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  • 1
    Electronic Resource
    Electronic Resource
    Racemisierungsstudien an cysteinhaltigen Peptiden (1978)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 3711-3718 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies upon the Racemisation of Cysteine-containing PeptidesThe thiosulfate derivatives of natural bovine insulin-A- and insulin-B chains and of several S-tritylcysteine peptides were hydrolysed and the degree of racemisation of the resulting amino acids was investigated by means of gas chromatography. It was found that those amino acids which are N-terminally linked to cysteine undergo racemisation to a high degree. GC-MS and UV spectroscopic investigations indicate that the racemisation occurs during hydrolysis and that it proceeds via a thiazoline derivative c. The method developed is generally applicable to the differentiation between D-enantiomers originally present in the sample and that formed by racemisation during hydrolysis.
    Notes: Die Thiosulfat-Derivate natürlicher Rinderinsulin-A- und Rinderinsulin-B-Ketten sowie einige S-Trityl-Cystein-Peptide wurden hydrolysiert und die Aminosäuren gaschromatographisch auf Racemisierung untersucht. Dabei zeigte sich, daß die jeweils an Cystein N-ständig gebundenen Aminosäuren ungewöhnlich hohe D-Anteile aufweisen. GC/MS-Experimente und UV-spektroskopische Untersuchungen weisen darauf hin, daß die Racemisierung unter den Hydrolysebedingungen erfolgt und über ein Thiazolin-Derivat c verläuft. Damit wurde eine Methode zur Unterscheidung der bei der Hydrolyse auftretenden D-Anteile von ursprünglich vorhandenen D-Enantiomeren-Anteilen erarbeitet.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19781111115
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Determination of the rate of acidic catalyzed racemization of protein amino acidsHerrn Prof. Dr. Helmut Zahn zum 65. Geburtstag gewidmet. (1981)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 354-365 
    Details
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Geschwindigkeitsbestimmung der säurekatalysierten Racemisierung von proteinogenen AminosäurenZur gaschromatographischen Bestimmung von Aminosäure-Enantiomeren in Proteinen und Peptiden müssen diese vorher sauer gespalten werden; die hierbei gleichzeitig ablaufende, durch Säure katalysierte Racemisierung führt zu erhöhten Anteilen von D-Enantiomeren, sowohl bei den gebundenen als auch bei den freien Aminosäuren. Zur Abschätzung dieses Beitrages wurde die Racemisierung aller proteinogenen Aminosäuren als Funktion der Zeit in stark saurem Medium bestimmt. Die erwartete Kinetik pseudoester Ordnung wurde in allen Fällen gefunden. Die ermittelten Inversionsgeschwindigkeiten sind mit den beim Insulin und Albumin gefundenen vergleichbar, außer in der Anfangsphase der Acidolyse, während der die Spaltung der Peptidbindungen noch unvollständig ist. Der größte Anteil der in Insulin und Albumin gefundenen D-Aminosäuren entsteht durch Racemisierung der freigesetzten Aminosäure und kann durch Verfolgung der Zeitabhängigkeit und Extrapolation auf t = 0 berücksichtigt werden. Die Racemisierungsgeschwindigkeit der proteinogenen Aminosäuren nimmt in der folgenden Reihenfolge ab: Asp = Cys 〉 Pro 〉 Glu 〉 Met 〉 His 〉 Leu 〉 Lys 〉 Phe 〉 Ala 〉 Tyr 〉 Arg 〉 Trp 〉 Val 〉 Ile 〉 Ser 〉 Thr.
