共查询到20条相似文献,搜索用时 0 毫秒
1.
A confined aquifer in the Malm Karst of the Franconian Alb, South Germany was investigated in order to understand the role of the vadose zone in denitrifiaction processes. The concentrations of chemical tracers Sr2+ and Cl– and concentrations of stable isotope 18O were measured in spring water and precipitation during storm events. Based on these measurements a conceptual model for runoff was constructed. The results indicate that pre-event water, already stored in the system at the beginning of the event, flows downslope on vertical and lateral preferential flow paths. Chemical tracers used in a mixing model for hydrograph separation have shown that the pre-event water contribution is up to 30%. Applying this information to a conceptual runoff generation model, the values of 15N and 18O in nitrate could be calculated. Field observations showed the occurence of significant microbial denitrification processes above the soil/bedrock interface before nitrate percolates through to the deeper horizon of the vadose zone. The source of nitrate could be determined and denitrification processes were calculated. Assuming that the nitrate reduction follows a Rayleigh process one could approximate a nitrate input concentration of about 170 mg/l and a residual nitrate concentration of only about 15%. The results of the chemical and isotopic tracers postulate fertilizers as nitrate source with some influence of atmospheric nitrate. The combined application of hydrograph separation and determination of isotope values in 15N and 18O of nitrate lead to an improved understanding of microbial processes (nitrification, denitrification) in dynamic systems. 相似文献
2.
Koh Takeuchi Dominique P. Frueh Zhen-Yu J. Sun Sebastian Hiller Gerhard Wagner 《Journal of biomolecular NMR》2010,47(1):55-63
We present a 13C direct detection CACA-TOCSY experiment for samples with alternate 13C–12C labeling. It provides inter-residue correlations between 13Cα resonances of residue i and adjacent Cαs at positions i − 1 and i + 1. Furthermore, longer mixing times yield correlations to Cα nuclei separated by more than one residue. The experiment also provides Cα-to-sidechain correlations, some amino acid type identifications and estimates for ψ dihedral angles. The power of the experiment
derives from the alternate 13C–12C labeling with [1,3-13C] glycerol or [2-13C] glycerol, which allows utilizing the small scalar 3JCC couplings that are masked by strong 1JCC couplings in uniformly 13C labeled samples. 相似文献
3.
We present two NMR experiments, (3,2)D HNHA and (3,2)D HNHB, for rapid and accurate measurement of 3J(H N-H alpha) and 3J(N-H beta) coupling constants in polypeptides based on the principle of G-matrix Fourier transform NMR spectroscopy and quantitative J-correlation. These experiments, which facilitate fast acquisition of three-dimensional data with high spectral/digital resolution and chemical shift dispersion, will provide renewed opportunities to utilize them for sequence specific resonance assignments, estimation/characterization of secondary structure with/without prior knowledge of resonance assignments, stereospecific assignment of prochiral groups and 3D structure determination, refinement and validation. Taken together, these experiments have a wide range of applications from structural genomics projects to studying structure and folding in polypeptides. 相似文献
4.
The limits of resolution that can be obtained in 1H–15N 2D NMR spectroscopy of isotopically enriched nanocrystalline proteins are explored. Combinations of frequency switched Lee–Goldburg (FSLG) decoupling, fast magic angle sample spinning (MAS), and isotopic dilution via deuteration are investigated as methods for narrowing the amide 1H resonances. Heteronuclear decoupling of 15N from the 1H resonances is also studied. Using human ubiquitin as a model system, the best resolution is most easily obtained with uniformly 2H and 15N enriched protein where the amides have been exchanged in normal water, MAS at 20 kHz, and WALTZ-16 decoupling of the 15N nuclei. The combination of these techniques results in average 1H lines of only 0.26 ppm full width at half maximum. Techniques for optimizing instrument stability and 15N decoupling are described for achieving the best possible performance in these experiments. 相似文献
5.
V. A. Belyaev M. M. Dubrovin D. A. Kozlov A. A. Terent’ev A. E. Trenin G. V. Sholin 《Plasma Physics Reports》2010,36(11):964-968
D2− ions produced in collisions of D− ions with relative energies of 2.5–9.2 eV were detected for the first time. It is shown that the effective cross section
for this reaction is no less than 1.5 × 10−14 cm2. Along with the theoretically predicted short-lived state of negative molecular deuterium ions, a state existing for more
than 1 μs was observed. 相似文献
6.
