Analytical and structural features of the gum exudate from Combretum hartmannianum schweinf.

The gum exudate from Combretum hartmannianum is water-soluble, forms very viscous solutions, and contains galactose (22%), arabinose (43%), mannose (10%), xylose (6%), rhamnose (4%), glucuronic acid (6%), 4-O-methylglucuronic acid (2%), and galacturonic acid (7%). The acidic components produced on hydrolysis of the gum were 6-O-(β-D-glucopyranosyluronic acid)-D-galactose, and two saccharides that had the same chromatographic mobility, and contained mannose and galacturonic acid, and galactose and 4-O-methylglucuronic acid, respectively. Methylation and methanolysis of the gum indicated the presence of terminal uronic acid, rhamnose, xylose, galactose, arabinofuranose, and arabinopyranose. Controlled, acid hydrolysis indicated the presence of (1→3)-linked arabinopyranose side-chains and (1→6)-linked galactose residues. C. hartmannianum gum, when subjected to two Smith-degradations, yielded Polysaccharides I and II, both of which contained galactose, arabinose, and mannose. Insufficient crude gum was available for a complete structural study, but the molecule was shown to contain long, sparsely branched chains of (1→6)-linked galactose residues, to which are attached (1→3)-linked arabinose and (1→3)-linked mannose side-chains.     

Gum polysaccharides from three Parkia species

Nigerian gum exudates from Parkia bicolor and P. biglobosa, and gum from the seed pods of P. pendula growing in Costa Rica have been analysed. The two gum exudates are proteinaceous and have closely similar physicochemical properties and compositions, with galactose, arabinose, glucuronic acid and 4-O-methylglucuronic acid as their constituent sugars; rhamnose is absent, and they are dextrorotatory. The gum from the seed pods of P. pendula contains the same constituent sugars in different proportions, and is laevorotatory. These data may be of interest in the continuing studies of plant-animal interactions and mechanisms of seed dispersal associated with the genus Parkia.     

The gum exudates from Brachystegia and Julbernardia species

Analytical data are presented for the water-soluble gum exudates from Brachystegia glaucescens, B. spiciformis, and Julbernardia globiflora. They are acidic polysaccharides containing glucuronic acid, 4-O-methylglucuronic acid and galacturonic acid, together with galactose, minor amounts of arabinose, and relatively high proportions of rhamnose. The exudate from B. glaucescens is of particular interest in having high molecular weight, high intrinsic viscosity, and a high methoxyl content. The nitrogen content of all three gums is low, but amino acid analysis shows that proteinaceous components are involved, as in the gum exudates from other genera.     

The composition of the gum exudates from some combretum species; the botanical nomenclature and systematics of the combretaceae

An analytical study has been made of gum specimens from Combretum collinum, C. collinum subsp. hypopilinum, C. erythrophyllum, C. nigricans, C. fragrans, and C. glutinosum. In comparison with the genus Acacia, both the botanical classification and synonymy, and the chemistry, are more complex. Glucuronic acid, galacturonic acid, 4-O-methylglucuronic acid, galactose, arabinose, and rhamnose are present in all the specimens studied. In addition, mannose and xylose are present in the gum from C. collinum, which is therefore similar to C. hartmannianum. The data now available suggest that, as a group, the genus Combretum produces gum exudates that are more viscous, of higher molecular weight, and more acidic than those of the Acacia group.     

The gum exudates from Chloroxylon swietenia,Sclerocarya caffra,Azadirachta indica and Moringa oleifera

Analytical data are presented for the polysaccharide and proteinaceous components of the gum exudates from Chloroxylon swietenia and Sclerocarya caffra, and for the amino acid compositions of the exudates from Azadirachta indica (two specimens) and Moringa oleifera. The gums from C. swietenia and S. caffra contain 4-O-methylglucuronic acid, glucuronic acid, galactose and arabinose; rhamnose is absent. Amino acid analysis shows that proteinaceous material is present in the gums from C. swietenia, S. caffra and M. oleifera despite their low nitrogen content. Hydroxyproline accounts for 28 % of the amino acid content of S. caffra gum. In contrast, A. indica gum has a high nitrogen content but contains very little hydroxyproline.     

