scholarly journals Microbiological degradation of bile acids. The preparation of some hypothetical metabolites involved in cholic acid degradation

1976 ◽  
Vol 154 (3) ◽  
pp. 577-587 ◽  
Author(s):  
S Hayakawa ◽  
Y Kanematsu ◽  
T Fujiwara ◽  
H Kako
Keyword(s):  
Fatty Acid ◽  
Carboxylic Acid ◽  
Bile Acids ◽  
Cholic Acid ◽  
Valeric Acid ◽  
Side Chain ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Acid Degradation ◽  
Oxidation Mechanisms

1. To identify the intermediates involved in the degradation of cholic acid, the further degradation of (4R)-4-[4a-(2-carboxyethyl)-3aa-hexahydro-7ab-methyl-5-oxoindan-1β-yl]valeric acid (IVa) by Arthrobacter simplex was attempted. The organism could not utilize this acid but some hypothetical intermediate metabolities of compound (IVa) were prepared for later use as reference compounds. 2. The nor homologue (IIIa) and the dinor homologue (IIIb) of compound (IVa) were prepared by exposure of 3-oxo-24-nor-5β-cholan-23-oic acid (I) and (20S)-3b-hydroxy-5-pregnene-20-carboxylic acid (II) to A. simplex respectively. These compounds correspond to the respective metabolites produced by the shortening of the valeric acid side chain of compound (IVa) in a manner analogous to the conventional fatty acid a- and b-oxidation mechanisms. Their structures were confirmed by partial synthesis. 3. The following authentic samples of reduction products of the oxodicarboxylic acids (IIIa), (IIIb) and (IVa) were also synthesized as hypothetical metabolities: (4R)-4-[3aa-hexahydro-5a-hydroxy-4a-(3-hydroxypropyl)-7ab-methylindan-1b-yl]valeric acid (Vb) and its nor homologue (VIIa) and dinor homologue (IXa);(4R)-4-[3Aaa-hexahydro-5a-hydroxy-4a-(3-hydroxypropyl)-7ab-methylindan-1b-yl]-pentan-1-ol (Vc); and their respective 5β epimers (Ve), (VIIc), (IXc) and (Vf). 4. In connexion with the non-utilization of compound (IVa) by A. simplex, the possibility that not all the metabolites formed from cholic acid by a certain micro-organism can be utilized by the same organism is considered.

scholarly journals Microbiological degradation of bile acids. Ring a cleavage and 7α,12α-dehydroxylation of cholic acid by Arthrobacter simplex

1969 ◽  
Vol 115 (2) ◽  
pp. 249-256 ◽  
Author(s):  
Shohei Hayakawa ◽  
Yoshiko Kanematsu ◽  
Takashi Fujiwara
Keyword(s):  
Bile Acids ◽  
Cholic Acid ◽  
Valeric Acid ◽  
Hydroxyl Groups ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Degradative Pathway ◽  
Acid Degradation

The metabolism of cholic acid by Arthrobacter simplex was investigated. This organism effected both ring a cleavage and elimination of the hydroxyl groups at C-7 and C-12 and gave a new metabolite, (4R)-4-[4α-(2-carboxyethyl)-3aα-hexahydro-7aβ-methyl-5-oxoindan-1β-yl]valeric acid, which was isolated and identified through its partial synthesis. A degradative pathway of cholic acid into this metabolite is tentatively proposed, and the possibility that the proposed pathway could be extended to the cholic acid degradation by other microorganisms besides A. simplex is discussed. The possibility that the observed reactions in vitro could occur during the metabolism of bile acids in vivo is considered.

scholarly journals Microbiological degradation of bile acids. The preparation of hexahydroindane derivatives as substrates for studying cholic acid degradation

1977 ◽  
Vol 164 (3) ◽  
pp. 709-714 ◽  
Author(s):  
S Hayakawa ◽  
T Takata ◽  
T Fujiwara ◽  
S Hashimoto
Keyword(s):  
Carboxylic Acid ◽  
Cholic Acid ◽  
Propionic Acid ◽  
Good Yield ◽  
Degradation Products ◽  
Chemical Oxidation ◽  
Compound Iiib ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Simple Method

