Methylation Analysis as a Tool for Structural Analysis of Wood Polysaccharides

Holzforschung ◽  
2002 ◽  
Vol 56 (6) ◽  
pp. 607-614 ◽  
Author(s):  
C. Laine ◽  
T. Tamminen ◽  
A. Vikkula ◽  
T. Vuorinen
Keyword(s):  
Structural Analysis ◽  
Model Compound ◽  
Glucuronic Acid ◽  
Calculation Model ◽  
Complex Mixtures ◽  
Methylation Analysis ◽  
Structural Units ◽  
Response Factors ◽  
Wood Polysaccharides ◽  
Relative Molar Response

Summary In modern structural analysis of complex mixtures of wood polysaccharides, methylation analysis is still a valuable and powerful tool for linkage analysis. In this paper, methylation analysis is described for the procedure methylation, methanolysis, silylation and GC/MS. The retention time indexes for the partly methylated methyl glycosides of the relevant wood polysaccharides are listed together with the ratios of the isomers of the different structural units. A calculation model for relative molar response factors is suggested based on a published model for FID detection and on experimental data. Tested for oligosaccharides of known structure including xylotetraose, mannotriose and 63, 64-α-D-galactosyl-mannopentaose, the model gives reproducible and sufficiently correct results. The fate of xylose units substituted with 4-O-methyl glucuronic acid at position 2 is investigated with a model compound.

Structural Analysis of an Acidic Polysaccharide from Tremella mesenterica NRRL Y-6158

1973 ◽  
Vol 51 (3) ◽  
pp. 219-224 ◽  
Author(s):  
C. G. Fraser ◽  
H. J. Jennings ◽  
P. Moyna
Keyword(s):  
Structural Analysis ◽  
Culture Medium ◽  
Glucuronic Acid ◽  
Side Chains ◽  
Methylation Analysis ◽  
Acidic Polysaccharide ◽  
Molar Ratios ◽  
Limited Variation ◽  
Branched Structure ◽  
End Group

An acidic polysaccharide has been isolated from the culture medium of T. mesenterica NRRL Y-6158. The heteropolymer contained D-xylose, D-mannose, D-glucuronic acid, and O-acetyl in the molar ratios of 7:5:1:0.7, respectively. Methylation analysis of the heteropolymer indicated that it was essentially a 1 → 3-α-linked mannopyranose backbone having approximately 80% of the backbone units substituted, thus forming a very highly branched structure. The substituents on the backbone were found to be D-glucopyranosyluronic acid end-group, β-linked to the O-2 positions of the mannopyranose units, and 2-O-β-D-linked xylopyranose side-chains, linked both to the O-2 and O-4 positions of the mannopyranose backbone. The methylation analysis suggests that these side-chains are probably two or three xylopyranose units long, although a limited variation in the length of the side-chains is a possibility.

scholarly journals Nitrogen-containing aromatic compounds: quantitative analysis using gas chromatography with nitrogen phosphorus detector

2021 ◽  
Author(s):  
Yuan Rao ◽  
Arno de Klerk
Keyword(s):  
Gas Chromatography ◽  
Quantitative Analysis ◽  
Aromatic Compounds ◽  
Process Development ◽  
Complex Mixtures ◽  
Response Factors ◽  
Cyanide Anion ◽  
Nitrogen Phosphorus Detector ◽  
Assurance Process ◽  
Nitrogen Containing Compounds

AbstractThe nitrogen-containing aromatic compounds found in the petrochemical industry are varied and extend beyond classes such as the anilines, pyrroles and pyridines. Quantification of these nitrogen-containing compounds that may occur in complex mixtures has practical application for quality assurance, process development and the evaluation of conversion processes. Selective detection of nitrogen-containing species in complex mixtures is possible by making use of gas chromatography coupled with a nitrogen phosphorous detector (GC-NPD), which is also called a thermionic detector. Despite the linearity of the NPD response to individual nitrogen-containing compounds, the response factor is different for different compounds and even isomers of the same species. Quantitative analysis using an NPD requires species-specific calibration. The reason for the sensitivity of the NPD to structure is related to the ease of forming the cyano-radical that is ionized to the cyanide anion, which is detected. The operation of the NPD was related to the processes of pyrolysis and subsequent ionization. It was possible to offer plausible explanations for differences in response factors for isomers based on pyrolysis chemistry. Due to this relationship, the NPD response can in the same way be used to provide information of practical relevance beyond its analytical value and a few possible applications were outlined.

