scholarly journals Structure revision of disaccharidic conjugates of bilirubin-IX α in human bile and identification of phenylazo derivatives B4, B5, and B6 as 2-, 3- and 4-O-acylglucuronides

1978 ◽  
Vol 175 (3) ◽  
pp. 1095-1101 ◽  
Author(s):  
F Compernolle
Keyword(s):  
Mass Spectrometry ◽  
Glucuronic Acid ◽  
Chain Structure ◽  
Positional Isomers ◽  
Human Bile ◽  
Hexuronic Acid ◽  
Structure Revision ◽  
Branched Chain ◽  
Trimethylsilyl Derivatives

Aniline azopigments B4, B5 and B6, derived from conjugates of bilirubin-IX alpha in human bile, and previously characterized as disaccharidic esters [Kuenzle (1970) Biochem. J. 119, 387-394 and 411-435], were analysed by using t.l.c. and mass spectrometry. The compounds were identified as partially separated mixtures of 2-, 3- and 4-O-acylglucuronide positional isomers. The 1-O-acylglucuronide was not detected in the mixtures and was the only compound hydrolysed with beta-glucuronidase. Further scrutiny of structural assignments made by Kuenzle [(1970) Biochem. J. 119, 411-435] led to identification of the lactone and hexuronic acid derivatives that were obtained from azopigment B5 along with glucuronolactone and glucuronic acid. A branched-chain structure, i.e. 3-C-hydroxy-methyl-D-riburonic acid, was assigned previously, but the derivatives have now been identified as various incompletely silylated forms of glucuronolactone and glucuronic acid. Several trimethylsilyl derivatives glucuronolactone were isolated and characterized by n.m.r. and mass spectrometry.

scholarly journals Bilirubin conjugates in bile of man, rat and dog. Semi-quantitative analysis of bile composition by thin-layer chromatography

1976 ◽  
Vol 155 (2) ◽  
pp. 365-373 ◽  
Author(s):  
B A. Noir
Keyword(s):  
Gall Bladder ◽  
Glucuronic Acid ◽  
Bile Pigments ◽  
Human Bile ◽  
Bile Composition ◽  
Hexuronic Acid ◽  
Normal Rat ◽  
Phenol Water ◽  
Layer Chromatography ◽  
Rat Bile

1. Conjugated bile pigments, separated in two fractions by semi-quantitative t.l.c. performed on silicic acid with phenol/water as the developing solvent, were treated with diazotized ethyl anthranilate. Resulting dipyrrylazo derivatives were analysed by quantitative t.l.c. 2. The tentative structure elucidation of tetrapyrrolic bilirubin conjugates and semi-quantitative evaluation of rat bile, post-obstructive human bile and dog bile composition is presented. 3. Homogeneous and mixed hexuronic acid diesters of bilirubin containing glucuronic acid constitute 51% of the total conjugates in normal rat bile, 45% of those in human post-obstructive bile and 38% of those in obstructed rat biles. 4. Monoconjugated bilirubin amounts to 33% of total conjugated bile pigments in normal rat bile, and 17 and 14% in post-obstructive hepatic human bile and gall-bladder bile of dog respectively. After loading with unconjugated bilirubin a greater amount of monoconjugates (56%) occur in the rat bile, whereas bilirubin diglucuronide excretion is decreased (34%). 5. In gall-bladder bile of normal dog, 40% of glucose-containing diconjugates, 32% of homogeneous and/or mixed hexuronic acid (mainly glucuronic acid) diesters of bilirubin and 14% of xylose-containing diconjugates are estimated. 6. Increased amounts of bilirubin conjugates, including some with unidentified uronic acid groups, were observed in cholestatic rat biles and quantities of conjugates with glucuronic acid were decreased.

scholarly journals Bilirubin conjugates of human bile. The excretion of bilirubin as the acyl glycosides of aldobiouronic acid, pseudoaldobiouronic acid and hexuronosylhexuronic acid, with a branched-chain hexuronic acid as one of the components of hexuronosylhexuronide

1970 ◽  
Vol 119 (3) ◽  
pp. 411-435 ◽  
Author(s):  
Clive C. Kuenzle
Keyword(s):  
Acyl Radical ◽  
Hepatic Bile ◽  
Human Bile ◽  
Hexuronic Acid ◽  
Acyl Radicals ◽  
Branched Chain