A heteroxylan from the husk of Sorghum grain

Polysaccharide H-1 from the husk of Sorghum bicolor contains xylose, arabinose, glucose, galactose, glucuronic acid and 4-O-methylglucuronic ac     

The extracellular polysaccharides of porphyridium cruentum and porphyridium aerugineum

The extracellular mucilages from Porphyridium cruentum and P. aerugineum contain D-xylose, D-glucose, D-and L-galactose, 3-O-methylxylose, 3- and 4-O-methyl-galactose, and D-glucoronic acid in the approximate molar proportions of 3:1:2.5:0.13:0.13:0.8 and 1.7:1:1.1:0.3:0.6:0.5, respectively. In addition, P cruentum mucilage contains 2-O-methylhexose (0.13) and 2-O-methylglucuronic acid (0.2), whereas P. aeruginum mucilage is devoid of these two sugars but contains 2,4-di-O-methylgalactose (0.5). Both polysaccharides contain ～10% of half-ester sulphate and appear to be linked to ～5% of protein. Attempted fractionation into homopolysaccharides was unsuccessful. Methylation, periodate oxidation, and partial hydrolysis studies revealed that the glucuronic acid is 1,3-linked and is attached solely to O–3 of D-galactose in both mucilages. The 2-O-methylglucuronic acid in P. cruentum is linked to O–4 of L-galactose. Xylose, glucose, and galactose are present in both mucilages as end groups, and 1,3- and 1,4-linked residues, with galactose and glucose also present as, 1,3,4-linked or sulphated residues. Molecular weight determinations on Sepharose 4B indicate a $\text{M}$_w of 4 x 10(su6) for P. cruentum mucilage and 5 x 10⁶ for that from P. aerugineum.     

Structural studies of sapote (Sapota achras) gum

Sapote gum contains residues of L-arabinose (pyranose and furanose), D-xylose, D-glucuronic acid, and 4-O-methyl-D-glucuronic acid in the ratio 1.0:2.8:0.48:0.52. The two uronic acids were conveniently determined by reducing the carboxyl functions with lithium borohydride and measuring the ratio of D-glucose to 4-O-methyl-D-glucose. Periodate oxidation of the carboxyl-reduced gum gave inter alia 2-O-methyl-D-erythritol and 4-O-methyl-D-glucose in amounts suggesting that 37% of the 4-O-methyl-D-glucuronic acid residues are unsubstituted in the polysaccharide. Acetolysis of the carboxyl-reduced gum gave O-α-D-glucopyranosyl-(1→2)-(4-O-β-D-xylopyranosyl)_0,1,2,-D-xylose, a hitherto undescribed series of oligosaccharides, together with 2-O-(4-O-methyl-α-D-glucopyranosyl)-D-xylose. Methylation confirmed that sapote gum has a highly branched structure, and commercial xylanases did not depolymerize the gum. An α-L-arabinofuranosidase liberated a substantial part of the arabinose residues. Sapote gum is a member of the uncommon class of plant gums having a D-xylose backbone and structurally resembles brea gum.     

Amino acid composition of gum exudates from some african Combretum terminalia and anogeissus species

Amino acid compositions are presented for the proteinaceous components of the gum exudates from Combretum glutinosum (syn. apiculatum), C. zeyheri, C. molle (syn. guenzii), C. psidioides (syn. grandifolium), C. obovatum, C. collinum (syn. binderanum), C. hartmannianum, C. fragrans (syn. ternifolium), Teminalia sericea and T. superba; and for Anogeissus schimperi. The principal amino acids common to these species are aspartic acid, alanine and glycine, but there are considerable variations; glutamic acid, histidine, lysine, proline, serine, threonine and valine are also major components of some of the species studied. The Combretaceae are therefore similar to the Sterculiaceae in containing very low proportions of hydroxyproline, which is the major amino acid component of the gums studied so far from genera within the Mimosoideae.     