Synthesis and Structural Analysis of the Anilides of Glucuronic Acid and Orientation of the Groups on the Carbohydrate Scaffolding

2005 ◽  
Vol 70 (10) ◽  
pp. 4096-4106 ◽  
Author(s):  
Manuela Tosin ◽  
Colin O'Brien ◽  
Geraldine M. Fitzpatrick ◽  
Helge Müller-Bunz ◽  
W. Kenneth Glass ◽  
...  
Keyword(s):  
Structural Analysis ◽  
Glucuronic Acid

Structural analysis of the specific capsular polysaccharide of Streptococcuspneumoniae type 22F

1989 ◽  
Vol 67 (6) ◽  
pp. 1038-1050 ◽  
Author(s):  
James C. Richards ◽  
Malcolm B. Perry ◽  
Peter J. Kniskern
Keyword(s):  
Capsular Polysaccharide ◽  
Glucuronic Acid ◽  
Periodate Oxidation ◽  
Resonance Spectroscopy ◽  
Methylation Analysis ◽  
Chemical Shift Correlation ◽  
Structure Formula ◽  
Correlation Techniques ◽  
Heteronuclear Chemical Shift ◽  
C Nmr

The structure of the specific capsular polysaccharide produced by Streptococcuspneumoniae type 22F (American type 22) was investigated by high-field 1H and 13C nuclear magnetic resonance spectroscopy, composition, methylation analysis, and periodate oxidation studies. The polysaccharide was found to be a high molecular weight acidic polymer composed of D-glucose, D-galactose, D-glucuronic acid, and L-rhamnose residues to form a regular repeating hexasaccharide unit having the structure[Formula: see text]in which the β-L-rhamnopyranosyl residues were substituted by O-acetyl groups in 80% of the repeating units. The 1H and 13C nmr resonances of the O-deacetylated type 22F polysaccharide were completely assigned by application of two-dimensional homo- and heteronuclear chemical shift correlation techniques. Keywords: Streptococcuspneumoniae polysaccharide, NMR analysis.

scholarly journals Molecular cohesion in plant cell walls. Methylation analysis of pectic polysaccharides from the cotyledons of white mustard

1969 ◽  
Vol 115 (3) ◽  
pp. 431-439 ◽  
Author(s):  
D. A. Rees ◽  
N. J. Wight
Keyword(s):  
Plant Cell ◽  
Cell Walls ◽  
Uronic Acid ◽  
Structural Elements ◽  
Plant Cell Walls ◽  
White Mustard ◽  
Methylation Analysis ◽  
Structural Units ◽  
Pectic Polysaccharides ◽  
Derivatives Of

Methylation analysis was used to characterize the pectic polysaccharides from mustard cotyledons, a tissue with potential for rapid biological change involving the walls. The methylated sugars were identified by g.l.c. and paper chromatography after conversion of uronic acid derivatives into [3H]hexoses, and confirmed by the formation of crystalline derivatives of most of the main products, which were: 2,3-di-O-methyl-d-[6−3H]galactose, 2-O-methyl-d-[6−3H]galactose, 3,4-di-O-methylrhamnose, 3-O-methylrhamnose, 2,3,5-tri-O-methyl-l-arabinose, 2,3-di-O-methyl-l-arabinose, 2-O-methyl-l-arabinose, 2,3,4-tri-O-methyl-d-xylose and 2,3,4,6-tetra-O-methyl-d-galactose in the molar proportions 1·00:1·14:0·54:0·74:2·86:2·50:2·24:1·88:0·32. The structural units present are similar to those in wellknown polysaccharides from mature tissues, but their proportions are strikingly different. Uninterrupted and unbranched galacturonan segments can therefore contribute little cohesion to these walls, and it is suggested that this correlates with a function of the wall matrix to hydrate and permit readjustment, during germination, of structural elements or wall surfaces or both.

