Methyl quantitative analysis

Noncatalytic Reactions Chemical kinetic methods are not as common for the quantitative analysis of analytes in noncatalytic reactions. Because they lack the enhancement of reaction rate obtained when using a catalyst, noncatalytic methods generally are not used for the determination of analytes at low concentrations. Noncatalytic methods for analyzing inorganic analytes are usually based on a com-plexation reaction. One example was outlined in Example 13.4, in which the concentration of aluminum in serum was determined by the initial rate of formation of its complex with 2-hydroxy-1-naphthaldehyde p-methoxybenzoyl-hydrazone. ° The greatest number of noncatalytic methods, however, are for the quantitative analysis of organic analytes. For example, the insecticide methyl parathion has been determined by measuring its rate of hydrolysis in alkaline solutions. 

Instmmental methods of analysis provide information about the specific composition and purity of the amines. QuaUtative information about the identity of the product (functional groups present) and quantitative analysis (amount of various components such as nitrile, amide, acid, and deterruination of unsaturation) can be obtained by infrared analysis. Gas chromatography (gc), with a Hquid phase of either Apiezon grease or Carbowax, and high performance Hquid chromatography (hplc), using siHca columns and solvent systems such as isooctane, methyl tert-huty ether, tetrahydrofuran, and methanol, are used for quantitative analysis of fatty amine mixtures. Nuclear magnetic resonance spectroscopy (nmr), both proton ( H) and carbon-13 ( C), which can be used for quaHtative and quantitative analysis, is an important method used to analyze fatty amines (8,81). 

As the majority of stabilisers has the structure of aromatics, which are UV-active and show a distinct UV spectrum, UV spectrophotometry is a very efficient analytical method for qualitative and quantitative analysis of stabilisers and similar substances in polymers. For UV absorbers, UV detection (before and after chromatographic separation) is an appropriate analytical tool. Haslam et al. [30] have used UV spectroscopy for the quantitative determination of UVAs (methyl salicylate, phenyl salicylate, DHB, stilbene and resorcinol monobenzoate) and plasticisers (DBP) in PMMA and methyl methacrylate-ethyl acrylate copolymers. From the intensity ratio... 

F.C. Y.Wang and P.B. Smith, Quantitative analysis and structure determination of styrene/ methyl methacrylate copolymers by pyrolysis gas chromatography, Anal. Chem., 68, 3033 3037(1996). 

There is a recent trend towards simultaneous CE separations of several classes of food additives. This has so far been applied to soft drinks and preserved fruits, but could also be used for other food products. An MEKC method was published (Lin et al., 2000) for simultaneous separation of intense sweeteners (dulcin, aspartame, saccharin and acesulfame K) and some preservatives (sorbic and benzoic acids, sodium dehydroacetate, methyl-, ethyl-, propyl- and isopropyl- p-hydroxybenzoates) in preserved fruits. Ion pair extraction and SPE cleanup were used prior to CE analysis. The average recovery of these various additives was 90% with good within-laboratory reproducibility of results. Another procedure was described by Frazier et al. (2000b) for separation of intense sweeteners, preservatives and colours as well as caffeine and caramel in soft drinks. Using the MEKC mode, separation was obtained in 15 min. The aqueous phase was 20 mM carbonate buffer at pH 9.5 and the micellar phase was 62 mM sodium dodecyl sulphate. A diode array detector was used for quantification in the range 190-600 nm, and limits of quantification of 0.01 mg/1 per analyte were reported. The authors observed that their procedure requires further validation for quantitative analysis. 

IR spectroscopy has been used for the quantitative analysis of a mixture of 5-ethyl-3-methyl-substituted thienothiophenes I and 2, and to detect traces of thienothiophene 2 in thienothiophene l. °... 

A continuous-flow reactor with a fixed catalyst bed was employed under pressurized conditions. The reactor was made of stainless steel with an inner diameter of 6 mm. All products and unreacted feed materials were withdrawn in the gaseous state from the reactor through a heated pressure let-down valve, A quantitative analysis of the products was carried out by gas chromatography. The time factor, which corresponds to contact time, is expressed by W/F, where W is the weight of catalyst (g) and F is the total flow rate of feed (mol/hr). Chemisorption of H2, CO and methyl iodide (Mel) were measured by a conventional glass vacuum system. 

In examining the structure of a polysaccharide, it is convenient to consider the methods involved under the three main headings (a) quantitative analysis, (b) methylation, and (c) periodate oxidation. These techniques may be supplemented by partial or enzymic hydrolysis as the circumstances indicate. Each of these aspects of polysaccharide chemistry may be aided by the application of gas-liquid chromatography, either qualitative or quantitative, or both. Thus, separations impossible by other techniques may often be achieved, and analytical data obtained in a fraction of the time demanded by other methods. 

