Use of 13C Nuclear Magnetic Resonance To Assess Fossil Fuel Biodegradation: Fate of [1-13C]Acenaphthene in Creosote Polycyclic Aromatic Compound Mixtures Degraded by Bacteria

1998 ◽  
Vol 64 (4) ◽  
pp. 1447-1453 ◽  
Author(s):  
Sergey A. Selifonov ◽  
Peter J. Chapman ◽  
Simon B. Akkerman ◽  
Jerome E. Gurst ◽  
Jacqueline M. Bortiatynski ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Mixed Culture ◽  
Isotope Labeling ◽  
Partial Transformation ◽  
Polycyclic Aromatic Compound ◽  
13C Nuclear Magnetic Resonance ◽  
Polycyclic Aromatic ◽  
C Nmr ◽  
Nuclear Magnetic

ABSTRACT [1-13C]acenaphthene, a tracer compound with a nuclear magnetic resonance (NMR)-active nucleus at the C-1 position, has been employed in conjunction with a standard broad-band-decoupled13C-NMR spectroscopy technique to study the biodegradation of acenaphthene by various bacterial cultures degrading aromatic hydrocarbons of creosote. Site-specific labeling at the benzylic position of acenaphthene allows 13C-NMR detection of chemical changes due to initial oxidations catalyzed by bacterial enzymes of aromatic hydrocarbon catabolism. Biodegradation of [1-13C]acenaphthene in the presence of naphthalene or creosote polycyclic aromatic compounds (PACs) was examined with an undefined mixed bacterial culture (established by enrichment on creosote PACs) and with isolates of individual naphthalene- and phenanthrene-degrading strains from this culture. From13C-NMR spectra of extractable materials obtained in time course biodegradation experiments under optimized conditions, a number of signals were assigned to accumulated products such as 1-acenaphthenol, 1-acenaphthenone, acenaphthene-1,2-diol and naphthalene 1,8-dicarboxylic acid, formed by benzylic oxidation of acenaphthene and subsequent reactions. Limited degradation of acenaphthene could be attributed to its oxidation by naphthalene 1,2-dioxygenase or related dioxygenases, indicative of certain limitations of the undefined mixed culture with respect to acenaphthene catabolism. Coinoculation of the mixed culture with cells of acenaphthene-grown strain Pseudomonas sp. strain A2279 mitigated the accumulation of partial transformation products and resulted in more complete degradation of acenaphthene. This study demonstrates the value of the stable isotope labeling approach and its ability to reveal incomplete mineralization even when as little as 2 to 3% of the substrate is incompletely oxidized, yielding products of partial transformation. The approach outlined may prove useful in assessing bioremediation performance.

Nuphar thiaspirane sulfoxides. 13C nuclear magnetic resonance determined configuration and utilization in the interconversion of thiaspirane stereochemical types

1978 ◽  
Vol 56 (1) ◽  
pp. 56-61 ◽  
Author(s):  
R. T. LaLonde ◽  
C. F. Wong
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Subsequent Reduction ◽  
13C Nuclear Magnetic Resonance ◽  
Sodium Borodeuteride ◽  
C Nmr ◽  
Nuclear Magnetic

The configuration of the sulfoxide oxygen in syn- and anti-thiobinupharidine sulfoxide was determined by employing the 13C nmr sulfoxidation increments of C-6. Establishment of the 13C nmr line assignments for C-6 included the study of the C-6 and C-6′ deuterated thiobinupharidine and the corresponding sulfoxides. Thermolysis of syn-thiobinupharidine sulfoxide in DMSO and subsequent reduction with sodium borodeuteride in methanol yielded thiobinupharidine, labelled with deuterium only at C-6, and thionuphlutine B, labelled with deuterium at both C-6 and C-6′. Treatment of the anti sulfoxide in xylene or DMSO resulted in no thiobinupharidine or thionuphlutine B. Similarly, syn-neothiobinupharidine sulfoxide gave neothiobinupharidine and a new thiaspirane, thionuphlutine C. These two compounds were not produced from anti-neothiobinupharidine sulfoxide heated in xylene.