Structure elucidations have been performed on the bilirubin conjugates isolated from human hepatic bile as the phenylazo derivatives. The major bilirubin conjugates are excreted, not as was formerly thought in the form of glucuronides, but as the acyl glycosides of aldobiouronic acid, pseudoaldobiouronic acid and hexuronosylhexuronic acid. The isolated aldobiouronides are proposed to have the structures of an acyl 6-O-hexopyranosyluronic acid-hexopyranoside, an acyl 4-O-hexofuranosyluronic acid-d-glucopyranoside, and an acyl 4-O-β-d-glucofuranosyluronic acid-d-glucopyranoside respectively, with the acyl radicals being those of the phenylazo derivative of bilirubin. The pseudoaldobiouronide is suggested to be the acyl 4-O-α-d-glucofuranosyl-β-d -glucopyranosiduronic acid, with the acyl radical being that of the phenylazo derivative of vinylneoxanthobilirubinic acid. The hexuronosylhexuronide presumably is the acyl 4-O-(3-C-hydroxymethylribofuranosyluronic acid)-β-d-glucopyranosiduronic acid, with the acyl radical being that of the phenylazo derivative of bilirubin. The 3-C-hydroxymethylriburonic acid, isolated as one of the components of the hexuronosylhexuronide, is the first natural branched-chain hexuronic acid to be detected, and the first branched-chain sugar ever detected in humans.

scholarly journals The isolation and characterization of bilirubin diglucuronide, the major bilirubin conjugate in dog and human bile

1976 ◽  
Vol 155 (3) ◽  
pp. 477-486 ◽  
Author(s):  
E R Gordon ◽  
C A Goresky ◽  
T H Chang ◽  
A S Perlin
Keyword(s):  
Mass Spectrometry ◽  
Glucuronic Acid ◽  
Methyl Esters ◽  
Water Soluble ◽  
Molar Ratio ◽  
Human Bile ◽  
Isolation And Characterization ◽  
Azo Derivatives ◽  
Derivatives Of

The chemical structure of the major conjugate of bilirubin was unequivocally elucidated by structural analysis. The conjugated bilirubins were first separated from the lipid components of human duodenal aspirates or dog gall-bladder bile, and then resolved by t.l.c. into a series of tetrapyrroles. The major tetrapyrrole was then converted into its more stable dipyrrolic azo derivative for further analysis. The conjugated moiety of the azopigment was characterized after methanolysis with sodium methoxide. This reaction yields two types of product, those soluble in water and those soluble in organic solvents. The organic-soluble fraction was shown by t.l.c. and mass spectrometry to contain the methyl esters of the dipyrrolic azo derivatives of bilirubin. The water-soluble materials were analysed by enzymic procedures, t.l.c., n.m.r. spectrometry and combined g.l.c. and mass spectrometry. This analysis showed that the only water-soluble product resulting from the methanolysis was glucuronic acid. The structure was identical with that of pure standards, on both mass spectrometry and n.m.r. spectroscopy. No contaminating moieties were found. Quantitative measurement indicated that the glucuronic acid had been released in a 1:1 molar ratio with the resulting methyl esters of the dipyrrolic azo derivatives of bilirubin. This unequivocally establishes bilirubin diglucuronide as the major pigment present in bile. Past problems with identification of bilirubin diglucuronide were shown to originate from procedures which resulted in incomplete separation and isolation of the azopigments of the conjugated bilirubins, owing to contamination by biliary lipids.

scholarly journals Detection of Acetaminophen and Its Glucuronide in Fingerprint by SALDI Mass Spectrometry Using Zeolite and Study of Time-Dependent Changes in Detected Ion Amount

Analytica ◽  
2021 ◽  
Vol 2 (3) ◽  
pp. 66-75
Author(s):  
Toshiki Horikoshi ◽  
Chihiro Kitaoka ◽  
Yosuke Fujii ◽  
Takashi Asano ◽  
Jiawei Xu ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Glucuronic Acid ◽  
Laser Desorption ◽  
The Body ◽  
Time Dependent ◽  
Laser Desorption Ionization ◽  
Fingerprint Analysis ◽  
Desorption Ionization ◽  
Acid Conjugate ◽  
Over Time

