacterium glutamicum was found to be a very efficient producer of L-glutamic acid. Since this time biotechnological processes with bacteria of the species Corynebacterium developed to be among the most important in terms of tonnage and economical value. L-Glutamic acid and L-lysine are bulk products nowadays. L-Valine, L-isoleucine, L-threonine, L-aspartic acid and L-alanine are among other amino acids produced by Corynebacteria. Applications range from feed to food and pharmaceutical products. The growing market for amino acids produced with Corynebacteria led to significant improvements in bioprocess and downstream technology as well as in molecular biology. During the last decade big efforts were made to increase the productivity and to decrease the production costs. This review gives an overview of the world market for amino acids produced by Corynebacteria. Significant improvements in bioprocess technology, i.e. repeated fed batch or continuous production are summarised. Bioprocess technology itself was improved furthermore by application of more sophisticated feeding and automatisation strategies. Even though several amino acids developed towards commodities in the last decade, side aspects of the production process like sterility or detection of contaminants still have increasing relevance. Finally one focus of this review is on recent developments in downstream technology.

  12. Degradation of amino acids to short-chain fatty acids in humans. An in vitro study

    DEFF Research Database (Denmark)

    Rasmussen, H S; Holtug, K; Mortensen, P B

    1988-01-01

    Short-chain fatty acids (SCFA) originate mainly in the colon through bacterial fermentation of polysaccharides. To test the hypothesis that SCFA may originate from polypeptides as well, the production of these acids from albumin and specific amino acids was examined in a faecal incubation system....... Albumin was converted to all C2-C5-fatty acids, whereas amino acids generally were converted to specific SCFA, most often through the combination of a deamination and decarboxylation of the amino acids, although more complex processes also took place. This study indicates that a part of the intestinal...

  13. Composition of antioxidants and amino acids in Stevia leaf infusions.

    Science.gov (United States)

    Periche, Angela; Koutsidis, Georgios; Escriche, Isabel

    2014-03-01

    Stevia, a non-caloric natural sweetener with beneficial properties and considerable antioxidants and amino acids, is increasingly consumed as an infusion. This work evaluates the influence of the conditions (temperature: 50, 70 or 90 °C and time: 1, 5, 20 or 40 min) applied to obtain Stevia infusions, on antioxidants (total phenols, flavonoids and antioxidant activity) and amino acids. The total concentration of the eleven amino acids found was 11.70 mg/g in dried leaves and from 6.84 to 9.11 mg/g per gram of Stevia in infusions. However, infusions showed higher levels of certain amino acids (alanine, asparagine, leucine and proline), and greater values of the three antioxidant parameters in comparison with dry leaves. Temperature had more influence (minimum values at 50 °C and maximum at 90 °C) than time in the case of antioxidants. At 90 °C there were no important increases in the extraction of antioxidant compounds after 5 min; each gram of Stevia had 117 mg trolox (total antioxidant activity), 90 mg gallic acid (total phenols) and 56 mg catechin equivalents (flavonoids). Varying the temperature and time conditions no notable differences were observed in the concentrations of the majority of amino acids. However, the infusion treatment at 90 °C for 5 min was the best, as it gave the highest yield of 8 of the 11 amino acids. Therefore, with respect to the compounds analyzed in this study, the best way to obtain Stevia leaf infusions is the same as the domestic process, almost boiling water for a short time.

  14. Role of mitochondrial transamination in branched chain amino acid metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, S.M.; Fenstermacher, D.; Mahar, C.

