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Sample records for acid racemization dating

  1. Amino acid racemization dating of fossil bones, I. inter-laboratory comparison of racemization measurements

    USGS Publications Warehouse

    Bada, J.L.; Hoopes, E.; Darling, D.; Dungworth, G.; Kessels, H.J.; Kvenvolden, K.A.; Blunt, D.J.

    1979-01-01

    Enantiomeric measurements for aspartic acid, glutamic acid, and alanine in twenty-one different fossil bone samples have been carried out by three different laboratories using different analytical methods. These inter-laboratory comparisons demonstrate that D/L aspartic acid measurements are highly reproducible, whereas the enantiomeric measurements for the other amino acids show a wide variation between the three laboratories. At present, aspartic acid measurements are the most suitable for racemization dating of bone because of their superior analytical precision. ?? 1979.

  2. Aspartic acid racemization dating of Holocene brachiopods and bivalves from the southern Brazilian shelf, South Atlantic

    NASA Astrophysics Data System (ADS)

    Barbour Wood, Susan L.; Krause, Richard A.; Kowalewski, Michał; Wehmiller, John; Simões, Marcello G.

    2006-09-01

    The extent of racemization of aspartic acid (Asp) has been used to estimate the ages of 9 shells of the epifaunal calcitic brachiopod Bouchardia rosea and 9 shells of the infaunal aragonitic bivalve Semele casali. Both taxa were collected concurrently from the same sites at depths of 10 m and 30 m off the coast of Brazil. Asp D/L values show an excellent correlation with radiocarbon age at both sites and for both taxa ( r2Site 9 B. rosea = 0.97, r2Site 1 B. rosea = 0.997, r2Site 9 S. casali = 0.9998, r2Site 1 S. casali = 0.93). The Asp ratios plotted against reservoir-corrected AMS radiocarbon ages over the time span of multiple millennia can thus be used to develop reliable and precise geochronologies not only for aragonitic mollusks (widely used for dating previously), but also for calcitic brachiopods. At each collection site, Bouchardia specimens display consistently higher D/L values than specimens of Semele. Thermal differences between sites are also notable and in agreement with theoretical expectations, as extents of racemization for both taxa are greater at the warmer, shallower site than at the cooler, deeper one. In late Holocene marine settings, concurrent time series of aragonitic and calcitic shells can be assembled using Asp racemization dating, and parallel multi-centennial to multi-millennial records can be developed simultaneously for multiple biomineral systems.

  3. Amino acid racemization dating of Upper Pleistocene - Holocene terrestrial gastropods from a Mediterranean region (Murcia, SE Spain)

    NASA Astrophysics Data System (ADS)

    Garcia-Mayordomo, Julian; Ortiz, Jose E.; Torres, Trinidad; Insua-Arevalo, Juan M.; Martinez-Diaz, Jose J.; Altolaguirre, Yul; Canales-Fernandez, Maria L.; Martin-Banda, Raquel

    2014-05-01

    The amino acid racemization method has become a widely used geochronological tool for dating Quaternary deposits. The method is based on the fact that living organisms contain only L-amino acids which gradually racemize into D-amino acids after death. Thus, the D/L ratio increases with time after death until it is equal to 1, that is, when equilibrium is reached. Gastropod shells are particularly useful for amino acid racemization dating. Because the amino acid racemization method is not a numerical dating method in isolation, it needs to be calibrated, mainly with radiometric dating methods. The racemization process is genus- and temperature-dependent. In this work we present a preliminary analysis that compares the radiometric age estimated from different dating methods of a number of gastropods recovered in localities from Murcia (Southeastern Spain), with the age obtained through the amino acid racemization method. Taking advantage of recent paleoseismological research in the Murcia region (SE Spain), 28 gastropods specimens were collected from different trenches dug in young Quaternary alluvial deposits. The specimens were subsequently classified and then analyzed according to the standards protocols of the Biomolecular Stratigraphy Laboratory (UPM, Madrid School of Mines). The species found were Otala lactea, Iberus gualterianus, Sphincterochila candidissima and Theba pisana. The D/L ratios of aspartic acid, leucine, phenylalanine and glutamic acid were determined, and the corresponding average age of each specimen was calculated introducing the D/L values in the age calculation algorithm of Torres et al. (1997) for gastropods of central and southern Spain. The racemization age for each locality was then compared to the radiometric age of the deposit where the specimens were collected. To this respect, the samples were classified in different groups considering the reliability on the age control method. The most reliable sample consists only on dates obtained

  4. Amino acid racemization dating of marine shells: A mound of possibilities.

    PubMed

    Demarchi, Beatrice; Williams, Matt G; Milner, Nicky; Russell, Nicola; Bailey, Geoff; Penkman, Kirsty

    2011-07-01

    Shell middens are one of the most important and widespread indicators for human exploitation of marine resources and occupation of coastal environments. Establishing an accurate and reliable chronology for these deposits has fundamental implications for understanding the patterns of human evolution and dispersal. This paper explores the potential application of a new methodology of amino acid racemization (AAR) dating of shell middens and describes a simple protocol to test the suitability of different molluscan species. This protocol provides a preliminary test for the presence of an intracrystalline fraction of proteins (by bleaching experiments and subsequent heating at high temperature), checking the closed system behaviour of this fraction during diagenesis. Only species which pass both tests can be considered suitable for further studies to obtain reliable age information. This amino acid geochronological technique is also applied to midden deposits at two latitudinal extremes: Northern Scotland and the Southern Red Sea. Results obtained in this study indicate that the application of this new method of AAR dating of shells has the potential to aid the geochronological investigation of shell mounds in different areas of the world. PMID:21776187

  5. Amino acid racemization dating of marine shells: A mound of possibilities

    PubMed Central

    Demarchi, Beatrice; Williams, Matt G.; Milner, Nicky; Russell, Nicola; Bailey, Geoff; Penkman, Kirsty

    2011-01-01

    Shell middens are one of the most important and widespread indicators for human exploitation of marine resources and occupation of coastal environments. Establishing an accurate and reliable chronology for these deposits has fundamental implications for understanding the patterns of human evolution and dispersal. This paper explores the potential application of a new methodology of amino acid racemization (AAR) dating of shell middens and describes a simple protocol to test the suitability of different molluscan species. This protocol provides a preliminary test for the presence of an intracrystalline fraction of proteins (by bleaching experiments and subsequent heating at high temperature), checking the closed system behaviour of this fraction during diagenesis. Only species which pass both tests can be considered suitable for further studies to obtain reliable age information. This amino acid geochronological technique is also applied to midden deposits at two latitudinal extremes: Northern Scotland and the Southern Red Sea. Results obtained in this study indicate that the application of this new method of AAR dating of shells has the potential to aid the geochronological investigation of shell mounds in different areas of the world. PMID:21776187

  6. Wide range of racemization of amino acids in peptides from human fossil bone and its implications for amino acid racemization dating

    SciTech Connect

    Kimber, R.W.L.; Hare, P.E. )

    1992-02-01

    Aspartic acid from an HCl hydrolyzed portion of 20-25th Dynasty Egyptian bone gave a D/L value of 0.28. Various peptide and molecular weight fractions separated before hydrolysis from another aliquot of the same bone portion yielded D/L aspartic acid values ranging from 0.09 to 0.68. Higher molecular weight and higher content of hydrophobic amino acids are factors leading to lower D/L aspartic acid values. Insoluble, high molecular weight polypeptide residues showed very low D/L aspartic acid values of 0.09. The authors propose that particularly stable peptides be isolated and characterized and then used for comparison with similarly isolated peptides from other fossil bone samples for purposes of age estimation.

  7. Comparison of amino acid racemization geochronometry with lithostratigraphy, biostratigraphy, uranium-series coral dating, and magnetostratigraphy in the Atlantic Coastal Plain of the southeastern United States

    NASA Astrophysics Data System (ADS)

    McCartan, L.; Owens, J. P.; Blackwelder, B. W.; Szabo, B. J.; Belknap, D. F.; Kriausakul, N.; Mitterer, R. M.; Wehmiller, J. F.

    1982-11-01

    The results of an integrated study comprising litho- and biostratigraphic investigations, uranium-series coral dating, amino acid racemization in molluscs, and paleomagnetic measurements are compared to ascertain relative and absolute ages of Pleistocene deposits of the Atlantic Coastal Plain in North and South Carolina. Four depositional events are inferred for South Carolina and two for North Carolina by all methods. The data suggest that there are four Pleistocene units containing corals that have been dated at about 100,000 yr, 200,000 yr, 450,000 yr, and over 1,000,000 yr. Some conflicts exist between the different methods regarding the correlation of the younger of these depositional events between Charleston and Myrtle Beach. Lack of good uranium-series dates for the younger material at Myrtle Beach makes the correlation with the deposits at Charleston more difficult.

  8. Comparison of amino acid racemization geochronometry with lithostratigraphy, biostratigraphy, uranium-series coral dating, and magnetostratigraphy in the Atlantic Coastal Plain of the southeastern United States

    USGS Publications Warehouse

    McCartan, L.; Owens, J.P.; Blackwelder, B. W.; Szabo, B. J.; Belknap, D.F.; Kriausakul, N.; Mitterer, R.M.; Wehmiller, J. F.

    1982-01-01

    The results of an integrated study comprising litho- and biostratigraphic investigations, uranium-series coral dating, amino acid racemization in molluscs, and paleomagnetic measurements are compared to ascertain relative and absolute ages of Pleistocene deposits of the Atlantic Coastal Plain in North and South Carolina. Four depositional events are inferred for South Carolina and two for North Carolina by all methods. The data suggest that there are four Pleistocene units containing corals that have been dated at about 100,000 yr, 200,000 yr, 450,000 yr, and over 1,000,000 yr. Some conflicts exist between the different methods regarding the correlation of the younger of these depositional events between Charleston and Myrtle Beach. Lack of good uranium-series dates for the younger material at Myrtle Beach makes the correlation with the deposits at Charleston more difficult. ?? 1982.

  9. Amino acid racemization analysis (AAR) as a successful tool for dating Holocene coastal sediments: Stratigraphy of a barrier island spit (Southern Sylt/North Sea)

    NASA Astrophysics Data System (ADS)

    Tillmann, Tanja; Ziehe, Daniel

    2014-05-01

    Dating of Holocene sediments in shallow coastal areas of the German North Sea by conventional techniques is commonly problematic. In particular the marine reservoir effect of radiocarbon means that radiocarbon dating cannot be applied to sediments younger than about 400 years. Amino acid racemization dating (AAR) is a viable alternative for dating young sediments. The method is based on the determination of ratios of D and L amino acid enantiomers in organic matrices of biogenic carbonates. In this study we use AAR as a tool for dating Holocene barrier islands sediments. Based on an AAR derived chronological framework we develop a model of barrier spit accretion which describes the interaction between extreme events, fair weather coastal processes and sedimentary development that constrains the major episodes of barrier island evolution. The stratigraphy was defined using ground-penetrating radar (GPR) surveys complemented by sedimentological coring data. The stratigraphy is then conceptualised in a AAR chronostratigraphic framework to define a chronological order and allow the development of a stratigraphic model of the evolution of Southern Sylt. The AAR data provide high temporal resolution and have been used for dating stages of barrier spit accretion. The time lines are marked as storm surge generated erosion unconformities in the stratigraphic profile. Individual shells and shell fragments of Cerastoderma edule, Mya arenaria, Mytilus edulis and Scrobicularia plana have been accumulated by short-term storm events as shell layers associated with the erosion unconformities and have been dated by AAR. Time lines reveal that the barrier spit accretion occurred episodically, and is dependant on the provided rate of sand delivery. The general trend is that sequences young to the. South. The AAR derived time lines have been verified and correlated by historic maps and sea charts. It is apparent that spit enlargement at this site increased significantly during the

  10. Application of the DCP model to a metastable racemate of mandelic acid

    NASA Astrophysics Data System (ADS)

    Pauchet, M.; Coquerel, G.

    2004-12-01

    Mandelic acid is a chiral molecule often used as a resolving agent in the separation of enantiomers. To date, three different crystalline structures have been characterized: the pure enantiomer and two polymorphs of the racemic compound. However, the metastable racemic and the pure enantiomeric crystal structures share analogies. Because of these similarities, the DCP model has been applied to rebuild the metastable racemic compound by recombining a periodic fragment extracted from the crystal structure of the enantiomer. As computations reveal another very similar crystal lattice of the racemic compound, possible disorder and/or twining and/or polytypism are surmised.

  11. Amino Acid Racemization and the Preservation of Ancient DNA

    NASA Technical Reports Server (NTRS)

    Poinar, Hendrik N.; Hoss, Matthias

    1996-01-01

    The extent of racemization of aspartic acid, alanine, and leucine provides criteria for assessing whether ancient tissue samples contain endogenous DNA. In samples in which the D/L ratio of aspartic acid exceeds 0.08, ancient DNA sequences could not be retrieved. Paleontological finds from which DNA sequences purportedly millions of years old have been reported show extensive racemization, and the amino acids present are mainly contaminates. An exception is the amino acids in some insects preserved in amber.

  12. A critical evaluation of the application of amino acid racemization to geochronology and geothermometry

    NASA Technical Reports Server (NTRS)

    Williams, K. M.; Smith, G. G.

    1977-01-01

    Attempts have been made to determine the age of biological samples by measuring the racemization of amino acids in protein samples. The pitfalls and inherent complications in diagenetic racemization studies are reviewed, and recent advances in improving techniques are outlined. Methodological topics include isolation of amino acids from geological samples, resolution of amino acid enantiomers, and the effects of acid hydrolysis. The theory and kinetics of amino acid racemization are discussed with attention to the derivation of the rate expression for amino acid racemization, isoleucine and the equilibrium constant, the mechanism of amino acid racemization, the racemization of 'bound' versus 'free' amino acids, and factors affecting the racemization rates of free amino acids in aqueous solution. Applications of amino acid racemization kinetics to geochronology is considered with reference to shells, marine sediments, and bones. Potential complications include heating and diagenesis, diagenetic formation of amino acids, the effect of clays, species effect, and contamination.

  13. Age estimation in forensic sciences: Application of combined aspartic acid racemization and radiocarbon analysis

    SciTech Connect

    Alkass, K; Buchholz, B A; Ohtani, S; Yamamoto, T; Druid, H; Spalding, S L

    2009-11-02

    Age determination of unknown human bodies is important in the setting of a crime investigation or a mass disaster, since the age at death, birth date and year of death, as well as gender, can guide investigators to the correct identity among a large number of possible matches. Traditional morphological methods used by anthropologists to determine age are often imprecise, whereas chemical analysis of tooth dentin, such as aspartic acid racemization has shown reproducible and more precise results. In this paper we analyze teeth from Swedish individuals using both aspartic acid racemization and radiocarbon methodologies. The rationale behind using radiocarbon analysis is that above-ground testing of nuclear weapons during the cold war (1955-1963) caused an extreme increase in global levels of carbon-14 ({sup 14}C) which have been carefully recorded over time. Forty-four teeth from 41 individuals were analyzed using aspartic acid racemization analysis of tooth crown dentin or radiocarbon analysis of enamel and ten of these were split and subjected to both radiocarbon and racemization analysis. Combined analysis showed that the two methods correlated well (R2=0.66, p < 0.05). Radiocarbon analysis showed an excellent precision with an overall absolute error of 0.6 {+-} 04 years. Aspartic acid racemization also showed a good precision with an overall absolute error of 5.4 {+-} 4.2 years. Whereas radiocarbon analysis gives an estimated year of birth, racemization analysis indicates the chronological age of the individual at the time of death. We show how these methods in combination can also assist in the estimation of date of death of an unidentified victim. This strategy can be of significant assistance in forensic casework involving dead victim identification.

  14. Patterns of racemization and epimerization of amino acids in land snail shells over the course of the Holocene

    SciTech Connect

    Goodfriend, G.A. )

    1991-01-01

    The patterns of racemization of six amino acids and of epimerization of isoleucine over the course of the Holocene were studied in a series of 38 radiocarbon-dated samples of the land snail Trochoidea seetzeni from the Negev Desert in southern Israel. The D/L ratios of each of the amino acids show a strong correlation with age (r = 0.84-0.94) and thus good age predictive ability. The patterns in faster-racemizing amino acids do not conform to first-order kinetics. Transformation to parabolic kinetics linearizes these faster-racemizing amino acids, except for aspartic acid (which shows a very high initial rate of racemization). After transformation, each amino acid shows an equally good correlation with age (r = 0.91-0.93). The D/L ratios of the various amino acids covary very strongly, even after the covariation due to sample age is removed from the data set. Thus, analysis of more than one amino acid provides largely redundant information on sample age. Nevertheless, because of differences in racemization rates, some amino acids provide better time resolution in different time ranges - aspartic acid is especially useful for very young samples, and glutamic acid and isoleucine for older samples. Neither the depth of burial of the samples nor the burial mode appears to affect the rate of racemization or epimerization.

  15. Excellent amino acid racemization results from Holocene sand dollars

    NASA Astrophysics Data System (ADS)

    Kosnik, M.; Kaufman, D. S.; Kowalewski, M.; Whitacre, K.

    2015-12-01

    Amino acid racemization (AAR) is widely used as a cost-effective method to date molluscs in time-averaging and taphonomic studies, but it has not been attempted for echinoderms despite their paleobiological importance. Here we demonstrate the feasibility of AAR geochronology in Holocene aged Peronella peronii (Echinodermata: Echinoidea) collected from Sydney Harbour (Australia). Using standard HPLC methods we determined the extent of AAR in 74 Peronella tests and performed replicate analyses on 18 tests. We sampled multiple areas of two individuals and identified the outer edge as a good sampling location. Multiple replicate analyses from the outer edge of 18 tests spanning the observed range of D/Ls yielded median coefficients of variation < 4% for Asp, Phe, Ala, and Glu D/L values, which overlaps with the analytical precision. Correlations between D/L values across 155 HPLC injections sampled from 74 individuals are also very high (pearson r2 > 0.95) for these four amino acids. The ages of 11 individuals spanning the observed range of D/L values were determined using 14C analyses, and Bayesian model averaging was used to determine the best AAR age model. The averaged age model was mainly composed of time-dependent reaction kinetics models (TDK, 71%) based on phenylalanine (Phe, 94%). Modelled ages ranged from 14 to 5539 yrs, and the median 95% confidence interval for the 74 analysed individuals is ±28% of the modelled age. In comparison, the median 95% confidence interval for the 11 calibrated 14C ages was ±9% of the median age estimate. Overall Peronella yields exceptionally high-quality AAR D/L values and appears to be an excellent substrate for AAR geochronology. This work opens the way for time-averaging and taphonomic studies of echinoderms similar to those in molluscs.

  16. Amino acid racemization on Mars: implications for the preservation of biomolecules from an extinct martian biota

    NASA Technical Reports Server (NTRS)

    Bada, J. L.; McDonald, G. D.; Miller, S. L. (Principal Investigator)

    1995-01-01

    Using kinetic data, we have estimated the racemization half-lives and times for total racemization of amino acids under conditions relevant to the surface of Mars. Amino acids from an extinct martian biota maintained in a dry, cold (<250 K) environment would not have racemized significantly over the lifetime of the planet. Racemization would have taken place in environments where liquid water was present even for time periods of only a few million years following biotic extinction. The best preservation of both amino acid homochirality and nucleic acid genetic information associated with extinct martian life would be in the polar regions.

  17. Amino Acid Racemization in Pseudomonas putida KT2440

    PubMed Central

    Radkov, Atanas D.

    2013-01-01

    d-Amino acids have been shown to play an increasingly diverse role in bacterial physiology, yet much remains to be learned about their synthesis and catabolism. Here we used the model soil- and rhizosphere-dwelling organism Pseudomonas putida KT2440 to elaborate on the genomics and enzymology of d-amino acid metabolism. P. putida KT2440 catabolized the d-stereoisomers of lysine, phenylalanine, arginine, alanine, and hydroxyproline as the sole carbon and nitrogen sources. With the exception of phenylalanine, each of these amino acids was racemized by P. putida KT2440 enzymes. Three amino acid racemases were identified from a genomic screen, and the enzymes were further characterized in vitro. The putative biosynthetic alanine racemase Alr showed broad substrate specificity, exhibiting measurable racemase activity with 9 of the 19 chiral amino acids. Among these amino acids, activity was the highest with lysine, and the kcat/Km values with l- and d-lysine were 3 orders of magnitude greater than the kcat/Km values with l- and d-alanine. Conversely, the putative catabolic alanine racemase DadX showed narrow substrate specificity, clearly preferring only the alanine stereoisomers as the substrates. However, DadX did show 6- and 9-fold higher kcat/Km values than Alr with l- and d-alanine, respectively. The annotated proline racemase ProR of P. putida KT2440 showed negligible activity with either stereoisomer of the 19 chiral amino acids but exhibited strong epimerization activity with hydroxyproline as the substrate. Comparative genomic analysis revealed differences among pseudomonads with respect to alanine racemase genes that may point to different roles for these genes among closely related species. PMID:23995642

  18. Numerical dating of a Late Quaternary spit-shoreline complex at the northern end of Silver Lake playa, Mojave Desert, California: A comparison of the applicability of radiocarbon, luminescence, terrestrial cosmogenic nuclide, electron spin resonance, U-series and amino acid racemization methods

    USGS Publications Warehouse

    Owen, L.A.; Bright, Jordon; Finkel, R.C.; Jaiswal, M.K.; Kaufman, D.S.; Mahan, S.; Radtke, U.; Schneider, J.S.; Sharp, W.; Singhvi, A.K.; Warren, C.N.

    2007-01-01

    A Late Quaternary spit-shoreline complex on the northern shore of Pleistocene Lake Mojave of southeastern California, USA was studied with the goal of comparing accelerator mass spectrometry (AMS) radiocarbon, luminescence, electron spin resonance (ESR), terrestrial cosmogenic radionuclide (TCN) surface exposure, amino acid racemization (AAR) and U-series dating methods. The pattern of ages obtained by the different methods illustrates the complexity of processes acting in the lakeshore environment and highlights the utility of a multi-method approach. TCN surface exposure ages (mostly ???20-30 ka) record the initial erosion of shoreline benches, whereas radiocarbon ages on shells (determined in this and previous studies) within the spit, supported by AAR data, record its construction at fluctuating lake levels from ???16 to 10 ka. Luminescence ages on spit sediment (???6-7 ka) and ESR ages on spit shells (???4 ka) are anomalously young relative to radiocarbon ages of shells within the same deposits. The significance of the surprisingly young luminescence ages is not clear. The younger ESR ages could be a consequence of post-mortem enrichment of U in the shells. High concentrations of detrital thorium in tufa coating spit gravels inhibited the use of single-sample U-series dating. Detailed comparisons such as this provide one of the few means of assessing the accuracy of Quaternary dating techniques. More such comparisons are needed. ?? 2007 Elsevier Ltd and INQUA.

  19. A comparative study of the kinetics of amino acid racemization/epimerization in fossil and modern mollusk shells

    SciTech Connect

    Goodfriend, G.A. Carnegie Inst. of Washington, Washington DC ); Meyer, V.R. )

    1991-11-01

    The present study examines the question of whether heating experiments on modern shell material accurately model the pattern of kinetics of racemization/epimerization in fossils. Using one modern sample and four fossil samples (dating to 9700-1700 yr B.P.) of a species of land snail from the Negev Desert, the kinetic behavior of the samples in laboratory heating experiments are compared. Results are then compared to the Holocene trend in kinetic patterns observed in a large series of radio-carbon-dated shells. For most amino acids (alanine, alloisoleucine/isoleucine, phenylalanine, and glutamic acid), the fossil material displays the same pattern of kinetics in relation to time as the modern shells; deviant patterns are observed for aspartic acid, proline, and methionine. Adherence to a first order kinetic pattern in heated shells occurs only in alloisoleucine/isoleucine (within the range of D/L ratios studied). Differences in the temperature dependence of racemization/epimerization rates are found between modern and fossil samples. In most cases this relationship when extrapolated to natural temperatures, does not agree well with observed rates of racemization/epimerization in the fossil series. However the pattern of change in rate of racemization/epimerization with time in heating experiments generally follows the trend observed in the fossil series rather well. The experiments indicate that heating experiment results for certain amino acids, such as the widely used alloisoleucine/isoleucine, do give good predictions of kinetic patterns in relation to time in fossils but that predictions of the temperature dependence of rates are less accurate.

  20. The Formation of Racemic Amino Acids by UV Photolysis of Interstellar Ice Analogs

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Small biologically relevant organic molecules including the amino acids glycine, alanine, and marine were formed in the laboratory by the UV (Ultraviolet) photolysis of realistic interstellar ice analogs, composed primarily of H2O, and including CH3OH, NH3, and HCN, under interstellar conditions. N-formyl glycine, cycloserine (4-amino-3-isoxazolidinone), and glycerol were detected before hydrolysis, and glycine, racemic alanine, racemic marine, glycerol, ethanolamine, and glyceric acid were found after hydrolysis. This suggests that some meteoritic amino acids (and other molecules) may be the direct result of interstellar ice photochemistry, expanding the current paradigm that they formed by reactions in liquid water on meteorite parent bodies.

  1. Amino acid racemization on planktic foraminifera from the central Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Hanslik, D.; Kaufman, D. S.; Jakobsson, M.

    2009-12-01

    Amino acid racemization (AAR) is the interconversion of amino acids from one chiral form (L - levo) to a mixture of L- and D- (dextro) forms as a function of time and temperature. The extent of AAR in foraminifera shells can be determined by measuring the ratio of D/L amino acids, and can be used as a relative dating method. The technique can also be used to determine numerical ages once the rate of racemization is calibrated for a study area using samples of known ages. In this study sediment cores from the Lomonosov Ridge (88°N) and Morris Jesup Rise (85°N), in the central Arctic Ocean, were analyzed for AAR on monospecific samples of the polar planktic foraminifera Neogloboquadrina pachyderma sinistral. Numerical ages were derived using an equation developed for aspartic and glutamic acids in a previous study on other cores from the Northwind, Mendeleev and Lomonosov ridges, which applies to samples younger than about 150 ka (Kaufman et al., 2008, Paleoceanography 23:PA3224). The calculated AAR ages are in relatively good agreement with 14C ages throughout the range of 14C dating for both of our cores. The core from Morris Jesup Rise includes older sediment beyond the range of 14C dating where ages were inferred from benthic foraminifera events and correlation with other cores with previously published age models. The AAR age for the level of unique occurrence of the benthic foramifera Bulimina aculeata from this core is about 85 ka, which agrees with previous work that assigned this level to MIS 5.1. Beyond about 85 ka, there is a progressively increasing age discrepancy between calculated AAR ages and estimated ages based on benthic foraminifera events. For MIS 5.5, the D/L values for the Epistominella exigua marker are lower in our core than in the cores analyzed by Kaufman et al. (2008). Assuming that this event is a chronostratigraphic marker, then the AAR results suggest that deepwater temperature at our site during MIS 5 was lower than at the other

  2. Are the Crystal Structures of Enantiopure and Racemic Mandelic Acids Determined by Kinetics or Thermodynamics?

    PubMed

    Hylton, Rebecca K; Tizzard, Graham J; Threlfall, Terence L; Ellis, Amy L; Coles, Simon J; Seaton, Colin C; Schulze, Eric; Lorenz, Heike; Seidel-Morgenstern, Andreas; Stein, Matthias; Price, Sarah L

    2015-09-01

    Mandelic acids are prototypic chiral molecules where the sensitivity of crystallized forms (enantiopure/racemic compound/polymorphs) to both conditions and substituents provides a new insight into the factors that may allow chiral separation by crystallization. The determination of a significant number of single crystal structures allows the analysis of 13 enantiopure and 30 racemic crystal structures of 21 (F/Cl/Br/CH3/CH3O) substituted mandelic acid derivatives. There are some common phenyl packing motifs between some groups of racemic and enantiopure structures, although they show very different hydrogen-bonding motifs. The computed crystal energy landscape of 3-chloromandelic acid, which has at least two enantiopure and three racemic crystal polymorphs, reveals that there are many more possible structures, some of which are predicted to be thermodynamically more favorable as well as slightly denser than the known forms. Simulations of mandelic acid dimers in isolation, water, and toluene do not differentiate between racemic and enantiopure dimers and also suggest that the phenyl ring interactions play a major role in the crystallization mechanism. The observed crystallization behavior of mandelic acids does not correspond to any simple "crystal engineering rules" as there is a range of thermodynamically feasible structures with no distinction between the enantiopure and racemic forms. Nucleation and crystallization appear to be determined by the kinetics of crystal growth with a statistical bias, but the diversity of the mandelic acid crystallization behavior demonstrates that the factors that influence the kinetics of crystal nucleation and growth are not yet adequately understood. PMID:26244445

  3. A critical evaluation of the application of amino acid racemization to geochronology and geothermometry.

    PubMed

    Williams, K M; Smith, G G

    1977-08-01

    In this review we have critically evaluated the application of the diagenetic racemization of amino acids to geochronology and geothermometry. Although there has been enthusiastic support given to this new method, it is our opinion that recent developments suggest a more cautious approach. We have discussed the pitfalls and inhereent complications, while outlining the advances which have been accomplished. We conclude that this is an innovative approach which will add valuable information to the scientific literature. However, since our fundamental understanding of diagnetic racemization is still limited, many of the age and paleotemperature estimates which have been assigned to fossil specimens may be unreliable. PMID:335314

  4. Amino acid racemization reveals differential protein turnover in osteoarthritic articular and meniscal cartilages

    PubMed Central

    Stabler, Thomas V; Byers, Samuel S; Zura, Robert D; Kraus, Virginia Byers

    2009-01-01

    Introduction Certain amino acids within proteins have been reported to change from the L form to the D form over time. This process is known as racemization and is most likely to occur in long-lived low-turnover tissues such as normal cartilage. We hypothesized that diseased tissue, as found in an osteoarthritic (OA) joint, would have increased turnover reflected by a decrease in the racemized amino acid content. Methods Using high-performance liquid chromatography methods, we quantified the L and D forms of amino acids reported to racemize in vivo on a biological timescale: alanine, aspartate (Asp), asparagine (Asn), glutamate, glutamine, isoleucine, leucine (Leu), and serine (Ser). Furthermore, using a metabolically inactive control material (tooth dentin) and a control material with normal metabolism (normal articular cartilage), we developed an age adjustment in order to make inferences about the state of protein turnover in cartilage and meniscus. Results In the metabolically inactive control material (n = 25, ages 13 to 80 years) and the normal metabolizing control material (n = 19, ages 17 to 83 years), only Asp + Asn (Asx), Ser, and Leu showed a significant change (increase) in racemization with age (P < 0.01). The age-adjusted proportions of racemized to total amino acid (D/D+L expressed as a percentage of the control material) for Asx, Ser, and Leu when compared with the normal articular cartilage control were 97%, 74%, and 73% in OA meniscal cartilage and 97%, 70%, and 78% in OA articular cartilage. We also observed lower amino acid content in OA articular and meniscal cartilages compared with normal articular cartilage as well as a loss of total amino acids with age in the OA meniscal but not the OA articular cartilage. Conclusions These data demonstrate comparable anabolic responses for non-lesioned OA articular cartilage and OA meniscal cartilage but an excess of catabolism over anabolism for the meniscal cartilage. PMID:19267899

  5. Racemization in Reverse: Evidence that D-Amino Acid Toxicity on Earth Is Controlled by Bacteria with Racemases

    PubMed Central

    Zhang, Gaosen; Sun, Henry J.

    2014-01-01

    D-amino acids are toxic for life on Earth. Yet, they form constantly due to geochemical racemization and bacterial growth (the cell walls of which contain D-amino acids), raising the fundamental question of how they ultimately are recycled. This study provides evidence that bacteria use D-amino acids as a source of nitrogen by running enzymatic racemization in reverse. Consequently, when soils are inundated with racemic amino acids, resident bacteria consume D- as well as L-enantiomers, either simultaneously or sequentially depending on the level of their racemase activity. Bacteria thus protect life on Earth by keeping environments D-amino acid free. PMID:24647559

  6. Amino acid racemization in amber-entombed insects: implications for DNA preservation

    NASA Technical Reports Server (NTRS)

    Bada, J. L.; Wang, X. S.; Poinar, H. N.; Paabo, S.; Poinar, G. O.

    1994-01-01

    DNA depurination and amino acid racemization take place at similar rates in aqueous solution at neutral pH. This relationship suggests that amino acid racemization may be useful in accessing the extent of DNA chain breakage in ancient biological remains. To test this suggestion, we have investigated the amino acids in insects entombed in fossilized tree resins ranging in age from <100 years to 130 million years. The amino acids present in 40 to 130 million year old amber-entombed insects resemble those in a modern fly and are probably the most ancient, unaltered amino acids found so far on Earth. In comparison to other geochemical environments on the surface of the Earth, the amino acid racemization rate in amber insect inclusions is retarded by a factor of >10(4). These results suggest that in amber insect inclusions DNA depurination rates would also likely be retarded in comparison to aqueous solution measurements, and thus DNA fragments containing many hundreds of base pairs should be preserved. This conclusion is consistent with the reported successful retrieval of DNA sequences from amber-entombed organisms.

  7. Comparison of acid anhydrides with carboxylic acids in enantioselective enzymatic esterification of racemic menthol.

    PubMed

    Xu, J; Zhu, J; Kawamoto, T; Atsuo, T; Hu, Y

    1997-01-01

    Optical resolution of racemic menthol has been efficiently achieved by lipase-catalyzed enantioselective esterification in an organic solvent. The performance of the reaction using an acid anhydride as an acyl donor was compared with that using its corresponding free acid. The reactivities of acid anhydrides were found to be higher than their corresponding free acids, but acid anhydrides were also found to be easily hydrolyzed into free acids under the catalysis of the same enzyme. The existence of a too-high concentration of an acid anhydride in a micro-aqueous reaction system will cause dehydration and thus deactivation of the enzyme, and will enhance non-selective esterification of a chiral alcohol, which will reduce the optical purity of the product. All these drawbacks, however, could be effectively overcome in a semi-batch reaction system into which propionic anhydride was continuously fed. This system showed some advantages over a batch reaction system using free propionic acid: the reaction time of dl-menthol was shortened by half, the stability of the enzyme was much enhanced, and the optical purity of the product (l-menthyl ester) was kept at a similarly high level (> 98% ee). PMID:9631262

  8. Assessing amino acid racemization variability in coral intra-crystalline protein for geochronological applications

    NASA Astrophysics Data System (ADS)

    Hendy, Erica J.; Tomiak, Peter J.; Collins, Matthew J.; Hellstrom, John; Tudhope, Alexander W.; Lough, Janice M.; Penkman, Kirsty E. H.

    2012-06-01

    Over 500 Free Amino Acid (FAA) and corresponding Total Hydrolysed Amino Acid (THAA) analyses were completed from eight independently-dated, multi-century coral cores of massive Porites sp. colonies. This dataset allows us to re-evaluate the application of amino acid racemization (AAR) for dating late Holocene coral material, 20 years after Goodfriend et al. (GCA56 (1992), 3847) first showed AAR had promise for developing chronologies in coral cores. This re-assessment incorporates recent method improvements, including measurement by RP-HPLC, new quality control approaches (e.g. sampling and sub-sampling protocols, statistically-based data screening criteria), and cleaning steps to isolate the intra-crystalline skeletal protein. We show that the removal of the extra-crystalline contaminants and matrix protein is the most critical step for reproducible results and recommend a protocol of bleaching samples in NaOCl for 48 h to maximise removal of open system proteins while minimising the induced racemization. We demonstrate that AAR follows closed system behaviour in the intra-crystalline fraction of the coral skeletal proteins. Our study is the first to assess the natural variability in intra-crystalline AAR between colonies, and we use coral cores taken from the Great Barrier Reef, Australia, and Jarvis Island in the equatorial Pacific to explore variability associated with different environmental conditions and thermal histories. Chronologies were developed from THAA Asx D/L, Ala D/L, Glx D/L and FAA Asx D/L for each core and least squares Monte Carlo modelling applied in order to quantify uncertainty of AAR age determinations and assess the level of dating resolution possible over the last 5 centuries. AAR within colonies follow consistent stratigraphic aging. However, there are systematic differences in rates between the colonies, which would preclude direct comparison from one colony to another for accurate age estimation. When AAR age models are developed from

  9. Assessing amino acid racemization variability in coral intra-crystalline protein for geochronological applications.

    PubMed

    Hendy, Erica J; Tomiak, Peter J; Collins, Matthew J; Hellstrom, John; Tudhope, Alexander W; Lough, Janice M; Penkman, Kirsty E H

    2012-06-01

    Over 500 Free Amino Acid (FAA) and corresponding Total Hydrolysed Amino Acid (THAA) analyses were completed from eight independently-dated, multi-century coral cores of massive Porites sp. colonies. This dataset allows us to re-evaluate the application of amino acid racemization (AAR) for dating late Holocene coral material, 20 years after Goodfriend et al. (GCA 56 (1992), 3847) first showed AAR had promise for developing chronologies in coral cores. This re-assessment incorporates recent method improvements, including measurement by RP-HPLC, new quality control approaches (e.g. sampling and sub-sampling protocols, statistically-based data screening criteria), and cleaning steps to isolate the intra-crystalline skeletal protein. We show that the removal of the extra-crystalline contaminants and matrix protein is the most critical step for reproducible results and recommend a protocol of bleaching samples in NaOCl for 48 h to maximise removal of open system proteins while minimising the induced racemization. We demonstrate that AAR follows closed system behaviour in the intra-crystalline fraction of the coral skeletal proteins. Our study is the first to assess the natural variability in intra-crystalline AAR between colonies, and we use coral cores taken from the Great Barrier Reef, Australia, and Jarvis Island in the equatorial Pacific to explore variability associated with different environmental conditions and thermal histories. Chronologies were developed from THAA Asx D/L, Ala D/L, Glx D/L and FAA Asx D/L for each core and least squares Monte Carlo modelling applied in order to quantify uncertainty of AAR age determinations and assess the level of dating resolution possible over the last 5 centuries. AAR within colonies follow consistent stratigraphic aging. However, there are systematic differences in rates between the colonies, which would preclude direct comparison from one colony to another for accurate age estimation. When AAR age models are developed

  10. Crystallization and sublimation of non-racemic mixtures of natural amino acids: a path towards homochirality

    NASA Astrophysics Data System (ADS)

    Tarasevych, Arkadii V.; Guillemin, Jean-Claude

    2012-07-01

    Homochirality of biologically important molecules such as amino acids and sugars is a prerequisite for the origin of life. There are different forces or mechanisms in the Universe to trigger off the primary imbalance in the enantiomeric ratio. Very likely the initial bias of one type of enantiomers over the other on Earth was arisen from the inflow of extraterrestrial matter (carbonaceous meteorites). The phase transitions (crystallization, sublimation) of non-racemic mixtures of enantiomers are ones of the most probable mechanisms for the homochirogenesis[1]. The sublimation, almost uninvestigated subject and forgotten for 30 years, revealed recently a pathway to the enantioenrichment of natural amino acids[2]. Starting from a mixture with a low content of an enantiopure amino acid a partial sublimation gives a considerable enrichment. In our further experiments we combined two first-order phase transitions of amino acid(s) mixtures: crystallization and sublimation. The results show the possibility of the transfer of enantiopurity between different amino acids[3]. Subliming a crystallized mixture of racemic amino acids with an enantiopure one we found that the sublimate is a non-racemic mixture of the same handedness for all components. The significance of the studies can be realized taking into account that just 5 of 22 proteinogenic amino acids are able to homochiral self-organization. The relevance of these studies to the Prebiotic Earth and to the evolution of the single handedness of biological molecules will be discussed. [1] Blackmond, Phil. Trans. R. Soc. B 2011, 366, 2878. [2] Guillemin et al., Chem. Commun. 2010 , 46, 1482. [3] Tarasevych, Guillemin et al., submitted.

  11. Comparative analysis of aspartic acid racemization methods using whole-tooth and dentin samples.

    PubMed

    Sakuma, Ayaka; Ohtani, Susumu; Saitoh, Hisako; Iwase, Hirotaro

    2012-11-30

    One way to estimate biological age is to use the aspartic acid (Asp) racemization method. Although this method has been performed mostly using enamel and dentin, we investigated whether an entire tooth can be used for age estimation. This study used 12 pairs of canines extracted from both sides of the mandible of 12 individuals of known age. From each pair, one tooth was used as a dentin sample and the other as a whole-tooth sample. Amino acids were extracted from each sample, and the integrated peak areas of D-Asp and L-Asp were determined using a gas chromatograph/mass spectrometer. Statistical analysis was performed using the D/L-Asp ratio. Furthermore, teeth from two unidentified bodies, later identified as Japanese and Brazilian, were examined in the same manner. Results showed that the D/L ratios of whole-tooth samples were higher overall than those of dentin samples. The correlation coefficient between the D/L ratios of dentin samples and their age was r=0.98, and that of the whole-tooth samples was r=0.93. The difference between estimated age and actual chronological age was -0.116 and -6.86 years in the Japanese and Brazilian cases, respectively. The use of whole teeth makes the racemization technique easier and can standardize the sampling site. Additionally, using only a few tooth samples per analysis made it possible to reanalyze known-age samples. Although the difficulty in obtaining a proper control sample has prevented racemization from being widely used, the method described here not only ensures the availability of a control tooth, but also enables the teeth to be used for other purposes such as DNA analysis. The use of a whole tooth will increase the application of the racemization technique for age determination. PMID:22989598

  12. Does aspartic acid racemization constrain the depth limit of the subsurface biosphere?

    PubMed

    Onstott, T C; Magnabosco, C; Aubrey, A D; Burton, A S; Dworkin, J P; Elsila, J E; Grunsfeld, S; Cao, B H; Hein, J E; Glavin, D P; Kieft, T L; Silver, B J; Phelps, T J; van Heerden, E; Opperman, D J; Bada, J L

    2014-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of ~89 years for 1 km depth and 27 °C and 1-2 years for 3 km depth and 54 °C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 °C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples. PMID:24289240

  13. Does aspartic acid racemization constrain the depth limit of the subsurface biosphere?

    SciTech Connect

    Onstott, T. C.; Aubrey, A.D.; Kieft, T L; Silver, B J; Phelps, Tommy Joe; Van Heerden, E.; Opperman, D. J.; Bada, J L.

    2014-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of ~89 years for 1 km depth and 27 C and 1 2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  14. Does Aspartic Acid Racemization Constrain the Depth Limit of the Subsurface Biosphere?

    NASA Technical Reports Server (NTRS)

    Onstott, T C.; Magnabosco, C.; Aubrey, A. D.; Burton, A. S.; Dworkin, J. P.; Elsila, J. E.; Grunsfeld, S.; Cao, B. H.; Hein, J. E.; Glavin, D. P.; Kieft, T. L.; Silver, B. J.; Phelps, T. J.; Heerden, E. Van; Opperman, D. J.; Bada, J. L.

    2013-01-01

    Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of approximately 89 years for 1 km depth and 27 C and 1-2 years for 3 km depth and 54 C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

  15. Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Brønsted Acid.

    PubMed

    Terada, Masahiro; Ota, Yusuke; Li, Feng; Toda, Yasunori; Kondoh, Azusa

    2016-08-31

    Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp(2)-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp(3)-hybridized carbon atom. In particular, substitution at the chiral sp(3)-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid. PMID:27490239

  16. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    NASA Astrophysics Data System (ADS)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  17. Enigmatic Isovaline: Investigating the Stability, Racemization, and Formation of a Non-biological Meteoritic Amino Acid

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie; Moore, Marla; Lewis, Ariel; Dworkin, Jason

    2008-01-01

    Among the Murchison meteoritic amino acids, isovaline stands out as being both nonbiological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L-isovaline have been reported in Murchison and other CM meteorites, the molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of D and L enantiomers. Ion-irradiated isovaline- and valinecontaining ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have undertaken experiments to synthesize isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings. -- Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM, AL) and the Astrobiology Analytical Laboratory (JPD, DPG) at the NASA Goddard Space Flight Center.

  18. Use Of Amino Acid Racemization To Investigate The Metabolic Activity Of ?Dormant? Microorganisms In Siberian Permafrost

    NASA Astrophysics Data System (ADS)

    Tsapin, A.; McDonald, G.

    2002-12-01

    search for extraterrestrial life or its remnants is based on studying the most probable environments in which life (extant or extinct) may be found, and determining the maximum period of time over which such life could be preserved. The terrestrial permafrost, inhabited by cold adapted microbes, can be considered as an extraterrestrial analog environment. The cells and their metabolic end-products in Earth's permafrost can be used in the search for possible ecosystems and potential inhabitants on extraterrestrial cryogenic bodies. The study of microorganisms (or their remnants) that were buried for a few million years in permafrost provides us with a unique opportunity to determine the long-term viability of (micro)organisms. We have analyzed the degree of racemization of aspartic acid in permafrost samples from Northern Siberia (Brinton et al. 2002, Astrobiology 2, 77), an area from which microorganisms of apparent ages up to a few million years have previously been isolated and cultured. We find that the extent of aspartic acid racemization in permafrost cores increases very slowly up to an age of approximately 25,000 years (around 5 m depth). The apparent temperature of racemization over the age range 0-25,000 years, determined using measured aspartic acid racemization rate constants, is ?19 C. This apparent racemization temperature is significantly lower than the measured environmental temperature (?11 to ?13 C), and suggests active recycling of D-aspartic acid in Siberian permafrost up to an age of around 25,000 years. This indicates that permafrost organisms are capable of repairing some molecular damage incurred while they are in a ?dormant? state over geologic time.

  19. Pharmacokinetics of (-)-folinic acid after oral and intravenous administration of the racemate.

    PubMed Central

    Greiner, P O; Zittoun, J; Marquet, J; Cheron, J M

    1989-01-01

    1. A pharmacokinetic study of the natural (-)-isomer of folinic acid ((-)-5 CHOTHF) and of total (-)-folates was performed in 12 healthy subjects after i.v. and oral administration of the racemic form of folinic acid. 2. After a 25 mg i.v. injection, (-)-5 CHOTHF kinetics were described by a biexponential function. The mean steady state volume of distribution (Vss) was 161; systemic and renal clearances averaged 335 and 53 ml min-1, respectively. After the same oral dose, (-)-5 CHOTHF was rapidly absorbed. Plasma concentrations of unchanged drug were much lower than those achieved after i.v. administration but in nine subjects, the disposition kinetics were also biexponential. Absolute bioavailability was only 4% as a consequence of a significant intestinal first pass effect. 3. AUC and t1/2Z values for total (-)-folates were similar after both routes of administration, indicating that the drug was fully absorbed. However the AUC of the active metabolite after i.v. dosage was only half that after oral dosage. 4. The amounts of total (-)-folates excreted in urine after both routes of administration were not significantly different and averaged one third of the dose after 24 h, whereas excretion of (-)-5 CHOTHF was three times less after oral treatment than after parenteral treatment. 5. Oral administration is a more suitable route for folinic acid therapy because more of the active metabolite is produced than after parenteral injection. PMID:2789922

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

    NASA Astrophysics Data System (ADS)

    Zorzano, María-Paz; Osuna-Esteban, Susana; Ruiz-Bermejo, Marta; Menor-Salván, Cesar; Veintemillas-Verdaguer, Sabino

    2014-06-01

    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.

  1. Two types of rare earth-organic frameworks constructed by racemic tartaric acid

    SciTech Connect

    Jiang Zhanguo; Lv Yaokang; Cheng Jianwen; Feng Yunlong

    2012-01-15

    Hydrothermal reactions of rare earth oxides with racemic tartaric acid (H{sub 2}tar) yielded 7 rare earth(III) MOFs with general formulas [R{sub 2}(tar){sub 3}(H{sub 2}O){sub 2}]{sub n} (R=Y (1), Sm (4), Eu (5), Tb (6), Dy (7)) and [R{sub 2}(tar){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 2}]{sub n}{center_dot}4nH{sub 2}O (R=La (2), Nd (3)). X-ray powder diffraction analysis and single-crystal X-ray diffraction analysis reveal that they present two different structural types. MOFs 1, 4, 5, 6 and 7 are isostructural and crystallize in the orthorhombic non-centrosymmetric space group Iba2, and feature unusual fsc-3,4-Iba2 topology. MOFs 2 and 3 are isostructural and crystallize in monoclinic P2{sub 1}/c space group and display rare fsx-4,5-P2{sub 1}/c topology containing hydrophilic channels bounded by triple helical chains along a axis. MOFs 3, 4, 5, 6 and 7 exhibit intense lanthanide characteristic photoluminescence at room temperature. - Graphical Abstract: [R{sub 2}(tar){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 2}]{sub n}{center_dot}4nH{sub 2}O (R=La (2), Nd (3)) display rare fsx-4,5-P2{sub 1}/c topology containing hydrophilic channels bounded by triple helical chains along a axis. Highlights: Black-Right-Pointing-Pointer Two types of rare earth MOFs were synthesized by hydrothermal conditions. Black-Right-Pointing-Pointer MOFs feature unusual fsc-3,4-Iba2 and rare fsx-4,5-P2{sub 1}/c topology structures. Black-Right-Pointing-Pointer MOFs exhibit intense lanthanide characteristic photoluminescence.

  2. Chemical Principles Revisited: Archaeological Dating.

    ERIC Educational Resources Information Center

    Rowe, M. W.

    1986-01-01

    Discusses methods used to date archaeological artifacts and other remains. They include: (1) nuclear dating techniques (radiocarbon dating, accelerator radiocarbon dating, thermoluminescence, and others); (2) chemical dating techniques (amino acid racemization, obsidian hydration dating, elemental content changes, and thermal analysis dating); and…

  3. Temperature calibration of amino acid racemization: age implications for the Yuha skeleton

    USGS Publications Warehouse

    Bischoff, J.L.; Childers, W.M.

    1979-01-01

    D/L of aspartic acid ranged from 0.52 to 0.56 for femur samples of the Yuha skeleton. Subsurface temperature measurements made at the burial site indicate average annual temperature is 18??C and diagenetic temperature is 21.6??C. These data and a relation derived for the dependence of the aspartic acid rate constant on diagenetic temperature indicate an age of 23,600. The result is consistent with 14C and 230Th dating of calcrete found coating the bones. ?? 1979.

  4. Immobilized chiral tropine ionic liquid on silica gel as adsorbent for separation of metal ions and racemic amino acids.

    PubMed

    Qian, Guofei; Song, Hang; Yao, Shun

    2016-01-15

    Tropine-type chiral ionic liquid with proline anion was immobilized on silica gel by chemical modification method for the first time, which was proved by elemental, infrared spectrum and thermogravimetric analysis. Secondly, the performance of this kind of ionic liquid-modified silica gel was investigated in the adsorption of some metal ions, which included Cu(2+), Fe(3+), Mn(2+) and Ni(2+). Then the effects of time, initial concentration and temperature on adsorption for Cu(2+) ions were studied in detail, which was followed by the further research of adsorption kinetics and thermodynamics. The adsorption could be better described by pseudo-second-order kinetics model and that the process was spontaneous, exothermic and entropy decreasing. In the mode of 'reuse after adsorption', the ionic liquid-modified silica gel with saturated adsorption of Cu(2+) was finally used in resolution of racemic amino acids for the first time. The static experiment showed that adsorption rate of two enantiomers was obviously different. Inspired by this, the complex was packed in chromatographic column for the separation of racemic amino acids and d-enantiomers were firstly eluted by water or ethanol. Steric hindrance was found as one of key influencing factors for its effect on the stability of the complex. PMID:26711153

  5. Phosphine-Catalyzed Doubly Stereoconvergent γ-Additions of Racemic Heterocycles to Racemic Allenoates: The Catalytic Enantioselective Synthesis of Protected α,α-Disubstituted α-Amino Acid Derivatives

    PubMed Central

    2015-01-01

    Methods have recently been developed for the phosphine-catalyzed asymmetric γ-addition of nucleophiles to readily available allenoates and alkynoates to generate useful α,β-unsaturated carbonyl compounds that bear a stereogenic center in either the γ or the δ position (but not both) with high stereoselectivity. The utility of this approach would be enhanced considerably if the stereochemistry at both termini of the new bond could be controlled effectively. In this report, we describe the achievement of this objective, specifically, that a chiral phosphepine can catalyze the stereoconvergent γ-addition of a racemic nucleophile to a racemic electrophile; through the choice of an appropriate heterocycle as the nucleophilic partner, this new method enables the synthesis of protected α,α-disubstituted α-amino acid derivatives in good yield, diastereoselectivity, and enantioselectivity. PMID:26192217

  6. Importance of Hydrogen-Bonding Sites in the Chiral Recognition Mechanism Between Racemic D3 Terbium(III) Complexes and Amino Acids

    PubMed Central

    MOUSSA, AHMED; PHAM, CHRISTINE; BOMMIREDDY, SHRUTHI; MULLER, GILLES

    2009-01-01

    The perturbation of the racemic equilibrium of luminescent D3 terbium(III) complexes with chelidamic acid (CDA), a hydroxylated derivative of 2,6-pyridine-dicarboxylic acid (DPA), by added chiral biomolecules such as l-amino acids has been studied using circularly polarized luminescence and 13C NMR spectroscopy. It is shown in this work that the chiral-induced equilibrium shift of [Tb(CDA)3]6− by l-amino acids (i.e. l-proline or l-arginine) was largely influenced by the hydrogen-bonding networks formed between the ligand interface of racemic [Tb(CDA)3]6− and these added chiral agents. The capping of potential hydrogen-bonding sites by acetylation in l-proline led to a ∼100-fold drop in the induced optical activity of the [Tb(CDA)3]6−:N-acetyl-l-proline system. This result suggested that the hydrogen-bonding networks serve as the basis for further noncovalent discriminatory interactions between racemic [Tb(CDA)3]6− and added l-amino acids. PMID:18698640

  7. Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George W.; Allamandola, Louis J.

    2002-01-01

    The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

  8. NON-RACEMIC AMINO ACID PRODUCTION BY ULTRAVIOLET IRRADIATION OF ACHIRAL INTERSTELLAR ICE ANALOGS WITH CIRCULARLY POLARIZED LIGHT

    SciTech Connect

    De Marcellus, Pierre; Nuevo, Michel; Danger, Gregoire; Deboffle, Dominique; Le Sergeant d'Hendecourt, Louis; Meinert, Cornelia; Filippi, Jean-Jacques; Meierhenrich, Uwe J.; Nahon, Laurent E-mail: ldh@ias.u-psud.fr

    2011-02-01

    The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.'s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.'s of up to 1.34% for ({sup 13}C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

  9. Aspartic Acid Racemization and Collagen Degradation Markers Reveal an Accumulation of Damage in Tendon Collagen That Is Enhanced with Aging*

    PubMed Central

    Thorpe, Chavaunne T.; Streeter, Ian; Pinchbeck, Gina L.; Goodship, Allen E.; Clegg, Peter D.; Birch, Helen L.

    2010-01-01

    Little is known about the rate at which protein turnover occurs in living tendon and whether the rate differs between tendons with different physiological roles. In this study, we have quantified the racemization of aspartic acid to calculate the age of the collagenous and non-collagenous components of the high strain injury-prone superficial digital flexor tendon (SDFT) and low strain rarely injured common digital extensor tendon (CDET) in a group of horses with a wide age range. In addition, the turnover of collagen was assessed indirectly by measuring the levels of collagen degradation markers (collagenase-generated neoepitope and cross-linked telopeptide of type I collagen). The fractional increase in d-Asp was similar (p = 0.7) in the SDFT (5.87 × 10−4/year) and CDET (5.82 × 10−4/year) tissue, and d/l-Asp ratios showed a good correlation with pentosidine levels. We calculated a mean (±S.E.) collagen half-life of 197.53 (±18.23) years for the SDFT, which increased significantly with horse age (p = 0.03) and was significantly (p < 0.001) higher than that for the CDET (34.03 (±3.39) years). Using similar calculations, the half-life of non-collagenous protein was 2.18 (±0.41) years in the SDFT and was significantly (p = 0.04) lower than the value of 3.51 (±0.51) years for the CDET. Collagen degradation markers were higher in the CDET and suggested an accumulation of partially degraded collagen within the matrix with aging in the SDFT. We propose that increased susceptibility to injury in older individuals results from an inability to remove partially degraded collagen from the matrix leading to reduced mechanical competence. PMID:20308077

  10. Enzymatic dynamic kinetic resolution of racemic N-formyl- and N-carbamoyl-amino acids using immobilized L-N-carbamoylase and N-succinyl-amino acid racemase.

    PubMed

    Soriano-Maldonado, Pablo; Las Heras-Vazquez, Francisco Javier; Clemente-Jimenez, Josefa María; Rodriguez-Vico, Felipe; Martínez-Rodríguez, Sergio

    2015-01-01

    Taking advantage of the catalytic promiscuity of L-carbamoylase from Geobacillus stearothermophilus CECT43 (BsLcar) and N-succinyl-amino acid racemase from Geobacillus kaustophilus CECT4264 (GkNSAAR), we have evaluated the production of different optically pure L-α-amino acids starting from different racemic N-formyl- and N-carbamoyl-amino acids using a dynamic kinetic resolution approach. The enzymes were immobilized on two different solid supports, resulting in improved stability of the enzymes in terms of thermostability and storage when compared to the enzymes in solution. The bienzymatic system retained up to 80% conversion efficiency after 20 weeks at 4 °C and up to 90% after 1 week at 45 °C. The immobilization process also resulted in a great enhancement of the activity of BsLcar toward N-formyl-tryptophan, showing for the first time that substrate specificity of L-carbamoylases can be influenced by this approach. The system was effective for the biosynthesis of natural and unnatural L-amino acids (enantiomeric excess (e.e.) >99.5%), such as L-methionine, L-alanine, L-tryptophan, L-homophenylalanine, L-aminobutyric acid, and L-norleucine, with a higher performance toward N-formyl-α-amino acid substrates. Biocatalyst reuse was studied, and after 10 reaction cycles, over 75% activity remained. PMID:24993356

  11. Polymorphic Crystallization and Crystalline Reorganization of Poly(l-lactic acid)/Poly(d-lactic acid) Racemic Mixture Influenced by Blending with Poly(vinylidene fluoride).