The structure of lannea coromandelica gum

Lannea coromandelica trees exude a water-soluble gum polysaccharide containing galactose (70%), arabinose (11%), rhamnose (2%), and uronic acids (17%). Three aldobiouronic acids are present (chromatographic analysis), namely 4-O-(α-d-galactopyranosyluronic acid)-d-galactose, 6-O-(β-d-glucopyranosyluronic acid)-d-galactose, and 6-O-(4-O-methyl-d-glucopyranosyluronic acid)-d-galactose. Linkage analysis of degraded gum A, obtained by controlled, acid hydrolysis, gave (chromatographic analysis) 3-O-β-l-arabinofuranosyl-l-arabinose, 3-O-β-l-arabinopyranosyl-l-arabinose, 3-O-α-d-galactopyranosyl-l-arabinose, 3-O-β-d-galactopyranosyl-d-galactose, and 6-O-β-D-galactopyranosyl-d-galactose. Degraded gum A was examined by methylation analysis, and was subjected to a Smith-degradation, giving degraded gum B, which was studied by linkage and methylation analysis. The O-methyl derivative of the whole gum was prepared by the Haworth and Purdie procedures and examined, after methanolysis, by g.l.c.: 2,3,4-tri-O-methyl-l-rhamnose, 2,3,5- and 2,3,4-tri- and 2,5-di-O-methyl-l-arabinose; 2,3,4,6-tetra-, 2,3,6-, 2,4,6-, and 2,3,4-tri-, and 2,6- and 2,4-di-O-methyl-d-galactose; 2,3,4-tri-O-methyl-d-glucuronic acid and 2,3,4-tri-O-methyl-d-galacturonic acid were identified. The whole gum was subjected to three successive Smith-degradations, giving Polysaccharides I–III which were examined by linkage and methylation analysis. The structural evidence obtained indicates that the gum molecules are very highly branched, based on a galactan framework consisting of short chains of β-(1→3)-linked d-galactose residues, branched and interspersed with β-(1→6) linkages. To positions 3 and 6 of this framework are attached either single d-galactose end-groups or short side-chains of d-galactose or of l-arabinose residues, and three aldobiouronic acids. The structure therefore appears to be very similar to that established recently for Lannea humilis gum.     

Formation of Novel Polysaccharides by Bradyrhizobium japonicum Bacteroids in Soybean Nodules

Certain strains of Bradyrhizobium japonicum form a previously unknown polysaccharide in the root nodules of soybean plants (Glycine max (L.) Merr.). The polysaccharide accumulates inside of the symbiosome membrane—the plant-derived membrane enclosing the bacteroids. In older nodules (60 days after planting), the polysaccharide occupies most of the symbiosome volume and symbiosomes become enlarged so that there is little host cytoplasm in infected cells. The two different groups of B. japonicum which produce different types of polysaccharide in culture produce polysaccharides of similar composition in nodules. Polysaccharide formed by group I strains (e.g., USDA 5 and USDA 123) is composed of rhamnose, galactose, and 2-O-methylglucuronic acid, while polysaccharide formed by group II strains (e.g., USDA 31 and USDA 39) is composed of rhamnose and 4-O-methylglucuronic acid. That the polysaccharide is a bacterial product is indicated by its composition plus the fact that polysaccharide formation is independent of host genotype but is dependent on the bacterial genotype. Polysaccharide formation in nodules is common among strains in serogroups 123, 127, 129, and 31, with 27 of 39 strains (69%) testing positive. Polysaccharide formation in nodules is uncommon among other B. japonicum serogroups, with only 1 strain in 18 (6%) testing positive.     