    1988-03-15

    Oxidative decarboxylation and transamination of 1-/sup 14/C-branched chain amino and alpha-keto acids were examined in mitochondria isolated from rat heart. Transamination was inhibited by aminooxyacetate, but not by L-cycloserine. At equimolar concentrations of alpha-ketoiso(1-/sup 14/C)valerate (KIV) and isoleucine, transamination was increased by disrupting the mitochondria with detergent which suggests transport may be one factor affecting the rate of transamination. Next, the subcellular distribution of the aminotransferase(s) was determined. Branched chain aminotransferase activity was measured using two concentrations of isoleucine as amino donor and (1-/sup 14/C)KIV as amino acceptor. The data show that branched chain aminotransferase activity is located exclusively in the mitochondria in rat heart. Metabolism of extramitochondrial branched chain alpha-keto acids was examined using 20 microM (1-/sup 14/C)KIV and alpha-ketoiso(1-/sup 14/C)caproate (KIC). There was rapid uptake and oxidation of labeled branched chain alpha-keto acid, and, regardless of the experimental condition, greater than 90% of the labeled keto acid substrate was metabolized during the 20-min incubation. When a branched chain amino acid (200 microM) or glutamate (5 mM) was present, 30-40% of the labeled keto acid was transaminated while the remainder was oxidized. Provision of an alternate amino acceptor in the form of alpha-keto-glutarate (0.5 mM) decreased transamination of the labeled KIV or KIC and increased oxidation. Metabolism of intramitochondrially generated branched chain alpha-keto acids was studied using (1-/sup 14/C)leucine and (1-/sup 14/C)valine. Essentially all of the labeled branched chain alpha-keto acid produced by transamination of (1-/sup 14/C)leucine or (1-/sup 14/C)valine with a low concentration of unlabeled branched chain alpha-keto acid (20 microM) was oxidized.

  15. β-Amino acid catalyzed asymmetric Michael additions: design of organocatalysts with catalytic acid/base dyad inspired by serine proteases.

    Science.gov (United States)

    Yang, Hui; Wong, Ming Wah

    2011-09-16

    A new type of chiral β-amino acid catalyst has been computationally designed, mimicking the enzyme catalysis of serine proteases. Our catalyst approach is based on the bioinspired catalytic acid/base dyad, namely, a carboxyl and imidazole pair. DFT calculations predict that this designed organocatalyst catalyzes Michael additions of aldehydes to nitroalkenes with excellent enantioselectivities and remarkably high anti diastereoselectivities. The unusual stacked geometry of the enamine intermediate, hydrogen bonding network, and the adoption of an exo transition state are the keys to understand the stereoselectivity.

  16. Regulation of uterine and umbilical amino acid uptakes by maternal amino acid concentrations.

    Science.gov (United States)

    Thureen, P J; Anderson, S M; Hay, W W

    2000-09-01

    We tested the hypothesis that decreased fetal amino acid (AA) supply, produced by maternal hypoaminoacidemia (low AA) during hyperglycemia (HG), is reversible with maternal AA infusion and regulates fetal insulin concentration ([I]). We measured net uterine and umbilical AA uptakes during maternal HG/low AA concentration ([AA]) and after maternal intravenous infusion of a mixed AA solution. After 5 days HG, all maternal [AA] except glycine were decreased >50%, particularly essential [AA] (P infusion increased net uterine uptakes of Val, Leu, Ile, Met, and Ser and net umbilical uptakes of Val, Leu, Ile, Met, Phe, and Arg but did not change net uteroplacental uptake of any AA. Fetal [I] increased 55 +/- 14%, P < 0.001, with correction of fetal [AA], despite the lack of change in fetal glucose concentration. Thus generalized maternal hypoaminoacidemia decreases uterine and umbilical uptakes of primarily the essential AA and decreases fetal branched-chain [AA]. These changes are reversed with correction of maternal [AA], which also increases fetal [I].

  17. Enantioselective separation of amino acids as biomarkers indicating life in extraterrestrial environments.

    Science.gov (United States)

    Pietrogrande, Maria Chiara

    2013-10-01

    Traces of prebiotic amino acids, i.e., the building blocks of proteins, are excellent biomarkers that could provide evidence of extinct or extant life in extra-terrestrial environments. In particular, characterization of the enantiomeric excess of amino acids gives relevant information about the biotic or abiotic origin of molecules, because it is generally assumed that life elsewhere could be based on either L or D amino acids, but not both. The analytical procedures used in in-situ space missions for chiral discrimination of amino acids must meet severe requirements imposed by flight conditions: short analysis time, low energy consumption, robustness, storage for long periods under extreme conditions, high efficiency and sensitivity, automation, and remote-control operation. Such methods are based on gas chromatography, high-pressure liquid chromatography, and capillary electrophoresis, usually coupled with mass spectrometry; of these, gas chromatography-mass spectrometry (GC-MS) is the only such combination yet used in space missions. Preliminary in-situ sample derivatization is required before GC-MS analysis to convert amino acids into volatile and thermally stable compounds. The silylation reagent most commonly used, N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide, is unsuitable for detection of homochirality, and alternative derivatization techniques have been developed that preserve the stereochemical configuration of the original compounds and are compatible with spaceflight conditions. These include the reagent N,N-dimethylformamide dimethylacetal, which has already been used in the Rosetta mission, a mixture of alkyl chloroformate, ethanol, and pyridine, a mixture of perfluorinated anhydrides and perfluoro alcohols, and hexafluoroacetone, the first gaseous derivatizing agent. In all the space instruments, solvent extraction of organic matter and chemical derivatization have been combined in a single automatic and remote-controlled procedure in a