    PubMed

    Yu, Chengtao; Han, Lili; Bao, Jianna; Shan, Guorong; Bao, Yongzhong; Pan, Pengju

    2016-08-18

    The effects of poly(vinylidene fluoride) (PVDF) on the crystallization kinetics, competing formations of homocrystallites (HCs) and stereocomplexes (SCs), polymorphic crystalline structure, and HC-to-SC crystalline reorganization of the poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic mixture were investigated. Even though the PLLA/PDLA/PVDF blends are immiscible, blending with PVDF enhances the crystallization rate and SC formation of PLLA/PDLA components at different temperatures that are higher or lower than the melting temperature of the PVDF component; it also facilitates the HC-to-SC melt reorganization upon heating. The crystallization rate and degree of SC crystallinity (Xc,SC) of PLLA/PDLA components in nonisothermal crystallization increase after immiscible blending with PVDF. At different isothermal crystallization temperatures, the crystallization half-time of PLLA/PDLA components decreases; its spherulitic growth rate and Xc,SC increase as the mass fraction of PVDF increases from 0 to 0.5 in the presence of either a solidified or a molten PVDF phase. The HCs formed in primary crystallization of PLLA/PDLA components melt and recrystallize into SCs upon heating; the HC-to-SC melt reorganization is promoted after blending with PVDF. We proposed that the PVDF-promoted crystallization, SC formation, and HC-to-SC melt reorganization of PLLA/PDLA components in PLLA/PDLA/PVDF blends stem from the enhanced diffusion ability of PLLA and PDLA chains. PMID:27414064

  12. Sediment accumulation, stratigraphic order, and the extent of time-averaging in lagoonal sediments: a comparison of 210Pb and 14C/amino acid racemization chronologies

    NASA Astrophysics Data System (ADS)

    Kosnik, Matthew A.; Hua, Quan; Kaufman, Darrell S.; Zawadzki, Atun

    2015-03-01

    Carbon-14 calibrated amino acid racemization (14C/AAR) data and lead-210 (210Pb) data are used to examine sediment accumulation rates, stratigraphic order, and the extent of time-averaging in sediments collected from the One Tree Reef lagoon (southern Great Barrier Reef, Australia). The top meter of lagoonal sediment preserves a stratigraphically ordered deposit spanning the last 600 yrs. Despite different assumptions, the 210Pb and 14C/AAR chronologies are remarkably similar indicating consistency in sedimentary processes across sediment grain sizes spanning more than three orders of magnitude (0.1-10 mm). Estimates of long-term sediment accumulation rates range from 2.2 to 1.2 mm yr-1. Molluscan time-averaging in the taphonomically active zone is 19 yrs, whereas below the depth of final burial (~15 cm), it is ~110 yrs/5 cm layer. While not a high-resolution paleontological record, this reef lagoon sediment is suitable for paleoecological studies spanning the period of Western colonization and development. This sedimentary deposit, and others like it, should be useful, albeit not ideal, for quantifying anthropogenic impacts on coral reef systems.

  13. Some considerations regarding the use of amino acid racemization in human dentine as an indicator of age at death.

    PubMed

    Carolan, V A; Gardner, M L; Lucy, D; Pollard, A M

    1997-01-01

    An HPLC method is described for simultaneously obtaining the enantiomeric ratio of three amino acids (aspartic acid, serine, and glutamic acid) from dental collagen, with a view to using this information for estimating age at death. Results are reported from a sample of twenty three known age modern teeth, six known age 19th C. AD teeth, and two unknown age Romano-British teeth. It was found (as expected) that all three D/L ratios changed significantly with chronological age. Standard calibration techniques were used to estimate ages for the six 19th C. AD specimens from regression equations estimated from the modern specimens, and also to predict (for the first time) the error associated with such estimates. Errors using aspartic acid were found to be similar to those obtained by other methods of age estimation from dental evidence, serine, and glutamic acid providing much poorer age estimates. Additionally, a systematic difference in the age-enantiomeric ratio relationship was observed between modern and older dental samples. It is concluded that there is some fundamental difference in the observed enantiomeric ratios between modern teeth and older samples, possibly as a result of the chemical alteration of the dental proteins. PMID:8988569

  14. Liquid chromatographic resolution of amino acid esters of acyclovir including racemic valacyclovir on crown ether-based chiral stationary phases.

    PubMed

    Ahn, Seong Ae; Hyun, Myung Ho

    2015-03-01

    Valacyclovir, a potential prodrug for the treatment of patients with herpes simplex and herpes zoster, and its analogs were resolved on two chiral stationary phases (CSPs) based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 covalently bonded to silica gel. In order to find out an appropriate mobile phase condition, various mobile phases consisting of various organic modifiers in water containing various acidic modifiers were applied to the resolution of valacyclovir and its analogs. When 30% acetonitrile in water containing any of 0.05 M, 0.10 M, or 0.15 M perchloric acid was used as a mobile phase, valacyclovir and its analogs were resolved quite well on the two CSPs with the separation factors (α) in the range of 2.49 ~ 6.35 and resolutions (RS ) in the range of 2.95 ~ 12.21. Between the two CSPs, the CSP containing residual silanol protecting n-octyl groups on the silica surface was found to be better than the CSP containing residual silanol groups. PMID:25626672

  15. Court date for EPA acid rain rule

    SciTech Connect

    Lobsenz, G.

    1994-03-04

    In an acid rain rulemaking that appears headed straight for the courtroom, the Environmental Protection Agency this week announced new limits on emissions of nitrogen oxides from coal-fired power plants. The regulations, announced March 1, are expected to achieve a 1.8 million ton per year reduction in power plant NOx emissions, which are considered a major contributor to acid rain. The agency issued companion regulations last year to cut power plant discharges of sulfur dioxide, the other major acid rain pollutant. The NOx rulemaking elicited contradictory responses from utility industry officials. One point of contention involves the agency's definition of low-NOx burner technology, a key regulatory determination. If a utility installs EPA-defined low-NOx burner technology and still cannot meet the new NOx limits, it can apply for a less stringent [open quotes]alternative emission limit.[close quotes] The other issue likely to be raised by industry officials involves the January 1995 compliance deadline for utilities included in Phase I of the NOx program. While EPA will allow individual utilities to seek a deadline extension until April 1996 in the event of operational difficulties, the agency rejected the industry's request for an across-the-board extension.

  16. Calibration of amino acid racemization (AAR) kinetics in United States mid-Atlantic Coastal Plain Quaternary mollusks using 87Sr/ 86Sr analyses: Evaluation of kinetic models and estimation of regional Late Pleistocene temperature history

    USGS Publications Warehouse

    Wehmiller, J. F.; Harris, W.B.; Boutin, B.S.; Farrell, K.M.

    2012-01-01

    The use of amino acid racemization (AAR) for estimating ages of Quaternary fossils usually requires a combination of kinetic and effective temperature modeling or independent age calibration of analyzed samples. Because of limited availability of calibration samples, age estimates are often based on model extrapolations from single calibration points over wide ranges of D/L values. Here we present paired AAR and 87Sr/ 86Sr results for Pleistocene mollusks from the North Carolina Coastal Plain, USA. 87Sr/ 86Sr age estimates, derived from the lookup table of McArthur et al. [McArthur, J.M., Howarth, R.J., Bailey, T.R., 2001. Strontium isotopic stratigraphy: LOWESS version 3: best fit to the marine Sr-isotopic curve for 0-509 Ma and accompanying Look-up table for deriving numerical age. Journal of Geology 109, 155-169], provide independent age calibration over the full range of amino acid D/L values, thereby allowing comparisons of alternative kinetic models for seven amino acids. The often-used parabolic kinetic model is found to be insufficient to explain the pattern of racemization, although the kinetic pathways for valine racemization and isoleucine epimerization can be closely approximated with this function. Logarithmic and power law regressions more accurately represent the racemization pathways for all amino acids. The reliability of a non-linear model for leucine racemization, developed and refined over the past 20 years, is confirmed by the 87Sr/ 86Sr age results. This age model indicates that the subsurface record (up to 80m thick) of the North Carolina Coastal Plain spans the entire Quaternary, back to ???2.5Ma. The calibrated kinetics derived from this age model yield an estimate of the effective temperature for the study region of 11??2??C., from which we estimate full glacial (Last Glacial Maximum - LGM) temperatures for the region on the order of 7-10??C cooler than present. These temperatures compare favorably with independent paleoclimate information

  17. Enhanced catalysis and enantioselective resolution of racemic naproxen methyl ester by lipase encapsulated within iron oxide nanoparticles coated with calix[8]arene valeric acid complexes.

    PubMed

    Sayin, Serkan; Akoz, Enise; Yilmaz, Mustafa

    2014-09-14

    In this study, two types of nanoparticles have been used as additives for the encapsulation of Candida rugosa lipase via the sol-gel method. In one case, the nanoparticles were covalently linked with a new synthesized calix[8]arene octa valeric acid derivative (C[8]-C4-COOH) to produce new calix[8]arene-adorned magnetite nanoparticles (NP-C[8]-C4-COOH), and then NP-C[8]-C4-COOH was used as an additive in the sol-gel encapsulation process. In the other case, iron oxide nanoparticles were directly added into the sol-gel encapsulation process in order to interact electrostatically with both C[8]-C4-COOH and Candida rugosa lipase. The catalytic activities and enantioselectivities of two novel encapsulated lipases (Enc-NP-C[8]-C4-COOH and Enc-C[8]-C4-COOH@Fe3O4) in the hydrolysis reaction of racemic naproxen methyl ester were evaluated. The results showed that the activity and enantioselectivity of the lipase were improved when the lipase was encapsulated in the presence of calixarene-based additives. Indeed, the encapsulated lipases have an excellent rate of enantioselectivity, with E = 371 and 265, respectively, as compared to the free enzyme (E = 137). The lipases encapsulated with C[8]-C4-COOH and iron oxide nanoparticles (Enc-C[8]-C4-COOH@Fe3O4) retained more than 86% of their initial activities after 5 repeated uses and 92% with NP-C[8]-C4-COOH. PMID:25012138

  18. Deuteration protects asparagine residues against racemization.

    PubMed

    Lowenson, Jonathan D; Shmanai, Vadim V; Shklyaruck, Denis; Clarke, Steven G; Shchepinov, Mikhail S

    2016-09-01

    Racemization in proteins and peptides at sites of L-asparaginyl and L-aspartyl residues contributes to their spontaneous degradation, especially in the biological aging process. Amino acid racemization involves deprotonation of the alpha carbon and replacement of the proton in the opposite stereoconfiguration; this reaction is much faster for aspartate/asparagine than for other amino acids because these residues form a succinimide ring in which resonance stabilizes the carbanion resulting from proton loss. To determine if the replacement of the hydrogen atom on the alpha carbon with a deuterium atom might decrease the rate of racemization and thus stabilize polypeptides, we synthesized a hexapeptide, VYPNGA, in which the three carbon-bound protons in the asparaginyl residue were replaced with deuterium atoms. Upon incubation of this peptide in pH 7.4 buffer at 37 °C, we found that the rate of deamidation via the succinimide intermediate was unchanged by the presence of the deuterium atoms. However, the accumulation of the D-aspartyl and D-isoaspartyl-forms resulting from racemization and hydrolysis of the succinimide was decreased more than five-fold in the deuterated peptide over a 20 day incubation at physiological temperature and pH. Additionally, we found that the succinimide intermediate arising from the degradation of the deuterated asparaginyl peptide was slightly less likely to open to the isoaspartyl configuration than was the protonated succinimide. These findings suggest that the kinetic isotope effect resulting from the presence of deuteriums in asparagine residues can limit the accumulation of at least some of the degradation products that arise as peptides and proteins age. PMID:27169868

  19. Synthesis of nano-sized stereoselective imprinted polymer by copolymerization of (S)-2-(acrylamido) propanoic acid and ethylene glycol dimethacrylate in the presence of racemic propranolol and copper ion.

    PubMed

    Alizadeh, Taher; Bagherzadeh, Azam; Shamkhali, Amir Nasser

    2016-06-01

    A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was obtained by reaction of (l)-alanine with acryloyl chloride. The resulting monomer was characterized by FT-IR and HNMR and then utilized for the preparation of chiral imprinted polymer (CIP). This was carried out by copolymerization of (l)-alanine-derived chiral monomer and ethylene glycol dimethacrylate, in the presence of racemic propranolol and copper nitrate, via precipitation polymerization technique, resulting in nano-sized networked polymer particles. The polymer obtained was characterized by scanning electron microscopy and FT-IR. The non-imprinted polymer was also synthesized and used as blank polymer. Density functional theory (DFT) was also employed to optimize the structures of two diasterometric ternary complexes, suspected to be created in the pre-polymerization step, by reaction of optically active isomers of propranolol, copper ion and (S)-2-(acrylamido) propanoic acid. Relative energies and other characteristics of the described complexes, calculated by the DFT, predicted the higher stability of (S)-propranolol involved complex, compared to (R)-propranolol participated complex. Practical batch extraction test which employed CIP as solid phase adsorbent, indicated that the CIP recognized selectively (S)-propranolol in the racemic mixture of propranolol; whereas, the non-imprinted polymer (NIP) showed no differentiation capability between two optically active isomers of propranolol. PMID:27040217

  20. Dual Role of Hydrophobic Racemic Thioesters of α-Amino Acids in the Generation of Isotactic Peptides and Co-peptides in Water; Implications for the Origin of Homochirality

    NASA Astrophysics Data System (ADS)

    Illos, Roni A.; Clodic, Gilles; Bolbach, Gerard; Weissbuch, Isabelle; Lahav, Meir

    2010-02-01

    Thioesters of α-amino acids are considered as plausible monomers for the generation of the primeval peptides. DL-Leucine-thioethyl esters (LeuSEt), where the L-enantiomer was tagged with deuterium atoms, undergo polycondensation in water or in bicarbonate or imidazole buffer solutions to yield mainly heterochiral (atactic) peptides and diketopiperazine, as analyzed by MALDI-TOF and ESI mass-spectrometry. In variance, when polymerization of DL(d10) -Leu, first activated with N,N'-carbonyldiimidazole, then initiated with ethanethiol or with DL(d3) -LeuSEt yielded a library of peptides up to 30 detectable residues where those of homochiral sequence (isotactic) are the dominant diastereoisomers. At these conditions, racemic β-sheets are formed and operate as stereoselective templates in the process of chain-elongation. Isotopic L: L(d10)-Leu co-peptides were obtained in the polymerization of L(d10)-Leu with L-LeuSEt. By contrast, mixtures of oligo- D-Leu and oligo- L(d10)-Leu were obtained in the polymerization of mixtures of D-LeuSEt with activated L(d10)-Leu. Isotactic co-peptides containing Leu and Val residues were formed in the polymerization of mixtures of activated DL(d8)-Val with DL(d3) -LeuSEt in water, implying that the racemic β-sheets exert regio-enantio-selection but not chemo-selection. A reaction pathway is suggested, where LeuSEt operates both as initiator of the reaction as well as a multimer.

  1. Rationally re-designed mutation of NAD-independent l-lactate dehydrogenase: high optical resolution of racemic mandelic acid by the engineered Escherichia coli

    PubMed Central

    2012-01-01

    Background NAD-independent l-lactate dehydrogenase (l-iLDH) from Pseudomonas stutzeri SDM can potentially be used for the kinetic resolution of small aliphatic 2-hydroxycarboxylic acids. However, this enzyme showed rather low activity towards aromatic 2-hydroxycarboxylic acids. Results Val-108 of l-iLDH was changed to Ala by rationally site-directed mutagenesis. The l-iLDH mutant exhibited much higher activity than wide-type l-iLDH towards l-mandelate, an aromatic 2-hydroxycarboxylic acid. Using the engineered Escherichia coli expressing the mutant l-iLDH as a biocatalyst, 40 g·L-1 of dl-mandelic acid was converted to 20.1 g·L-1 of d-mandelic acid (enantiomeric purity higher than 99.5%) and 19.3 g·L-1 of benzoylformic acid. Conclusions A new biocatalyst with high catalytic efficiency toward an unnatural substrate was constructed by rationally re-design mutagenesis. Two building block intermediates (optically pure d-mandelic acid and benzoylformic acid) were efficiently produced by the one-pot biotransformation system. PMID:23176608

  2. Amino acids in modern and fossil woods

    NASA Technical Reports Server (NTRS)

    Lee, C.; Bada, J. L.; Peterson, E.

    1976-01-01

    The amino acid composition and the extent of racemization in several modern and fossil woods are reported. The method of analysis is described, and data are presented on the total amino acid concentration, the amino acid ratios, and the enantiomeric ratios in each sample. It is found that the amino acid concentration per gram of dry wood decreases with age of the sample, that the extent of racemization increases with increasing age, and that the amounts of aspartic acid, threonine, and serine decrease relative to valine with increasing age. The relative racemization rates of amino acids in wood, bone, and aqueous solution are compared, and it is shown that racemization in wood is much slower than in bone or aqueous solution. Racemization results for woods from the Kalambo Falls area of Zambia are used to calculate a minimum age of 110,000 years for the transition between the Sangoan and Acheulian industries at that site. This result is shown to be consistent with numerous radiometric dates for older Acheulian sites in Africa and to compare well with geologically inferred dates for the beginning of the Eemian and the end of the Acheulian industry in southern Africa.

  3. 40 CFR 72.69 - Issuance and effective date of acid rain permits.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 16 2010-07-01 2010-07-01 false Issuance and effective date of acid rain permits. 72.69 Section 72.69 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Federal Acid Rain Permit Issuance Procedures § 72.69 Issuance and effective date of acid rain permits....

  4. Single amino acid radiocarbon dating of Upper Paleolithic modern humans.

    PubMed

    Marom, Anat; McCullagh, James S O; Higham, Thomas F G; Sinitsyn, Andrey A; Hedges, Robert E M

    2012-05-01

    Archaeological bones are usually dated by radiocarbon measurement of extracted collagen. However, low collagen content, contamination from the burial environment, or museum conservation work, such as addition of glues, preservatives, and fumigants to "protect" archaeological materials, have previously led to inaccurate dates. These inaccuracies in turn frustrate the development of archaeological chronologies and, in the Paleolithic, blur the dating of such key events as the dispersal of anatomically modern humans. Here we describe a method to date hydroxyproline found in collagen (~10% of collagen carbon) as a bone-specific biomarker that removes impurities, thereby improving dating accuracy and confidence. This method is applied to two important sites in Russia and allows us to report the earliest direct ages for the presence of anatomically modern humans on the Russian Plain. These dates contribute considerably to our understanding of the emergence of the Mid-Upper Paleolithic and the complex suite of burial behaviors that begin to appear during this period. PMID:22517758

  5. Single amino acid radiocarbon dating of Upper Paleolithic modern humans

    PubMed Central

    Marom, Anat; McCullagh, James S. O.; Higham, Thomas F. G.; Sinitsyn, Andrey A.; Hedges, Robert E. M.

    2012-01-01

    Archaeological bones are usually dated by radiocarbon measurement of extracted collagen. However, low collagen content, contamination from the burial environment, or museum conservation work, such as addition of glues, preservatives, and fumigants to “protect” archaeological materials, have previously led to inaccurate dates. These inaccuracies in turn frustrate the development of archaeological chronologies and, in the Paleolithic, blur the dating of such key events as the dispersal of anatomically modern humans. Here we describe a method to date hydroxyproline found in collagen (∼10% of collagen carbon) as a bone-specific biomarker that removes impurities, thereby improving dating accuracy and confidence. This method is applied to two important sites in Russia and allows us to report the earliest direct ages for the presence of anatomically modern humans on the Russian Plain. These dates contribute considerably to our understanding of the emergence of the Mid-Upper Paleolithic and the complex suite of burial behaviors that begin to appear during this period. PMID:22517758

  6. 40 CFR 72.69 - Issuance and effective date of acid rain permits.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Federal Acid Rain Permit Issuance Procedures § 72.69 Issuance and effective date of acid rain permits. (a) After the close of the public comment period, the Administrator will issue or deny an Acid Rain permit. The Administrator will serve a copy of any Acid...

  7. 40 CFR 72.69 - Issuance and effective date of acid rain permits.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Federal Acid Rain Permit Issuance Procedures § 72.69 Issuance and effective date of acid rain permits. (a) After the close of the public comment period, the Administrator will issue or deny an Acid Rain permit. The Administrator will serve a copy of any Acid...

  8. 40 CFR 72.69 - Issuance and effective date of acid rain permits.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Federal Acid Rain Permit Issuance Procedures § 72.69 Issuance and effective date of acid rain permits. (a) After the close of the public comment period, the Administrator will issue or deny an Acid Rain permit. The Administrator will serve a copy of any Acid...

  9. 40 CFR 72.69 - Issuance and effective date of acid rain permits.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Federal Acid Rain Permit Issuance Procedures § 72.69 Issuance and effective date of acid rain permits. (a) After the close of the public comment period, the Administrator will issue or deny an Acid Rain permit. The Administrator will serve a copy of any Acid...

  10. Enantiomeric resolution of multiple chiral centres racemates by capillary electrophoresis.

    PubMed

    Ali, Imran; Suhail, Mohd; Al-Othman, Zeid A; Alwarthan, Abdulrahman; Aboul-Enein, Hassan Y

    2016-05-01

    Enantiomeric resolution of multichiral centre racemates is an important area as some multichiral centre racemates are of great medicinal importance. However, enantioseparation of such types of racemates is a challenging task. Amongst many analytical techniques, capillary electrophoresis is a powerful technique and may be used to resolve such racemates. Only few papers are available describing enantiomeric resolution of such racemates. Therefore, efforts have been made to describe the enantiomeric resolution of multichiral centre racemates by capillary electrophoresis. This article discusses the importance of multichiral racemates, the need for capillary electrophoresis in enantiomeric resolution and chiral resolution of multichiral centre racemates using various chiral selectors. Further, attempts have been made to discuss the future challenges and prospects of enantiomeric resolution of multichiral racemates. The various chiral selectors used for the purpose are chiral crown ether, cyclodextrins, polysaccharides, macrocyclic glycopeptide antibiotics and ligand exchange. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26840015

  11. Characterization and quantification of racemic and meso-ethylenediamine-N,N'-bis(2-hydroxy-5-sulfophenylacetic) acid/iron (III) by ion-pair ultra-high performance liquid chromatography coupled with diode array detector and electrospray tandem mass spectrometry.

    PubMed

    Biasone, Alessandro; Cianci, Giusto; Di Tommaso, Donata; Piaggesi, Alberto; Tagliavini, Emilio; Galletti, Paola; Moretti, Fabio

    2013-03-22

    EDDHSA/Fe is a promising substitute of EDDHA/Fe to fight iron chlorosis. o,o-EDDHSA structure contains two chiral carbons giving the racemic and meso couples of stereoisomers. Ion-pair HPLC and UHPLC-UV/Vis-ESI-MS/MS methods were developed for the determination of racemic and meso-o,o-EDDHSA/Fe in commercial samples of chelates. The lack of a commercial EDDHSA standard was overcome by sulfonation of a commercial available o,o-EDDHA standard and subsequent quantification by (1)H-NMR. Assignment of configurations was carried out starting from racemic and meso-o,o-EDDHA/Fe by direct sulfonation to give the corresponding o,o-EDDHSA/Fe isomers. The performances of these methods were assessed in terms of intra and inter-day precision, linearity and selectivity. The high selectivity and lower detection limit (nanomolar) of the UHPLC-ESI-MS/MS method could allow to deepen the knowledge relative to meso and rac-o,o-EDDHSA/Fe interactions with plants, its fate in different soil conditions, its mobility and other environmental aspects. PMID:23411145

  12. Geochemical evolution of amino acids in dentine of Pleistocene bears.

    PubMed

    De Torres, T; Ortiz, J E; García, M J; Llamas, J F; Canoira, L; De La Morena, M A; Juliá, R

    2001-08-01

    A linear correlation was established between aspartic acid racemization ratio from cave bear dentine collagen and absolute dating. The high correlation coefficient obtained allowed age calculation through amino acid racemization. Aspartic acid and glutamic acid racemization kinetics have also been explored in dentine from a North American black bear (Ursus americanus Pallas). Three sample sets were prepared for kinetic heating experiments in nitrogen atmosphere: one water soaked, one with a water-saturated nitrogen atmosphere, and one without any moisture. It was possible to show that the presence of water is a factor controlling amino acid racemization rate. The aspartic acid in a heating experiment at 105 degrees C shows an "apparent kinetics reversal" which can be explained by a progressive hydrolysis of amino acid chains (proteins and polypeptides). Because of the low potential of collagen preservation over long periods of time, the apparent kinetics reversal phenomenon will not affect the dating of old material where no traces of collagen remain. An apparent kinetics reversal was not observed in glutamic acid, which racemizates more slowly. PMID:11466777

  13. Racemization of Isobornyl Chloride via Carbocations: A Nonclassical Look at a Classic Mechanism

    ERIC Educational Resources Information Center

    Rzepa, Henry S.; Allan, Charlotte S. M.

    2010-01-01

    Our understanding of carbonium ions as intermediates in chemical reaction mechanisms derives from the early work of Julius Stieglitz and the more famous Hans Meerwein, the latter studying the racemization of isobornyl chloride when treated with Lewis acids. This review analyzes how key mechanistic concepts for this reaction evolved and gives the…

  14. Direct dating of human fossils.

    PubMed

    Grün, Rainer

    2006-01-01

    The methods that can be used for the direct dating of human remains comprise of radiocarbon, U-series, electron spin resonance (ESR), and amino acid racemization (AAR). This review gives an introduction to these methods in the context of dating human bones and teeth. Recent advances in ultrafiltration techniques have expanded the dating range of radiocarbon. It now seems feasible to reliably date bones up to 55,000 years. New developments in laser ablation mass spectrometry permit the in situ analysis of U-series isotopes, thus providing a rapid and virtually non-destructive dating method back to about 300,000 years. This is of particular importance when used in conjunction with non-destructive ESR analysis. New approaches in AAR analysis may lead to a renaissance of this method. The potential and present limitations of these direct dating techniques are discussed for sites relevant to the reconstruction of modern human evolution, including Florisbad, Border Cave, Tabun, Skhul, Qafzeh, Vindija, Banyoles, and Lake Mungo. PMID:17103430

  15. Spin crossover properties of enantiomers, co-enantiomers, racemates, and co-racemates.

    PubMed

    Qin, Long-Fang; Pang, Chun-Yan; Han, Wang-Kang; Zhang, Feng-Li; Tian, Lei; Gu, Zhi-Guo; Ren, Xuehong; Li, Zaijun

    2016-04-25

    Through multi-component self-assembly of chiral phenylethylamine, 1-alkyl-2-imidazolecarboxaldehyde and iron(ii) ions, two couples of enantiomeric iron(ii) complexes , , and with the formula of fac-Λ or Δ-[Fe(L)3](2+)(L = R or S-1-phenyl-N-(1-alkyl-1H-imidazol-2-ylmethylene)ethanamine) have been designed and synthesized as building blocks. Further binary cocrystallization of the prefabricated enantiomers enabled us to construct spin crossover co-enantiomers and , racemates and , and co-racemate . Compared with in a high spin state and with spin crossover at 291 K, the co-enantiomers exhibited gradual spin crossover at a higher temperature of 301 K, and the racemic alloys showed hysteresis loops induced by desolvation above room temperature. It was demonstrated that molecular chirality could be used effectively for stereochemical engineering of spin crossover materials. In addition, crystal packing, intramolecular π-π stacking, intermolecular C-Hπ interactions and solvent effects were elucidated to be responsible for the distinct spin crossover properties. This collective structural and magnetic study not only enriched the spin crossover library, but also provided a full comparison of optically pure, homochiral, and racemic materials with similar molecular structures. PMID:27021212

  16. Racemization of undesired enantiomers: Immobilization of mandelate racemase and application in a fixed bed reactor.

    PubMed

    Wrzosek, Katarzyna; Rivera, Mariel A García; Bettenbrock, Katja; Seidel-Morgenstern, Andreas

    2016-03-01

    Production of optically pure products can be based on simple unselective synthesis of racemic mixtures combined with a subsequent separation of the enantiomers; however, this approach suffers from a 50% yield limitation which can be overcome by racemization of the undesired enantiomer and recycling. Application of biocatalyst for the racemization steps offers an attractive option for high-yield manufacturing of commercially valuable compounds. Our work focuses on exploiting the potential of racemization with immobilized mandelate racemase. Immobilization of crude mandelate racemase via covalent attachment was optimized for two supports: Eupergit(®) CM and CNBr-activated Sepharose 4 Fast Flow. To allow coupling of enzymatic reaction with enantioselective chromatography, a mobile phase composition compatible with both processes was used in enzymatic reactor. Kinetic parameters obtained analyzing experiments carried out in a batch reactor could be successfully used to predict fixed-bed reactor performance. The applicability of the immobilized enzyme and the determined kinetic parameters were validated in transient experiments recording responses to pulse injections of R-mandelic acid. The approach investigated can be used for futher design and optimization of high yield combined resolution processes. The characterized fixed-bed enzymatic reactor can be integrated e.g. with chromatographic single- or multicolumn steps in various configurations. PMID:26773335

  17. Enantioselective enzymatic hydrolysis of racemic drugs by encapsulation in sol-gel magnetic sporopollenin.

    PubMed

    Yilmaz, Elif

    2012-05-01

    Candida rugosa lipase was encapsulated within a sol-gel procedure and improved considerably by fluoride-catalyzed hydrolysis of mixtures of octyltriethoxysilane and tetraethoxysilane in the presence of magnetic sporopollenin. The catalytic properties of the immobilized lipases were evaluated into model reactions, i.e., the hydrolysis of p-nitrophenylpalmitate (p-NPP), and the enantioselective hydrolysis of racemic naproxen methyl ester, mandelic acid methyl ester or 2-phenoxypropionic acid methyl ester that were studied in aqueous buffer solution/isooctane reaction system. The encapsulated magnetic sporopollenin (Spo-M-E) was found to give 319 U/g of support with 342% activity yield. It has been observed that the percent activity yields and enantioselectivity of the magnetic sporopollenin encapsulated lipase were higher than that of the encapsulated lipase without support. The substrate specificity of the encapsulated lipase revealed more efficient hydrolysis of the racemic naproxen methyl ester and 2-phenoxypropionic acid methyl ester than racemic mandelic acid methyl ester. It was observed that excellent enantioselectivity (E > 400) was obtained for encapsulated lipase with magnetic sporopollenin with an ee value of S-Naproxen and R-2 phenoxypropionic acid about 98%. PMID:21932062

  18. Dating and context of three middle stone age sites with bone points in the Upper Semliki Valley, Zaire.

    PubMed

    Brooks, A S; Helgren, D M; Cramer, J S; Franklin, A; Hornyak, W; Keating, J M; Klein, R G; Rink, W J; Schwarcz, H; Smith, J N

    1995-04-28

    The extent to which the earliest anatomically modern humans in Africa exhibited behavioral and cognitive traits typical of Homo sapiens sapiens is controversial. In eastern Zaire, archaeological sites with bone points have yielded dates older than 89(-15)+22 thousand years ago by several techniques. These include electron spin resonance, thermoluminescence, optically stimulated luminescence, uranium series, and amino acid racemization. Faunal and stratigraphic data are consistent with this age. PMID:7725099

  19. Chronometric dating in archaeology: a review.

    PubMed

    Schwarcz, Henry P

    2002-08-01

    Most archaeological dating methods are based on decay of a naturally occurring radioisotope. (14)C activity of fossil bones and charcoal decreases with age, but must be calibrated for past changes in atmospheric activity. Uranium absorbed by shells and stalagmites is used to date on a 10(5)-year scale by observing the decay of (234)U to (230) Th. Thermoluminescence, optical luminescence, and electron spin resonance detect trapped electronic charges generated by natural radioactivity in burned flint, beach sands, shells, and tooth enamel. Rate of racemization of amino acids in fossil shells is constant at constant T, and age can be tracked from an increase in the D/L ratio. PMID:12186568

  20. Enzymatic saccharification and fermentation of cellulosic date palm wastes to glucose and lactic acid

    PubMed Central

    Alrumman, Sulaiman A.

    2016-01-01

    The bioconversion of cellulosic wastes into high-value bio-products by saccharification and fermentation processes is an important step that can reduce the environmental pollution caused by agricultural wastes. In this study, enzymatic saccharification of treated and untreated date palm cellulosic wastes by the cellulases from Geobacillus stearothermophilus was optimized. The alkaline pre-treatment of the date palm wastes was found to be effective in increasing the saccharification percentage. The maximum rate of saccharification was found at a substrate concentration of 4% and enzyme concentration of 30 FPU/g of substrate. The optimum pH and temperature for the bioconversions were 5.0 and 50 °C, respectively, after 24 h of incubation, with a yield of 31.56 mg/mL of glucose at a saccharification degree of 71.03%. The saccharification was increased to 94.88% by removal of the hydrolysate after 24 h by using a two-step hydrolysis. Significant lactic acid production (27.8 mg/mL) was obtained by separate saccharification and fermentation after 72 h of incubation. The results indicate that production of fermentable sugar and lactic acid is feasible and may reduce environmental pollution by using date palm wastes as a cheap substrate. PMID:26887233

  1. Enzymatic saccharification and fermentation of cellulosic date palm wastes to glucose and lactic acid.

    PubMed

    Alrumman, Sulaiman A

    2016-01-01

    The bioconversion of cellulosic wastes into high-value bio-products by saccharification and fermentation processes is an important step that can reduce the environmental pollution caused by agricultural wastes. In this study, enzymatic saccharification of treated and untreated date palm cellulosic wastes by the cellulases from Geobacillus stearothermophilus was optimized. The alkaline pre-treatment of the date palm wastes was found to be effective in increasing the saccharification percentage. The maximum rate of saccharification was found at a substrate concentration of 4% and enzyme concentration of 30 FPU/g of substrate. The optimum pH and temperature for the bioconversions were 5.0 and 50°C, respectively, after 24h of incubation, with a yield of 31.56mg/mL of glucose at a saccharification degree of 71.03%. The saccharification was increased to 94.88% by removal of the hydrolysate after 24h by using a two-step hydrolysis. Significant lactic acid production (27.8mg/mL) was obtained by separate saccharification and fermentation after 72h of incubation. The results indicate that production of fermentable sugar and lactic acid is feasible and may reduce environmental pollution by using date palm wastes as a cheap substrate. PMID:26887233

  2. Racemization and the origin of optically active organic compounds in living organisms

    NASA Technical Reports Server (NTRS)

    Bada, J. L.; Miller, S. L.

    1987-01-01

    The organic compounds synthesized in prebiotic experiments are racemic mixtures. A number of proposals have been offered to explain how asymmetric organic compounds formed on the Earth before life arose, with the influence of chiral weak nuclear interactions being the most frequent proposal. This and other proposed asymmetric syntheses give only sight enantiomeric excess and any slight excess will be degraded by racemization. This applies particularly to amino acids where half-lives of 10(5)-10(6) years are to be expected at temperatures characteristic of the Earth's surface. Since the generation of chiral molecules could not have been a significant process under geological conditions, the origins of this asymmetry must have occurred at the time of the origin of life or shortly thereafter. It is possible that the compounds in the first living organisms were prochiral rather than chiral; this is unlikely for amino acids, but it is possible for the monomers of RNA-like molecules.

  3. Nephroprotective effect of date fruit extract against dichloroacetic acid exposure in adult rats.

    PubMed

    El Arem, Amira; Thouri, Amira; Zekri, Mouna; Saafi, Emna Behija; Ghrairi, Fatma; Zakhama, Abdelfattah; Achour, Lotfi

    2014-03-01

    The aim of this study was to investigate the protective effects of aqueous date extract (ADE) on dichloroacetic acid (DCA)-induced nephrotoxicity. In vitro, total phenolic content estimated in the ADE were 417.71mg gallic acid equivalents/100g fresh weights (FW), while total flavonoid and tannins contents were 285.23 and 73.65mg catechin equivalents/100g FW, respectively. The ADE has strong scavenging activity. Ferulic, caffeic and p-coumaric acids are the major's compounds. Nephrotoxicity was induced in male Wistar rats by the administration of 0.5 and 2g/L DCA as drinking water. Some of these rats received also by gavage ADE (4mL/kg) before the administration of DCA. After two months of experiment, DCA administration caused elevated levels of renal MDA, significant depletion of GSH levels, altered the antioxidant enzyme activities and deteriorated the renal functions as assessed by the increased plasma urea, uric acid and creatinine levels compared to control rats. The treatment with the ADE significantly normalized the increased plasma levels of creatinine, urea and uric acid, reduced the elevated MDA levels, significantly normalized the antioxidant enzyme activities and GSH level and restored the altered kidney histology in rats treated with DCA. Therefore, it was speculated that ADE protects rats from kidney damage through its antioxidant capacity. PMID:24394489

  4. Racemic crystallography of synthetic protein enantiomers used to determine the X-ray structure of plectasin by direct methods

    PubMed Central

    Mandal, Kalyaneswar; Pentelute, Brad L; Tereshko, Valentina; Thammavongsa, Vilasak; Schneewind, Olaf; Kossiakoff, Anthony A; Kent, Stephen B H

    2009-01-01

    We describe the use of racemic crystallography to determine the X-ray structure of the natural product plectasin, a potent antimicrobial protein recently isolated from fungus. The protein enantiomers l-plectasin and d-plectasin were prepared by total chemical synthesis; interestingly, l-plectasin showed the expected antimicrobial activity, while d-plectasin was devoid of such activity. The mirror image proteins were then used for racemic crystallization. Synchrotron X-ray diffraction data were collected to atomic resolution from a racemic plectasin crystal; the racemate crystallized in the achiral centrosymmetric space group with one l-plectasin molecule and one d-plectasin molecule forming the unit cell. Dimer-like intermolecular interactions between the protein enantiomers were observed, which may account for the observed extremely low solvent content (13%–15%) and more highly ordered nature of the racemic crystals. The structure of the plectasin molecule was well defined for all 40 amino acids and was generally similar to the previously determined NMR structure, suggesting minimal impact of the crystal packing on the plectasin conformation. PMID:19472324

  5. Racemic crystallography of synthetic protein enantiomers used to determine the X-ray structure of plectasin by direct methods

    SciTech Connect

    Mandal, Kalyaneswar; Pentelute, Brad L.; Tereshko, Valentina; Thammavongsa, Vilasak; Schneewind, Olaf; Kossiakoff, Anthony A.; Kent, Stephen B.H.

    2009-06-30

    We describe the use of racemic crystallography to determine the X-ray structure of the natural product plectasin, a potent antimicrobial protein recently isolated from fungus. The protein enantiomers L-plectasin and D-plectasin were prepared by total chemical synthesis; interestingly, L-plectasin showed the expected antimicrobial activity, while D-plectasin was devoid of such activity. The mirror image proteins were then used for racemic crystallization. Synchrotron X-ray diffraction data were collected to atomic resolution from a racemic plectasin crystal; the racemate crystallized in the achiral centrosymmetric space group P1 with one L-plectasin molecule and one D-plectasin molecule forming the unit cell. Dimer-like intermolecular interactions between the protein enantiomers were observed, which may account for the observed extremely low solvent content (13%-15%) and more highly ordered nature of the racemic crystals. The structure of the plectasin molecule was well defined for all 40 amino acids and was generally similar to the previously determined NMR structure, suggesting minimal impact of the crystal packing on the plectasin conformation.

  6. Synthesis and Antifeedant Activity of Racemic and Optically Active Hydroxy Lactones with the p-Menthane System.

    PubMed

    Grudniewska, Aleksandra; Kłobucki, Marek; Dancewicz, Katarzyna; Szczepanik, Maryla; Gabryś, Beata; Wawrzeńczyk, Czesław

    2015-01-01

    Two racemic and two enantiomeric pairs of new δ-hydroxy-γ-lactones based on the p-menthane system were prepared from racemic and optically active cis- and trans-piperitols. The Johnson-Claisen rearrangement of the piperitols, epoxidation of the γδ-unsaturated esters, and acidic lactonization of the epoxy esters were described. The structures of the compounds were confirmed spectroscopically. The antifeedant activities of the hydroxy lactones and racemic piperitone were evaluated against three insect pests: lesser mealworm, Alphitobius diaperinus (Panzer); Colorado potato beetle, Leptinotarsa decemlineata (Say); and peach-potato aphid, Myzus persicae (Sulz.). The chemical transformation of piperitone by the introduction of a lactone moiety and a hydroxy group changed its antifeedant properties. Behavioral bioassays showed that the feeding deterrent activity depended on the insect species and the structure of the compounds. All hydroxy lactones deterred the settling of M. persicae. Among chewing insects, the highest sensitivity showed A. diaperinus adults. PMID:26132506

  7. Synthesis and Antifeedant Activity of Racemic and Optically Active Hydroxy Lactones with the p-Menthane System

    PubMed Central

    Grudniewska, Aleksandra; Kłobucki, Marek; Dancewicz, Katarzyna; Szczepanik, Maryla; Gabryś, Beata; Wawrzeńczyk, Czesław

    2015-01-01

    Two racemic and two enantiomeric pairs of new δ-hydroxy-γ-lactones based on the p-menthane system were prepared from racemic and optically active cis- and trans-piperitols. The Johnson-Claisen rearrangement of the piperitols, epoxidation of the γδ-unsaturated esters, and acidic lactonization of the epoxy esters were described. The structures of the compounds were confirmed spectroscopically. The antifeedant activities of the hydroxy lactones and racemic piperitone were evaluated against three insect pests: lesser mealworm, Alphitobius diaperinus (Panzer); Colorado potato beetle, Leptinotarsa decemlineata (Say); and peach-potato aphid, Myzus persicae (Sulz.). The chemical transformation of piperitone by the introduction of a lactone moiety and a hydroxy group changed its antifeedant properties. Behavioral bioassays showed that the feeding deterrent activity depended on the insect species and the structure of the compounds. All hydroxy lactones deterred the settling of M. persicae. Among chewing insects, the highest sensitivity showed A. diaperinus adults. PMID:26132506

  8. Localizing Perturbations of the Racemic Equilibria Involving Dipicolinate-Derived Lanthanide(III) Complexes.

    PubMed

    Nguyen, Brian T; Ingram, Andrew J; Muller, Gilles

    2016-04-01

    Helical D3 tris(4-amino-2,6-pyridine-dicarboxylate)terbium(III) and europium(III) complexes, which form a racemic equilibrium in aqueous solution, were prepared to study their secondary coordination sphere interactions with chiral amino acids. These interactions were probed using a combination of circularly polarized luminescence (CPL) and 13C NMR spectroscopy. The results indicate that, regardless of the interaction between the chiral molecule and the complex, without an accessible hydrogen-bond donor on the associating molecule, perturbation of the racemic equilibrium cannot occur. A generalized conclusion is established that indicates that the mechanism of chiral recognition by tris(dipicolinate)lanthanide(III) complexes is similar across a variety of analogous ligands. PMID:26935003

  9. Utilization of date stones for production of activated carbon using phosphoric acid

    SciTech Connect

    Haimour, N.M. . E-mail: nomanhaimour@hotmail.com; Emeish, S. . E-mail: s_emiesh@yahoo.com

    2006-07-01

    Date stone wastes have been utilized for production of activated carbon by chemical activation with phosphoric acid using a fluidized-bed reactor. The effects of the activation time, activation temperature, impregnation ratio, and particle size on the yield and the adsorptive capacity towards iodine were studied. The yield and the quality of the activated carbon prepared by using H{sub 3}PO{sub 4} were compared with that prepared from date stones using the same equipment, and under similar conditions by using ZnCl{sub 2} as an oxidizing agent. The maximum value of the iodine number of the activated carbon produced using H{sub 3}PO{sub 4} in this work was about 495 under the following conditions: impregnation ratio 0.4, activation time 60 min, activation temperature 800 deg. C, particle size 0.60 mm. The iodine number for the produced activated carbon was higher when phosphoric acid was used, compared to that when zinc chloride was used as impregnation reagent; however, the yield obtained when H{sub 3}PO{sub 4} was used was lower than the yield when ZnCl{sub 2} was used. The iodine number increases significantly with increasing the activation temperature. By increasing the impregnation ratio at the same temperature, the iodine number decreased sharply and an oscillation is noticed for all the cases but it was clearer at 800 deg. C. The average variation of the iodine number for the whole range of particle size used in this work is {+-}10%.

  10. Racemized and Isomerized Proteins in Aging Rat Teeth and Eye Lens.

    PubMed

    Warmack, Rebeccah A; Mansilla, Eduardo; Goya, Rodolfo G; Clarke, Steven G

    2016-08-01

    The quantification of aspartic acid racemization in the proteins of nonmetabolically active tissues can be used as a measure of chronological aging in humans and other long-lived organisms. However, very few studies have been conducted in shorter-lived animals such as rodents, which are increasingly used as genetic and metabolic models of aging. An initial study had reported significant changes in the ratio of d- to l-aspartate in rat molars with age. Using a sensitive HPLC method for the determination of d- and l-aspartate from protein hydrolysates, we found no accumulation of d-aspartate in the molars of 17 rats that ranged in age from 2 to 44 months, and the amount of d-aspartate per molar did not correspond with molar eruption date as had been previously reported. However, developing an alternate approach, we found significant accumulation of isomerized aspartyl residues in eye lens proteins that are also formed by spontaneous degradation processes. In this study, we used the human protein l-isoaspartate/d-aspartate O-methyltransferase (PCMT1) as an analytical reagent in a sensitive and convenient procedure that could be used to rapidly examine multiple samples simultaneously. We found levels of isomerized aspartyl residues to be about 35 times higher in the lens extracts of 18-month-old rats versus 2-month-old rats, suggesting that isomerization may be an effective marker for biological aging in this range of ages. Importantly, we found that the accumulation appeared to plateau in rats of 18 months and older, indicating that potentially novel mechanisms for removing altered proteins may develop with age. PMID:26650547

  11. Solubility properties of racemic praziquantel and its enantiomers.

    PubMed

    el-Arini, S K; Giron, D; Leuenberger, H

    1998-11-01

    The purpose of this study was to characterize the solubility and thermodynamic properties of the optical isomers of the anti-schistosomal drug, praziquantel (PZQ) and to compare these properties to those of the racemic product used in commercial preparations (Biltricide, generic drugs). The crystalline enantiomers of PZQ exhibited different thermal properties than the racemic drug. The melting points and the enthalpies of fusion obtained from the differential scanning calorimetry (DSC) scans were nearly identical between the isomers and were substantially lower than those of racemic PZQ [(+/-)-PZQ]. The DSC results indicate that (+/-)-PZQ is a racemic compound and not a racemic mixture. This was confirmed by powder x-ray diffraction analysis and the IR spectra. The 30 degrees decrease in the melting point was reflected in increased solubility of the enantiomers, which amounted to twice that of the racemic PZQ. The behavior of the isomers in the presence of beta-cyclodextrin (beta-CD) was studied in water at 37 degrees C. The solubility data (phase solubility diagrams) were linear for up to the highest concentration of added beta-CD investigated. The apparent stability constants determined from the phase solubility diagrams showed that both the (+) and (-) enantiomers as well as (+/-)-PZQ exhibited moderate affinity to form a 1:1 complex in solution with beta-CD. The findings of this study may be of importance when efforts are considered to improve pharmaceutical formulation of this anti-schistosomal drug. PMID:9834959

  12. The real gordian knot: racemic mixtures versus pure enantiomers.

    PubMed

    Szelenyi, I; Geisslinger, G; Polymeropoulos, E; Paul, W; Herbst, M; Brune, K

    1998-04-01

    Many drugs exist as asymmetric three-dimensional (chiral) molecules and will therefore have several stereoisomers. There are often pharmacodynamic, pharmacokinetic and/or toxicological differences between enantiomers. The choice between developing a racemate or single enantiomers depends on therapeutic advances and developmental costs involved. Regarding the target environment for drug intervention, even if natural physiological mediators are achiral, their receptors may demonstrate a preference for the (-)- or (+)-enantiomer of agonists or antagonists. It is also obvious that the majority of enzymes and channels are stereospecific, at least to a variable extent. From a pharmacokinetics point of view, chirality can have an influence on drug absorption, distribution, metabolism and elimination. With a few exceptions, toxicological differences between isomers of known drugs are less dramatic than thought to be and only seldom substantiate the necessity of a racemic switch. The pharmaceutical industry is currently very interested in the so-called "racemic switch." Before proceeding to a racemic switch it is necessary to determine if 1) it is chemically feasible to produce a single enantiomer; 2) a clinical advantage is obtainable through a racemic switch; and 3) a marketing advantage is obtainable. The real goal of a racemic switch should be the rational development of compounds that are profitable for the company and--first of all--beneficial for the patient. PMID:15616615

  13. Chiroptical properties and the racemization of pyrene and tetrathiafulvalene-substituted allene: substitution and solvent effects on racemization in tetrathiafulvalenylallene.

    PubMed

    Hasegawa, Masashi; Iwata, Seiya; Sone, Yasuto; Endo, Junta; Matsuzawa, Hideyo; Mazaki, Yasuhiro

    2014-01-01

    Dissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thio)tetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC, and its chiroptical properties were examined with optical rotation and electronic circular dichroism (ECD) spectra. The title compound underwent photoracemization under daylight. This behavior was investigated in various solvents and compared with that of 1,3-bis(tetrathiafulvalenyl)allene (bis-TTF-allene) derivative 2. The first-order rate plot of the intensity of the ECD spectra at a given time interval gave the rate of racemization. Mild racemization was observed in polar solvents, whereas a relatively fast rate was obtained in less polar solvents. In addition, the TTF groups of the allene also accelerate the racemization rate. These results suggest that the racemization mechanism occurs via a non-polar diradical structure. PMID:24599123

  14. The use of date waste for lactic acid production by a fed-batch culture using Lactobacillus casei subsp. rhamnosus

    PubMed Central

    Nancib, Aicha; Nancib, Nabil; Boubendir, Abdelhafid; Boudrant, Joseph

    2015-01-01

    The production of lactic acid from date juice by Lactobacillus caseisubsp. rhamnosus in batch and fed-batch cultures has been investigated. The fed-batch culture system gave better results for lactic acid production and volumetric productivity. The aim of this work is to determine the effects of the feeding rate and the concentration of the feeding medium containing date juice glucose on the cell growth, the consumption of glucose and the lactic acid production by Lactobacillus casei subsp. rhamnosus in fed-batch cultures. For this study, two concentrations of the feeding medium (62 and 100 g/L of date juice glucose) were tested at different feeding rates (18, 22, 33, 75 and 150 mL/h). The highest volumetric productivity (1.3 g/L.h) and lactic acid yield (1.7 g/g) were obtained at a feeding rate of 33 mL/h and a date juice glucose concentration of 62 g/L in the feeding medium. As a result, most of the date juice glucose was completely utilised (residual glucose 1 g/L), and a maximum lactic acid production level (89.2 g/L) was obtained. PMID:26413076

  15. Antinociceptive activity of NK1 receptor antagonists: non-specific effects of racemic RP67580.

    PubMed Central

    Rupniak, N. M.; Boyce, S.; Williams, A. R.; Cook, G.; Longmore, J.; Seabrook, G. R.; Caeser, M.; Iversen, S. D.; Hill, R. G.

    1993-01-01

    1. Release of substance P in the dorsal horn is considered a primary event in the perception of pain. The profile of racemic RP67580, a non-peptide antagonist at the NK1 (substance P) receptor, was examined in a range of antinociception tests on rodents. 2. At doses up to 30 mg kg-1, s.c. racemic RP67580 exhibited antinociceptive activity in writhing and formalin paw tests in mice and gerbils. Acetic acid induced writhing and the licking response to formalin were reduced to 40-50% of the level observed in vehicle-treated animals (P < 0.05). However, this agent was not active in mouse tail flick, rat paw pressure or rat and guinea-pig formalin paw tests. 3. Like racemic RP67580, the calcium channel blockers nifedipine (30 mg kg-1, i.p.) and verapamil (10 or 20 mg kg-1, s.c.) inhibited the response to formalin by approximately 60% in gerbils (P < 0.05 compared with vehicle-treated animals). 4. Evidence for calcium channel antagonist activity of RP67580 was obtained in vitro. Racemic RP67580 inhibited calcium entry into depolarized strips of guinea-pig ileum longitudinal muscle myenteric plexus (apparent KB = 587 +/- 115 nM), inhibited [3H]-diltiazem binding to rabbit skeletal membranes (IC50 = 298 nM) and depressed high threshold calcium currents in neurones cultured from rat cortex (10% inhibition at 10 microM). 5. These findings indicate that the acute antinociceptive effects of RP67580 may not be attributable to a specific interaction with NK1 receptors and may be mediated via calcium channel blockade. PMID:8306108

  16. Stereoselective sulphate conjugation of racemic terbutaline by human liver cytosol.

    PubMed

    Walle, T; Walle, U K

    1990-07-01

    1. The enantioselectivity of the sulphation of racemic terbutaline by phenolsulphotransferases was examined in vitro using cytosol from human livers (n = 3) and [35S]-3'-phosphoadenosine-5'-phosphosulphate (PAP35S) as the sulphate donor. 2. The radioactive sulphate conjugate formed was isolated by h.p.l.c. and its enantiomers were separated intact by h.p.l.c. after chiral derivatization. 3. Sulphation of racemic terbutaline occurred with the same apparent Km value for both enantiomers (270 microM). The extent of sulphation of the (+)-enantiomer was double that of the (-)-enantiomer, solely due to a difference in their apparent Vmax values. 4. Sulphation of racemic prenalterol, a structural analogue of terbutaline, also showed a two-fold preference for the (+)-enantiomer. 5. These findings suggest that enantioselective sulphate conjugation of chiral phenolic sympathomimetic amine drugs may lead to enantioselective pharmacokinetics that should be considered in the clinical use of these drugs. PMID:2390423

  17. The cost effectiveness of levalbuterol versus racemic albuterol.

    PubMed

    Quinn, Campion

    2004-07-01

    Albuterol is a selective beta2-agonist that is widely used in the prevention and treatment of reactive airway disease. It is formulated as a racemic mixture containing equal parts of the R- and S-isomers. The therapeutic activity of albuterol is due entirely to the R-isomer, whereas the S-isomer may actually have detrimental effects. Because the slowly metabolized S-isomer tends to accumulate in the body, there has been concern that chronic use of racemic albuterol might lead to loss of effectiveness and clinical deterioration, with potentially serious health and cost consequences. Levalbuterol is a formulation containing only the R-isomer of albuterol, and clinical trials have demonstrated that it offers therapeutic advantages over racemic albuterol. The cost effectiveness of levalbuterol derives mainly from reduced need for acute medical care and hospitalization. PMID:15354680

  18. Induced circularly polarized luminescence arising from anion or protein binding to racemic emissive lanthanide complexes

    NASA Astrophysics Data System (ADS)

    Carr, Rachel; Puckrin, Robert; McMahon, Brian K.; Pal, Robert; Parker, David; Pålsson, Lars-Olof

    2014-06-01

    A circularly polarized luminescence (CPL) spectrometer has been built and used to study the binding interaction of lactate and four different proteins with racemic EuIII and TbIII complexes in aqueous solution. Lactate binding gives rise to strong induced CPL spectra, and the observed emission dissymmetry factors vary linearly with enantiomeric composition. Particularly strong induced TbIII CPL also characterizes the binding interaction of alpha-1-acid glycoprotein with a dissociation constant, Kd, of 2.5 μM.

  19. Diversity in a simple co-crystal: racemic and kryptoracemic behaviour.

    PubMed

    Rao Khandavilli, U B; Lusi, Matteo; Bhogala, Balakrishna R; Maguire, Anita R; Stein, Matthias; Lawrence, Simon E

    2016-07-01

    The crystal structure containing (±)-3-methyl-2-phenylbutyramide with salicylic acid is the first example of a kryptoracemate co-crystal. It exhibits the first temperature mediated reversible single-crystal to single-crystal transition between two kryptoracemate forms, in addition to crystallising in another, racemic, form. Theoretical calculations and structural analysis reveal that there are only small differences in both energy and packing arrangements between the three forms. These results suggest that co-crystals can be an opportunity to investigate kryptoracemate behaviour. PMID:27297725

  20. Which bioequivalence study for a racemic drug? Application to milnacipran.

    PubMed

    Deprez, D; Chassard, D; Baille, P; Mignot, A; Ung, H L; Puozzo, C

    1998-01-01

    Milnacipran, a new non tricyclic antidepressant drug, is a racemic mixture (F2207) composed of two enantiomers: F2695 and F2696, both demonstrated to be active. A randomized open label, single-dose latin square study was undertaken in 24 healthy volunteers to compare, based on racemate data, the relative bioavailability of two new formulations to that of a reference formulation. Later on, as suggested by actual regulatory trend, analysis was carried out on enantiomer data, although in a supportive way. Bioequivalence was assessed on calculation of 90% confidence intervals for log-transformed Cmax and AUC(0-infinity) and on Wilcoxon test for Tmax with a 5% level of significance. Based on racemate data, both test formulations were demonstrated to be equivalent to the reference capsule in terms of Cmax and AUC-(0-infinity). Differences in Tmax reached statistical significance, although their mean magnitude was small, and probably not relevant when related to antidepressant long-term therapy. When considering the test capsule - reference capsule comparison, the equivalence demonstrated for the racemate reflect that of each enantiomer. On the contrary, equivalence between the test tablet and the reference capsule demonstrated for the racemate, is not supported by both enantiomers as Cmax of F2696 fails to reach bioequivalence criteria, making more uncertain the conclusion of bioequivalence. From this experience, it seems than when equivalence is demonstrated close to the limits for the racemate, it is difficult, especially for a low variability drug such as milnacipran, to comply with equivalence criteria for both enantiomers. PMID:9725476

  1. Uranium series dating of human skeletal remains from the Del Mar and Sunnyvale sites, California

    USGS Publications Warehouse

    Bischoff, J.L.; Rosenbauer, R.J.