The structure of Lannea humilis gum

Lannea humilis trees exude a water-soluble gum polysaccharide containing galactose (75%), arabinose (11%), rhamnose (2%), and uronic acids (12%). Three aldobiouronic acids are present (chromatographic analysis), namely 4-O-(α-D-galactopyranosyluronic acid)-D-galactose, 6-O-(β-D-glucopyranosyluronic acid)-D-galactose, and 6-O-(4-O-methyl-β-D-glucopyranosyluronic acid)-D-galactose. Linkage analysis of degraded gums A and B, obtained by controlled, acid hydrolysis, gave (chromatographic analysis) 3-O-β-L-arabinofuranosyl-L-arabinose, 3-O-β-L-arabinopyranosyl-L-arabinose, 3-O-α-D-galactopyranosyl-L-arabinose, 3-O-β-D-galactopyranosyl-D-galactose, and 6-O-β-D-galactopyranosyl-D-galactose. Degraded gums A and B were examined by methylation analysis, and the former was subjected to a Smith-degradation, giving degraded gum C, which was studied by linkage and methylation analysis. The O-methyl derivative of the whole gum was prepared (a) by the Haworth and Purdie procedures, and (b) by the sodium hydride-methyl iodide-methyl sulphoxide technique. Both products were examined, after methanolysis, by g.l.c.: 2,3,4-tri-O-methyl-L-rhamnose; 2,3,5- and 2,3,4-tri- and 2,5-di-O-methyl-L-arabinose; 2,3,4,6-tetra-, 2,3,6-, 2,4,6- and 2,3,4-tri-, 2,6- and 2,4-di-, and 2-O-methyl-D-galactose; 2,3,4-tri-O-methyl-D-glucuronic acid and 2,3,4-tri-O-methyl-D-galacturonic acid were identified. The whole gum was subjected to four successive Smith-degradations giving Polysaccharides I–IV, which were examined by linkage and methylation analysis. Polysaccharide IV is a branched galactan; the arabinose-containing sidechains in L. humilis gum therefore do not contain more than four residues, and only a few of that length occur. The evidence obtained indicates that the gum molecules are very highly branched. The galactan framework consists of short chains of β-(1→3)-linked D-galactose residues, branched and interspersed with β-(1→6)-linkages. To positions 3 and 6 of this framework are attached either single D-galactose end-groups or short side-chains of D-galactose or of L-arabinose residues, and three aldobiouronic acids. A possible structural fragment that shows these features is proposed.     

Antimycobacterial,antibacterial and antifungal activities of Terminalia superba (Combretaceae)

The methanol extract from the stem bark of Terminalia superba (TSB), fractions (TSB1–7) and two compounds isolated following bio-assay guided fractionation namely 3,4′-di-O-methylellagic acid 3′-O-β-d-xylopyranoside (1) and 4′-O-galloy-3,3′-di-O-methylellagic acid 4-O-β-d-xylopyranoside (2) were evaluated for their antimycobacterial, antibacterial and antifungal activities. The broth microdilution, the microplate Alamar Blue assay (MABA) and the agar disc diffusion methods were used for the investigations. The results of the antimycobacterial assays showed that the crude extract, fractions TSB5–7 and compound 1 were able to prevent the growth of all the studied mycobacteria. The lowest minimal inhibitory concentration (MIC) value of 39.06 µg/ml for this extract was recorded on both M. smegmatis and M. tuberculosis MTCS2. The corresponding values were 19.53 µg/ml and 4.88 µg/ml for fractions and compounds respectively. The MIC determination results on other organisms indicated values ranging from 19.53 to 78.12 µg/ml for TSB and compound 2 on 90.9% of the tested organisms, meanwhile compound 1 as well as fractions TSB 6 and 7 exhibited detectable MIC values on all studied microorganisms. The overall results provide promising baseline information for the potential use of the crude extract from T. superba, fractions 6–7 and the tested compounds in the treatment of tuberculosis, bacterial and fungal infections.     