  18. Hidden thermodynamic information in protein amino acid mutation tables

    Science.gov (United States)

    Phillips, J. C.

    2017-03-01

    We combine the standard 1992 20 × 20 substitution matrix based on block alignment, BLOSUM62, with the standard 1982 amino acid hydropathicity scale KD as well as the modern 2007 hydropathicity scale MZ, and compare the results. The 20-parameter KD and MZ hydropathicity scales have different thermodynamic character, corresponding to first- and second-order transitions. The KD and MZ comparisons show that the mutation rates reflect quantitative iteration of qualitative amino acid-phobic and -philic binary 2 × 10 properties that define quaternary 4 × 5 subgroups (but not quinary 5 × 4 subgroups), with the modern MZ bioinformatic scale giving much better results. The quaternary 5-mer MZ 4 × 5 subgroups are called mutons (Mu5). Among all hydropathicity scales, the MZ scale uniquely exhibits a smooth, deep mutational minimum at its center associated with alanine, glycine, the smallest amino acid, and histidine.

  19. Amino acid sequences of proteins from Leptospira serovar pomona

    Directory of Open Access Journals (Sweden)

    Alves Selmo F

    2000-01-01

    Full Text Available This report describes a partial amino acid sequences from three putative outer envelope proteins from Leptospira serovar pomona. In order to obtain internal fragments for protein sequencing, enzymatic and chemical digestion was performed. The enzyme clostripain was used to digest the proteins 32 and 45 kDa. In situ digestion of 40 kDa molecular weight protein was accomplished using cyanogen bromide. The 32 kDa protein generated two fragments, one of 21 kDa and another of 10 kDa that yielded five residues. A fragment of 24 kDa that yielded nineteen residues of amino acids was obtained from 45 kDa protein. A fragment with a molecular weight of 20 kDa, yielding a twenty amino acids sequence from the 40 kDa protein.

  20. Thermochemical study of amino acid imprinted polymer films.

    Science.gov (United States)

    Chai, Ziyi; BelBruno, Joseph J

    2015-11-01

    Molecularly imprinted polymers provide an alternative to traditional methods of amino acid analysis. The imprinted polymers are more robust and significantly less expensive than, for example, ELISA analysis. Amino acid imprinted nylon-6 thin films were studied by differential scanning calorimetry and scanning electron microscopy. Endothermic peaks were observed for imprinted films at temperatures higher than that for pure nylon, indicating the formation of a more-ordered, hydrogen bonded polymer. Removal of the amino acid from the imprinted film resulted in reversion to the peak observed for pure nylon-6. Additives, β-cyclodextrin and multiwalled carbon nanotubes, were added to the imprinted polymer solutions as a means to increase the porosity of the films. These studies resulted in alternative morphologies and calorimetric results that provide additional functionalities and applications for imprinted polymers.

  1. THz time-domain spectroscopy of amino acids

    Institute of Scientific and Technical Information of China (English)

    WANG Weining; YUE Weiwei; YAN Haitao; ZHANG Cunlin; ZHAO Guozhong

    2005-01-01

    The optical characteristics of four kinds of amino acids (tyrosine, arginine, histidine and glutamine) filled with nitrogen at room temperature were studied by THz time-domain spectroscopy (THz-TDS). Well-resolved absorption and refractive spectrums between 0.1 and 2.8 THz were obtained based on the physical model for extracting the optical parameters of materials in THz range. The results not only fill up the spectra gap of amino acids in far-infrared range, supply data for amino acid molecular identification and conformation analysis, but also demonstrate significantly potential to promote the research and application of biological materials in bio-chemical and medical fields by THz-TDS.