    1981-01-01

    Uranium series analyses of human bone samples from the Del Mar and Sunnyvale sites indicate ages of 11,000 and 8,300 years, respectively. The dates are supported by internal concordancy between thorium-230 and protactinium-231 decay systems. These ages are significantly younger than the estimates of 48,000 and 70,000 years based on amino acid racemization, and indicate that the individuals could derive from the population waves that came across the Bering Strait during the last sea-level low. Copyright ?? 1981 AAAS.

  2. Uranium series dating of human skeletal remains from the Del Mar and Sunnyvale sites, California

    SciTech Connect

    Bischoff, J.L.; Rosenbauer, R.J.

    1981-08-28

    Uranium series analyses of human bone samples from the Del Mar and Sunnyvale sites indicate ages of 11,000 and 8300 years, respectively. The dates are supported by internal concordancy between thorium-230 and protactinium-231 decay systems. These ages are significantly younger than the estimates of 48,000 and 70,000 years based on amino acid racemization, and indicate that the individuals could derive from the population waves that came across the Bering Strait during the last sea-level low.

  3. Uranium series dating of human skeletal remains from the del mar and sunnyvale sites, california.

    PubMed

    Bischoff, J L; Rosenbauer, R J

    1981-08-28

    Uranium series analyses of human bone samples from the Del Mar and Sunnyvale sites indicate ages of 11,000 and 8,300 years, respectively. The dates are supported by internal concordancy between thorium-230 and protactinium-231 decay systems. These ages are significantly younger than the estimates of 48,000 and 70,000 years based on amino acid racemization, and indicate that the individuals could derive from the population waves that came across the Bering Strait during the last sea-level low. PMID:17789030

  4. Protein L-isoaspartyl methyltransferase catalyzes in vivo racemization of Aspartate-25 in mammalian histone H2B.

    PubMed

    Young, Glen W; Hoofring, Sarah A; Mamula, Mark J; Doyle, Hester A; Bunick, Gerard J; Hu, Yonglin; Aswad, Dana W

    2005-07-15

    Protein L-isoaspartyl methyltransferase (PIMT) has been implicated in the repair or metabolism of proteins containing atypical L-isoaspartyl peptide bonds. The repair hypothesis is supported by previous studies demonstrating in vitro repair of isoaspartyl peptides via formation of a succinimide intermediate. Utilization of this mechanism in vivo predicts that PIMT modification sites should exhibit significant racemization as a side reaction to the main repair pathway. We therefore studied the D/L ratio of aspartic acid at specific sites in histone H2B, a known target of PIMT in vivo. Using H2B from canine brain, we found that Asp25 (the major PIMT target site in H2B) was significantly racemized, exhibiting d/l ratios as high as 0.12, whereas Asp51, a comparison site, exhibited negligible racemization (D/L < or = 0.01). Racemization of Asp25 was independent of animal age over the range of 2-15 years. Using H2B from 2-3-week mouse brain, we found a similar D/L ratio (0.14) at Asp25 in wild type mice, but substantially less racemization (D/L = 0.035) at Asp25 in PIMT-deficient mice. These findings suggest that PIMT functions in the repair, rather than the metabolic turnover, of isoaspartyl proteins in vivo. Because PIMT has numerous substrates in cells, these findings also suggest that D-aspartate may be more common in cellular proteins than hitherto imagined and that its occurrence, in some proteins at least, is independent of animal age. PMID:15908425

  5. Determining D/L Ratios of Amino Acids Found in Ice Above Lake Vostok Using ESI/CIT Mass Spectroscopy

    NASA Technical Reports Server (NTRS)

    Tsapin, A.; Kanik, I.; Beegle, L. W.; Wu, L.; Cooks, R. G.

    2003-01-01

    Astrobiology is an area where longevity of (micro) organisms is of great interest. Cryospheres are common phenomena in the solar system, particularly on satellites, comets and asteroids, as well as at least some of the planets. Recent data from the Mars Global Surveyor mission suggest the possibility of permafrost or perhaps even liquid water under the Martian surface [2]. These environments may be the areas in which the probability of finding life is the highest. This issue is of concern due to the probable evolution of planetary environments such as that of Mars from more hospitable to less hospitable conditions over the history of the solar system. In addition, evaluation of the possible transfer of living organisms between planets via impact ejecta [3] is dependent on knowledge of the maximum time periods over which microorganisms can remain dormant and subsequently revive and reproduce.Amino acid racemization dating, or aminostratigraphy, has been used for many years to date biological systems, and has been examined as a possible biosignature detection technique for Mars. We have suggested using amino acid racemization as one of the most indicative biosignatures [4]. Only life systems produce preferential synthesis of L-amino acids versus D-amino acids. Almost all amino acids in terrestrial organisms can be found only in the L-enantiomeric form.We studied the level of amino acid racemization, specifically of aspartic acid, in permafrost samples from eastern Siberia. Also we analyzed samples of ice from borehole drilled to lake Vostok, Antarctica.

  6. Application of direct crystallization for racemic compound propranolol hydrochloride.

    PubMed

    Wang, Xiujuan; Lu, Jie; Ching, Chi Bun

    2007-10-01

    The application of direct crystallization integrating with chromatography to the resolution of a racemic compound propranolol hydrochloride was studied and the crystallization progression was clearly illustrated in terms of the diagram of solubility and metastable zone widths with different enantiomeric compositions. The solubility and metastable zone widths of propranolol hydrochloride in the mixture of methanol and isopropanol were determined using an in situ Lasentec Focused Beam Reflectance Measurement (FBRM) probe. The direct crystallizations were carried out in an automatic lab reactor (Mettler Toledo LabMax) system. The optical purity of final product crystals was examined using differential scanning calorimetry (DSC), HPLC and PXRD. The crystal size distribution and morphology were analyzed using Malvern Mastersizer and Jeol SEM. It was found that optically pure crystal product could be obtained within certain safe supersaturation limit and there was no evidence of polymorph or solvate/hydrate transformation during the crystallization process. There was no selectivity of crystal growth or nucleation between the pure enantiomer and its racemate when the solution reaches the temperature lower than saturation temperature of the racemate. Hence, the critical supersaturation control of a solution was essential to obtain pure enantiomers from a partially resolved racemate. PMID:17549769

  7. Cysteine Racemization on IgG Heavy and Light Chains

    PubMed Central

    Zhang, Qingchun; Flynn, Gregory C.

    2013-01-01

    Under basic pH conditions, the heavy chain 220-light chain 214 (H220-L214) disulfide bond, found in the flexible hinge region of an IgG1, can convert to a thioether. Similar conditions also result in racemization of the H220 cysteine. Here, we report that racemization occurs on both H220 and L214 on an IgG1 with a λ light chain (IgG1λ) but almost entirely on H220 of an IgGl with a κ light chain (IgG1κ) under similar conditions. Likewise, racemization was detected at significant levels on H220 and L214 on endogenous human IgG1λ but only at the H220 position on IgG1κ. Low but measurable levels of d-cysteines were found on IgG2 cysteines in the hinge region, both with monoclonal antibodies incubated under basic pH conditions and on antibodies isolated from human serum. A simplified reaction mechanism involving reversible β-elimination on the cysteine is presented that accounts for both base-catalyzed racemization and thioether formation at the hinge disulfide. PMID:24142697

  8. Determination of relative enantiomer migration order using a racemic sample.

    PubMed

    Müllerová, Ludmila; Dubský, Pavel; Ördögová, Magda; Gaš, Bohuslav

    2015-12-11

    We developed a method that enables us to distinguish between the same or the opposite enantiomer migration order (EMO) of two enantiomers of a chiral compound with two different selectors. The method is applicable to racemic samples and thus a standard of the pure enantiomeric form(s) is not required. First, complexation constants and mobilities of complexes of the two enantiomers with the first and second selector are determined. However, for a racemic sample it is not possible to deduce whether the first migrating enantiomer with one selector is the same one as the first migrating enantiomer with the second selector. A specific mixture of the two selectors is designed to resolve this. In case the two enantiomers exhibit the same, respectively the opposite EMO in the two selectors, the mixture does, respectively does not separate the racemic sample. Thus two peaks are detected in the first case, while a single coalescent peak is recorded in the opposite case. We demonstrate the method on a racemic sample of amphetamine. Its relative EMO is determined with three cyclodextrins, heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, (2-hydroxypropyl)-β-cyclodextrin and heptakis(2,3-di-O-acetyl-6-O-sulfo)-β-cyclodextrin. PMID:26585204

  9. Oxyma-based phosphates for racemization-free peptide segment couplings

    PubMed Central

    Mitachi, Katsuhiko; Kurosu, Yuki E.; Hazlett, Brandon T.; Kurosu, Michio

    2016-01-01

    Glyceroacetonide-Oxyma [(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-cyano-2-(hydroxyimino)acetate (1)] displayed remarkable physico-chemical properties as an additive for peptide-forming reactions. Although racemization-free amide-forming reactions have been established for N-urethane-protected α-amino acids with EDCI, 1, and NaHCO3 in water or DMF-water media, amide-forming reactions of N-acyl-protected α-amino acids and segment couplings of oligopeptides still require further development. Diethylphosphoryl-Glyceroacetonide-Oxyma (DPGOx, 3) exhibits relative stability in aprotic solvents and is an effective coupling reagent for N-acyl-protected α-amino acids and oligo peptide segments. The conditions reported here is also effective in lactam-forming reactions. Unlike most of the reported coupling reagents, simple aqueous work-up procedures can remove the reagent and by-products generated in the reactions. PMID:26856693

  10. Homochiral oligopeptides via surface recognition and enantiomeric cross impediment in the polymerization of racemic phenylalanine N-carboxyanhydride crystals suspended in water.

    PubMed

    Nery, Jose Geraldo; Eliash, Ran; Bolbach, Gerard; Weissbuch, Isabelle; Lahav, Meir

    2007-08-01

    As part of our program on the search of possible prebiotic routes for the formation of oligopeptides of homochiral sequence (isotactic) from racemic precursors in aqueous environment, we report the polymerization of racemic crystals of phenylalanine N-carboxyanhydrides, enantioselectively tagged with five deuterium atoms, suspended in water containing various amine initiators. Racemic mixtures of isotactic oligopeptides, comprising up to 25 repeat units of the same handedness, as the dominant component for each length, were observed in a MALDI-TOF mass spectrometry analysis. The racemic mixtures of the peptides could be desymmetrized by initiating the polymerization reaction with water-soluble methyl esters of either enantiopure alpha-amino acids or dipeptides. A three-step mechanism is proposed to account for these results: (i) Surface recognition of the chiral initiator by the chiral sites present at specific faces of the crystal; (ii) Oligopeptide elongation at the polymer/crystal interface; and (iii) Self-assembly of the short isotactic peptides into racemic antiparallel beta-sheets as templates followed by cross-enantiomeric impediment in the growth of enantiomeric chains at the peptide beta-sheet/crystal interface. PMID:17354263

  11. Chiral separation of metolachlor ethane sulfonic acid as a groundwater dating tool

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have studied the hydrologic fate of metolachlor and its two predominant metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid, in groundwater and base flows of streams for several years. These two metabolites are excellent markers for groundwater processes related to...

  12. Using chiral identification of metolachlor ethane sulfonic acid as a groundwater dating tool

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have studied the hydrologic fate of metolachlor and its two predominant metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid, in groundwater and base flows of streams for several years. These two metabolites are excellent markers for groundwater processes related to...

  13. Copper-catalyzed divergent kinetic resolution of racemic allylic substrates.

    PubMed

    Pineschi, Mauro; Di Bussolo, Valeria; Crotti, Paolo

    2011-10-01

    When a racemic mixture is fully consumed the products may still be enantiomerically enriched. In particular, the regiodivergent kinetic resolution is a process in which a single chiral catalyst or reagent reacts with a racemic substrate to form regioisomers possessing an opposite configuration on the newly-formed stereogenic centers. This review reports the major advances in the field of the copper-catalyzed regiodivergent and stereodivergent kinetic resolution of allylic substrates with organometallic reagents. The chiral recognition matching phenomena found with particular allylic substrates with the absolute configuration of the chiral catalyst allows in some cases an excellent control of the regio- and stereoselectivity, sheding some light on the so-called "black-box" mechanism of a copper-catalyzed asymmetric allylic alkylation. PMID:21837639

  14. Hidden chirality in superficially racemic patchy silver films.

    PubMed

    Larsen, George K; He, Yizhuo; Ingram, Whitney; Zhao, Yiping

    2013-01-01

    Chiral patchy particle films where morphological enantiomers exist in equal proportion are found to have significant circular dichroism. It is determined that the rotation direction during glancing angle deposition breaks the racemic symmetry, resulting in a distribution of material which enhances the chirality of one set of enantiomers relative to the other. Microscopic analysis and geometric chirality calculations reveal that the chirality of the bulk film results from incomplete cancellations of even stronger local chiralities. PMID:24256449

  15. 14C dating of bone using (gamma) Carboxyglutamic Acid and Carboxyglycine (Aminomalonate)

    SciTech Connect

    Southon, J R; Burky, R T; Kirner, D L; Taylor, R E; Hare, P E

    1999-04-27

    Radiocarbon determinations have been obtained on {gamma}-carboxyglutamic acid [Gla] and {alpha}-carboxyglycine (aminomalonate) [Am] as well as acid- and base-hydrolyzed total amino acids isolated from a series of fossil bones. As far as they are aware, Am has not been reported previously in fossil bone and neither Gla nor Am {sup 14}C values have been measured previously. Interest in Gla, an amino acid found in the non-collagen proteins osteocalcin and matrix Gla-protein (MGP), proceeds from the suggestion that it may be preferentially retained and more resistant to diagenetic contamination affecting {sup 14}C values in bones exhibiting low and trace amounts of collagen. The data do not support these suggestions. The suite of bones examined showed a general tendency for total amino acid and Gla concentrations to decrease in concert. Even for bones retaining significant amounts of collagen, Gla (and Am extracts) can yield {sup 14}C values discordant with their expected age and with {sup 14}C values obtained on total amino-acid fractions isolated from the same bone sample.

  16. Enantioselectivity of hydroxylation of racemic piperitone by fungi.

    PubMed

    Grudniewska, Aleksandra; Gniłka, Radosław; Wawrzeńczyk, Czesław

    2010-11-01

    The biotransformation of racemic piperitone ((±)-1) was investigated using four strains of fungi selected in the screening procedure. The substrate was transformed by Botrytis cinerea AM235, Absidia cylindrospora AM336, Absidia coerulea AM93, and Absidia glauca AM177 into more polar metabolites. The transformation of racemic piperitone ((±)-1) catalyzed by B. cinerea AM235 gave 7-hydroxypiperitone (2) as the only product. The biotransformation of (±)-1 by A. cylindrospora AM336 afforded mixture of three products: (-)-(R)-7-hydroxypiperitone ((-)-2), (+)-(4S,6R)-trans-6-hydroxypiperitone ((+)-3), and (+)-(4R,6R)-cis-6-hydroxypiperitone ((+)-4). The transformation of this substrate ((±)-1) by A. coerulea AM93 gave (±)-7-hydroxypiperitone ((±)-2), (-)-(4R,6S)-trans-6-hydroxypiperitone (-)-3), and (-)-(4S,6S)-cis-6-hydroxypiperitone ((-)-4). The last strain studied, A. glauca AM177, converted racemic piperitone ((±)-1) to four products: (+)-(S)-7-hydroxypiperitone (2), (+)-(4S,6R)-trans-6-hydroxypiperitone ((+)-3), (±)-cis-6-hydroxypiperitone ((±)-4), and 8-hydroxypiperitone (5). PMID:20872669

  17. Scalemic and racemic imprinting with a chiral crosslinker.

    PubMed

    Hebert, Britney; Meador, Danielle S; Spivak, David A

    2015-08-26

    The development of molecularly imprinted chiral stationary phases has traditionally been limited by the need for a chiral pure template. Paradoxically, availability of a chiral pure template largely defeats the purpose of developing a chiral stationary phase. To solve this paradox, imprinting of scalemic and racemic template mixtures was investigated using both chiral (N-α-bismethacryloyl-L-alanine) and achiral (N,O-bisacrylamide ethanolamine) crosslinkers. Imprinting of scalemic mixtures provided polymers capable of partial separation of Boc-tyrosine enantiomers with virtually the same results when using either the chiral or achiral crosslinker. However, the chiral crosslinker was required for chiral differentiation by the racemic imprinted polymers which were evaluated in both batch rebinding and chromatographic modes. Batch rebinding analysis revealed intersecting binding isotherms for the L- and D-Boc-tyrosine, indicating bias for the D or L enantiomer is concentration dependent. Partial chromatographic separation was achieved by the racemic imprinted polymers providing variable D or L bias in equal probability over multiple replicates of polymer synthesis. Correlation of enantiomer bias with the batch rebinding results and optimization of HPLC parameters are discussed. PMID:26347178

  18. Enzymatic kinetic resolution of racemic ibuprofen: past, present and future.

    PubMed

    José, Carla; Toledo, María Victoria; Briand, Laura E

    2016-10-01

    This review is a journey concerning the investigations of the kinetic resolution of racemic ibuprofen for the last 20 years. The relevancy of the pharmacological uses of the S( + ) enantiomer along with its higher cost compared with racemic profen are the driving forces of a variety of scientific research studies addressing the enzymatic resolution of ibuprofen through enantiomeric esterification using lipases as biocatalysts. Lipases of fungal sources such as Candida rugosa, Rhizomucor miehei and the lipase B of Candida antarctica have been extensively studied both in homogeneous and heterogeneous (immobilized on solid supports) processes. In this context, the various alcohols and organic co-solvents frequently used in the esterification of racemic ibuprofen are summarized and discussed in this review. Moreover, recent investigations using membranes as reactors coupled with the separation of the desired product and microfluidic devices are presented. Finally, some guidelines about future perspectives regarding the technology of the kinetic resolution of profens and research niches are given. PMID:26121932

  19. Geochemistry of amino acids in shells of the clam Saxidomus

    USGS Publications Warehouse

    Kvenvolden, K.A.; Blunt, D.J.; McMenamin, M.A.; Straham, S.E.

    1980-01-01

    Concentrations of amino acids and their corresponding d l enantiomeric ratios have been measured in shells of the bivalve mollusk Saxidomus from eleven localities, ranging in age from modern to probably more than 500,000 yr, along the Pacific coast of North America. Natural logarithms of amino acid concentrations correlate well with d l ratios, and the relationship provides a possible guide to the selection of fossils for use in amino acid dating. The relative order of the extents of racemization of amino acids at any given time appears to change with increasing sample age. Application of the amino acid dating method to shells from Whidbey Island, Washington, yields an age of about 80,000 yr, in contrast to the previously determined radiocarbon age of 36,000 yr which was measured on some shell carbonate and considered a minimum age. The amino acid age is compatible with the geologic record in the area. ?? 1980.

  20. Aqueous microwave-assisted solid-phase peptide synthesis using Fmoc strategy. III: racemization studies and water-based synthesis of histidine-containing peptides.

    PubMed

    Hojo, Keiko; Shinozaki, Natsuki; Hidaka, Koushi; Tsuda, Yuko; Fukumori, Yoshinobu; Ichikawa, Hideki; Wade, John D

    2014-10-01

    In this study, we describe the first aqueous microwave-assisted synthesis of histidine-containing peptides in high purity and with low racemization. We have previously shown the effectiveness of our synthesis methodology for peptides including difficult sequences using water-dispersible 9-fluorenylmethoxycarbonyl-amino acid nanoparticles. It is an organic solvent-free, environmentally friendly method for chemical peptide synthesis. Here, we studied the racemization of histidine during an aqueous-based coupling reaction with microwave irradiation. Under our microwave-assisted protocol using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, the coupling reaction can be efficiently performed with low levels of racemization of histidine. Application of this water-based microwave-assisted protocol with water-dispersible 9-fluorenylmethoxycarbonyl-amino acid nanoparticles led to the successful synthesis of the histidine-containing hexapeptide neuropeptide W-30 (10-15), Tyr-His-Thr-Val-Gly-Arg-NH₂, in high yield and with greatly reduced histidine racemization. PMID:24965528

  1. [Gamma-hydroxybutyric acid (GHB): more than a date rape drug, a potentially addictive drug].

    PubMed

    Karila, Laurent; Novarin, Johanne; Megarbane, Bruno; Cottencin, Olivier; Dally, Sylvain; Lowenstein, William; Reynaud, Michel

    2009-10-01

    According to available information, GHB and its precursors--gamma-butyrolactone (GBL) and 1,4-butanediol (1,4BD)--are used especially in a nightlife scene characterized by the search for amplified sensations through the combination of electronic music, marathon dancing, and substance abuse. Evidence indicates that GHB/GHL is used particularly in some subpopulations and in places, such as in gay nightclubs. Commonly known as Gorliquid ecstasy, it was misused in the 1980s for its bodybuilding effects and in the 1990s as a recreational drug at music venues. In the same period, media coverage of the use of GHB in sexual assault (often referred to as date rape) brought the drug into the spotlight. GHB/GHL addiction is a recognized clinical entity evidenced by severe withdrawal symptoms when the drug is abruptly discontinued after regular or chronic use. There is evidence that negative health and social consequences may occur in recreational and chronic users. Nonfatal overdoses and deaths related to GHB have been reported. These undesirable effects and especially the deaths appear to have prompted campaigns to limit the use of GHB. Clinicians must also be aware of GBL, which is being sold and used as a substitute for GHB. PMID:19762202

  2. Oil content and saturated fatty acids in sunflower (Helianthus annuus L.) as a function of planting date, N rate, and hybrid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The fatty acids (FA) composition of sunflower determines its uses and health effects on humans, while oil content determines the price paid to producers. The hypothesis of this study was that agronomic factors (genotype, planting date, and N rate) will affect total saturated fatty acid (TSFA) concen...

  3. Comparison of racemic epi-inosose and (-)-epi-inosose.

    PubMed

    Krishnaswamy, Shobhana; Patil, Madhuri T; Shashidhar, Mysore S

    2011-11-01

    The conversion of myo-inositol to epi-inositol can be achieved by the hydride reduction of an intermediate epi-inosose derived from myo-inositol. (-)-epi-Inosose, (I), crystallized in the monoclinic space group P2(1), with two independent molecules in the asymmetric unit [Hosomi et al. (2000). Acta Cryst. C56, e584-e585]. On the other hand, (2RS,3SR,5SR,6SR)-epi-inosose, C(6)H(10)O(6), (II), crystallized in the orthorhombic space group Pca2(1). Interestingly, the conformation of the molecules in the two structures is nearly the same, the only difference being the orientation of the C-3 and C-4 hydroxy H atoms. As a result, the molecular organization achieved mainly through strong O-H···O hydrogen bonding in the racemic and homochiral lattices is similar. The compound also follows Wallach's rule, in that the racemic crystals are denser than the optically active form. PMID:22051958

  4. Amino acid epimerization dating of Quaternary coastal deformation in SE Iberian Peninsula: The region between Aguas and Antas Rivers' mouths

    NASA Astrophysics Data System (ADS)

    Torres, Trinidad; Ortiz, José E.; Sánchez-Palencia, Yolanda

    2016-05-01

    The coastal area between the mouths of the Aguas and Antas Rivers presents a deformed system of raised marine deposits, some of which have been strongly affected by active tectonics. The use of amino acid epimerization dating of Glycymeris shells from raised coastal deposits allowed determining the age of these marine deposits, all of them linked to highstand sea levels in the Mediterranean realm, with ages between MIS 11 and MIS 1. These results allowed corroborating the age of some previously studied sites, and using new sampling sites, the general aminostratigraphy for the Quaternary raised marine deposits on the Mediterranean coast was confirmed. The main deformation event took place after MIS 11 and continued until MIS 5, and was linked to the activity of the Palomares Fault.

  5. Separation and enrichment of enantiopure from racemic compounds using magnetic levitation.

    PubMed

    Yang, Xiaochuan; Wong, Shin Yee; Bwambok, David K; Atkinson, Manza B J; Zhang, Xi; Whitesides, George M; Myerson, Allan S

    2014-07-18

    Crystallization of a solution with high enantiomeric excess can generate a mixture of crystals of the desired enantiomer and the racemic compound. Using a mixture of S-/RS-ibuprofen crystals as a model, we demonstrated that magnetic levitation (MagLev) is a useful technique for analysis, separation and enantioenrichment of chiral/racemic products. PMID:24875274

  6. Aqueous microwave-assisted solid-phase peptide synthesis using fmoc strategy. II. Racemization studies and water based synthesis of cysteine-containing peptides.

    PubMed

    Hojo, Keiko; Shinozaki, Natsuki; Hara, Asaki; Onishi, Mare; Fukumori, Yoshinobu; Ichikawa, Hideki

    2013-10-01

    We have developed a microwave (MW)-assisted peptide synthesis using Fmoc-amino acid nanoparticles in water previously. It is an organic solvent-free, environmentally friendly method for peptide synthesis. In this study, we have investigated the racemization of cysteine during an aqueous based coupling reaction with MW irradiation. Under our MW-assisted protocol using WSCI and DMTMM, the coupling reaction can be performed with low levels of racemization of cysteine. We also demonstrated the synthesis of the nonapeptide oxytocin analogue, Cys(Acm)-Tyr-Ile-Gln-Asn- Cys(Acm)-Pro-Leu-Gly-NH2 using our water based MW-assisted protocol with Fmoc-amino acid nanoparticles. PMID:23517723

  7. [Ketamine racemate and S-(+)-ketamine. Cerebrovascular effects and neuroprotection following focal ischemia].

    PubMed

    Werner, C; Reeker, W; Engelhard, K; Lu, H; Kochs, E

    1997-03-01

    The phencyclidine derivative ketamine is a non-competitive N-methyl-D-aspartate (NMDA) receptor antagonist with the thalamo-neocortical projection system as the primary site of action. Racemic ketamine consists of the enantiomers S(+)-ketamine and R(-)-ketamine. Racemic ketamine has never been considered an adequate anaesthetic agent in neurosurgical patients since it produces regionally specific stimulation of cerebral metabolism (CMRO2) and increases cerebral blood flow (CBF) and intracranial pressure (ICP). However, recent experiments suggest that both tracemic ketamine and S(+)-ketamine may reduce infarct size in animal models of incomplete cerebral ischaemia and brain injury. This experimental protective effect appears to be related to decreases in Ca++ influx and maintenance of brain tissue magnesium levels due to NMDA and quisqualate receptor blockade by ketamine. Studies in dogs have shown that racemic ketamine (2.0 mg/kg) increases CBF in the presence of the cerebral vasodilator N2O. In contrast, studies in rats without background anaesthesia showed increases in CBF after racemic ketamine (100 mg/kg i.p.). This suggests that the cerebrovascular effects of racemic ketamine are related to the pre-existing cerebrovascular tone induced by background anaesthetics. Cerebrovascular CO2 reactivity was maintained regardless of the baseline cerebrovascular resistance. There are several mechanisms by which racemic ketamine may increase CBF. It induces dose-dependent respiratory depression with consequent mild hypercapnia in spontaneously ventilating subjects. This produces vasodilation due to the intact cerebrovascular CO2 reactivity. Racemic ketamine also induces regional neuroexcitation, which leads to stimulation of cerebral glucose consumption in the limbic, extrapyramidal, auditory, and sensory-motor systems. This regional neuroexcitation with increased CMRO2 produces increases in CBF that can be blocked by infusion of barbiturates or benzodiazepines. However

  8. Is the required therapeutic effect always achieved by racemic switch of proton-pump inhibitors?

    PubMed Central

    Zhou, Quan; Yan, Xiao-Feng; Pan, Wen-Sheng; Zeng, Su

    2008-01-01

    Many of the drugs currently used in medical practice are racemates. The enantiomers of a racemic drug differ in pharmacodynamics and/or pharmacokinetics, thus in some cases it is preferable to develop pure enantiomers by racemic switch. In a recent study by Pai et al, dexrabeprazole [R(+)-rabeprazole] (10 mg) was found to be more effective than rabeprazole (20 mg) in the treatment of gastroesophageal reflux disease. We read with great interest in this study and discussed whether such racemic switch would be applicable to other proton-pump inhibitors (PPIs). A literature review indicates that stereoselective pharmacokinetics, rather than stereoselective pharmacological activity, is the main cause of differences in clinical efficacy between pure enantiomer and racemic PPI. Racemic switches of PPI provide the therapeutic advantages such as reducing metabolic load on the body, simplifying pharmacokinetics, providing benefit to the non-responders to standard dose of racemate, more homogenous response to treatment and better efficacy with equal safety. Further studies in quantitative structure-activity relationships (QSARs) are needed to address the fact that the preferred enantiomer of PPI is not always in the same absolute configuration, i.e., S-form is for omeprazole, pantoprazole and tenatoprazole whereas R-form is for lansoprazole and rabeprazole. PMID:18442220

  9. A patient satisfaction survey comparing levalbuterol with racemic albuterol in children.

    PubMed

    Berger, William E; Ames, Dale E; Harrison, Doug

    2004-01-01

    Patient preference studies provide important data on the impact of asthma symptoms and the effects of medication on patients' quality of life and functional activity levels. Such studies are lacking in the evaluation of short-acting beta2-agonist treatment for asthma, especially for racemic albuterol. The introduction in 1999 of levalbuterol, the (R)-isomer of racemic albuterol, has provided the opportunity to assess patient preference between racemic albuterol and levalbuterol. Studies with levalbuterol, 1.25 mg, indicated greater bronchodilation than and comparable beta2-mediated side effects to the standard 2.5-mg dose of racemic albuterol, while lower doses of levalbuterol (0.63 mg) provided comparable bronchodilation with reduced beta2-mediated side effects in patients with asthma. This study evaluated treatment satisfaction by the caregivers of children with asthma who currently use and/or have used either levalbuterol (n = 66) or racemic albuterol (n = 76). Twenty-minute-long telephone surveys were administered to caregivers, asking them to rate satisfaction with their child's asthma treatment and provide reasons for satisfaction and dissatisfaction. Significantly more caregivers administering levalbuterol (92%) were "extremely" or "very satisfied" with therapy versus those who currently administered racemic albuterol (51%; p = 0.001). Symptom relief was graded 8.7 (out of 10) for levalbuterol treatment versus 7.5 for racemic albuterol (p = 0.001). Although these differences, in part, may have been influenced by some of the study limitations (e.g., open-label, non-placebo-controlled and nonrandomized design, and potential caregiver recall bias), the statistically significant differences consistently favored levalbuterol and are consistent with results obtained from other clinical studies. The efficacy, dosing flexibility, and improved side effect profile of levalbuterol were the sources of greatest satisfaction for parents/ caregivers in the levalbuterol

  10. Enzymatic Synthesis of (S)-(-)-gamma-Methyl-gamma-butyrolactone from Racemic Methyl gamma-hydroxypentanoate Using Porcine Pancreatic Lipase: A Microscale Advanced Bioorganic Chemistry Laboratory Project

    NASA Astrophysics Data System (ADS)

    Lee, Moses

    1998-02-01

    The use of enzymes in academic as well as industrial chemical laboratories is now common, and in some cases live organisms are utilized. In this laboratory project, porcine pancreatic lipase (PPL) is used to convert a racemic sample of methyl gamma-hydroxypentanoate into gamma-methyl-gamma-butyrolactone in an effort to demonstrate the ability of enzymes to differentiate between enantiomeric substrates. This project also uses a number of chemical and spectroscopic techniques commonly used by organic and biochemists. Students are asked to complete two lactonization reactions of racemic methyl gamma-hydroxypentanoate: one is catalyzed by PPL and the other by para-toluenesulfonic acid, which produces a racemic mixture of gamma-methyl-gamma-butyrolactone. Both samples of the gamma-lactone are analyzed by TLC, purified by silica gel column chromatography, and characterized by infrared and 1H-NMR studies. While the sample of g-lactone obtained from the PPL catalyzed reaction is optically active, [alpha]D25° = -13.4° (c = 0.0098, chloroform), the sample from the acid catalyzed reaction is not. Results from 1H-NMR studies of these lactones with a mole equivalent of (R)-(-)-2,2,2-trifluoro-1-(9-anthryl)ethanol show the enantiomeric excess of the optically active lactone to be 37 + 4 % favoring the S-enantiomer.

  11. Comparative clinical trial of S-pantoprazole versus racemic pantoprazole in the treatment of gastro-esophageal reflux disease

    PubMed Central

    Pai, Vikas G; Pai, Nitin V; Thacker, Hemant P; Shinde, Jaisingh K; Mandora, Vijay P; Erram, Subhash S

    2006-01-01

    AIM: To compare the efficacy and tolerability of S-pantoprazole (20 mg once a day) versus racemic Pantoprazole (40 mg once a day) in the treatment of gastro-esophageal reflux disease (GERD). METHODS: This multi-centre, randomized, double-blind clinical trial consisted of 369 patients of either sex suffering from GERD. Patients were randomly assigned to receive either one tablet (20 mg) of S-pantoprazole once a day (test group) or 40 mg racemic pantoprazole once a day (reference group) for 28 d. Patients were evaluated for reduction in baseline on d 0, GERD symptom score on d 14 and 28, occurrence of any adverse effect during the course of therapy. Gastrointestinal (GI) endoscopy was performed in 54 patients enrolled at one of the study centers at baseline and on d 28. RESULTS: Significant reduction in the scores (mean and median) for heart burn (P < 0.0001), acid regurgitation (P < 0.0001), bloating (P < 0.0001), nausea (P < 0.0001) and dysphagia (P < 0.001) was achieved in both groups on d 14 with further reduction on continuing the therapy till 28 d. There was a statistically significant difference in the proportion of patients showing improvement in acid regurgitation and bloating on d 14 and 28 (P = 0.004 for acid regurgitation; P = 0.03 for bloating) and heart burn on d 28 (P = 0.01) between the two groups, with a higher proportion in the test group than in the reference group. Absolute risk reductions for heartburn/acid regurgitation/bloating were approximately 15% on d 14 and 10% on d 28. The relative risk reductions were 26%-33% on d 14 and 15% on d 28. GI endoscopy showed no significant difference in healing of esophagitis (P = 1) and gastric erosions (P = 0.27) between the two groups. None of the patients in either group reported any adverse effect during the course of therapy. CONCLUSION: In GERD, S-pantoprazole (20 mg) is more effective than racemic pantoprazole (40 mg) in improving symptoms of heartburn, acid regurgitation, bloating and equally

  12. Structure elucidation of the Pribnow box consensus promoter sequence by racemic DNA crystallography.

    PubMed

    Mandal, Pradeep K; Collie, Gavin W; Srivastava, Suresh C; Kauffmann, Brice; Huc, Ivan

    2016-07-01

    It has previously been shown that the use of racemic mixtures of naturally chiral macromolecules such as protein and DNA can significantly aid the crystallogenesis process, thereby addressing one of the major bottlenecks to structure determination by X-ray crystallographic methods-that of crystal growth. Although previous studies have provided convincing evidence of the applicability of the racemic crystallization technique to DNA through the study of well-characterized DNA structures, we sought to apply this method to a historically challenging DNA sequence. For this purpose we chose a non-self-complementary DNA duplex containing the biologically-relevant Pribnow box consensus sequence 'TATAAT'. Four racemic crystal structures of this previously un-crystallizable DNA target are reported (with resolutions in the range of 1.65-2.3 Å), with further crystallographic studies and structural analysis providing insight into the racemic crystallization process as well as structural details of this highly pertinent DNA sequence. PMID:27137886

  13. Disposition of Chiral and Racemic Fluoxetine and Norfluoxetine Across Childbearing

    PubMed Central

    Sit, Dorothy; Perel, James M.; Luther, James F.; Wisniewski, Stephen R.; Helsel, Joseph C.; Wisner, Katherine L.

    2011-01-01

    Objective To add to the limited data on the clinical pharmacology of antidepressants during pregnancy, we examined the dose-corrected chiral and racemic levels (level/dose) of fluoxetine (FLX) and norfluoxetine (NorFLX) during pregnancy and early postpartum. Methods The authors evaluated 17 pregnant women who received fluoxetine therapy. Doses were recorded weekly across gestation and postpartum. At 20, 30, and 36 weeks of gestation, during delivery, and 12 weeks after delivery, the depression level was assessed with the Hamilton Rating Scale for Depression (HRS-D), and plasma samples were analyzed for levels of S- and R-FLX and S- and R-NorFLX. Results The mean ratios of the chiral parent drug (S-FLX + R-FLX) to metabolite levels (S-NorFLX + R-NorFLX) decreased across pregnancy. The differences were significant between 20–36 weeks and 30–36 weeks. After delivery, the mean dose–corrected level of the active moiety S-FLX and the mean ratio of the chiral parent drug (S-FLX + R-FLX) to metabolite level (S-NorFLX + R-NorFLX) significantly increased between delivery and 12 weeks postpartum. Most of the fluoxetine-treated subjects experienced remitted depressive episodes and euthymic mood levels during pregnancy and postpartum. Conclusions The findings extend earlier reports of increased antidepressant metabolism during pregnancy and refractory metabolism after delivery. These data may inform treatment decisions related to dosing in patients who receive fluoxetine during pregnancy. PMID:20631556

  14. Chiral resolution and absolute configuration of a pair of rare racemic spirodienone sesquineolignans from Xanthium sibiricum.

    PubMed

    Shi, Yusheng; Liu, Yunbao; Li, Yong; Li, Li; Qu, Jing; Ma, Shuanggang; Yu, Shishan

    2014-10-17

    A pair of racemic spirodienone neolignan enantiomers, (±)-sibiricumin A, were isolated from the extract of the fruits of Xanthium sibiricum. The resolution of (+)- and (-)-sibiricumin A was achieved by chiral HPLC. The absolute configurations of the racemes were assigned by X-ray and by electronic circular dichroism (ECD). This experiment is the first unambiguous determination of the absolute configuration of spirodienone neolignan. PMID:25275854

  15. Enantioselective autocatalysis. II. Racemization studies on a 1,4-benzodiazepinooxazole derivative

    NASA Astrophysics Data System (ADS)

    Bonner, William A.

    1995-08-01

    Since the bromofluoro-1,4-benzodiazepinooxazole derivativeI may undergo spontaneous resolution on crystallization from methanol solution, it provides an ideal substrate on which to study the phenomenon of enantioselective autocatalysis involving spontaneous resolution under racemizing conditions (srurc). in order to augment the understanding of factors which might be important in such a process we have now undertaken to study the racemization ofI in more detail by observing its rate under a wide variety of experimental conditions.

  16. A Study on Amino Acids: Synthesis of Alpha-Aminophenylacetic Acid (Phenylglycine) and Determination of its Isoelectric Point.

    ERIC Educational Resources Information Center

    Barrelle, M.; And Others

    1983-01-01

    Background information and procedures are provided for an experimental study on aminophenylacetic acid (phenylglycine). These include physical chemistry (determination of isoelectric point by pH measurement) and organic chemistry (synthesis of an amino acid in racemic form) experiments. (JN)

  17. Experimental and theoretical study of racemization, stability and tautomerism of vitamin C stereoisomers.

    PubMed

    Dabbagh, Hossein A; Azami, Fatemeh

    2014-12-01

    Experimental degradation of vitamin C (VC) in water was monitored using specific rotation, FT-IR and (1)H NMR at room temperature and at 80-90°C. The optical activity was reduced (100%) to zero after 6 and 63 days at 80-90°C (≅25% in less than 24h) and room temperature, respectively. (1)H NMR and FT-IR was performed after these periods which indicated the formation of a complex mixture at higher stirring time and elevated temperature. These observations indicated that vitamin C is unstable in solution at room temperature or at elevated temperature. The solid VC did not lose optical activity after several mounts at room temperature. The instability of VC was related to isomerization (loss of optical activity) of the l-enantiomer either to d-enantiomer (racemization), degradation to undesired products or tautomerization to other isomers. Theoretical investigation (at B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels of theory in vacuo and aqueous phases) formulated tautomerization for RS-stereoisomers of ascorbic acids (AA). The mechanism for deactivation of VC was examined. PMID:24996345

  18. Antioxidant and antiatherogenic properties of phenolic acid and flavonol fractions of fruits of 'Amari' and 'Hallawi' date (Phoenix dactylifera L.) varieties.

    PubMed

    Borochov-Neori, Hamutal; Judeinstein, Sylvie; Greenberg, Amnon; Volkova, Nina; Rosenblat, Mira; Aviram, Michael

    2015-04-01

    Date (Phoenix dactylifera L.) fruit phenolic-acid or flavonol fractions were examined in vitro for antioxidant and antiatherogenic properties. Two fractions of each subgroup were prepared from two date varieties, 'Amari' and 'Hallawi', by solid phase extraction on C18. The fractions were analyzed for phenolics composition by RP-HPLC and tested for ferric-reducing antioxidant power, free radical scavenging capacity, inhibition of Cu(2+)-induced LDL oxidation, and enhancement of HDL-mediated cholesterol efflux from macrophages. All four fractions exhibited variable capacities to reduce ferric ions, scavenge radicals, and inhibit LDL oxidation. Flavonol fractions were considerably better inhibitors of LDL oxidation compared to phenolic acid fractions, with IC50's of 9-31 nmol GAE mL(-1) compared to 85-116 nmol GAE mL(-1), respectively. Only the flavonol fractions stimulated cholesterol removal from macrophages. Within each subgroup, the levels of all the activities varied with fraction composition. The results demonstrated strong structure-activity relationships for date phenolics and identified date flavonols as potential antiatherogenic bioactives. PMID:25765921

  19. Pairwise comparison of levalbuterol versus racemic albuterol in the treatment of moderate-to-severe asthma.

    PubMed

    Pleskow, Warren W; Nelson, Harold S; Schaefer, Kendyl; Claus, Raymond; Roach, James M

    2004-01-01

    The object of this study is a post hoc pairwise comparison of levalbuterol versus racemic albuterol for asthma in a multicenter, double-blind, randomized, placebo-controlled clinical trial. The participants are patients > or =12 years of age (n = 362) with FEV1 45-70% of predicted. The patients received nebulized levalbuterol (0.63 or 1.25 mg), racemic albuterol (1.25 or 2.5 mg), or placebo t.i.d. for 4 weeks. The primary endpoints, published in Nelson HS, Bensch G, Pleskow WW, et al. Improved bronchodilation with levalbuterol compared with racemic albuterol in patients with asthma. J Allergy Clin Immunol 102:943-952, 1998, included comparisons of active treatments with placebo and of the combined levalbuterol with the combined racemic albuterol groups for pulmonary function and rescue medication use. After the first dose, levalbuterol 1.25 mg produced a significantly greater increase in the mean peak change in FEV1 compared with both doses of racemic albuterol (p < 0.03) in all patients and in those with more severe asthma. Levalbuterol 1.25 mg also produced a significantly greater (p < 0.05) mean area under the curve (AUC) of the FEV1 versus time plot (AUC FEV1) compared with all other treatments after the first dose in all patients and in the subset with more severe disease, illustrating better overall improvement in FEV1. Active treatment groups demonstrated significant improvements compared with the placebo group (p < 0.05), except for AUC FEV1 in the racemic albuterol 1.25-mg group at week 4. Levalbuterol in the absence of the (S)-isomer provided greater bronchodilation than the same quantity of (R)-albuterol delivered as the racemate. These data suggest that (S)-albuterol may compromise the efficacy of (R)-albuterol. PMID:15709454

  20. Quasi-Racemic X-ray Structures of K27-Linked Ubiquitin Chains Prepared by Total Chemical Synthesis.

    PubMed

    Pan, Man; Gao, Shuai; Zheng, Yong; Tan, Xiaodan; Lan, Huan; Tan, Xianglong; Sun, Demeng; Lu, Lining; Wang, Tian; Zheng, Qingyun; Huang, Yichao; Wang, Jiawei; Liu, Lei

    2016-06-15

    Quasi-racemic crystallography has been used to determine the X-ray structures of K27-linked ubiquitin (Ub) chains prepared through total chemical synthesis. Crystal structures of K27-linked di- and tri-ubiquitins reveal that the isopeptide linkages are confined in a unique buried conformation, which provides the molecular basis for the distinctive function of K27 linkage compared to the other seven Ub chains. K27-linked di- and triUb were found to adopt different structural conformations in the crystals, one being symmetric whereas the other triangular. Furthermore, bioactivity experiments showed that the ovarian tumor family de-ubiquitinase 2 significantly favors K27-linked triUb than K27-linked diUb. K27-linked triUb represents the so-far largest chemically synthesized protein (228 amino acids) that has been crystallized to afford a high-resolution X-ray structure. PMID:27268299

  1. meso-Tetrahydropyranylperoxides: molecular structures in solution, in the crystal, and by DFT calculations and their isomerization to the racemate.

    PubMed

    Balaban, Teodor Silviu; Eichhöfer, Andreas; Ghiviriga, Ion; Hugo, Holger; Wenzel, Wolfgang

    2003-06-27

    The crystalline peroxide 3a is the main product (out of 10 theoretically possible) from the aerial peroxidation of all-cis-2,4,6-trimethyltetrahydropyran (2a). It has a similar structure both in solution and in the crystal as shown by nuclear Overhauser effects and X-ray analysis, respectively. Theoretical calculations at a density functional theory level (B3LYP/6-31G) provide insight into the stabilities of the different stereoisomers of this peroxide, accounting for the facile, acid-catalyzed isomerization from the meso form to the racemate. Peroxide 3b, which is the 2-tert-butyl analogue of 3a, out of 22 theoretically possible isomers, crystallizes in a similar meso form. As a result of crystal packing effects and the intrinsically (axial) chiral peroxy "chromophore" that deviates slightly from the antiperiplanar conformation, both enantiomorphic forms of 3b are encountered in the lattice. PMID:12816495

  2. Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols.

    PubMed

    Bornschein, Christoph; Gustafson, Karl P J; Verho, Oscar; Beller, Matthias; Bäckvall, Jan-E

    2016-08-01

    Fe and Ru pincer-type catalysts are used for the racemization of benzylic alcohols. Racemization with the Fe catalyst was achieved within 30 minutes under mild reaction conditions, with a catalyst loading as low as 2 mol %. This reaction constitutes the first example of an iron-catalyzed racemization of an alcohol. The efficiency for racemization of the Fe catalyst and its Ru analogue was evaluated for a wide range of sec-benzylic alcohols. The commercially available Ru complex proved to be highly robust and even tolerated the presence of water in the reaction mixture. PMID:27311070

  3. Enantiomeric Excesses of Acid Labile Amino Acid Precursors of the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Pizzarello, Sandra

    1998-01-01

    Amino acids present in carbonaceous chondrite are extracted in water in part as free compounds and in approximately equal part as acid labile precursors. On the assumption that they would be free of contamination, the precursors of two Murchison amino acids that have terrestrial occurrence, alanine and glutamic acid, have been targeted for analysis of their enantiomeric ratios. Pyroglutamic acid, the precursor of glutamic acid, was found with an L-enantiomeric excess comparable to that of the free acid, while alanine's precursor, N-acetyl alanine, appears approximately racemic. Also alpha-imino propioacetic acid, a proposed end product of alanine synthesis in the meteorite, was analyzed and found racemic.

  4. Emulsification-Induced Homohelicity in Racemic Helical Polymer for Preparing Optically Active Helical Polymer Nanoparticles.

    PubMed

    Zhao, Biao; Deng, Jinrui; Deng, Jianping

    2016-04-01

    Optically active nano- and microparticles have constituted a significant category of advanced functional materials. However, constructing optically active particles derived from synthetic helical polymers still remains as a big challenge. In the present study, it is attempted to induce a racemic helical polymer (containing right- and left-handed helices in equal amount) to prefer one predominant helicity in aqueous media by using emulsifier in the presence of chiral additive (emulsification process). Excitingly, the emulsification process promotes the racemic helical polymer to unify the helicity and directly provides optically active nanoparticles constructed by chirally helical polymer. A possible mechanism is proposed to explain the emulsification-induced homohelicity effect. The present study establishes a novel strategy for preparing chirally helical polymer-derived optically active nanoparticles based on racemic helical polymers. PMID:26829250

  5. Highly efficient photochemically induced thiyl radical-mediated racemization of aliphatic amines at 30 degrees C.

    PubMed

    Routaboul, Lucie; Vanthuyne, Nicolas; Gastaldi, Stéphane; Gil, Gérard; Bertrand, Michèle

    2008-01-18

    UV irradiation in the presence of thiol enables the performance of highly efficient aliphatic amines racemization, under mild conditions at 30 degrees C. The reaction proceeds via the reversible generation of prochiral alpha-aminoalkyl radicals. The latter may result either from a redox process between the thiyl radical and the amine or from direct hydrogen atom abstraction by thiyl radical. As hydrogen atom donor, the thiol plays a crucial role. While the racemization of both primary and secondary amines were fast processes, the racemization of tertiary amines was sluggish. A tentative rationale is based on the photostimulated amine-catalyzed oxidation of the thiol into the corresponding disulfide, which makes the hydrogen atom donor concentration in the reaction medium drop up to trace amount at a rate that depends on the nature of the amine. PMID:18076189

  6. Kinetic model-based feed-forward controlled fed-batch fermentation of Lactobacillus rhamnosus for the production of lactic acid from Arabic date juice.

    PubMed

    Choi, Minsung; Al-Zahrani, Saeed M; Lee, Sang Yup

    2014-06-01

    Arabic date is overproduced in Arabic countries such as Saudi Arabia and Iraq and is mostly composed of sugars (70-80 wt%). Here we developed a fed-batch fermentation process by using a kinetic model for the efficient production of lactic acid to a high concentration from Arabic date juice. First, a kinetic model of Lactobacillus rhamnosus grown on date juice in batch fermentation was constructed in EXCEL so that the estimation of parameters and simulation of the model can be easily performed. Then, several fed-batch fermentations were conducted by employing different feeding strategies including pulsed feeding, exponential feeding, and modified exponential feeding. Based on the results of fed-batch fermentations, the kinetic model for fed-batch fermentation was also developed. This new model was used to perform feed-forward controlled fed-batch fermentation, which resulted in the production of 171.79 g l(-1) of lactic acid with the productivity and yield of 1.58 and 0.87 g l(-1) h(-1), respectively. PMID:24100793

  7. Racemic R,S-venlafaxine hydrochloride-DNA interaction: Experimental and computational evidence

    NASA Astrophysics Data System (ADS)

    Shahabadi, Nahid; Hadidi, Saba; Ghasemian, Zeinab; Taherpour, Avat(Arman)

    2015-06-01

    The interaction of racemic R,S-venlafaxine hydrochloride (rac-VEN) drug with calf thymus deoxyribonucleic acid (ct-DNA) was studied using various physico-chemical techniques and molecular docking at simulated physiological conditions (pH = 7.4). The fluorescence study shows that ct-DNA interacted with rac-VEN and quenched its intrinsic fluorescence in a static quenching process. These results are further supported by UV-Vis spectra. The binding constant of rac-VEN with ct-DNA (0.57 × 104) obtained from the spectroscopic techniques, which is more in keeping with the groove binding with DNA. Furthermore, the competition experiment using Hoechst33258 indicated that rac-VEN may bind to ct-DNA by a minor groove binding mode. In addition, iodide quenching effect on the fluorescence of rac-VEN before and after the interaction with ct-DNA is another evidence to groove binding. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrogen bonds and van der Waals interactions played major roles in the binding reaction. Molecular simulation studies carried out by using the AutoDock4 and Spartan10 programs. From the best docking map, we found that R and S-isomers fit in the A6T7T8/T19A18A17 region in minor groove of B-DNA. Finally, these results indicated that the docking of S-VEN-B-DNA is more stable than R-VEN-B-DNA.

  8. The "racemic approach" in the evaluation of the enantiomeric NorA efflux pump inhibition activity of 2-phenylquinoline derivatives.

    PubMed

    Carotti, Andrea; Ianni, Federica; Sabatini, Stefano; Di Michele, Alessandro; Sardella, Roccaldo; Kaatz, Glenn W; Lindner, Wolfgang; Cecchetti, Violetta; Natalini, Benedetto

    2016-09-10

    Among the mechanisms adopted by bacteria, efflux pumps (EPs) have been recognized as being significantly involved in contributing to resistance to commonly used antibacterial agents. However, little is known about their three-dimensional structures or the steric requirements for their inhibition. Lack of such knowledge includes NorA, one of the most studied Staphylococcus aureus EPs. In the present study, the use of two commercialized Cinchona alkaloid-based zwitterionic chiral stationary phases allowed the enantioseparation of four 2-((2-(4-propoxyphenyl)quinolin-4-yl)oxy)alkylamines 1-4 previously found to be potent S. aureus NorA efflux pump inhibitors when tested as racemates. In the identified optimal polar-ionic conditions (MeOH/THF/H2O-49/49/2 (v/v/v)+25mM formic acid, 12.5mM diethylamine), repeated consecutive injections of 1 allowed the isolation of sufficient amount of its enantiomers (2.6mg and 2.8mg, for (R)-1 and (S)-1, respectively) and then to evaluate their ability to inhibit the S. aureus NorA efflux pump. The biological evaluation highlighted the main contribution of the (R)-1 enantiomer to both the EtBr efflux inhibition and synergistic effect with against SA-1199B (norA+/A116E GrlA) respect to the racemate activity. The comparison between the experimental electronic circular dichroism and the time-dependent density functional theory calculations spectra of the two isolated enantiomeric fractions allowed for all compounds a clear and easy assignment of the enantiomeric elution order. PMID:27429367

  9. Dating Violence

    MedlinePlus

    ... Parents of Teens Crime, Teens, and Trauma Assault Bullying and Harassment Child Sexual Abuse Dating Violence Sexual ... Parents of Teens Crime, Teens, and Trauma Assault Bullying and Harassment Child Sexual Abuse Dating Violence Sexual ...

  10. Radiocarbon Dating

    SciTech Connect

    Buchholz, B A

    2007-12-20

    Radiocarbon dating can be used to determine the age of objects that contain components that were once alive. In the case of human remains, a radiocarbon date can distinguish between a crime scene and an archeological site. Documents, museum artifacts and art objects can be dated to determine if their age is correct for the historical context. A radiocarbon date does not confirm authenticity, but it can help identify a forgery.

  11. The effects of acid leaching on 40Ar/39Ar age dating results using samples from the Walvis Ridge hotspot trail

    NASA Astrophysics Data System (ADS)

    Klath, J. F.; Koppers, A. A.; Heaton, D. E.; Schnur, S.

    2013-12-01

    In this study we systematically explore how acid leaching can be used to reduce the negative effects of seawater alteration on the 40Ar/39Ar age dating of submarine basalts. Koppers et al (2000) showed that acid leaching of groundmass samples generated more consistent ages as well as ages more concordant with phenocrystic mineral phases, compared to samples that were left untreated. By studying the effects of progressively increasing the strength and length of acid treatment, we will show how acid leaching of groundmass separates reduces alteration while leaving the initial eruption signature intact. Samples were chosen from the Walvis ridge hotspot trail in the southeast Atlantic. Three samples were selected based on degree and style of alteration. Two samples (basalt and basaltic andesite) appear highly altered in thin section. The basalt contains diffuse iddingsite alteration that is pervasive throughout the groundmass. The basaltic andesite displays focused secondary mineral phases within and around abundant vesicles. The third sample, a trachyte, shows relatively minor degrees of alteration in thin section. These groundmass separates were divided into four splits and treated with a progressively stronger acid and for longer duration. One split from each rock was left untreated to act as a baseline. Of the other three splits from each sample, one was treated with a mild leach (1N HCl and 1N HNO3), one a strong leach (1N HCl, 1N HNO3, 6N HCl, and 3N HNO3), and lastly the strong leach performed twice. The samples were then handpicked to remove any remaining visible alteration. The untreated samples were picked as well, removing the most distinctly altered grains. All splits were analyzed by electron microprobe, x-ray fluorescence (XRF) and the incremental heating 40Ar/39Ar dating method. We will report on the results of an image analysis of microprobe backscatter images and elemental maps taken of individual groundmass grains. This analysis will show the location

  12. X-ray Structure of Native Scorpion Toxin BmBKTx1 by Racemic Protein Crystallography Using Direct Methods

    SciTech Connect

    Mandal, Kalyaneswar; Pentelute, Brad L.; Tereshko, Valentina; Kossiakoff, Anthony A.; Kent, Stephen B.H.

    2009-04-08

    Racemic protein crystallography, enabled by total chemical synthesis, has allowed us to determine the X-ray structure of native scorpion toxin BmBKTx1; direct methods were used for phase determination. This is the first example of a protein racemate that crystallized in space group I41/a.