Mode of action of a xylanase and its significance for the structural investigation of the branched l-arabino-d-glucurono-d-xylan from redwood (Sequoia sempervirens)

The substitution pattern of the water-soluble l-arabino-(4-O-methyl-d-glucurono)-d-xylan from redwood (Sequoia sempervirens) has been studied by enzymic degradation. Exhaustive hydrolysis by an endo-xylanase (EC 3.2.1.8) from a Basidiomycete Sporotrichum dimorphosporum left a residue accounting for 20% of the original d-xylan. In the dialyzable material, oligosaccharides having arabinose or 4-O-methylglucuronic acid residues attached to the non-reducing d-xylosyl end-group of xylobiose or xylotriose, respectively, were the smallest branched oligomers released. Action of the xylanase appears to involve a region of the polysaccharide backbone having three xylosyl residues. A mode of action is proposed that requires unsubstituted hydroxyl groups at C-2, C-3, and C-2′ of a xylobiosyl residue. The binding site seems to correspond to a shallow cavity. The composition and structure of the final residue of attack shows that the enzyme has no action when the xylosyl residues branched through O-2 are separated by only one, unsubstituted xylose residue. This pattern of action, the nature of the dialyzable products, and the production of a final residue in which the substituents are accumulated, suggest that the arabinosyl and glucosyl-uronic groups are irregularly distributed on the main chain of the xylan from redwood and that in some regions they are in close vicinity when not actually on adjacent xylosyl residues.     

Hemicellulosic polymers from the leaves of coffea arabica

Polysaccharide fractions from leaves of Coffea arabica var. Mundo Novo were obtained by extraction with 24% potassium hydroxide solution and were found to contain rhamnose, arabinose, xylose, mannose, galactose, glucose, glucuronic acid and 4-O-methylglucuronic acid in different proportions. 2-Acetamido-2-deoxygalactose was detected in all fractions. The structures of the carbohydrate portions were analysed by methylation and Smith degradation. A high amount of 2,3,5-tri-O-methylarabinose and 2,3,4-tri-O-methylxylose units, which are related through end groups, suggested a large degree of branching in the polysaccharide fractions. Glucose was present mainly as (1 → 4)-linked residues, as indicated by the presence of 2,3,6-tri-O-methylglucitol in the hydrolysates of the methylated fractions. A greater proportion of monomethylxylitol in acidic fraction B-IV indicated that it was more branched than the others. The glucose and galactose residues are 4,6- and 3,4-di-O-substituted, respectively. Three successive Smith degradations gave mainly glycerol with some erythritol and threitol. In the linkage of carbohydrate—protein, the presence of O-glycosyl linkages between arabinose and hydroxyproline was indicated. A phenolic compound was detected in all polysaccharide fractions from leaves of the coffee tree and is probably derived from chlorogenic acid.     

Monomethyl sugars in extracellular polysaccharides from slow-growing Rhizobia

Two monosaccharides present as components of extracellular gum produced by several strains of slow-growing Rhizobia have been shown to be 4-O-methyl-D-galactose and 4-O-methyl-D-glucose. The occurrence of mannose in several of these polysaccharides has been confirmed.     

Division of Rhizobitoxine-Producing and Hydrogen-Uptake Positive Strains of Bradyrhizobium japonicum by nifDKE Sequence Divergence

Genomic digests from 25 strains of Bradyrhizobium japonicum,for which the phenotypes have been determined with respect toproduction of rhizobitoxine, hydrogen uptake (Hup) and compositionof extracellular polysaccharide (EPS), were hybridized withprobe DNAs of the nifDK and nifE genes of B. japonicum USDA110. The degree of the estimated base substitution in and aroundnifDKE clearly divided the strains of B. japonicum into twomarkedly divergent groups, which were designated as genotypeI and II. Moreover, a strict correlation was observed betweenthese genotypes, production of rhizobitoxine and EPS composition.The genotype I strains produced no rhizobitoxine and an EPScomposed of glucose, mannose, galactose, 4-O-methyl galactoseand galacturonic acid, whereas the genotype II strains producedrhizobitoxine and an EPS composed of rhamnose and 4-O-methylglucuronic acid. Hup⁺ strains were confined exclusively to thegenotype I. Hind III digests of genomic DNAs from the 25 strainswere hybridized with probe DNA of structural genes for the uptakehydrogenase from B. japonicum. In 23 wild-type strains, Hup⁺strains generated a 5.9-kb band that hybridized to the probeunder high-stringency conditions, while Hup^– strains didnot generate the band. These results suggest that the genotypesI and II are two highly divergent evolutionary lines that definea marked division of various phenotypes, such as productionof rhizobitoxine, EPS composition and hydrogen uptake. (Received July 10, 1989; Accepted November 4, 1989)     