  2. The Studies of the Reactions of 2, 4, 6-Triphenylpyrylium Tetrafluoroborate with Amino Acids

    Institute of Scientific and Technical Information of China (English)

    Shrong Shi LIN; Xian Jing KONG; Jing Yuan LIU; Cheng Yong LI

    2003-01-01

    The reactions of triphenylpyrylium salt 1 with various amino acids were explored andcompared. The reactions with most α-amino acids yielded decarboxylation products 2 viadecarboxylation. The reactions with glutamic acid, lysine and ACC (1-aminocyclopropyl-carboxylic acid) gave triphenylpyridine 8, dimer 9 and acid 5a-acc, respectively. The reactionswith β and γ-amino acids yielded triphenylpyridine by intramolecular elimination.

  3. Analysis of amino acids and carbohydrates in green coffee.

    Science.gov (United States)

    Murkovic, Michael; Derler, Karin

    2006-11-30

    The analysis of carbohydrates and amino acids in green coffee is of the utmost importance since these two classes of compounds act as precursors of the Maillard reaction during which the colour and aroma are formed. During the course of the Maillard reaction potentially harmful substances like acrylamide or 5-hydroxymethyl-furfural accrue as well. The carbohydrates were analysed by anion-exchange chromatography with pulsed amperometric detection and the amino acids by reversed phase chromatography after derivatization with 6-amino-quinolyl-N-hydroxysuccinimidyl carbamate and fluorescence detection. Both methods had to be optimized to obtain a sufficient resolution of the analytes for identification and quantification. Sucrose is the dominant carbohydrate in green coffee with a concentration of up to 90 mg/g (mean = 73 mg/g) in arabica beans and significantly lower amounts in robusta beans (mean=45 mg/g). Alanine is the amino acid with the highest concentration (mean = 1200 microg/g) followed by asparagine (mean = 680 microg/g) in robusta and 800 microg/g and 360 microg/g in arabica respectively. In general, the concentration of amino acids is higher in robusta than in arabica.

  4. AMINO ACID METABOLISM IN COWS DURING THE TRANSITION PERIOD IN BALANCING DIET ON THE EXCHANGE PROTEIN AND DIGESTIBLE AMINO ACIDS

    Directory of Open Access Journals (Sweden)

    Ryadchikov V. G.

    2014-02-01

    Full Text Available Application of a factorial method for determining the needs in metabolic protein and essential amino acids, helps to deepen knowledge on physiology of protein and amino acid supply and allow to improve the standards for dairy cows during the transition period; in insufficient of metabolic protein and essential amino acids increased coefficients of their transformation into net protein and absorptive amino acids as a result of mobilization of body of cows; with an optimal protein nutrition their transformation in net milk protein, lysine and methionine accordingly amounted to 0.67, 0,83 and 0,82. The most significant changes in the concentration of methionine, proline, glutamate, glutamine, glycine were observed in cows before calving and immediately after birth, stabilization of their level starts with a 24 lactation day, that is connected with the peculiarities of the feeding behavior of the cows and the gradual intensification of the processes of metabolism and milk production. To control the status of protein metabolism we have offered benchmarks compositions of free amino acids in cows’ blood plasma phases: 21-0 days before calving, 0-21 and 22-120 days after calving

  5. Solid state radiolysis of amino acids in an astrochemical perspective

    Energy Technology Data Exchange (ETDEWEB)

    Cataldo, Franco, E-mail: franco.cataldo@fastwebnet.i [Istituto Nazionale di Astrofisica-Osservatorio Astrofisica di Catania, Via S. Sofia 78, 95123 Catania (Italy); Lupi Chemical Research, Via Casilina 1626/A, 00133 Rome (Italy); Angelini, Giancarlo [Istituto di Metodologie Chimiche, CNR, Via Salaria Km 29300, 00016 Monterotondo Stazione, Rome (Italy); Iglesias-Groth, Susana [Instituto de Astrofisica de Canarias, Via Lactea s/n, E-38200, La Laguna, Tenerife (Spain); Manchado, Arturo [Instituto de Astrofisica de Canarias, Via Lactea s/n, E-38200, La Laguna, Tenerife (Spain) and CSIC (Spain)

