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1.
By applying a two-dimensional double-quantum carbon-13 nuclear magnetic resonance experiment to a protein uniformly enriched to 26 percent carbon-13, networks of directly bonded carbon atoms were identified by virtue of their one-bond spin-spin couplings and were classified by amino acid type according to their particular single- and double-quantum chemical shift patterns. Spin systems of 75 of the 98 amino acid residues in a protein, oxidized Anabaena 7120 ferredoxin (molecular weight 11,000), were identified by this approach, which represents a key step in an improved methodology for assigning protein nuclear magnetic resonance spectra. Missing spin systems corresponded primarily to residues located adjacent to the paramagnetic iron-sulfur cluster.  相似文献   

2.
Individual pentacene-d(14) molecules doped into a p-terphenyl-d(14) host crystal have been studied by optically detected electron paramagnetic resonance spectroscopy. The magnetic resonance transitions between the triplet sublevels of the pentacene molecule and the splitting of the resonance lines for a molecule that contains a carbon-13 nucleus have been observed in an external magnetic field. This splitting is caused by the hyperfine interaction of the triplet electron spin with the single carbon-13 nuclear spin.  相似文献   

3.
Human serum lipoproteins have been studied by Fourier transform nuclear magnetic resonance of carbon-13 in natural abundance. Spectra of highdensity, low-density, and very-low-density lipoproteins were recorded and partly assigned. The prominent features of these spectra reflect the qualitative and quantitative composition of the lipid moiety of these complexes. The results suggest that carbon-13 nuclear magnetic resonance will be a useful technique for studies of the structural and dynamic parameters of lipoproteins.  相似文献   

4.
本文报道了从Hackelia californica中分离和鉴定的两种新的吡略里西啶类生物碱的结构,并与相近结构的latifoline拉替夫林进行了比较。  相似文献   

5.
An intracellular coenzyme has been observed by carbon-13 nuclear magnetic resonance spectroscopy. The pyridine nucleotides in Escherichia coli were specifically labeled with carbon-13 from the biosynthetic precursor, nicotinic acid. The intracellular redox status and metabolic transformations of the pyridine nucleotides were examined under a variety of conditions. A highly reduced nicotinamide adenine dinucleotide pool was observed under anaerobic conditions only in cells that were cultured aerobically on glycerol.  相似文献   

6.
A method is presented that dramatically improves the resolution of protein nuclear magnetic resonance (NMR) spectra by increasing their dimensionality to four. The power of this technique is demonstrated by the application of four-dimensional carbon-13--nitrogen-15 (13C-15N)--edited nuclear Overhauser effect (NOE) spectroscopy to interleukin-1 beta, a protein of 153 residues. The NOEs between NH and aliphatic protons are first spread out into a third dimension by the 15N chemical shift of the amide 15N atom and subsequently into a fourth dimension by the 13C chemical shift of the directly bonded 13C atoms. By this means ambiguities in the assignment of NOEs between NH and aliphatic protons that are still present in the three-dimensional 15N-edited NOE spectrum due to extensive chemical shift overlap and degeneracy of aliphatic resonances are completely removed. Consequently, many more approximate interproton distance restraints can be obtained from the NOE data than was heretofore possible, thereby expanding the horizons of three-dimensional structure determination by NMR to larger proteins.  相似文献   

7.
The development of line-narrowing techniques, such as magic-angle spinning (MAS) and high-power decoupling, has led to powerful high-resolution nuclear magnetic resonance approaches for solid samples. In favorable cases (for instance, where high abundances of protons are present) cross polarization (CP) provides a means of circumventing the time bottleneck caused by inefficient spinlattice relaxation in many solids. The combined CP-MAS approach for carbon-13 with proton decoupling has become a popular and routine experiment for organic solids. For many nuclides with spin quantum number /> (1/2) the central nuclear magnetic resonance transition can be employed in high-resolution experiments that involve rapid sample spinning. A continuing stream of advances holds great promise for the use of high-resolution techniques for the characterization of solids by a wide range of nuclides.  相似文献   