  13. Dating Violence

    ERIC Educational Resources Information Center

    Stader, David L.

    2011-01-01

    Dating violence is a form of student-on-student victimization and is a serious school safety issue. Research indicates that at a minimum, 10 percent of high school students are victims of dating violence in one form or another. Among female high school students that date, some data indicate that as many as 30 percent may be victims of dating…

  14. DATE PALM

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This book chapter reviews date palm biology and cultivation. Date palm (Phoenix dactylifera L.) is one of the oldest fruit crops grown in the arid regions of the Arabian Peninsula, North Africa, and the Middle East. The exact origin of the date palm is unknown but most probably the area of origin w...

  15. An evaluation of Mesodon and other larger terrestrial gastropod shells for dating late Holocene and historic alluvium in the Midwestern USA

    NASA Astrophysics Data System (ADS)

    Rakovan, Monica T.; Rech, Jason A.; Pigati, Jeffrey S.; Nekola, Jeffrey C.; Wiles, Gregory C.

    2013-07-01

    Understanding the history of stream erosion and changes in channel morphology is important for managing and restoring unstable streams. One of the significant challenges in this type of research is establishing accurate dating of late Holocene and historic alluvium. Here we evaluate the potential of using 14C dating and amino acid racemization (AAR) to date large terrestrial gastropod shells that are often preserved within alluvial sediments. Many terrestrial gastropods incorporate old carbon from limestone or other carbonate rocks into their shells and therefore are unsuitable for radiocarbon dating. Recent studies, however, have shown that some taxa avoid this 'limestone problem' and can yield reliable 14C ages. In this study, we measured the 14C activity of specimens for the genera Mesodon, Ventridens, and Allogona collected live and from alluvial sequences dated independently by dendrochronology, 14C dating of wood, and/or 137Cs analyses. Mesodon zaletus contained old carbon in similar concentrations (up to ~ 30%) found in previous studies of other large taxa and should be avoided for 14C dating when possible. In contrast, shells of Ventridens ligera and Allogona profunda showed minimal limestone effects and therefore may be suitable for dating late Holocene alluvium. These results highlight the importance of taxonomic identification of gastropod taxa prior to their use for 14C dating and demonstrate that shell fragments that are not identifiable should be avoided. We also measured d/l ratios (n = 17) of aspartic and glutamic acid from eight different taxa of terrestrial gastropods recovered from four late Holocene and historic stratigraphic sequences. Average d/l ratios of aspartic and glutamic acid from historic sediments < 300 years old are lower in shells from younger stratigraphic units, indicating that AAR can be used to differentiate between multiple historic stratigraphic units.

  16. An evaluation of Mesodon and other larger terrestrial gastropod shells for dating late Holocene and historic alluvium in the Midwestern USA

    USGS Publications Warehouse

    Rakovan, Monica T.; Rech, Jason A.; Pigati, Jeffery S.; Nekola, Jeffery C.; Wiles, Gregory C.

    2013-01-01

    Understanding the history of stream erosion and changes in channel morphology is important for managing and restoring unstable streams. One of the significant challenges in this type of research is establishing accurate dating of late Holocene and historic alluvium. Here we evaluate the potential of using 14C dating and amino acid racemization (AAR) to date large terrestrial gastropod shells that are often preserved within alluvial sediments. Many terrestrial gastropods incorporate old carbon from limestone or other carbonate rocks into their shells and therefore are unsuitable for radiocarbon dating. Recent studies, however, have shown that some taxa avoid this ‘limestone problem’ and can yield reliable 14C ages. In this study, we measured the 14C activity of specimens for the genera Mesodon, Ventridens, and Allogona collected live and from alluvial sequences dated independently by dendrochronology, 14C dating of wood, and/or 137Cs analyses. Mesodon zaletus contained old carbon in similar concentrations (up to ~ 30%) found in previous studies of other large taxa and should be avoided for 14C dating when possible. In contrast, shells of Ventridens ligera and Allogona profunda showed minimal limestone effects and therefore may be suitable for dating late Holocene alluvium. These results highlight the importance of taxonomic identification of gastropod taxa prior to their use for 14C dating and demonstrate that shell fragments that are not identifiable should be avoided. We also measured d/l ratios (n = 17) of aspartic and glutamic acid from eight different taxa of terrestrial gastropods recovered from four late Holocene and historic stratigraphic sequences. Average d/l ratios of aspartic and glutamic acid from historic sediments < 300 years old are lower in shells from younger stratigraphic units, indicating that AAR can be used to differentiate between multiple historic stratigraphic units.

  17. Analysis of metolachlor ethane sulfonic acid chirality in groundwater: A tool for dating groundwater movement in agricultural settings

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chemical chirality of pesticides can be a useful tool for studying environmental processes. The chiral forms of metolachlor ethane sulfonic acid (MESA), an abundant metabolite of metolachlor, and metolachlor were examined over a 6 year period in groundwater and a groundwater-fed stream in a riparia...

  18. Early human occupation of Western Europe: paleomagnetic dates for two paleolithic sites in Spain.

    PubMed

    Oms, O; Parés, J M; Martinez-Navarro, B; Agusti, J; Toro, I; Martinez-Fernández, G; Turq, A

    2000-09-12

    The lacustrine deposits infilling the intramontane Guadix-Baza Basin, in the Betic Range of Southern Spain, have yielded abundant well-preserved lithic artifacts. In addition, the lake beds contain a wide range of micromammals including Mimomys savini and Allophaiomys burgondiae and large mammals such as Mammuthus and Hippopotamus together with the African saber-toothed felid Megantereon. The association of the lithic artifacts along with the fossil assemblages, themselves of prime significance in the Eurasian mammal biochronology, is providing new insight into the controversy of the human settlement in Southern Europe. Despite the importance of the artifacts and fossil assemblage, estimates of the geological age of the site are still in conflict. Some attempts at dating the sediments have included biochronology, uranium series, amino acid racemization, and stratigraphic correlation with other well-dated sections in the basin, but so far have failed to yield unambiguous ages. Here we present paleomagnetic age dating at the relevant localities and thus provide useful age constraints for this critical paleoanthropological and mammal site. Our data provide firm evidence for human occupation in Southern Europe in the Lower Pleistocene, around 1 mega-annum ago. The current view of when and how hominids first dispersed into Europe needs to be reevaluated. PMID:10973485

  19. Early human occupation of Western Europe: Paleomagnetic dates for two paleolithic sites in Spain

    PubMed Central

    Oms, O.; Parés, J. M.; Martínez-Navarro, B.; Agustí, J.; Toro, I.; Martínez-Fernández, G.; Turq, A.

    2000-01-01

    The lacustrine deposits infilling the intramontane Guadix-Baza Basin, in the Betic Range of Southern Spain, have yielded abundant well-preserved lithic artifacts. In addition, the lake beds contain a wide range of micromammals including Mimomys savini and Allophaiomys burgondiae and large mammals such as Mammuthus and Hippopotamus together with the African saber-toothed felid Megantereon. The association of the lithic artifacts along with the fossil assemblages, themselves of prime significance in the Eurasian mammal biochronology, is providing new insight into the controversy of the human settlement in Southern Europe. Despite the importance of the artifacts and fossil assemblage, estimates of the geological age of the site are still in conflict. Some attempts at dating the sediments have included biochronology, uranium series, amino acid racemization, and stratigraphic correlation with other well-dated sections in the basin, but so far have failed to yield unambiguous ages. Here we present paleomagnetic age dating at the relevant localities and thus provide useful age constraints for this critical paleoanthropological and mammal site. Our data provide firm evidence for human occupation in Southern Europe in the Lower Pleistocene, around 1 mega-annum ago. The current view of when and how hominids first dispersed into Europe needs to be reevaluated. PMID:10973485

  20. Structure elucidation of the Pribnow box consensus promoter sequence by racemic DNA crystallography

    PubMed Central

    Mandal, Pradeep K.; Collie, Gavin W.; Srivastava, Suresh C.; Kauffmann, Brice; Huc, Ivan

    2016-01-01

    It has previously been shown that the use of racemic mixtures of naturally chiral macromolecules such as protein and DNA can significantly aid the crystallogenesis process, thereby addressing one of the major bottlenecks to structure determination by X-ray crystallographic methods—that of crystal growth. Although previous studies have provided convincing evidence of the applicability of the racemic crystallization technique to DNA through the study of well-characterized DNA structures, we sought to apply this method to a historically challenging DNA sequence. For this purpose we chose a non-self-complementary DNA duplex containing the biologically-relevant Pribnow box consensus sequence ‘TATAAT’. Four racemic crystal structures of this previously un-crystallizable DNA target are reported (with resolutions in the range of 1.65–2.3 Å), with further crystallographic studies and structural analysis providing insight into the racemic crystallization process as well as structural details of this highly pertinent DNA sequence. PMID:27137886

  1. Synthesis of a Racemic Ester and Its Lipase Catalyzed Kinetic Resolution

    NASA Astrophysics Data System (ADS)

    Stetca, Delia; Arends, Isabel W. C. E.; Hanefeld, Ulf

    2002-11-01

    A first-year organic chemistry laboratory experiment is described in which an enzyme is utilized for the kinetic resolution of a racemic ester. In the first step, the racemic ester is synthesized from racemic 1-phenylethanol and acetic anhydride in the presence of pyridine. In the second step, only one of the two enantiomers of the racemic ester is selectively hydrolyzed. This reaction is enzyme-catalyzed and it clearly demonstrates the great ease with which enzymes can be used for the synthesis of enantiomerically-enriched compounds. The two enantiomerically-enriched compounds formed are isolated and analyzed for their optical purity. In these experiments the students are exposed to enzyme chemistry in combination with standard organic methods. Indeed, all the products are purified by techniques that are applied in the research laboratory (column chromatography and distillation), ensuring that these experiments come as close to the research environment as possible. By means of these experiments, topics such as enantioselective synthesis, enzymes in synthesis, enzyme kinetics, and analytical techniques such as IR, TLC, and optical rotation can be introduced to the students.

  2. [Ketamine racemate or S-(+)-ketamine and midazolam. The effect on vigilance, efficacy and subjective findings].

    PubMed

    Doenicke, A; Kugler, J; Mayer, M; Angster, R; Hoffmann, P

    1992-10-01

    Ketamine is a racemic mixture containing equal amounts of optical isomers that have almost identical pharmacokinetic properties but different pharmacodynamic effects. The S-(+)-isomer of ketamine has about twice the anaesthetic and analgesic potency of the racemic ketamine preparation and is judged to induce less psychic emergence reactions and to be followed by a more rapid recovery of vigilance. The present study was designed to assess whether the S-(+)-isomer of ketamine is superior to the racemic mixture in cardiovascular characteristics, emergence reactions and cognitive functions, and whether side effects may be reduced or prevented by administration of midazolam prior to injection of S-(+)-ketamine. METHODS. Following ethics committee approval and informed consent, 30 volunteers were randomly allocated in this double-blind study to three groups of 10 each. Group 1 received 2 mg/kg bw racemic ketamine, group 2, 1 mg/kg bw S-(+)-ketamine and group 3, 1 mg/kg bw S-(+)-ketamine after premedication with 0.1 mg/kg midazolam i.v. Cardiovascular changes, state of vigilance, cognitive performance, subjective mood and acceptance of anaesthesia were assessed by means of haemodynamic routine monitoring, electroencephalography (EEG), psychometric tests and interview. RESULTS. The increases in mean arterial pressure and heart rate following the injection of racemic ketamine and S-(+)-ketamine were identical and the differences from baseline values significant after both. Premedication with midazolam ensured stable haemodynamics after injection of S-(+)-ketamine. EEG analysis displayed the characteristic changes well known from ketamine anaesthesia for both racemic and S-(+)-ketamine. The vigilosomnoscript showed an identical profile of vigilance up to 30 min after injection of both drugs. The vigilance status after 125 min was less impaired by S-(+)-ketamine than by racemic ketamine. Psychological assessment showed a prompter recovery of visual attentiveness and

  3. Enantioselective Regulation of Lactate Racemization by LarR in Lactobacillus plantarum

    PubMed Central

    Desguin, Benoît; Goffin, Philippe; Bakouche, Nordine; Diman, Aurélie; Viaene, Eric; Dandoy, Damien; Fontaine, Laetitia; Hallet, Bernard

    2014-01-01

    Lactobacillus plantarum is a lactic acid bacterium that produces a racemic mixture of l- and d-lactate from sugar fermentation. The interconversion of lactate isomers is performed by a lactate racemase (Lar) that is transcriptionally controlled by the l-/d-lactate ratio and maximally induced in the presence of l-lactate. We previously reported that the Lar activity depends on the expression of two divergently oriented operons: (i) the larABCDE operon encodes the nickel-dependent lactate racemase (LarA), its maturases (LarBCE), and a lactic acid channel (LarD), and (ii) the larR(MN)QO operon encodes a transcriptional regulator (LarR) and a four-component ABC-type nickel transporter [Lar(MN), in which the M and N components are fused, LarQ, and LarO]. LarR is a novel regulator of the Crp-Fnr family (PrfA group). Here, the role of LarR was further characterized in vivo and in vitro. We show that LarR is a positive regulator that is absolutely required for the expression of Lar activity. Using gel retardation experiments, we demonstrate that LarR binds to a 16-bp palindromic sequence (Lar box motif) that is present in the larR-larA intergenic region. Mutations in the Lar box strongly affect LarR binding and completely abolish transcription from the larA promoter (PlarA). Two half-Lar boxes located between the Lar box and the −35 box of PlarA promote LarR multimerization on DNA, and point mutations within one or both half-Lar boxes inhibit PlarA induction by l-lactate. Gel retardation and footprinting experiments indicate that l-lactate has a positive effect on the binding and multimerization of LarR, while d-lactate antagonizes the positive effect of l-lactate. A possible mechanism of LarR regulation by lactate enantiomers is proposed. PMID:25349156

  4. Radiocarbon Dating.

    PubMed

    Van Strydonck, Mark

    2016-04-01

    Although most historians and art historians consider the radiocarbon dating technique not to be very precise by their criteria, the method has gained much importance over the last decades. Radiocarbon dating is increasingly used in the field of textile research and old polychrome statues, but also objects made of ivory, stucco, paper, and parchment are dated with the technique. Especially after the introduction of the AMS technique, a boom of this type of research has been noticed. PMID:27573138

  5. Optimization of ethanol, citric acid, and α-amylase production from date wastes by strains of Saccharomyces cerevisiae, Aspergillus niger, and Candida guilliermondii.

    PubMed

    Acourene, S; Ammouche, A

    2012-05-01

    The present study deals with submerged ethanol, citric acid, and α-amylase fermentation by Saccharomyces cerevisiae SDB, Aspergillus niger ANSS-B5, and Candida guilliermondii CGL-A10, using date wastes as the basal fermentation medium. The physical and chemical parameters influencing the production of these metabolites were optimized. As for the ethanol production, the optimum yield obtained was 136.00 ± 0.66 g/l under optimum conditions of an incubation period of 72 h, inoculum content of 4% (w/v), sugars concentration of 180.0 g/l, and ammonium phosphate concentration of 1.0 g/l. Concerning citric acid production, the cumulative effect of temperature (30°C), sugars concentration of 150.0 g/l, methanol concentration of 3.0%, initial pH of 3.5, ammonium nitrate concentration of 2.5 g/l, and potassium phosphate concentration of 2.5 g/l during the fermentation process of date wastes syrup did increase the citric acid production to 98.42 ± 1.41 g/l. For the production of α-amylase, the obtained result shows that the presence of starch strongly induces the production of α-amylase with a maximum at 5.0 g/l. Among the various nitrogen sources tested, urea at 5.0 g/l gave the maximum biomass and α-amylase estimated at 5.76 ± 0.56 g/l and 2,304.19 ± 31.08 μmol/l/min, respectively after 72 h incubation at 30°C, with an initial pH of 6.0 and potassium phosphate concentration of 6.0 g/l. PMID:22193823

  6. Dating Violence

    MedlinePlus

    ... Dating violence can cause serious harm to your body and your emotions. If you are in an abusive relationship, get help. Leaving an abusive dating relationship See a doctor or nurse to take care of any physical problems. And reach out for support for your emotional ...

  7. Enantioselective Synthesis of (2R, 3S)- and (2S, 3R)-4,4,4-trifluoro-N-Fmoc-O-tert-butyl-threonine and their Racemization-free Incorporation into Oligopeptides via Solid-phase Synthesis

    PubMed Central

    Xiao, Nu; Jiang, Zhong-Xing; Yu, Y. Bruce

    2010-01-01

    An efficient method for the enantioselective synthesis of (2R, 3S)- and (2S, 3R)-4,4,4-trifluoro-N-Fmoc-O-tert-butyl-threonine (tfT) on multi-gram scales was developed. Absolute configurations of the two stereoisomers were ascertained by X-ray crystallography. Racemization-free coupling conditions for the incorporation of tfT into oligopeptides were then explored. For solution-phase synthesis, tfT racemization was not an issue under conventional coupling conditions. For solid-phase synthesis, the following conditions were identified to achieve racemization-free synthesis: if tfT (3.0 eq.) was not the first amino acid to be linked to the resin (1.0 eq.), the condition is: 2.7 eq. DIC/3.0 eq. HOBt as the coupling reagent at 0 °C for 20 h; if tfT (3.0 eq.) was the first amino acid to be linked to the resin (1.0 eq.), then 1.0 eq. of CuCl2 needs to be added to the coupling reagent. PMID:17702025

  8. Dating lacustrine episodes in the eastern Sahara by the epimerization of isoleucine in ostrich eggshells

    USGS Publications Warehouse

    Miller, G.H.; Wendorf, F.; Ernst, R.; Schild, R.; Close, A.E.; Friedman, I.; Schwarcz, H.P.

    1991-01-01

    The eggshell of the African ostrich, Struthio camelus, closely approximates a closed system for the retention of indigenous proteinaceous residues. Epimerization of the protein amino acid isoleucine follows linear first-order kinetics in laboratory simulations nearly to racemic equilibrium, and the variation in D/L ratio within a single fragment, or between fragments of the same age, is significantly less than in other carbonate systems. These observations suggest that the extent of isoleucine epimerization (aIle/Ile ratio) in ostrich eggshell offers the potential for high-resolution geochronology of Quaternary deposits. From the simulation experiments, and dated early Holocene samples for which we have in situ mean annual sediment temperature measurements, Arrhenius parameters have been calculated; the activation energy is 30.33 kcal mol-1, similar to that of other carbonate systems. We have measured the aIle/Ile ratio in ostrich eggshell associated with lacustrine episodes at Bir Tarfawi and Bir Sahara East, two depressions in what is currently the hyperarid eastern Sahara. The ratios can be used directly to indicate qualitatively the time represented by each series of lake sediment, and to correlate disjunct lacustrine deposits within and between the basins. Uranium-series disequilibrium dating of algal mats contained within some of the lake beds indicate that a major wet interval occurred about 130 ka ago. Using the U-series date for calibration, the amino acid ratios are used to date the most recent lacustrine interval to about 100 ka B.P., and two older intervals, one about 200 ?? 25 ka B.P., and an older interval that occurred prior to 250 ka ago. ?? 1991.

  9. 40 CFR 75.4 - Compliance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... of this chapter, the expiration date of a combustion source's opt-in permit under § 74.14(e) of this... become applicable upon the issuance date of the Acid Rain permit. For combustion sources seeking to enter... following dates: (i) January 1, 1995; or (ii) 90 days after the issuance date of the Acid Rain permit...

  10. 40 CFR 75.4 - Compliance dates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... of this chapter, the expiration date of a combustion source's opt-in permit under § 74.14(e) of this... become applicable upon the issuance date of the Acid Rain permit. For combustion sources seeking to enter... following dates: (i) January 1, 1995; or (ii) 90 days after the issuance date of the Acid Rain permit...

  11. The effects of racemization rate for age estimation of pink teeth.

    PubMed

    Sakuma, Ayaka; Saitoh, Hisako; Ishii, Namiko; Iwase, Hirotaro

    2015-03-01

    Pink teeth is thought to result from the seepage of hemoglobin caused by dental pulp decomposition. We investigated whether racemization can be applied for age estimation in cases of pink teeth where the whole tooth is used. The pink teeth used were three cases and the normal teeth for control were five mandibular canines of known age. Age of the pink teeth was calculated on the basis of regression formula obtained from the five control teeth. Only a slight error was noted between the actual and estimated ages of the pink teeth (R(2) = 0.980, r = 0.990): Cases 1-3 actually aged 23, 53, and 59 years were estimated to be 26, 52, and 60 years. Based on our results of testing pink teeth of known age, we suggest that racemization techniques allow for the age estimation of pink teeth using the same methods for normally colored teeth. PMID:25684096

  12. Crystalline CO2-based polycarbonates prepared from racemic catalyst through intramolecularly interlocked assembly

    PubMed Central

    Liu, Ye; Ren, Wei-Min; Zhang, Wei-Ping; Zhao, Rong-Rong; Lu, Xiao-Bing

    2015-01-01

    The crystalline stereocomplexed polycarbonates can be prepared by mixing enantiopure polymers with opposite configuration, which derived from the asymmetric copolymerization with CO2 using enantiopure catalyst or/and chiral epoxides. Herein, we develop a powerful strategy for producing crystalline intramolecular stereocomplexed polycarbonates from racemic catalysts, which possess similar thermal stability and crystalline behaviour in comparison with the stereocomplexes by mixing opposite enantiopure polymers. Living polymer chains shuttle between catalyst molecules with different configurations to produce diastereomeric active species which is suggested to be responsible for the formation of isotactic multiblock polycarbonates in racemic bimetallic cobalt catalyst-mediated stereoselective copolymerization of CO2 and meso-epoxides. Solid-state NMR spectroscopy study suggests that the interaction in the carbonyl and methine regions is responsible for the strong crystallization capacity and compact package structure in the crystalline polycarbonates. PMID:26469884

  13. A functional role of Rv1738 in Mycobacterium tuberculosis persistence suggested by racemic protein crystallography

    DOE PAGESBeta

    Bunker, Richard D.; Mandal, Kalyaneswar; Bashiri, Ghader; Chaston, Jessica J.; Pentelute, Bradley L.; Lott, J. Shaun; Kent, Stephen B. H.; Baker, Edward N.

    2015-04-07

    Racemic protein crystallography was used to determine the X-ray structure of the predicted Mycobacterium tuberculosis protein Rv1738, which had been completely recalcitrant to crystallization in its natural L-form. Native chemical ligation was used to synthesize both L-protein and D-protein enantiomers of Rv1738. Crystallization of the racemic {D-protein + L-protein} mixture was immediately successful. The resulting crystals diffracted to high resolution and also enabled facile structure determination because of the quantized phases of the data from centrosymmetric crystals. The X-ray structure of Rv1738 revealed striking similarity with bacterial hibernation factors, despite minimal sequence similarity. As a result, we predict that Rv1738,more » which is highly up-regulated in conditions that mimic the onset of persistence, helps trigger dormancy by association with the bacterial ribosome.« less

  14. Radiation Damage and Racemic Protein Crystallography Reveal the Unique Structure of the GASA/Snakin Protein Superfamily.

    PubMed

    Yeung, Ho; Squire, Christopher J; Yosaatmadja, Yuliana; Panjikar, Santosh; López, Gemma; Molina, Antonio; Baker, Edward N; Harris, Paul W R; Brimble, Margaret A

    2016-07-01

    Proteins from the GASA/snakin superfamily are common in plant proteomes and have diverse functions, including hormonal crosstalk, development, and defense. One 63-residue member of this family, snakin-1, an antimicrobial protein from potatoes, has previously been chemically synthesized in a fully active form. Herein the 1.5 Å structure of snakin-1, determined by a novel combination of racemic protein crystallization and radiation-damage-induced phasing (RIP), is reported. Racemic crystals of snakin-1 and quasi-racemic crystals incorporating an unnatural 4-iodophenylalanine residue were prepared from chemically synthesized d- and l-proteins. Breakage of the C-I bonds in the quasi-racemic crystals facilitated structure determination by RIP. The crystal structure reveals a unique protein fold with six disulfide crosslinks, presenting a distinct electrostatic surface that may target the protein to microbial cell surfaces. PMID:27145301

  15. 40 CFR 75.4 - Compliance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... designated under the Acid Rain permit which governs that unit and contains the approved substitution or... become applicable upon the issuance date of the Acid Rain permit. For combustion sources seeking to enter... following dates: (i) January 1, 1995; or (ii) 90 days after the issuance date of the Acid Rain permit...

  16. 40 CFR 75.4 - Compliance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... designated under the Acid Rain permit which governs that unit and contains the approved substitution or... become applicable upon the issuance date of the Acid Rain permit. For combustion sources seeking to enter... following dates: (i) January 1, 1995; or (ii) 90 days after the issuance date of the Acid Rain permit...

  17. Stabilization of the Columnar Mesophase of Perylenediimide by Racemic Triple Tails.

    PubMed

    Pereira de Oliveira Santos, Deise M; Belarmino Cabral, Marilia G; Bentaleb, Ahmed; Cristiano, Rodrigo; Gallardo, Hugo; Durola, Fabien; Bock, Harald

    2016-05-23

    Whereas perylene tetracarboxdiimides derived from amino-n-alkanes if at all only show monotropic (thermodynamically unstable) mesogenic self-assembly, the hexagonal columnar liquid crystalline state can be stabilized over a broad temperature range with doubly branched, doubly racemic alkyl residues. An improved tendency to homeotropic surface orientation is observed, and the orientation of the liquid crystalline domains is maintained upon cycling through the crystalline state at room temperature. PMID:27145525

  18. From Racemic Alcohols to Enantiopure Amines: Ru-Catalyzed Diastereoselective Amination

    PubMed Central

    2015-01-01

    A commercially available ruthenium(II) PNP-type pincer catalyst (Ru-Macho) promotes the formation of α-chiral tert-butanesulfinylamines from racemic secondary alcohols and Ellman’s chiral tert-butanesulfinamide via a hydrogen borrowing strategy. The formation of α-chiral tert-butanesulfinylamines occurs in yields ranging from 31% to 89% with most examples giving >95:5 dr. PMID:25170560

  19. From racemic alcohols to enantiopure amines: Ru-catalyzed diastereoselective amination.

    PubMed

    Oldenhuis, Nathan J; Dong, Vy M; Guan, Zhibin

    2014-09-10

    A commercially available ruthenium(II) PNP-type pincer catalyst (Ru-Macho) promotes the formation of α-chiral tert-butanesulfinylamines from racemic secondary alcohols and Ellman's chiral tert-butanesulfinamide via a hydrogen borrowing strategy. The formation of α-chiral tert-butanesulfinylamines occurs in yields ranging from 31% to 89% with most examples giving >95:5 dr. PMID:25170560

  20. Racemization as a stereochemical measure of dynamics and robustness in shape-shifting organic molecules

    PubMed Central

    He, Maggie; Bode, Jeffrey W.

    2011-01-01

    Bullvalene is a structurally unique dynamic molecule thought to interconvert among 1.2 million degenerate isomers. The incorporation of different chemical substituents onto the bullvalene core should lead to a “shape-shifting” molecule that can interconvert among thousands of discrete structural isomers. Previous NMR spectroscopy and HPLC studies on substituted bullvalenes ascertained the fact that these compounds are dynamic, but they could not attest to whether the molecules are only interconverting among only a few isomers or if a multitude of structures are being accessed. Here we confirm the remarkable shape-shifting property of a tetrasubstituted bullvalene by means of a racemization experiment. We show that a single, though fleeting, chiral, enantioenriched tetrasubstituted bullvalene isomer can spontaneously equilibrate to a racemic population of dynamic compounds. Despite the fact that conversion from one enantiomer of a bullvalene isomer to the other may require dozens or even hundreds of rearrangements and involve many potential pathways, CD spectroscopy and HPLC analysis of different bullvalene populations showed that multiple pathways exist and result in the complete racemization of an initial enantioenriched chiral bullvalene. These oligosubstituted bullvalenes represent a very rare example of an entity that can spontaneously transform itself into different discrete structures using ambient thermal energy. The confirmation that these shape-shifting organic molecules are chemically robust yet structurally dynamic is an important step toward their further use as materials, sensors, and biologically active compounds. PMID:21873220

  1. 3-Dimethylphosphinothioyl-2(3H)-oxazolone (MPTO), a promising new reagent for racemization-free couplings.

    PubMed

    Katoh, T; Ueki, M

    1993-09-01

    3-Dimethylphosphinothioyl-2(3H)-oxazolone (MPTO) was synthesized, and its ability to effect racemization-free couplings and cyclization of a peptide and its C-terminal epimer was examined. MPTO showed good reactivity in aprotic polar solvents such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone. In reactivity MPTO resembles DPPA and dimethylphosphinothioyl azide (MPTA) previously developed by us, but it is much better than these reagents because the side reactions specific to the azide method could be avoided. In coupling of Z-Gly-Val-OH with H-Val-OMe in DMF at 0 degree C, no racemization was observed without use of racemization-suppressing additives. Slight racemization observed at room temperature could be completely suppressed by addition of HOBt but not by HOSu. The utility of MPTO was demonstrated by the synthesis of cyclo-(D-Trp-D-Glu(OBzl)-Ala-D-Val-Leu), an intermediate for an endothelin-binding inhibitor BE 18257A. In a comparative study using DPPA, MPTA and MPTO, no racemization was observed for MPTA or MPTO, while DPPA caused considerable racemization. When MPTO was used in the presence of HOBt rapid cyclization (3 h at RT) occurred to give the optically pure cyclic product. PMID:8225782

  2. An Integrated Experimental and Computational Approach for Characterizing the Kinetics and Mechanism of Triadimefon Racemization.

    PubMed

    Cheng, Qianyi; Teng, Quincy; Marchitti, Satori A; Dillingham, Caleb M; Kenneke, John F

    2016-09-01

    Enantiomers of chiral molecules commonly exhibit differing pharmacokinetics and toxicities, which can introduce significant uncertainty when evaluating biological and environmental fates and potential risks to humans and the environment. However, racemization (the irreversible transformation of one enantiomer into the racemic mixture) and enantiomerization (the reversible conversion of one enantiomer into the other) are poorly understood. To better understand these processes, we investigated the chiral fungicide, triadimefon, which undergoes racemization in soils, water, and organic solvents. Nuclear magnetic resonance (NMR) and gas chromatography / mass spectrometry (GC/MS) techniques were used to measure the rates of enantiomerization and racemization, deuterium isotope effects, and activation energies for triadimefon in H2 O and D2 O. From these results we were able to determine that: 1) the alpha-carbonyl carbon of triadimefon is the reaction site; 2) cleavage of the C-H (C-D) bond is the rate-determining step; 3) the reaction is base-catalyzed; and 4) the reaction likely involves a symmetrical intermediate. The B3LYP/6-311 + G** level of theory was used to compute optimized geometries, harmonic vibrational frequencies, nature population analysis, and intrinsic reaction coordinates for triadimefon in water and three racemization pathways were hypothesized. This work provides an initial step in developing predictive, structure-based models that are needed to identify compounds of concern that may undergo racemization. Chirality 28:633-641, 2016. © 2016 Wiley Periodicals, Inc. PMID:27479933

  3. Date Rape

    MedlinePlus

    ... erasers GHB (gamma hydroxybutyric acid), called cherry meth, energy drink, gook ketamine , called bump, special K, and super acid These drugs can be mixed in to drinks and are almost impossible to detect, especially in dark-colored drinks such as cola or dark beer, ...

  4. Meteoritic Amino Acids: Diversity in Compositions Reflects Parent Body Histories.

    PubMed

    Elsila, Jamie E; Aponte, José C; Blackmond, Donna G; Burton, Aaron S; Dworkin, Jason P; Glavin, Daniel P

    2016-06-22

    The analysis of amino acids in meteorites dates back over 50 years; however, it is only in recent years that research has expanded beyond investigations of a narrow set of meteorite groups (exemplified by the Murchison meteorite) into meteorites of other types and classes. These new studies have shown a wide diversity in the abundance and distribution of amino acids across carbonaceous chondrite groups, highlighting the role of parent body processes and composition in the creation, preservation, or alteration of amino acids. Although most chiral amino acids are racemic in meteorites, the enantiomeric distribution of some amino acids, particularly of the nonprotein amino acid isovaline, has also been shown to vary both within certain meteorites and across carbonaceous meteorite groups. Large l-enantiomeric excesses of some extraterrestrial protein amino acids (up to ∼60%) have also been observed in rare cases and point to nonbiological enantiomeric enrichment processes prior to the emergence of life. In this Outlook, we review these recent meteoritic analyses, focusing on variations in abundance, structural distributions, and enantiomeric distributions of amino acids and discussing possible explanations for these observations and the potential for future work. PMID:27413780

  5. Meteoritic Amino Acids: Diversity in Compositions Reflects Parent Body Histories

    PubMed Central

    2016-01-01

    The analysis of amino acids in meteorites dates back over 50 years; however, it is only in recent years that research has expanded beyond investigations of a narrow set of meteorite groups (exemplified by the Murchison meteorite) into meteorites of other types and classes. These new studies have shown a wide diversity in the abundance and distribution of amino acids across carbonaceous chondrite groups, highlighting the role of parent body processes and composition in the creation, preservation, or alteration of amino acids. Although most chiral amino acids are racemic in meteorites, the enantiomeric distribution of some amino acids, particularly of the nonprotein amino acid isovaline, has also been shown to vary both within certain meteorites and across carbonaceous meteorite groups. Large l-enantiomeric excesses of some extraterrestrial protein amino acids (up to ∼60%) have also been observed in rare cases and point to nonbiological enantiomeric enrichment processes prior to the emergence of life. In this Outlook, we review these recent meteoritic analyses, focusing on variations in abundance, structural distributions, and enantiomeric distributions of amino acids and discussing possible explanations for these observations and the potential for future work. PMID:27413780

  6. Rhodium-Catalyzed Asymmetric Cycloisomerization and Parallel Kinetic Resolution of Racemic Oxabicycles.

    PubMed

    Loh, Charles C J; Schmid, Matthias; Webster, Robert; Yen, Andy; Yazdi, Shabnam K; Franke, Patrick T; Lautens, Mark

    2016-08-16

    While desymmetrizations by intermolecular asymmetric ring-opening reactions of oxabicyclic alkenes with various nucleophiles have been reported over the past two decades, the demonstration of an intramolecular variant is unknown. Reported herein is the first rhodium-catalyzed asymmetric cycloisomerization of meso-oxabicyclic alkenes tethered to bridgehead nucleophiles, thus providing access to tricyclic scaffolds through a myriad of enantioselective C-O, C-N, and C-C bond formations. Moreover, we also demonstrate a unique parallel kinetic resolution, whereby racemic oxabicycles bearing two different bridgehead nucleophiles can be resolved enantioselectively. PMID:27416818

  7. X-ray structure of snow flea antifreeze protein determined by racemic crystallization of synthetic protein enantiomers.

    PubMed

    Pentelute, Brad L; Gates, Zachary P; Tereshko, Valentina; Dashnau, Jennifer L; Vanderkooi, Jane M; Kossiakoff, Anthony A; Kent, Stephen B H

    2008-07-30

    Chemical protein synthesis and racemic protein crystallization were used to determine the X-ray structure of the snow flea antifreeze protein (sfAFP). Crystal formation from a racemic solution containing equal amounts of the chemically synthesized proteins d-sfAFP and l-sfAFP occurred much more readily than for l-sfAFP alone. More facile crystal formation also occurred from a quasi-racemic mixture of d-sfAFP and l-Se-sfAFP, a chemical protein analogue that contains an additional -SeCH2- moiety at one residue and thus differs slightly from the true enantiomer. Multiple wavelength anomalous dispersion (MAD) phasing from quasi-racemate crystals was then used to determine the X-ray structure of the sfAFP protein molecule. The resulting model was used to solve by molecular replacement the X-ray structure of l-sfAFP to a resolution of 0.98 A. The l-sfAFP molecule is made up of six antiparallel left-handed PPII helixes, stacked in two sets of three, to form a compact brick-like structure with one hydrophilic face and one hydrophobic face. This is a novel experimental protein structure and closely resembles a structural model proposed for sfAFP. These results illustrate the utility of total chemical synthesis combined with racemic crystallization and X-ray crystallography for determining the unknown structure of a protein. PMID:18598029

  8. X-ray Structure of Snow Flea Antifreeze Protein Determined by Racemic Crystallization of Synthetic Protein Enantiomers

    SciTech Connect

    Pentelute, Brad L.; Gates, Zachary P.; Tereshko, Valentina; Dashnau, Jennifer L.; Vanderkooi, Jane M.; Kossiakoff, Anthony A.; Kent, Stephen B.H.

    2008-08-20

    Chemical protein synthesis and racemic protein crystallization were used to determine the X-ray structure of the snow flea antifreeze protein (sfAFP). Crystal formation from a racemic solution containing equal amounts of the chemically synthesized proteins d-sfAFP and l-sfAFP occurred much more readily than for l-sfAFP alone. More facile crystal formation also occurred from a quasi-racemic mixture of d-sfAFP and l-Se-sfAFP, a chemical protein analogue that contains an additional -SeCH2- moiety at one residue and thus differs slightly from the true enantiomer. Multiple wavelength anomalous dispersion (MAD) phasing from quasi-racemate crystals was then used to determine the X-ray structure of the sfAFP protein molecule. The resulting model was used to solve by molecular replacement the X-ray structure of l-sfAFP to a resolution of 0.98 {angstrom}. The l-sfAFP molecule is made up of six antiparallel left-handed PPII helixes, stacked in two sets of three, to form a compact brick-like structure with one hydrophilic face and one hydrophobic face. This is a novel experimental protein structure and closely resembles a structural model proposed for sfAFP. These results illustrate the utility of total chemical synthesis combined with racemic crystallization and X-ray crystallography for determining the unknown structure of a protein.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. Dynamic kinetic resolution of secondary alcohols combining enzyme-catalyzed transesterification and zeolite-catalyzed racemization.

    PubMed

    Zhu, Yongzhong; Fow, Kam-Loon; Chuah, Gaik-Khuan; Jaenicke, Stephan

    2007-01-01

    Hydrophobic zeolite beta containing low concentrations of Zr or Al was found to be a good catalyst for the racemization of 1-phenylethanol. The formation of styrene as a side product could be minimized by reducing the metal concentration in the zeolite beta. Combined with an immobilized lipase from Candida antarctica, the dynamic kinetic resolution of 1-phenylethanol to the (R)-phenylethylester can be achieved with high yield and selectivity. The reaction was best conducted in toluene as solvent at 60 degrees C, with higher temperatures leading to a loss in the enantioselectivity of the formed ester. By using high-molecular-weight acyl-transfer reagents, such as vinyl butyrate or vinyl octanoate, a high enantiomeric excess of the product esters of 92 and 98 %, respectively, could be achieved. This is attributed to a steric effect: the bulky ester is less able to enter the pore space of the zeolite catalyst where the active sites for racemization are localized. Close to 100 % conversion of the alcohol was achieved within 2 h. If the more common acyl donor, isopropenyl acetate, was used, the enantiomeric excess (ee) of the formed ester was only 67 %, and the reaction was considerably slower. PMID:17004277

  11. Enzymatic Hydrolytic Resolution of Racemic Ibuprofen Ethyl Ester Using an Ionic Liquid as Cosolvent.

    PubMed

    Wei, Tao; Yang, Kunpeng; Bai, Bing; Zang, Jie; Yu, Xuan; Mao, Duobin

    2016-01-01

    The aim of this study was to develop an ionic liquid (IL) system for the enzymatic resolution of racemic ibuprofen ethyl ester to produce (S)-ibuprofen. Nineteen ILs were selected for use in buffer systems to investigate the effects of ILs as cosolvents for the production of (S)-ibuprofen using thermostable esterase (EST10) from Thermotoga maritima. Analysis of the catalytic efficiency and conformation of EST10 showed that [OmPy][BF₄] was the best medium for the EST10-catalyzed production of (S)-ibuprofen. The maximum degree of conversion degree (47.4%), enantiomeric excess of (S)-ibuprofen (96.6%) and enantiomeric ratio of EST10 (177.0) were achieved with an EST10 concentration of 15 mg/mL, racemic ibuprofen ethyl ester concentration of 150 mM, at 75 °C , with a reaction time of 10 h. The reaction time needed to achieve the highest yield of (S)-ibuprofen was decreased from 24 h to 10 h. These results are relevant to the proposed application of ILs as solvents for the EST10-catalyzed production of (S)-ibuprofen. PMID:27420042

  12. Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines.

    PubMed

    Yan, Liang; Xu, Jing-Kun; Huang, Chao-Fan; He, Zeng-Yang; Xu, Ya-Nan; Tian, Shi-Kai

    2016-09-01

    A new strategy has been established for the kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl-hydrazide-catalyzed asymmetric OH-substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]2 , 4 mol % (S)-SegPhos, and 10 mol % 2,5-dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcohols were smoothly resolved with selectivity factors of more than 400 through an asymmetric allylic alkylation of monosubstituted hydrazines under air at room temperature. Importantly, this kinetic resolution process provided various allylic alcohols and allylic hydrazine derivatives with high enantiopurity. PMID:27339655

  13. Organic geochemistry of amino acids: Precambrian to recent

    SciTech Connect

    Engel, M.H.; Macko, S.A.

    1985-01-01

    Since the discovery of amino acids in fossils (Abelson, 1954), considerable effort has been made to elucidate the origin and distribution of amino acids in geologic materials. Racemization and decomposition reactions of amino acids and peptides derived via the natural hydrolysis of protein constituents of organisms have been extensively studied. While the ubiquity of amino acids presents a challenge for discerning their indigeneity in geologic samples, careful analyses have resulted in successful applications of amino acid racemization and decomposition reactions for investigations of geochronologic, paleoclimatic, stratigraphic, diagenetic and chemotaxonomic problems for Quaternary age samples. An investigation of amino acids in sediments from Baffin Island fjords indicates that their distribution may also provide data with respect to the relative contributions of marine and terrigenous organic matter to recent sediments. While the absence of unstable amino acids and the presence of racemic amino acids in a sample may preclude very recent contamination, the possibility of retardation of amino acid racemization rates subsequent to geopolymer formation must also be considered. Studies of amino acids in Paleozoic, Mesozoic and early Cenozoic age samples are limited. Precambrian samples, however, have received much attention, given the potential (however slight) for isolating compounds representative of the earliest living systems. A future approach for elucidating the origin(s) of amino acids in ancient samples may be analyses of their individual stable isotopic compositions.

  14. Estimation of past intermittent methane seep activity using radiocarbon dating of Calyptogena shells in the eastern Nankai subduction zone

    NASA Astrophysics Data System (ADS)

    Yagasaki, K.; Ashi, J.; Yokoyama, Y.; Miyairi, Y.; Kuramoto, S.

    2013-12-01

    Radioisotope carbon dating samples from the deep ocean has always been a difficult phenomenon due to the carbon offset present. This research presents a way of utilizing such method to date shell samples in order to study past fault activities. The research presented will be based on the preliminary data collected thus far. The Nankai and the Tokai regions are common areas for cold seeps, where seepage of hydrogen sulfide and methane rich fluid occurs. These various substances encourage the growth of Calyptogena colonies to flourish at these sites. Cold seeps generally occur at tectonically active continental margins and are mostly ephemeral. This suggests that the cold seep events are possibly influenced by the tectonic activity during the plate divergence. In 1997, a submersible dive by Shinkai 2000 discovered an unusually large Calyptogena colony ranging over 200 m2 off Daini Tenryu Knoll. Majority of the shells were fossilized with few live shells remaining. It is assumed that past tectonic events in the region may have caused a high flux of methane fluid or gas to be released, making it possible to support such a vast scale colony to survive until their eventual death. Previous attempt to reconstruct the cold seep activity history through amino acid racemisation dating revealed two different age grouped shells. Further data using a different method is required to prove its reliability, as acid racemization dating technique can easily be affected by seawater temperature changes and microbial activity. This consequently alters the protein structure of the sample and its overall age. As 14C radioisotope dating is not affected by temperature change, it will provide additional information to the accuracy of the acid racemisation dating of the shell. However, the possibility of contamination is likely due to the shells incorporating older carbon from the sediments during their early stages of growth. The old carbon value can be calculated by subtracting the formerly

  15. Synthesis of α-aminoboronic acids.

    PubMed

    Andrés, Patricia; Ballano, Gema; Calaza, M Isabel; Cativiela, Carlos

    2016-04-21

    This review describes available methods for the preparation of α-aminoboronic acids in their racemic or in their enantiopure form. Both, highly stereoselective syntheses and asymmetric procedures leading to the stereocontrolled generation of α-aminoboronic acid derivatives are included. The preparation of acyclic, carbocyclic and azacyclic α-aminoboronic acid derivatives is covered. Within each section, the different synthetic approaches have been classified according to the key bond which is formed to complete the α-aminoboronic acid skeleton. PMID:26853637

  16. Lactate Racemization as a Rescue Pathway for Supplying d-Lactate to the Cell Wall Biosynthesis Machinery in Lactobacillus plantarum

    PubMed Central

    Goffin, Philippe; Deghorain, Marie; Mainardi, Jean-Luc; Tytgat, Isabelle; Champomier-Vergès, Marie-Christine; Kleerebezem, Michiel; Hols, Pascal

    2005-01-01

    Lactobacillus plantarum is a lactic acid bacterium that produces d- and l-lactate using stereospecific NAD-dependent lactate dehydrogenases (LdhD and LdhL, respectively). However, reduction of glycolytic pyruvate by LdhD is not the only pathway for d-lactate production since a mutant defective in this activity still produces both lactate isomers (T. Ferain, J. N. Hobbs, Jr., J. Richardson, N. Bernard, D. Garmyn, P. Hols, N. E. Allen, and J. Delcour, J. Bacteriol. 178:5431-5437, 1996). Production of d-lactate in this species has been shown to be connected to cell wall biosynthesis through its incorporation as the last residue of the muramoyl-pentadepsipeptide peptidoglycan precursor. This particular feature leads to natural resistance to high concentrations of vancomycin. In the present study, we show that L. plantarum possesses two pathways for d-lactate production: the LdhD enzyme and a lactate racemase, whose expression requires l-lactate. We report the cloning of a six-gene operon, which is involved in lactate racemization activity and is positively regulated by l-lactate. Deletion of this operon in an L. plantarum strain that is devoid of LdhD activity leads to the exclusive production of l-lactate. As a consequence, peptidoglycan biosynthesis is affected, and growth of this mutant is d-lactate dependent. We also show that the growth defect can be partially restored by expression of the d-alanyl-d-alanine-forming Ddl ligase from Lactococcus lactis, or by supplementation with various d-2-hydroxy acids but not d-2-amino acids, leading to variable vancomycin resistance levels. This suggests that L. plantarum is unable to efficiently synthesize peptidoglycan precursors ending in d-alanine and that the cell wall biosynthesis machinery in this species is specifically dedicated to the production of peptidoglycan precursors ending in d-lactate. In this context, the lactate racemase could thus provide the bacterium with a rescue pathway for d-lactate production upon

  17. Randomized placebo controlled assessment of airway inflammation due to racemic albuterol and levalbuterol via exhaled nitric oxide testing

    PubMed Central

    Freiler, John F; Arora, Rajiv; Kelley, Thomas C; Hagan, Larry; Allan, Patrick F

    2006-01-01

    Study Objectives The S-stereoisomer found in racemic albuterol may have associated proinflammatory properties. We tested the hypothesis that airway inflammation as assessed by exhaled nitric oxide is no different in patients with COPD when using racemic albuterol relative to levalbuterol or placebo. Measurements Twelve mild to moderate COPD patients were assigned to five days each of nebulized racemic albuterol, levalbuterol, and saline placebo. Before and after each course of treatment, airway inflammation was assessed via exhaled nitric oxide breath testing. Secondary functional outcomes that were measured included spirometry, a functional assessment utilizing a six-minute walk, and symptoms score using the University of California, San Diego Shortness of Breath Questionnaire. Results There was no statistically significant difference in pre and post FeNO levels within and between treatment groups (p = 0.121). There were also no significant differences within or between treatment groups for the secondary outcome measurements of FEV1 (p = 0.913), functional assessment utilizing a six-minute walk (p = 0.838) and the symptom scores using Shortness of Breath Questionnaire (p = 0.500). Conclusion We found no difference in mild to moderate COPD patients treated with racemic albuterol, levalbuterol or placebo for measurement of exhaled nitric oxide or the secondary outcomes that were measured. PMID:18044102

  18. Determination of the D and L isomers of some protein amino acids present in soils

    NASA Technical Reports Server (NTRS)

    Pollock, G. E.; Cheng, C.-N.; Cronin, S. E.

    1977-01-01

    The D and L isomers of some protein amino acids present in soils were measured by using a gas chromatographic technique. The results of two processing procedures were compared to determine the better method. Results of the comparison indicated that the determination of D and L percentages requires amino acid purification if one is to obtain accurate data. It was found that very significant amounts of D-alanine, D-aspartic acid, and D-glutamic acid were present in the contemporary soils studied. Valine, isoleucine, leucine, proline, and phenylalanine generally contained only a trace to very small amounts of the D isomer. It is probable that the D-amino acids from the alanine, aspartic, and glutamic acids are contributed to the soil primarily via microorganisms. The finding of very significant quantities of some D-amino acids (about 5-16%) in present-day soils may alert some investigators of geological sediments to a possible problem in using amino acid racemization as an age-dating technique.

  19. S-Methylidene Agents: Preparation of Chiral Non-Racemic Heterocycles

    PubMed Central

    Forbes, David C.; Bettigeri, Sampada V.; Patrawala, Samit A.; Pischek, Susanna C.; Standen, Michael C.

    2008-01-01

    Reaction of sulfur ylide with aldehyde, imine, and ketone functionality affords the desired three-membered heterocycle in excellent yield. The sulfur ylide is generated in situ upon decarboxylation of carboxymethylsulfonium betaine functionality. Of the seven carboxymethylsulfonium betaine derivatives surveyed, the highest level of conversion of π-acceptor to heterocycle was obtained having S-methyl and S-phenyl functionality bound to a thioacetate derivative. Methylene aziridinations and epoxidations involving the decarboxylation of carboxymethylsulfonium betaine functionality complements existing technologies with the advantages of the reaction protocol, levels of conversion and scope. While moderate levels of diastereocontrol were observed in the aziridination of imine functionality, the four oxiranes resolved using Jacobsen’s Co(II)-salen complex were obtained in both high yield and enantioselectivity. The isolated chiral non-racemic oxiranes constitute the formal synthesis of chelonin-B and combretastatin starting from 3-bromo-4-methoxybenzaldehyde and 3,4,5-trimethoxybenzaldehyde respectively. PMID:20049065

  20. A functional role of Rv1738 in Mycobacterium tuberculosis persistence suggested by racemic protein crystallography.

    PubMed

    Bunker, Richard D; Mandal, Kalyaneswar; Bashiri, Ghader; Chaston, Jessica J; Pentelute, Bradley L; Lott, J Shaun; Kent, Stephen B H; Baker, Edward N

    2015-04-01

    Protein 3D structure can be a powerful predictor of function, but it often faces a critical roadblock at the crystallization step. Rv1738, a protein from Mycobacterium tuberculosis that is strongly implicated in the onset of nonreplicating persistence, and thereby latent tuberculosis, resisted extensive attempts at crystallization. Chemical synthesis of the L- and D-enantiomeric forms of Rv1738 enabled facile crystallization of the D/L-racemic mixture. The structure was solved by an ab initio approach that took advantage of the quantized phases characteristic of diffraction by centrosymmetric crystals. The structure, containing L- and D-dimers in a centrosymmetric space group, revealed unexpected homology with bacterial hibernation-promoting factors that bind to ribosomes and suppress translation. This suggests that the functional role of Rv1738 is to contribute to the shutdown of ribosomal protein synthesis during the onset of nonreplicating persistence of M. tuberculosis. PMID:25831534

  1. A functional role of Rv1738 in Mycobacterium tuberculosis persistence suggested by racemic protein crystallography

    PubMed Central

    Bunker, Richard D.; Mandal, Kalyaneswar; Bashiri, Ghader; Chaston, Jessica J.; Pentelute, Bradley L.; Lott, J. Shaun; Kent, Stephen B. H.; Baker, Edward N.

    2015-01-01

    Protein 3D structure can be a powerful predictor of function, but it often faces a critical roadblock at the crystallization step. Rv1738, a protein from Mycobacterium tuberculosis that is strongly implicated in the onset of nonreplicating persistence, and thereby latent tuberculosis, resisted extensive attempts at crystallization. Chemical synthesis of the l- and d-enantiomeric forms of Rv1738 enabled facile crystallization of the d/l-racemic mixture. The structure was solved by an ab initio approach that took advantage of the quantized phases characteristic of diffraction by centrosymmetric crystals. The structure, containing l- and d-dimers in a centrosymmetric space group, revealed unexpected homology with bacterial hibernation-promoting factors that bind to ribosomes and suppress translation. This suggests that the functional role of Rv1738 is to contribute to the shutdown of ribosomal protein synthesis during the onset of nonreplicating persistence of M. tuberculosis. PMID:25831534

  2. Kinetic resolution of 2-hydroxybutanoate racemic mixtures by NAD-independent L-lactate dehydrogenase.

    PubMed

    Gao, Chao; Zhang, Wen; Ma, Cuiqing; Liu, Peng; Xu, Ping

    2011-04-01

    Optically active D-2-hydroxybutanoate is an important building block intermediate for medicines and biodegradable poly(2-hydroxybutanoate). Kinetic resolution of racemic 2-hydroxybutanoate may be a green and desirable alternative for D-2-hydroxybutanoate production. In this work, D-2-hydroxybutanoate at a high concentration (0.197 M) and a high enantiomeric excess (99.1%) was produced by an NAD-independent L-lactate dehydrogenase (L-iLDH) containing biocatalyst. 2-Oxobutanoate, another important intermediate, was co-produced at a high concentration (0.193 M). Using a simple ion exchange process with the macroporous anion exchange resin D301, D-2-hydroxybutanoate was separated from the biotransformation system with a high recovery of 84.7%. PMID:21295977

  3. Non-racemic Antifolates Stereo-selectively Recruit Alternate Cofactors and Overcome Resistance in S. aureus

    PubMed Central

    Keshipeddy, Santosh; Reeve, Stephanie M.; Anderson, Amy C.; Wright, Dennis L.

    2016-01-01

    While antifolates such as Bactrim (trimethoprim-sulfamethoxazole; TMP-SMX) continue to play an important role in treating community-acquired methicillin-resistant Staphylococcus aureus (CA-MRSA), resistance-conferring mutations, specifically F98Y of dihydrofolate reductase (DHFR), have arisen and compromise continued use. In an attempt to extend the lifetime of this important class, we have developed a class of propargyl-linked antifolates (PLAs) that exhibit potent inhibition of the enzyme and bacterial strains. Probing the role of the configuration at the single propargylic stereocenter in these inhibitors required us to develop a new approach to non-racemic 3-aryl-1-butyne building blocks by the pairwise use of asymmetric conjugate addition and aldehyde dehydration protocols. Using this new route, a series of non-racemic PLA inhibitors was prepared and shown to possess potent enzyme inhibition (IC50 values < 50 nM), antibacterial effects (several with MIC values < 1 µg/mL) and to form stable ternary complexes with both wild-type and resistant mutants. Unexpectedly, crystal structures of a pair of individual enantiomers in the wild-type DHFR revealed that the single change in configuration of the stereocenter drove the selection of an alternative NADPH cofactor, with the minor α-anomer appearing with R-27. Remarkably, this cofactor switching becomes much more prevalent when the F98Y mutation is present. The observation of cofactor site plasticity leads to a postulate for the structural basis of TMP resistance in DHFR and also suggests design strategies that can be used to target these resistant enzymes. PMID:26098608

  4. Investigation of bone disease using isomerized and racemized fragments of type I collagen.

    PubMed

    Cloos, P A C; Fledelius, C; Christgau, S; Christiansen, C; Engsig, M; Delmas, P; Body, J-J; Garnero, P

    2003-01-01

    In the collagen type I C-telopeptide an aspartyl-glycine site within the sequence AHDGGR is susceptible to molecular rearrangement. In newly synthesized collagen this site is in the native form, denoted alpha L. During aging a spontaneous reaction occurs resulting in three age-modified forms: an isomerized form (beta L) a racemized form (alpha D), and an isomerized/racemized form (beta D). In this study, we measured the urinary excretion of the four forms of C-telopeptides (CTX) in healthy adults and in patients with bone diseases. Levels of all CTX forms were higher in healthy postmenopausal women (P<0.001) compared with premenopausal controls. Levels decreased within 3 days of bisphosphonate treatment indicating that all CTX forms reflect bone resorption. In hyperthyroidism, characterized by a generalized increased bone turnover, native (alpha L) and age-modified (beta L, alpha D and beta D) forms increased to a similar extent compared to controls, resulting in normal ratios between the alpha L and age-modified forms of CTX. Conversely, in Paget's disease and prostate cancer-induced bone metastases, conditions characterized by focal increased bone turnover, alpha L CTX levels were more elevated than those of age-related CTX forms, resulting in increased ratios between native and age-modified CTX. For example, the ratio alpha L/alpha D was increased 7-fold in Paget's disease (P<0.001) and 2-fold in prostate cancer-induced bone metastases (P<0.002). In conclusion, the study suggests that in conditions with a localized alteration in bone turnover the ratio between alpha L CTX and the age-modified forms is significantly elevated. This may provide a new diagnostic and monitoring tool for diseases such as metastatic bone cancer and Paget's disease. PMID:12384813

  5. Stereochemistry during aflatoxin biosynthesis: cyclase reaction in the conversion of versiconal to versicolorin B and racemization of versiconal hemiacetal acetate.