    2011-01-15

    The aliphatic amino acids L-alanine and L-leucine and the aromatic amino acids L-phenylalanine, L-tyrosine and L-tryptophan were irradiated in the solid state to a dose of 3.2 MGy. The degree of decomposition was measured by differential scanning calorimetry (DSC). Furthermore the degree of radioracemization was measured by optical rotatory dispersion (ORD) spectroscopy. From the DSC measurement a radiolysis rate constant k and the half life T{sub 1/2} for each amino acid have been determined and extrapolated to a dose of 14 MGy, which corresponds to the expected total dose delivered by the decay of radionuclides to the organic molecules present in comets and asteroids in 4.6x10{sup 9} years, the age of the Solar System. It is shown that all the amino acids studied can survive a radiation dose of 14 MGy although they are reduced to 1/4-1/5 of their original value they had at the beginning of the history of the Solar System. Consequently, the amount of alanine or leucine found today in the meteorites known as carbonaceous chondrites is just 1/4-1/5 of the amount originally present at the epoch of the formation of the Solar System 4.6x10{sup 9} years ago. Among the amino acids studied, tyrosine shows the highest radiation resistance while tryptophan does not combine its relatively high radiation resistance with an elevated level of radioracemization resistance. Apart from the exception of tryptophan, it is shown that the radiolysis rate constants k of all the amino acids studied are in reasonable agreement with the radioracemization rate constant k{sub rac}.

  6. Solid state radiolysis of amino acids in an astrochemical perspective

    Science.gov (United States)

    Cataldo, Franco; Angelini, Giancarlo; Iglesias-Groth, Susana; Manchado, Arturo

    2011-01-01

    The aliphatic amino acids L-alanine and L-leucine and the aromatic amino acids L-phenylalanine, L-tyrosine and L-tryptophan were irradiated in the solid state to a dose of 3.2 MGy. The degree of decomposition was measured by differential scanning calorimetry (DSC). Furthermore the degree of radioracemization was measured by optical rotatory dispersion (ORD) spectroscopy. From the DSC measurement a radiolysis rate constant k and the half life T1/2 for each amino acid have been determined and extrapolated to a dose of 14 MGy, which corresponds to the expected total dose delivered by the decay of radionuclides to the organic molecules present in comets and asteroids in 4.6×109 years, the age of the Solar System. It is shown that all the amino acids studied can survive a radiation dose of 14 MGy although they are reduced to 1/4-1/5 of their original value they had at the beginning of the history of the Solar System. Consequently, the amount of alanine or leucine found today in the meteorites known as carbonaceous chondrites is just 1/4-1/5 of the amount originally present at the epoch of the formation of the Solar System 4.6×109 years ago. Among the amino acids studied, tyrosine shows the highest radiation resistance while tryptophan does not combine its relatively high radiation resistance with an elevated level of radioracemization resistance. Apart from the exception of tryptophan, it is shown that the radiolysis rate constants k of all the amino acids studied are in reasonable agreement with the radioracemization rate constant krac.

  7. [Spectrophotometric determination of aromatic amino compounds with J-acid].

    Science.gov (United States)

    Yin, Xiao-hang; Shi, Wen-jian; Shen, Xin; Ma, Jun-tao; Li, Liang

    2015-01-01

    The problems such as chromogenic reaction selectivity, reaction rate, sensitivity and water-solubility of azo compounds were considered. The molecular structures of coupling components were theoretically designed and screened in the present research The reaction conditions and methods of chromogenic reaction were investigated. J-Acid (2-amino-5-naphthol-7-sulfonic acid) as a coupling reagent to determine aromatic amino compounds was established. In the presence of potassium bromide, at room temperature, nitrite reacted with aromatic amino compounds in the medium of thin hydrochloric acid. Then diazonium salt reacted with J-Acid in the aqueous solution of sodium carbonate, forming coloured azo dye, which had a maximum adsorption at 480 nm. The molar adsorption coeffcients of aniline, 4-aminobenzene sulfonic acid and 1-naphthylamine were 3. 95 X 10(4), 3. 24 X 10(4) and 3. 91 X 10(4) L . mol-1 . cm-1 , respectively. Experimental results showed that common coexisting ions on the surface water did not affect the results of determination. J-Acid of spectrophotometry was used to determine the samples of Shanghai Fu Xing Dao canal. Meanwhile, recovery experiments by standard addition method were done. Experiment results showed that the recoveries of aniline were in the range of 98. 5%-102. 1%, and RSD was 2. 08%. J-Acid is a common organic reagent. It is soluble in water and low volatile, and its toxicity is much lower than N-ethylenediamine. spectrophotometric determination of aromatic amino compounds by J-Acid has the advantage of high sensitivity, good selectivity, simple rapid operation and accurate results, and thus it can be used for the determination of trace aromatic amino compounds in the environmental water.