The highest OAVs were found for 4-hydroxy-2,5-dimethyl-3(2H)-fura-none, followed by ethyl 2-methylpropanoate, ethyl 2-methylbutanoate, methyl 2-methylbutanoate and ( ,Z)-l,3,5-undecatriene. It is assumed that these odorants contribute strongly to the aroma of pineapples [50]. However, FD factors and OAVs are functions of the odorants concentrations in the extract, and are not psychophysical measures for perceived odour intensity [71,72]. To take this criticism into account, aroma models are prepared on the basis of the results of the quantitative analysis (reviewed in [9]) and in addition omission experiments are performed [9]. 

Several techniques have been described in the past for the analysis of VLCFA, pristanic acid and phytanic acid [1, 10]. In our hands gas chromatography-mass spectrometry (GC-MS) analysis after derivatisation with N-methyl-N-(tert-butyldi-methylsilyl) trifluoroacetamide (MTBSTFA), is a robust and reliable method for the quantitative analysis of VLCFA, pristanic acid and phytanic acid, especially when combined with stable isotopes for C26 0, C24 0, C22 0, phytanic acid and pristanic acid [13]. In order to allow measurement of the total pool of VLCFA, pristanic acid and phytanic acid, samples need to be subjected to both acidic and alkaline hydrolysis, followed by extraction into hexane. After the hexane phase is washed once more, the sample is dried under nitrogen followed by addition of pyridine and MTBSTFA and heating of the samples at 80°C. The sample is subsequently dried again under nitrogen and taken up in hexane, followed by GC-MS analysis. 

Capillary GLC analysis (12 m, cross-linked methyl silicone, programmed, 45°C, 3°C/min, retention time of ethyl (Z)-crotonate, 2.5 min). Ethyl (E)-crotonate has a retention time of 2.95 min under the same conditions. Careful quantitative analysis reveals that the ratio of 1 and E isomers is reproducibly in the range 58 1 to 59 1. 

A number of methods have been reported recently for the gas chromatographic separation of nonderivatized "free" barbiturates. The method (35) below is applicable to the qualitative and quantitative analysis of barbiturates, glutethimide and Dilantin from serum. It is a simple, rapid but accurate procedure using only 3 cm of serum. Dilantin could be separated on the same column as the barbiturates after it had been converted to its methylated derivative. 

The biotransformation of linalool by Botrytis cinerea has also been described [60]. After addition of linalool to botrytised must, a series of transformation products was identified (E)- (49) and (Z)-2,6-dimethyl-2,7-octadiene-l,6-diol (48), trans- (76) and cw-furanoid linalool oxide (77), trans- (78) and c/s-pyranoid linalool oxide (79) and their acetates (80, 81), 3,9-epoxy-p-menth-1 -ene (75) and 2-methyl-2-vinyltetrahydrofuran-5-one (66) (unsaturated lactone), Fig. (11). Quantitative analysis however, showed that linalool was predominantly (> 90%) metabolised to ( )-2,6-dimethyl-2,7-octadiene-l,6-diol (49) by B. cinerea. The other compounds were only found as by-products in minor concentrations. 

The quantitative analysis was performed with the technique of gas chromato-graphy/mass spectroscopy. A radioactive sample of Cisobitan , which was labelled with 14C at the geminal methyl groups and which was hexadeuterated in the 4,4-dimethyl-siloxy position, was used for this investigation. Silylation of the metabolic products was carried out with hexamethyldisilazane. 

Methyl esters were identified by comparison with authentic compounds on both the Carbowax 20M column and a XE-60 (a General Electric cyanosilicone gum) column. Some of the earlier identifications were made with a Carbowax 20M + H3P04 column and confirmed on l,2,3-tris(2-cyanoethoxy) propane. Also, some of the analyses of free acids were run on a Carbowax 20M-TPA(terephthalic acid terminated) column rather than the FFAP. Quantitative analysis of free acids and methyl esters was carried out using internal standards. Acetophenone was used with the acids, and veratrole was used with the methyl esters. Formic acid in the nitrobenzene and nitric acid liquors was analyzed quantitatively by direct calibration. 

The reaction between ammonia and methyl halides has been studied by using ab initio quantum-chemical methods.90 An examination of the stationary points in the reaction potential surface leads to a possible new interpretation of the detailed mechanism of this reaction in different media, hr the gas phase, the product is predicted to be a strongly hydrogen-bonded complex of alkylammonium and halide ions, in contrast to the observed formation of the free ions from reaction hr a polar solvent. Another research group has also studied the reaction between ammonia and methyl chloride.91 A quantitative analysis was made of the changes induced on the potential-energy surface by solvation and static uniform electric fields, with the help of different indexes. The indexes reveal that external perturbations yield transition states which are both electronically and structurally advanced as compared to the transition state in the gas phase. 

T. Niwaguchi and T. Inoue, Direct quantitative analysis of lysergic acid diethylamide (LSD) and 2,5-dimethoxy-4-methyl-amphet-amine (STP) on thin-layer chromatograms, J. Chromatogr., 121 165 (1976). 

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