8.
The tritium and carbon-14 activities of seawater samples collected from 22 to 200 meters below the ice at the Ross Ice Shelf Project ice hole are reported. The tritium results show that the waters below the ice have exchanged with Ross Sea water since the advent of nuclear testing. The carbon-14 results indicate that waters in the upper layer exchange in time periods of less than 6 years. Measurements of these isotopes in seawater under the Ross Ice Shelf in McMurdo Sound show that this water has a different history.  相似文献   

9.
High-field carbon-13 nuclear magnetic resonance (NMR) spectroscopy has been used to monitor the isotopic dilution of doubly carbon-13-labeled precursors for 2,3-cyclopyrophosphoglycerate, a novel primary metabolite that occurs in certain methanogens. A unique carbon dioxide fixation pathway that gives rise to asymmetric labeling of acetyl coenzyme A has been demonstrated in Methanobacterium thermoautotrophicum. The effect of selected metabolic inhibitors on the labeled species in the pathway has been examined by NMR. These techniques establish a general, sensitive method for the delineation of convergent biosynthetic pathways.  相似文献   

10.
GOPEB based upon known mesons have been found which realistically describe a massive accumulation of the experimental nuclear data up to 400 Mev. The N-N potential according to these models consists primarily of weak residual central terms surviving the cancellation of large repulsive and attractive vector and scalar static components; relativistic interactions arising from the exchange of pseudoscalar, vector, and scalar mesons and dipole type terms arising from the rho meson. The major dynamic terms are direct analogs of magnetic interactions illustrated in Fig. 1. Allowance must be made for the effective dependence of the coupling constants upon spin and isospin states. The nucleons are distributed sources which give rise to nonsingular generalized Yukawa functions in N-N potentials.  相似文献   

11.
The carbon-13/carbon-12 ratios of the carbonate and collagen fractions of bone of the sympatric hyrax species Procavia johnstoni and Heterohyrax brucei indicate that the former obtains most of its diet by grazing while the latter is primarily a browser. The carbon-13/carbon-12 ratios of these fractions in fossil bone will record information about diet if they have not been altered during diagenesis.  相似文献   

12.
High-resolution carbon-13 nuclear magnetic resonance (NMR) spectra of enzyme-inhibitor and enzyme-substrate complexes provide detailed structural and stereochemical information on the mechanism of enzyme action. The proteases trypsin and papain are shown to form tetrahedrally coordinated complexes and acyl derivatives with a variety of compounds artificially enriched at the site or sites of interest. These results are compared with the structural information derived from x-ray diffraction. Detailed NMR studies have provided a clearer picture of the ionization state of the residues participating in enzyme-catalyzed processes than other more classical techniques. The dynamics of enzymic catalysis can be observed at sub-zero temperatures by a combination of cryoenzymology and carbon-13 NMR spectroscopy. With these powerful techniques, transient, covalently bound intermediates in enzyme-catalyzed reactions can be detected and their structures rigorously assigned.  相似文献   

13.
Understanding and controlling the complex environment of solid-state quantum bits is a central challenge in spintronics and quantum information science. Coherent manipulation of an individual electron spin associated with a nitrogen-vacancy center in diamond was used to gain insight into its local environment. We show that this environment is effectively separated into a set of individual proximal 13C nuclear spins, which are coupled coherently to the electron spin, and the remainder of the 13C nuclear spins, which cause the loss of coherence. The proximal nuclear spins can be addressed and coupled individually because of quantum back-action from the electron, which modifies their energy levels and magnetic moments, effectively distinguishing them from the rest of the nuclei. These results open the door to coherent manipulation of individual isolated nuclear spins in a solid-state environment even at room temperature.  相似文献   

