Analytical uses

In the presence of many metal ions, diorthohydroxyazo dyes exhibit two polarographic reduction waves, the first due to free dye and the second to metal-dye complex. Highly sensitive analytical methods based on this principle have been developed for example, Ni or Fe may be determined in the presence of an excess of aluminum thank to thiazolylazo derivatives (563). 

NHCHO 2-(5-nitrofuryl) H Carcinogenic activity in mice 950-952 

Another line of analytical use is exemplified by the properties of l-(2-thiazolylazoi-2-naphthol (305), whose complexes with metals may be used for their spectrophotometric and titrimetric determination, as wel] as for their separation by solvent extraction (564, 568, 953-957, 1040). 

Some representative analytical uses of 2-aminothiazole derivatives are reported in Table VI-13. The use of azoderivatives of thiazoles in analysis has been reviewed (958). 

Recently their potential as analytical reagents for U(VI) was tested (959). 

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As shown in [16], the two corresponding flow maps, exp(rLH,) and exp(rLHj), can be represented analytically. Using the second order Strang... 

The sulfur atom of the thiocarbonyl group is a good nucleophile, and reaction between benzyl bromide and l-(2-thiazolyl)thiourea yields the isothiouronium salt (496). The sulfur atom may also be engaged in a chelate, as exemplified by the Cu chelate of 2-thioureido-4-methylthiazole (491). These chelates with metal ions were thoroughly studied in acidic, neutral, and alkaline media for 66 metal ions in order to define their analytical use. They are formed in the molar ratio of 1 2 for metal II compounds (498). 

TABLE VI-13. ANALYTICAL USES OF 2-AZOTHIAZOLE (A) AND 2-AMINOTHIAZOLE (Bl DERIVATIVES... 

In a quantitative analysis, we measure a signal and calculate the amount of analyte using one of the following equations. 

The integrated form of the rate law for equation 13.4, however, is still too complicated to be analytically useful. We can simplify the kinetics, however, by carefully adjusting the reaction conditions. For example, pseudo-first-order kinetics can be achieved by using a large excess of R (i.e. [R]o >> [A]o), such that its concentration remains essentially constant. Under these conditions... 

To be analytically useful equation 13.16 needs to be written in terms of the concentrations of enzyme and substrate. This is accomplished by applying the steady-state approximation, in which we assume that the concentration of ES is essentially constant. After an initial period in which the enzyme-substrate complex first forms, the rate of formation of ES... 

The dependence of chiral recognition on the formation of the diastereomeric complex imposes constraints on the proximity of the metal binding sites, usually either an hydroxy or an amine a to a carboxyHc acid, in the analyte. Principal advantages of this technique include the abiHty to assign configuration in the absence of standards, enantioresolve non aromatic analytes, use aqueous mobile phases, acquire a stationary phase with the opposite enantioselectivity, and predict the likelihood of successful chiral resolution for a given analyte based on a weU-understood chiral recognition mechanism. 

R. Berg, The Analytical Uses of o-Oyyquinoline and its Derivatives, 2nd ed., Eerd. Enke, Stuttgart, Germany, 1938, p. 34. 

Silver compounds, available from commercial suppHers, are expensive. Reagent grades of sHver(I) carbonate, cyanide, diethjldithiocarbamate, iodate, nitrate, oxide, phosphate, and sulfate are available. Standardized solutions of silver nitrate are also available for analytical uses. Purified grades of sHver(I) acetate, bromide, cyanide, and iodide can be purchased silver nitrate is also made as a USP XX grade for medicinal uses (6). 

Future Trends. Methods of laser cooling and trapping are emerging as of the mid-1990s that have potential new analytical uses. Many of the analytical laser spectroscopies discussed herein were first employed for precise physical measurements in basic research. AppHcations to analytical chemistry occurred as secondary developments from 10 to 15 years later. 

Given that one sample is to be analy2ed for r analytes usings sensors (p > r) by making a series of n standard additions in > r) to the sample and recording the sensor responses after each addition, the equation becomes... 