Relatively large amounts of 3-(3aalpha-hexahydro-7abeta-methyl-1,5-dioxoindan-4alpha-yl)propionic acid (IIb), which is believed to be one of the intermediates involved in the degradation of cholic acid (I), were needed to identify is further degradation products. A simple method for the preparation of this compound was then investigated. Arthrobacter simplex could degrade-3-oxoandrost-4-ene-17beta-carboxylic acid (IIIa) to 3-(1beta-carboxy-3aalpha-hexahydro-7abeta-methyl-5-oxoindan-4alpha-yl)propionic acid (IVa) in good yield, the structure of which was established by partial synthesis. It was therefore expected that, if a similar degradation by this organism occurred with 17alpha-hydroxy-3-oxoandrost-4-ene-17beta-carboxylic acid (IIIb), which is easily obtained by chemical oxidation of commercially availabe 17alpha-hydroxydeoxycorticosterone, the resulting product, 3-(1beta-carboxy-3aalpha-hexahydro-1alpha-hydroxy-7abeta-methyl-5-oxoindan-4alpha-yl)propionic acid (IVb), could be readily converted chemically into the required dioxocarboxylic acid, (IIb). Exposure of compound (IIIb) to A. simplex produced, as expected, compound (IVb) which was then oxidized with NaBiO3 to give a reasonable yield of compound (IIb).

scholarly journals Microbiological degradation of bile acids. Nitrogenous hexahydroindane derivatives formed from cholic acid by Streptomyces rubescens

1976 ◽  
Vol 160 (3) ◽  
pp. 745-755 ◽  
Author(s):  
S Hayakawa ◽  
S Hashimoto ◽  
T Onaka
Keyword(s):  
Cholic Acid ◽  
Bond Formation ◽  
Valeric Acid ◽  
Amide Bond ◽  
Side Chain ◽  
Mechanism Of Formation ◽  
Partial Synthesis ◽  
Degradative Pathway ◽  
Amide Bond Formation ◽  
New Compounds

The metabolism of cholic acid (I) by Streptomyces rubescens was investigated. This organism effected ring A cleavage, side-chain shortening and amide bond formation and gave the following metabolites: (4R)-4-[4α-(2-carboxyethyl)-3aα-hexahydro-7aβ-methyl-5-oxoindan-1 β-yl]valeric acid (IIa) and its mono-amide (valeramide) (IIb); and 2,3,4,6, 6aβ,7,8,9,9aα,9bβ-decahydro-6aβ-methyl-1H-cyclopenta[f]quinoline-3,7-dione(IIIe)and its homologues with the β-oriented side chains, valeric acid, valeramide, butanone and propionic acid, in the place of the oxo group at C-7, i.e.compounds (IIIa), (IIIb), (IIIc) and (IIId) respectively. All the nitrogenous metabolites were new compounds, and their structures were established by partial synthesis except for the metabolite (IIIc). The mechanism of formation of these metabolites is considered. A degradative pathway of cholic acid (I) into the metabolites is also tentatively proposed.

scholarly journals The bile acid composition of gastric contents from neonates with high intestinal obstruction

1982 ◽  
Vol 206 (3) ◽  
pp. 489-498 ◽  
Author(s):  
P T Clayton ◽  
D P R Muller ◽  
A M Lawson
Keyword(s):  
Bile Acid ◽  
Intestinal Obstruction ◽  
Bile Acids ◽  
Cholic Acid ◽  
Oxidation Products ◽  
Side Chain ◽  
Gastric Contents ◽  
Alpha 7 ◽  
Hyocholic Acid ◽  
High Intestinal Obstruction

The study was designed to identify ‘atypical’ bile acids in gastric contents from three neonates with high intestinal obstruction on the basis that this was likely to represent a rich source of primary bile acids. Cholic acid was the major component, and related ‘atypical’ bile acids included its C-3 and C-7 oxidation products, its 3 beta-epimer and 2 beta- and 6 alpha-hydroxylation products. Allocholic acid was the only 5 alpha-cholanic acid derivative identified. 7 alpha, 12 alpha-Dihydroxy-3-oxochol-4-en-24-oic acid was found in all three specimens and might be an intermediate in a biosynthetic pathway from cholesterol to cholic acid in which side-chain oxidation precedes at least some of the nuclear changes. Side-chain-hydroxylated derivatives of trihydroxycoprostanic acid were also detected and these may represent intermediates in biosynthetic pathways from cholesterol to cholic acid via 5 beta-cholestan-3 alpha, 7 alpha, 12 alpha-triol. The most abundant bile acid of this type was (25 epsilon)-3 alpha, 7 alpha, 12 alpha, 25-tetrahydroxy-5 beta-cholestan-26-oic acid, which suggested that C-25 hydroxylation may be an important step in the shortening of the C8 side chain of the cholestane triol to the C5 side chain of cholic acid in the neonatal period. Bile acids lacking a substituent at C-12 included chenodeoxycholic acid, its C-3 and C-7 oxidation products, its 3 beta-epimer and its 6 alpha-hydroxylation product (hyocholic acid).

