Carbohydrates, acidic derivatives analysis

The techniques developed for the LF 3600 N-terminal protein sequencer (Beckman Instr.) provide a fast and efficient way to positively identify Ser (0-linked Sac), -Thr (0-linked Sac) and Asn (N-linked Sac) carbohydrate structures during N-terminal sequence analysis (Gooley et al., 1995). Liquid phase anhydrous trifluoroacetic acid (TEA) is used to extract glycosylated, polar amino acid derivatives from the reaction cartridge. These amino acids are then converted into PTH derivatives which can be... 

Native and microcrystalline cellulose precoated plates are used in the life sciences for the separation of polar compounds (e.g. carbohydrates, carboxylic acids, amino acids, nucleic acid derivatives, phosphates, etc) [85]. These layers are unsuitable for the separation of compounds of low water solubility unless first modified, for example, by acetylation. Several chemically bonded layers have been described for the separation of enantiomers (section 10.5.3). Polyamide and polymeric ion-exchange resins are available in a low performance grade only for the preparation of laboratory-made layers [82]. Polyamide layers are useful for the reversed-phase separation and qualitative analysis of phenols, amino acid derivatives, heterocyclic nitrogen compounds, and carboxylic and sulfonic acids. Ion-exchange layers prepared from poly(ethyleneimine), functionalized poly(styrene-divinylbenzene) and diethylaminoethyl cellulose resins and powders and are used primarily for the separation of inorganic ions and biopolymers. 

Other analytical procedures based on h.p.l.c.-m.s. or g.c.-m.s. include the monitoring of dermatan sulphate and heparin,34 analysis of complex mixtures of carbohydrate-derived urinary acids,35 analysis of 2,3 -dideoxycytidine in plasma,36 and the characterisation of the radiation-induced decomposition of thymine and thymidine. ... 

Although Edson2298 postulates that carbohydrates, as well as their derivatives are antiketogenic and compete with fatty acids for oxygen in the liver (as demonstrated by the Warburg technic), his results are only inferential since they are not based on the direct determination of the fatty acid decrease. Bobbitt and Deuel,82 on the other hand, found that not only was the formation of ketone bodies depressed when glycogen was added to the medium, but also that the disappearance of butyrate, as determined by direct analysis, was increased under such circumstances. 

First attempts to combine pyrolysis with in situ HMDS silylation of organic art materials were reported by Chiavari et al., who were successful in obtaining trimethylsilyl derivatives of fatty acids [52], amino acids [53] and carbohydrates [54]. The same authors also applied pyrolysis-silylation to the analysis of different kinds of natural resins and for each of them diagnostic silylated compounds were identified, even if many were difficult to assign precise structures [55],... 

In polymer applications derivatives of oils and fats, such as epoxides, polyols and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector oleochemically-based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives has provided extraordinary performance benefits to the end-customer. Selected products, such as the anionic surfactant fatty alcohol sulfate have been investigated thoroughly with regard to their environmental impact compared with petrochemical based products by life-cycle analysis. Other product examples include carbohydrate-based surfactants as well as oleochemical based emulsifiers, waxes and emollients. 

Despite the many advantages of converting free sugars into their O-trimethylsilyl derivatives, the formation of anomeric and isomeric derivatives (see Section IV, p. 38) may constitute a problem, especially with complex mixtures. Much effort has, therefore, been expended in seeking carbohydrate derivatives, suitable for analysis, in which the anomeric center has been eliminated. This may conveniently be accomplished by oxidation to the acid or lactone, by... 

The major limitation of GC is the requirement for heat stability and volatility of the sample. Obviously, compounds that decompose at elevated temperatures (below 250°C) cannot normally be subjected to GC analysis. Many compounds of biochemical interest are not volatile in the useful temperature range of GC (up to about 200-250°C). Such compounds can often be converted to volatile derivatives. Hydroxyl groups in alcohols, carbohydrates, and sterols are converted to derivatives by trimethylsilylation or acetylation. Amino groups can also be converted to volatile derivatives by acetylation and silylation. Fatty acids are transformed to methyl esters for GC analysis, as described in Experiment 6. 

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