  8. Chiral Biomarkers in Meteorites

    Science.gov (United States)

    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

  9. A Soluble, Folded Protein without Charged Amino Acid Residues

    DEFF Research Database (Denmark)

    Højgaard, Casper; Kofoed, Christian; Espersen, Roall;

    2016-01-01

    Charges are considered an integral part of protein structure and function, enhancing solubility and providing specificity in molecular interactions. We wished to investigate whether charged amino acids are indeed required for protein biogenesis and whether a protein completely free of titratable...... side chains can maintain solubility, stability, and function. As a model, we used a cellulose-binding domain from Cellulomonas fimi, which, among proteins of more than 100 amino acids, presently is the least charged in the Protein Data Bank, with a total of only four titratable residues. We find...

  10. Control of immune response by amino acid metabolism.

    Science.gov (United States)

    Grohmann, Ursula; Bronte, Vincenzo

    2010-07-01

    The interaction between pathogenic microorganisms and their hosts is regulated by reciprocal survival strategies, including competition for essential nutrients. Though paradoxical, mammalian hosts have learned to take advantage of amino acid catabolism for controlling pathogen invasion and, at the same time, regulating their own immune responses. In this way, ancient catabolic enzymes have acquired novel functions and evolved into new structures with highly specialized functions, which go beyond the struggle for survival. In this review, we analyze the evidence supporting a critical role for the metabolism of various amino acids in regulating different steps of both innate and adaptive immunity.

  11. Regulation of intestinal mucosal growth by amino acids.

    Science.gov (United States)

    Ray, Ramesh M; Johnson, Leonard R

    2014-03-01

    Amino acids, especially glutamine (GLN) have been known for many years to stimulate the growth of small intestinal mucosa. Polyamines are also required for optimal mucosal growth, and the inhibition of ornithine decarboxylase (ODC), the first rate-limiting enzyme in polyamine synthesis, blocks growth. Certain amino acids, primarily asparagine (ASN) and GLN stimulate ODC activity in a solution of physiological salts. More importantly, their presence is also required before growth factors and hormones such as epidermal growth factor and insulin are able to increase ODC activity. ODC activity is inhibited by antizyme-1 (AZ) whose synthesis is stimulated by polyamines, thus, providing a negative feedback regulation of the enzyme. In the absence of amino acids mammalian target of rapamycin complex 1 (mTORC1) is inhibited, whereas, mTORC2 is stimulated leading to the inhibition of global protein synthesis but increasing the synthesis of AZ via a cap-independent mechanism. These data, therefore, explain why ASN or GLN is essential for the activation of ODC. Interestingly, in a number of papers, AZ has been shown to inhibit cell proliferation, stimulate apoptosis, or increase autophagy. Each of these activities results in decreased cellular growth. AZ binds to and accelerates the degradation of ODC and other proteins shown to regulate proliferation and cell death, such as Aurora-A, Cyclin D1, and Smad1. The correlation between the stimulation of ODC activity and the absence of AZ as influenced by amino acids is high. Not only do amino acids such as ASN and GLN stimulate ODC while inhibiting AZ synthesis, but also amino acids such as lysine, valine, and ornithine, which inhibit ODC activity, increase the synthesis of AZ. The question remaining to be answered is whether AZ inhibits growth directly or whether it acts by decreasing the availability of polyamines to the dividing cells. In either case, evidence strongly suggests that the regulation of AZ synthesis is the

  12. Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

    Science.gov (United States)

    Leung, Sam H.

