Spectrophotometric differential

Kuokkanen (1986, 1987 a, 1991) supported the proposal of Nakazumi et al. (1983) based on kinetic and spectrophotometric comparisons of arenediazonium salt solutions in the presence of 18-crown-6 and pentaglyme. He also extended the systematic work on complex formation of benzenediazonium salts, substituted in the 2-position, and in the presence of 15-crown-5 (Kuokkanen, 1990 Kuokkanen et al, 1991). He discovered a useful way to differentiate between the two types of complexes in Scheme 11-2. Increasing the relative concentration of the host compound shifts the ultraviolet absorption band of both types of complex hypsochromically, whereas the NN stretching frequencies are significantly increased only in the case of insertion complexes. ... 

A multiwavelength approach might have been considered as an alternative to chemical derivatisation. Ruddle and Wilson [62] reported UV characterisation of PE extracts of three antioxidants (Topanol OC, Ionox 330 and Binox M), all with identical UV spectra and 7max = 277 nm, after reaction with nickel peroxide in alkaline ethanolic solutions, to induce marked differentiation in different solvents and allow positive identification. Nonionic surfactants of the type R0(CH2CH20) H were determined by UV spectrophotometry after derivatisation with tetrabromophenolphthalein ethyl ester potassium salt [34]. Magill and Becker [63] have described a rapid and sensitive spectrophotometric method to quantitate the peroxides present in the surfactants sorbitan monooleate and monostearate. The method, which relies on the peroxide conversion of iodide to iodine, works also for Polysorbate 60 and other surfactants and is more accurate than a titrimetric assay. 

Ferren, W.P. and Shane, N.A., Differential spectrophotometric determination of caffeine in soluble coffee and drug combinations, JAOAC, 51,573,1968. 

Selective differential UV spectrophotometric method was presented for the determination of niclosamide in bulk and in its pharmaceuticals [43]. The method was based on measuring niclosamide in alkaline solutions against their neutral ethanolic solutions as blanks. The proposed method was sensitive, highly specific, and advantageous over the conventional UV assays, since the interference of the excipients, impurities, degradation products, or other accompanying drugs was nullified. 

Sanghavi and Kulkami estimated the drug in the presence of its degraded products by differential spectroscopy [22]. Sastry et al. determined diloxanide furoate by a spectrophotometric method [23]. 

Two differential spectrophotometric methods were used by Chatterjee et al. for the simultaneous analysis of diloxanide furoate and metronidazole in pharmaceutical formulations [24]. The first method involved measurement of the absorbance of a methanolic solution of the two drugs at 259 and 311 nm. Since the absorbance of diloxanide furoate at 311 nm is zero, the concentration of metronidazole is directly measured, and a simple equation based on absorbance ratios is used to calculate the concentration of diloxanide furoate. The second method was a differential spectrophotometric determination based on pH-induced spectral changes, on changing from an acidic to an alkaline solution. A marked bathochromic shift was exhibited by metronidazole, while diloxanide furoate showed a slight hypsochromic shift. The wavelength of maximum absorption difference for diloxanide furoate was 267 nm, where metronidazole did not absorb. Similarly, diloxanide furoate did not interfere with metronidazole at when measured at 322 nm. 

Absorption and Deposition of CLA in Animal Tissues. Miller etal (27) described a method employing the methyl ester of conjugated dienes prepared from com oil as tracers of fat metabolism. It was postulated that the conjugated dienoic isomers could be differentiated from other fatty acids in body fat by spectrophotometric absorbance at 233 nm. 

Chromatographic determination of protoporphyrins in erythrocytes has the same indications as the spectrophotometric one. In addition, the method enables the differentiation between zinc-protoporphyrin and (metal-)free protoporphyrin. The first is elevated in iron deficiency and lead intoxication, the second in erythropoietic protoporphyria. 

Direct spectrophotometric methods using fluorometric detection have been reported for screening of tetracycline in milk extracts (126,282), and three tetracyclines in tissues extracts (302, 310). In a different approach, Salinas et al. (212) described a fourth-derivative spectrophotometric method for the determination of oxytetracycline in honey. Although useful, these methods cannot differentiate among individual tetracycline antibiotics and are less sensitive than the screening tests used for regulatory purposes. 

A sensitive spectrophotometric method based on the strong absorption of the aminochrome-sodium bisulfite addition products (see Section IV, F) at ca. 350 m/x. has been described recently by van Espen128and Oesterling and Tse 277-278 for determining total catecholamines. While not as sensitive as the fluorimetric procedures, this method is considerably more sensitive than the older colorimetric methods based on the visible absorption peak of the aminochromes. Also, it does not have many of the disadvantages (e.g. costly equipment and unstable blanks) often associated with fluorimetric techniques. The basic procedure can be satisfactorily applied to the differential determination of mixtures of adrenaline, noradrenaline, dopamine, metanephrine, and normetanephrine.178... 

From the above discussion, it is obvious that the simple spectrophotometric DPO assays cannot be used to differentiate these two processes since they rely on measuring the colored end-products of reaction. Here, use of the 02 electrode assay has a major advantage since it measures 02, one of the prime reactants, and hence the actual activity of the DPO in question. 

AG Fogg, AM Summan. Further differential-pulse polarographic and visible spectrophotometric studies of the degradation of permitted synthetic food coloring matters without the addition of ascorbic acid accelerated heat degradation studies. Analyst 109(6) 743-747, 1984. 

The detection of products derived from the N-oxygenation of C=N functionalities presents many problems, which illustrate difficulties that are associated with the isolation, identification and quantification of small amounts of water-soluble metabolites. Spectrophotometric methods19 as well as differential pulse polarographic techniques20 previously used to determine oximes, nitrones and N-oxides frequently lack sensitivity and/or specificity. Improved analytical methods for the quantification of these N-oxy compounds include chromatographic techniques taking into account the chemical peculiarities of the individual N-oxygenated C=N functionalities. These procedures usually require the chemical synthesis of authentic material for comparison with data obtained with the isolated metabolites, and also for the construction of calibration curves. 

The same three spectrophotometric reagents were compared for their abilities to differentiate mono- and polynuclear hydroxy-aluminium complexes in solutions typical of those used in phytotoxicity studies (Parker et al., 1988b). Methods based upon each of the three reagents yielded estimates of the mononuclear aluminium fraction of adequate precision for most purposes. Studies using ferron demonstrated its utility for characterising the non-mononuclear aluminium fraction using kinetic analyses. The ferron spectrophotometric procedure was preferred for its simplicity, level of precision and moderate rate of reaction with aluminium. 

Parker, D.R., Zelazny, L.W. and Kinraide, T.B. (1988b) Comparison of three spectrophotometric methods for differentiating mono- and polynuclear hydroxy-aluminium complexes. Soil Sci. Soc.Am.J., 52, 67-75. 

---