    PubMed Central

    Yabe, K; Hamasaki, T

    1993-01-01

    (1'R,2'S)-(-)-aflatoxins are produced from racemic versiconal hemiacetal acetate (VHA) through complicated pathways, including a metabolic grid involving VHA, versiconol acetate (VOAc), versiconol, and versiconal (VHOH), and a reaction sequence from VHOH to versicolorin A (VA) through (-)-versicolorin B (VB) [or (+/-)-versicolorin C] (K. Yabe, Y. Ando, and Y. Hamasaki, J. Gen. Microbiol. 137:2469-2475, 1991; K. Yabe, Y. Ando, and T. Hamasaki, Agric. Biol. Chem. 55:1907-1911, 1991). In this study, we examined stereochemical changes of substances formed during the conversion of VHA to VA by using chiral high-performance liquid chromatography. In cell-free experiments using the cytosol of Aspergillus parasiticus NIAH-26, both (2'S)- and (2'R)-VOAc enantiomers were formed at about a 1:2 ratio from racemic VHA in the presence of NADPH and dichlorvos (dimethyl 2,2-dichlorovinylphosphate). Also, the esterase activity catalyzing the conversion of VHA to VHOH or of VOAc to versiconol did not show the stereospecificity for the 2' carbon atom of VHA or VOAc. However, when racemic VHA or racemic VHOH was incubated with the cytosol, (1'R,2'S)-(-)-VB was formed exclusively. Furthermore, only (1'R,2'S)-(-)-VB, and not (1'S,2'R)-(+) antipode, served as a substrate for desaturase activity in the microsome fraction catalyzing the conversion of VB to VA. These results demonstrate that the stereoconfiguration of bis-furan moiety in aflatoxin molecules is determined by the cyclase enzyme catalyzing the reaction from VHOH to VB, and the (1'R,2'S)-(-) configuration was further confirmed by the subsequent desaturase reaction. Remarkably, we found nonenzymatic racemization in both the (2'R)- and (2'S)-VHA enantiomers, and it was dependent upon the temperature and alkaline conditions. PMID:8368837

  6. The optical nature of methylsuccinic acid in human urine

    NASA Technical Reports Server (NTRS)

    Zeitman, B.; Lawless, J. G.

    1975-01-01

    Methylsuccinic acid was isolated from human urine, derivatized as the di-S-(+)-2-butyl ester, and analyzed using a gas chromatographic system capable of separating the enantiomers of the derivative. The R-(+)-isomer was found to be present. Methylsuccinic acid is potentially important as a criterion for abiogenicity, having been obtained as a racemic mixture from sources known to be abiotic.

  7. A Multi-Enzymatic Cascade Reaction for the Stereoselective Production of γ-Oxyfunctionalyzed Amino Acids.

    PubMed

    Enoki, Junichi; Meisborn, Jaqueline; Müller, Ann-Christin; Kourist, Robert

    2016-01-01

    A stereoselective three-enzyme cascade for synthesis of diasteromerically pure γ-oxyfunctionalized α-amino acids was developed. By coupling a dynamic kinetic resolution (DKR) using an N-acylamino acid racemase (NAAAR) and an L-selective aminoacylase from Geobacillus thermoglucosidasius with a stereoselective isoleucine dioxygenase from Bacillus thuringiensis, diastereomerically pure oxidized amino acids were produced from racemic N-acetylamino acids. The three enzymes differed in their optimal temperature and pH-spectra. Their different metal cofactor dependencies led to inhibitory effects. Under optimized conditions, racemic N-acetylmethionine was quantitatively converted into L-methionine-(S)-sulfoxide with 97% yield and 95% de. The combination of these three different biocatalysts allowed the direct synthesis of diastereopure oxyfunctionalized amino acids from inexpensive racemic starting material. PMID:27092111

  8. A Multi-Enzymatic Cascade Reaction for the Stereoselective Production of γ-Oxyfunctionalyzed Amino Acids

    PubMed Central

    Enoki, Junichi; Meisborn, Jaqueline; Müller, Ann-Christin; Kourist, Robert

    2016-01-01

    A stereoselective three-enzyme cascade for synthesis of diasteromerically pure γ-oxyfunctionalized α-amino acids was developed. By coupling a dynamic kinetic resolution (DKR) using an N-acylamino acid racemase (NAAAR) and an L-selective aminoacylase from Geobacillus thermoglucosidasius with a stereoselective isoleucine dioxygenase from Bacillus thuringiensis, diastereomerically pure oxidized amino acids were produced from racemic N-acetylamino acids. The three enzymes differed in their optimal temperature and pH-spectra. Their different metal cofactor dependencies led to inhibitory effects. Under optimized conditions, racemic N-acetylmethionine was quantitatively converted into L-methionine-(S)-sulfoxide with 97% yield and 95% de. The combination of these three different biocatalysts allowed the direct synthesis of diastereopure oxyfunctionalized amino acids from inexpensive racemic starting material. PMID:27092111

  9. Non-cyclooxygenase prostaglandin synthesis in the sea whip coral, Plexaura homomalla: an 8(R)-lipoxygenase pathway leads to formation of an alpha-ketol and a Racemic prostanoid

    SciTech Connect

    Brash, A.R.; Baertschi, S.W.; Ingram, C.D.; Harris, T.M.

    1987-11-25

    Plexaura homomalla is a rich natural source of prostaglandins and recent evidence suggest the prostaglandin biosynthesis could occur through a lipoxygenase pathway. We have investigated the metabolism of arachidonic acid in homogenates and acetone powders of the fresh frozen coral. The biosynthesis of natural prostaglandins was not detected. However, we find a prominent 8(R)-lipoxygenase pathway leading to an alpha-ketol, characterized by high pressure liquid chromatography, gas chromatography-mass spectrometry, and NMR as 8-hydroxy, 9-keto-eicosa-5Z, 11Z, 14Z-trienoic acid, and a prostaglandin A-like cyclopentenone identified as 9-oxo-(8, 12-cis)-prosta-5Z, 10, 14Z-trienoic acid. These reactions appear analogous to the transformation of linolenic acid hydroperoxide by isomerase and cyclase of corn and flaxseed. From analysis of the absolute configurations of the coral products, and from additional stable isotope labeling experiments in H/sub 2//sup 18/O and D/sub 2/O, we deduce that both compounds arise via conversion of 8(R)-HPETE to an 8(R), 9-allene oxide, 8R,9-oxido-eicosa-5Z, 9, 11Z, 14Z-tetraenoic acid. This unstable intermediate undergoes hydrolysis to form the alpha-ketol or cyclization to give the cyclopentenone. Significantly, we find that the prostaglandin-like product is a racemic mixture of cis side chain enantiomers, pointing to its nonenzymatic origin from the allene oxide. The alpha-ketol is formed with partial racemization and inversion of configuration, also compatible with formation in a nonenzymatic reaction. We conclude that the isomerase and cyclase reactions may merely reflect nonenzymatic breakdown of the enzymatically formed allene oxide.

  10. Enantioselective assembly of amphipathic chiral polymer and racemic chiral small molecules during preparation of micro-scale polymer vesicles.

    PubMed

    Wang, Yingjue; Zhuang, Yiwei; Gao, Jiangang; Zou, Gang; Zhang, Qijin

    2016-03-14

    Enantioselective assembly is observed during preparation of vesicles from a solution mixture of an amphipathic block copolymer bearing pendent chiral l- or d-phenylalanine groups in hydrophobic segments and racemic chiral small molecules. Primary experimental results reveal that racemic chiral small molecules have been enantioselectively encapsulated into the hydrophobic shells of assembled vesicles with homochiral bilayer membrane structure, showing reverse CD signals compared with the original vesicles. A further study shows that the enantiomeric excess obtained through the enantioselective assembly is directly dependent on the molecular weight of the hydrophobic chiral chain segments, implying both the hydrophobic interaction and chirality are key points during the assembly of vesicles. Other factors, such as hydrogen-bonding interactions and π-π stacking interaction, are also found to be responsible for the enantioselective assembly phenomenon during the formation of the vesicles. PMID:26853976

  11. A functional role of Rv1738 in Mycobacterium tuberculosis persistence suggested by racemic protein crystallography

    SciTech Connect

    Bunker, Richard D.; Mandal, Kalyaneswar; Bashiri, Ghader; Chaston, Jessica J.; Pentelute, Bradley L.; Lott, J. Shaun; Kent, Stephen B. H.; Baker, Edward N.

    2015-04-07

    Racemic protein crystallography was used to determine the X-ray structure of the predicted Mycobacterium tuberculosis protein Rv1738, which had been completely recalcitrant to crystallization in its natural L-form. Native chemical ligation was used to synthesize both L-protein and D-protein enantiomers of Rv1738. Crystallization of the racemic {D-protein + L-protein} mixture was immediately successful. The resulting crystals diffracted to high resolution and also enabled facile structure determination because of the quantized phases of the data from centrosymmetric crystals. The X-ray structure of Rv1738 revealed striking similarity with bacterial hibernation factors, despite minimal sequence similarity. As a result, we predict that Rv1738, which is highly up-regulated in conditions that mimic the onset of persistence, helps trigger dormancy by association with the bacterial ribosome.

  12. From racemic precursors to fully stereocontrolled products: one-pot synthesis of chiral α-amino lactones and lactams.

    PubMed

    You, Zhi-Hao; Chen, Ying-Han; Liu, Yan-Kai

    2016-07-14

    Substituted racemic lactols or cyclic hemiaminals were directly used as nucleophiles in enamine-based asymmetric amination reactions to access enantioenriched α-amino lactones or lactams via a one-pot sequence. The desired products, which are very important building blocks in organic synthesis but difficult to be prepared in the optically enriched form, could be afforded with two stereogenic centers in high yields with excellent enantioselectivities. Moreover, starting from the racemic precursors and catalyzed by the enantiomeric pair of the catalyst, all possible stereoisomeric products were discretely provided only after simple column chromatography. Additionally, this protocol provides facile access to several novel bicyclic carbamates, and such drug-like heterocyclic compounds should be potentially useful in medicinal chemistry. PMID:27270561

  13. Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

    PubMed

    Shinozawa, Toru; Terasaki, Shou; Mizuno, Shota; Kawatsura, Motoi

    2016-07-01

    We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value. PMID:27276556

  14. A novel control of enzymatic enantioselectivity through the racemic temperature influenced by reaction media.

    PubMed

    Jin, Xin; Liu, Bokai; Ni, Zhong; Wu, Qi; Lin, Xianfu

    2011-05-01

    The influence of reaction media on the racemic temperature (T(r)) in the lipase-catalyzed resolution of ketoprofen vinyl ester was investigated. An effective approach to the control of the enzymatic enantioselectivity and the prediction of the increasing tendency was developed based on the T(r) influenced by reaction media. The T(r) for the resolution catalyzed by Candida rugosa lipase (CRL) was found at 29 °C in aqueous and S-ketoprofen was obtained predominantly at 40 °C. However, CRL showed R-selectivity at 40 °C in diisopropyl ether because the T(r) was changed to 56 °C. CRL, lipase from AYS Amano(®) and Mucor javanicus lipase were further applied for the investigation of the enzymatic enantioselectivity in dioxane, DIPE, isooctane and their mixed media with water. The effects of the reaction medium on T(r) could be related to the solvent hydrophobicity, the lipase conformational flexibility and the interaction between the enantiomers and the lipase. PMID:22113016

  15. Inhalation of racemic epinephrine in children with asthma. Dose-response relation and comparison with salbutamol.

    PubMed

    Kjellman, B; Tollig, H; Wettrell, G

    1980-10-01

    In this study the effects of nebulized racemic epinephrine (Micronephrine) were investigated in children with asthma. The drug was inhaled by a compressor nebulizer with a plastic mask. In the first part of the study it is shown that nebulized Micronephrine has a dose-dependent bronchodilatory effect. In the second part the effect is compared with that of nebulized salbutamol in 10 children (7-16 years of age) with bronchial asthma. The highest dose used in the dose-response trials (=0.9 mg Micronephrine/kg body-weight) was compared with 0.15 mg salbutamol/kg body-weight, which is the dose commonly used in Sweden. There was no significant difference between the drugs as regards increase of forced expiratory volume in 1 sec or duration of the increase. There was a small but significant increase in systolic blood pressure, measured 5 min after the inhalation of Micronephrine but no significant change in diastolic pressure or heart rate. Four children complained of temporary sore throat after the inhalation. PMID:7468946

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

    USGS Publications Warehouse

    Abidi, S.L.

    1987-01-01

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

  17. Racemization of alanine by the alanine racemases from Salmonella typhimurium and Bacillus stearothermophilus: energetic reaction profiles

    SciTech Connect

    Faraci, W.S.; Walsh, C.T.

    1988-05-03

    Alanine racemases are bacterial pyridoxal 5'-phosphate (PLP) dependent enzymes providing D-alanine as an essential building block for biosynthesis of the peptidoglycan layer of the cell wall. Two isozymic alanine racemases, encoded by the dadB gene and the alr gene, from the Gram-negative mesophilic Salmonella typhimurium and one from the Gram-positive thermophilic Bacillus stearothermophilus have been examined for the racemization mechanism. Substrate deuterium isotope effects and solvent deuterium isotope effects have been measured in both L ..-->.. D and D..-->.. L directions for all three enzymes to assess the degree to which abstraction of the ..cap alpha..-proton or protonation of substrate PLP carbanion is limiting in catalysis. Additionally, experiments measuring internal return of ..cap alpha..-/sup 3/H from substrate to product and solvent exchange/substrate conversion experiments in /sup 3/H/sub 2/O have been used with each enzyme to examine the partitioning of substrate PLP carbanion intermediates and to obtain the relative heights of kinetically significant energy barriers in alanine racemase catalysis.

  18. Racemic salbutamol and levosalbutamol in mild persistent asthma: A comparative study of efficacy and safety

    PubMed Central

    Maiti, Rituparna; Prasad, Chenimilla Nagender; Jaida, Jyothirmai; Mukkisa, Sruthi; Koyagura, Narendar; Palani, Anuradha

    2011-01-01

    Aim: The effect of monotherapy with racemic salbutamol and levosalbutamol on symptoms, quality of life, and pulmonary function has been assessed and compared in mild persistent asthma. Materials and Methods: A randomized, open, parallel clinical study was conducted on 60 patients of mild persistent asthma. After baseline assessments, salbutamol was prescribed to 30 patients and levosalbutamol to another 30 for 4 weeks. The efficacy variables were change in asthma symptom scoring, pulmonary function test, and Mini Asthma Quality of Life Questionnaire (MiniAQLQ) scoring. At follow-up, the patients were re-evaluated and analyzed by statistical tools. Results: Shortness of breath (P<0.001), chest tightness (P=0.033), wheeze (P=0.01), cough (P=0.024), and overall asthma symptom score (P<0.001) were significantly decreased in the levosalbutamol group in comparison to the salbutamol group. Results of MiniAQLQ revealed that improvement in symptoms (P=0.018), activity limitations (P=0.03), environmental stimuli (P=0.013)-related scoring and overall MiniAQLQ scoring (P<0.001) was statistically significant in the levosalbutamol group. Percentage reversibility of forced expiratory volume at one second (P=0.034), forced vital capacity (P=0.029), peak expiratory flow rate (P=0.0003) was found to be superior in the levosalbutamol group. Conclusion: Levosalbutamol was found to be superior compared to recemic salbutamol in mild persistent asthma. PMID:22144765

  19. Levalbuterol compared with racemic albuterol in the treatment of acute asthma: results of a pilot study.

    PubMed

    Nowak, Richard M; Emerman, Charles L; Schaefer, Kendyl; Disantostefano, Rachel L; Vaickus, Louis; Roach, James M

    2004-01-01

    This was a prospective, open-label, nonrandomized pilot study to evaluate efficacy and tolerability of levalbuterol (LEV) in acute asthma. Asthmatics (forced expiratory volume in 1 second [FEV1], 20-55% predicted) were sequentially enrolled into cohorts of 12 to 14 and received 0.63, 1.25, 2.5, 3.75, or 5.0 mg LEV or 2.5 or 5.0 mg racemic albuterol (RAC) every 20 minutes x 3. After the first dose, FEV1 changes were 56% (0.6 L) for 1.25 mg LEV and 6% (0.07 L) and 14% (0.21 L) for 2.5 and 5 mg RAC respectively. After three doses, FEV1 changes were 74% (0.9 L), 39% (0.5 L), and 37% (0.6 L) for 1.25 mg, LEV 2.5 mg, RAC and 0.63 mg LEV respectively. LEV doses greater than 1.25 mg did not further improve bronchodilation. Baseline plasma (S)-albuterol levels were negatively correlated with baseline FEV1 (R = - 0.3, P = .004) and percent change in FEV1 (R = -0.3, P = .006). LEV at a dose of 1.25 mg produced effective bronchodilation that was greater than both RAC doses. The negative correlation between (S)-albuterol levels and FEV1 could suggest a deleterious effect of (S)-albuterol. Larger comparative studies are warranted. PMID:14724875

  20. Changes in heart rate associated with nebulized racemic albuterol and levalbuterol in intensive care patients.

    PubMed

    Lam, Sum; Chen, Julie

    2003-10-01

    The effects of equipotent doses of racemic albuterol and levalbuterol on heart rate (HR) in intensive care patients with and without baseline tachycardia were studied. Patients were included if they were hemodynamically stable and required bronchodilator therapy every four hours; patients were excluded if they were maintained on a beta-blocker. Four hours after the most recent bronchodilator treatment, each patient was randomized to receive at least two consecutive doses of albuterol 2.5 mg or levalbuterol 1.25 mg four hours apart via nebulization. HR was recorded at the end of the second dose and 5, 10, 15, 30, 60, 90, 120, 180, and 240 minutes after treatment. Twenty intensive care patients, including 10 with baseline tachycardia and 10 without baseline tachycardia, were enrolled. In patients with baseline tachycardia, the mean largest HR increase was 1.4 beats/min (1.3%) with albuterol and 2.0 beats/min (2.1%) with levalbuterol (both increases were not significant). In patients without baseline tachycardia, the mean largest HR increase was 4.4 beats/min (6.7%) with albuterol (p = 0.04) and 3.6 beats/min (5.0%) with levalbuterol (p = 0.03). Short-term use of nebulized albuterol and levalbuterol was associated with similar changes in HR in intensive care patients with or without baseline tachycardia. PMID:14531242

  1. Tolerability and effectiveness of (S)-amlodipine compared with racemic amlodipine in hypertension: A systematic review and meta-analysis

    PubMed Central

    Liu, Fang; Qiu, Meng; Zhai, Suo-Di

    2010-01-01

    Background: Amlodipine is a calcium channel blocker prescribed for the management of angina and hypertension. As a racemic mixture, amlodipine contains (R)- and (S)-amlodipine isomers, but only (S)-amlodipine as the active moiety possesses therapeutic activity. Based on pharmacologic research, it remains uncertain if (S)-amlodipine alone has similar efficacy and fewer associated adverse events (AEs) compared with the racemic mixtures. Objective: The aim of this systematic review and meta-analysis was to determine the effectiveness and tolerability of (S)-amlodipine compared with that of racemic amlodipine. Methods: A systematic literature search was performed using MEDLINE (1966–2009), EMBASE (1966–2009), the Cochrane Central Register of Controlled Trials (issue 3, 2009), the Chinese Biomedical Database (1978–2009), and the China National Knowledge Internet (1980–2009). All randomized controlled trials (RCTs) comparing (S)-amlodipine 2.5 mg and racemic amlodipine 5.0 mg in the treatment of hypertension were included in the review. The outcome measures to be collected were cardiovascular events, systolic blood pressure (SBP), diastolic BP (DBP), and AEs. Quality assessments of clinical trials were conducted using a modified Jadad Scale, with trials being rated as low quality (score 0–3) or high quality (score 4–7). Meta-analysis of the included studies was performed using RevMan software. Results: Of the 229 references identified, 214 were excluded after screening the titles, abstracts, or full texts. Fifteen RCTs were included, of which 13 were in Chinese and 2 in English. Based on the Jadad Scale score, 3 of the RCTs were classified as high quality (score 5 or 6) and the remaining 12 as low quality (score 1–3). None of the trials evaluated cardiovascular events beyond 40 weeks. Meta-analysis of the 15 trials indicated that (S)-amlodipine was not significantly different from racemic amlodipine in the effect on BP. When only high-quality studies were

  2. D-amino acid formation in sterilized alkali-treated olives.

    PubMed

    Casado, Francisco Javier; Sánchez, Antonio Higinio; Rejano, Luis; Montaño, Alfredo

    2007-05-01

    The occurrence of d-amino acids in commercial ripe olives, a well-known sterilized alkali-treated product, was investigated by high-performance liquid chromatography (HPLC) with precolumn automatic derivatization. Absolute amounts of D-amino acids were in total 18.6-38.2 mg/100 g edible portion. The major D-amino acids were D-aspartic acid, D-glutamic acid, D-serine, and D-leucine. Furthermore, to evaluate the effects of sterilization time and olive pH on amino acid racemization, a simulated processing of green ripe olives was carried out. Serine (both free and bound form) was the most-racemized amino acid after heat treatment. Sterilization (15-35 min at 121 degrees C) increased the racemization values of both free and protein-bound amino acids, although in case of protein-bound phenylalanine the increase was not statistically significant. With an increase of pH from 8 to 10 units, the racemization values of all amino acids increased significantly, except for free forms of aspartic and glutamic acids. In general, the effects of the sterilization time and olive pH on total concentration (L + D enantiomers) of each amino acid were also significant. PMID:17407322

  3. Difference in the dynamic properties of chiral and racemic crystals of serine studied by Raman spectroscopy at 3-295 K.

    PubMed

    Kolesov, B A; Boldyreva, E V

    2007-12-27

    Single-crystal polarized Raman spectra (60-4000 cm(-1) at 3 < or = T < or = 295 K) were measured for chiral L- and racemic DL-serine, alpha-amino-beta-hydroxypropionic acid, (NH3)+CH(CH2OH)(COO)-. The Raman spectra of dl-serine do not show any striking changes with temperature or on storage. In contrast to that, the dynamical properties of L-serine change at about 140 K. These changes can be interpreted as the reorientation of the side chain -CH2OH fragments of the zwitterions with respect to the backbone C-C bonds, resulting in the positional disorder of the O-H...O intermolecular H-bonds. The redistribution in the intensities of the Raman spectra of the crystals of L-serine stored for a long time (about a year) indicates the changes in the orientation of the molecular fragments in the direction normal to the axes of the head-to-tail chains. The difference in the thermodynamic functions of L- and DL-serine reported previously [Drebushchak, V. A.; Kovalevskaya, Yu. A.; Paukov, I. E.; Boldyreva, E. V. J. Therm. Anal. Calorim. 2007, 89 (2), 649-654] is explained by the difference in the spectra of external vibrations of the crystals. PMID:18052147

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

    PubMed

    Ahmed, Marwa; Gwairgi, Marina; Ghanem, Ashraf

    2014-11-01

    A comparative enantioselective analysis using immobilized amylose tris-(3-chlorophenylcarbamate) as chiral stationary phase in conventional high-performance liquid chromatography (HPLC) with Chiralpak ID (4.6 mm ID × 250 mm, 5 µm silica gel) and micro-HPLC with Chiralpak ID-3 (0.30 mm ID × 150 mm, 3 µm silica gel) was conducted. Pharmaceutical racemates of 12 pharmacological classes, namely, α- and β-blockers, anti-inflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs were screened under normal phase conditions. The effect of an organic modifier on the analyte retentions and enantiomer recognition was investigated. Baseline separation was achieved for 1-acenaphthenol, carprofen, celiprolol, cizolirtine carbinol, miconazole, tebuconazole, 4-hydroxy-3-methoxymandelic acid, 1-indanol, 1-(2-chlorophenyl)ethanol, 1-phenyl-2-propanol, flavanone, 6-hydroxyflavanone, 4-bromogluthethimide, and pentobarbital on the 4.6 mm ID packed with a 5 µm silica column using conventional HPLC. Nonetheless, baseline separation was achieved for aminoglutethimide, naftopidil, and thalidomide on the 0.3 mm ID packed with a 3 µm silica capillary column. PMID:25271972

  5. Teen Dating Violence

    MedlinePlus

    ... dating violence prevention initiative seeks to reduce dating violence and increase healthy relationships in high-risk urban communities through comprehensive, multisector prevention. Division of Adolescent ...

  6. 40 CFR 63.609 - Compliance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Emission Standards for Hazardous Air Pollutants From Phosphoric Acid Manufacturing Plants § 63.609 Compliance dates. (a) Each owner or operator of an existing affected source at a phosphoric acid... existing phosphoric acid manufacturing plant shall fulfill the applicable requirements of § 63.606 no...

  7. 40 CFR 63.609 - Compliance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Emission Standards for Hazardous Air Pollutants From Phosphoric Acid Manufacturing Plants § 63.609 Compliance dates. (a) Each owner or operator of an existing affected source at a phosphoric acid... existing phosphoric acid manufacturing plant shall fulfill the applicable requirements of § 63.606 no...

  8. 40 CFR 63.609 - Compliance dates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Emission Standards for Hazardous Air Pollutants From Phosphoric Acid Manufacturing Plants § 63.609 Compliance dates. (a) Each owner or operator of an existing affected source at a phosphoric acid... existing phosphoric acid manufacturing plant shall fulfill the applicable requirements of § 63.606 no...

  9. 40 CFR 63.609 - Compliance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Emission Standards for Hazardous Air Pollutants From Phosphoric Acid Manufacturing Plants § 63.609 Compliance dates. (a) Each owner or operator of an existing affected source at a phosphoric acid... existing phosphoric acid manufacturing plant shall fulfill the applicable requirements of § 63.606 no...

  10. 40 CFR 63.609 - Compliance dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Emission Standards for Hazardous Air Pollutants From Phosphoric Acid Manufacturing Plants § 63.609 Compliance dates. (a) Each owner or operator of an existing affected source at a phosphoric acid... existing phosphoric acid manufacturing plant shall fulfill the applicable requirements of § 63.606 no...

  11. Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization.

    PubMed

    Heeb, Norbert V; Schweizer, W Bernd; Mattrel, Peter; Haag, Regula; Kohler, Martin; Schmid, Peter; Zennegg, Markus; Wolfensberger, Max

    2008-04-01

    Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD

  12. The effects of racemic albuterol versus levalbuterol in very low birth weight infants.

    PubMed

    Mhanna, Maroun J; Patel, Jigisha S; Patel, Swati; Cohn, Robert

    2009-08-01

    Bronchodilators have been used in premature infants. Levalbuterol (LEV) an R-isomer of Albuterol has fewer hemodynamic side effects than Racemic Albuterol (RAC) in adults and children. In a retrospective study we sought to investigate the effects of LEV (0.31 mg) versus RAC (1.25 mg) in very low-birth weight infants (VLBW) who were treated with a beta-2 agonist for > or =2 weeks. Medical records (between January 2001 and December 2006) were reviewed for patients' demographics, medications use, hemodynamic and respiratory parameters, hypokalemia and hyperglycemia. Among 811 VLBW infants who were admitted to our NICU, 16 infants received RAC and 31 infants received LEV for > or =2 weeks. Infants who received RAC were younger, smaller, and received less Ipratropium Bromide (IB) than infants who received LEV [26.1 +/- 1.2 weeks vs. 28.1 +/- 3.7 weeks (P = 0.01), 817 +/- 211 g vs. 1,127 +/- 589 g (P = 0.01) and 2/16 (12%) vs. 15/31 (48%; P = 0.01); respectively]. In infants treated exclusively with RAC or LEV without IB, mean arterial blood pressures were lower in the RAC (n = 14) than the LEV group (n = 16, P = 0.05 by general linear model with repeated measures); however there were no differences in daily heart rates, oxygen supplementations, oxygen saturations, or respiratory rates. Also there were no differences between the two groups in hypokalemia or hyperglycemia. We conclude that LEV at a dose of 0.31 mg might have an indication in VLBW infants who are at risk for hemodynamic instability. PMID:19598281

  13. A colorimetric sensor array for the detection of the date-rape drug γ-hydroxybutyric acid (GHB): a supramolecular approach.

    PubMed

    Baumes, Laurent A; Buaki Sogo, Mireia; Montes-Navajas, Pedro; Corma, Avelino; Garcia, Hermenegildo

    2010-04-19

    γ-Hydroxybutyric acid (GHB), a colourless, odourless and tasteless chemical, has become one of the most dangerous illicit drugs of abuse today. At low doses, this drug is a central nervous system depressant that reduces anxiety and produces euphoria and relaxation, sedating the recipient. There is an urgent need for simple, easy-to-use sensors for GHB in solution. Here, we present a colorimetric sensor array based on supramolecular host-guest complexes of fluorescent dyes with organic capsules (cucurbiturils) for the detection of GHB. PMID:20309968

  14. Dating and Marriage

    MedlinePlus

    ... Family : Dating & Marriage Subscribe Translate Text Size Print Dating and Marriage Dating and Marriage If you are living with HIV, ... Living! Having HIV does not prevent you from dating or marrying—it just may require a little ...

  15. [Nonsteroidal anti-inflammatory agents. XIII. 4-Cyclohexylphenylhydroxyalkanoic acids].

    PubMed

    Guarnieri, A; Burnelli, S; Varoli, L; Fabbri, G; Scapini, G; Sarret, M; Bertoli, D

    1983-09-01

    The preparation of some homologues of 2-(4-cyclohexylphenyl)-3-hydroxypropionic acid, the separation of the diastereomeric race-mates, their attribution to erythro and threo series, and the optical resolution of the enantiomers are described. The optical antipodes were screened for acute toxicity, as well as for antiinflammatory and analgesic activity. PMID:6641934

  16. Experiments on the origins of optical activity. [in amino acids

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Flores, J. J.

    1975-01-01

    An investigation was conducted concerning the asymmetric adsorption of phenylalanine enantiomers by kaolin. No preferential adsorption of either phenylalanine enantiomer could be detected and there was no resolution of the racemic phenylalanine by kaolin. The attempted asymmetric polymerization of aspartic acid by kaolin is also discussed along with a strontium-90 bremsstrahlung radiolysis of leucine.

  17. Synthesis and evaluation of the racemate and individual enantiomers of C-11 labeled methylphenidate as radioligands for the presynaptic dopaminergic neuron

    SciTech Connect

    Ding, Y.S.; Fowler, J.S.; Volkow, N.D.

    1994-05-01

    Methylphenidate (MP, ritalin) is a psychostimulant drug widely used to treat attention deficit hyperactivity disorder and narcolepsy. Its therapeutic properties are attributed to inhibition of the dopamine (DA) transporter enhancing synaptic DA. MP has two chiral centers and is marketed as the dl-threo racemic form. However, its pharmacological activity is believed due solely to the d-enantiomer. We have synthesized [{sup 11}C]d,l-threo-methylphenidate ([{sup 11}C]MP) in order to examine its pharmacokinetics in vivo and to examine its suitability as a radioligand for PET studies of the presynaptic DA neuron. [{sup 11}C]MP was prepared by O-{sup 11}C-alkylation of a protected derivative of ritalinic acid with labeled methyl iodide. Serial studies at baseline and after treatment with methylphenidate (0.5 mg/kg, 20 min prior); GBR 12909 (1.5 mg/kg; 30 min prior); tomoxetine (1.5 mg/kg, 20 min prior) and citalopram (2.0 mg/kg, 30 min prior) were performed to assess non-specific binding and binding to the DA, norepinephrine and serotonin transporters respectively. Only MP and GBR 12909 changed the SR/CB distribution volume ratio (decrease of 38 and 37% respectively) demonstrating selectivity for DA transporters over other monoamine transporters. We then pursued the synthesis of enantiomerically pure C-{sup 11} labeled d- and l-MP by using enantiomerically pure protected d- and l-ritalinic acids as precursors. A striking difference in SR/CB ratio (3.3 and 1.1 for d- and l-respectively at 1 hr. after i.v. injections) strongly suggests that the pharmacological specificity of MP resides entirely in the d-isomer and the binding of l-isomer was mostly non-specific. Further evaluations are underway. Radioligand reversibility, selectivity and the fact that MP is an approved drug are advantages of using [{sup 11}C]MP.

  18. 40 CFR 62.3632 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Indiana Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.3632 Effective date. The effective date of the plan for municipal solid waste landfills is May 30, 2000. Metals, Acid Gases, Organic Compounds and Nitrogen...

  19. 40 CFR 62.3632 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Indiana Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.3632 Effective date. The effective date of the plan for municipal solid waste landfills is May 30, 2000. Metals, Acid Gases, Organic Compounds and Nitrogen...

  20. 40 CFR 62.9637 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Pennsylvania Landfill Gas Emissions from Existing Municipal Solid Waste Landfills (section 111(d) Plan) § 62.9637 Effective date. The effective date of the plan for municipal solid waste landfills is January 28, 2004. Metals, Acid Gases,...

  1. 40 CFR 62.9637 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Pennsylvania Landfill Gas Emissions from Existing Municipal Solid Waste Landfills (section 111(d) Plan) § 62.9637 Effective date. The effective date of the plan for municipal solid waste landfills is January 28, 2004. Metals, Acid Gases,...

  2. Copper-catalysed asymmetric allylic alkylation of alkylzirconocenes to racemic 3,6-dihydro-2H-pyrans

    PubMed Central

    Rideau, Emeline

    2015-01-01

    Summary Asymmetric allylic alkylation is a powerful reaction that allows the enantioselective formation of C–C bonds. Here we describe the asymmetric alkylation of alkylzirconium species to racemic 3,6-dihydro-2H-pyrans. Two systems were examined: 3-chloro-3,6-dihydro-2H-pyran using linear optimization (45–93% ee, up to 33% yield, 5 examples) and 3,6-dihydro-2H-pyran-3-yl diethyl phosphate with the assistance of a design of experiments statistical approach (83% ee, 12% yield). 1H NMR spectroscopy was used to gain insight into the reaction mechanisms. PMID:26734091

  3. Crystal structure of racemic cis-2-amino-1,2-di­phenyl­ethanol (ADE)

    PubMed Central

    Fujii, Isao

    2015-01-01

    In the title racemic compound, C14H15NO, the hy­droxy and amino groups form a bent tweezer-like motif towards the phenyl groups. In the crystal, enanti­omers aggregate with each other and are linked by O—H⋯N hydrogen bonds, forming chiral 21-helical columnar structures from C(5) chains along the b-axis direction. Left- and right-handed 21 helices are formed from (1S,2R)-2-amino-1,2-di­phenyl­ethanol and (1R,2S)-2-amino-1,2-di­phenyl­ethanol, respectively. PMID:26870424

  4. Differential Influences of Ethanol on Early Exposure to Racemic Methylphenidate Compared with Dexmethylphenidate in Humans

    PubMed Central

    Straughn, Arthur B.; Reeves, Owen T.; Bernstein, Hilary; Bell, Guinevere H.; Anderson, Erica R.; Malcolm, Robert J.

    2013-01-01

    Enantioselective hydrolysis of oral racemic methylphenidate (dl-MPH) by carboxylesterase 1 (CES1) limits the absolute bioavailability of the pharmacologically active d-MPH isomer to approximately 30% and that of the inactive l-MPH to only 1–2%. Coadministration of dl-MPH with ethanol results in elevated d-MPH plasma concentrations accompanied by CES1-mediated enantioselective transesterification of l-MPH to l-ethylphenidate (EPH). The present study tested the hypothesis that administration of the pure isomer dexmethylphenidate (d-MPH) will overcome the influence of ethanol on d-MPH absorption by eliminating competitive CES1-mediated presystemic metabolism of l-MPH to l-EPH. Twenty-four healthy volunteers received dl-MPH (0.3 mg/kg) or d-MPH (0.15 mg/kg), with or without ethanol (0.6 g/kg). During the absorption phase of dl-MPH, concomitant ethanol significantly elevated d-MPH plasma concentrations (44–99%; P < 0.005). Furthermore, immediately following the ethanol drink the subjective effects of “high,” “good,” “like,” “stimulated,” and overall “effect” were significantly potentiated (P ≤ 0.01). Plasma l-EPH concentrations exceeded those of l-MPH. Ethanol combined with pure d-MPH did not elevate plasma d-MPH concentrations during the absorption phase, and the ethanol-induced potentiation of subjective effects was delayed relative to dl-MPH-ethanol. These findings are consistent with l-MPH competitively inhibiting presystemic CES1 metabolism of d-MPH. Ethanol increased the d-MPH area under the curve (AUC)0-inf by 21% following dl-MPH (P < 0.001) and 14% for d-MPH (P = 0.001). In men receiving d-MPH-ethanol, the d-MPH absorption partial AUC0.5–2 hours was 2.1 times greater and the time to maximum concentration (Tmax) occurred 1.1 hours earlier than in women, consistent with an increased rate of d-MPH absorption reducing hepatic extraction. More rapid absorption of d-MPH carries implications for increased abuse liability. PMID:23104969

  5. Influence of formulation on the pharmacokinetics and bioavailability of racemic ketoprofen in horses.

    PubMed

    Landoni, M F; Lees, P

    1995-12-01

    The bioavailability of S(+) and R(-) ketoprofen (KTP) in six horses was investigated after oral administration of the racemic (rac) mixture. Two oral formulations were studied, an oil-based paste containing micronised rac-KTP and powder from the same source in hard gelatin capsules, each at a dose rate of 2.2 mg/kg. For the oil-based paste two feeding schedules were used; horses were either allowed free access to food or access to food was restricted for 4 h before and 5 h after dosing. The drug in hard gelatin capsules was administered to horses with restricted access to food. After intravenous administration of rac-KTP, S(+) enantiomer concentrations exceeded those of the R(-) enantiomer. For S(+) and R(-)KTP, respectively, pharmacokinetic parameters were, t1/2 beta 0.99 +/- 0.14 h, 0.70 +/- 0.13 h; ClB 0.56 +/- 0.09, 0.92 +/- 0.20 L/h/kg; Vd(ss) 0.53 +/- 0.11, 0.61 +/- 0.10 L/kg. Following oral administration of rac-KTP as the oil-based paste to horses with free access to food, there were no detectable concentrations in plasma in three animals at any sampling time, while a fourth animal showed very low concentrations at two sampling times only. In the two remaining horses very low but detectable concentrations were present for 5 h. In the horses with restricted access to food, rac-KTP paste administration produced higher concentrations in plasma. However, bioavailability was very low, 2.67 +/- 0.43 and 5.75 +/- 1.48% for R(-) and S(+)KTP, respectively. When administered as pure drug substance in hard gelatin capsules, absorption of KTP was fairly rapid, but incomplete. Bioavailability was 50.55 +/- 10.95 and 54.17 +/- 9.9% for R(-) and S(+)KTP, respectively. This study demonstrates that rac-KTP had a modest bioavailability when administered as a micronised powder in hard gelatin capsules to horses with restricted access to food. When powder from the same source was administered as an oil-based paste, it was for practical purposes not bioavailable, regardless on

  6. Differential influences of ethanol on early exposure to racemic methylphenidate compared with dexmethylphenidate in humans.

    PubMed

    Patrick, Kennerly S; Straughn, Arthur B; Reeves, Owen T; Bernstein, Hilary; Bell, Guinevere H; Anderson, Erica R; Malcolm, Robert J

    2013-01-01

    Enantioselective hydrolysis of oral racemic methylphenidate (dl-MPH) by carboxylesterase 1 (CES1) limits the absolute bioavailability of the pharmacologically active d-MPH isomer to approximately 30% and that of the inactive l-MPH to only 1-2%. Coadministration of dl-MPH with ethanol results in elevated d-MPH plasma concentrations accompanied by CES1-mediated enantioselective transesterification of l-MPH to l-ethylphenidate (EPH). The present study tested the hypothesis that administration of the pure isomer dexmethylphenidate (d-MPH) will overcome the influence of ethanol on d-MPH absorption by eliminating competitive CES1-mediated presystemic metabolism of l-MPH to l-EPH. Twenty-four healthy volunteers received dl-MPH (0.3 mg/kg) or d-MPH (0.15 mg/kg), with or without ethanol (0.6 g/kg). During the absorption phase of dl-MPH, concomitant ethanol significantly elevated d-MPH plasma concentrations (44-99%; P < 0.005). Furthermore, immediately following the ethanol drink the subjective effects of "high," "good," "like," "stimulated," and overall "effect" were significantly potentiated (P ≤ 0.01). Plasma l-EPH concentrations exceeded those of l-MPH. Ethanol combined with pure d-MPH did not elevate plasma d-MPH concentrations during the absorption phase, and the ethanol-induced potentiation of subjective effects was delayed relative to dl-MPH-ethanol. These findings are consistent with l-MPH competitively inhibiting presystemic CES1 metabolism of d-MPH. Ethanol increased the d-MPH area under the curve (AUC)(0-inf) by 21% following dl-MPH (P < 0.001) and 14% for d-MPH (P = 0.001). In men receiving d-MPH-ethanol, the d-MPH absorption partial AUC(0.5-2 hours) was 2.1 times greater and the time to maximum concentration (T(max)) occurred 1.1 hours earlier than in women, consistent with an increased rate of d-MPH absorption reducing hepatic extraction. More rapid absorption of d-MPH carries implications for increased abuse liability. PMID:23104969

  7. Racemic ketamine in adult head injury patients: use in endotracheal suctioning

    PubMed Central

    2013-01-01

    Introduction Endotracheal suctioning (ETS) is essential for patient care in an ICU but may represent a cause of cerebral secondary injury. Ketamine has been historically contraindicated for its use in head injury patients, since an increase of intracranial pressure (ICP) was reported; nevertheless, its use was recently suggested in neurosurgical patients. In this prospective observational study we investigated the effect of ETS on ICP, cerebral perfusion pressure (CPP), jugular oxygen saturation (SjO2) and cerebral blood flow velocity (mVMCA) before and after the administration of ketamine. Methods In the control phase, ETS was performed on patients sedated with propofol and remifentanil in continuous infusion. If a cough was present, patients were assigned to the intervention phase, and 100 γ/kg/min of racemic ketamine for 10 minutes was added before ETS. Results In the control group ETS stimulated the cough reflex, with a median cough score of 2 (interquartile range (IQR) 1 to 2). Furthermore, it caused an increase in mean arterial pressure (MAP) (from 89.0 ± 11.6 to 96.4 ± 13.1 mmHg; P <0.001), ICP (from 11.0 ± 6.7 to 18.5 ± 8.9 mmHg; P <0.001), SjO2 (from 82.3 ± 7.5 to 89.1 ± 5.4; P = 0.01) and mVMCA (from 76.8 ± 20.4 to 90.2 ± 30.2 cm/sec; P = 0.04). CPP did not vary with ETS. In the intervention group, no significant variation of MAP, CPP, mVMCA, and SjO2 were observed in any step; after ETS, ICP increased if compared with baseline (15.1 ± 9.4 vs. 11.0 ± 6.4 mmHg; P <0.05). Cough score was significantly reduced in comparison with controls (P <0.0001). Conclusions Ketamine did not induce any significant variation in cerebral and systemic parameters. After ETS, it maintained cerebral hemodynamics without changes in CPP, mVMCA and SjO2, and prevented cough reflex. Nevertheless, ketamine was not completely effective when used to control ICP increase after administration of 100 γ/kg/min for 10

  8. Tuning of the electronic properties of a cyclopentadienylruthenium catalyst to match racemization of electron-rich and electron-deficient alcohols.

    PubMed

    Verho, Oscar; Johnston, Eric V; Karlsson, Erik; Bäckvall, Jan-E

    2011-09-26

    The synthesis of a new series of cyclopentadienylruthenium catalysts with varying electronic properties and their application in racemization of secondary alcohols are described. These racemizations involve two key steps: 1) β-hydride elimination (dehydrogenation) and 2) re-addition of the hydride to the intermediate ketone. The results obtained confirm our previous theory that the electronic properties of the substrate determine which of these two steps is rate determining. For an electron-deficient alcohol the rate-determining step is the β-hydride elimination (dehydrogenation), whereas for an electron-rich alcohol the re-addition of the hydride becomes the rate-determining step. By matching the electronic properties of the catalyst with the electronic properties of the alcohol, we have now shown that a dramatic increase in racemization rate can be obtained. For example, electron-deficient alcohol 15 racemized 30 times faster with electron-deficient catalyst 6 than with the unmodified standard catalyst 4. The application of these protocols will extend the scope of cyclopentadienylruthenium catalysts in racemization and dynamic kinetic resolution. PMID:21882268

  9. Food Product Dating

    MedlinePlus

    ... Formula What do can codes mean? Dates on Egg Cartons UPC or Bar Codes Storage Times Refrigerator ... primarily on perishable foods such as meat, poultry, eggs and dairy products. "Closed" or "coded" dating might ...

  10. A Date with Violence.

    ERIC Educational Resources Information Center

    Lowe, Robert; And Others

    1997-01-01

    Teen dating violence is common but preventable. A survey of Texas high schoolers showed that half of respondents had been victims of dating violence. A majority of both sexes believed that certain behaviors justified being hit by their dating partners. It is important to raise the awareness of school personnel, parents, and students. Peer…

  11. Radiometric Dating Does Work!

    ERIC Educational Resources Information Center

    Dalrymple, G. Brent

    2000-01-01

    Discusses the accuracy of dating methods and creationist arguments that radiometric dating does not work. Explains the Manson meteorite impact and the Pierre shale, the ages of meteorites, the K-T tektites, and dating the Mount Vesuvius eruption. (Author/YDS)

  12. D:L-AMINO Acids and the Turnover of Microbial Biomass

    NASA Astrophysics Data System (ADS)

    Lomstein, B. A.; Braun, S.; Mhatre, S. S.; Jørgensen, B. B.

    2015-12-01

    Decades of ocean drilling have demonstrated wide spread microbial life in deep sub-seafloor sediment, and surprisingly high microbial cell numbers. Despite the ubiquity of life in the deep biosphere, the large community sizes and the low energy fluxes in the vast buried ecosystem are still poorly understood. It is not know whether organisms of the deep biosphere are specifically adapted to extremely low energy fluxes or whether most of the observed cells are in a maintenance state. Recently we developed and applied a new culture independent approach - the D:L-amino acid model - to quantify the turnover times of living microbial biomass, microbial necromass and mean metabolic rates. This approach is based on the built-in molecular clock in amino acids that very slowly undergo chemical racemization until they reach an even mixture of L- and D- forms, unless microorganisms spend energy to keep them in the L-form that dominates in living organisms. The approach combines sensitive analyses of amino acids, the unique bacterial endospore marker (dipicolinic acid) with racemization dynamics of stereo-isomeric amino acids. Based on a heating experiment, we recently reported kinetic parameters for racemization of aspartic acid, glutamic acid, serine and alanine in bulk sediment from Aarhus Bay, Denmark. The obtained racemization rate constants were faster than the racemization rate constants of free amino acids, which we have previously applied in Holocene sediment from Aarhus Bay and in up to 10 mio yr old sediment from ODP Leg 201. Another important input parameter for the D:L-amino acid model is the cellular carbon content. It has recently been suggested that the cellular carbon content most likely is lower than previously thought. In recognition of these new findings, previously published data based on the D:L-amino acid model were recalculated and will be presented together with new data from an Arctic Holocene setting with constant sub-zero temperatures.

  13. Chiral separation of amino acids in ultrafiltration through DNA-immobilized cellulose membranes

    NASA Astrophysics Data System (ADS)

    Higuchi, Akon; Hayashi, Akiyuki; Kanda, Naoki; Sanui, Kohei; Kitamura, Hanako

    2005-04-01

    Ultrafiltration experiments for the chiral separation of racemic tryptophan, phenylglycine and phenylalanine were investigated through immobilized DNA membranes having various pore sizes. L-tryptophan preferentially permeated through immobilized DNA membranes with a pore size<2.0 nm (molecular weight cut-off (MWCO)<5000) while D-tryptophan preferentially permeated through immobilized DNA membranes with a pore size>2.0 nm (MWCO>5000). These results are completely opposite tendency in the ultrafiltration of racemic phenylalanine through the immobilized DNA membranes. This may be originated from the different interaction between DNA and tryptophan compared to that between DNA and phenylalanine. However, in both cases the pore size of the immobilized DNA membranes regulated preferential permeation of the enantiomer through the membranes. The immobilized DNA membranes are categorized as channel type membranes and not as affinity membranes. Chiral separation models were proposed from using the chiral separation results of racemic amino acids, preferential adsorption of amino acid enantiomers and EPMA results.

  14. Comparison of chiral separations of aminophosphonic acids and their aminocarboxylic acid analogs using a crown ether column.

    PubMed

    Barnhart, Wesley W; Xia, Xiaoyang; Jensen, Randy; Gahm, Kyung H

    2013-07-01

    Crown ethers are capable of complexing with primary amines and have been utilized in chromatography to separate amino acid racemates. This application has been extended to resolve (1-amino-1-phenylmethyl)phosphonic acid and (1-aminoethyl)phosphonic acid racemates, along with their aminocarboxylic acid analogs (2-phenylglycine and alanine, respectively), via a ChiroSil RCA crown ether based chiral stationary phase. Effects of the organic modifier, temperature, and acid type and concentration on retention and selectivity were also investigated. Trends in retention and selectivity varied between aminophosponic acids and their aminocarboxylic analogs. Computer modeling and (1)H NMR analyses were performed to potentially gain a better understanding of interactions of the aforementioned molecules with the ChiroSil RCA chiral stationary phase. Theoretical predictions of the most stable conformations for (R)- and (S)-enantiomers were compared to elution order; it was found that the elution order agreed with molecular modeling such that the longest retention correlated with the predicted most stable complex between the enantiomer and crown ether. (1)H NMR demonstrated interactions of aminophosphonic and aminocarboxylic racemates with (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid in solution and was utilized to determine enantiomeric excess of (1-amino-1-phenylmethyl)phosphonic acid after its enantioenrichment via crystallization through diastereomeric salt formation with the crown ether followed by filtration. PMID:23703726

  15. Syntheses, structures and photocatalytic properties of five new praseodymium-antimony oxochlorides: from discrete clusters to 3D inorganic-organic hybrid racemic compounds.

    PubMed

    Zou, Guo-Dong; Wang, Ze-Ping; Song, Ying; Hu, Bing; Huang, Xiao-Ying

    2014-07-14

    Five novel praseodymium-antimony oxochloride (Pr-Sb-O-Cl) cluster-based compounds, namely (2-MepyH)2[Fe(1,10-phen)3]2[Pr4Sb12O18Cl14.6(OH)2.4(Hsal)]·H2O (1), (2-MepyH)2[Fe(1,10-phen)3]4{[Pr4Sb12O18Cl13.5(OH)0.5](bcpb)2[Pr4Sb12O18Cl13.5(OH)0.5]}·42H2O (2), (3-MepyH)2[Fe(1,10-phen)3]{[Pr4Sb12O18Cl13(H2O)2](bcpb)}·2(3-Mepy)·3H2O (3), [Fe(1,10-phen)3]2{[Pr4Sb12O18Cl10(H2O)2](bcpb)2}·3(3-Mepy)·13H2O (4), and (2-MepyH)6[Fe(1,10-phen)3]10{[Pr4Sb12O18Cl13(OH)2]2[Pr4Sb12O18Cl9][Pr4Sb12O18Cl9(OH)2]2(Hpdc)10(pdc)2}·110H2O (5) (2-Mepy = 2-methylpyridine, 3-Mepy = 3-methylpyridine, 1,10-phen = 1,10-phenanthroline, H2sal = salicylic acid, H3bcpb = 3,5-bis(4-carboxyphenoxy)benzoic acid, H3pdc = 3,5-pyrazoledicarboxylic acid) have been solvothermally synthesized and structurally characterized. Compound 1 is the first zero-dimensional (0D) Pr-Sb-O-Cl cluster decorated by an organic ligand. Compounds 2-4 are constructed from the same H3bcpb ligands but adopt different structures: 2 represents a rare example of a one-dimensional (1D) nanotubular structure based on high-nuclearity clusters; 3 exhibits a two-dimensional (2D) mono-layered structure, in which left-handed and right-handed helical chains are alternately arranged, while 4 features a double-layered structure with an unprecedented (3,3,6)-connected 3-nodal topological net. Compound 5 is a unique three-dimensional (3D) 2-fold interpenetrating racemic compound, simultaneously containing three kinds of Pr-Sb-O-Cl-pdc clusters. UV-light photocatalytic H2 evolution activity was observed for compound 3 with Pt as a co-catalyst and MeOH as a sacrificial electron donor. In addition, the magnetic properties of compounds 1 and 5 are also studied. PMID:24869770

  16. Comparison of uranium-series, radiocarbon, and amino acid data from marine molluscs, Baffin Island, Arctic Canada

    SciTech Connect

    Szabo, B.J.; Miller, G.H.; Andrews, J.T.; Stuiver, M.

    1981-10-01

    Uranium-series and /sup 14/C dates and the extent of amino acid racemization are reported for 24 marine shell samples from three areas of Baffin Island, Arctic Canada. When the radiometric dates are plotted against the ratio of D-alloisoleucene:L-isoleucene in the shells, five broad age groups are recognized. The uranium-series data indicate that /sup 231/Pa is incompletely retained in most fossil shells and that /sup 230/Th is lost from some of the samples. Therefore, their apparent ages are minimum. However, a few dated samples in each group have yielded useful age results, and the minimum ages of the five groups of samples are estimated as 7,000 to 11,000, greater than or equal to70,000, greater than or equal to136,000, greater than or equal to190,000 and >300,000 yr. Calculated integrated thermal histories based on the epimerization reaction in the mollusc Hiatella arctica Linne give paleotemperature estimates of around -5/sup o/C, compared to the present mean annual air temperature of about -11/sup o/C.

  17. Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

    PubMed Central

    Krivickas, Sara Jane; Hashimoto, Chiho; Yoshida, Junya; Ueda, Akira; Takahashi, Kazuyuki; Wallis, John D

    2015-01-01

    Summary Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl)-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and the chiral salt α’-[(R,R)-2]ClO4(H2O) were carried out. In the former θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2, there are two sets of three crystallographically independent donor molecules [(S,S)-2]2[(R,R)-2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[(R,R)-2]ClO4(H2O) is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α’-[(S,S)-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4 − anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å) were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with E a = 86 meV for θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and 0.6 ohm cm with E a = 140 meV for α'-[(R,R)-2]2ClO4(H2O), respectively. The variety of donor

  18. Date Palm Germplasm

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This book chapter reviews date palm genetic resources and their conservation. Date palm (Phoenix dactylifera) is an important food crop in the Middle East and North Africa. Its center of origin and diversity most probably is the area near Iraq/Iran. From there, it spread throughout its present range...

  19. Radiometric Dating in Geology.

    ERIC Educational Resources Information Center

    Pankhurst, R. J.

    1980-01-01

    Described are several aspects and methods of quantitatively measuring geologic time using a constant-rate natural process of radioactive decay. Topics include half lives and decay constants, radiogenic growth, potassium-argon dating, rubidium-strontium dating, and the role of geochronology in support of geological exploration. (DS)

  20. Dating Violence in Russia

    ERIC Educational Resources Information Center

    Lysova, A. V.

    2007-01-01

    The phenomenon of violence in interpersonal relationships has been little studied in Russia, and the phenomenon of violence between dating partners has not been the object of scientific interest at all. The study on which the present article is based was designed to obtain information about the violence in dating among students enrolled in…

  1. Choosing a Calving Date

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Calving date affects cost and timing of production events. Due to the polyestrous nature of beef females, producers can choose a calving date that fits their production system and geographic region. Any time an entire production system is considered, decision making becomes complex. Any calving syst...

  2. Teen Dating Violence.

    ERIC Educational Resources Information Center

    O'Keeffe, Nona K.; And Others

    1986-01-01

    Surveyed high school students (N=256) in Sacramento, California. Found that 35.1 percent had experienced some form of abuse in their dating relationships. Explored the severity of the violence and its intergenerational component. (Author/ABB)

  3. Primate molecular divergence dates.

    PubMed

    Steiper, Michael E; Young, Nathan M

    2006-11-01

    With genomic data, alignments can be assembled that greatly increase the number of informative sites for analysis of molecular divergence dates. Here, we present an estimate of the molecular divergence dates for all of the major primate groups. These date estimates are based on a Bayesian analysis of approximately 59.8 kbp of genomic data from 13 primates and 6 mammalian outgroups, using a range of paleontologically supported calibration estimates. Results support a Cretaceous last common ancestor of extant primates (approximately 77 mya), an Eocene divergence between platyrrhine and catarrhine primates (approximately 43 mya), an Oligocene origin of apes and Old World monkeys (approximately 31 mya), and an early Miocene (approximately 18 mya) divergence of Asian and African great apes. These dates are examined in the context of other molecular clock studies. PMID:16815047

  4. Dating the Vinland Map

    ScienceCinema

    None

    2013-07-17

    Scientists from Brookhaven National Laboratory, the University of Arizona, and the Smithsonian Institution used carbon-dating technology to determine the age of a controversial parchment that might be the first-ever map of North America.

  5. Dating the Vinland Map

    SciTech Connect

    2013-01-04

    Scientists from Brookhaven National Laboratory, the University of Arizona, and the Smithsonian Institution used carbon-dating technology to determine the age of a controversial parchment that might be the first-ever map of North America.