    2000-01-01

    Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

  13. Effects of dietary protein and amino acid levels on the expression of selected cationic amino acid transporters and serum amino acid concentration in growing pigs.

    Science.gov (United States)

    García-Villalobos, Héctor; Morales-Trejo, Adriana; Araiza-Piña, Benedicto A; Htoo, John K; Cervantes-Ramírez, Miguel

    2012-08-01

    The absorption of lysine is facilitated by leucine, but there is no information regarding the effect of crude protein, lysine and leucine levels on the expression of cationic amino acid transporters in pigs. Therefore, an experiment was conducted with 20 pigs (14.9 +/- 0.62 kg initial body weight) to evaluate the effect of two protein levels, and the content of lysine, threonine, methionine and leucine in low crude protein diets on the expression of b(0,+) and CAT-1 mRNA in jejunum, Longissimus dorsi and Semitendinosus muscles and serum concentration of amino acids. Treatments were as follows: (i) wheat-soybean meal diet, 20% crude protein (Control); (ii) wheat diet deficient in lysine, threonine and methionine (Basal diet); (iii) Basal diet plus 0.70% L-lysine, 0.27% L-threonine, 0.10% DL-methionine (Diet LTM); (iv) Diet LTM plus 0.80% L-leucine (Diet LTM + Leu). Despite the Basal diet, all diets were formulated to meet the requirements of lysine, threonine and methionine; Diet LTM + Leu supplied 60% excess of leucine. The addition of lysine, threonine and methionine in Diet LTM increased the expression of b(0,+) in jejunum and CAT-1 in the Semitendinosus and Longissiums muscles and decreased CAT-1 in jejunum; the serum concentration of lysine was also increased (p Pigs fed the Control diet expressed less b(0,+) in jejunum, and CAT-1 in the Semitendinosus and Longissiums muscles expressed more CAT-1 in jejunum (p dietary amino acids, affect the expression of cationic amino acid transporters in pigs fed wheat-based diets.

  14. Genetic analysis of amino acid content in wheat grain

    Indian Academy of Sciences (India)

    Xiaoling Jiang; Peng Wu; Jichun Tian

    2014-08-01

    Complete diallel crosses with five parents of common wheat (Triticum aestivum L.) were conducted to analyse inheritance of 17 amino acid contents by using the genetic model including seed, cytoplasmic, maternal and environment interaction effects on quantitative traits of seeds in cereal crops. The results showed that inheritance of 17 amino acid contents, except tyrosine, was controlled by several genetic systems including seed, cytoplasmic, and maternal effects, and by significant gene × environment interaction effects. Seed-direct additive and maternal effects constituted a major part of genetic effects for lysine, tyrosine, arginine, methionine, and glutamic acid content. Seed-direct additive effect formed main part in inheritance of isoleucine and serine contents. Threonine content was mainly governed by maternal additive effect. The other nine amino acid contents were almost entirely controlled by dominance effects. High general heritability of tyrosine (36.3%), arginine (45.8%), lysine (24.7%) and threonine (21.4%) contents, revealed that it could be effective to improve them by direct selection in progenies from appropriate crosses. Interaction heritability for phenylalanine, proline, and histidine content, which was 36.1%, 39.5% and 25.7%, respectively, was higher than for the other amino acids.

  15. Fate of microbial nitrogen, carbon, hydrolysable amino acids, monosaccharides, and fatty acids in sediment

    OpenAIRE

    Veuger, Bart; van Oevelen, Dick; Middelburg, Jack J.

    2012-01-01

    The fate of microbial carbon, nitrogen, hydrolysable amino acids (HAAs), monosaccharides, and fatty acids in sediment was investigated experimentally. The microbial community of a tidal flat sediment was labeled with C-13-enriched glucose and N-15-enriched ammonium, and sediment was incubated for up to 371 days. Analysis of total concentrations and C-13- and N-15 content of bulk sediment, hydrolysable amino acids (including D-alanine), monosaccharides, total fatty acids (TFAs), and phospholip...