    Notes: Determination of the enantiomeric composition of the amino acids of protein or peptide hydrolyzates by gas chromatography involves a hydrolytic step, in the course of which racemization may occur, leading to erroneously high values of D-enantiomer. Racemization of both protein-bound and free amino acids contribute to this formation of D-enantiomers. In order to estimate the latter contribution, the time-dependance of racemization for all protein amino acids during exposure to strong acid has been determined. The expected pseudo-first-order kinetic was confirmed in all cases. The rate constants are compared with those obtained for insulin and albumin and found to be of similar magnitude, except for the initial period of hydrolysis, when cleavage of peptide bonds is still incomplete. Most of the racemate generated during hydrolysis can be accounted for by a study of the time-dependance of racemization and extrapolation to zero-time. Racemization of the protein amino acids is decreasing in the following order: Asp = Cys, Pro, Glu, Met, His, Leu, Lys, Phe, Ala, Tyr, Arg, Trp, Val, Ile, Ser, Thr.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.198119810303
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  • 3
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    Synthesis of theC-terminal Decapeptide of Bovine Insulin B-Chain (1979)
    De Gruyter
    Details
    Publication Date: 1979-01-01
    Print ISSN: 0018-4888
    Topics: Biology , Chemistry and Pharmacology
    Published by De Gruyter
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  • 4
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    Mesoscale fine structure of a tropopause fold over mountains (2018)
    Copernicus
    Details
    Publication Date: 2018-10-30
    Description: We report airborne remote-sensing observations of a tropopause fold during two crossings of the polar front jet over northern Italy on 12 January 2016. The GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) observations allowed for a simultaneous mapping of temperature, water vapour, and ozone. They revealed deep, dry, and ozone-rich intrusions into the troposphere. The mesoscale fine structures of dry filaments at the cyclonic shear side north of the jet and tongues of moist air entraining tropospheric air into the stratosphere along the anticyclonic shear side south of the jet were clearly resolved by GLORIA observations. Vertically propagating mountain waves with recorded temperature residuals exceeding ±3 K were detected above the Apennines. Their presence enhanced gradients of all variables locally in the vicinity of the tropopause. The combination of H2O−O3 correlations with potential temperature reveals an active mixing region and shows clear evidence of troposphere-to-stratosphere and stratosphere-to-troposphere exchange. High-resolution short-term deterministic forecasts of ECMWF's integrated forecast system (IFS) applying GLORIA's observational filter reproduce location, shape, and depth of the tropopause fold very well. The fine structure of the mixing region, however, cannot be reproduced even with the 9 km horizontal resolution of the IFS, used here. This case study demonstrates convincingly the capabilities of linear limb-imaging observations to resolve mesoscale fine structures in the upper troposphere and lower stratosphere, validates the high quality of the IFS data, and suggests that mountain wave perturbations have the potential to modulate exchange processes in the vicinity of tropopause folds.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 5
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    Airborne limb-imaging measurements of temperature, HNO3, O3, ClONO2, H2O and CFC-12 during the Arctic winter 2015/2016: characterization, in situ validation and comparison to Aura/MLS (2018)
    Copernicus
    Details
    Publication Date: 2018-08-14
    Description: The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) was operated on board the German High Altitude and Long Range Research Aircraft (HALO) during the PGS (POLSTRACC/GW-LCYCLE/SALSA) aircraft campaigns in the Arctic winter 2015/2016. Research flights were conducted from 17 December 2015 until 18 March 2016 within 25–87∘ N, 80∘ W–30∘ E. From the GLORIA infrared limb-emission measurements, two-dimensional cross sections of temperature, HNO3, O3, ClONO2, H2O and CFC-12 are retrieved. During 15 scientific flights of the PGS campaigns the GLORIA instrument measured more than 15 000 atmospheric profiles at high spectral resolution. Dependent on flight altitude and tropospheric cloud cover, the profiles retrieved from the measurements typically range between 5 and 14 km, and vertical resolutions between 400 and 1000 m are achieved. The estimated total (random and systematic) 1σ errors are in the range of 1 to 2 K for temperature and 10 % to 20 % relative error for the discussed trace gases. Comparisons to in situ instruments deployed on board HALO have been performed. Over all flights of this campaign the median differences and median absolute deviations between in situ and GLORIA observations are -0.75K±0.88 K for temperature, -0.03ppbv±0.85 ppbv for HNO3, -3.5ppbv±116.8 ppbv for O3, -15.4pptv±102.8 pptv for ClONO2, -0.13ppmv±0.63 ppmv for H2O and -19.8pptv±46.9 pptv for CFC-12. Seventy-three percent of these differences are within twice the combined estimated errors of the cross-compared instruments. Events with larger deviations are explained by atmospheric variability and different sampling characteristics of the instruments. Additionally, comparisons of GLORIA HNO3 and O3 with measurements of the Aura Microwave Limb Sounder (MLS) instrument show highly consistent structures in trace gas distributions and illustrate the potential of the high-spectral-resolution limb-imaging GLORIA observations for resolving narrow mesoscale structures in the upper troposphere and lower stratosphere (UTLS).
