Chemical composition of volatile oils from leaves of Nectandra megapotamica Spreng. (Lauraceae)

The volatile oils from Nectandra megapotamica Spreng. leaves, collected in February and August of 2007 and at 7:00 and 12:00 h (samples A - D), were extracted by hydrodistillation and the chemical composition was analyzed by GC-FID and GC/MS. A total of nineteen compounds were identified with predominance of oxygenated sesquiterpenes, among them, α-bisabolol, was the main constituent (62.3-69.4 %). After chromatographic separation procedures, this compound was purified from crude oil and its structure was confirmed by analysis of NMR data. This paper describes for the first time the composition of the leaves volatile oil from N. megapotamica.

Chemical constituents from red algae Bostrychia radicans (Rhodomelaceae): new amides and phenolic compounds

This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl)-benzamide (0.019%) and N,4-dihydroxy-N-(2'-hydroxyethyl)-benzeneacetamide (0.023%). These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl)-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl)-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl)-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family.

Isolation and antitrichomonal activity of the chemical constituents of the leaves of Maytenus phyllanthoides Benth. (Celastraceae)

Cyclolignan (+)-lyoniresinol (1), veratric acid (2), vanillic acid (3), lupeol, oleanolic acid, 3β-hydroxy-urs-11-en-28,13β-lactone (4), the mixture of α- and β-amyrin, trans-polyisoprene, and β-sitosterol were isolated from the leaves of Maytenus phyllanthoides. The structures of the isolated compounds were established based on spectroscopic data, mainly ¹H and 13C nuclear magnetic resonance (NMR). Compound 1, its acetate analog 1a, and compounds 2, 3, and 4 were tested against Trichomonas vaginalis. (+)-Lyoniresinol showed activity corresponding to IC50 17.57 µM. This is the first report on the occurrence of 3β-hydroxy-urs-11-en-28,13β-lactone (4) in the Celastraceous family and lyoniresinol in the Maytenus genus, and on the antitrichomonal activity of lyoniresinol.

Salacia crassifolia (Celastraceae): CHEMICAL CONSTITUENTS AND ANTIMICROBIAL ACTIVITY

The phytochemical study of hexane extract from leaves of Salacia crassifolia resulted in the isolation of 3β-palmitoxy-urs-12-ene, 3-oxofriedelane, 3β-hydroxyfriedelane, 3-oxo-28-hydroxyfriedelane, 3-oxo-29-hydroxyfriedelane, 28,29-dihydroxyfriedelan-3-one, 3,4-seco-friedelan-3-oic acid, 3β-hydroxy-olean-9(11):12-diene and the mixture of α-amirin and β-amirin. β-sitosterol, the polymer gutta-percha, squalene and eicosanoic acid were also isolated. The chemical structures of these constituents were established by IR, 1H and 13C NMR spectral data. Crude extracts and the triterpenes were tested against Entamoeba histolytica, Giardia lamblia and Trichomonas vaginalis and no activity was observed under the in vitro assay conditions. The hexane, chloroform, ethyl acetate and ethanol crude extracts, and the constituent 3,4-seco-friedelan-3-oic acid and 28,29-dihydroxyfriedelan-3-one showed in vitro antimicrobial activity against Salmonella typhimurium, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus cereus, Listeria monocytogenes, Streptococcus sanguinis and Candida albicans.

CHEMICAL CONSTITUENTS, ANTI-INFLAMMATORY, AND FREE-RADICAL SCAVENGING ACTIVITIES OF Guettarda viburnoides CHAM. & SCHLTDL. (RUBIACEAE)

Chemical investigation of Guettarda viburnoides (leaves) led to the isolation of ursolic acid, uncaric acid, secoxyloganin, and grandifloroside, along with a mixture of quercetin-3-O-β-D-galactopyranoside and quercetin-3-O-β-D-glucopyranoside, and of β-sitosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of their NMR data. The crude extract, ethyl acetate fraction, aqueous-methanol fraction, and grandifloroside showed significant DPPH free-radical scavenging activities with IC50 ranging from 18.92 to 26.47 µg mL-1. The topical administration of the crude extract and fractions markedly reduced the croton oil-induced mice ear edema in 67.0%-99.0%. Inhibition of tissue MPO activity was also observed, which demonstrated an anti-inflammatory effect of the G. viburnoides species.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Explaining the Shifts of International Trade in Pulp and Paper Industry