Calculation Model of Mass Action Concentrations for CaO-MnO-FeO-SiO2-MgO-Al2O3 Slags Based on the Ion and Molecule Coexistence Theory

2012 ◽  
Vol 476-478 ◽  
pp. 134-138
Author(s):  
Xiao Hong Yang ◽  
Xiao Chun Ma ◽  
Cheng Chuan Wu ◽  
Guo Guang Cheng
Keyword(s):  
Phase Diagrams ◽  
Thermodynamic Model ◽  
Slag System ◽  
Calculation Model ◽  
Mass Action ◽  
Structural Units ◽  
Coexistence Theory ◽  
Slag Structure ◽  
Calculation Results ◽  
Good Agreement

According to the ion and molecule coexistence theory (IMCT) of slag structure and corresponding phase diagrams, a thermodynamic model for calculating mass action concentrations of structural units or ion couples of CaO-MnO-FeO-SiO2-MgO-Al2O3 slags was established. Equilibrium mass action concentrations of each structure unit were gained. And the calculation results of NFeO and NMnO were compared with measured aFeO and aMnO. The comparison shows that the calculated values of NFeO and NMnO are in good agreement with the reported measured values of aFeO and aMnO, so this calculating model could fairly describe the characteristics of the slag system.

scholarly journals Structure of heparan sulphate oligosaccharides and their degradation by exo-enzymes

1979 ◽  
Vol 183 (3) ◽  
pp. 711-720 ◽  
Author(s):  
A Linker
Keyword(s):  
Structural Analysis ◽  
Nitrous Acid ◽  
Uronic Acid ◽  
Glucuronic Acid ◽  
Heparan Sulphate ◽  
Major Fraction ◽  
Sulphate Content ◽  
Acid Degradation ◽  
Iduronic Acid ◽  
Heparan Sulphate Chain

Oligosaccharides obtained from heparan sulphate by nitrous acid degradation were shown to be degraded sequentially by beta-D-glucuronidase or alpha-L-iduronidase followed by alpha D-N-acetylglucosaminidase. Structural analysis of the tetrasaccharide fraction showed the following. (1) N-Acetylglucosamine is preceded by a non-sulphated uronic acid residue that can be either D-glucuronic of L-iduronic acid, but followed by a glucuronic acid residue. (2) The N-acetylglucosamine in the major fraction is sulphated. (3) Very few if any of the uronic acid residues are sulphated (4). The results indicate that the area of the heparan sulphate chain where disaccharides containing N-acetylglucosamine and N-sulphated glucosamine residues alternate is higher in sulphate content than expected and that the sulphate groups are mainly located on the hexosamine units.

scholarly journals Physical properties of chondroitin sulphate/dermatan sulphate proteoglycans from bovine aorta

1986 ◽  
Vol 240 (2) ◽  
pp. 575-583 ◽  
Author(s):  
R Kapoor ◽  
C F Phelps ◽  
T N Wight
Keyword(s):  
Uronic Acid ◽  
Glucuronic Acid ◽  
Core Protein ◽  
Chondroitin Sulphate ◽  
Polymer Concentration ◽  
Dermatan Sulphate ◽  
Guanidinium Chloride ◽  
Structural Units ◽  
The Core ◽  
Covalently Linked

Bovine aortic chondroitin sulphate/dermatan sulphate proteoglycans (PG-25, PG-35 and PG-50) were differentially precipitated with ethanol and analysed by a variety of chemical and physical techniques. The glycosaminoglycan chains of PG-25 and PG-35 contained a mixture of glucuronic acid and iduronic acid, whereas the uronic acid component of PG-50 was primarily glucuronic acid. In addition, various amounts of oligosaccharides containing small amounts of mannose, a galactose/hexosamine ratio of 1:1 and an absence of uronic acid were covalently linked to the core protein of all proteoglycans. The weight-average Mr (Mw) values of the proteoglycans determined by light-scattering in 4 M-guanidinium chloride were 1.3 × 10(6) (PG-25), 0.30 × 10(6) (PG-35) and 0.88 × 10(6) (PG-50). The s0 values of the proteoglycans were distributed between 7 and 8 S, and the reduced viscosities, eta sp./c, of all proteoglycans were dependent on the shear rate and polymer concentration. Electron microscopy of spread molecules revealed that PG-25 contained small structural units that appeared to self-associate into large aggregates, whereas PG-35 and PG-50 appeared mainly as monomers consisting of a core with various numbers of side projections. Hyaluronic acid-proteoglycan complexes occurred only with a small proportion of the molecules present in PG-35, and their formation could be inhibited by oligosaccharides. These results suggest the presence in the aorta of subspecies of chondroitin sulphate and dermatan sulphate proteoglycans, which show large variations in their physicochemical and inter- and intra-molecular association properties.

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