The structures and stabilities of eleven N13
+ and N13
– isomers have been investigated with second-order Møller–Plesset (MP2) and density functional theory (DFT) methods. Five N13
+ isomers and six N13
– isomers are all reasonable local minima on their potential energy hypersurfaces. The most stable N13
+ cation is structure C-2 with C2v symmetry, which contains a pentazole ring and two N4 open chains. It is different from those of the N7
+ and N9
+ clusters, but similar to the N11
+ cluster. Meanwhile, the most stable N13
– structure A-2 is composed of a pentazole ring and a six-membered ring connected by two nitrogen atoms. It is not only different from those of the N7
– and N9
– clusters, but also from the N11
– cluster. The decomposition pathways of structures C-2 and A-2 were investigated at the B3LYP/(aug)-cc-pVDZ level. From the barrier heights of the structures C-2 and A-2 decomposition processes, it is suggested that C-2 is difficult to observe experimentally and A-2 may be observed as a short-lived species.
Figure Optimized geometrical parameters of N13
+ isomer C-2
相似文献
7.
Morgan Botrel Laura A. Bristow Mark A. Altabet Irene Gregory-Eaves Roxane Maranger 《Biogeochemistry》2017,135(3):221-237
Nitrate dual stable isotopes (δ15N and δ18O of NO3 ?) have proven to be a powerful technique to elucidate nitrogen (N) cycling pathways in aquatic systems. We applied this technique for the first time in the pelagic zone of a small temperate meso-eutrophic lake to identify the dominant N cycling pathways, and their spatial and temporal variability. We measured the lake NO3 ? δ15N and δ18O signatures over an annual cycle and compared them to that of the watershed. Both δ15N and δ18O of NO3 ? in the lake increased during summer relative to the inputs. Relationships between lake NO3 ? isotopic composition and concentrations were different across thermal strata with an apparent isotope effect in the epilimnion of 15εepi = 4.6‰ and 18εepi = 10.9‰. We found a strong deviation of the lake NO3 ? δ18O and δ15N from the expected 1:1 line for assimilation (slope = 1.73) suggesting that nitrification was co-occurring. We estimated that nitrification could support between 5 and 30% of nitrate-based production during the growing season, but was negligible in early spring and fall, and probably more dominant under ice. We showed that the technique is promising to study N processes at the ecosystem scale in shallow lakes, particularly during winter. Our results suggest that recycled NO3 ? could support primary productivity and influence phytoplankton composition in the surface waters of small lakes. 相似文献
8.
V. A. Belyaev D. A. Kozlov A. A. Terent’ev A. E. Trenin 《Plasma Physics Reports》2017,43(10):1039-1041
A method for determining the lifetime of unstable ions is described. The method is based on measuring the decrease in the ion beam current onto a fixed detector with increasing path length of the ion beam from the ion source to the detector. The measurements performed for D? 2 and HD? molecular ions have shown that their lifetimes are 3.5 ± 0.1 and 4.4 ± 0.1 μs, respectively. 相似文献
9.
10.
Martin D. Gelenter Tuo Wang Shu-Yu Liao Hugh O’Neill Mei Hong 《Journal of biomolecular NMR》2017,68(4):257-270
Site-specific determination of molecular motion and water accessibility by indirect detection of 2H NMR spectra has advantages over dipolar-coupling based techniques due to the large quadrupolar couplings and the ensuing high angular resolution. Recently, a Rotor Echo Short Pulse IRrAdiaTION mediated cross polarization (RESPIRATIONCP) technique was developed, which allowed efficient transfer of 2H magnetization to 13C at moderate 2H radiofrequency field strengths available on most commercial MAS probes. In this work, we investigate the 2H–13C magnetization transfer characteristics of one-bond perdeuterated CD n spin systems and two-bond H/D exchanged C–(O)–D and C–(N)–D spin systems in carbohydrates and proteins. Our results show that multi-bond, broadband 2H–13C polarization transfer can be achieved using 2H radiofrequency fields of ~50 kHz, relatively short contact times of 1.3–1.7 ms, and with sufficiently high sensitivity to enable 2D 2H–13C correlation experiments with undistorted 2H spectra in the indirect dimension. To demonstrate the utility of this 2H–13C technique for studying molecular motion, we show 2H–13C correlation spectra of perdeuterated bacterial cellulose, whose surface glucan chains exhibit a motionally averaged C6 2H quadrupolar coupling that indicates fast trans-gauche isomerization about the C5–C6 bond. In comparison, the interior chains in the microfibril core are fully immobilized. Application of the 2H–13C correlation experiment to H/D exchanged Arabidopsis primary cell walls show that the O–D quadrupolar spectra of the highest polysaccharide peaks can be fit to a two-component model, in which 74% of the spectral intensity, assigned to cellulose, has a near-rigid-limit coupling, while 26% of the intensity, assigned to matrix polysaccharides, has a weakened coupling of 50 kHz. The latter O–D quadrupolar order parameter of 0.22 is significantly smaller than previously reported C–D dipolar order parameters of 0.46–0.55 for pectins, suggesting that additional motions exist at the C–O bonds in the wall polysaccharides. 2H–13C polarization transfer profiles are also compared between statistically deuterated and H/D exchanged GB1. 相似文献
11.