13C nuclear magnetic resonance spectra of the spirobenzylisoquinoline alkaloids and related model compounds

1977 ◽  
Vol 55 (18) ◽  
pp. 3304-3311 ◽  
Author(s):  
Donald W. Hughes ◽  
Bala C. Nalliah ◽  
Herbert L. Holland ◽  
David B. MacLean
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Isoquinoline Alkaloids ◽  
Model Compounds ◽  
Related Model ◽  
Nuclear Magnetic Resonance Spectra ◽  
13C Nuclear Magnetic Resonance ◽  
C Nmr ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The natural abundance 13C nuclear magnetic resonance spectra of a number of spirobenzylisoquinoline alkaloids and related model compounds have been recorded. The carbon resonances of the alkaloids were assigned by comparison with the spectra of other isoquinoline alkaloids and with those of the model compounds. It has been shown that 13C nmr spectroscopy may be used to differentiate between diastereomers in this series.

15N and 13C nuclear magnetic resonance of deoxydinucleotide monophosphates. II. Protonation of the homo dimers deoxycytidylyl-(3′,5′)-deoxycytidine, thymidylyl-(3′,5′)-thymidine, and deoxyadenylyl-(3′,5′)-deoxyadenosine in dimethyl sulfoxide

1990 ◽  
Vol 68 (11) ◽  
pp. 2033-2038 ◽  
Author(s):  
Giovanna Barbarella ◽  
Massimo Luigi Capobianco ◽  
Luisa Tondelli ◽  
Vitaliano Tugnoli
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Dimethyl Sulfoxide ◽  
Phosphate Group ◽  
Nmr Data ◽  
13C Nuclear Magnetic Resonance ◽  
C Nmr ◽  
Nuclear Magnetic

The preferential protonation sites of the homo dimers deoxycytidylyl-(3′,5′)-deoxycytidine, thymidylyl-(3′,5′)-thymidine, and deoxyadenylyl-(3′,5′)-deoxyadenosine were established by nitrogen-15 and carbon-13 NMR in dimethyl sulfoxide, in the presence of varying amounts of CF3COOH. The nitrogen-15 NMR data show that in d(CpC) the capability of the two N3 nitrogens to accept the proton is slightly different. In d(TpT) and d(ApA) the protonation of the phosphate group leads to significant variations of the chemical shift of the carbons adjacent to phosphorus. Keywords: deoxydinucleotides, protonation, 15N and 13C NMR.

13C nuclear magnetic resonance studies. 58. 13C spectra of a variety of bicyclo[2.2.2]octane derivatives. Further definition of the deshielding δ effect

1976 ◽  
Vol 54 (6) ◽  
pp. 917-925 ◽  
Author(s):  
J. B. Stothers ◽  
C. T. Tan
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Magnetic Resonance Studies ◽  
13C Nuclear Magnetic Resonance ◽  
Definition Of ◽  
C Nmr ◽  
Nuclear Magnetic

The 13C nmr spectra of 35 bicyclo[2.2.2]octane and -octene derivatives have been determined to extend our examinations of the effects of stereochemistry on the shieldings of closely neighboring carbons. This series includes a variety of methyl substituted bicyclooctanols and -octenols as well as the corresponding hydrocarbons and some bicyclooctanones. With the bicyclo[2.2.2]octane skeleton it is possible to examine an array of systems having substituents separated by three and four bonds in a variety of orientations. The interactions, termed γ and δ effects, respectively, produce distinctive shielding variations which are useful for stereochemical elucidations. Particularly interesting are the pronounced shifts observed for the carbons bearing closely neighboring substituents. Characteristically, for vicinal substituents, these carbons are shielded while for syn-axial δ interactions, these carbons are deshielded by as much as 8.6 ppm. The results are compared with the trends found in other sterically crowded Systems.