Cha.rging Current. In most cases, appHcation of a voltage to an electrode is iatended to produce an analytically useful current that depends solely on the concentration of the analyte. Unfortunately, current flows even ia the complete absence of the analyte. Thus, the current may have nothing to do with the electroactive species ia the sample. This charging current must be circumvented or otherwise compensated. 

The chronoamperometric technique illustrates the principle that analytically useful current responses depend critically on the efficiency of analyte mass transport within the solution. The analyte mass transport in turn depends on the efficiency with which an appHed voltage can maintain the surface concentrations of oxidized and reduced species at values specified by the Nemst equation. It is generally the case in chronoamperometry that the bulk concentration of one of the species is zero whereas the surface concentration of the other species is forced to zero by the appHed potential, but this is not always so. 

Electrodes may also be rendered selective to more complex analytes using enzyme or other overcoats (see Biopolymers, analytical techniques Biosensors). The enzyme converts the analyte into a detectable ion or gas. Glucose and blood urea nitrogen sensors can be made in this way. 

Naphthalene-3,6-disulfonic acid, l,8-dihydroxy-2-(2-thiazolylazo)-analytical uses, 6, 328 Naphthalenes... 

Naphtho[l, 2-c]furazans electrophilic reactions, 6, 410 synthesis, 6, 418 Naphtho[l, 2-c]furoxans eleetrophilic reactions, 6, 410 3-Naphthoic acid, 2-hydroxy-l-(2-thiazolylazo)-analytical uses, 6, 328 Naphtho[ 1,2-h]imidazoles oxidation, 5, 405... 

Naphtho[2,3-h]indolizine-6,l 1-dione, 1, 337 Naphthoisocoumarin synthesis, 3, 831, 832 Naphtho[l,2-c]isothiazole, 3-amino-synthesis, 5, 136 2-Naphthol, l-(2-thiazolylazo)-analytical uses, 6, 328 Naphtholactam, 1, 326 Naphtholactone dyes, 1, 326... 

Claisen ester condensation, 6, 279 Thiazolecarboxylic acid chlorides reactions, 6, 279-280 Thiazolecarboxylic acid hydrazides synthesis, 6, 280 Thiazolecarboxylic acids acidity, 6, 279 decarboxylation, 6, 279 reactions, S, 92 6, 274 Thiazole-2-carboxylic acids decarboxylation, S, 92 Thiazole-4-carboxylic acids stability, S, 92 Thiazole-5-carboxylic acids decarboxylation, S, 92 Thiazole-4,5-dicarboxylic acid, 2-amino-diethyl ester reduction, 6, 279 Thiazole-4,5-dicarboxylic acids diethyl ester saponification, 6, 279 Thiazolediones diazo coupling, 5, 59 Thiazoles, 6, 235-331 ab initio calculations, 6, 236 acidity, S, 49 acylation, 6, 256 alkylation, S, 58, 73 6, 253, 256 analytical uses, 6, 328 antifogging agents... 

Other cases, involving an arbitrary relationship between the solute retention factor and the modulator concentration can be handled analytically using the approaches of Frey [Biotechnol. Bioeng., 35, 1055 (1990)] and Carta and Striugfield []. Chromatogr, 605, 151 (1992)]. 

The book scries Electron Spectroscopy Theory, Techniques, and Applications, edited by C. R. Brundle and A D. Baker, published by Academic Press has a number of chapters in its 5 volumes which are useful for those wanting to learn about the analytical use of XPS In Volume 1, An Introduction to Electron Spectroscopy (Baker and Brundle) in Volume 2, Basic Concepts of XPS (Fadley) in Volume 3, Analytical. plications of XPS (Briggs) and in Volume 4, XPSfor the Investigation of Polymeric Materials (Dilks). 

There now exist alternatives or sufficient quantities of controlled substances for almost all applications of ozone-depleting solvents. Exceptions have been noted for certain laboratory and analytical uses and for manufacture of space shuttle rocket motors. HCFCs have not been adopted on a large scale as alternatives to CFC solvents. In the near term, however, they may be needed as the conventional substances in some limited and unique applications. HCFC-141b is not a good replacement for methyl chloroform (1,1,1 -trichloroethane) because its ODP is three times higher. Alternatives for specific uses of ozone-depleting solvents are briefly described below. 

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