Search results for "carbon isotopes"
showing 10 items of 111 documents
Noble gas and CO2 isotopic signatures of the lithospheric mantle underneath Mexico and the Canary Islands: clues from mantle xenoliths and arc lavas
2022
Studying the isotopic composition of fluids trapped in mantle xenoliths opens avenues to understand the origin and cycling of volatiles in the Earth’s upper mantle. In this PhD dissertation, new and in most cases the very first data regarding the isotopic (noble gases and CO2) characterization of the lithospheric mantle portions of three different geodynamic environments are presented: (i) Central and NW Mexico, a continental setting dominated by extension; (ii) the Transmexican Volcanic Belt (TMVB) a subduction setting, and (iii) the Canary Islands, particularly El Hierro and Lanzarote, two oceanic islands formed by mantle plume-derived intraplate volcanism. In total 32 peridotites (includ…
Unraveling the role of protein dynamics in dihydrofolate reductase catalysis
2013
Protein dynamics have controversially been proposed to be at the heart of enzyme catalysis, but identification and analysis of dynamical effects in enzyme-catalyzed reactions have proved very challenging. Here, we tackle this question by comparing an enzyme with its heavy ((15)N, (13)C, (2)H substituted) counterpart, providing a subtle probe of dynamics. The crucial hydride transfer step of the reaction (the chemical step) occurs more slowly in the heavy enzyme. A combination of experimental results, quantum mechanics/molecular mechanics simulations, and theoretical analyses identify the origins of the observed differences in reactivity. The generally slightly slower reaction in the heavy e…
A computationally feasible quantum chemical model for 13C NMR chemical shifts of PCB-derived carboxylic acids.
2004
Two quantum chemical models have been derived for the prediction of 13C NMR chemical shifts of novel PCB acids obtained from PCBs by catalytic carbonylation. 13C isotropic shielding constants were calculated employing the GIAO (gauge-independent atomic orbital) method with density functional theory (DFT). The best results were obtained by cluster calculations, which took the solvent effects into account properly. In this approach, a solvent molecule (acetone) was attached by a hydrogen bond to every hydrogen atom present in a PCB acid, and the geometry of the molecular cluster was optimized employing the AM1 method. For 158 chemical shifts, the cross-validated standard error was 2.8 ppm and…
What is the form of muscimol from fly agaric mushroom (Amanita muscaria) in water? An insight from NMR experiment supported by molecular modeling.
2020
ARTYKUŁ Z BADAŃ SPECJALNYCH
Structural, Thermoanalytical and Molecular Modeling Studies on N-(3-hydroxypropyl) 3a,12a-Dihydroxy-5b-cholan-24-amide and Its Monohydrates
2007
The synthetic method for preparing N-(3-hydroxypropyl) 3 alpha,12 alpha-dihydroxy-5 beta-cholan-24-amide can lead to formation of at least three different crystal forms - an anhydrous compound and two monohydrates. The structural and thermal properties of these forms have been characterized by 13C-CP/MAS-NMR and IR spectroscopy, thermo- gravimetry, differential scanning calorimetry and by powder and single crystal x-ray crystallography. In addition, theoretical 13C-NMR chemical shift calculations were also performed for the anhydrous compound and for the first monohydrate, starting from single crystal structures and the structures of these species have now been verified. The first monohydra…
Combined use of 13C chemical shift and 1H alpha-13C alpha heteronuclear NOE data in monitoring a protein NMR structure refinement.
1995
A large portion of the 13C resonance assignments for murine epidermal growth factor (mEGF) at pH 3.1 and 28 degrees C has been determined at natural isotope abundance. Sequence-specific 13C assignments are reported for 100% of the assignable C alpha, 96% of the C beta, 86% of the aromatic and 70% of the remaining peripheral aliphatic resonances of mEGF. A good correlation was observed between experimental and back-calculated C alpha chemical shifts for regions of regular beta-sheet structure. These assignments also provide the basis for interpreting 1H alpha-13C alpha heteronuclear NOE (HNOE) values in mEGF at natural isotope abundance. Some of the backbone polypeptide segments with high in…
Protein isotope effects in dihydrofolate reductase from Geobacillus stearothermophilus show entropic-enthalpic compensatory effects on the rate const…
2014
Catalysis by dihydrofolate reductase from the moderately thermophilic bacterium Geobacillus stearothermophilus (BsDHFR) was investigated by isotope substitution of the enzyme. The enzyme kinetic isotope effect for hydride transfer was close to unity at physiological temperatures but increased with decreasing temperatures to a value of 1.65 at 5 °C. This behavior is opposite to that observed for DHFR from Escherichia coli (EcDHFR), where the enzyme kinetic isotope effect increased slightly with increasing temperature. These experimental results were reproduced in the framework of variational transition-state theory that includes a dynamical recrossing coefficient that varies with the mass of…
High-resolution records of growth temperature and life history of two Nacella limpet species, Tierra del Fuego, Argentina
2020
Stable isotope ratios in patelloid limpets of the genus Patella have been established as proxies for coastal environmental change at sub-monthly resolution along the eastern North Atlantic and Mediterranean Sea. Nacella deaurata (Gmelin, 1791) and N. magellanica (Gmelin, 1791) are common intertidal species of patelloid limpets inhabiting the coast of Tierra del Fuego, Argentina/Chile and are commonly found in Holocene archaeological deposits. Here, we examine oxygen and carbon isotope ratios (δ18Oshell and δ13Cshell, respectively) of modern specimens of N. deaurata and N. magellanica to test the hypotheses that: 1) they form their shells in isotopic equilibrium with ambient water; and 2) pr…
Stable carbon isotopic composition of peat columns, subsoil and vegetation on natural and forestry-drained boreal peatlands.
2018
We studied natural and forestry-drained peatlands to examine the effect of over 34 years lowered water table on the δ13C values of vegetation, bulk peat and subsoil. In the seven studied sites, δ13C in the basal peat layer was 1.1 and 1.2 ‰ lower than that of the middle-layer and surface layer, respectively. Furthermore, there was a positive correlation between the δ13C values of the basal and surface peat layers, possibly due to carbon (C) recycling within the peat column. In the same mire complex, natural fen peat δ13C values were lower than those of the nearby bog, possibly due to the dominance of vascular plants on fen and the generally larger share of recycled C in the fens than in the…
Methanotrophy induces nitrogen fixation during peatland development
2013
Significance In peatlands, the external sources of nitrogen are mainly atmospheric, but the atmospheric nitrogen deposition alone cannot explain the long-term annual nitrogen accumulation rates to these ecosystems. Because of methodological problems, methane-induced fixation of atmospheric dinitrogen gas has been previously overlooked as an additional nitrogen input mechanism. We found that the activity of methane-oxidizing bacteria provides not only carbon but also nitrogen to peat mosses and, thus, contributes to carbon and nitrogen accumulation in peatlands, which store approximately one-third of the global soil carbon pool. Our results imply that nitrogen fixation in wetlands may be str…