scholarly journals Microbiological degradation of bile acids, further degradation of a cholic acid metabolite containing the hexahydroindane nucleus by Corynebacterium equi

1977 ◽  
Vol 162 (2) ◽  
pp. 387-397 ◽  
Author(s):  
S Hayakawa ◽  
T Fujiwara
Keyword(s):  
Cholic Acid ◽  
Propionic Acid ◽  
Metabolic Pathways ◽  
Ring Opening ◽  
Initial Step ◽  
Valeric Acid ◽  
Acid Metabolite ◽  
Partial Synthesis ◽  
Initial Oxidation ◽  
Dioic Acid

1. The further degradation of a cholic acid (I) metabolite, (4R)-4-[4alpha-(2-carboxyethyl)-3aalpha-hexahydro-7abeta-methyl-5-oxoindan-1beta-yl]valeric acid (IIa), by Corynebacterium equi was investigated. This organism effected ring-opening and gave (4R)-4-[2alpha-(2-carboxyethyl)-3beta-(3-carboxypropionyl)-2beta-methylcyclopent-1beta-yl]valeric acid (VI). The new metabolite was isolated as its trimethyl ester and identified by partical synthesis. It was not utilized by C. equi. 2. (4R)-4[4alpha-(2-Carboxyethyl)-3aalpha-decahydro-8abeta-methyl5-oxa-6-oxoazulen-1beta-yl]valeric acid (IVa), which is a hypothetical initial oxidation product in the above degradation, was not converted by C. equi into the expected metabolite (VI), but into 3 - [2beta - [(2S) - tetrahydro - 5 - oxofur - 2 - yl] - 1beta - methyl - 5 - oxocyclopent - 1alpha - yl]-propionic acid (VIII), the structure of which was established by partial synthesis. 3. Both the possible precursors of the metabolite (VI), an isomer of the epsilon-lactone (IVa), the gamma-lactone (XIa), and the open form of these lactones, the hydroxytricarboxylic acid (V), were also not utilized by C. equi. 4. Under some incubation conditions, C. equi also converted compound (IIa) and 3-(3aalpha-hexahydro-7abeta-methyl-1,5-dioxoindan-4alpha-yl)propionic acid (IIb) into 5-methyl-4-oxo-octane-1,8-dioic acid (III), (4R)-4-(2,3,4,6,6abeta,7,8,9,9aalpha,9bbeta-decahydro-6abeta-methyl-3-oxo-1H-cyclopenta[f]quinolin-7beta-yl)valeric acid (VII) and probably a monohydroxy derivative of compound (IIa) and compound (III), respectively. 5. The possibility that an initial step in the degradation of compound (IIa) by C. equi is oxygenation of the Baeyer-Villiger type, yielding compound (IVa), is discussed. Metabolic pathways of compound (IIa) to compounds (III), (VI), (VII) and (VIII) are also considered.

scholarly journals Formation of Amphiphilic Molecules from the Most Common Marine Polysaccharides, toward a Sustainable Alternative?

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4445
Author(s):  
Tiphaine Wong ◽  
Lorette Brault ◽  
Eric Gasparotto ◽  
Romuald Vallée ◽  
Pierre-Yves Morvan ◽  
...  
Keyword(s):  
Fatty Acid ◽  
Carboxylic Acid ◽  
Bioactive Compounds ◽  
Biological Properties ◽  
Cross Linking ◽  
Structural Modifications ◽  
Chemical Structures ◽  
Amphiphilic Molecules

Marine polysaccharides are part of the huge seaweeds resources and present many applications for several industries. In order to widen their potential as additives or bioactive compounds, some structural modifications have been studied. Among them, simple hydrophobization reactions have been developed in order to yield to grafted polysaccharides bearing acyl-, aryl-, alkyl-, and alkenyl-groups or fatty acid chains. The resulting polymers are able to present modified physicochemical and/or biological properties of interest in the current pharmaceutical, cosmetics, or food fields. This review covers the chemical structures of the main marine polysaccharides, and then focuses on their structural modifications, and especially on hydrophobization reactions mainly esterification, acylation, alkylation, amidation, or even cross-linking reaction on native hydroxyl-, amine, or carboxylic acid functions. Finally, the question of the necessary requirement for more sustainable processes around these structural modulations of marine polysaccharides is addressed, considering the development of greener technologies applied to traditional polysaccharides.

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