The biosynthesis of cyclopropane fatty acids. II. Mechanistic studies using methionine labelled with one, two, and three deuterium atoms in the methyl group

1982 ◽  
Vol 60 (4) ◽  
pp. 371-378 ◽  
Author(s):  
Peter H. Buist ◽  
David B. MacLean
Keyword(s):  
Fatty Acids ◽  
Fatty Acid ◽  
Cyclopropane Ring ◽  
Isotope Effects ◽  
Slow Step ◽  
Cyclopropane Fatty Acid ◽  
Methyl Group ◽  
Feeding Experiments ◽  
Cyclopropane Fatty Acids ◽  
Methyl Group Transfer

The mechanism of formation of monodeuterated cyclopropane fatty acids on administration of L-methione-methyl-d3 to L. plantarum has been investigated. It has been found that the extent of exchange is not affected by the presence of oxygen in the medium, that neither formate-d0 nor formaldehyde-d2 is significantly incorporated into the fatty acid, and that methionine reisolated from the intracellular pool does not contain any exchanged species. These experiments militate against any mechanism involving exchange prior to methyl group transfer. Parallel feeding experiments using methionine labelled in the methyl group with one, two, or three deuterium atoms were carried out and in this way that extent of exchange was quantitated. It was found that at least one-third of the cyclopropane fatty acid from methionine methyl-d3 experiments is derived from an exchanged methyl group. The intramolecular and intermolecular primary deuterium isotope effects for biological cyclopropane ring formation were measured and found to be 3.2 ± 0.5, and 1.01 ± 0.04, respectively. These results are consistent with a mechanism in which a methyl group is transferred in a slow step which is followed by a fast, partially reversible, protonation-deprotonation step.

The biosynthesis of cyclopropane fatty acids. I. Feeding experiments with oleic acid-9,10-d2, oleic acid-8,8,11,11-d4, and L-methionine-methyl-d3

1981 ◽  
Vol 59 (5) ◽  
pp. 828-838 ◽  
Author(s):  
Peter H. Buist ◽  
David B. Maclean
Keyword(s):  
Oleic Acid ◽  
Fatty Acid ◽  
Double Bond ◽  
Cyclopropane Ring ◽  
Octadecenoic Acid ◽  
Cyclopropane Fatty Acid ◽  
Feeding Experiments ◽  
Cyclopropane Fatty Acids ◽  
Methylene Unit ◽  
Methylene Group

cis-9-Octadecenoic acid-9,10-d2 and cis-9-octadecenoic acid-8,8,11,11-d4 and L-methionine-methyl-d3 were administered to cultures of Lactobacillus plantarum and converted by the organism to the corresponding cyclopropyl compounds. The first experiment showed that no scrambling or loss of label occurred when a methylene unit was added across the double bond of the labelled substrate. In the second experiment, again, no loss or scrambling of label occurred, a result which ruled out any mechanism for biological cyclopropanation involving allylic activation of the double bond. The third experiment yielded a biosynthetic cyclopropane fatty acid containing deuterium located exclusively at the methylene group of the cyclopropane ring. Up to 17% of a d1-species accompanied the major dideuterated compound. The lone deuterium in the d1-cyclopropane fatty acid occupies both positions of the methylene group to the same extent. It has been shown that the extent to which d1-cyclopropane fatty acid is produced increases with cell growth. The extent of exchange was similar in the cyclopropanation of both the 9,10-and 11,12-isomers of cis-octadecenoic acid.

The effect of temperature and other growth conditions on the fatty acid composition of Escherichia coli

1981 ◽  
Vol 27 (8) ◽  
pp. 835-840 ◽  
Author(s):  
James T. McGarrity ◽  
John B. Armstrong
Keyword(s):  
Escherichia Coli ◽  
Fatty Acids ◽  
Fatty Acid Composition ◽  
Fatty Acid ◽  
Acid Composition ◽  
Exponential Growth ◽  
Growth Conditions ◽  
Cyclopropane Fatty Acid ◽  
Cyclopropane Fatty Acids ◽  
K 12

During exponential growth, strain AW405 of Escherichia coli K-12 did not regulate the fatty acid composition of its lipids in response either to temperature or to the addition of NaCl, KCl, or MgCl2 to the medium. Growth was severely restricted at temperatures below 21 °C. Differential scanning calorimetry (DSC) of the isolated lipids from a culture with a typical exponential-phase composition yielded a broad transition, extending from approximately 0 to 33 °C, with a midpoint at 19 °C.During late stages of growth, the fatty acid composition changed. The percentage of palmitic acid increased and cyclopropane fatty acids replaced some of the equivalent unsaturated fatty acids. The increase in palmitate seemed largely independent of growth conditions, whereas the increase in the cyclopropane fatty acids was stimulated by the addition of salts or sucrose. Cultures grown in the presence of sucrose also had higher cyclopropane fatty acid levels during exponential growth. DSC of lipids from a sucrose culture, in which the compositional changes were most pronounced, yielded a much narrower transition with a midpoint at 27 °C.