The pulp and paper industry is currently facing broad structural changes due to global shifts in demand and supply. These changes have significant impacts on national economies worldwide. In this paper, we describe the recent trends in the pulp and recovered paper (RP) production, and estimate augmented gravity models of bilateral trade for chemical pulp and RP exports with panel data. According to our results, there is some variation in the effects of the traditional gravity-model variables between pulp grades and RP. The results imply also that, in comparison to export supply, import demand plays a larger role in determining the volume of exports. Finally, it is evident that Asia, particularly China, is the most important driver of chemical pulp and RP trade: China is hungry for fiber, and must import to satisfy its growing needs. Moreover, the speed of China’s growth in chemical pulp and RP imports has been driving the increased significance of planted forests in the exports of hardwood pulp (BHKP) as well.

Chemical changes in biomass during torrefaction

Torrefaction is moderate thermal treatment (~200-300 °C) of biomass in an inert atmosphere. The torrefied fuel offers advantages to traditional biomass, such as higher heating value, reduced hydrophilic nature, increased its resistance to biological decay, and improved grindability. These factors could, for instance, lead to better handling and storage of biomass and increased use of biomass in pulverized combustors. In this work, we look at several aspects of changes in the biomass during torrefaction. We investigate the fate of carboxylic groups during torrefaction and its dependency to equilibrium moisture content. The changes in the wood components including carbohydrates, lignin, extractable materials and ashforming matters are also studied. And at last, the effect of K on torrefaction is investigated and then modeled. In biomass, carboxylic sites are partially responsible for its hydrophilic characteristic. These sites are degraded to varying extents during torrefaction. In this work, methylene blue sorption and potentiometric titration were applied to measure the concentration of carboxylic groups in torrefied spruce wood. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic group contents. Thus, both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction. This provides new information to the chemical changes occurring during torrefaction. The effect of torrefaction temperature on the chemistry of birch wood was investigated. The samples were from a pilot plant at Energy research Center of the Netherlands (ECN). And in that way they were representative of industrially produced samples. Sugar analysis was applied to analyze the hemicellulose and cellulose content during torrefaction. The results show a significant degradation of hemicellulose already at 240 °C, while cellulose degradation becomes significant above 270 °C torrefaction. Several methods including Klason lignin method, solid state NMR and Py-GC-MS analyses were applied to measure the changes in lignin during torrefaction. The changes in the ratio of phenyl, guaiacyl and syringyl units show that lignin degrades already at 240 °C to a small extent. To investigate the changes in the extractives from acetone extraction during torrefaction, gravimetric method, HP-SEC and GC-FID followed by GC-MS analysis were performed. The content of acetone-extractable material increases already at 240 °C torrefaction through the degradation of carbohydrate and lignin. The molecular weight of the acetone-extractable material decreases with increasing the torrefaction temperature. The formation of some valuable materials like syringaresinol or vanillin is also observed which is important from biorefinery perspective. To investigate the change in the chemical association of ash-forming elements in birch wood during torrefaction, chemical fractionation was performed on the original and torrefied birch samples. These results give a first understanding of the changes in the association of ashforming elements during torrefaction. The most significant changes can be seen in the distribution of calcium, magnesium and manganese, with some change in water solubility seen in potassium. These changes may in part be due to the destruction of carboxylic groups. In addition to some changes in water and acid solubility of phosphorous, a clear decrease in the concentration of both chlorine and sulfur was observed. This would be a significant additional benefit for the combustion of torrefied biomass. Another objective of this work is studying the impact of organically bound K, Na, Ca and Mn on mass loss of biomass during torrefaction. These elements were of interest because they have been shown to be catalytically active in solid fuels during pyrolysis and/or gasification. The biomasses were first acid washed to remove the ash-forming matters and then organic sites were doped with K, Na, Ca or Mn. The results show that K and Na bound to organic sites can significantly increase the mass loss during torrefaction. It is also seen that Mn bound to organic sites increases the mass loss and Ca addition does not influence the mass loss rate on torrefaction. This increase in mass loss during torrefaction with alkali addition is unlike what has been found in the case of pyrolysis where alkali addition resulted in a reduced mass loss. These results are important for the future operation of torrefaction plants, which will likely be designed to handle various biomasses with significantly different contents of K. The results imply that shorter retention times are possible for high K-containing biomasses. The mass loss of spruce wood with different content of K was modeled using a two-step reaction model based on four kinetic rate constants. The results show that it is possible to model the mass loss of spruce wood doped with different levels of K using the same activation energies but different pre-exponential factors for the rate constants. Three of the pre-exponential factors increased linearly with increasing K content, while one of the preexponential factors decreased with increasing K content. Therefore, a new torrefaction model was formulated using the hemicellulose and cellulose content and K content. The new torrefaction model was validated against the mass loss during the torrefaction of aspen, miscanthus, straw and bark. There is good agreement between the model and the experimental data for the other biomasses, except bark. For bark, the mass loss of acetone extractable material is also needed to be taken into account. The new model can describe the kinetics of mass loss during torrefaction of different types of biomass. This is important for considering fuel flexibility in torrefaction plants.