12.
Khandekar Jishan Bari Shrikant Sharma Kandala V. R. Chary 《Biomolecular NMR assignments》2018,12(1):51-55
γS-crystallin is a major structural component of the human eye lens, which maintains its stability over the lifetime of an organism with negligible turnover. The G57W mutant of human γS-crystallin (abbreviated hereafter as γS-G57W) is associated with dominant congenital cataracts. In order to provide a structural basis for the ability of γS-G57W causing cataract, we have cloned, overexpressed, isolated and purified the protein. The 2D [15N–1H]-HSQC spectrum recorded with uniformly 13C/15N-labelled γS-G57W was highly dispersed indicating the protein to adopt an ordered conformation. In this paper, we report almost complete sequence-specific 1H, 13C and 15N resonance assignments of γS-G57W using a suite of heteronuclear 3D NMR experiments. 相似文献
13.
Nishit Goradia Amelie Wißbrock Christoph Wiedemann Frank Bordusa Ramadurai Ramachandran Diana Imhof Oliver Ohlenschläger 《Biomolecular NMR assignments》2016,10(2):329-333
Interleukin-36α (IL-36α) is a recently characterised member of the interleukin-1 superfamily. It is involved in the pathogenesis of inflammatory arthritis in one third of psoriasis patients. By binding of IL-36α to its receptor IL-36R via the NF-κB pathway other cytokines involved in inflammatory and apoptotic cascade are activated. The efficacy of complex formation is controlled by N-terminal processing. To obtain a more detailed view on the structure function relationship we performed a heteronuclear multidimensional NMR investigation and here report the 1H, 13C, and 15N resonance assignments for the backbone and side chain nuclei of the pro-inflammatory cytokine interleukin-36α. 相似文献
14.
15.
Muhammad Usman Akbar Tanveer Hussain Bokhari Samina Roohi Khalid Mahmood Zia Mohammad Zuber Nadia Parveen Narmeen Ali 《Russian Journal of Bioorganic Chemistry》2016,42(5):491-496
Human biosynthetic insulin is a polypeptide hormone that plays an important and essential role in control of the level of carbohydrate, protein, and fat metabolism in the blood. Human pancreatic insulin was labeled with 99mTc to form a new radiopharmaceutical with a labeling yield of 99 ± 1% under optimum conditions: 0.1 mL insulin, pH 7, 25 μg stannous chloride, 1 mL (19 mCi) of pertechnetate, room temperature, and 10 min reaction time. The 99mTc–insulin complex was examined using paper chromatography, ITLC, electrophoresis, and HPLC. In addition, in vitro and in vivo study of 99mTc–insulin complex was performed at different time intervals. 相似文献
16.
In two mountain ecosystems at the Alptal research site in central Switzerland, pulses of 15NO3 and 15NH4 were separately applied to trace deposited inorganic N. One forested and one litter meadow catchment, each approximately
1600 m2, were delimited by trenches in the Gleysols. K15NO3 was applied weekly or fortnightly over one year with a backpack sprayer, thus labelling the atmospheric nitrate deposition.