  6. Helical sense selective domains and enantiomeric superhelices generated by Langmuir-Schaefer deposition of an axially racemic chiral helical polymer

    NASA Astrophysics Data System (ADS)

    Rodríguez, R.; Ignés-Mullol, J.; Sagués, F.; Quiñoá, E.; Riguera, R.; Freire, F.

    2016-02-01

    The chiral polymer poly-(R)-1 behaves in solution, despite its chiral pendants, as a dynamic axially racemic (i.e., 1 : 1) mixture of left- and right-handed helices, but its deposition on graphite by a Langmuir-Schaefer (LS) technique leads to a helical sense-selective packing that forms separate enantiomeric domains of left- and right-handed helical chains observed by high resolution atomic force microscopy (AFM). The polymer structure within these domains is very uniform, seldom altered by the presence of reversals, grouped always in contiguous pairs maintaining a single helical sense along the polymer chain. The LS deposition technique has been shown to be crucial to obtain good quality monolayers from poly-(R)-1 and other poly(phenylacetylene)s (PPAs: poly-2, poly-3 and poly-4) with short pendants, where spin coating, drop casting and Langmuir-Blodgett (LB) failed, and suggests that this technique could be the method of choice for the preparation of 2D monolayers for high resolution AFM studies of PPAs with short pendants. Key helical parameters (i.e., sense, pitch, packing angle) are easily measured in this way.The chiral polymer poly-(R)-1 behaves in solution, despite its chiral pendants, as a dynamic axially racemic (i.e., 1 : 1) mixture of left- and right-handed helices, but its deposition on graphite by a Langmuir-Schaefer (LS) technique leads to a helical sense-selective packing that forms separate enantiomeric domains of left- and right-handed helical chains observed by high resolution atomic force microscopy (AFM). The polymer structure within these domains is very uniform, seldom altered by the presence of reversals, grouped always in contiguous pairs maintaining a single helical sense along the polymer chain. The LS deposition technique has been shown to be crucial to obtain good quality monolayers from poly-(R)-1 and other poly(phenylacetylene)s (PPAs: poly-2, poly-3 and poly-4) with short pendants, where spin coating, drop casting and Langmuir

  7. On the reported optical activity of amino acids in the Murchison meteorite

    USGS Publications Warehouse

    Bada, J.L.; Cronin, J.R.; Ho, M.-S.; Kvenvolden, K.A.; Lawless, J.G.; Miller, S.L.; Oro, J.; Steinberg, S.

    1983-01-01

    In analyses of extracts from the Murchison meteorite (a carbonaceous chondrite), Engel and Nagy1 reported an excess of L-enantiomers for several protein amino acids but found that the non-protein amino acids were racemic. They suggested that the excess of L-isomers might have resulted from an asymmetric synthesis or decomposition. Their results disagree with those obtained previously2-4 and they claim this is due to improved methodology. In fact, their extraction method and analytical procedure (gas chromatography-mass spectrometry, GC-MS) was similar to those used in the original report2 of amino acids in the Murchison meteorite except that they used specific ion monitoring in the GC-MS measurements. We found the results of Engel and Nagy odd in that likely contaminants (the protein amino acids ala, leu, glu, asp and pro) were nonracemic while unlikely contaminants (isovaline and ??-amino-n-butyric acid) were racemic. For example, Engel and Nagy report that the leucine is ???90% L-enantiomer in the water-extracted sample whereas isovaline (??-methyl-??-aminobutyric acid) is racemic. It would be most unusual for an abiotic stereoselective decomposition or synthesis of amino acids to occur with protein amino acids but not with non-protein amino acids. We now show here that the explanation of terrestrial contamination is consistent with their results and is much more probable. ?? 1983 Nature Publishing Group.

  8. Amino acids in the Yamato carbonaceous chrondrite from Antarctica

    NASA Technical Reports Server (NTRS)

    Shimoyama, A.; Ponnamperuma, C.; Yanai, K.

    1979-01-01

    Evidence for the presence of amino acids of extraterrestrial origin in the Antarctic Yamato carbonaceous chrondrite is presented. Hydrolyzed and nonhydrolyzed water-extracted amino acid samples from exterior, middle and interior portions of the meteorite were analyzed by an amino acid analyzer and by gas chromatography of N-TFA-isopropyl amino acid derivatives. Nine protein and six nonprotein amino acids were detected in the meteorite at abundances between 34 and less than one nmole/g, with equal amounts in interior and exterior portions. Nearly equal abundances of the D and L enantiomers of alanine, aspartic acid and glutamic acid were found, indicating the abiotic, therefore extraterrestrial, origin of the amino acids. The Antarctic environment and the uniformity of protein amino acid abundances are discussed as evidence against the racemization of terrestrially acquired amino acids, and similarities between Yamato amino acid compositions and the amino acid compositions of the Murchison and Murray type II carbonaceous chrondrites are indicated.

  9. Radiocarbon Dating the Anthropocene

    NASA Astrophysics Data System (ADS)

    Chaput, M. A.; Gajewski, K. J.

    2015-12-01

    The Anthropocene has no agreed start date since current suggestions for its beginning range from Pre-Industrial times to the Industrial Revolution, and from the mid-twentieth century to the future. To set the boundary of the Anthropocene in geological time, we must first understand when, how and to what extent humans began altering the Earth system. One aspect of this involves reconstructing the effects of prehistoric human activity on the physical landscape. However, for global reconstructions of land use and land cover change to be more accurately interpreted in the context of human interaction with the landscape, large-scale spatio-temporal demographic changes in prehistoric populations must be known. Estimates of the relative number of prehistoric humans in different regions of the world and at different moments in time are needed. To this end, we analyze a dataset of radiocarbon dates from the Canadian Archaeological Radiocarbon Database (CARD), the Palaeolithic Database of Europe and the AustArch Database of Australia, as well as published dates from South America. This is the first time such a large quantity of dates (approximately 60,000) has been mapped and studied at a global scale. Initial results from the analysis of temporal frequency distributions of calibrated radiocarbon dates, assumed to be proportional to population density, will be discussed. The utility of radiocarbon dates in studies of the Anthropocene will be evaluated and potential links between population density and changes in atmospheric greenhouse gas concentrations, climate, migration patterning and fire frequency coincidence will be considered.

  10. Plutonium age dating reloaded

    NASA Astrophysics Data System (ADS)

    Sturm, Monika; Richter, Stephan; Aregbe, Yetunde; Wellum, Roger; Mayer, Klaus; Prohaska, Thomas

    2014-05-01

    Although the age determination of plutonium is and has been a pillar of nuclear forensic investigations for many years, additional research in the field of plutonium age dating is still needed and leads to new insights as the present work shows: Plutonium is commonly dated with the help of the 241Pu/241Am chronometer using gamma spectrometry; in fewer cases the 240Pu/236U chronometer has been used. The age dating results of the 239Pu/235U chronometer and the 238Pu/234U chronometer are scarcely applied in addition to the 240Pu/236U chronometer, although their results can be obtained simultaneously from the same mass spectrometric experiments as the age dating result of latter. The reliability of the result can be tested when the results of different chronometers are compared. The 242Pu/238U chronometer is normally not evaluated at all due to its sensitivity to contamination with natural uranium. This apparent 'weakness' that renders the age dating results of the 242Pu/238U chronometer almost useless for nuclear forensic investigations, however turns out to be an advantage looked at from another perspective: the 242Pu/238U chronometer can be utilized as an indicator for uranium contamination of plutonium samples and even help to identify the nature of this contamination. To illustrate this the age dating results of all four Pu/U clocks mentioned above are discussed for one plutonium sample (NBS 946) that shows no signs of uranium contamination and for three additional plutonium samples. In case the 242Pu/238U chronometer results in an older 'age' than the other Pu/U chronometers, contamination with either a small amount of enriched or with natural or depleted uranium is for example possible. If the age dating result of the 239Pu/235U chronometer is also influenced the nature of the contamination can be identified; enriched uranium is in this latter case a likely cause for the missmatch of the age dating results of the Pu/U chronometers.

  11. The Realities of Date Rape.

    ERIC Educational Resources Information Center

    Presley, Cara; Watson, Jennifer; Williams, Audrey R.

    This poster presentation addresses the issue of date rape, specifically in the college environment. Highlighted are date rape statistics, demographics, and date rape drugs. Also discussed are date rape warnings and prevention strategies. It is concluded that college and university administrators must place the issue of date rape and acquaintance…

  12. (+)-Gibberellin C: hydrogen-bonding pattern of the monohydrate of a non-racemic pentacyclic diterpenoid.

    PubMed

    Thompson, H W; Brunskill, A P; Lalancette, R A

    2000-12-01

    In the monohydrate of the title compound, (+)-2beta, 4aalpha-dihydroxy-1,7-dimethyl-8-oxo-4bbeta,7alpha- gibbane-1alpha, 10beta-dicarboxylic acid-1,4a-lactone, C(19)H(24)O(6).H(2)O, intermolecular hydrogen bonding progresses helically along b from carboxyl to ketone [O...O = 2.694 (5) A]. The carboxyl and lactone carbonyl groups in translationally related molecules within a helix both accept hydrogen bonds from the same water of hydration. The oxygen of this water in turn accepts a hydrogen bond from the hydroxyl group of a third screw-related molecule in an adjacent counterdirectionally oriented helix, yielding a complex three-dimensional hydrogen-bonding array. Intermolecular O...H-C close contacts were found to the carboxyl and lactone carbonyls, the hydroxyl, and the water. PMID:11119009

  13. Helical sense selective domains and enantiomeric superhelices generated by Langmuir-Schaefer deposition of an axially racemic chiral helical polymer.

    PubMed

    Rodríguez, R; Ignés-Mullol, J; Sagués, F; Quiñoá, E; Riguera, R; Freire, F

    2016-02-14

    The chiral polymer poly-(R)-1 behaves in solution, despite its chiral pendants, as a dynamic axially racemic (i.e., 1 : 1) mixture of left- and right-handed helices, but its deposition on graphite by a Langmuir-Schaefer (LS) technique leads to a helical sense-selective packing that forms separate enantiomeric domains of left- and right-handed helical chains observed by high resolution atomic force microscopy (AFM). The polymer structure within these domains is very uniform, seldom altered by the presence of reversals, grouped always in contiguous pairs maintaining a single helical sense along the polymer chain. The LS deposition technique has been shown to be crucial to obtain good quality monolayers from poly-(R)-1 and other poly(phenylacetylene)s (PPAs: poly-2, poly-3 and poly-4) with short pendants, where spin coating, drop casting and Langmuir-Blodgett (LB) failed, and suggests that this technique could be the method of choice for the preparation of 2D monolayers for high resolution AFM studies of PPAs with short pendants. Key helical parameters (i.e., sense, pitch, packing angle) are easily measured in this way. PMID:26791332

  14. The pharmacokinetics of pimobendan enantiomers after oral and intravenous administration of racemate pimobendan formulations in healthy dogs.

    PubMed

    Bell, E T; Devi, J L; Chiu, S; Zahra, P; Whittem, T

    2016-02-01

    Pimobendan is a benzimidazole-pyridazinone derivative, marketed as a racemic mixture for the management of canine heart failure. Pharmacokinetics of the enantiomers of pimobendan and its oral bioavailability have not been described in dogs. The aim of this study was to describe pharmacokinetics of three formulations of pimobendan in healthy dogs: the licensed capsule product, and novel liquid and intravenous formulations. A three-period, nested randomized two-treatment crossover design was used. Pimobendan was administered p.o. at 0.25 and i.v. at 0.125 mg/kg. Blood and plasma samples were analysed by liquid chromatography-mass spectrometry. Noncompartmental modelling was used to describe the pharmacokinetics. Parameters were compared between formulations using a general linear model. Bioequivalence of the oral formulations was tested using CI90 for AUC(0-∞) and Cmax . Bioavailability of pimobendan after oral dosing was 70%. Liquid and capsule formulations were bioequivalent only for AUC. The positive enantiomer of pimobendan (PE) had a larger volume of distribution than the negative enantiomer (NE) (281 ± 48 vs. 215 ± 68 mL/kg; P = 0.003) and a shorter half-life (21.7 vs. 29.9 min; P = 0.004). The NE was distributed more quickly than the PE into blood cells. Enantiomers of pimobendan have differing absorption, distribution and elimination. The pharmacokinetics of pimobendan in healthy dogs was described. PMID:25989021

  15. Mass-transfer limitations for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor.

    PubMed

    Xiu, G H; Jiang, L; Li, P

    2001-07-01

    A mathematical model has been developed for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor in which the enzyme-catalyzed reaction (the irreversible uni-uni competitive Michaelis-Menten kinetics is chosen as an example) was coupled with intraparticle diffusion, external mass transfer, and axial dispersion. The effects of mass-transfer limitations, competitive inhibition of substrates, deactivation on the enzyme effective enantioselectivity, and the optical purity and yield of the desired product are examined quantitatively over a wide range of parameters using the orthogonal collocation method. For a first-order reaction, an analytical solution is derived from the mathematical model for slab-, cylindrical-, and spherical-enzyme supports. Based on the analytical solution for the steady-state resolution process, a new concise formulation is presented to predict quantitatively the mass-transfer limitations on enzyme effective enantioselectivity and optical purity and yield of the desired product for a continuous steady-state kinetic resolution process in a fixed-bed reactor. PMID:11353408

  16. Comparison of levalbuterol and racemic albuterol combined with ipratropium bromide in acute pediatric asthma: a randomized controlled trial.

    PubMed

    Ralston, Mark E; Euwema, Michael S; Knecht, Kenneth R; Ziolkowski, Timothy J; Coakley, Timothy A; Cline, Shane M

    2005-07-01

    Our study compared levalbuterol (LEV) to the combination of racemic albuterol (RAC) and ipratropium bromide (IB) in 140 patients aged 6-18 years presenting to a tertiary hospital Emergency Department with acute asthma and a peak expired flow rate (PEF)<80% predicted. Patients were randomized to: LEV (

  17. Microfluidic chip capillary electrophoresis coupled with electrochemiluminescence for enantioseparation of racemic drugs using central composite design optimization.

    PubMed

    Guo, Wen Peng; Rong, Zhi Bin; Li, Ying Hong; Fung, Ying Sing; Gao, Guo Quan; Cai, Zhi Ming

    2013-11-01

    Optimization based on central composite design (CCD) for enantioseparation of anisodamine (AN), atenolol (AT), and metoprolol (ME) in human urine was developed using a microfluidic chip-CE device. Coupling the flexible and wide working range of microfluidic chip-CE device to CCD for chiral separation of AN, AT, and ME in human urine, a total of 15 experiments is needed for the optimization procedure as compared to 75 experiments using the normal one variable at a time optimization. The optimum conditions obtained are found to be more robust as shown by the curvature effects of the interaction factors. The developed microfluidic chip-CE-ECL system with adjustable dilution ratios has been validated by satisfactory recoveries (89.5-99% for six enanotiomers) in urine sample analysis. The working range (0.3-600 μM), repeatability (3.1-4.9% RSD for peak height and 4.0-5.2% RSD for peak area), and detection limit (0.3-0.6 μM) of the method developed are found to meet the requirements for bedside monitoring of AN, AT, and ME in patients under critical conditions. In summary, the hyphenation of CCD with the microfluidic chip-CE device is shown to offer a rapid means for optimizing the working conditions on simultaneous separation of three racemic drugs using the microfluidic chip-CE device developed. PMID:24037989

  18. A comparative Analysis of In Vitro and In Vivo Efficacies of the Enantiomers of Thioridazine and Its Racemate

    PubMed Central

    Christensen, Jørn B.; Hendricks, Oliver; Chaki, Shaswati; Mukherjee, Sayanti; Das, Ayan; Pal, Tapan K.; Dastidar, Sujata G.; Kristiansen, Jette E.

    2013-01-01

    A long list of chemotherapeutical drugs used in the treatment of the peripheral and the central nervous systems possess anti-microbial activity. Some of these neurotropic compounds are chiral, with the one stereo isomeric form exaggerating reduced neurotropism. This is the case for the levorotatory form of thioridazine. The phenothiazine thioridazine is an interesting compound, characterized by exhibiting a significant growth inhibiting activity on a wide array of micro-organisms. Thioridazine is characterized by another challenging feature, because the compound is concentrated in certain human tissue cells. The present study describes a comparative study of the two enantiomers as well as the racemic form of thioridazine. The study exploits the stereochemical aspect and the in vitro and in vivo potential of these compounds, with a focus on the effects on Gram negative organism Salmonella enterica serover Typhimurium. In summary, the results of this study yielded a significant antibacterial activity of all forms of thioridazine, indicating the levorotatory (–)- form to be superior in terms of both its in vitro and in vivo efficacies. PMID:23505431

  19. Anaesthesia recovery quality after racemic ketamine or S-ketamine administration to male cats undergoing neutering surgery.

    PubMed

    Larenza, M P; Althaus, H; Conrot, A; Balmer, C; Schatzmann, U; Bettschart-Wolfensberger, R

    2008-12-01

    Postoperative anaesthesia recovery and analgesia qualities were compared in cats anaesthetised with racemic ketamine (RS-ket) or S-ketamine (S-ket) undergoing orchiectomy. Twenty client-owned male cats received medetomidine (0.03 mg/kg) and S-ket (6 mg/kg; n = 10) or RS-ket (10 mg/kg; n = 10), all intramuscularly. After routine orchiectomy, animals received atipamezole (0.15 mg/kg) intramuscularly. Thirty and 60 min after atipamezole administration, one observer unaware of the treatment identity evaluated analgesia using a visual analogue scale (VAS) and, by means of four points scales, sedation, unprovoked behaviour and behavioural reactions to external stimuli. Cats with a VAS > or = 15 mm were to receive butorphanol. Times to sternal and standing positions were recorded. After 60 min, cats were given carprofen (4 mg/kg) subcutaneously. Anaesthesia with S-ket, at 60% of the RS-ket dose, provided faster recoveries. At 60 min, undisturbed cats in S-ket group had a trend towards fewer behavioural changes. Cats in RS-ket group were more sedate at 30 min and responded with a lower intensity to external stimulation. Immediate postoperative analgesia was considered adequate for both groups and no cat required butorphanol administration. PMID:19034844

  20. The Origin of Amino Acids in Lunar Regolith Samples

    NASA Technical Reports Server (NTRS)

    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.

  1. Bulky metallocavitands with a chiral cavity constructed by aluminum and magnesium atrane-likes: enantioselective recognition and separation of racemic alcohols.

    PubMed

    Li, Yingguo; Yu, Dawei; Dai, Zhongran; Zhang, Jinjin; Shao, Yongliang; Tang, Ning; Wu, Jincai

    2015-03-28

    Seven new type metallocavitand complexes 1–7 were synthesized via the self-assembly of aluminum and magnesium atrane-likes. The recognition of R-2-butanol from racemic 2-butanol can be achieved in the chiral cavity of metallocavitand complex 5. The crystal structure of complex 5 showed that the enantioselectivity of the center cavity for the inclusion of two 2-butanol molecules is higher than that of the groups at the outer rim, which indicates that the size-limited cavity is more sensitive to the chirality of 2-butanol. Furthermore, desorption of R-2-butanol is successful through vacuumization which afforded complex 6 and gives R-2-butanol with an enantiomeric excess (ee) value of 53(±1)%. The reaction of enantiopure H3L2, MgnBu2, and racemic 1-phenylethanol afforded complex 7. The structure of complex 7 showed that the center cavity was occupied by three H2O molecules and one molecular R-1-phenylethanol suspended in the outer rim of the metallocavitand via a hydrogen bond, which indicated that 1-phenylethanol is too bulky for the size-limited cavity. Because a certain amount of racemic 1-phenylethanol is also co-crystallized in the unit cell, the final separated 1-phenylethanol has an ee value of 33(±1)%. The host–guest mechanism for the separation is clearly determined through X-ray crystal structural analysis. PMID:25710446

  2. The Dating Game.

    ERIC Educational Resources Information Center

    Zerger, Monte J.

    1998-01-01

    Presents activities to cultivate the tendency to see special qualities in numbers that can be played on certain calendar days. Includes games on the constant of the day, Fibonacci and golden ratio dates, primes, powers, December 25, and the day of the year. (ASK)

  3. Biodiversity of date palm

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The date palm (Phoenix dactylifera) is the dominant component upon which the sustainable biophysical and socio-economic structures of the oasis ecosystem are based; a fruit tree with unique nutritional, biochemical and biophysical characteristics, a rich source of aesthetic and cultural values, and ...

  4. Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance.

    PubMed

    Zhu, Guanghui; Hoffman, Christopher D; Liu, Yang; Bhattacharyya, Souryadeep; Tumuluri, Uma; Jue, Melinda L; Wu, Zili; Sholl, David S; Nair, Sankar; Jones, Christopher W; Lively, Ryan P

    2016-07-25

    Both known and new CC3-based porous organic cages are prepared and exposed to acidic SO2 in vapor and liquid conditions. Distinct differences in the stability of the CC3 cages exist depending on the chirality of the diamine linkers used. The acid catalyzed CC3 degradation mechanism is probed via in situ IR and a degradation pathway is proposed and supported with computational results. CC3 crystals synthesized with racemic mixtures of diaminocyclohexane exhibited enhanced stability compared to CC3-R and CC3-S. Confocal fluorescent microscope images reveal that the stability difference in CC3 species originates from an abundance of mesoporous grain boundaries in CC3-R and CC3-S, allowing facile access of aqueous SO2 throughout the crystal, promoting decomposition. These grain boundaries are absent from CC3 crystals made with racemic linkers. PMID:27253350

  5. Enantioseparation of Mandelic Acid Enantiomers With Magnetic Nano-Sorbent Modified by a Chiral Selector.

    PubMed

    Tarhan, Tuba; Tural, Bilsen; Tural, Servet; Topal, Giray

    2015-11-01

    In this study, R(+)-α-methylbenzylamine-modified magnetic chiral sorbent was synthesized and assessed as a new enantioselective solid phase sorbent for separation of mandelic acid enantiomers from aqueous solutions. The chemical structures and magnetic properties of the new sorbent were characterized by vibrating sample magnetometry, transmission electron microscopy, Fourier transform infrared spectroscopy, and dynamic light scattering. The effects of different variables such as the initial concentration of racemic mandelic acid, dosage of sorbent, and contact time upon sorption characteristics of mandelic acid enantiomers on magnetic chiral sorbent were investigated. The sorption of mandelic acid enantiomers followed a pseudo-second-order reaction and equilibrium experiments were well fitted to a Langmuir isotherm model. The maximum adsorption capacity of racemic mandelic acid on to the magnetic chiral sorbent was found to be 405 mg g(-1). The magnetic chiral sorbent has a greater affinity for (S)-(+)-mandelic acid compared to (R)-(-)-mandelic acid. The optimum resolution was achieved with 10 mL 30 mM of racemic mandelic acid and 110 mg of magnetic chiral sorbent. The best percent enantiomeric excess values (up to 64%) were obtained by use of a chiralpak AD-H column. PMID:26370608

  6. 40 CFR 63.1160 - Compliance dates and maintenance requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Facilities and Hydrochloric Acid Regeneration Plants § 63.1160 Compliance dates and maintenance requirements.../or hydrochloric acid regeneration plant subject to this subpart shall achieve initial compliance with... reconstructed steel pickling facility and/or hydrochloric acid regeneration plant subject to this subpart...

  7. 40 CFR 63.1160 - Compliance dates and maintenance requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Facilities and Hydrochloric Acid Regeneration Plants § 63.1160 Compliance dates and maintenance requirements.../or hydrochloric acid regeneration plant subject to this subpart shall achieve initial compliance with... reconstructed steel pickling facility and/or hydrochloric acid regeneration plant subject to this subpart...

  8. 40 CFR 63.1160 - Compliance dates and maintenance requirements.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Facilities and Hydrochloric Acid Regeneration Plants § 63.1160 Compliance dates and maintenance requirements.../or hydrochloric acid regeneration plant subject to this subpart shall achieve initial compliance with... reconstructed steel pickling facility and/or hydrochloric acid regeneration plant subject to this subpart...

  9. 40 CFR 63.1160 - Compliance dates and maintenance requirements.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Facilities and Hydrochloric Acid Regeneration Plants § 63.1160 Compliance dates and maintenance requirements.../or hydrochloric acid regeneration plant subject to this subpart shall achieve initial compliance with... reconstructed steel pickling facility and/or hydrochloric acid regeneration plant subject to this subpart...

  10. (±)-2-Oxocyclo­penta­neacetic acid: catemeric hydrogen bonding in a γ-keto acid

    PubMed Central

    Efthimiopoulos, Georgia; Papadakis, Markos M.; Thompson, Hugh W.; Lalancette, Roger A.

    2009-01-01

    The title racemate, C7H10O3, aggregates in the solid as acid-to-ketone hydrogen-bonding catemers [O⋯O = 2.7050 (13) Å and O—H⋯O = 166.1 (17)°] having glide-related components. Four such heterochiral chains, paired centrosymmetrically about (, , ) in the cell, proceed through the cell in the 010 direction, with alignment with respect to the c axis of ++−−. PMID:21582637

  11. Development of a Method for the N-Arylation of Amino Acid Esters with Aryl Triflates.

    PubMed

    King, Sandra M; Buchwald, Stephen L

    2016-08-19

    A general method for the N-arylation of amino acid esters with aryl triflates is described. Both α- and β-amino acid esters, including methyl, tert-butyl, and benzyl esters, are viable substrates. Reaction optimization was carried out by design of experiment (DOE) analysis using JMP software. The mild reaction conditions, which use t-BuBrettPhos Pd G3 or G4 precatalyst, result in minimal racemization of the amino acid ester. This method is the first synthetic application of the t-BuBrettPhos Pd G4 precatalyst. Mechanistic studies show that the observed erosion in enantiomeric excess is due to racemization of the amino acid ester starting material and not of the product. PMID:27498618

  12. Bispalladacycle-catalyzed Brønsted acid/base-promoted asymmetric tandem azlactone formation-Michael addition.

    PubMed

    Weber, Manuel; Jautze, Sascha; Frey, Wolfgang; Peters, René

    2010-09-01

    Cooperative activation by a soft bimetallic catalyst, a hard Brønsted acid, and a hard Brønsted base has allowed the formation of highly enantioenriched, diastereomerically pure masked alpha-amino acids with adjacent quaternary and tertiary stereocenters in a single reaction starting from racemic N-benzoylated amino acids. The products can, for example, be used to prepare bicyclic dipeptides. PMID:20715774

  13. Enantiomeric excesses in meteoritic amino acids

    NASA Technical Reports Server (NTRS)

    Cronin, J. R.; Pizzarello, S.

    1997-01-01

    Gas chromatographic-mass spectral analyses of the four stereoisomers of 2-amino-2,3-dimethylpentanoic acid (dl-alpha-methylisoleucine and dl-alpha-methylalloisoleucine) obtained from the Murchison meteorite show that the L enantiomer occurs in excess (7.0 and 9.1%, respectively) in both of the enantiomeric pairs. Similar results were obtained for two other alpha-methyl amino acids, isovaline and alpha-methylnorvaline, although the alpha hydrogen analogs of these amino acids, alpha-amino-n-butyric acid and norvaline, were found to be racemates. With the exception of alpha-amino-n-butyric acid, these amino acids are either unknown or of limited occurrence in the biosphere. Because carbonaceous chondrites formed 4.5 billion years ago, the results are indicative of an asymmetric influence on organic chemical evolution before the origin of life.

  14. Racemic gamma vinyl-GABA (R,S-GVG) blocks methamphetamine-triggered reinstatement of conditioned place preference

    PubMed Central

    DEMARCO, AMY; DALAL, REEMA M.; PAI, JESSICA; AQUILINA, STEFANIE D.; MULLAPUDI, UMA; HAMMEL, CRYSTIE; KOTHARI, SHIVA K.; KAHANDA, MILAN; LIEBLING, COURTNEY N.B.; PATEL, VINAL; SCHIFFER, WYNNE K.; BRODIE, JONATHAN D.; DEWEY, STEPHEN L.

    2016-01-01

    Preventing relapse poses a significant challenge to the successful management of methamphetamine (METH) dependence. Although no effective medication currently exists for its treatment, racemic gamma vinyl-GABA (R,S-GVG, vigabatrin) shows enormous potential as it blocks both the neurochemical and behavioral effects of a variety of drugs, including METH, heroin, morphine, ethanol, nicotine, and cocaine. Using the reinstatement of a conditioned place preference (CPP) as an animal model of relapse, the present study specifically investigated the ability of an acute dose of R,S-GVG to block METH-triggered reinstatement of a METH-induced CPP. Animals acquired a METH CPP following a 20 day period of conditioning, in which they received 10 pairings of alternating METH and saline injections. During conditioning, rats were assigned to one of four METH dosage groups: 1.0, 2.5, 5.0, or 10.0 mg/kg (i.p., n = 8/group). Animals in all dosage groups demonstrated a robust and consistent CPP. This CPP was subsequently extinguished in each dosage group with repeated saline administration. Upon extinction, all groups reinstated following an acute METH challenge. On the following day, an acute dose of R,S-GVG (300 mg/kg, i.p.) was administered 2.5 hours prior to an identical METH challenge. R,S-GVG blocked METH-triggered reinstatement in all four groups. Given that drug re-exposure may potentiate relapse to drug-seeking behavior, the ability of R,S-GVG to block METH-triggered reinstatement offers further support for its use in the successful management of METH dependence. PMID:19016239

  15. Antinociceptive Effect of Racemic Flurbiprofen and Caffeine Co-Administration in an Arthritic Gout-Type Pain in Rats.

    PubMed

    Liévano-Reyes, Ricardo; Pérez-Méndez, Hermínia Ines; Solís-Oba, Aida; Jaramillo-Morales, Osmar Antonio; Espinosa-Juárez, Josué Vidal; López-Muñoz, Francisco Javier

    2016-06-01

    Preclinical Research Drug combinations are routinely used in the treatment of pain. In drug associations, adjuvants such as caffeine, are employed with different non-steroidal anti-inflammatories drugs (NSAIDs), however, at present does not exist studies showing the effect of the combination of racemic flurbiprofen (rac-Flur) in association with caffeine. The objective of this work was to evaluate the combination of rac-Flur + caffeine oral in arthritic gout-type pain in rats. The antinociceptive effects of the rac-Flur alone and in combination with caffeine were analyzed on a pain-induced functional impairment model in rat. rac-Flur induced a dose-dependent antinociceptive effect and caffeine did not present any effect. The combination of rac-Flur and caffeine achieve a higher percentage of antinociceptive effect compared with the individual administration of rac-Flur. The dose-response curve (DRCs) shows that the combination of rac-Flur (31.6 mg/kg) + caffeine (17.8 mg/kg) exhibited the maximal antinociceptive efficacy (294.0 ± 21.2 area units), while rac-Flur alone (31.6 mg/kg) showed 207.2 ± 35.2 au, thus indicating an increase in efficacy (potentiation). Furthermore, the DRCs of the combinations presented a displacement to the left, indicating a change in the potency. Caffeine is able to increase the effect of rac-Flur in the arthritic gout-type pain in rats. Drug Dev Res 77 : 192-198, 2016.   © 2016 Wiley Periodicals, Inc. PMID:27241234

  16. Dating Violence among College Students

    ERIC Educational Resources Information Center

    Iconis, Rosemary

    2013-01-01

    Dating violence is a significant problem on college campuses. More than one-fifth of the undergraduate dating population are physically abused by their dating partners and an even greater percentage are psychologically abused. Researchers have identified risk factors for college student dating violence. Preventive interventions are strongly…

  17. Laboratory for Radiokrypton Dating

    NASA Astrophysics Data System (ADS)

    Zappala, J. C.; Jiang, W.; Bailey, K. G.; Lu, Z. T.; Mueller, P.; O'Connor, T. P.

    2015-12-01

    Due to its simple production and transport in the terrestrial environment, 81Kr (half-life = 230,000 yr) is the ideal tracer for old water and ice with mean residence times in the range of 105-106 years, a range beyond the reach of 14C. 81Kr-dating is now available to the earth science community at large thanks to the development of an efficient and selective atom counter based on the Atom Trap Trace Analysis (ATTA) method. ATTA is a laser-based atom counting method where individual neutral atoms of the desired isotope are selectively captured by laser beams, and their fluorescence detected via a CCD camera. ATTA is unique among trace analysis techniques in that it is free of interferences from any other isotopes, isobars, atomic or molecular species. The ATTA instrument at Argonne's Laboratory for Radiokrypton Dating is capable of measuring both 81Kr/Kr and 85Kr/Kr ratios of environmental samples in the range of 10-14-10-10. For 81Kr-dating in the age range of 150 kyr - 1500 kyr, the required sample size is 5 micro-L STP of krypton gas, which can be extracted from approximately 100 kg of water or 40 kg of ice. For 85Kr/Kr analysis, the sample size can be smaller by an order of magnitude. We are continually developing the method towards higher counting efficiency, smaller sample sizes requirements, and higher sample throughput rates. In the past four years, we have performed radiokrypton analysis of over 150 groundwater and ice samples extracted by collaborators from all seven continents. Sample collection and purification was performed by groups including the University of Chicago, the University of Illinois at Chicago, the University of Bern, and the International Atomic Energy Agency. This work is supported by the U.S. DOE, Office of Nuclear Physics, under contract DE-AC02-06CH11357.

  18. 210Pb dating

    USGS Publications Warehouse

    Swarzenski, Peter W.

    2014-01-01

    Roughly fifty years ago, a small group of scientists from Belgium and the United States, trying to better constrain ice sheet accumulation rates, attempted to apply what was then know about environmental lead as a potential geochronometer. Thus Goldberg (1963) developed the first principles of the 210Pb dating method, which was soon followed by a paper by Crozaz et al. (1964), who examined accumulation history of Antarctic snow using 210Pb. Shortly thereafter, Koide et al. (1972, 1973) adapted this technique to unravel sediment deposition and accumulation records in deep-sea environments. Serendipitously, they chose to work in a deep basin off California, where an independent and robust age model had already been developed. Krishanswami et al. (1971) extended the use of this technique to lacustrine deposits to reconstruct depositional histories of lake sediment, and maybe more importantly, contaminant inputs and burial. Thus, the powerful tool for dating recent (up to about one century old) sediment deposits was established and soon widely adopted. Today almost all oceanographic or limnologic studies that address recent depositional reconstructions employ 210Pb as one of several possible geochronometers (Andrews et al., 2009; Gale, 2009; Baskaran, 2011; Persson and Helms, 2011). This paper presents a short overview of the principles of 210Pb dating and provides a few examples that illustrate the utility of this tracer in contrasting depositional systems. Potential caveats and uncertainties (Appleby et al., 1986; Binford, 1990; Binford et al., 1993; Smith, 2001; Hancock et al., 2002) inherent to the use and interpretation of 210Pb-derived age-models are also introduced. Recommendations as to best practices for most reliable uses and reporting are presented in the summary.

  19. Vulcanism and Radiocarbon Dates

    DOE R&D Accomplishments Database

    Libby, L. M.; Libby, W. F.

    1972-10-01

    We consider whether the long term perturbation of radiocarbon dates, which is known to be approximately a sin function of period about 8000 years and amplitude of about 8% peak-to-peak, could have been caused in any major part by vulcanism. We conclude that this is not the case. On the contrary, present day volcanoes are a far less important source of inert CO{sub 2} (about 100 fold less) than is man's burning of fossil fuels which has caused the Suess dilution of about 2%. (auth)

  20. Date with Science.

    ERIC Educational Resources Information Center

    Science and Children, 1988

    1988-01-01

    Provides a calendar for the month of November on which are placed directions and pictures for different activities that can be performed each day. Outlines materials and procedures for an experiment. Includes information on an acid rain teachers kit, availability, and price. (RT)

  1. ESR dating of pseudotachylite

    NASA Astrophysics Data System (ADS)

    Shimada, A.; Toyoda, S.; Takagi, H.; Arita, K.

    2002-12-01

    ESR (electron spin resonance) dating method has been used to determine the ages of quaternary events. When a mineral receives natural radiation, a part of paired electrons in quartz are ionized, and are trapped by lattice defects and impurties as unpaired electrons. The amount of unpaired electrons increases with time. The ESR age is obtained by dividing the total dose of natural radiation by the natural dose rate. Gamma ray doses are given to the sample to obtain the total dose by extrapolating the dose response of the signal intensity to the zero ordinate. The natural dose rate is calculated from U, Th, and K concentrations, and so on. Quartz is one of the promising minerals useful for ESR dating. In the present paper, we attempted to obtain ages of a land slide event. We collected pseudotachylite from Lantan, Himalaya. A land of about 4 km in diameter has found to have slid several kilometers resulting in pseudotachylite at the base. The samples were gently crushed sieved and soaked in 6N HCl for 1 night and then in 20% HF for two hours, but quartz grains were too small to be extracted. However, ESR signals of characteristic quartz were observed. As long as the sample is uniform, it is not crucial to extract pure quartz grains. With the usual procedure of ESR dating, gamma ray irradiation and ESR measurements, we obtained accumulated natural doses of 290 to 450 Gy. The concentrations of radioactive elements, K, U, Th, which give most of the natural dose to quartz grains, were measured by the low background gamma ray spectrometry. We obtained 7.62 ppm of uranium, 21.1 ppm of thorium, and 3.72% of K2O. Assuming the cosmic dose rate of 0.1mGy/y, we obtained 6.08 mGy/y as the natural dose rate. The ESR ages are obtained by dividing the accumulated doses by the natural dose rate to be 49ka from Al center signal (an electronic hole trapped at Al impurity in quartz) and 74ka from Ti center signal (an electron trapped at Ti impurity in quartz) for a sample, and 56ka and

  2. Amino acid preservation in saline halite core samples: Analogs for Martian dry evaporitic regions

    NASA Astrophysics Data System (ADS)

    Bada, J.; Aubrey, A.; Lowenstein, T.; Timofeeff, M.

    2008-12-01

    Recent data returned from several Mars spacecraft show substantial evidence for mineral precipitation from bodies of liquid water. Evaporitic minerals such as gypsum, kieserite and poly-hydrated magnesium sulfates have been detected remotely by orbiting spacecraft [1], jarosite has been detected in situ by the MER Opportunity [2], and chlorides are highly abundant upon the surface of Mars [3], often in correlation with siliclastic deposits [4]. Terrestrial environments can provide analogs for these systems identified on the Martian surface, and in-depth characterization of the terrestrial systems can provide valuable insights into processes that may have occurred on Mars during the late Noachian/early Hesperian. This is especially true in ancient playa or evaporative basin environments where deep core sampling offers a method of observing the geochemical diagenetic changes with time within a constrained environment. Deep coring can provide samples upwards of 200 ka within hundreds of meters of core [5]. The analysis of these sections can allow for the determination of preservation of various biosignatures from extinct microbial communities as well as their in situ diagenetic rates. Amino acids are powerful biomarkers that can be used to estimate biomass [6] and determine ages of extinct microbial communities [7]. Preliminary data for a core sample collected from Saline Valley, CA, shows the effect of time on amino acid biosignatures. The core has been dated by U-series: 35 feet, 20.9 ± 1.1 ka; 127 feet, 61.1 ±2.8 ka; 204 feet, 73.9 ±4.8 ka; and 310 feet, 150.3 ± 7.8 ka. The abundance of amino acids is observed to decrease drastically over the first 20 ka and then stabilize, although the overall composition changes. Acidic amino acids along with alanine and valine are the dominant amino acids. The enantiomeric (D/L) ratios generally increase with age because of in situ racemization, although the enantiomeric ratios for alanine and glutamic acid show a decrease

  3. Chemical synthesis and X-ray structure of a heterochiral {D-protein antagonist plus vascular endothelial growth factor} protein complex by racemic crystallography

    SciTech Connect

    Mandal, Kalyaneswar; Uppalapati, Maruti; Ault-Riché, Dana; Kenney, John; Lowitz, Joshua; Sidhu, Sachdev S.; Kent, Stephen B.H.

    2012-10-23

    Total chemical synthesis was used to prepare the mirror image (D-protein) form of the angiogenic protein vascular endothelial growth factor (VEGF-A). Phage display against D-VEGF-A was used to screen designed libraries based on a unique small protein scaffold in order to identify a high affinity ligand. Chemically synthesized D- and L- forms of the protein ligand showed reciprocal chiral specificity in surface plasmon resonance binding experiments: The L-protein ligand bound only to D-VEGF-A, whereas the D-protein ligand bound only to L-VEGF-A. The D-protein ligand, but not the L-protein ligand, inhibited the binding of natural VEGF{sub 165} to the VEGFR1 receptor. Racemic protein crystallography was used to determine the high resolution X-ray structure of the heterochiral complex consisting of {l_brace}D-protein antagonist + L-protein form of VEGF-A{r_brace}. Crystallization of a racemic mixture of these synthetic proteins in appropriate stoichiometry gave a racemic protein complex of more than 73 kDa containing six synthetic protein molecules. The structure of the complex was determined to a resolution of 1.6 {angstrom}. Detailed analysis of the interaction between the D-protein antagonist and the VEGF-A protein molecule showed that the binding interface comprised a contact surface area of approximately 800 {angstrom}{sup 2} in accord with our design objectives, and that the D-protein antagonist binds to the same region of VEGF-A that interacts with VEGFR1-domain 2.

  4. Chemical synthesis and X-ray structure of a heterochiral {D-protein antagonist plus vascular endothelial growth factor} protein complex by racemic crystallography.

    PubMed

    Mandal, Kalyaneswar; Uppalapati, Maruti; Ault-Riché, Dana; Kenney, John; Lowitz, Joshua; Sidhu, Sachdev S; Kent, Stephen B H

    2012-09-11

    Total chemical synthesis was used to prepare the mirror image (D-protein) form of the angiogenic protein vascular endothelial growth factor (VEGF-A). Phage display against D-VEGF-A was used to screen designed libraries based on a unique small protein scaffold in order to identify a high affinity ligand. Chemically synthesized D- and L- forms of the protein ligand showed reciprocal chiral specificity in surface plasmon resonance binding experiments: The L-protein ligand bound only to D-VEGF-A, whereas the D-protein ligand bound only to L-VEGF-A. The D-protein ligand, but not the L-protein ligand, inhibited the binding of natural VEGF(165) to the VEGFR1 receptor. Racemic protein crystallography was used to determine the high resolution X-ray structure of the heterochiral complex consisting of {D-protein antagonist + L-protein form of VEGF-A}. Crystallization of a racemic mixture of these synthetic proteins in appropriate stoichiometry gave a racemic protein complex of more than 73 kDa containing six synthetic protein molecules. The structure of the complex was determined to a resolution of 1.6 Å. Detailed analysis of the interaction between the D-protein antagonist and the VEGF-A protein molecule showed that the binding interface comprised a contact surface area of approximately 800 Å(2) in accord with our design objectives, and that the D-protein antagonist binds to the same region of VEGF-A that interacts with VEGFR1-domain 2. PMID:22927390

  5. Enantioselective excited-state quenching of racemic Tb (III) and Eu (III) Tris (pyridine-2,6-dicarboxylate) by vitamin B 12 derivatives

    NASA Astrophysics Data System (ADS)

    Meskers, Stefan C. J.; Dekkers, Harry P. J. M.

    1999-08-01

    Enantioselectivity in the dynamic quenching of the luminescence of the Δ and Λ enantiomers of racemic Tb(III)(pyridine-2,6-dicarboxylate=DPA) 33- and Eu(DPA) 33- by a series of corrinoids is demonstrated by time resolved luminescence and circular-polarization-of-luminescence (CPL) spectroscopy. Studied are cyanocobalamin (vitamin B 12), aquacobalamin (B 12a) and its conjugated base hydroxocobalamin (HOCbl), dicyanocobinamide ((CN) 2Cbi) and the heptamethyl ester of dicyanocobyrinic acid ((CN) 2Cby(OMe) 7). For this set of quenchers (Q), the diastereomeric quenching rate constants ( kqΔ and kqΛ) are reported together with the degree of enantioselectivity Eq=( kqΔ- kqΛ)/( kqΔ+ kqΛ). In the systems with Tb, values of the average rate constant kqavg(=( kqΔ+ kqΛ)/2) are 1.0, 2.9 and 0.53 10 8 M -1 s -1 for CNCbl, (CN) 2Cbi, (CN) 2Cby(OMe) 7 with Eq=-0.24, -0.20, +0.01 (standard error of Eq is 0.01). The quenching by B 12a is strongly dependent on pH and ionic strength ( I); when I=12 mM we find kqavg=5.3, Eq=-0.23 at pH 6.7 and kqavg=1.3, Eq=-0.27 at pH 8.9. Corresponding rates for Eu are 0.41, 27, 3.4 10 7 M -1 s -1 and for B 12a, 7.3 and 1.2 10 7 M -1 s -1, corresponding values for Eq -0.27, -0.29, +0.02, -0.21 and -0.29. The quenching reaction is modeled as a pre-equilibrium involving the formation of an encounter complex (association constant K) followed by the actual electronic energy transfer step (rate ket). By relating the quenching data with molecular structure it is argued that the binding in the encounter complex involves two hydrogen bonds between the uncoordinated carboxylate oxygen atom of two DPA ligands of Ln(DPA) 33- and two amide groups of the corrinoid, presumably involving the a and g, the a and b, or the b and g side chains. For some corrinoid/Ln(DPA) 33- complexes the association constants and enantioselectivities in the ground state are known (Spectrochimica Acta 55A (1999) 1837-1855), which allows for an estimate of the average rate of

  6. Laboratory for Radiokrypton Dating

    NASA Astrophysics Data System (ADS)

    Lu, Z.; Bailey, K.; Jiang, W.; Müller, P.; O'Connor, T. P.; Zappala, J. C.

    2013-12-01

    Due to its simple production and transport processes in the terrestrial environment, the long-lived noble-gas isotope 81Kr (half-life = 230 kyr) is the ideal tracer for studying old water and ice in the age range of 10^5-10^6 years, a range beyond the reach of 14C. 81Kr dating, a concept pursued in the past four decades by numerous laboratories employing a variety of techniques, is now available for the first time to the earth science community at large. This is made possible by the development of ATTA-3 (Jiang et al., GCA 91, 1-6; 2012), an efficient and selective atom counter based on the Atom Trap Trace Analysis method (Chen et al., Science 286, 1139-1141; 1999). The instrument is capable of measuring both 81Kr/Kr and 85Kr/Kr ratios of environmental samples in the range of 10^-14-10^-10. For 81Kr-dating in the age range of 150 - 1,500 kyr, the required sample size is 5 - 10 micro-L STP of krypton gas, which can be extracted from approximately 100 - 200 kg of water or 40 - 80 kg of ice. For 85Kr/Kr analysis, the required sample size is generally smaller by an order of magnitude because of the isotope's higher initial abundance in the atmosphere. The Laboratory for Radiokrypton Dating is currently equipped to analyze up to 120 samples per year. With future equipment upgrades, this limit can be increased as demand grows. In the period since November 2011, the Laboratory has measured both 81Kr/Kr and 85Kr/Kr ratios in over 50 samples that had been extracted by collaborators from six different continents. The samples were from groundwater wells in the Great Artesian Basin (Australia), Guarani Aquifer (Brazil), and Locust Grove (Maryland); from brine wells of the Waste Isolation Pilot Plant (New Mexico); from geothermal steam vents in Yellowstone National Park; from near-surface ice at Taylor Glacier, Antarctica; and from deep mines in South Africa. Sample collection and purification was performed by groups including the University of Illinois at Chicago, University

  7. Evaluation of blackberry cultivars and breeding selections for fruit quality traits and flowering and fruiting dates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A collection of 122 Rubus (L.) cultivars and breeding selections, primarily semi-erect Eastern blackberry, were evaluated for fruit antioxidant capacity (ORAC), total phenolics, total anthocyanins, percentage soluble solids, titratable acids, flowering dates and fruiting dates. The highly correlated...

  8. Violence in Adolescent Dating Relationships

    ERIC Educational Resources Information Center

    Jouriles, Ernest N.; Platt, Cora; McDonald, Renee

    2009-01-01

    Beginning with a definition of dating and dating violence among adolescents, this article explores the factors which impact such violence. It concludes with a review of two school-based prevention/intervention programs (Safe Dates and The Youth Relationships Project). (Contains 1 table.)

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Radiocarbon Dating, Memories, and Hopes

    DOE R&D Accomplishments Database

    Libby, W. F.

    1972-10-01

    The history of radiocarbon dating from 1939 to the present is reviewed. The basic principles of radiocarbon dating are that cosmic rays make living things radioactive with {sup 14}C to a certain level fixed by the environment and that at death the intake of food stops so no replenishment of the {sup 14}C steadily lost by the immutable decay occurs. Therefore measurement of the degree of decay gives the time lapse since death, i.e., the radiocarbon age. The equipment developed and experiments performed to measure the specific activity of specimens to be dated are described. The results obtained by world-wide experimenters are discussed. These showed that on simultaneity radiocarbon dating is apparently reliable but that absolute dates may be incorrect by as much as 600 to 700 y. The value of radiocarbon dating to archaeologists, geologists, climatologists, and historians is stressed. (LCL)

  11. Nonsteroidal antiinflammatory agents. Part 16: Stereomeric 3-aryl-biphenylyl-hydroxy-propionic acids.

    PubMed

    Guarnieri, A; Burnelli, S; Varoli, L; Ghedini, N; Scapini, G; Ferri, S; Cavicchini, E

    1985-08-01

    As part of a wider research project on structure-activity relationships of chiral arylalkanoic acids, stereomeric aryl- biphenylyl-hydroxypropionic acids 3a-d have been prepared and their antiinflammatory activity evaluated. Diastereomeric racemic erythro- and threo-acids have been synthesized by reaction of alpha-lithiated biphenylyl-acetic acid salts with the appropriate aldehyde. They were separated, and after attribution of their relative configuration by 1H-NMR analysis, resolved. The antiinflammatory activities of the enantiomeric potassium salts were determined by the carrageenan test. PMID:4080796

  12. VIEW OF DATE DRIVE, SHOWING DATE PALMS. NOTE TRELLIS ON ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    VIEW OF DATE DRIVE, SHOWING DATE PALMS. NOTE TRELLIS ON TYPE 11 FACILITY, FACILITY 808. VIEW FACING NORTHWEST - Camp H.M. Smith and Navy Public Works Center Manana Title VII (Capehart) Housing, Intersection of Acacia Road and Brich Circle, Pearl City, Honolulu County, HI

  13. Thermal synthesis and hydrolysis of polyglyceric acid. [in orgin of life studying

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1989-01-01

    Polyglyceric acid was synthesized by thermal condensation of glyceric acid at 80 C in the presence and absence of two mole percent of sulfuric acid catalyst. The acid catalyst accelerated the polymerization over 100-fold and made possible the synthesis of insoluble polymers of both L- and DL-glyceric acid by heating for less than 1 day. Racemization of L-glyceric acid yielded less than 1 percent D-glyceric acid in condensations carried out at 80 C with catalyst for 1 day and without catalyst for 12 days. The condensation of L-glyceric acid yielded an insoluble polymer much more readily than condensation of DL-glyceric acid. Studies of the hydrolysis of poly-DL-glyceric acid revealed that it was considerably more stable under mild acidic conditions compared to neutral pH. The relationship of this study to the origin of life is discussed.

  14. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago. PMID:17768978

  15. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  16. Radiocarbon Dating: An Annotated Bibliography.

    ERIC Educational Resources Information Center

    Fortine, Suellen

    This selective annotated bibliography covers various sources of information on the radiocarbon dating method, including journal articles, conference proceedings, and reports, reflecting the most important and useful sources of the last 25 years. The bibliography is divided into five parts--general background on radiocarbon, radiocarbon dating,…

  17. National Date Palm Germplasm Repository

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The National Clonal Germplasm Repository for Citrus & Dates (NCGRCD), located in Riverside, California USA, is a project of the Agricultural Research Service (ARS) of the United States Department of Agriculture (USDA). The NCGRCD maintains a collection of germplasm of date palm (Phoneix dactylifera ...

  18. Bacterial defluorination of 4-fluoroglutamic acid.

    PubMed

    Donnelly, Clár; Murphy, Cormac D

    2007-12-01

    Fluorinated amino acids are used as enzyme inhibitors, mechanistic probes and in the production of pharmacologically active peptides. Because enantiomerically pure 4-fluoroglutamate is difficult to prepare, the selective degradation of the L-isomer is a potentially convenient method of obtaining D-4-fluoroglutamate from the racemate. In this paper, we describe our investigations on the degradation of 4-fluoroglutamate by bacteria. Fluoride ion was detected in resting-cell cultures of a number of bacteria that were incubated with racemic 4-fluoroglutamate. Analysis of the culture supernatants by chiral gas chromatography-mass spectrometry revealed that only the L-isomer was degraded. The degradation of 4-fluoroglutamate was also examined in cell-free extracts of Streptomyces cattleya and Proteus mirabilis, and it was observed that equimolar concentrations of fluoride ion and ammonia were generated. The activity was located in the soluble fraction of cell extracts, thus is not related to the L-2-amino-4-chloro-4-pentenoic acid dehydrochlorinase previously identified in membrane fractions of P. mirabilis. PMID:17901951

  19. Z-Selective Hydrothiolation of Racemic 1,3-Disubstituted Allenes: An Atom-Economic Rhodium-Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Pritzius, Adrian B; Breit, Bernhard

    2015-12-21

    A Z-selective rhodium-catalyzed hydrothiolation of 1,3-disubstituted allenes and subsequent oxidation towards the corresponding allylic sulfones is described. Using the bidentate 1,4-bis(diphenylphosphino)butane (dppb) ligand, Z/E-selectivities up to >99:1 were obtained. The highly atom-economic desymmetrization reaction tolerates functionalized aromatic and aliphatic thiols. Additionally, a variety of symmetric internal allenes, as well as unsymmetrically disubstituted substrates were well tolerated, thus resulting in high regioselectivities. Starting from chiral but racemic 1,3-disubstituted allenes a dynamic kinetic resolution (DKR) could be achieved by applying (S,S)-Me-DuPhos as the chiral ligand. The desired Z-allylic sulfones were obtained in high yields and enantioselectivities up to 96 % ee. PMID:26418035

  20. Crystallization of Enantiomerically Pure Proteins from Quasi-Racemic Mixtures: Structure Determination by X-Ray Diffraction of Isotope-Labeled Ester Insulin and Human Insulin.

    PubMed

    Mandal, Kalyaneswar; Dhayalan, Balamurugan; Avital-Shmilovici, Michal; Tokmakoff, Andrei; Kent, Stephen B H

    2016-03-01

    As a part of a program aimed towards the study of the dynamics of human insulin-protein dimer formation using two-dimensional infrared spectroscopy, we used total chemical synthesis to prepare stable isotope labeled [(1-(13) C=(18) O)Phe(B24) )] human insulin, via [(1-(13) C=(18) O)Phe(B24) )] ester insulin as a key intermediate product that facilitates folding of the synthetic protein molecule (see preceding article). Here, we describe the crystal structure of the synthetic isotope-labeled ester insulin intermediate and the product synthetic human insulin. Additionally, we present our observations on hexamer formation with these two proteins in the absence of phenol derivatives and/or Zn metal ions. We also describe and discuss the fractional crystallization of quasi-racemic protein mixtures containing each of these two synthetic proteins. PMID:26707939

  1. Selective inhibition of human immunodeficiency viruses by racemates and enantiomers of cis-5-fluoro-1-[2-(hydroxymethyl)-1,3-oxathiolan-5-yl]cytosine.

    PubMed Central

    Schinazi, R F; McMillan, A; Cannon, D; Mathis, R; Lloyd, R M; Peck, A; Sommadossi, J P; St Clair, M; Wilson, J; Furman, P A

    1992-01-01

    2',3'-Dideoxy-5-fluoro-3'-thiacytidine (FTC) has been shown to be a potent and selective compound against human immunodeficiency virus type 1 in acutely infected primary human lymphocytes. FTC is also active against human immunodeficiency virus type 2, simian immunodeficiency virus, and feline immunodeficiency virus in various cell culture systems, including human monocytes. The antiviral activity can be prevented by 2'-deoxycytidine, but not by other natural nucleosides, suggesting that FTC must be phosphorylated to be active and 2'-deoxycytidine kinase is responsible for the phosphorylation. By using chiral columns or enzymatic techniques, the two enantiomers of FTC were separated. The (-)-beta-enantiomer of FTC was about 20-fold more potent than the (+)-beta-enantiomer against human immunodeficiency virus type 1 in peripheral blood mononuclear cells and was also effective in thymidine kinase-deficient CEM cells. Racemic FTC and its enantiomers were nontoxic to human lymphocytes and other cell lines at concentrations of up to 100 microM. Studies with human bone marrow cells indicated that racemic FTC and its (-)-enantiomer had a median inhibitory concentration of > 30 microM. The (+)-enantiomer was significantly more toxic than the (-)-enantiomer to myeloid progenitor cells. The susceptibilities to FTC of pretherapy isolates in comparison with those of posttherapy 3'-azido-3'-deoxythymidine-resistant viruses in human lymphocytes were not substantially different. Similar results were obtained with well-defined 2',3'-dideoxyinosine- and nevirapine-resistant viruses. (-)-FTC-5'-triphosphate competitively inhibited human immunodeficiency virus type 1 reverse transcriptase, with an inhibition constant of 2.9 microM, when a poly(I)n.oligo(dC)19-24 template primer was used. These results suggest that further development of the (-)-Beta-enantiomer of FTC is warranted as an antiviral agent for infections caused by human immunodeficiency viruses. Images PMID:1283296

  2. (2RS,8aRS)-6-Oxo-1,2,3,4,6,7,8,8a-octa­hydro­naphthalene-2-carboxylic acid

    PubMed Central

    Efthimiopoulos, Georgia; Lalancette, Roger A.; Thompson, Hugh W.