FT-IR and MAS NMR analysis of montmorillonite K10 supported MF2 reagents and their activity as catalysis /

ZnF2, CdF2, and CUF2 have been adsorbed onto the surface of montmorillonite K10, and the infrared and 19F, 27 AI, and 29Si MAS NMR spectra of the reagents over a range of loadings have been obtained. CUF2 was observed to attack the Si02 layer and form the complex CuSiF6, Zn F2 tends to attack the aluminium oxide layer, in which Zn isomorphously replaces AI, and forms AIF3 and AIF4 - complexes. All the spectroscopic evidence ruled out the formation of any AI-F and/or Si-F free species as CdF2 is adsorbed on the surface of montmorillonite K10. The reactivity of MF2-K10 reagents towards Friedel-Crafts benzylation of benzene with benzyl chloride varied from one reagent to another. ZnF2-K10 was observed to be the most reactive and CUF2 was the least reactive.

Simultaneous extraction of order parameters and orientational distribution fuctions from 31[superscript]P NMR spectra of magnetically partially oriented phospholipid bilayers

Order parameter profiles extracted from the NMR spectra of model membranes are a valuable source of information about their structure and molecular motions. To al1alyze powder spectra the de-Pake-ing (numerical deconvolution) ~echnique can be used, but it assumes a random (spherical) dist.ribution of orientations in the sample. Multilamellar vesicles are known to deform and orient in the strong magnetic fields of NMR magnets, producing non-spherical orientation distributions. A recently developed technique for simultaneously extracting the anisotropies of the system as well as the orientation distributions is applied to the analysis of partially magnetically oriented 31p NMR spectra of phospholipids. A mixture of synthetic lipids, POPE and POPG, is analyzed to measure distortion of multilamellar vesicles in a magnetic field. In the analysis three models describing the shape of the distorted vesicles are examined. Ellipsoids of rotation with a semiaxis ratio of about 1.14 are found to provide a good approximation of the shape of the distorted vesicles. This is in reasonable agreement with published experimental work. All three models yield clearly non-spherical orientational distributions, as well as a precise measure of the anisotropy of the chemical shift. Noise in the experimental data prevented the analysis from concluding which of the three models is the best approximation. A discretization scheme for finding stability in the algorithm is outlined

The effects of additives and chemical modification on the solution properties of thermo-sensitive polymers

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes.