1H and 13C Nuclear Magnetic Resonance Studies of the Hindered Phencyclone Adducts of Some Smaller Branched N-Alkyl Maleimides: Rigorous Aryl Proton Assignments with High-Resolution Two-Dimensional (COSY45) Spectroscopy, and Anisotropic Shielding Effects and Ab Initio Geometry Optimizations

2005 ◽  
Vol 59 (3) ◽  
pp. 354-365 ◽  
Author(s):  
Ronald Callahan ◽  
Ron Prip ◽  
Navroz Shariff ◽  
Olga Sklyut ◽  
Robert Rothchild ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
High Resolution ◽  
Basis Set ◽  
Nmr Studies ◽  
Alkyl Groups ◽  
13C Nuclear Magnetic Resonance ◽  
C Nmr ◽  
Shielding Effects ◽  
Nuclear Magnetic

Phencyclone, 1, a potent Diels-Alder diene, reacts with a series of N-alkylmaleimides, 2, to form hindered adducts, 3. The 300 MHz 1H and 75 MHz 13C NMR studies of these adducts at ambient temperatures have demonstrated slow rotations on the nuclear magnetic resonance (NMR) timescales for the unsubstituted bridgehead phenyl groups, and have revealed substantial magnetic anisotropic shielding effects in the 1H spectra of the N-alkyl groups of the adducts. The selected N-alkyl groups for the target compounds emphasized smaller branched alkyls, including C3 (isopropyl, a); C4 (isobutyl, b; and t-butyl, c); C5 (n-pentyl, d; isopentyl [isoamyl], e; 1-ethylpropyl, f; t-amyl, g;) and a related C8 isomer (1,1,3,3-tetramethylbutyl [“t-octyl”], h). The straight-chain n-pentyl analog was included as a reference. This present work on the branched N-alkylmaleimide adducts appreciably extends our earlier compilation on the N-n-alkylmaleimide adducts. Key methods for proton assignments included “high-resolution” 1H–1H chemical shift correlation spectroscopy, COSY45. 13C NMR of the adducts, 3, verified the expected number of aryl carbons for slow exchange limit (SEL) spectra of the bridgehead phenyl groups. The synthetic routes involved reaction of the corresponding amines, 4, with maleic anhydride to give the N-alkylmaleamic acids, 5, which underwent cyclodehydration to form the maleimides, 2. Magnetic anisotropic shielding magnitudes for alkyl group protons in the adducts were calculated relative to corresponding proton chemical shifts in the maleimides. Geometry optimizations for the above adducts (and for the N-n-butylmaleimide adduct) were performed at the Hartree-Fock level with the 6–31G* basis set. The existence of different contributing conformers for the adducts is discussed with respect to their calculated energies and implications regarding experimentally observed anisotropic shielding magnitudes.

On the structure, chemistry, and 13C nuclear magnetic resonance of ravidomycin

1983 ◽  
Vol 61 (2) ◽  
pp. 323-327 ◽  
Author(s):  
John A. Findlay ◽  
Jia-Sen Liu ◽  
Lajos Radics
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Cross Correlation ◽  
Degradation Products ◽  
Chemical Degradation ◽  
Antitumor Antibiotic ◽  
13C Nuclear Magnetic Resonance ◽  
C Nmr ◽  
Nuclear Magnetic

Full spectral details in support of the earlier proposed structure 1a for the antitumor antibiotic ravidomycin are presented together with an account of chemical degradation products. A complete corroboration of structure is provided by cross correlation of 1H and 13C nmr for ravidomycin and its diacetate 1b.

