Analysis Of LCABs And LACHs In Environmental And Geological Samples And Separation Of Bioactive Compounds From Cranberry

Linear long chain alkylbenzenes (LCABs) are present as an impurity in linear alkylbenzene sulfonates (LAS), widely used surfactants. They have also been identified from geological samples. It is thought that they have no geological origin but present in geological samples as an impurity during washing and cleaning the laboratory equipments. In the first part of our research a review article has been written to show that LCABs have both synthetic and geological origin. The range of LCABs in geological samples is wider than that used in surfactants, which indicates that both have different origin. Linear LCABs containing 10-14 carbon atoms in their alkyl chain are used for the manufacturing of LAS, used as surfactants. Linear LCABs found in the riverine and marine water and sediments are usually in the same range as that in the surfactant formulations. All of it concludes that the main source of linear LCABs in riverine and marine water and sediments are synthetic alkylbenzenes. On the other hand, the range of LCABs found in air samples, crude oil, coal beds, coal smoke and cigarette smoke is much higher than that found in surfactants. The relative abundance of LCABs isomers in mixtures derived from synthetic sources is markedly different from those isolated from natural sources. Long chain fatty acids and alcohols are common compounds in bacteria and algae. Unsaturated fatty acids are also considered to be too unstable to persist in geological samples for long period of time. Moreover the results of experiments of some researchers, who showed how these compounds can be converted into LCABs, also strengthen their geological origin. Sulfur, lignin and clay can play an important role for such kind of conversions. Such reactions involve thermal cyclization, aromatization and decarboxylation. The reactions of long chain alcohols and fatty acids with benzene in the presence of clay can also be another source of LCABs in geological samples. They have also been identified in the resistant biopolymer and lipid extracts from different species of bacteria. All these represent unequivocal evidence for a natural origin for LCABs. Polyenes are another source of LCABs in geological samples. Quinone and desulfurization of organic sulfur molecules can produce di- or trialkylbenzenes by the process of catagenesis and thermal maturation, but they were not the major source of LCABs in geological samples. It can be concluded that LCABs in water have synthetic origin but air samples might have both synthetic and geological origins. LCABs present in the coal and crude oil also have geological origin.A GC-MS method was developed for the analysis of hydrogenated vacuum gas oil (HVGO). Open chain hydrocarbons, aromatic hydrocarbons, naphthalenic hydrocarbons and long chain alkylcyclohexanes (LACHs) were analyzed in a single run. Complete molecular description of hydrogenated vacuum gas oil (HVGO) had been obtained at different stages of hydrogenation process. HVGO contains a very small amount of sulfur and nitrogen. No nitrogen was detected in HVGO 3 and HVGO 4 but as compare to other HVGO samples they contain relatively high percentage of sulfur i.e.0.258% and 0.140% respectively. HVGO 1 has highest percentage of C/H ratio which indicates that it contains lowest percentage of aromatics. Group type analysis verifies this conclusion and no aromatics were detected in HVGO 1 and HVGO 2. Quantitative analysis was also done. For quantitative analysis we used external standard curve method and similar deduced method. Quantitative analysis showed that HVGO mainly consisted of long chain molecules. Quantity of short chain molecule was negligible. It was concluded that HVGO contained n-paraffins from C5 to C38 while the range of long chain alkylbenzenes (LACHs) present in HVGO was from C7 to C32 in side chain. C32 was the heavier detectable LACH in the HVGO. LACHs ranging from C18 to C27 were the main constituent of cyclohexanes in HVGO. Maximum concentration of LACHs was found at C26 (7.4g/L), C28 (2.0g/L), C25 (10.9g/L), C26 (7.1g/L), C25 (3.6g/L) and C26 (1.4g/L) for HVGO1, HVGO 2, HVGO 3, HVGO 4, HVGO 5, HVGO 6 respectively. Very low concentration of alkylbenzenes and high concentration of LACHs proved that many aromatic compounds had been converted into saturated compounds during hydrogenation process. These results would increase the analytical information concerning heavy cuts and would be helpful to optimize petroleum conversion processes like hydrotreatment, hydrocraking or FCC.Counter-current chromatography (CCC) was used for the separation of flavonol on a preparative scale from crude extract of cranberry. The preparative separation of p-coumaric acid, delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside from cranberry by countercurrent chromatography (CCC) was presented. The separation was performed with a two phase solvent system composed of butanol-methanol-water including 0.05% trifluoroacetic acid at a volume ratio of 4:1:5, The two-phase solvent system was selected through partition factor (K value) using Robot and further selected by analytical CCC. For CCC separation analytical CCC instrument Model GS10AB was used. After the sample injection the absorbance was measured at 254 nm. Thus three compounds p-coumaric acid at 98% purity, delphinidin-3-O-sambubioside at 95% purity and cyanidin-3-O-sambubioside at 73% purity were obtained. Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside were again separated by prep-HPLC, yielding delphinidin-3-O-sambubioside at 99% purity and cyanidin-3-O-sambubioside more than 95%. The identification of p-coumaric acid, delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside was performed by ESI-MS, 1H-NMR and 13C-NMR spectra.