The structure of bael (Aegle marmelos) gum

Purified, bael-gum polysaccharide containsd-galactose (71%),l-arabinose (12.5%),l-rhamnose (6.5%), andd-galacturonic acid (7%). Hydrolysis of one mole of the fully methylated polysaccharide gave: (a) from the neutral part, 2,3,4-tri-O-methyl-l-rhamnose (2 moles), 2,3,5-tri-O-methyl-l-arabinose (4 moles), 2,3,4,6-tetra-O-methyl-d-galactose (8 moles), 3,4-di-O-methyl-l-rhamnose (2 moles), 2,5-di-O-methyl-l-arabinose (1 mole), 2,4,6-tri-O-methyl-d-galactose (10 moles), 2,3-di-O-methyl-l-arabinose (1 mole), 2,4-di-O-methyl-d-galactose (14 moles), and 2-O-methyl-d-galactose (2 moles); and (b) from the acidic part, 2,3,4-tri-O-methyl-d-galacturonic acid (1 mole), 2,4,6-tri-O-methyl-3-O-(2,3,4-tri-O-methyl-d-galactopyranosyluronic acid)-d-galactose (2.6 moles), and 2,4,6-tri-O-methyl-3-O-[2,4,6-tri-O-methyl-3-O-(2,3,4-tri-O-methyl-d-galactopyranosyluronic acid)-d-galactopyranosyl]-d-galactose (1 mole). Mild hydrolysis of the whole gum yielded oligosaccharides from which 3-O-β-d-galactopyranosyl-l-arabinose, 5-O-β-d-galactopyranosyl-l-arabinose, 3-O-β-d-galactopyranosyl-d-galactose, and 6-O-β-d-galactopyranosyl-d-galactose could be isolated and characterized. The results of methylation, periodate oxidation, Smith degradation, Barry degradation, and graded hydrolysis studies were employed for the elucidation of the structure of the whole gum.     

Distribution of D-galactosyl groups in guaran and locust-bean gum

Distribution of α-d-galactopyranosyl side-chain groups in two galactomannans, guaran and locust-bean gum, was determined by measurement of the O-acetyl-O-methyl-d-mannitol derivatives obtained from the corresponding primary C-p-tolylsulfonyl polysaccharide derivatives. The O-acetyl-O-methyl-d-mannitol derivatives were produced by β-elimination and methylation, with sodium (methylsulfinyl)methide and methyl iodide, of the primary C-p-toluenesulfinylated galactomannans, followed by sequential acid hydrolysis, reduction, and acetylation of the partially degraded p-tolyl sulfones. The results indicated that side-chain units of guaran are alternately disposed along the d-mannan backbone, whereas those of locust-bean gum are disposed in uniform blocks along the backbone.     

Isolation and structure of d-xylans from pericarp seeds of Opuntia ficus-indica prickly pear fruits

Xylans were isolated from the pericarp of prickly pear seeds of Opuntia ficus-indica (OFI) by alkaline extraction, fractionated by precipitation and purified. Six fractions were obtained and characterized by sugar analysis and NMR spectroscopy. They were assumed to be (4-O-methyl-d-glucurono)-d-xylans, with 4-O-α-d-glucopyranosyluronic acid groups linked at C-2 of a (1→4)-β-d-xylan. The sugar composition and the ¹H and ¹³C NMR spectra showed that their chemical structures were very similar, but with different proportions of d-Xyl and 4-O-Me-d-GlcA. Our results showed that, on average, the water soluble xylans have one nonreducing terminal residue of 4-O-methyl-d-glucuronic acid for every 11 to 14 xylose units, whereas in the water non-soluble xylans, xylose units can varied from 18 to 65 residues for one nonreducing terminal residue of 4-O-methyl-d-glucuronic acid.