A stereochemical investigation of substituted ethylene sulfites via 13C nuclear magnetic resonance

1976 ◽  
Vol 54 (9) ◽  
pp. 1428-1432 ◽  
Author(s):  
Gerald W. Buchanan ◽  
Desmond G. Hellier
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Conformational Analysis ◽  
Sulfur Atom ◽  
Chemical Shifts ◽  
Nmr Chemical Shifts ◽  
13C Nuclear Magnetic Resonance ◽  
Ethylene Sulfite ◽  
C Nmr ◽  
Nuclear Magnetic

13C nmr chemical shifts for ethylene sulfite and 17 derivatives are presented. From the magnitudes of the γ shifts and the tenets of conformational analysis, support is gained for the existence of twist-envelope conformations in solution. Pseudorotational paths are suggested which do not involve inversion at the sulfur atom.

13C nuclear magnetic resonance spectra of some C19-diterpenoid alkaloids and their derivatives

1979 ◽  
Vol 57 (13) ◽  
pp. 1652-1655 ◽  
Author(s):  
S. William Pelletier ◽  
Naresh V. Mody ◽  
Rajinder S. Sawhney
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Conformational Changes ◽  
Nmr Spectra ◽  
Diterpenoid Alkaloids ◽  
Nuclear Magnetic Resonance Spectra ◽  
13C Nuclear Magnetic Resonance ◽  
C Nmr ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The natural abundance carbon-13 nuclear magnetic resonance spectra of some C19-diterpenoid alkaloids and their alkamines (lappaconitine, lappaconine, lapaconidine, ranaconine, 14-dehydrobrowniine, aconine, pseudoaconine, deoxyaconine, and hypaconine) have been determined at 15.03 MHz. With the aid of proton decoupling techniques, additivity relationships, and comparison with spectra of related alkaloids, self-consistent and unambiguous assignments of nearly all carbon resonances for these alkaloids have been made. Some important chemical shift trends have been observed, which are useful for identifying the basic C19-diterpenoid alkaloid skeleton and the hydroxy and methoxy group substitution patterns in these alkaloids. On the basis of 13C nmr spectra of lappaconitine and lappaconine, the anthranoyl ester moiety is assigned to the C-4 position in lappaconitine. The 13C nmr spectra of lapaconidine, aconine, and pseudoaconine taken in pyridine and chloroform have been compared to determine the conformational changes of the ring A hydroxy groups in these alkaloids.

scholarly journals Using 13C nuclear magnetic resonance spectroscopy for the study of northern hardwood tissues

2005 ◽  
Vol 35 (8) ◽  
pp. 1821-1831 ◽  
Author(s):  
Chris E Johnson ◽  
Ronald J Smernik ◽  
Thomas G Siccama ◽  
David K Kiemle ◽  
Zhihong Xu ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Structural Chemistry ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
Betula Alleghaniensis ◽  
13C Nuclear Magnetic Resonance ◽  
Bark Chemistry ◽  
C Nmr ◽  
Nuclear Magnetic

Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for examining the structural chemistry of natural organic matter. The use of cross-polarization and magic-angle spinning to study 13C functionality (CPMAS 13C NMR) is convenient, but not always quantitative. We used various 13C NMR techniques to examine the structural chemistry of bark and wood of sugar maple (Acer saccharum Marsh.), American beech (Fagus grandifolia Ehrh.), and yellow birch (Betula alleghaniensis Britt.). Spin counting experiments showed that 87%–97% of the 13C in the samples was observable by CPMAS 13C NMR. A comparison of CPMAS and Bloch decay experiments revealed few differences in spectral properties. Together, these results suggest that CPMAS 13C NMR is quantitative for these tissues. We observed little variation in the structural chemistry of wood, either among samples of the same species or among species. Within-species variations in bark chemistry were greater than in wood, probably because of variations in environmental conditions. However, we observed no significant differences in bark chemistry among the species. Bark and wood chemistry differed significantly, with the bark spectra displaying greater contributions from lignin, suberin, waxes, and resins. Hardwood spectra differ from softwood spectra in the aromatic C regions because of the contribution of syringyl units to hardwood lignin. Hardwood bark appears to contain less tannins than softwood bark. Together, the quantitative and qualitative features of CPMAS 13C NMR spectra are useful for studying the ecology of living and detrital wood and bark.

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