  16. Formation of Chiral a-Monofluorinated-.8-amino Esters through Organocatalytic Asymmetric Reduction of a-Fluoro-j3-enamino Esters by Trichlorosilane

    Institute of Scientific and Technical Information of China (English)

    张鹏; 王超; 周莉; 孙健

    2012-01-01

    A concise method was developed to prepare chiral a-monofluorinated-β-amino esters through N-sulfinyl urea catalyzed asymmetric hydrosilylation of a-fluoro-β-enamino esters, which affords high yields, good to high di- astereoselectivities (up to〉99/1), and moderate to good enantioselectivities (up to 83% ee).

  17. 3-{[(Benzyloxycarbonyl]amino}butanoic acid

    Directory of Open Access Journals (Sweden)

    Isao Fujii

    2011-10-01

    Full Text Available In the title compound, C12H15NO4, the butyric acid group has a stretched trans conformation. The dihedral angle between the phenyl ring and the oxycarboxyamino N—(C=O—O—C plane is 56.6 (2°. In the crystal, an inversion dimer is formed by a pair of O—H...O hydrogen bonds. The dimers are further linked by N—H...O hydrogen bonds between amide groups, forming a tape along the b axis.

  18. Unique roles of acidic amino acids in phase transformation of calcium phosphates.

    Science.gov (United States)

    Chu, Xiaobin; Jiang, Wenge; Zhang, Zhisen; Yan, Yang; Pan, Haihua; Xu, Xurong; Tang, Ruikang

    2011-02-10

    Although phase transformation is suggested as a key step in biomineralization, the chemical scenario about how organic molecules mediate inorganic phase transformations is still unclear. The inhibitory effect of amino acids on hydroxyapatite (HAP, the main inorganic component of biological hard tissues such as bone and enamel) formation was concluded by the previous biomimetic modeling based upon direct solution crystallization. Here we demonstrate that acidic amino acids, Asp and Glu, could promote HAP crystallization from its precursor crystal, brushite (DCPD). However, such a promotion effect could not be observed when the nonacidic amino acids were applied in the transformation-based HAP formation. We found that the specific modification of acidic amino acid on crystal-solution interfaces played a key role in the phase transition. The distinct properties between DCPD and HAP in the solution resulted in an interfacial energy barrier to suppress the spontaneous formation of HAP phase on DCPD phase. Different from the other amino acids, the carboxylate-rich amino acids, Asp and Glu, could modify the interfacial characteristics of these two calcium phosphate crystals to make them similar to each other. The experiments confirmed that the involvement of Asp or Glu reduced the interfacial energy barrier between DCPD and HAP, leading to a trigger effect on the phase transformation. An in-depth understanding about the unique roles of acidic amino acids may contribute to understanding phase transformation controls druing biomineralization.

  19. Finding coevolving amino acid residues using row and column weighting of mutual information and multi-dimensional amino acid representation

    DEFF Research Database (Denmark)

    Oliveira, Rodrigo Gouveia; Pedersen, Anders Gorm

    2007-01-01

    ABSTRACT: BACKGROUND: Some amino acid residues functionally interact with each other. This interaction will result in an evolutionary co-variation between these residues - coevolution. Our goal is to find these coevolving residues. RESULTS: We present six new methods for detecting coevolving...... residues. Among other things, we suggest measures that are variants of Mutual Information, and measures that use a multidimensional representation of each residue in order to capture the physico-chemical similarities between amino acids. We created a benchmarking system, in silico, able to evaluate...

  20. Analysis of Peptides and Conjugates by Amino Acid Analysis

    DEFF Research Database (Denmark)

    Højrup, Peter

    2015-01-01

    Amino acid analysis is a highly accurate method for characterization of the composition of synthetic peptides. Together with mass spectrometry, it gives a reliable control of peptide quality and quantity before conjugation and immunization.Peptides are hydrolyzed, preferably in gas phase, with 6 M...... HCl at 110 °C for 20-24 h and the resulting amino acids analyzed by ion-exchange chromatography with post-column ninhydrin derivatization. Depending on the hydrolysis conditions, tryptophan is destroyed, and cysteine also, unless derivatized, and the amides, glutamine and asparagine, are deamidated...... to glutamic acid and aspartic acid, respectively. Three different ways of calculating results are suggested, and taking the above limitations into account, a quantitation better than 5 % can usually be obtained....