The ingredients of an antipyretic (acetaminophen, AAP) and their metabolites excreted into fingerprint were detected by surface-assisted laser desorption ionization (SALDI) mass spectrometry using zeolite. In the fingerprint taken 4 h after AAP ingestion, not only AAP but also the glucuronic acid conjugate of AAP (GAAP), caffeine (Caf), ethenzamide (Eth), salicylamide (Sala; a metabolite of Eth), and urea were detected. Fingerprints were collected over time to determine how the amounts of AAP and its metabolite changed with time, and the time dependence of the peak intensities of protonated AAP and GAAP was measured. It was found that the increase of [GAAP+H]+ peak started later than that of [AAP+H]+ peak, reflecting the metabolism of AAP. Both AAP and GAAP reached maximum concentrations approximately 3 h after ingestion, and were excreted from the body with a half-life of approximately 3.3 h. In addition, fingerprint preservation was confirmed by optical microscopy, and fingerprint shape was retained even after laser irradiation of the fingerprint. Our method may be used in fingerprint analysis.

scholarly journals Effect of Surfactant Molecular Structure on Emulsion Stability Investigated by Interfacial Dilatational Rheology

Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1127
Author(s):  
Yuejie Jin ◽  
Dingrong Liu ◽  
Jinhua Hu
Keyword(s):  
Emulsion Stability ◽  
Chain Structure ◽  
Interfacial Film ◽  
Future Design ◽  
Rheological Method ◽  
Viscoelastic Modulus ◽  
Hydrophobic Chain ◽  
Branched Chain ◽  
The Stability ◽  
Branched Structure

Polyglycerol polyricinolate (PGPR) and polyglycerol-2 dioleate were selected as model surfactants to construct water-in-oil (W/O) emulsions, and the effect of interfacial rheological properties of surfactant film on the stability of emulsions were investigated based on the interfacial dilatational rheological method. The hydrophobicity chain of PGPR is polyricinic acid condensed from ricinic acid, and that of polyglycerol-2 dioleate is oleic acid. Their dynamic interfacial tensions in 15 cycles of interfacial compression-expansion were determined. The interfacial dilatational viscoelasticity was analyzed by amplitude scanning in the range of 1–28% amplitude and frequency sweep in the range of 5–45 mHz under 2% amplitude. It was found that PGPR could quickly reach adsorption equilibrium and form interfacial film with higher interfacial dilatational viscoelastic modulus to resist the deformation of interfacial film caused by emulsion coalescence, due to its branched chain structure and longer hydrophobic chain, and the emulsion thus presented good stability. However, polyglycerol-2 dioleate with a straight chain structure had lower interfacial tension, and it failed to resist the interfacial disturbance caused by coalescence because of its lower interfacial dilatational viscoelastic modulus, and thus the emulsion was unstable. This study reveals profound understanding of the influence of branched structure of PGPR hydrophobic chain on the interfacial film properties and the emulsion stability, providing experimental reference and theoretical guidance for future design or improvement of surfactant.

scholarly journals Quantifying Positional Isomers (QPI) by Top-Down Mass Spectrometry

2021 ◽  
Vol 20 ◽  
pp. 100070
Author(s):  
Andrea M. Brunner ◽  
Philip Lössl ◽  
Paul P. Geurink ◽  
Huib Ovaa ◽  
P. Albanese ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Positional Isomers ◽  
Top Down ◽  
Top Down Mass Spectrometry

Cellular fatty acids of Peptococcus variabilis and Peptostreptococcus anaerobius

1977 ◽  
Vol 5 (6) ◽  
pp. 665-667
Author(s):  
C W Moss ◽  
M A Lambert ◽  
G L Lombard
Keyword(s):  
Mass Spectrometry ◽  
Fatty Acids ◽  
Gas Chromatography ◽  
Analytical Techniques ◽  
Gas Chromatography Mass Spectrometry ◽  
Cellular Fatty Acids ◽  
Chromatography Mass Spectrometry ◽  
Branched Chain

Cellular fatty acids of Peptococcus variables and Peptostreptococcus anaerobius were identified by gas chromatography, mass spectrometry, and associated analytical techniques. Iso- and anteiso-branched-chain acids were major components in both species.

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