Decomposition in soil and chemical characteristics of pollen

The input to soils made by pollen and its subsequent mineralization has rarely been investigated from a soil microbiological point of view even though the small but significant quantities of C and N in pollen may make an important contribution to nutrient cycling. The relative resistance to decomposition of pollen exines (outer layers) has led to much of the focus of pollen in soil being on its preservation for archaeological and palaeo-ecological purposes. We have examined aspects of the chemical composition and decomposition of pollen from birch (Betula alba) and maize (Zea mays) in soil. The relatively large N contents, small C-to-N ratios and large water-soluble contents of pollen from both species indicated that they would be readily mineralized in soil. When added to soil and incubated at 16 degrees C an amount of C equivalent to 22-26% of the added pollen C was lost as CO2 within 22 days, with the Z. mays pollen decomposing faster. For B. alba pollen, the water-soluble fraction decomposed faster than the whole pollen and the insoluble fraction decomposed more slowly over 22 days. By contrast, there were no significant differences in the decomposition rates of the different fractions from Z. mays pollen. Solid-state C-13 nuclear magnetic resonance (NMR) revealed no gross chemical differences between the pollen of these two species, with strong resonances in the alkyl- and methyl-C region (0-45 p.p.m.) indicative of aliphatic compounds, the O-alkyl-C (60-90 p.p.m.) and the acetal- and ketal-C region (90-110 p.p.m.) indicative of polysaccharides, and the carbonyl-C region indicative of peptides and carboxylic acids. In addition, both pollens gave a small but distinct resonance at 55 p.p.m. attributed to N-alkyl-C. The resonances attributed to polysaccharides were lost completely or substantially reduced after decomposition.

Liming upland grassland: the effects on earthworm communities and the chemical characteristics of carbon in casts

Different earthworm species have different tolerances of acid soil conditions, and the application of lime to upland grassland to improve the grazing quality may therefore alter the size and diversity of the earthworm community. Altering soil properties may also affect the chemical characteristics of organic C in earthworm casts. We surveyed the earthworm community of an upland grassland in southern Scotland at the outset of annual lime applications, and after 3 years, and used C-13 nuclear magnetic resonance (NMR) spectroscopy to assess the distribution of C between different functional groups in the organic matter. In addition, soil was incubated for 8 weeks with several earthworm species in the presence or absence of lime, and the earthworm casts were subsequently analysed by C-13 NMR spectroscopy. Liming did not significantly affect earthworm abundance or species diversity, but it did affect the chemical composition of the casts. Casts from earthworms incubated in unlimed soil had greater ratios of alkyl-C to O-alkyl-C, indicative of more decomposed, recalcitrant C, and spectra from litter-feeding species had the greatest intensities of O-alkyl-C signals. In limed soil, the largest O-alkyl-C signal intensities were not restricted to litter-feeding species, indicating an increase in the quality of organic matter ingested by geophagous species.

Decomposition in soil and chemical characteristics of pollen

The input to soils made by pollen and its subsequent mineralization has rarely been investigated from a soil microbiological point of view even though the small but significant quantities of C and N in pollen may make an important contribution to nutrient cycling. The relative resistance to decomposition of pollen exines (outer layers) has led to much of the focus of pollen in soil being on its preservation for archaeological and palaeo-ecological purposes. We have examined aspects of the chemical composition and decomposition of pollen from birch (Betula alba) and maize (Zea mays) in soil. The relatively large N contents, small C-to-N ratios and large water-soluble contents of pollen from both species indicated that they would be readily mineralized in soil. When added to soil and incubated at 16 degrees C an amount of C equivalent to 22-26% of the added pollen C was lost as CO2 within 22 days, with the Z. mays pollen decomposing faster. For B. alba pollen, the water-soluble fraction decomposed faster than the whole pollen and the insoluble fraction decomposed more slowly over 22 days. By contrast, there were no significant differences in the decomposition rates of the different fractions from Z. mays pollen. Solid-state C-13 nuclear magnetic resonance (NMR) revealed no gross chemical differences between the pollen of these two species, with strong resonances in the alkyl- and methyl-C region (0-45 p.p.m.) indicative of aliphatic compounds, the O-alkyl-C (60-90 p.p.m.) and the acetal- and ketal-C region (90-110 p.p.m.) indicative of polysaccharides, and the carbonyl-C region indicative of peptides and carboxylic acids. In addition, both pollens gave a small but distinct resonance at 55 p.p.m. attributed to N-alkyl-C. The resonances attributed to polysaccharides were lost completely or substantially reduced after decomposition.