    2008-01-01

    The title racemate, C11H14O3, aggregates in the crystal structure as acid-to-ketone O—H⋯O hydrogen-bonding catemers whose components are glide-related. The relative stereochemistry at the carboxyl group arises spontaneously during the synthesis. Two inter­molecular C—H⋯O=C close contacts were found, both involving the acid group. PMID:21581270

  3. Separation of octopamine racemate on (R,S)-2-amino-1-phenylethanol imprinted polymer--Experimental and computational studies.

    PubMed

    Sobiech, Monika; Żołek, Teresa; Luliński, Piotr; Maciejewska, Dorota

    2016-01-01

    Ten molecularly imprinted polymers coded as MIP1-MIP10 were prepared by the radical bulk polymerization using (R,S)-(±)-2-amino-1-phenylethanol as the structural analog of the target analyte (R,S)-octopamine. The functional monomers, 4-vinylbenzoic acid (1), methacrylic acid (2), acrylic acid (3), trifluoromethacrylic acid (4), itaconic acid (5), acrylamide (6), isopropenylbenzene (7), 2-hydroxyethyl methacrylate (8), 2-(diethylamino)ethyl methacrylate (9), allylamine (10) were polymerized consecutively with the ethylene glycol dimethacrylate cross-linker in methanol as the porogen. On the basis of the binding capacity of (R,S)-octopamine MIP1 with affinity factor equal to 6.37 was selected for further analysis. The affinity of polymer matrix MIP1 was tested by the non-competitive binding experiments of eight structurally related analytes. Finally, molecularly imprinted solid phase extraction (MISPE) of (R,S)-octopamine from spiked human serum albumin was carried out in order to verify the applicability of novel sorbent. The molecular modeling was employed to rationalize the stereodifferentiation of the analytes by the stereospecific sites formed in the polymer matrix. PMID:26695304

  4. Radiocarbon dating of terrestrial carbonates

    USGS Publications Warehouse

    Pigati, Jeffrey S.

    2014-01-01

    Terrestrial carbonates encompass a wide range of materials that potentially could be used for radiocarbon (14C) dating. Biogenic carbonates, including shells and tests of terrestrial and aquatic gastropods, bivalves, ostracodes, and foraminifera, are preserved in a variety of late Quaternary deposits and may be suitable for 14C dating. Primary calcareous deposits (marls, tufa, speleothems) and secondary carbonates (rhizoliths, fracture fill, soil carbonate) may also be targeted for dating when conditions are favorable. This chapter discusses issues that are commonly encountered in 14C dating of terrestrial carbonates, including isotopic disequilibrium and open-system behavior, as well as methods used to determine the reliability of ages derived from these materials. Recent methodological advancements that may improve the accuracy and precision of 14C ages of terrestrial carbonates are also highlighted.

  5. Dating sediments using luminescence signals

    SciTech Connect

    Wintle, A. )

    1993-05-01

    Before siting a nuclear power station or a nuclear waste repository, it is necessary to establish that the area has been free of earthquake activity for a sufficient period of time. Evidence of past earthquake activity is often provided by faults in surface sediments. Age limits for fault formation can be set by obtaining the depositional ages of the sediment unit in which the fault was formed and the overlying sediment. A useful technique would be one that dating could be applied to the mineral grains that make up the sediments and that would give the time that has passed since the grains were blown or washed into position. Luminescence dating techniques, of which the most well known is thermo-luminescence (TL), provide such information. This approach has been successful in dating movement on the Wasatch Fault in Utah. A combination of TL and radiocarbon dates indicated that three faulting events had occurred within the past 5000 years. 2 refs., 1 fig.

  6. Ovulation and Due Date Calculator

    MedlinePlus

    ... Mom-to-be tools Ovulation and due date calculator Preconception health quiz Pregnancy know-how quiz Government ... Pregnancy > Pregnancy This information in Spanish ( en español ) Calculator Content last updated September 27, 2010. Resources last ...

  7. Asymmetric Reduction of Lactam-Based β-Aminoacrylates. Synthesis of Heterocyclic β(2)-Amino Acids.

    PubMed

    Campello, Hugo Rego; Parker, Jeremy; Perry, Matthew; Ryberg, Per; Gallagher, Timothy

    2016-08-19

    The ability to affect asymmetric reduction of heterocyclic β-aminoacrylates 1 (n = 1-3) has been assessed with pyrrolidine and piperidone variants generating the corresponding N-heterocyclic β(2)-amino acids 3b and 5b with high enantioselectivity (≥97% ee) using a Rh/WALPHOS catalyst combination. The use of the carboxylic acid substrate was essential; the corresponding esters do undergo reduction but led to racemic products. The seven-ring azepanone variant (as the carboxylic acid 9b) underwent reduction, but only a minimal level of asymmetric induction was observed. PMID:27508307

  8. Kinetic resolution of acids in acylation reactions in the presence of chiral tertiary amines

    SciTech Connect

    Potapov, V.M.; Dem'yanovich, V.M.; Khlebnikov, V.A.

    1988-07-10

    Asymmetric synthesis has now become an important method for the production of optically active compounds, and its most attractive form is asymmetric catalysis. This work was devoted to an investigation into asymmetric catalysis with chiral tertiary amines in acylation reactions. During the acylation of alcohols and amines by the action of racemic 2-phenylpropionic and 2-methyl-3-phenylpropionic acids in the presence of S-nicotine the initial acids are resolved kinetically. The (R)-2-phenylpropionic acid obtained in this way had an optical purity of 0.5-1.5%.

  9. Microscale radiocarbon dating of paintings

    NASA Astrophysics Data System (ADS)

    Hendriks, Laura; Hajdas, Irka; McIntyre, Cameron; Küffner, Markus; Scherrer, Nadim C.; Ferreira, Ester S. B.

    2016-03-01

    In this paper, radiocarbon dating of paintings using minimal sample sizes has been investigated, in an effort to address the problem of limited access to sample material in paintings. 14C analyses were conducted on signed and dated paintings from two Swiss artists of the twentieth century. The selected paintings dated from the 1930s and 1960s, provided the opportunity to evaluate the dating accuracy on paintings realized before and after 1950 AD when the 14C bomb peak was created, as a result of the nuclear tests conducted in the 1950/1960s. The work focused on the one hand on minimizing the size of the canvas sample required for accelerator mass spectrometer radiocarbon measurement on the gas ion source of the MICADAS and, on the other hand, on testing the possibility of dating the organic binder of the paint. Following careful characterization of the paint composition by X-ray fluorescence spectroscopy, Fourier transformed infrared spectroscopy, and Raman spectroscopy, paints containing no other carbon source than the natural organic binder were identified and dated.

  10. The fruit of the date palm: its possible use as the best food for the future?

    PubMed

    Al-Shahib, Walid; Marshall, Richard J

    2003-07-01

    The fruits (dates) of the date palm (Phoenix dactylifera L.) contain a high percentage of carbohydrate (total sugars, 44-88%), fat (0.2-0.5%), 15 salts and minerals, protein (2.3-5.6%), vitamins and a high percentage of dietary fibre (6.4-11.5%). The flesh of dates contains 0.2-0.5% oil, whereas the seed contains 7.7-9.7% oil. The weight of the seed is 5.6-14.2% of the date. The fatty acids occur in both flesh and seed as a range of saturated and unsaturated acids, the seeds containing 14 types of fatty acids, but only eight of these fatty acids occur in very low concentration in the flesh. Unsaturated fatty acids include palmitoleic, oleic, linoleic and linolenic acids. The oleic acid content of the seeds varies from 41.1 to 58.8%, which suggests that the seeds of date could be used as a source of oleic acid. There are at least 15 minerals in dates. The percentage of each mineral in dried dates varies from 0.1 to 916 mg/100 g date depending on the type of mineral. In many varieties, potassium can be found at a concentration as high as 0.9% in the flesh while it is as high as 0.5% in some seeds. Other minerals and salts that are found in various proportions include boron, calcium, cobalt, copper, fluorine, iron, magnesium, manganese, potassium, phosphorous, sodium and zinc. Additionally, the seeds contain aluminum, cadmium, chloride, lead and sulphur in various proportions. Dates contain elemental fluorine that is useful in protecting teeth against decay. Selenium, another element believed to help prevent cancer and important in immune function, is also found in dates. The protein in dates contains 23 types of amino acids, some of which are not present in the most popular fruits such as oranges, apples and bananas. Dates contain at least six vitamins including a small amount of vitamin C, and vitamins B(1) thiamine, B(2) riboflavin, nicotinic acid (niacin) and vitamin A. The dietary fibre of 14 varieties of dates has been shown to be as high as 6.4-11.5% depending

  11. Dating of Modern Human Evolution

    NASA Astrophysics Data System (ADS)

    Grun, R.

    Dating studies on palaoeanthropological sites is usually carried out on material associ- ated with the human remains, such as the sediment, charcoal or other fauna rather than the human specimen itself. The reason lies in the fact that most dating techniques are destructive and because the hominid remains are too rare to be sacrificed for dating. This indirect dating approach is in many cases not satisfactory, because: (i) the human remains are often buried into the sediments and the association with other materials is uncertain (e.g. Skhul, Qafzeh, etc.); (ii) faunal remains or minerals from the sediment are re-worked from older deposits (see e.g. present discussion of the age of the Homo erectus remains in Indonesia; (iii) the hominid fossils were discovered at a time when no careful excavations were carried out and it is impossible to correlate the specimen with other datable material (which applies tonearly 90% of all palaeoanthropological specimens). For example, the hominid burial site of Qafzeh in Israel has been dated by several independent dating laboratories with a multitude of methods. However, the data are still not accepted by some because the dating has not been carried out on the hominid specimen. Until recently, hominid fossils could only be dated by radiocarbon. This method reaches back to about 40,000 years. As a consequence, all the older fossils could not be analysed and many important questions in our understanding of human evolution could not be addressed. Human remains are scarce and extremely valuable, therefore any sort of destruction has to be kept to an absolute minimum. This is of particular importance in Australia where any human fossils are sacred. Thus, for the analysis of hominid material it was necessary to develop a more or less non-destructive techniques. This has been ac- complished in recent years by the application of ESR dating of tooth enamel and a combination of gamma spectrometric and TIMS U-series dating of bones. The exam

  12. Enantioselective Metabolism of Chiral 3-Phenylbutyric Acid, an Intermediate of Linear Alkylbenzene Degradation, by Rhodococcus rhodochrous PB1

    PubMed Central

    Simoni, S.; Klinke, S.; Zipper, C.; Angst, W.; Kohler, H. E.

    1996-01-01

    Rhodococcus rhodochrous PB1 was isolated from compost soil by selective culture with racemic 3-phenylbutyric acid as the sole carbon and energy source. Growth experiments with the single pure enantiomers as well as with the racemate showed that only one of the two enantiomers, (R)-3-phenylbutyric acid, supported growth of strain PB1. Nevertheless, (S)-3-phenylbutyric acid was cometabolically transformed to, presumably, (S)-3-(2,3-dihydroxyphenyl)butyric acid (the absolute configuration at the C-3 atom is not known yet) by (R)-3-phenylbutyric acid-grown cells of strain PB1, as shown by (sup1)H nuclear magnetic resonance spectroscopy of the partially purified compound and gas chromatography-mass spectrometry analysis of the trimethylsilyl derivative. Oxygen uptake rates suggest that either 3-phenylpropionic acid or cinnamic acid (trans-3-phenyl-2-propenoic acid) is the substrate for aromatic ring hydroxylation. This view is substantiated by the fact that 3-(2,3-dihydroxyphenyl)propionic acid was a substrate for meta cleavage in cell extracts of (R)-3-phenylbutyric acid-grown cells of strain PB1. Gas chromatography-mass spectrometry analysis of trimethylsilane-treated ethyl acetate extracts of incubation mixtures showed that both the meta-cleavage product, 2-hydroxy-6-oxo-2,4-nonadiene-1,9-dicarboxylic acid, and succinate, a hydrolysis product thereof, were formed during such incubations. PMID:16535265

  13. Dating of ballpoint pen ink.

    PubMed

    Hofer, R

    2004-11-01

    In this paper we describe a case in which a cash book, dated of the year 2000, was sent to the Forensic Science Division, Document Laboratory, Zurich Canton Police in March 2003. The questioned document was a list of 29 pages containing a consecutive handwritten numbering and dated entries (payments) made of blue ballpoint pen ink. By definition, a cash book has to be written by hand and the entries have to be made daily. The questioned document was suspected to have been written within a short period (e.g., a few hours) and backdated. The document lab was asked to determine the date of the entries of the questioned list. On one hand, we were asked, if the cash book had been kept on account consecutively during the period of one year, and on the other hand, the judges were interested in knowing, if the document could have been written in 2003 and back dated to 2000. To answer these questions, the document was examined for latent elements by electrostatic detection device (ESDA). The relative dating of the entries was performed by the quantification of the ballpoint pen ink dyes and their degradation products using HPLC. Results show that it is possible to determine the relative age of entries written by ballpoint pen within a relatively short time scale, if storage and supporting material of the different samples are the same or at least similar. PMID:15568713

  14. Polymerization of amino acids containing nucleotide bases

    NASA Technical Reports Server (NTRS)

    Ben Cheikh, Azzouz; Orgel, Leslie E.

    1990-01-01

    The nucleoamino acids 1-(3'-amino,3'-carboxypropyl)uracil (3) and 9-(3'-amino,3'-carboxypropyl)adenine (4) have been prepared as (L)-en-antiomers and as racemic mixtures. When 3 or 4 is suspended in water and treated with N,N'-carbon-yldiimidazole, peptides are formed in good yield. The products formed from the (L)-enantiomers are hydrolyzed to the monomeric amino acids by pronase. Attempts to improve the efficiency of these oligomerizations by including a polyuridylate template in the reaction mixture were not successful. Similarly, oligomers derived from the (L)-enantiomer of 3 did not act as templates to facilitate the oligomerization of 4.

  15. Peer Group Influences on Adolescent Dating Aggression

    ERIC Educational Resources Information Center

    Connolly, Jennifer; Friedlander, Laura

    2009-01-01

    The peer group is a critical social context for dating and romantic relationships. Peer groups provide opportunities to meet potential dating partners and set norms for acceptable dating behaviors. This article explores how peer groups influence dating and dating aggression, as well as how they can be used in prevention efforts. It also reviews…

  16. 21 CFR 1312.25 - Expiration date.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 9 2010-04-01 2010-04-01 false Expiration date. 1312.25 Section 1312.25 Food and... SUBSTANCES Exportation of Controlled Substances § 1312.25 Expiration date. An export permit shall not be valid after the date specified therein, which date shall conform to the expiration date specified in...

  17. 21 CFR 1312.25 - Expiration date.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 9 2013-04-01 2013-04-01 false Expiration date. 1312.25 Section 1312.25 Food and... SUBSTANCES Exportation of Controlled Substances § 1312.25 Expiration date. An export permit shall not be valid after the date specified therein, which date shall conform to the expiration date specified in...

  18. 21 CFR 1312.25 - Expiration date.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 9 2012-04-01 2012-04-01 false Expiration date. 1312.25 Section 1312.25 Food and... SUBSTANCES Exportation of Controlled Substances § 1312.25 Expiration date. An export permit shall not be valid after the date specified therein, which date shall conform to the expiration date specified in...

  19. 21 CFR 1312.25 - Expiration date.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 9 2011-04-01 2011-04-01 false Expiration date. 1312.25 Section 1312.25 Food and... SUBSTANCES Exportation of Controlled Substances § 1312.25 Expiration date. An export permit shall not be valid after the date specified therein, which date shall conform to the expiration date specified in...

  20. 21 CFR 1312.25 - Expiration date.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 9 2014-04-01 2014-04-01 false Expiration date. 1312.25 Section 1312.25 Food and... SUBSTANCES Exportation of Controlled Substances § 1312.25 Expiration date. An export permit shall not be valid after the date specified therein, which date shall conform to the expiration date specified in...

  1. The Next Generation MOD: A Microchip Amino Acid Analyzer for Detecting Extraterrestrial Life

    NASA Technical Reports Server (NTRS)

    Mathies, R. A.; Hutt, L. D.; Bada, J. L.; Glavin, D.; Grunthaner, F. J.; Grunthaner, P. J.

    2000-01-01

    The MOD (Mars Organic Detector) instrument which has selected for the definition phase of the BEDS package on the 2005 Mars Explorer Program spacecraft is designed to simply detect the presence of amino acids in Martian surface samples at a sensitivity of a few parts per billion (ppb). An additional important aspect of amino acid analyses of Martian samples is identifying and quantifying which compounds are present, and also distinguishing those produced abiotically from those synthesized by either extinct or extant life. Amino acid homochirality provides an unambiguous way of distinguishing between abiotic vs. biotic origins. Proteins made up of mixed D- and L-amino acids would not likely have been efficient catalysts in early organisms because they could not fold into bioactive configurations such as the a-helix. However, enzymes made up of all D-amino acids function just as well as those made up of only L-amino acids, but the two enzymes use the opposite stereoisomeric substrates. There are no biochemical reasons why L-amino acids would be favored over Damino acids. On Earth, the use of only L-amino acids in proteins by life is probably simply a matter of chance. We assume that if proteins and enzymes were a component of extinct or extant life on Mars, then amino acid homochirality would have been a requirement. However, the possibility that Martian life was (or is) based on D-amino acids would be equal to that based on L-amino acids. The detection of a nonracemic mixture of amino acids in a Martian sample would be strong evidence for the presence of an extinct or extant biota on Mars. The finding of an excess of D-amino acids would provide irrefutable evidence of unique Martian life that could not have been derived from seeding the planet with terrestrial life (or the seeding of the Earth with Martian life). In contrast, the presence of racemic amino acids, along with non-protein amino acids such as alpha-aminoisobutyric acid and isovaline, would be indicative

  2. Teen-Age Dating Violence.

    ERIC Educational Resources Information Center

    Kyle, Karla J.

    It has been estimated that one out of three teenage girls will be involved in an abusive relationship or experience violence in their relationships. Given the fact that studies are showing higher incidence of dating violence reported among teenagers, the importance and usefulness of this topic for anyone who works with adolescents cannot be…

  3. Online Dating and Conjugal Bereavement

    ERIC Educational Resources Information Center

    Young, Dannagal Goldthwaite; Caplan, Scott E.

    2010-01-01

    This study examined self-presentation in the online dating profiles of 241 widowed and 280 divorced individuals between 18 and 40 years old. A content analysis of open-ended user-generated profiles assessed the presence or absence of various themes, including the user's marital status, the backstory of their lost relationship, and whether they…

  4. 40 CFR 63.403 - Compliance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... compliance date shall be 18 months after September 8, 1994. (b) For new IPCT's that have an initial startup... initial startup on or after September 8, 1994, the compliance date shall be the date of the initial startup....

  5. 40 CFR 63.403 - Compliance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... initial startup before September 8, 1994, the compliance date shall be September 8, 1994. (c) For new IPCT's that have an initial startup on or after September 8, 1994, the compliance date shall be the date of the initial startup....

  6. 40 CFR 63.403 - Compliance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... initial startup before September 8, 1994, the compliance date shall be September 8, 1994. (c) For new IPCT's that have an initial startup on or after September 8, 1994, the compliance date shall be the date of the initial startup....

  7. 40 CFR 63.403 - Compliance dates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... initial startup before September 8, 1994, the compliance date shall be September 8, 1994. (c) For new IPCT's that have an initial startup on or after September 8, 1994, the compliance date shall be the date of the initial startup....

  8. Dating techniques in archaeology and paleoanthropology

    SciTech Connect

    Taylor, R.E.

    1987-02-15

    Archaeologists have an increasing array of physical dating methods at their disposal. R.E. Taylor of the University of California discusses available techniques, recent advances in radiocarbon dating, and current developments in radiocalcium dating.

  9. 40 CFR 62.3672 - Effective Date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Sewage Sludge Incinerators § 62.3672 Effective Date. The Federal effective date of the Indiana State Plan for existing Sewage Sludge Incinerators is August 12, 2013. Effective Date Note: At 78 FR 34920,...

  10. Dating Techniques in Archaeology and Paleoanthropology.

    ERIC Educational Resources Information Center

    Taylor, R. E.

    1987-01-01

    Discusses some of the new physical dating methods being used by archaeologists and paleoanthropologists to study the material remains of ancient primates. Describes the quaternary physical dating techniques, advances in radiocarbon dating, and the radiocalcium data method. (TW)

  11. Nicotinic acid metabolism. 2,3-Dimethylmalate lyase.

    PubMed

    Pirzer, P; Lill, U; Eggerer, H

    1979-12-01

    1) A new enzyme, 2,3-dimethylmalate lyase, was purified from Clostridium barkeri to about 80% homogeneity. Some of the properties of the enzyme are described. 2) It is shown that the 2,3-dimethylmalic acid (m.p. 143 degrees C) described in the literature represents only one racemic pair. This pair is not attacked by 2,3-dimethylmalate lyase. 3) The isolation of both racemic pairs of 2,3-dimethylmalic acid is described. Half of one pair, m.p. 104-106 degrees C, was converted to propionate and pyruvate by 2,3-dimethylmalate lyase. 4) In combination with earlier work performed by E.R. Stadtman and coworkers the results given under points 1--3 establish 2,3-dimethylmalate as an intermediate in the degradation of nicotinic acid by C. barkeri. 5) Experimental evidence indicates the 2,3-dimethylmalate lyase is no acyl-S-enzyme and that it is different in this respect as well as in quaternary structure from the apparently related enzymes citrate lyase and citramalate lyase. PMID:527937

  12. The radiolysis and radioracemization of amino acids on silica surfaces

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Lemmon, R. M.

    1981-01-01

    Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

  13. Ice Core Dating Software for Interactive Dating of Ice Cores

    NASA Astrophysics Data System (ADS)

    Kurbatov, A. V.; Mayewski, P. A.; Abdul Jawad, B. S.

    2005-12-01

    Scientists involved in ice core dating are well familiar with the problem of identification and recording the depth of annual signals using stable isotopes, glaciochemistry, ECM (electrical conductivity), DEP (dielectric properties) and particle counter data. Traditionally all parameters used for ice core dating were plotted as a function of depth, printed and after years were marked on the paper, converted to depth vs. age time scale. To expedite this tedious and manual process we developed interactive computer software, Ice core Dating (ICD) program. ICD is written in Java programming language, and uses GPL and GPL site licensed graphic libraries. The same 3.5 Mb in size pre-compiled single jar file, that includes all libraries and application code, was successfully tested on WinOS, Mac OSX, Linux, and Solaris operating systems running Java VM version 1.4. We have followed the modular design philosophy in our source code so potential integration with other software modules, data bases and server side distributed computer environments can be easily implemented. We expect to continue development of new suites of tools for easy integration of ice core data with other available time proxies. ICD is thoroughly documented and comes with a technical reference and cookbook that explains the purpose of the software and its many features, and provides examples to help new users quickly become familiar with the operation and philosophy of the software. ICD is available as a free download from the Climate Change Institute web site ( under the terms of GNU GPL public license.

  14. Highly Stereocontrolled Ring-Opening Polymerization of Racemic Alkyl β-Malolactonates Mediated by Yttrium [Amino-alkoxy-bis(phenolate)] Complexes.

    PubMed

    Jaffredo, Cédric G; Chapurina, Yulia; Kirillov, Evgueni; Carpentier, Jean-François; Guillaume, Sophie M

    2016-05-23

    Yttrium [amino-alkoxy-bis(phenolate)]amido complexes have been used for the ring-opening polymerization (ROP) of racemic alkyl β-malolactonates (4-alkoxycarbonyl-2-oxetanones, rac-MLA(R) s) bearing an allyl (All), benzyl (Bz) or methyl (Me) lateral ester function. The nature of the ortho-substituent on the phenolate rings in the metal ancillary dictated the stereocontrol of the ROP, and consequently the syndiotactic enrichment of the resulting polyesters. ROP promoted by catalysts with halogen (Cl, Br)-disubstituted ligands allowed the first reported synthesis of highly syndiotactic PMLA(R) s (Pr ≥ 0.95); conversely, catalysts bearing bulky alkyl and aryl ortho-substituted ligands proved largely ineffective. All polymers have been characterized by (1) H and (13) C{(1) H} NMR spectroscopy, MALDI-ToF mass spectrometry and DSC analyses. Statistical and thermal analyses enabled the rationalization of the chain-end control mechanism. Whereas the stereocontrol of the polymerization obeyed a Markov first-order (Mk1) model for the ROP of rac-MLA(Bz) and rac-MLA(All) , the ROP of rac-MLA(Me) led to a chain end-control of Markov second-order type (Mk2). DFT computations suggest that the high stereocontrol ability featured by catalysts bearing Cl- and Br-substituted ligands does not likely originate from halogen bonding between the halogen substituent and the growing polyester chain. PMID:27080758

  15. Enhanced production of Penicillium expansum PED-03 lipase through control of culture conditions and application of the crude enzyme in kinetic resolution of racemic Allethrolone.

    PubMed

    Dai, Dazhang; Xia, Liming

    2005-01-01

    Alkaline lipase production was performed in submerged fermentation by Penicillium expansum PED-03. It was found that the suitable carbon source and nitrogen source for lipase production were 0.5% starch and 4.0% soybean meal, respectively. The maximal lipase activity (850 U/mL) of production was achieved at initial pH 5.5-6.0, 26 degrees C, 72 h. Tween-80 was an effective enhancer for lipase production. Agitation speed of the fermentor played an important role, and the suitable agitation speed for lipase production was 500 r/min. The lipase was stable within the range of pH 7.0-10.0 and 20-40 degrees C, and the optimum conditions for the enzymatic reaction were 35 degrees C and pH 9.5. The enzymatic resolution of racemic allethrolone (4-hydroxy-3-methyl-2-(2-propenyl)-2- cyclopenten-1-one) was carried out by the lipase from P. expansum PED-03, and the conversion reached 48% with excellent enantioselectivity (E > 100), which showed a good application potential in the production of optically pure allethrolone. PMID:16080697

  16. Responsive organogels formed by supramolecular self assembly of PEG-block-allyl-functionalized racemic polypeptides into β-sheet-driven polymeric ribbons†

    PubMed Central

    Zou, Jiong; Zhang, Fuwu; Chen, Yingchao; Raymond, Jeffery E.; Zhang, Shiyi; Fan, Jingwei; Zhu, Jiahua; Li, Ang; Seetho, Kellie; He, Xun; Pochan, Darrin J.

    2014-01-01

    A chemically reactive hybrid diblock polypeptide gelator poly(ethylene glycol)-block-poly(dl-allylglycine) (PEG-b-PDLAG) is an exceptional material, due to the characteristics of thermo-reversible organogel formation driven by the combination of a hydrophilic polymer chain linked to a racemic oligomeric homopeptide segment in a range of organic solvents. One-dimensional stacking of the block copolymers is demonstrated by ATR-FTIR spectroscopy, wide-angle X-ray scattering to be driven by the supramolecular assembly of β-sheets in peptide blocks to afford well-defined fiber-like structures, resulting in gelation. These supramolecular interactions are sufficiently strong to achieve ultra low critical gelation concentrations (ca. 0.1 wt%) in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and methanol. The critical gel transition temperature was directly proportional to the polymer concentration, so that at low concentrations, thermoreversibility of gelation was observed. Dynamic mechanical analysis studies were employed to determine the organogel mechanical properties, having storage moduli of ca. 15.1 kPa at room temperature. PMID:25788968

  17. 31 CFR 536.302 - Effective date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY NARCOTICS TRAFFICKING SANCTIONS REGULATIONS General... of specially designated narcotics traffickers designated after that date, the earlier of the date...

  18. 31 CFR 536.302 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY NARCOTICS TRAFFICKING SANCTIONS REGULATIONS General... of specially designated narcotics traffickers designated after that date, the earlier of the date...

  19. 31 CFR 536.302 - Effective date.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY NARCOTICS TRAFFICKING SANCTIONS REGULATIONS General... of specially designated narcotics traffickers designated after that date, the earlier of the date...

  20. 31 CFR 536.302 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY NARCOTICS TRAFFICKING SANCTIONS REGULATIONS General... of specially designated narcotics traffickers designated after that date, the earlier of the date...

  1. 31 CFR 536.302 - Effective date.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY NARCOTICS TRAFFICKING SANCTIONS REGULATIONS General... of specially designated narcotics traffickers designated after that date, the earlier of the date...

  2. 76 FR 77831 - 2012 Presidential Candidate Matching Fund Submission Dates and Post Date of Ineligibility Dates...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-14

    ... (``DOI''). Candidates are required to submit a NOCO statement prior to each regularly scheduled date on..., and accounts receivable. 11 CFR 9034.5(a). Candidates will be notified of their DOI by the Commission. A Candidate who has net outstanding campaign obligations post-DOI may continue to submit...

  3. Identification of diamino acids in the Murchison meteorite

    PubMed Central

    Meierhenrich, Uwe J.; Muñoz Caro, Guillermo M.; Bredehöft, Jan Hendrik; Jessberger, Elmar K.; Thiemann, Wolfram H.-P.

    2004-01-01

    Amino acids identified in the Murchison chondritic meteorite by molecular and isotopic analysis are thought to have been delivered to the early Earth by asteroids, comets, and interplanetary dust particles where they may have triggered the appearance of life by assisting in the synthesis of proteins via prebiotic polycondensation reactions [Oró, J. (1961) Nature 190, 389–390; Chyba, C. F. & Sagan, C. (1992) Nature 355, 125–132]. We report the identification of diamino acids in the Murchison meteorite by new enantioselective GC-MS analyses. dl-2,3-diaminopropanoic acid, dl-2,4-diaminobutanoic acid, 4,4′-diaminoisopentanoic acid, 3,3′-diaminoisobutanoic acid, and 2,3-diaminobutanoic acid were detected in the parts per billion range after chemical transformation into N,N-diethoxycarbonyl ethyl ester derivatives. The chiral diamino acids show a racemic ratio. Laboratory data indicate that diamino acids support the formation of polypeptide structures under primitive Earth conditions [Brack, A. & Orgel, L. E. (1975) Nature 256, 383–387] and suggest polycondensation reactions of diamino acids into early peptide nucleic acid material as one feasible pathway for the prebiotic evolution of DNA and RNA genomes [Joyce, G. F. (2002) Nature 418, 214–221]. The results obtained in this study favor the assumption that not only amino acids (as the required monomers of proteins) form in interstellar/circumstellar environments, but also the family of diamino monocarboxylic acids, which might have been relevant in prebiotic chemistry. PMID:15194825

  4. Identification of diamino acids in the Murchison meteorite

    NASA Astrophysics Data System (ADS)

    Meierhenrich, Uwe J.; Muñoz Caro, Guillermo M.; Hendrik Bredehöft, Jan; Jessberger, Elmar K.; Thiemann, Wolfram H.-P.

    Amino acids identified in the Murchison chondritic meteorite by molecular and isotopic analysis are thought to have been delivered to the early Earth by asteroids, comets, and interplanetary dust particles where they may have triggered the appearance of life by assisting in the synthesis of proteins via prebiotic polycondensation reactions [Oró, J. (1961) Nature 190, 389-390; Chyba, C. F. & Sagan, C. (1992) Nature 355, 125-132]. We report the identification of diamino acids in the Murchison meteorite by new enantioselective GC-MS analyses. DL-2,3-diaminopropanoic acid, DL-2,4-diaminobutanoic acid, 4,4'-diaminoisopentanoic acid, 3,3'-diaminoisobutanoic acid, and 2,3-diaminobutanoic acid were detected in the parts per billion range after chemical transformation into N,N-diethoxycarbonyl ethyl ester derivatives. The chiral diamino acids show a racemic ratio. Laboratory data indicate that diamino acids support the formation of polypeptide structures under primitive Earth conditions [Brack, A. & Orgel, L. E. (1975) Nature 256, 383-387] and suggest polycondensation reactions of diamino acids into early peptide nucleic acid material as one feasible pathway for the prebiotic evolution of DNA and RNA genomes [Joyce, G. F. (2002) Nature 418, 214-221]. The results obtained in this study favor the assumption that not only amino acids (as the required monomers of proteins) form in interstellar/circumstellar environments, but also the family of diamino monocarboxylic acids, which might have been relevant in prebiotic chemistry.

  5. Extraterrestrial Amino Acids in Orgueil and Ivuna: Tracing the Parent Body of CI Type Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Meyer, Michael (Technical Monitor); Ehrenfreund, Pascale; Glavin, Daniel P.; Bota, Oliver; Cooper, George; Bada, Jeffrey

    2001-01-01

    Amino acid analyses using HPLC of pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna have found that beta-alanine, glycine, and gamma-amino-n-butyric acid (ABA) are the most abundant amino acids in these two meteorites, with concentrations ranging from approx. 600 to 2,000 parts per billion (ppb). Other alpha-amino acids such as alanine, alpha-ABA, alpha-aminoisobutyric acid (AIB), and isovaline are present only in trace amounts (less than 200 ppb). Carbon isotopic measurements of beta-alanine and glycine and the presence of racemic (D/L 1) alanine and beta-ABA in Orgueil suggest that these amino acids are extraterrestrial in origin. In comparison to the CM carbonaceous chondrites Murchison and Murray, the amino acid composition of the CIs is strikingly distinct, suggesting that these meteorites came from a different type of parent body, possibly an extinct comet, than did the CM carbonaceous chondrites.

  6. Amino Acids from Icy Amines: A Radiation-Chemical Approach to Extraterrestrial Synthesis

    NASA Technical Reports Server (NTRS)

    Dworkin, J. P.; Moore, M. H.

    2010-01-01

    Detections of amino acids in meteorites go back several decades, with at least 100 such compounds being reported for the Murchison meteorite alone. The presence of these extraterrestrial molecules raises questions as to their formation, abundance, thermal stability, racemization, and possible subsequent reactions. Although all of these topics have been studied in laboratories, such work often involves many variables and unknowns. This has led us to seek out model systems with which to uncover reaction products, test chemical predictions, and sited light on underlying reaction mechanisms. This presentation will describe one such study, focusing on amino-acid formation in ices.

  7. Immobilized β-cyclodextrin-based silica vs polymer monoliths for chiral nano liquid chromatographic separation of racemates.

    PubMed

    Ghanem, Ashraf; Ahmed, Marwa; Ishii, Hideaki; Ikegami, Tohru

    2015-01-01

    The enantioselectivity of immobilized β-cyclodextrin phenyl carbamate-based silica monolithic capillary columns was compared to our previously described polymer counterpart. 2,3,6-Tris(phenylcarbamoyl)-β-cyclodextrin-6-methacrylate was used as a functional monomer for the preparation of β-cyclodextrin (β-CD)-based silica and polymer monoliths. The silica monoliths were prepared via the sol-gel technique in fused silica capillary followed by modification of the bare silica monoliths with an anchor group prior to polymerization with β-CD methacrylate using either 2,2'-azobis(isobutyronitrile) or benzoylperoxide as radical initiators. On the other hand, the polymer monoliths were prepared via the copolymerization of β-CD methacrylate and ethylene glycol dimethacrylate in different ratios in situ in fused silica capillary. The prepared silica/polymer monoliths were investigated for the chiral separation of different classes of pharmaceuticals namely; α- and β-blockers, anti-inflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs and antiarrhythmic drugs. Baseline separation was achieved for alprenolol, bufuralol, carbuterol, cizolertine, desmethylcizolertine, eticlopride, ifosfamide, 1-indanol, propranolol, tebuconazole, tertatolol and o-methoxymandelic acid under reversed phase conditions using mobile phase composed of methanol and water. The silica-based monoliths showed a comparative enantioselectivity to the polymer monoliths. PMID:25476312

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

    NASA Astrophysics Data System (ADS)

    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.

  9. School Counselors' Role in Dating Violence Intervention

    ERIC Educational Resources Information Center

    Craigen, Laurie M.; Sikes, April; Healey, Amanda; Hays, Danica

    2009-01-01

    Dating violence among adolescents is a major public health concern. The purpose of this paper is to examine five factors of which school counselors must be aware in order to recognize, intervene, and report incidence of dating violence. These factors are (a) understanding the diverse definitions of dating violence, (b) recognizing dating violence…

  10. 7 CFR 987.12 - Marketable dates.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.12 Marketable dates. Marketable... exeption of Canada. The Committee may establish different requirements for different countries. (d) Product dates. Product dates are marketable dates that are inspected and certified as meeting the...

  11. 38 CFR 21.9635 - Discontinuance dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... individual is enrolled in an institution of higher learning on the date of expiration of his or her period of... Discontinuance dates. The effective date of a reduction or discontinuance of educational assistance will be as... payment, the discontinuance date of educational assistance for the purpose of that lump sum payment...

  12. 38 CFR 21.7135 - Discontinuance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) Eligibility expires. If the veteran is pursuing a course on the date of expiration of eligibility as... Bill-Active Duty) Payments-Educational Assistance § 21.7135 Discontinuance dates. The effective date of... dependent. If more than one type of reduction or discontinuance is involved, the earliest date will...

  13. 38 CFR 21.7135 - Discontinuance dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) Eligibility expires. If the veteran is pursuing a course on the date of expiration of eligibility as... Bill-Active Duty) Payments-Educational Assistance § 21.7135 Discontinuance dates. The effective date of... dependent. If more than one type of reduction or discontinuance is involved, the earliest date will...

  14. 38 CFR 21.3332 - Discontinuance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... expiration of the eligible person's entitlement. (e) Date of interruption of course as determined by the... special training allowance as provided in this section on the earliest date of the following: (a) The ending date of the course. (b) The ending date of the period of enrollment as certified by the...

  15. 38 CFR 21.3332 - Discontinuance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... expiration of the eligible person's entitlement. (e) Date of interruption of course as determined by the... special training allowance as provided in this section on the earliest date of the following: (a) The ending date of the course. (b) The ending date of the period of enrollment as certified by the...

  16. 38 CFR 21.3332 - Discontinuance dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... expiration of the eligible person's entitlement. (e) Date of interruption of course as determined by the... special training allowance as provided in this section on the earliest date of the following: (a) The ending date of the course. (b) The ending date of the period of enrollment as certified by the...

  17. 38 CFR 21.7135 - Discontinuance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) Eligibility expires. If the veteran is pursuing a course on the date of expiration of eligibility as... Bill-Active Duty) Payments-Educational Assistance § 21.7135 Discontinuance dates. The effective date of... dependent. If more than one type of reduction or discontinuance is involved, the earliest date will...

  18. 38 CFR 21.9635 - Discontinuance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... individual is enrolled in an institution of higher learning on the date of expiration of his or her period of... Discontinuance dates. The effective date of a reduction or discontinuance of educational assistance will be as... payment, the discontinuance date of educational assistance for the purpose of that lump sum payment...

  19. 38 CFR 21.9635 - Discontinuance dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... individual is enrolled in an institution of higher learning on the date of expiration of his or her period of... Discontinuance dates. The effective date of a reduction or discontinuance of educational assistance will be as... payment, the discontinuance date of educational assistance for the purpose of that lump sum payment...

  20. 38 CFR 21.3332 - Discontinuance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... expiration of the eligible person's entitlement. (e) Date of interruption of course as determined by the... special training allowance as provided in this section on the earliest date of the following: (a) The ending date of the course. (b) The ending date of the period of enrollment as certified by the...

  1. Enrichment of Non-Terrestrial L-Proteinogenic Amino Acids by Aqueous Alteration on the Tagish Lake Meteorite Parent Body

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel P.; Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael P.; Dworkin, Jason P.; Herd, Christopher D. K.

    2012-01-01

    The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2-type carbonaceous chondrite were investigated via liquid chromatography fluorescence detection time-of-flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large L-enantiomeric excesses (L(sub ee) approx. 43 to 59%) of the a-hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another alpha-hydrogen protein amino acid, was found to be nearly racemic (D approx. L) using both techniques. Carbon isotope measurements of D- and L-aspartic acid and D- and L-alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the Lexcesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid-solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals.

  2. Radioactive dating of the elements

    NASA Technical Reports Server (NTRS)

    Cowan, John J.; Thielemann, Friedrich-Karl; Truran, James W.

    1991-01-01

    The extent to which an accurate determination of the age of the Galaxy, and thus a lower bound on the age of the universe, can be obtained from radioactive dating is discussed. Emphasis is given to the use of the long-lived radioactive nuclei Re-187, Th-232, U-238, and U-235. The nature of the production sites of these and other potential Galactic chronometers is examined along with their production ratios. Age determinations from models of nucleocosmochronology are reviewed and compared with age determination from stellar sources and age constraints form cosmological considerations.

  3. Birthday and date of death.

    PubMed Central

    Angermeyer, M C; Kühn, L; Osterwald, P

    1987-01-01

    The relation between birthday and date of death has so far been studied from two different perspectives: birthdays were either conceived of as emotionally invested deadlines motivating people to ward off their death which causes a 'dip' in death rates before their birthday, or they were considered as stressful events leading to an increase of mortality on or after their birthday. Using a collection of biographies of famous people from the whole world and another of well-known Swiss citizens we tested hypotheses derived from these assumptions. Neither the 'death-dip' hypotheses nor the 'birthday stress' hypothesis was supported by our results. PMID:3655631

  4. Dating tectonic structures on Mercury

    NASA Astrophysics Data System (ADS)

    Giacomini, L.; Massironi, M.; Marchi, S.; Cremonese, G.

    2012-09-01

    Mercury surface appears to be interested by several tectonic structures, the most interesting ones being numerous lobate scarps formed mainly thanks to planet cooling and contraction. The Messenger cameras (MDIS WAC and NAC) allowed us to map several structures not previously detected. Among these a 250 km-long thrust has been detected crossing a peak ring basin. The region encircled within the inner ring of the basin is covered by a smooth plain with evidence of a sin-deformational emplacement. Dating this smooth plain with crater counting technique allowed us to give an age constrain of the tectonic structure.

  5. [The knowledge about "date rape drugs" among Polish students].

    PubMed

    Dziuban', Agata; Ratecka, Anna; Brzyski, Piotr; Foryś, Zofia; Gomółka, Ewa; Ogonowska, Dorota

    2009-01-01

    The Main Department of Police in Poland notes about 2000 rapes a year. Some of the crimes are performed with "Date Rape Drugs". The term means substances helping comitting a rape such as GHB (gamma hydroxybutyric acid), ketamine, flunitrazepam and other benzodiazepines derivatives, MDMA ("ecstasy"), marihuana, amphetamine. The substances are often joined with alcohol. The victims are usually young women, and not all the cases are recorded by the police or physicians, because the victims often do not remember details of the event. The toxicological analysis of blood or urine would be helpful to explain the circumstances of the case and to prove using "Date Rape Drug". The samples for toxicological determinations should be collected as soon as possible (24 to 72 hours after admission). Preventing violence with "Date Rape Drugs" include wide education by media, police, teachers and parents. The purpose of the research was to check the level of knowledge about "Date Rape Drugs". The consciousness of risk behavior when the kind of substances is used and the ways of preventing the risk of being a sexual victim were checked. Material for the research were the results of questionnaire prepared by The Department of Medicine Sociology Collegium Medicum Jagiellonian University in Krakow, carried out on 740 students. Most of respondents (77%) were women. The age of respondents was between 19-36 years (mean 21.41; SD - 1.29). The results of the research showed, that respondents didn't have completed knowledge about "Date Rape Drugs". They did not know the ways of recognizing and preventing the risk of being given this kind of substances. The main source of information about "Date Rape Drugs" were internet and colleagues. There is a need to start education about "Date Rape Drugs" by serious institutions such as the police and schools in Poland. This is the best way to prevent young people against a risk of being given "Date Rape Drugs" and being a victim of sexual crimes. PMID

  6. A revised dated phylogeny of the arachnid order Opiliones.

    PubMed

    Sharma, Prashant P; Giribet, Gonzalo

    2014-01-01

    Dating the Opiliones tree of life has become an important enterprise for this group of arthropods, due to their ancient origins and important biogeographic implications. To incorporate both methodological innovations in molecular dating as well as new systematic discoveries of harvestman diversity, we conducted total evidence dating on a data set uniting morphological and/or molecular sequence data for 47 Opiliones species, including all four well-known Palaeozoic fossils, to test the placement of both fossils and newly discovered lineages in a single analysis. Furthermore, we investigated node dating with a phylogenomic data set of 24,202 amino acid sites for 14 species of Opiliones, sampling all extant suborders. In this way, we approached molecular dating of basal harvestman phylogeny using different data sets and approaches to assess congruence of divergence time estimates. In spite of the markedly different composition of data sets, our results show congruence across all analyses for age estimates of basal nodes that are well constrained with respect to fossil calibrations (e.g., Opiliones, Palpatores). By contrast, derived nodes that lack fossil calibrations (e.g., the suborders Cyphophthalmi, and Laniatores) have large uncertainty intervals in diversification times, particularly in the total evidence dating analysis, reflecting the dearth of calibration points and undersampling of derived lineages. Total evidence dating consistently produced older median ages than node dating for ingroup nodes, due to the nested placement of multiple Palaeozoic fossils. Our analyses support basal diversification of Opiliones in the Ordovician-Devonian period, corroborating the inferred ancient origins of this arthropod order, and underscore the importance of diversity discovery-both paleontological and neontological-in evolutionary inference. PMID:25120562

  7. A revised dated phylogeny of the arachnid order Opiliones

    PubMed Central

    Sharma, Prashant P.; Giribet, Gonzalo

    2014-01-01

    Dating the Opiliones tree of life has become an important enterprise for this group of arthropods, due to their ancient origins and important biogeographic implications. To incorporate both methodological innovations in molecular dating as well as new systematic discoveries of harvestman diversity, we conducted total evidence dating on a data set uniting morphological and/or molecular sequence data for 47 Opiliones species, including all four well-known Palaeozoic fossils, to test the placement of both fossils and newly discovered lineages in a single analysis. Furthermore, we investigated node dating with a phylogenomic data set of 24,202 amino acid sites for 14 species of Opiliones, sampling all extant suborders. In this way, we approached molecular dating of basal harvestman phylogeny using different data sets and approaches to assess congruence of divergence time estimates. In spite of the markedly different composition of data sets, our results show congruence across all analyses for age estimates of basal nodes that are well constrained with respect to fossil calibrations (e.g., Opiliones, Palpatores). By contrast, derived nodes that lack fossil calibrations (e.g., the suborders Cyphophthalmi, and Laniatores) have large uncertainty intervals in diversification times, particularly in the total evidence dating analysis, reflecting the dearth of calibration points and undersampling of derived lineages. Total evidence dating consistently produced older median ages than node dating for ingroup nodes, due to the nested placement of multiple Palaeozoic fossils. Our analyses support basal diversification of Opiliones in the Ordovician-Devonian period, corroborating the inferred ancient origins of this arthropod order, and underscore the importance of diversity discovery—both paleontological and neontological—in evolutionary inference. PMID:25120562

  8. Occurrence of Free d-Amino Acids and Aspartate Racemases in Hyperthermophilic Archaea

    PubMed Central

    Matsumoto, Megumi; Homma, Hiroshi; Long, Zhiqun; Imai, Kazuhiro; Iida, Toshii; Maruyama, Tadashi; Aikawa, Yuko; Endo, Isao; Yohda, Masafumi

    1999-01-01

    The occurrence of free d-amino acids and aspartate racemases in several hyperthermophilic archaea was investigated. Aspartic acid in all the hyperthermophilic archaea was highly racemized. The ratio of d-aspartic acid to total aspartic acid was in the range of 43.0 to 49.1%. The crude extracts of the hyperthermophiles exhibited aspartate racemase activity at 70°C, and aspartate racemase homologous genes in them were identified by PCR. d-Enantiomers of other amino acids (alanine, leucine, phenylalanine, and lysine) in Thermococcus strains were also detected. Some of them might be by-products of aspartate racemase. It is proven that d-amino acids are produced in some hyperthermophilic archaea, although their function is unknown. PMID:10515953

  9. Kinetic Trapping of Metastable Amino Acid Polymorphs

    PubMed Central

    2015-01-01

    Second harmonic generation (SHG) microscopy measurements indicate that inkjet-printed racemic solutions of amino acids can produce nanocrystals trapped in metastable polymorph forms upon rapid solvent evaporation. Polymorphism impacts the composition, distribution, and physico-kinetic properties of organic solids, with energetic arguments favoring the most stable polymorph. In this study, unfavored noncentrosymmetric crystal forms were observed by SHG microscopy. Polarization-dependent SHG measurement and synchrotron X-ray microdiffraction analysis of individual printed drops are consistent with formation of homochiral crystal production. Fundamentally, these results provide evidence supporting the ubiquity of Ostwald’s Rule of Stages, describing the hypothesized transitioning of crystals between metastable polymorphic forms in the early stages of crystal formation. Practically, the presence of homochiral metastable forms has implications on chiral resolution and on solid form preparations relying on rapid solvent evaporation. PMID:24451055

  10. Kinetic trapping of metastable amino acid polymorphs.

    PubMed

    Chowdhury, Azhad U; Dettmar, Christopher M; Sullivan, Shane Z; Zhang, Shijie; Jacobs, Kevin T; Kissick, David J; Maltais, Thora; Hedderich, Hartmut G; Bishop, Patricia A; Simpson, Garth J

    2014-02-12

    Second harmonic generation (SHG) microscopy measurements indicate that inkjet-printed racemic solutions of amino acids can produce nanocrystals trapped in metastable polymorph forms upon rapid solvent evaporation. Polymorphism impacts the composition, distribution, and physico-kinetic properties of organic solids, with energetic arguments favoring the most stable polymorph. In this study, unfavored noncentrosymmetric crystal forms were observed by SHG microscopy. Polarization-dependent SHG measurement and synchrotron X-ray microdiffraction analysis of individual printed drops are consistent with formation of homochiral crystal production. Fundamentally, these results provide evidence supporting the ubiquity of Ostwald's Rule of Stages, describing the hypothesized transitioning of crystals between metastable polymorphic forms in the early stages of crystal formation. Practically, the presence of homochiral metastable forms has implications on chiral resolution and on solid form preparations relying on rapid solvent evaporation. PMID:24451055

  11. Sublimation of natural amino acids and induction of asymmetry by meteoritic amino acids

    NASA Astrophysics Data System (ADS)

    Tarasevych, Arkadii V.; Guillemin, Jean-Claude

    It is believed that the homochirality of building blocks of life like amino acids (AAs) and sugars is a prerequisite requirement for the origin and evolution of life. Among different mechanisms that might have triggered the initial disparity in the enantiomeric ratio on the primitive Earth, the key roles were assigned to: (i) local chiral symmetry breaking and (ii) the inflow of extraterrestrial matter (eg the carbonaceous meteorites containing non-racemic AAs). Recently it has been revealed that sublimation, a subject almost completely neglected for a long time, gives a pathway to enantioenrichment of natural AAs (1,2 and references herein). Sublimation is however one of the key physical processes that occur on comets. Starting from a mixture with a low content of an enantiopure AA, a partial sublimation gives an important enrichment of the sublimate (1,2). The resulted disparity in the ratio between enantiomers of a partial sublimate is determined by the crystalline nature of the starting mixture: we observed a drastic difference in the behavior of (i) mixtures based on true racemic compounds and (ii) mechanical mixtures of two enantiopure solid phases. On the other hand, combination of crystallization and sublimation can lead to segregation of enantioenriched fractions starting from racemic composition of sublimable aliphatic AAs (Ala, Leu, Pro, Val) in mixtures with non-volatile enantiopure ones (Asn, Asp, Glu, Ser, Thr) (3). The resulted sense of chirality correlates with the handedness of the non-volatile AAs: the observed changes in enantiomeric ratios clearly demonstrate the preferential homochiral interactions and a tendency of natural amino acids to homochiral self-organization. It is noteworthy that just these 5 (Asn, Asp, Glu, Ser, Thr) out of 22 proteinogenic amino acids are able to local symmetry breaking. On the other hand, recent data on the enantiomeric composition of the Tagish Lake, a C2-type carbonaceous meteorite, revealed a large L

  12. Chirality of meteoritic free and IOM-derived monocarboxylic acids and implications for prebiotic organic synthesis

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; Tarozo, Rafael; Alexandre, Marcelo R.; Alexander, Conel M. O.'D.; Charnley, Steven B.; Hallmann, Christian; Summons, Roger E.; Huang, Yongsong

    2014-04-01

    The origin of homochirality and its role in the development of life on Earth are among the most intriguing questions in science. It has been suggested that carbonaceous chondrites seeded primitive Earth with the initial organic compounds necessary for the origin of life. One of the strongest pieces of evidence supporting this theory is that certain amino acids in carbonaceous chondrites display a significant L-enantiomeric excess (ee), similar to those use by terrestrial life. Analyses of ee in meteoritic molecules other than amino acids would shed more light on the origins of homochirality. In this study we investigated the stereochemistry of two groups of compounds: (1) free monocarboxylic acids (MCAs) from CM2 meteorites LON 94101 and Murchison; and (2) the aliphatic side chains present in the insoluble organic matter (IOM) and extracted in the form of monocarboxylic acids (MCAs) from EET 87770 (CR2) and Orgueil (CI1). Contrary to the well-known ee observed for amino acids in meteorites, we found that meteoritic branched free and IOM-derived MCAs with 5-8 carbon atoms are essentially racemic. The racemic nature of these compounds is used to discuss the possible influence of ultraviolet circularly polarized light (UVCPL) and aqueous alterations on the parent body on chirality observed in in carbonaceous chondrites.

  13. Unusual Nonterrestrial L-proteinogenic Amino Acid excesses in the Tagish Lake Meteorite

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel P.; Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael P.; Dworkin, Jason P.; Hilts, Robert W.; Herd, D. K.

    2012-01-01

    The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2-type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time-of-flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large L-enantiomeric excesses (L(sub ee) approximately 43-59%) of the alpha-hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another alpha hydrogen protein amino acid, was found to be nearly racemic (D much approximately L) using both techniques. Carbon isotope measurements of D- and L-aspartic acid and 1)- and L-alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the L-excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid-solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial L-enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large L-enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of non terrestrial L-proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.

  14. Optimization of phenolics and dietary fibre extraction from date seeds.

    PubMed

    Al-Farsi, Mohamed Ali; Lee, Chang Yong

    2008-06-01

    This work was conducted to optimise extraction conditions of phenolics and dietary fibre from date seeds. The effects of solvent to sample ratio, temperature, extraction time, number of extractions and solvent type on phenolic extraction efficiency were studied. At two-stage extraction, each stage 1h duration at 45°C with a solvent to sample ratio of 60:1, is considered optimum. Acetone (50%), and butanone were the most efficient solvents for extraction and purification, increasing the yield and phenolic contents of seed concentrate to 18.10 and 36.26g/100g, respectively. The total dietary fibre of seeds (57.87g/100g) increased after water and acetone extractions to 83.50 and 82.17g/100g, respectively. Nine phenolic acids (free and liberated) were detected in seeds with p-hydroxybenzoic (9.89mg/100g), protocatechuic (8.84mg/100g), and m-coumaric (8.42mg/100g) acids found to be among the highest. After extraction and purification, total phenolic acid content increased significantly from 48.64 to 193.83mg/100g. Protocatechuic, caffeic and ferulic acids were the major phenolic acids found in the concentrates. Based on this study, we believe date seed concentrates could potentially be an inexpensive source of natural dietary fibre and antioxidants and possibly used as a functional food ingredient. PMID:26065761

  15. 7-Chloro-5-(furan-3-yl)-3-methyl-4H-benzo[e][1,2,4]thiadiazine 1,1-Dioxide as Positive Allosteric Modulator of α-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic Acid (AMPA) Receptor. The End of the Unsaturated-Inactive Paradigm?