    Print ISSN: 1867-1381
    Electronic ISSN: 1867-8548
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 6
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    Mixing and ageing in the polar lower stratosphere in winter 2015–2016 (2018)
    Copernicus
    Details
    Publication Date: 2018-05-02
    Description: We present data from winter 2015–2016, which were measured during the POLSTRACC (The Polar Stratosphere in a Changing Climate) aircraft campaign between December 2015 and March 2016 in the Arctic upper troposphere and lower stratosphere (UTLS). The focus of this work is on the role of transport and mixing between aged and potentially chemically processed air masses from the stratosphere which have midlatitude and low-latitude air mass fractions with small transit times originating at the tropical lower stratosphere. By combining measurements of CO, N2O and SF6 we estimate the evolution of the relative contributions of transport and mixing to the UTLS composition over the course of the winter. We find an increasing influence of aged stratospheric air partly from the vortex as indicated by decreasing N2O and SF6 values over the course of the winter in the extratropical lower and lowermost stratosphere between Θ=360 K and Θ=410 K over the North Atlantic and the European Arctic. Surprisingly we also found a mean increase in CO of (3.00 ± 1.64) ppbV from January to March relative to N2O in the lower stratosphere. We show that this increase in CO is consistent with an increased mixing of tropospheric air as part of the fast transport mechanism in the lower stratosphere surf zone. The analysed air masses were partly affected by air masses which originated at the tropical tropopause and were quasi-horizontally mixed into higher latitudes. This increase in the tropospheric air fraction partly compensates for ageing of the UTLS due to the diabatic descent of air masses from the vortex by horizontally mixed, tropospheric-influenced air masses. This is consistent with simulated age spectra from the Chemical Lagrangian Model of the Stratosphere (CLaMS), which show a respective fractional increase in tropospheric air with transit times under 6 months and a simultaneous increase in aged air from upper stratospheric and vortex regions with transit times longer than 2 years. We thus conclude that the lowermost stratosphere in winter 2015–2016 was affected by aged air from the upper stratosphere and vortex region. These air masses were significantly affected by increased mixing from the lower latitudes, which led to a simultaneous increase in the fraction of young air in the lowermost Arctic stratosphere by 6 % from January to March 2016.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 7
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    Widespread polar stratospheric ice clouds in the 2015–2016 Arctic winter – implications for ice nucleation (2018)
    Copernicus
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    Publication Date: 2018-10-30
    Description: Low planetary wave activity led to a stable vortex with exceptionally cold temperatures in the 2015–2016 Arctic winter. Extended areas with temperatures below the ice frost point temperature Tice persisted over weeks in the Arctic stratosphere as derived from the 36-year temperature climatology of the ERA-Interim reanalysis data set of the European Centre for Medium-Range Weather Forecasts (ECMWF). These extreme conditions promoted the formation of widespread polar stratospheric ice clouds (ice PSCs). The space-borne Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument on board the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) satellite continuously measured ice PSCs for about a month with maximum extensions of up to 2×106 km2 in the stratosphere. On 22 January 2016, the WALES (Water Vapor Lidar Experiment in Space – airborne demonstrator) lidar on board the High Altitude and Long Range Research Aircraft HALO detected an ice PSC with a horizontal length of more than 1400 km. The ice PSC extended between 18 and 24 km altitude and was surrounded by nitric acid trihydrate (NAT) particles, supercooled ternary solution (STS) droplets and particle mixtures. The ice PSC occurrence histogram in the backscatter ratio to particle depolarization ratio optical space exhibits two ice modes with high or low particle depolarization ratios. Domain-filling 8-day back-trajectories starting in the high particle depolarization (high-depol) ice mode are continuously below the NAT equilibrium temperature TNAT and decrease below Tice∼10 h prior to the observation. Their matches with CALIPSO PSC curtain plots demonstrate the presence of NAT PSCs prior to high-depol ice, suggesting that the ice had nucleated on NAT. Vice versa, STS or no PSCs were detected by CALIPSO prior to the ice mode with low particle depolarization ratio. In addition to ice nucleation in STS potentially having meteoric inclusions, we find evidence for ice nucleation on NAT in the Arctic winter 2015–2016. The observation of widespread Arctic ice PSCs with high or low particle depolarization ratios advances our understanding of ice nucleation in polar latitudes. It further provides a new observational database for the parameterization of ice nucleation schemes in atmospheric models.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 8
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    Denitrification, dehydration and ozone loss during the 2015/2016 Arctic winter (2017)
    Copernicus
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    Publication Date: 2017-11-01
    Description: The 2015/2016 Arctic winter was one of the coldest stratospheric winters in recent years. A stable vortex formed by early December and the early winter was exceptionally cold. Cold pool temperatures dropped below the nitric acid trihydrate (NAT) existence temperature of about 195 K, thus allowing polar stratospheric clouds (PSCs) to form. The low temperatures in the polar stratosphere persisted until early March, allowing chlorine activation and catalytic ozone destruction. Satellite observations indicate that sedimentation of PSC particles led to denitrification as well as dehydration of stratospheric layers. Model simulations of the 2015/2016 Arctic winter nudged toward European Centre for Medium-Range Weather Forecasts (ECMWF) analysis data were performed with the atmospheric chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC) for the Polar Stratosphere in a Changing Climate (POLSTRACC) campaign. POLSTRACC is a High Altitude and Long Range Research Aircraft (HALO) mission aimed at the investigation of the structure, composition and evolution of the Arctic upper troposphere and lower stratosphere (UTLS). The chemical and physical processes involved in Arctic stratospheric ozone depletion, transport and mixing processes in the UTLS at high latitudes, PSCs and cirrus clouds are investigated. In this study, an overview of the chemistry and dynamics of the 2015/2016 Arctic winter as simulated with EMAC is given. Further, chemical–dynamical processes such as denitrification, dehydration and ozone loss during the 2015/2016 Arctic winter are investigated. Comparisons to satellite observations by the Aura Microwave Limb Sounder (Aura/MLS) as well as to airborne measurements with the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) performed aboard HALO during the POLSTRACC campaign show that the EMAC simulations nudged toward ECMWF analysis generally agree well with observations. We derive a maximum polar stratospheric O3 loss of ∼ 2 ppmv or 117 DU in terms of column ozone in mid-March. The stratosphere was denitrified by about 4–8 ppbv HNO3 and dehydrated by about 0.6–1 ppmv H2O from the middle to the end of February. While ozone loss was quite strong, but not as strong as in 2010/2011, denitrification and dehydration were so far the strongest observed in the Arctic stratosphere in at least the past 10 years.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 9
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    Superposition of gravity waves with different propagation characteristics observed by airborne and space-borne infrared sounders (2020)
    Copernicus
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    Publication Date: 2020-10-07
