Oxidative fluorescence-producing

Chemical Characteristics of the Oxidative Fluorescence-Producing Reaction and Presumptive Implication of Malonaldehyde The reaction producing measurable fluorescence on polyamide powder can be carried out in the gas phase by exposure to the volatiles from oxidizing polyunsaturated lipids, whether acids, esters, triglycerides, or phosphatides. It can be also carried out within either the oil phase or a water emulsion, and, as noted above, it can be followed in the vapor above an emulsion, providing the pH is 5.5 or below. 

Subsequent studies (63,64) suggested that the nature of the chemical activation process was a one-electron oxidation of the fluorescer by (27) followed by decomposition of the dioxetanedione radical anion to a carbon dioxide radical anion. Back electron transfer to the radical cation of the fluorescer produced the excited state which emitted the luminescence characteristic of the fluorescent state of the emitter. The chemical activation mechanism was patterned after the CIEEL mechanism proposed for dioxetanones and dioxetanes discussed earher (65). Additional support for the CIEEL mechanism, was furnished by demonstration (66) that a linear correlation existed between the singlet excitation energy of the fluorescer and the chemiluminescence intensity which had been shown earher with dimethyl dioxetanone (67). 

Recent work by Schmidt and Schuster (1978a, 1980a) has shown that the addition of any of several easily oxidized, fluorescent aromatic hydrocarbons or amines to solutions of [21] results in greatly enhanced chemiluminescence. Moreover, addition of these molecules accelerates the rate of reaction of [21]. The catalyzed reaction is first order in both [21] and aromatic hydrocarbon or amine (which is termed the activator, act). Acetone is still produced quantitatively, and the activator is not consumed in the reaction, but rather serves as a catalyst for the decomposition of the dioxetanone. The kinetic behavior is thus described by the simple rate law (27), where kt is the rate... 

The chemistry and analysis of sialic acids have been reviewed. Picomole quantities of sialic acids have been measured by the fluorescence produced by the periodate-oxidized acid in the thiobarbituric acid reaction. " Contamination of the sialic acids with 2-deoxy-D-eryt/iro-pentose (derived from cellular material) could be detected by a downfield shift of the excitation maximum. Fluorescent derivatives are also produced when free sialic acids react with pyridoxamine, a procedure that compares favourably with the thiobarbituric acid reaction for determining sialic acids. Keto-acids e.g. pyruvic acid) interfere with the determination, but 2-deoxy-D-arabmo-hexose and 2-deoxy-D-c/-ytliro-pentose do not. A nonfading chromophore is produced when DMSO is used instead of n-butanol in the thiobarbituric acid ssay for sialic acids. A new histochemical method for the visualization and identification of unmodified or 0-acylated sialic acids has been reported. ... 

A flow injection fluorimetric method has been reported for the determination of thiamin using copper as catalyst (Perez-Ruiz et al. 1992). Thiamin is oxidized to produce fluorescent thiochrome by copper(ii) in basic medium. The method is successfully applied to determine thiamin in pharmaceutical samples. 

Analysis of thermally oxidised PET by fluorescence spectroscopy has shown the presence of hy-droxylated terephthalate units [523]. These groups are formed by hydroxyl radical attack on the terephthalate units and then undergo further oxidation to produce stilbene-quinone units causing discoloration of the polymer. Fluorescence analysis has also been used to study photobleaching and photo-induced discoloration reactions in EVA formulations [22]. Fluorescence spectroscopy offers a... 

The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

Because of the time and expense involved, biological assays are used primarily for research purposes. The first chemical method for assaying L-ascorbic acid was the titration with 2,6-dichlorophenolindophenol solution (76). This method is not appHcable in the presence of a variety of interfering substances, eg, reduced metal ions, sulfites, tannins, or colored dyes. This 2,6-dichlorophenolindophenol method and other chemical and physiochemical methods are based on the reducing character of L-ascorbic acid (77). Colorimetric reactions with metal ions as weU as other redox systems, eg, potassium hexacyanoferrate(III), methylene blue, chloramine, etc, have been used for the assay, but they are unspecific because of interferences from a large number of reducing substances contained in foods and natural products (78). These methods have been used extensively in fish research (79). A specific photometric method for the assay of vitamin C in biological samples is based on the oxidation of ascorbic acid to dehydroascorbic acid with 2,4-dinitrophenylhydrazine (80). In the microfluorometric method, ascorbic acid is oxidized to dehydroascorbic acid in the presence of charcoal. The oxidized form is reacted with o-phenylenediamine to produce a fluorescent compound that is detected with an excitation maximum of ca 350 nm and an emission maximum of ca 430 nm (81). 

TRS Converter To measure hydrogen sulfide and reduced-organic sulfur compounds, the technique used is thermal oxidation, in which sulfur dioxide is produced. Hydrogen sulfide and other reduced-sulfur compounds are measured by using methods applicable to the measurement of sulfur dioxide concentrations. One method is a technique based on ultraviolet fluorescence. 

Perlolidine, C25H4j02N4, occurs naturally and is also produced in small yield by the oxidation of perloline in various ways. It crystallises in silky needles, m.p. 325-6°, sublimes at 180°/0-04 mm., and yields a dihydrochloride, B. 2HC1.2H2O, m.p. > 350°. It shows a marked blue fluorescence in neutral or acid aqueous solution, which with the hydrochloride is visible at 0-15 parts per million. The base is phenolic it... 

Important organic applications are to the determination of quinine and the vitamins riboflavin (vitamin B2) and thiamine (vitamin Bj). Riboflavin fluoresces in aqueous solution thiamine must first be oxidised with alkaline hexacyanoferrate(III) solution to thiochrome, which gives a blue fluorescence in butanol solution. Under standard conditions, the net fluorescence of the thiochrome produced by oxidation of the vitamin Bj is directly proportional to its concentration over a given range. The fluorescence can be measured either by reference to a standard quinine solution in a null-point instrument or directly in a spectrofluorimeter.27... 

The aromatic nucleus adsorbs in the UV and thus, the derivative can be detected by a UV detector. This is the most common type of chemical derivatization but the derivative may be chosen to be appropriate for different types of detector. For example, the solute can be reacted with a fluorescing reagent, producing a fluorescent derivative and thus be detectable by the fluorescence detector. Alternatively, a derivative can be made that is easily oxidized and, consequently, would be detectable by an electrochemical detector. 

With respect to using methyl viologen as electron relay, it might be of interest to note tlmt MV " can be oxidized by positive holes produced in illuminated colloidal semiconductors such as Ti02 Two oxidation products of MV are 1, 2 -di-hydro-l,r-dimethyl-2 -oxo-4,4 -bipyridylium chloride and 3,4-dihydro-l,r-dime-thyl-3-oxo-4,4 -bipyridylium chloride, which can readily be detected by their strong fluorescences at 516 nm and 528 nm, respectively. These products are also produced in the direct photolysis of MV " solutions and in the reaction of MV "" with OH radicals in homogeneous solution... 

Mooradian (1993) has studied the antioxidant properties of 14 steroids in a non-membranous system in which the fluorescence of the protein phycoerythrin was measured in the presence of a lipid peroxyl radical generator (ABAP). Oxidation of the protein produces a fluorescent species. Quenching of fluorescence by a test compound indicates antioxidant activity. Oestrone, testosterone, progesterone, androstenedione, dehydroepian-drosterone, cortisol, tetrahydrocortisone, deoxycorti-... 

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