Aldehydes, detection identification

Many impurities are present in commercial caprolactam which pass into the liquid wastes from PCA manufacture from which caprolactam monomer may be recovered. Also, the products of die thermal degradation of PCA, dyes, lubricants, and other PCA fillers may be contained in the regenerated CL. Identification of die contaminants by IR spectroscopy has led to the detection of lower carboxylic acids, secondary amines, ketones, and esters. Aldehydes and hydroperoxides have been identified by polarography and thin-layer chromatography. 

The identification and quantification of potentially cytotoxic carbonyl compounds (e.g. aldehydes such as pentanal, hexanal, traw-2-octenal and 4-hydroxy-/mAW-2-nonenal, and ketones such as propan- and hexan-2-ones) also serves as a useful marker of the oxidative deterioration of PUFAs in isolated biological samples and chemical model systems. One method developed utilizes HPLC coupled with spectrophotometric detection and involves precolumn derivatization of peroxidized PUFA-derived aldehydes and alternative carbonyl compounds with 2,4-DNPH followed by separation of the resulting chromophoric 2,4-dinitrophenylhydrazones on a reversed-phase column and spectrophotometric detection at a wavelength of378 nm. This method has a relatively high level of sensitivity, and has been successfully applied to the analysis of such products in rat hepatocytes and rat liver microsomal suspensions stimulated with carbon tetrachloride or ADP-iron complexes (Poli etui., 1985). 

Identification of pyridoxal phosphate as coenzyme suggested the aldehyde group on pyridoxine might form an intermediate Schiff s base with the donor amino acid. Pyridoxamine phosphate thus formed would in turn donate its NH2 group to the accepting a-ketonic acid, a scheme proposed by Schlenk and Fisher. 15N-labeling experiments and, later, the detection of the Schiff s base by its absorption in UV, confirmed the overall mechanism. Free pyridoxamine phosphate however does not participate in the reaction as originally proposed. Pyridoxal phosphate is invariably the coenzyme form of pyridoxine. 

Volatile compounds generated by model systems of zeln, corn amylopectin and corn oil extruded at barrel temepratures of 120°C and 165°C were analyzed by GC and GC/MS. The largest quantities of lipid oxidation products were detected in systems containing all three components. In each system, the quantity of 2,4-deca-dienal was low relative to the quantities of hexanal, heptanal and benzaldehyde. Identification of the Maillard reaction products, 2-methyl-3(or 6)-pentyl-pyrazine, 2-methyl-3(or 6)-hexylpyrazine and 2,5-di-methyl-3-pentylpyrazine, suggested that lipid-derived aldehydes might be involved in the formation of substituted pyrazines. 4-Methylthiazole was identified as a major decomposition product of thiamin when corn meal containing 0.5% thiamin was extruded at a final temperature of 180°C. 

Cordis, G.A., Das, D.K., and Riedel, W. 1998a. High-performance liquid chromato-graphic peak identification of 2,4-dinitrophenylhydrazine derivatives of lipid peroxidation aldehydes by photodiode array detection. J. Chromatogr. 798 117-123. 

Determination of free 4-hydroxy-2,3-trans-alkenals by HPLC Esterbauer (1982) has developed a procedure for the qualitative detection and quantitative measurement of steady-state concentrations of free hydroxyalkenals (specifically HNE) in tissues, tissue extracts and lipid containing foodstuffs. Their method utilizes UV-detection of the free aldehyde at its 220 nm UV-absorption maximum and peak identification was confirmed by mass spectrometry. An effective purification and concentration step is employed using dichloromethane to extract hydroxyalkenals from samples trapped on Extrelut columns. The samples are subsequently purified by solid-phase extraction on octadecyl-bonded silica (ODS) disposable cartridges and then analysed by HPLC. 

Amino acids are quickly deaminated by L-ascorbic acid, leading to browning reactions (66). In the presence of oxygen, iron, and ascorbic acid or DHA, the amino acids gave ammonia, carbon dioxide, and an aldehyde with one carbon less than the original acid (67,68). The aldehydes are isolated as dimedone derivatives and are useful for identification of the amino acids. In the presence of copper and UV light, the deamination is increased. The red color 69-73) formed upon reaction of DHA with amino acids was used for their detection. Recent studies (74-78) of the reaction of DHA with amino acids led to the isolation of a product that changes readily to a novel, stable, free radical species... 

Use Reagent for the detection of ethyl alcohol and the identification of aldehydes. 

Odor compounds may also be released from the plastic materials used in cars. The variety of plastics and possible chemical compounds is broad, which makes the identification of odor causing compounds an extremely comphcated task. An effective and rapid screening of VOCs and semi-VOCs from materials used in automobiles was developed by utihzing the SPME technique [28]. The low molecular weight compoimds extracted from five different automobile materials included different benzene derivatives, aldehydes, esters, biphenyls, phthalates, butylated hydroxytoluene, phenols, alcohols, styrene, triethylene-diamine, carboxylic acids and ketones. A considerable munber of VOCs and semi-VOCs were detected, indicating that more attention should be paid to the selection of materials and additives for automotive parts. 

Simultaneous detection of aldehydes and hydroxyl substituted compounds, focused on identification of compounds in ozonated drinking water... 

In aliphatic or aromatic hydrocarbons, alcohols may be detected sensitively on the basis of the strongly infrared-active OH bands, as may aldehydes or ketones on the basis of the similarly high-intensity CO bands the presence of organic amines is revealed by the NH bands, and that of nitriles by the CN bands. These same bands may be used, although with lower sensitivity, for the determination of aldehyde impurities in alcohols, or alcohol impurities in nitriles. The appearance of new bands in the infrared spectrum does not always lead to identification of the impurity component, but it definitely draws attention to the contaminated nature of the solvent. 

A number of hydrocarbons were photolysed in a reaction vessel according to the system described by Prof. Wameck, MPI Mainz. Measurements were made with fluorometric and polarographic detection. The photolysis experiment were reproducible with a standard deviation of 3-6 %. Several hydroperoxides could be identifred by "cross"-identifications by comparing the retention times of different photolysed hydrocarbons, aldehydes, ketones and alcohol s with the unknown peaks. 

---