    Description: Many gravity wave analyses, based on either observations or model simulations, assume the presence of only a single dominant wave. This paper shows that there are much more complex cases with gravity waves from multiple sources crossing each others' paths. A complex gravity wave structure consisting of a superposition of multiple wave packets was observed above southern Scandinavia on 28 January 2016 with the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA). The tomographic measurement capability of GLORIA enabled a detailed 3-D reconstruction of the gravity wave field and the identification of multiple wave packets with different horizontal and vertical scales. The larger-scale gravity waves with horizontal wavelengths of around 400 km could be characterised using a 3-D wave-decomposition method. The smaller-scale wave components with horizontal wavelengths below 200 km were discussed by visual inspection. For the larger-scale gravity wave components, a combination of gravity-wave ray-tracing calculations and ERA5 reanalysis fields identified orography as well as a jet-exit region and a low-pressure system as possible sources. All gravity waves are found to propagate upward into the middle stratosphere, but only the orographic waves stay directly above their source. The comparison with ERA5 also shows that ray tracing provides reasonable results even for such complex cases with multiple overlapping wave packets. Despite their coarser vertical resolution compared to GLORIA measurements, co-located AIRS measurements in the middle stratosphere are in good agreement with the ray tracing and ERA5 results, proving once more the validity of simple ray-tracing models. Thus, this paper demonstrates that the high-resolution GLORIA observations in combination with simple ray-tracing calculations can provide an important source of information for enhancing our understanding of gravity wave propagation.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
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  • 10
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    Nitrification of the lowermost stratosphere during the exceptionally cold Arctic winter 2015–2016 (2019)
    Copernicus
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    Publication Date: 2019-11-11
    Description: The Arctic winter 2015–2016 was characterized by exceptionally low stratospheric temperatures, favouring the formation of polar stratospheric clouds (PSCs) from mid-December until the end of February down to low stratospheric altitudes. Observations by GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) on HALO (High Altitude and LOng range research aircraft) during the PGS (POLSTRACC–GW-LCYCLE II–SALSA) campaign from December 2015 to March 2016 allow the investigation of the influence of denitrification on the lowermost stratosphere (LMS) with a high spatial resolution. Two-dimensional vertical cross sections of nitric acid (HNO3) along the flight track and tracer–tracer correlations derived from the GLORIA observations document detailed pictures of wide-spread nitrification of the Arctic LMS during the course of an entire winter. GLORIA observations show large-scale structures and local fine structures with enhanced absolute HNO3 volume mixing ratios reaching up to 11 ppbv at altitudes of 13 km in January and nitrified filaments persisting until the middle of March. Narrow coherent structures tilted with altitude of enhanced HNO3, observed in mid-January, are interpreted as regions recently nitrified by sublimating HNO3-containing particles. Overall, extensive nitrification of the LMS between 5.0 and 7.0 ppbv at potential temperature levels between 350 and 380 K is estimated. The GLORIA observations are compared with CLaMS (Chemical Lagrangian Model of the Stratosphere) simulations. The fundamental structures observed by GLORIA are well reproduced, but differences in the fine structures are diagnosed. Further, CLaMS predominantly underestimates the spatial extent of HNO3 maxima derived from the GLORIA observations as well as the overall nitrification of the LMS. Sensitivity simulations with CLaMS including (i) enhanced sedimentation rates in case of ice supersaturation (to resemble ice nucleation on nitric acid trihydrate (NAT)), (ii) a global temperature offset, (iii) modified growth rates (to resemble aspherical particles with larger surfaces) and (iv) temperature fluctuations (to resemble the impact of small-scale mountain waves) slightly improved the agreement with the GLORIA observations of individual flights. However, no parameter could be isolated which resulted in a general improvement for all flights. Still, the sensitivity simulations suggest that details of particle microphysics play a significant role for simulated LMS nitrification in January, while air subsidence, transport and mixing become increasingly important for the simulated HNO3 distributions towards the end of the winter.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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