Raman spectroscopy as a tool for tracking cyclopropane fatty acids in genetically engineeredSaccharomyces cerevisiae

The Analyst ◽  
2019 ◽  
Vol 144 (3) ◽  
pp. 901-912 ◽  
Author(s):  
Kamila Kochan ◽  
Huadong Peng ◽  
Eunice S. H. Gwee ◽  
Ekaterina Izgorodina ◽  
Victoria Haritos ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Raman Spectroscopy ◽  
Fatty Acid ◽  
Cyclopropane Fatty Acid ◽  
Cyclopropane Fatty Acids

We demonstrate the first spectrum of cyclopropane fatty acid and track its presence in yeast using Raman spectroscopy and PLS-DA.

scholarly journals Occurrence of Cis-11,12-Methylene-Hexadecanoic Acid in the Red Alga Solieria pacifica (Yamada) Yoshida

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2286
Author(s):  
Gwang-Woo Kim ◽  
Jae-Man Sim ◽  
Yutaka Itabashi ◽  
Min-Jeong Jung ◽  
Joon-Young Jun
Keyword(s):  
Fatty Acids ◽  
Fatty Acid ◽  
Red Alga ◽  
Proton Nuclear Magnetic Resonance ◽  
Animal Origin ◽  
Monoenoic Acid ◽  
Resonance Spectroscopy ◽  
Hexadecenoic Acid ◽  
Cyclopropane Fatty Acid ◽  
Hexadecanoic Acid

Fatty acids in marine algae have attracted the attention of natural chemists because of their biological activity. The fatty acid compositions of the Solieriaceae families (Rhodophyceae, Gaigartinales) provide interesting information that unusual cyclic fatty acids have been occasionally found. A survey was conducted to profile the characteristic fatty acid composition of the red alga Solieria pacifica (Yamada) Yoshida using gas chromatography-mass spectrometry (GC-MS), infrared spectroscopy (IR), and proton nuclear magnetic resonance spectroscopy (1H-NMR). In S. pacifica, two cyclopentyl fatty acids, 11-cyclopentylundecanoic acid (7.0%), and 13-cyclopentyltridecanoic acid (4.9%), and a cyclopropane fatty acid, cis-11,12-methylene-hexadecanoic acid (7.9%) contributed significantly to the overall fatty acid profile. In particular, this cyclopropane fatty acid has been primarily found in bacteria, rumen microorganisms or foods of animal origin, and has not previously been found in any other algae. In addition, this alga contains a significant amount of the monoenoic acid cis-11-hexadecenoic acid (9.0%). Therefore, cis-11,12-methylene-hexadecanoic acid in S. pacifica was likely produced by methylene addition to cis-11-hexadecenoic acid.

scholarly journals Asymmetric and Regiospecific Synthesis of Isotopically Labelled Cyclopropane Fatty Acid (9R,10S)-Dihydrosterculic Acid: Overcoming Spontaneous Protonation During Lithium-Sulfoxide Exchange­

SynOpen ◽  
2018 ◽  
Vol 02 (02) ◽  
pp. 0168-0175
Author(s):  
Samuel Shields ◽  
Peter Buist ◽  
Jeffrey Manthorpe
Keyword(s):  
Fatty Acid ◽  
Total Synthesis ◽  
Cyclopropane Ring ◽  
Rapid Quenching ◽  
Cyclopropane Fatty Acid ◽  
Deuterium Incorporation ◽  
Biologically Relevant ◽  
Dihydrosterculic Acid

The total synthesis of isotopically labelled (9R,10S)-dihydro­sterculic acid, a usual cyclopropane fatty acid with biologically relevant toxicity upon desaturation in vivo, is reported. A diastereoselective Corey­–Chaykovsky reaction was employed to form the cyclopropane ring. Rapid quenching of a lithium-sulfoxide exchange was required to achieve the requisite high levels of deuterium incorporation.

scholarly journals Formation of trans Fatty Acids Is Not Involved in Growth-Linked Membrane Adaptation of Pseudomonas putida

2005 ◽  
Vol 71 (4) ◽  
pp. 1915-1922 ◽  
Author(s):  
Claus Härtig ◽  
Norbert Loffhagen ◽  
Hauke Harms
Keyword(s):  
Fatty Acids ◽  
Fatty Acid ◽  
Pseudomonas Putida ◽  
De Novo ◽  
Isomerization Reaction ◽  
Cyclopropane Fatty Acid ◽  
Substrate Uptake ◽  
Resting Cells ◽  
Saturation Degree ◽  
Fatty Acid Compositions