14.
The variability of the carbon-13/carbon-12 ratio in honeys was evaluated preliminary to use of the ratio to detect the addition of high-fructose corn syrup to honey. Eighty-four honey samples representing 34 states and including 37 floral types from 17 plant families were analyzed. The mean value of the per mil increment in carbon-13 (delta13C) for all samples is -25.2 per mil, and the coefficient of variation is 3.7 percent. This is the smallest variation yet encountered for a honey constituent or physical property. The range and magnitude of the values suggest that the floral sources are C(3) plants.  相似文献   

15.
The process of osmoregulation in a unicellular blue-green alga, Synechococcus sp., has been studied by natural-abundance carbon-13 nuclear magnetic resonance spectroscopy of intact cells and cell extracts. 2-O-alpha-D-Glucopyranosylglycerol was identified as the major organic osmoregulatory solute. This demonstrates the presence of a major osmoregulatory solute in a blue-green alga and is also an example of an osmoregulatory role for glucosylglycerol.  相似文献   

16.
Multiplicities in the resonances of chemically equivalent carbons, which appear in the solid-state carbon-13 nuclear magnetic resonance spectra of native celluloses, have been examined at high resolution. The patterns of variation are consistent with the existence of two distinct crystalline forms. One form is dominant in bacterial and algal celluloses, whereas the other is dominant in celluloses from higher plants.  相似文献   

17.
The chain conformation of glassy poly(ethylene terephthalate) (PET) was characterized by two-dimensional double-quantum nuclear magnetic resonance (NMR). In amorphous carbon-13-labeled PET, the statistics of the O-13CH2-13CH2-O torsion angle were determined, on the basis of the distinct shapes of the two-dimensional NMR patterns of trans and gauche conformations. In crystalline PET, the trans content is 100 percent, but in the amorphous PET it is only 14 percent (+/-5 percent). An average gauche torsion angle of 70 degrees (+/-9 degrees) was obtained. Implications for materials properties of polyesters are discussed.  相似文献   

18.
Glucose naturally labeled with carbon-13: use for metabolic studies in man   总被引:2,自引:0,他引:2  
The ratio of carbon-13 to carbon-12 is much higher in most commerical preparations of glucose used for oral glucose tolerance tests than it is in carbon dioxide in expired air. This recent discovery provided a novel and potentially significant means of studying glucose metabolism. The changes in the ratio of carbon-13 to carbon-12 in carbon dioxide expired after oral glucose administration were determined by mass spectrometry. In six healthy male volunteers, the administration of glucose resulted in a marked, reproducible rise in the isotopic ratio in expired carbon dioxide; the ratio reached its maximum at 4 hours and then declined progressively.  相似文献   

19.
The Murchison and Allende chondrites contain up to 5 parts per million carbon that is enriched in carbon-13 by up to + 1100 per mil (the ratio of carbon-12 to carbon-13 is approximately 42, compared to 88 to 93 for terrestrial carbon). This "heavy" carbon is associated with neon-22 and with anomalous krypton and xenon showing the signature of the s-process (neutron capture on a slow time scale). It apparently represents interstellar grains ejected from late-type stars. A second anomalous xenon component ("CCFXe") is associated with a distinctive, light carbon (depleted in carbon-13 by 38 per mil), which, however, falls within the terrestrial range and hence may be of either local or exotic origin.  相似文献   

20.
Lignins and suberins are complex plant cell-wall macromolecules that are composed mainly of phenylpropanoid residues derived from L-phenylalanine. Lignins and suberins are considered to be covalently linked to carbohydrates and to lipids, respectively. The bonding of these important structural materials within cell walls has never been established. By feeding specifically labeled [(13)C] ferulic acid over extended durations to seedlings of Triticum aestivum L. and by using solid-state carbon-13 nuclear magnetic resonance techniques, the major resonances due to specific carbons in the propanoid side chains of these cell-wall polymers have been identified in situ. The signals were found to differ significantly from those of synthetic lignins, which have usually been considered to be good approximations of natural lignin structure.  相似文献   

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