After the sampling and a one-year break, 15NH4Cl was applied as a second one-year pulse, followed by a second sampling campaign. Trees (needles, branches and bole wood),
ground vegetation, litter layer and soil (LF, A and B horizon) were sampled at the end of each labelling period. Extractable
inorganic N, microbial N, and immobilised soil N were analysed in the LF and A horizons. During the whole labelling period,
the runoff water was sampled as well. Most of the added tracer remained in both ecosystems. More NO3− than NH4+ tracer was retained, especially in the forest. The highest recovery was in the soil, mainly in the organic horizon, and in
the ground vegetation, especially in the mosses. Event-based runoff analyses showed an immediate response of 15NO3− in runoff, with sharp 15N peaks corresponding to discharge peaks. NO3− leaching showed a clear seasonal pattern, being highest in spring during snowmelt. The high capacity of N retention in these
ecosystems leads to the assumption that deposited N accumulates in the soil organic matter, causing a progressive decline
of its C:N ratio. 相似文献
17.
Imino 1H–15N residual dipolar couplings (RDCs) provide additional structural information that complements standard 1H–1H NOEs leading to improvements in both the local and global structure of RNAs. Here, we report measurement of imino 1H–1H RDCs for the Iron Responsive Element (IRE) RNA and native E. coli tRNAVal using a BEST-Jcomp-HMQC2 experiment. 1H–1H RDCs are observed between the imino protons in G–U wobble base pairs and between imino protons on neighboring base pairs
in both RNAs. These imino 1H–1H RDCs complement standard 1H–15N RDCs because the 1H–1H vectors generally point along the helical axis, roughly perpendicular to 1H–15N RDCs. The use of longitudinal relaxation enhancement increased the signal-to-noise of the spectra by ~3.5-fold over the
standard experiment. The ability to measure imino 1H–1H RDCs offers a new restraint, which can be used in NMR domain orientation and structural studies of RNAs.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
18.
Simon Drew Iona Flett Joanne Wilson Henk Heijnis C. Gregory Skilbeck 《Hydrobiologia》2008,608(1):35-47
In an attempt to determine the trophic history of the Myall Lakes complex (New South Wales, Australia) δ13Corg, δ15N and Corg:N profiles were determined for bulk organic matter of two short sediment cores from Bombah Broadwater and Myall Lake. 210Pb profiles and sediment types indicate significantly different trophic trajectories during the time periods examined. δ13Corg and Corg:N indicate Bombah Broadwater has been dominated by increasing inputs of terrestrial organic material over the last century,
thought to be related to watershed disturbance including agricultural activity. Primary production appears to be dominated
by phytoplankton. δ15N remained relatively stable at around 1‰ until the mid–1970s when there was a sharp increase to 4.7‰, interpreted as an influx
of sewage-derived material. These observations offer an insight into the recent trophic changes at the site. Sedimentation
rates are noticeably lower in Myall Lake and the most recent sediment is a flocculent organic rich deposit overlying mineral
clay. δ13Corg and Corg:N values indicate a transition from plankton to macrophyte dominated primary production around 1800AD. δ15N values become increasingly negative from approximately 1900AD. This is interpreted as being due to increasing reliance by
macrophytes on nitrogen recycled from decomposing sediments driven by natural infilling and eutrophication in this basin.
The contrasting sedimentation rates, sediment types and geochemical profiles suggest the different basins of this water body
are subject to substantially different internal and external influences which should be considered in management decisions. 相似文献
19.
Cui Y Karunasekara Y Harvey PJ Board PG Dulhunty AF Casarotto MG 《Journal of biomolecular NMR》2005,32(1):89-90
20.
E. Yu. Aleshina N. V. Pyndyk A. A. Moisa M. A. Sanzhakov O. N. Kharybin E. N. Nikolaev E. F. Kolesanova 《Biochemistry (Moscow) Supplemental Series B: Biomedical Chemistry》2008,2(3):288-292
The peptide RHDSGY, a fragment of the human β-amyloid Zn-binding site, and its isomers RH(D-Asp)SGY and RH(β-Asp)SGY have been obtained as amides by means of solid-phase synthesis and analyzed by HPLC and various mass spectrometric methods. The problem of low yield of the RHDSGY peptide and its isomers attributed to 9-fluorenylmethoxycarbonyl (Fmoc)-amino acids and/or formation of such side-products as RH(β-Asp)SGY (or RHDSGY during synthesis of RH(β-Asp)SGY) and RH(Asp-imide) SGY was solved via selection of individual reagents for removal of Fmoc groups from α-amino groups of the growing peptide chain. 相似文献