ABSTRACT Fatty acid compositions in growing and resting cells of several strains of Pseudomonas putida (P8, NCTC 10936, and KT 2440) were studied, with a focus on alterations of the saturation degree, cis-trans isomerization, and cyclopropane formation. The fatty acid compositions of the strains were very similar under comparable growth conditions, but surprisingly, and contrary to earlier reports, trans fatty acids were not found in either exponentially growing cells or stationary-phase cells. During the transition from growth to the starvation state, cyclopropane fatty acids were preferentially formed, an increase in the saturation degree of fatty acids was observed, and larger amounts of hydroxy fatty acids were detected. A lowered saturation degree and concomitant higher membrane fluidity seemed to be optimal for substrate uptake and growth. The incubation of cells under nongrowth conditions rapidly led to the formation of trans fatty acids. We show that harvesting and sample preparation for analysis could provoke the enzyme-catalyzed formation of trans fatty acids. Freeze-thawing of resting cells and increased temperatures accelerated the formation of trans fatty acids. We demonstrate that cis-trans isomerization only occurred in cells that were subjected to an abrupt disturbance without having the possibility of adapting to the changed conditions by the de novo synthesis of fatty acids. The cis-trans isomerization reaction was in competition with the cis-to-cyclopropane fatty acid conversion. The potential for the formation of trans fatty acids depended on the cyclopropane content that was already present.

scholarly journals Determination of Cyclopropane Fatty Acids in Food of Animal Origin by 1H NMR

2018 ◽  
Vol 2018 ◽  
pp. 1-8 ◽  
Author(s):  
Veronica Lolli ◽  
Angela Marseglia ◽  
Gerardo Palla ◽  
Emanuela Zanardi ◽  
Augusta Caligiani
Keyword(s):  
Fatty Acids ◽  
Dairy Products ◽  
Cyclopropane Ring ◽  
Food Sources ◽  
Animal Origin ◽  
Animal Fats ◽  
H Nmr ◽  
Cyclopropane Fatty Acids ◽  
Food Of Animal Origin ◽  
Full Scan

Cyclopropane fatty acids (CPFAs) are unusual fatty acids of microbial origin, recently detected in milk and dairy products. CPFAs have been demonstrated to be interesting molecular markers for authentication of dairy products obtained without ensiled feeds. Moreover, they can also be recognized as a new secondary component of human diet. Information is lacking on the presence of cyclic fatty acids in other food sources. Cyclopropane fatty acids have been detected by GC-MS analysis in cheese and other animal fats in concentration ranging from 200 to 1000 mg/kg fat, but in some cases, the complex fatty acid profile and the possible presence of interfering peaks make the separation not straightforward and the quantification uneasy. Therefore, a new reliable 1H NMR method was developed to detect and measure CPFA content in different foods of animal origin, based on the detection of the characteristic signals of cyclopropane ring. The 1H NMR (600 MHz) method showed detection limits comparable with those of full scan GC-MS, and it allowed the identification and quantitation of the cyclopropane fatty acids in different foods.

Characterization of Pseudomonas aeruginosa fatty acid profiles in biofilms and batch planktonic cultures

2010 ◽  
Vol 56 (12) ◽  
pp. 1028-1039 ◽  
Author(s):  
Jerry Chao ◽  
Gideon M. Wolfaardt ◽  
Michael T. Arts
Keyword(s):  
Fatty Acids ◽  
Pseudomonas Aeruginosa ◽  
Fatty Acid ◽  
Saturated Fatty Acids ◽  
Monounsaturated Fatty Acids ◽  
Bulk Liquid ◽  
Strain Pao1 ◽  
Fatty Acid Chain ◽  
Cyclopropane Fatty Acids ◽  
Gradual Loss

The fatty acid composition of Pseudomonas aeruginosa PAO1 was compared between biofilm and batch planktonic cultures. Strain PAO1 biofilms were able to maintain a consistent fatty acid profile for up to 6 days, whereas strain PAO1 batch planktonic cultures showed a gradual loss of cis-monounsaturated fatty acids over 4 days. Biofilms exhibited a greater proportion of hydroxy fatty acids but a lower proportion of both cyclopropane fatty acids and saturated fatty acids (SAFAs). SAFAs with ≥16 carbons, in particular, decreased in biofilms when compared with that in batch planktonic cultures. A reduced proportion of SAFAs and a decline in overall fatty acid chain length indicate more fluidic biophysical properties for cell membranes of P. aeruginosa in biofilms. Separating the biofilms into 2 partitions and comparing their fatty acid compositions revealed additional trends that were not observed in the whole biofilm: the shear-nonremovable layer consistently showed greater proportions of hydroxy fatty acid than the bulk liquid + shear-removable portion of the biofilm. The shear-nonremovable portion demonstrated a relatively immediate decline in the proportion of monounsaturated fatty acids between days 2 and 4; which was offset by an increase in the proportion of cyclopropane fatty acids, specifically 19:0cyc(11,12). Simultaneously, the shear-removable portion of the biofilm showed an increase in the proportion of trans-monounsaturated fatty acids and cyclopropane fatty acids.

Sign in / Sign up

Export Citation Format

Share Document