    PubMed

    Citti, Cinzia; Battisti, Umberto M; Cannazza, Giuseppe; Jozwiak, Krzysztof; Stasiak, Natalia; Puja, Giulia; Ravazzini, Federica; Ciccarella, Giuseppe; Braghiroli, Daniela; Parenti, Carlo; Troisi, Luigino; Zoli, Michele

    2016-02-17

    5-Arylbenzothiadiazine type compounds acting as positive allosteric modulators of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor (AMPA-PAMs) have received particular attention in the past decade for their nootropic activity and lack of the excitotoxic side effects of direct agonists. Recently, our research group has published the synthesis and biological activity of 7-chloro-5-(3-furanyl)-3-methyl-3,4-dihydro-2H-1,2,4-benzothiadiazine 1,1-dioxide (1), one of the most active benzothiadiazine-derived AMPA-PAMs in vitro to date. However, 1 exists as two stereolabile enantiomers, which rapidly racemize in physiological conditions, and only one isomer is responsible for the pharmacological activity. In the present work, experiments carried out with rat liver microsomes show that 1 is converted by hepatic cytochrome P450 to the corresponding unsaturated derivative 2 and to the corresponding pharmacologically inactive benzenesulfonamide 3. Surprisingly, patch-clamp experiments reveal that 2 displays an activity comparable to that of the parent compound. Molecular modeling studies were performed to rationalize these results. Furthermore, mice cerebral microdialysis studies suggest that 2 is able to cross the blood-brain barrier and increases acetylcholine and serotonin levels in the hippocampus. The experimental data disclose that the achiral hepatic metabolite 2 possesses the same pharmacological activity of its parent compound 1 but with an enhanced chemical and stereochemical stability, as well as an improved pharmacokinetic profile compared with 1. PMID:26580317

  16. Sexual assault in dating relationships.

    PubMed

    Rhynard, J; Krebs, M; Glover, J

    1997-03-01

    This article focuses on acquaintance rape, which under Canadian law constitutes a form of sexual assault. Frequency of acquaintance rape often is underestimated due to under-reporting, resulting in a local perception that acquaintance rape rarely occurs in a small Canadian community. A survey was conducted to determine whether acquaintance rape does occur in this community. One hundred sixty-four male and female students from grades 8-12 completed a questionnaire. Twenty-six percent of respondents reported being forced into some type of sexual activity. Based on the survey, this article explores the type of force used, the relationship between acquaintance rape and use of alcohol and drugs, and the relationship between acquaintance rape and the ability to indicate to a partner to stop a behavior. Results confirmed a need to develop programs to prevent rather than merely respond to issues of sexual assault on a date. PMID:9071669

  17. Retrospective Birth Dating of Cells

    SciTech Connect

    L.Spalding, K; Bhardwaj, R D; Buchholz, B A; Druid, H; Frisen, J

    2005-04-19

    The generation of cells in the human body has been difficult to study and our understanding of cell turnover is limited. Extensive testing of nuclear weapons resulted in a dramatic global increase in the levels of the isotope {sup 14}C in the atmosphere, followed by an exponential decrease after the test ban treaty in 1963. We show that the level of {sup 14}C in genomic DNA closely parallels atmospheric levels, and can be used to establish the time point when the DNA was synthesized and cells were born. We use this strategy to determine the age of cells in the cortex of the adult human brain, and show that whereas non-neuronal cells are exchanged, occipital neurons are as old as the individual, supporting the view that postnatal neurogenesis does not take place in this region. Retrospective birth dating is a generally applicable strategy that can be used to measure cell turnover in man under physiological and pathological conditions.

  18. New Radiocarbon Dates on Upper Mid-West Proboscideans: Determining Date Robustness

    NASA Astrophysics Data System (ADS)

    Hodgins, G.; Widga, C.; Lengyel, S. N.; Saunders, J.; Walker, J. D.

    2013-12-01

    With the objective of refining the picture of Megafaunal extinction patterns in the upper Midwest in the terminal Pleistocene, we have assembled for radiocarbon dating specimens from more than 80 distinct Mammut and Mammuthus remains from potentially late sites. So far, we have measurements for 65 bones, tusks and teeth, nearly double the extant number of published dates . These new specimens were all from museums rather than excavation sites, and 60% were known to be coated with a consolidant. The predominant consolidant was Butvar B-76, however shellac, Elmer's Glue, Glyptol were also noted in the conservation records, or deduced from knowledge of a particular museum's practices. Given the objective of the project is to identify extinction patterns, coupled with the wide prevalence of consolidants amongst the specimen set, it was imperative that testing be carried out to confirm that radiocarbon laboratory protocols removed the consolidants, so that ultimately the dates can be considered robust. To this end, key specimens were dated three times using different sample preparation protocols. These were 1) a solvent extraction followed by a modified Longin-plus -Base continuous flow collagen extraction method used in the NSF-Arizona AMS facility, 2) the solvent/modified Longin method plus ultrafiltration, and 3) solvent/modified Longin method plus hydroxyproline single amino acid dating. Among the specimens subjected to triplicate testing were some of the youngest late Wisconsin proboscidean specimens from the Upper Midwest Region. The data reveal general agreement between the different protocols, and suggested either limited penetration of consolidants into the specimens, or that the standard laboratory cleaning protocols were sufficient to remove traces from deep within bone, tooth or tusk tissue. The preservation of each specimen, recorded in terms of collagen content, C/N ratio and stable isotope values, indicated that most were actually well preserved, implying

  19. Thermoluminescence dating of Hawaiian basalt

    USGS Publications Warehouse

    May, Rodd James

    1979-01-01

    The thermoluminescence (TL) properties of plagioclase separates from 11 independently dated alkalic basalts 4,500 years to 3.3 million years old and 17 tholeiitic basalts 16 years to 450,000 years old from the Hawaiian Islands were investigated for the purpose of developing a TL dating method for young volcanic rocks. Ratios of natural to artificial TL intensity, when normalized for natural radiation dose rates, were used to quantify the thermoluminescence response of individual samples for age-determination purposes. The TL ratios for the alkalic basalt plagioclase were found to increase with age at a predictable exponential rate that permits the use of the equation for the best-fit line through a plot of the TL ratios relative to known age as a TL age equation. The equation is applicable to rocks ranging in composition from basaltic andesite to trachyte over the age range from about 2,000 to at least 250,000 years before present (B.P.). The TL ages for samples older than 50,000 years have a calculated precision of less than :t 10 percent and a potential estimated accuracy relative to potassium-argon ages of approximately :t 10 percent. An attempt to develop a similar dating curve for the tholeiitic basalts was not as successful, primarily because the dose rates are on the average lower than those for the alkalic basalts by a factor of 6, resulting in lower TL intensities in the tholeiitic basalts for samples of equivalent age, and also because the age distribution of dated material is inadequate. The basic TL properties of the plagioclase from the two rock types are similar, however, and TL dating of tholeiitic basalts should eventually be feasible over the age range 10,000 to at least 200,000 years B.P. The average composition of the plagioclase separates from the alkalic basalts ranges from oligoclase to andesine; compositional variations within this range have no apparent effect on the TL ratios. The average composition of the plagioclase from the tholeiitic

  20. A reexamination of amino acids in lunar soil

    NASA Technical Reports Server (NTRS)

    Brinton, K. L. F.; Bada, J. L.; Arnold, J. R.

    1993-01-01

    Amino acids in lunar soils provide an important indicator of the level of prebiotic organic compounds on the moon. The results provide insight into the chemistry of amino acid precursors, and furthermore, given the flux of carbonaceous material to the moon, we can evaluate the survival of organics upon impact. The amino acid contents of both hydrolyzed and unhydrolyzed hot-water extracts of Apollo 17 lunar soil were determined using ophthaldialdehyde/N-acetyl cysteine (OPA/NAC) derivatization followed by HPLC analysis. Previous studies of lunar amino acids were inconclusive, as the technique used (derivatization with ninhydrin followed by HPLC analysis) was unable to discriminate between cosmogenic amino acids and terrestrial contaminants. Cosmogenic amino acids are racemic, and many of the amino acids found in carbonaceous meteorites such as Murchison, i.e., alpha-amino-i-butyric acid (aib), are extremely rare on Earth. The ninhydrin method does not distinguish amino acid enantiomers, nor does it detect alpha-alkyl amino acids such as aib, whereas the OPA/NAC technique does both.

  1. A reexamination of amino acids in lunar soil

    NASA Astrophysics Data System (ADS)

    Brinton, K. L. F.; Bada, J. L.; Arnold, J. R.

    1993-03-01

    Amino acids in lunar soils provide an important indicator of the level of prebiotic organic compounds on the moon. The results provide insight into the chemistry of amino acid precursors, and furthermore, given the flux of carbonaceous material to the moon, we can evaluate the survival of organics upon impact. The amino acid contents of both hydrolyzed and unhydrolyzed hot-water extracts of Apollo 17 lunar soil were determined using ophthaldialdehyde/N-acetyl cysteine (OPA/NAC) derivatization followed by HPLC analysis. Previous studies of lunar amino acids were inconclusive, as the technique used (derivatization with ninhydrin followed by HPLC analysis) was unable to discriminate between cosmogenic amino acids and terrestrial contaminants. Cosmogenic amino acids are racemic, and many of the amino acids found in carbonaceous meteorites such as Murchison, i.e., alpha-amino-i-butyric acid (aib), are extremely rare on Earth. The ninhydrin method does not distinguish amino acid enantiomers, nor does it detect alpha-alkyl amino acids such as aib, whereas the OPA/NAC technique does both.

  2. 10 CFR 784.13 - Effective dates.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... following dates: (a) For advance waivers of identified inventions, i.e., inventions conceived prior to the...., inventions conceived or first actually reduced to practice after the effective date of the contract, on...

  3. 10 CFR 784.13 - Effective dates.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... following dates: (a) For advance waivers of identified inventions, i.e., inventions conceived prior to the...., inventions conceived or first actually reduced to practice after the effective date of the contract, on...

  4. 10 CFR 784.13 - Effective dates.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... following dates: (a) For advance waivers of identified inventions, i.e., inventions conceived prior to the...., inventions conceived or first actually reduced to practice after the effective date of the contract, on...

  5. 10 CFR 784.13 - Effective dates.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... following dates: (a) For advance waivers of identified inventions, i.e., inventions conceived prior to the...., inventions conceived or first actually reduced to practice after the effective date of the contract, on...

  6. 10 CFR 784.13 - Effective dates.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... following dates: (a) For advance waivers of identified inventions, i.e., inventions conceived prior to the...., inventions conceived or first actually reduced to practice after the effective date of the contract, on...

  7. 40 CFR 62.7102 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Nevada Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.7102 Effective date. The effective date of EPA approval...

  8. 40 CFR 62.602 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Arizona Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.602 Effective date. The effective date of EPA approval of...

  9. 40 CFR 62.602 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Arizona Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.602 Effective date. The effective date of EPA approval of...

  10. 40 CFR 62.7102 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Nevada Landfill Gas Emissions from Existing Municipal Solid Waste Landfills § 62.7102 Effective date. The effective date of EPA approval...

  11. Peer involvement in adolescent dating violence.

    PubMed

    Stephenson, Pam S; Martsolf, Donna; Draucker, Claire Burke

    2013-06-01

    This study investigated the ways in which peers are involved in adolescent dating violence. Eighty-eight young adults aged 18-21 were interviewed and asked to reflect on aggressive dating relationships they experienced as teens. The researchers used grounded theory to analyze the data. Findings showed that male and female peers were involved in adolescent dating violence in unique ways. Male peers were involved in dating violence by participating in the aggression, agitating the aggression, being the competition, trivializing the aggression, and keeping tabs on the recipient. Female peers were involved in dating violence by deserting the recipient, cheating with the boyfriend, being the audience, needling the male dating partner, and helping the recipient. Male and female peers were involved similarly in adolescent dating violence by confronting the partner. School nurses working with adolescents are uniquely positioned to approach adolescents about dating violence. Interventions aimed at promoting discussions with adolescents are discussed. PMID:23239788

  12. 7 CFR 1773.8 - Audit date.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... (CONTINUED) POLICY ON AUDITS OF RUS BORROWERS RUS Audit Requirements § 1773.8 Audit date. (a) The annual... change the as of audit date is obtained, in writing, from RUS. (1) A borrower may request a change in...

  13. 16 CFR 1207.2 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... STANDARD FOR SWIMMING POOL SLIDES § 1207.2 Effective date. This part 1207 shall become effective July 17, 1976. All swimming pool slides manufactured after that date must meet the requirements of this...

  14. 40 CFR 62.4626 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Phosphate Fertilizer Plants § 62.4626 Effective date. (a) The effective date of the portion of the plan applicable to phosphate fertilizer plants is July 12, 1982. Fluoride Emissions From Existing Primary...

  15. 40 CFR 62.4626 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Phosphate Fertilizer Plants § 62.4626 Effective date. (a) The effective date of the portion of the plan applicable to phosphate fertilizer plants is July 12, 1982. Fluoride Emissions From Existing Primary...

  16. 16 CFR 1207.2 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... STANDARD FOR SWIMMING POOL SLIDES § 1207.2 Effective date. This part 1207 shall become effective July 17, 1976. All swimming pool slides manufactured after that date must meet the requirements of this...

  17. Teaching the Mathematics of Radioactive Dating.

    ERIC Educational Resources Information Center

    Shea, James H.

    2001-01-01

    Describes a method used to teach the concept of radiometric dating using mathematical equations. Explores the lack of information in textbooks on how to solve radiometric dating problems using mathematical concepts. (SAH)

  18. What Is Rape and Date Rape?

    MedlinePlus

    ... What is rape and date rape? What is rape and date rape? Get help National Sexual Assault Hotline 800-656- ... drinking, it is NOT your fault. What is sexual assault? Sexual assault and abuse is any kind of ...

  19. 40 CFR 62.4671 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Industrial Solid Waste Incineration Units § 62.4671 Effective date. The effective date of this portion of the State's plan applicable to existing commercial and industrial solid waste incineration units is May...

  20. What are we Dating? An Evaluation of Chemical Pretreatment Methods for AMS 14C Dating of Peat

    NASA Astrophysics Data System (ADS)

    Scharer, K.; Kashgarian, M.; Zermeno, P.; Kurdyla, D.

    2006-12-01

    Progressive deformation of landforms commonly creates depositional environments where organic-rich sediment layers such as peats are preserved (e.g., Wrightwood, Coachella, Vedanta paleoseismic sites). Field studies using 3-D excavation methods can improve estimates of landform displacement, while AMS 14C dating of well characterized organic material sampled during field work is essential for determining slip rates associated with landform deformations. Here we present results of a test of chemical pretreatment used for AMS 14C dating of peat in an attempt to better characterize what we are dating and how the age of organic fractions is affected by different extraction procedures. Standard chemical pretreatment of organic materials for AMS 14C analysis typically isolates three broad organic fractions: humic acids, humin, and fulvic acids. Humic acids, the focus of this study, are thought to result from complex degradation of lignin and related compounds, and in principle should provide the most accurate age of in-situ organic layers (i.e., the decomposed leaf of a plant). The extraction of humic acid from organic-rich sediments or soils is operationally defined by chemical solubility and is not directly associated with a particular starting material. This means that chemical extracts are likely to contain humic acids derived from different starting materials which may have different ages and origins. In earlier studies of the duration of chemical pretreatment, Cook et al. (1998) found that increasing the amount of time that peat was exposed to NaOH increased the quantity of humics extracted, and Williams (1989) reported that increasing the duration of the NaOH wash will sometimes, but not always, result in an older sample age. Thus, a long base extraction time may solubilize more resistant and potentially older humics. To test whether the duration of the base extraction step affects dates, we extracted humic acid from three peat layers from the Wrightwood

  1. 7 CFR 987.58 - Terminal date.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Terminal date. 987.58 Section 987.58 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements... Terminal date. Dates covered by §§ 987.55 and 987.56 shall, by September 30 of the subsequent crop year...

  2. 16 CFR 1201.7 - Effective date.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 16 Commercial Practices 2 2012-01-01 2012-01-01 false Effective date. 1201.7 Section 1201.7 Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS SAFETY STANDARD FOR ARCHITECTURAL GLAZING MATERIALS The Standard § 1201.7 Effective date. The effective date of this part 1201 shall be July 6, 1977 except:...

  3. 29 CFR 4007.11 - Due dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Due dates. (a) In general. For flat-rate and variable-rate premiums, the premium filing due date for... variable-rate premium payment must be made by the last day of the sixteenth full calendar month following... payment year. (ii) The due date for the variable-rate premium required by § 4006.3(b) of this chapter...

  4. 16 CFR 1301.8 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 16 Commercial Practices 2 2010-01-01 2010-01-01 false Effective date. 1301.8 Section 1301.8 Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS BAN OF UNSTABLE REFUSE BINS § 1301.8 Effective date. The effective date of this ban shall be June 13, 1978....

  5. 19 CFR 351.701 - Applicability dates.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 19 Customs Duties 3 2011-04-01 2011-04-01 false Applicability dates. 351.701 Section 351.701 Customs Duties INTERNATIONAL TRADE ADMINISTRATION, DEPARTMENT OF COMMERCE ANTIDUMPING AND COUNTERVAILING DUTIES Applicability Dates § 351.701 Applicability dates. The regulations contained in this part...

  6. 19 CFR 351.701 - Applicability dates.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 19 Customs Duties 3 2010-04-01 2010-04-01 false Applicability dates. 351.701 Section 351.701 Customs Duties INTERNATIONAL TRADE ADMINISTRATION, DEPARTMENT OF COMMERCE ANTIDUMPING AND COUNTERVAILING DUTIES Applicability Dates § 351.701 Applicability dates. The regulations contained in this part...

  7. 29 CFR 4281.11 - Valuation dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false Valuation dates. 4281.11 Section 4281.11 Labor Regulations... Valuation of Plan Benefits and Plan Assets § 4281.11 Valuation dates. (a) Annual valuations of mass-withdrawal-terminated plans. The valuation dates for the annual valuation required under section 4281(b)...

  8. 20 CFR 217.16 - Filing date.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 20 Employees' Benefits 1 2010-04-01 2010-04-01 false Filing date. 217.16 Section 217.16 Employees... LUMP SUM Filing An Application § 217.16 Filing date. An application filed in a manner and form... received will result in the loss or reduction of benefits. (e) On the date the Social...

  9. 40 CFR 63.826 - Compliance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 11 2014-07-01 2014-07-01 false Compliance dates. 63.826 Section 63... Emission Standards for the Printing and Publishing Industry § 63.826 Compliance dates. (a) The compliance... is May 30, 1999. (b) The compliance date for an owner or operator of a new affected source subject...

  10. 40 CFR 51.1004 - Attainment dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 2 2012-07-01 2012-07-01 false Attainment dates. 51.1004 Section 51....5 National Ambient Air Quality Standards § 51.1004 Attainment dates. (a) Consistent with section 172(a)(2)(A) of the Act, the attainment date for an area designated nonattainment for the PM2.5...

  11. 7 CFR 987.13 - Free dates.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 8 2013-01-01 2013-01-01 false Free dates. 987.13 Section 987.13 Agriculture... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.13 Free dates. Free dates means... to acquire them at prices reasonably comparable with prices received domestically) and which are...

  12. 7 CFR 987.13 - Free dates.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 8 2012-01-01 2012-01-01 false Free dates. 987.13 Section 987.13 Agriculture... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.13 Free dates. Free dates means... to acquire them at prices reasonably comparable with prices received domestically) and which are...

  13. 7 CFR 987.13 - Free dates.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Free dates. 987.13 Section 987.13 Agriculture... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.13 Free dates. Free dates means... to acquire them at prices reasonably comparable with prices received domestically) and which are...

  14. 7 CFR 987.13 - Free dates.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 8 2014-01-01 2014-01-01 false Free dates. 987.13 Section 987.13 Agriculture... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.13 Free dates. Free dates means... to acquire them at prices reasonably comparable with prices received domestically) and which are...

  15. 7 CFR 987.13 - Free dates.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Free dates. 987.13 Section 987.13 Agriculture... RIVERSIDE COUNTY, CALIFORNIA Order Regulating Handling Definitions § 987.13 Free dates. Free dates means... to acquire them at prices reasonably comparable with prices received domestically) and which are...

  16. 21 CFR 211.137 - Expiration dating.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ..., strength, quality, and purity at the time of use, it shall bear an expiration date determined by appropriate stability testing described in § 211.166. (b) Expiration dates shall be related to any storage... for both the reconstituted and unreconstituted drug products. (d) Expiration dates shall appear...

  17. 37 CFR 42.407 - Filing date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 37 Patents, Trademarks, and Copyrights 1 2013-07-01 2013-07-01 false Filing date. 42.407 Section... COMMERCE TRIAL PRACTICE BEFORE THE PATENT TRIAL AND APPEAL BOARD Derivation § 42.407 Filing date. (a) Complete petition. A petition to institute a derivation proceeding will not be accorded a filing date...

  18. 40 CFR 57.106 - Expiration date.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Expiration date. 57.106 Section 57.106 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PRIMARY NONFERROUS SMELTER ORDERS General § 57.106 Expiration date. Each NSO shall state its expiration date. No...

  19. 37 CFR 42.206 - Filing date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 37 Patents, Trademarks, and Copyrights 1 2013-07-01 2013-07-01 false Filing date. 42.206 Section... date. (a) Complete petition. A petition to institute a post-grant review will not be accorded a filing date until the petition satisfies all of the following requirements: (1) Complies with § 42.204 or §...

  20. 21 CFR 211.137 - Expiration dating.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ..., strength, quality, and purity at the time of use, it shall bear an expiration date determined by appropriate stability testing described in § 211.166. (b) Expiration dates shall be related to any storage... for both the reconstituted and unreconstituted drug products. (d) Expiration dates shall appear...

  1. 40 CFR 57.106 - Expiration date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Expiration date. 57.106 Section 57.106 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PRIMARY NONFERROUS SMELTER ORDERS General § 57.106 Expiration date. Each NSO shall state its expiration date. No...

  2. 40 CFR 57.106 - Expiration date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Expiration date. 57.106 Section 57.106 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PRIMARY NONFERROUS SMELTER ORDERS General § 57.106 Expiration date. Each NSO shall state its expiration date. No...

  3. 40 CFR 57.106 - Expiration date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Expiration date. 57.106 Section 57.106 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PRIMARY NONFERROUS SMELTER ORDERS General § 57.106 Expiration date. Each NSO shall state its expiration date. No NSO issued under this regulation...

  4. 21 CFR 211.137 - Expiration dating.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ..., strength, quality, and purity at the time of use, it shall bear an expiration date determined by appropriate stability testing described in § 211.166. (b) Expiration dates shall be related to any storage... for both the reconstituted and unreconstituted drug products. (d) Expiration dates shall appear...

  5. 37 CFR 42.407 - Filing date.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 37 Patents, Trademarks, and Copyrights 1 2014-07-01 2014-07-01 false Filing date. 42.407 Section... COMMERCE TRIAL PRACTICE BEFORE THE PATENT TRIAL AND APPEAL BOARD Derivation § 42.407 Filing date. (a) Complete petition. A petition to institute a derivation proceeding will not be accorded a filing date...

  6. 40 CFR 57.106 - Expiration date.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Expiration date. 57.106 Section 57.106 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PRIMARY NONFERROUS SMELTER ORDERS General § 57.106 Expiration date. Each NSO shall state its expiration date. No...

  7. 21 CFR 211.137 - Expiration dating.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ..., strength, quality, and purity at the time of use, it shall bear an expiration date determined by appropriate stability testing described in § 211.166. (b) Expiration dates shall be related to any storage... for both the reconstituted and unreconstituted drug products. (d) Expiration dates shall appear...

  8. 37 CFR 42.206 - Filing date.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 37 Patents, Trademarks, and Copyrights 1 2014-07-01 2014-07-01 false Filing date. 42.206 Section... date. (a) Complete petition. A petition to institute a post-grant review will not be accorded a filing date until the petition satisfies all of the following requirements: (1) Complies with § 42.204 or §...

  9. Formation of Meteoritic Amino Acids: Isovaline and its Isomers

    NASA Astrophysics Data System (ADS)

    Hudson, Reggie; Moore, Marla; Dworkin, Jason

    It has been known for several decades that amino acids, and other complex organics, are found in meteorites. In particular, Murchison (CM) samples contain over seventy amino acids, these being identified by high-level chromatographic methods. Among Murchison's amino acids, isovaline stands out as being both non-biological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L- isovaline have been reported in Murchison and other CM meteorites, this molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of their D and L enantiomers. Ion-irradiated isovalineand valine-containing ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino-acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have synthesized isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings and place them in a context of related work. - Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM) and the Astrobiology Analytical Laboratory (JPD) at the NASA Goddard Space Flight Center.

  10. Amino acid geochemistry of fossil bones from the Rancho La Brea asphalt deposit, California

    USGS Publications Warehouse

    McMenamin, M.A.S.; Blunt, D.J.; Kvenvolden, K.A.; Miller, S.E.; Marcus, L.F.; Pardi, R.R.

    1982-01-01

    Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 ?? 10-6yr-1. Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 ?? 10-6yr-1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits. ?? 1982.

  11. Isoaspartic acid is present at specific sites in myelin basic protein from multiple sclerosis patients: could this represent a trigger for disease onset?

    PubMed

    Friedrich, Michael G; Hancock, Sarah E; Raftery, Mark J; Truscott, Roger J W

    2016-01-01

    Multiple sclerosis (MS) is associated with breakdown of the myelin sheath that coats neurons in the central nervous system. The cause of MS is not known, although the pathogenesis involves destruction of myelin by the immune system. It was the aim of this study to examine the abundant myelin protein, myelin basic protein (MBP), to determine if there are sites of modification that may be characteristic for MS. MBP from the cerebellum was examined from controls and MS patients across the age range using mass spectrometry and amino acid analysis. Amino acid racemization data indicated that myelin basic protein is long-lived and proteomic analysis of MBP showed it to be highly modified. A common modification of MBP was racemization of Asp and this was significantly greater in MS patients. In long-lived proteins, L-Asp and L-Asn can racemize to three other isomers, D-isoAsp, L-isoAsp and D-Asp and this is significant because isoAsp formation in peptides renders them immunogenic.Proteomic analysis revealed widespread modifications of MBP with two surface regions that are altered in MS. In particular, isoAsp was significantly elevated at these sites in MS patients. The generation of isoAsp could be responsible for eliciting an immune response to modified MBP and therefore be implicated in the etiology of MS. PMID:27519525

  12. Paleomagnetic dating of liesegang bands

    SciTech Connect

    Cochran, K.A.; Elmore, R.

    1985-01-01

    Paleomagnetic analysis, in conjunction with petrographic studies, was used to date the formation of hematite liesegang bands in the Ordovician Upper Arbuckle Group in southern Oklahoma. The hematite bands form symmetrical patterns on both sides of calcite-filled fractures in dolomite beds. The bands decrease in abundance and become more diffuse away from the fractures. Dedolomite is common near the fractures. Samples from distinctly banded dolomite near the fractures contain a relatively strong chemical remanent magnetization (CRM) with a southeasterly declination and shallow inclination. Samples farther from the fractures that are less distinctly banded or have no bands contain a weaker and less table CRM. Petrographic evidence and stable demagnetization to 600/sup 0/C indicate that the CRM resides in hematite. Samples were collected from both flanks of the Arbuckle Anticline (late Pennsylvanian folding), and a fold test demonstrates that the CRM is post-folding. The pole position for the CRM corresponds to the Early Permian (approx. 280 Ma) part of the Apparent Polar Wander Path for stable North America. These results suggest that the liesegang bands formed in the Early Permian, probably by rhythmic precipitation of hematite from fluids that moved out from the fractures. The fluids also apparently caused dedolomitization and precipitation of calcite in intercrystalline pore spaces. These fluids were probably the source of iron for the bands, although iron released from dedolimitization of ferroan dolomite may have been a local source.

  13. Two 1999 Dates Worth Noting

    NASA Technical Reports Server (NTRS)

    Stern, David P.

    1999-01-01

    Two dates in 1999 can serve as pivots for space-related educational outreach. On August 11 a total solar eclipse will sweep across Europe and also across the Near East, where it will come remarkably close to matching the ancient eclipse (probably in 129 BC) used by Hipparchus to estimate the distance of the Moon. Using published eclipse data, students may conduct a similar calculation for 1999 and in the process obtain insights about astronomy, history and the way scientists work. October 19, 1999 will be the 100th anniversary of the day when a teen-age Robert Goddard climbed a cherry tree near the Worcester home where his family was staying, intending to prune it. Sitting in that tree, Goddard began daydreaming about space flight, and by the time he came down he had resolved to dedicate his life to implementing that dream. He later marked that day as "Anniversary day," a personal holiday. Material on both subjects can be reached from http://www-spof.gsfc.nasa.gov/stargaze/Sintro.htm, sections 8a and 26. The section on Goddard includes his experiments with a ballistic pendulum and the DeLaval nozzle, which laid the essential scientific foundation of spaceflight and which is also suitable for classroom presentation.

  14. Thai female adolescents' perceptions of dating violence.

    PubMed

    Thongpriwan, Vipavee; McElmurry, Beverly J

    2009-10-01

    We explored how Thai female adolescents describe the meaning and context of dating violence. Twenty-four students, aged 15-17, were purposively recruited from a secondary school in Bangkok for individually audio-taped interviews. The interviews lasted 45- 70 minutes. ATLAS ti 5.2 was selected for content analysis. Five themes emerged, including characteristics of adolescent romantic relationships, influences on adolescent romantic relationships, perceptions of dating violence, cycle of dating-violence experiences, and influences on adolescents' perceptions of dating violence. The findings indicate a foundation for developing culturally sensitive programs for dating-violence prevention among Thai adolescents. PMID:19742362

  15. Abscisic Acid Structure-Activity Relationships in Barley Aleurone Layers and Protoplasts (Biological Activity of Optically Active, Oxygenated Abscisic Acid Analogs).

    PubMed

    Hill, R. D.; Liu, J. H.; Durnin, D.; Lamb, N.; Shaw, A.; Abrams, S. R.

    1995-06-01

    Optically active forms of abscisic acid (ABA) and their oxygenated metabolites were tested for their biological activity by examining the effects of the compounds on the reversal of gibberellic acid-induced [alpha]-amylase activity in barley (Hordeum vulgare cv Himalaya) aleurone layers and the induction of gene expression in barley aleurone protoplasts transformed with a chimeric construct containing the promoter region of an albumin storage protein gene. Promotion of the albumin storage protein gene response had a more strict stereochemical requirement for elicitation of an ABA response than inhibition of [alpha]-amylase gene expression. The naturally occurring stereoisomer of ABA and its metabolites were more effective at eliciting an ABA-like response. ABA showed the highest activity, followed by 7[prime]-hydroxyABA, with phaseic acid being the least active. Racemic 8[prime]-hydroxy-2[prime],3[prime]-dihydroABA, an analog of 8[prime]-hydroxyABA, was inactive, whereas racemic 2[prime],3[prime]-dihydroABA was as effective as ABA. The differences in response of the same tissue to the ABA enantiomers lead us to conclude that there exists more than one type of ABA receptor and/or multiple signal transduction pathways in barley aleurone tissue. PMID:12228494

  16. Abscisic Acid Structure-Activity Relationships in Barley Aleurone Layers and Protoplasts (Biological Activity of Optically Active, Oxygenated Abscisic Acid Analogs).

    PubMed Central

    Hill, R. D.; Liu, J. H.; Durnin, D.; Lamb, N.; Shaw, A.; Abrams, S. R.

    1995-01-01

    Optically active forms of abscisic acid (ABA) and their oxygenated metabolites were tested for their biological activity by examining the effects of the compounds on the reversal of gibberellic acid-induced [alpha]-amylase activity in barley (Hordeum vulgare cv Himalaya) aleurone layers and the induction of gene expression in barley aleurone protoplasts transformed with a chimeric construct containing the promoter region of an albumin storage protein gene. Promotion of the albumin storage protein gene response had a more strict stereochemical requirement for elicitation of an ABA response than inhibition of [alpha]-amylase gene expression. The naturally occurring stereoisomer of ABA and its metabolites were more effective at eliciting an ABA-like response. ABA showed the highest activity, followed by 7[prime]-hydroxyABA, with phaseic acid being the least active. Racemic 8[prime]-hydroxy-2[prime],3[prime]-dihydroABA, an analog of 8[prime]-hydroxyABA, was inactive, whereas racemic 2[prime],3[prime]-dihydroABA was as effective as ABA. The differences in response of the same tissue to the ABA enantiomers lead us to conclude that there exists more than one type of ABA receptor and/or multiple signal transduction pathways in barley aleurone tissue. PMID:12228494

  17. Memory for time: how people date events.

    PubMed

    Janssen, Steve M J; Chessa, Antonio G; Murre, Jaap M J

    2006-01-01

    The effect of different formats on the accuracy of dating news and the distribution of personal events was examined in four conditions. In the first, participants had to date events in the absolute time format (e.g., "July 2004"), and in the second, they had to date events in the relative time format (e.g., "3 weeks ago"). In the other conditions, they were asked to choose between the two formats. We found a small backward telescoping effect for recent news events and a large forward telescoping effect for remote events. Events dated in the absolute time format were more accurate than those dated in the relative time format. Furthermore, participants preferred to date news events with the relative time format and personal events with the absolute time format, as well as preferring to date remote events in the relative time format and recent events in the absolute time format. PMID:16686113

  18. Microstructures and Argon age dating

    NASA Astrophysics Data System (ADS)

    Forster, Marnie; Fitz Gerald, John; Lister, Gordon

    2010-05-01

    Microstructures can be dated using 40Ar/39Ar geochronology, but certain conditions apply. In particular the nature of the physical processes that took place during development of need be identified, and the pattern of gas release (and/or retention) during their evolution in nature, and subsequently in the mass spectrometer, during the measurement process. Most researchers cite temperature as the sole variable of importance. There is a belief that there is a single "closure temperature" or a "closure interval" above which the mineral is incapable of retaining radiogenic argon. This is a false conception. Closure is practically relevant only in circumstances that see a rock cooled relatively rapidly from temperatures that were high enough to prevent significant accumulation of radiogenic argon, to temperatures below which there is insignificant loss of radiogenic argon through the remainder of the geological history. These conditions accurately apply only to a limited subset - for example to rocks that cool rapidly from a melt and thereafter remain at or close to the Earth's surface, without subsequent ingress of fluids that would cause alteration and modification of microstructure. Some minerals in metamorphic rocks might display such "cooling ages" but in principle these data are difficult to interpret since they depend on the rate of cooling, the pressures that applied, and the subsequent geological history. Whereas the science of "cooling ages" is relatively well understood, the science of the Argon Partial Retention Zone is in its infancy. In the Argon PRZ it is evident that ages should (and do) show a strong correlation with microstructure. The difficulty is that, since diffusion of Argon is simultaneously multi-path and multi-scale, it is difficult to directly interrogate the distinct reservoirs that store gas populations and thus the age information that can be recorded as to the multiple events during the history of an individual microstructure. Laser

  19. Dating tectonic structures on Mercury

    NASA Astrophysics Data System (ADS)

    Giacomini, Lorenza; Massironi, Matteo; Marchi, Simone; Cremonese, Gabriele

    2013-04-01

    Mercury is a planet dominated by contractional features at a global scale, represented mainly by lobate scarps. These structures are the expression of surface-breaking thrust faults and are linear or arcuate features widely distributed on Mercury. Since they display a broad distribution of orientations their origin is hypothesized to be related to a global contraction. By summing of the crustal shortening associated to scarps, a decreasing of the planet radius of about 1-2 km (Strom et al., 1975, JGR, 80, 2478-2507) or more (Di Achille et al., 2012, Icarus, 221, 456-460) was calculated. This process was hypothesized to occur at the edge of the Late Heavy Bombardment (≥3.8 Ga ago) (Strom et al., 1975, JGR, 80, 2478-2507; Watters and Nimmo, 2010, in Planetary tectonics, 15-80). The Messenger cameras (MDIS WAC and NAC), acquired images of new regions of the Mercury surface that allowed us to detect several new lobate scarps especially where the illumination geometry is more favorable for structural analysis (Di Achille et al., 2012, Icarus, 221, 456-460). Among these a 350 km-long thrust has been detected crossing a peak ring basin (about 186 km of diameter), located at 3°87' N and 87°17'E. The region encircled within the inner ring of the basin is covered by a smooth plain with evidence of a sin-deformational emplacement. This allowed us to give an age constrain of the tectonic structure. Indeed our preliminary crater count dates the smooth plain at 3.7-3.6 Ga fixing a straight upper limit to the contractional deformation in this sector of the planet.

  20. Recyclable Ligands for the Non-Enzymatic Dynamic Kinetic Resolution of Challenging α-Amino Acids.

    PubMed

    Nian, Yong; Wang, Jiang; Zhou, Shengbin; Wang, Shuni; Moriwaki, Hiroki; Kawashima, Aki; Soloshonok, Vadim A; Liu, Hong

    2015-10-26

    Structurally simple and inexpensive chiral tridentate ligands were employed for substantially advancing the purely chemical dynamic kinetic resolution (DKR) of unprotected racemic tailor-made α-amino acids (TM-α-AAs), enabling the first DKR of TM-α-AAs bearing tertiary alkyl chains as well as multiple unprotected functional groups. Owing to the operationally convenient conditions, virtually complete stereoselectivity, and full recyclability of the source of chirality, this method should find wide applications for the preparation of TM-α-AAs, especially on large scale. PMID:26367134

  1. Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

    NASA Technical Reports Server (NTRS)

    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.

  2. Extraterrestrial amino acids in the Almahata Sitta meteorite

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

    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, β-amino-n-butyric acid, 2-amino-2-methylbutanoic acid (isovaline), and 2-aminopentanoic acid (norvaline) in the meteorite were racemic (D/L ˜ 1), indicating that these amino acids are indigenous to the meteorite and not terrestrial contaminants. Several other nonprotein amino acids were also identified in the meteorite above background levels including α-aminoisobutyric acid (α-AIB), 4-amino-2-methylbutanoic acid, 4-amino-3-methylbutanoic acid, and 3-, 4-, and 5-aminopentanoic acid. The total abundances of isovaline and α-AIB in Almahata Sitta are approximately 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 CI, 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, or introduced as a contaminant from unrelated meteorite clasts and chemically altered by α-decarboxylation.

  3. 16 CFR 680.28 - Effective date, compliance date, and prospective application.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Effective date, compliance date, and prospective application. 680.28 Section 680.28 Commercial Practices FEDERAL TRADE COMMISSION THE FAIR CREDIT REPORTING ACT AFFILIATE MARKETING § 680.28 Effective date, compliance date, and prospective application....

  4. 16 CFR 680.28 - Effective date, compliance date, and prospective application.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 16 Commercial Practices 1 2011-01-01 2011-01-01 false Effective date, compliance date, and prospective application. 680.28 Section 680.28 Commercial Practices FEDERAL TRADE COMMISSION THE FAIR CREDIT REPORTING ACT AFFILIATE MARKETING § 680.28 Effective date, compliance date, and prospective application....

  5. 16 CFR 680.28 - Effective date, compliance date, and prospective application.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 16 Commercial Practices 1 2014-01-01 2014-01-01 false Effective date, compliance date, and prospective application. 680.28 Section 680.28 Commercial Practices FEDERAL TRADE COMMISSION THE FAIR CREDIT REPORTING ACT AFFILIATE MARKETING § 680.28 Effective date, compliance date, and prospective application....

  6. 16 CFR 680.28 - Effective date, compliance date, and prospective application.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 16 Commercial Practices 1 2012-01-01 2012-01-01 false Effective date, compliance date, and prospective application. 680.28 Section 680.28 Commercial Practices FEDERAL TRADE COMMISSION THE FAIR CREDIT REPORTING ACT AFFILIATE MARKETING § 680.28 Effective date, compliance date, and prospective application....

  7. 16 CFR 680.28 - Effective date, compliance date, and prospective application.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 16 Commercial Practices 1 2013-01-01 2013-01-01 false Effective date, compliance date, and prospective application. 680.28 Section 680.28 Commercial Practices FEDERAL TRADE COMMISSION THE FAIR CREDIT REPORTING ACT AFFILIATE MARKETING § 680.28 Effective date, compliance date, and prospective application....

  8. Metabolic annotation of 2-ethylhydracrylic acid.

    PubMed

    Ryan, Robert O

    2015-08-25

    Increased levels of the organic acid, 2-ethylhydracrylic acid (2-EHA) occur in urine of subjects with impaired L(+)-isoleucine metabolism. Chiral intermediates formed during isoleucine degradation are (S) enantiomers. Blockage of (S) pathway flux drives racemization of (2S, 3S) L(+)-isoleucine and its (2S, 3R) stereoisomer, L(+)-alloisoleucine. This non-protein amino acid is metabolized to (R)-2-methylbutyryl CoA via enzymes common to branched chain amino acid degradation. Subsequently, (R) intermediates serve as alternate substrates for three valine metabolic enzymes, generating 2-EHA. Once formed, 2-EHA accumulates because it is poorly recognized by distal valine pathway enzymes. Thus, urinary 2-EHA represents a biomarker of isoleucine pathway defects. 2-EHA levels are also increased in rats exposed to the industrial solvent, ethylene glycol monomethyl ether or the neurotoxin precursor, 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine. In these cases, a block in (S) pathway isoleucine catabolism occurs at the level of (S)-2-methylbutyryl CoA conversion to tiglyl CoA via inhibition of electron transferring flavoprotein/ubiquinone oxidoreductase dependent reactions. Elevated urinary 2-EHA in propionyl CoA carboxylase deficiency and methylmalonic aciduria results from a buildup of distal intermediates in the (S) pathway of isoleucine degradation. In Barth syndrome and dilated cardiomyopathy with ataxia syndrome, 2-EHA is a byproduct of impeded propionyl CoA entry into the Krebs cycle. PMID:26115894

  9. Prionic Acid: An Effective Sex Attractant for an Important Pest of Sugarcane, Dorysthenes granulosus (Coleoptera: Cerambycidae: Prioninae).

    PubMed

    Wickham, Jacob D; Lu, Wen; Jin, Tao; Peng, Zhengqiang; Guo, Dongfeng; Millar, Jocelyn G; Hanks, Lawrence M; Chen, Yi

    2016-02-01

    Male Dorysthenes granulosus (Thomson, 1860) (Coleoptera: Cerambycidae: Prioninae) were caught in traps baited with racemic 3,5-dimethyldodecanoic acid (prionic acid) during field screening trials in China that tested known cerambycid pheromones. This species is an important pest of sugarcane (Saccharum officinarum L.). In follow-up dose-response trials, plastic sachets loaded with 1 or 0.1 mg of prionic acid were equally attractive to male beetles, whereas lower doses were no better than controls. Two commercial prionic acid lures also were attractive, suggesting that traps baited with prionic acid can be rapidly incorporated into integrated pest management programs targeting this major pest. It is likely that this compound is a major component of the female-produced sex pheromone of D. granulosus because this species is in the same subfamily as Prionus californicus Motschulsky, 1845, the species from which prionic acid was originally identified. PMID:26362990

  10. Correlates of cyber dating abuse among teens.

    PubMed

    Zweig, Janine M; Lachman, Pamela; Yahner, Jennifer; Dank, Meredith

    2014-08-01

    Recent advancements in technology (e.g., social networking, texting) have created new ways for dating youth to relate to one another, including in abusive ways via "cyber dating abuse." Cyber dating abuse is a form of teen dating violence that overlaps with other types of abuse (e.g., psychological) but also has several unique characteristics. Given the phenomenon's limited presence in dating violence literature, we focus on identifying how experiencing cyber dating abuse relates to youths' individual behaviors and experiences (e.g., substance use, sexual activity), psychosocial adjustment, school connection, family relationships, and partner relationships. A total of 3,745 youth (52% female, 74% White) in three northeastern states participated in the survey and reported currently being in a dating relationship or having been in one during the prior year. We found that experiences of cyber dating abuse were most significantly correlated with being female, committing a greater variety of delinquent behaviors, having had sexual activity in one's lifetime, having higher levels of depressive symptoms, and having higher levels of anger/hostility. Further, cyber dating abuse appeared somewhat more strongly related to depressive symptoms and delinquency than did other forms of teen dating violence and abuse. PMID:24198083

  11. Radiocarbon dates on bones of extinct birds from Hawaii

    SciTech Connect

    James, H.F.; Stafford, T.W. Jr.; Steadman, D.W.; Olson, S.L.; Martin, P.S.; Jull, A.J.; McCoy, P.C.

    1987-04-01

    Bones from a stratified sedimentary deposit in the Puu Naio Cave site on Maui, Hawaiian Islands, reveal the late Holocene extinction of 19 species of birds. The age of the sediment and associated fauna was determined by direct radiocarbon dating (tandem particle accelerator-mass spectrometer; TAMS) of amino acids extracted from bones weighing as little as 450 mg. The /sup 14/C dates indicate that sediment has been accumulating in the lava tube for at least the last 7750 years, a suitable time frame for testing the hypothesis that Holocene extinction on islands began after human colonization. Despite growing evidence that a worldwide wave of extinctions coincided with human colonization of oceanic islands, little radiometric data have been available to date the extinction of most small fossil vertebrates on islands. The TAMS technique of dating purified collagen from the bones of small vertebrates could lead to vastly improved chronologies of extinction for oceanic islands where catastrophic mid- to late-Holocene extinction is expected or known to have occurred. Chronologies derived from nonarcheological sites that show continuous sedimentation, such as the Puu Naio Cave deposit, may also yield key evidence on the timing of earliest human settlement of Oceania.

  12. Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

    NASA Technical Reports Server (NTRS)

    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.

  13. Solid-Phase Formation Of Isovaline, A Non-Biological, Meteoritic Amino Acid

    NASA Astrophysics Data System (ADS)

    Hudson, Reggie L.; Lewis, A. S.; Moore, M. H.; Dworkin, J. P.; Glavin, D. P.

    2007-10-01

    Among the Murchison (CM) meteoritic amino acids, isovaline stands out as being non-biological (nonprotein) and having a high abundance. Approximately equal amounts of D- and L-isovaline have been reported in CM meteorites, but the molecule's structure appears to prohibit racemization in aqueous solutions. While it is possible that isovaline could be made by the oft-studied Strecker reaction, laboratory experiments have seldom been able to produce this molecule from realistic molecular precursors. Recently we have investigated the low-temperature solid-phase chemistry of isovaline with an eye toward the molecule's formation, its stability, and the interconversion of its D- and L-enantiomers. Ion-irradiated isovaline-containing ices were examined by IR spectroscopy and highly-sensitive LC/ToF-MS methods to assess both amino acid destruction and racemization. Samples were studied both in the presence and absence of water-ice, and the destruction of isovaline was measured as a function of radiation dose. In addition, we have continued our earlier work on solid-phase amino acid formation, extending it to cover isovaline. In this presentation we will report the results of these newer investigations. This work was supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. AL was supported by an award from the Summer Undergraduate Internship in Astrobiology program.

  14. New 4-hydroxy-N-(2-hydroxyethyl)butanamides: Structure and acidity

    NASA Astrophysics Data System (ADS)

    Duarte-Hernández, Angélica M.; Contreras, Rosalinda; Suárez-Moreno, Galdina V.; González, Felipe J.; Flores-Parra, Angelina

    2015-02-01

    Optically active new 4-hydroxy-N-(2-hydroxyethyl)butanamides are reported. The structure in the solid state of four racemic mixtures and three enantiomeric pure compounds was determined by X-ray diffraction. The solid state arrangements of enantiomerically pure compounds were compared with those of their racemic mixtures. The butanamides prefer lineal conformations in the solid state. They form dimers and polymers through intermolecular hydrogen bonds. Variable temperature 1H NMR experiments were performed in order to analyse the strength of the hydrogen bonds in the neutral molecules in solution. The pKa values of the dihydroxybutanamides in DMSO determined by cyclic voltammetric (11.1-14.5) were lower than those reported for amides RNHCOR without hydroxyl groups (25.9). The latter motivated us to investigate the role of hydrogen bonds in the stabilization of the corresponding anions and in consequence in the acidity of the amides. The explanation of the enhanced Nsbnd H acidity of dihydroxybutanamides was found in the cyclic voltammetric experiments, in conductimetric titrations using nBu4NOH in methanol and titration with CsOH in acetonitrile. The optimised structures for the neutral molecules and their mono and dianions calculated by ab-initio HF(6-31 + G∗) and B3LYP(6-31 + G∗) methods supported the explanation of the enhanced Nsbnd H acidity.

  15. Binding of [alpha, alpha]-Disubstituted Amino Acids to Arginase Suggests New Avenues for Inhibitor Design

    SciTech Connect

    Ilies, Monica; Di Costanzo, Luigi; Dowling, Daniel P.; Thorn, Katherine J.; Christianson, David W.

    2011-10-21

    Arginase is a binuclear manganese metalloenzyme that hydrolyzes L-arginine to form L-ornithine and urea, and aberrant arginase activity is implicated in various diseases such as erectile dysfunction, asthma, atherosclerosis, and cerebral malaria. Accordingly, arginase inhibitors may be therapeutically useful. Continuing our efforts to expand the chemical space of arginase inhibitor design and inspired by the binding of 2-(difluoromethyl)-L-ornithine to human arginase I, we now report the first study of the binding of {alpha},{alpha}-disubstituted amino acids to arginase. Specifically, we report the design, synthesis, and assay of racemic 2-amino-6-borono-2-methylhexanoic acid and racemic 2-amino-6-borono-2-(difluoromethyl)hexanoic acid. X-ray crystal structures of human arginase I and Plasmodium falciparum arginase complexed with these inhibitors reveal the exclusive binding of the L-stereoisomer; the additional {alpha}-substituent of each inhibitor is readily accommodated and makes new intermolecular interactions in the outer active site of each enzyme. Therefore, this work highlights a new region of the protein surface that can be targeted for additional affinity interactions, as well as the first comparative structural insights on inhibitor discrimination between a human and a parasitic arginase.

  16. Radioiodinated methyl-branched fatty acids: Evaluation of catabolites formed in vivo

    SciTech Connect

    Knapp, F.F. Jr.; Reske, S.N.; Kirsch, G.; Ambrose, K.R.; Blystone, S.L.; Goodman, M.M.

    1987-01-01

    Radioiodinated terminal iodophenyl-substituted long-chain fatty acids containing either racemic mono-methyl or geminal dimethyl-branching in the alkyl chain have been shown to exhibit delayed myocardial clearance properties which make these agents useful for the SPECT evaluation of myocardial fatty acid uptake patterns. Although the myocardial clearance rate of 15-(p-iodophenyl)-3-R,S- methylpentadecanoic acid (BMIPP) is considerably delayed, in comparison with the IPPA straight-chain analogue, analysis of the radioiodinated lipids present in the outflow tract of isolated rat hearts administered BMIPP have clearly demonstrated the presence of a polar metabolite. The synthesis of ..beta..-hydroxy fatty acids has been developed to allow investigation of the possible formation of ..beta..-hydroxy catabolites in vivo. The preparation of ..beta..-hydroxy BMIPP and ..beta..-hydroxy IPPA are described, and the possible significance of their formation in vivo discussed. 4 figs.

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

    NASA Technical Reports Server (NTRS)

    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.

  18. 7 CFR 1485.24 - Applicability date.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... OF AGRICULTURE LOANS, PURCHASES, AND OTHER OPERATIONS COOPERATIVE AGREEMENTS FOR THE DEVELOPMENT OF FOREIGN MARKETS FOR AGRICULTURAL COMMODITIES Market Access Program § 1485.24 Applicability date....

  19. Desert date (Balanites aegyptiaca) as an arid lands sustainable bioresource for biodiesel.

    PubMed

    Chapagain, Bishnu P; Yehoshua, Yariv; Wiesman, Zeev

    2009-02-01

    The aim of this study was to assess the suitability of Desert date (Balanites aegyptiaca L. Delile) as an oil crop in arid lands for large-scale sustainable industrial biodiesel production. Characterization of the Desert date plant material showed that using proper cultivation practices with emphasis on low quality irrigation water trees can be extremely well developed in hyper-arid conditions of the Israeli Arava desert and yield oil-rich fruits. Best selected trees can yield date fruits up to 52 kg/trees. Desert date kernels oil content may reach up to 46.7% (based on dry weight). The oil is consisted on four major fatty acids: palmitic (16:0), stearic (18:0), oleic (18:1), and linoleic (18:2), constituting 98-100% of the total fatty acids in the oil of all tested genotypes. Linoleic acid was the most prevalent fatty acid, ranging from 31% to 51% of the fatty acids profile, very similar to soybean oil profile. In situ biodiesel production directly from oil-enriched powder was successfully developed. Yield efficiency for both conventional and in situ biodiesel production was about 90%. The qualities of the produced biodiesel well meet the international biodiesel standards. The present study clearly demonstrated Desert date as a model for the utilization of bioresources in the Israeli Arava desert and potentially other similar areas for cost-effective biodiesel production. PMID:18848776

  20. Analysis of Chiral Carboxylic Acids in Meteorites

    NASA Technical Reports Server (NTRS)

    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

  1. Development of HPLC Chiral Stationary Phases Based on (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic Acid and Their Applications.

    PubMed

    Hyun, Myung Ho

    2015-09-01

    Crown ether-based chiral stationary phases (CSPs) have been known to be useful for the resolution of racemic primary amino compounds. In particular, CSPs based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid have been reported to be useful for the resolution of secondary amino compounds as well as primary amino compounds. In this article, the process of developing various CSPs based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid to improve the chiral recognition efficiency and/or the stability of the CSPs and their applications to the resolution of various primary and nonprimary amino compounds are reviewed. PMID:26237013

  2. Lewis acid catalysed methylation of N-(9H-fluoren-9-yl)methanesulfonyl (Fms) protected lipophilic α-amino acid methyl esters.

    PubMed

    Leggio, Antonella; Alò, Danila; Belsito, Emilia Lucia; Di Gioia, Maria Luisa; Romio, Emanuela; Siciliano, Carlo; Liguori, Angelo

    2015-08-01

    This work reports an efficient Lewis acid catalysed N-methylation procedure of lipophilic α-amino acid methyl esters in solution phase. The developed methodology involves the use of the reagent system AlCl3/diazomethane as methylating agent and α-amino acid methyl esters protected on the amino function with the (9H-fluoren-9-yl)methanesulfonyl (Fms) group. The removal of Fms protecting group is achieved under the same conditions to those used for Fmoc removal. Thus the Fms group can be interchangeable with the Fmoc group in the synthesis of N-methylated peptides using standard Fmoc-based strategies. Finally, the absence of racemization during the methylation reaction and the removal of Fms group were demonstrated by synthesising a pair of diastereomeric dipeptides. PMID:25921656

  3. 40 CFR 141.6 - Effective dates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS (CONTINUED) NATIONAL PRIMARY DRINKING WATER REGULATIONS General § 141.6 Effective dates. (a) Except as provided in paragraphs...) shall take effect 2 years after the date of promulgation of these regulations for community...

  4. 40 CFR 141.6 - Effective dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS (CONTINUED) NATIONAL PRIMARY DRINKING WATER REGULATIONS General § 141.6 Effective dates. (a) Except as provided in paragraphs...) shall take effect 2 years after the date of promulgation of these regulations for community...

  5. 40 CFR 62.9171 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 8 2011-07-01 2011-07-01 false Effective date. 62.9171 Section 62.9171 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Oklahoma Effective Date. §...

  6. 40 CFR 62.9171 - Effective date.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Effective date. 62.9171 Section 62.9171 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Oklahoma Effective Date. §...

  7. 40 CFR 62.9171 - Effective date.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 9 2014-07-01 2014-07-01 false Effective date. 62.9171 Section 62.9171 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Oklahoma Effective Date. §...

  8. 40 CFR 62.9171 - Effective date.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 9 2013-07-01 2013-07-01 false Effective date. 62.9171 Section 62.9171 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Oklahoma Effective Date. §...

  9. 40 CFR 62.9171 - Effective date.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 9 2012-07-01 2012-07-01 false Effective date. 62.9171 Section 62.9171 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF STATE PLANS FOR DESIGNATED FACILITIES AND POLLUTANTS Oklahoma Effective Date. §...

  10. Teen Dating Violence Prevention Program Assessment

    ERIC Educational Resources Information Center

    Lucas, Quincy Arrianna Rose

    2013-01-01

    The American Psychological Association (APA) has identified the prevention of and intervention in relationship violence as a top priority (APA, n.d.). According to the Center for Disease Control and Prevention's 2012 Teen Dating Violence Fact Sheet, dating violence is a serious problem in the United States. In accordance with Foshee et al. (1998):…

  11. 39 CFR 601.101 - Effective date.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 39 Postal Service 1 2011-07-01 2011-07-01 false Effective date. 601.101 Section 601.101 Postal Service UNITED STATES POSTAL SERVICE PROCUREMENT SYSTEM FOR THE U.S. POSTAL SERVICE: INTELLECTUAL PROPERTY RIGHTS OTHER THAN PATENTS PURCHASING OF PROPERTY AND SERVICES § 601.101 Effective date. These...

  12. Peer Involvement in Adolescent Dating Violence

    ERIC Educational Resources Information Center

    Stephenson, Pam S.; Martsolf, Donna; Draucker, Claire Burke

    2013-01-01

    This study investigated the ways in which peers are involved in adolescent dating violence. Eighty-eight young adults aged 18-21 were interviewed and asked to reflect on aggressive dating relationships they experienced as teens. The researchers used grounded theory to analyze the data. Findings showed that male and female peers were involved in…

  13. 33 CFR 106.110 - Compliance dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 1 2014-07-01 2014-07-01 false Compliance dates. 106.110 Section 106.110 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY MARITIME SECURITY MARINE SECURITY: OUTER CONTINENTAL SHELF (OCS) FACILITIES General § 106.110 Compliance dates. (a) On...

  14. 33 CFR 106.110 - Compliance dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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  15. Dating Modern Deltas: Progress, Problems, and Prognostics

    NASA Astrophysics Data System (ADS)

    Stanley, Jean-Daniel

    Radiocarbon dating is the method most frequently used to date Holocene deltaic sequences, but less than one quarter of 14C dates are within +/-500 years of predicted age. Such dates tend to be unreliable, in other words, often too old and commonly inverted upsection, and core sample dates obtained near deltaic plain surfaces may be as old as mid- to late Holocene. Stratigraphic irregularities result primarily from downslope reworking of upland alluvial sediment, with displacement of "old carbon" in the sediment that accumulates in lower valleys and deltaic plains. Use of dates that are too old results in inaccurately calculated rates (most often too low) of relative sea-level rise and/or land subsidence. More reliable timing of deltaic sediment requires a multiple-method dating approach, including, where possible, identification of associated archaeological material. Developing an accurate dating strategy is a critical step for implementing reliable coastal protection measures needed for the rapidly increasing human populations in these low-lying, vulnerable nearshore settings.

  16. 40 CFR 211.202 - Effective date.

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    2013-07-01

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    Code of Federal Regulations, 2012 CFR

    2012-07-01

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    Code of Federal Regulations, 2014 CFR

    2014-07-01

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