Radicals reaction+DPPH

Most radicals are transient species. They (e.%. 1-10) decay by self-reaction with rates at or close to the diffusion-controlled limit (Section 1.4). This situation also pertains in conventional radical polymerization. Certain radicals, however, have thermodynamic stability, kinetic stability (persistence) or both that is conferred by appropriate substitution. Some well-known examples of stable radicals are diphenylpicrylhydrazyl (DPPH), nitroxides such as 2,2,6,6-tetramethylpiperidin-A -oxyl (TEMPO), triphenylniethyl radical (13) and galvinoxyl (14). Some examples of carbon-centered radicals which are persistent but which do not have intrinsic thermodynamic stability are shown in Section 1.4.3.2. These radicals (DPPH, TEMPO, 13, 14) are comparatively stable in isolation as solids or in solution and either do not react or react very slowly with compounds usually thought of as substrates for radical reactions. They may, nonetheless, react with less stable radicals at close to diffusion controlled rates. In polymer synthesis these species find use as inhibitors (to stabilize monomers against polymerization or to quench radical reactions - Section 5,3.1) and as reversible termination agents (in living radical polymerization - Section 9.3). 

Stable radicals can show selectivity for particular radicals. For example, nitroxides do not trap oxygcn-ecntcrcd radicals yet react with carbon-ccntcrcd radicals by coupling at or near diffusion controlled rates.179,184 This capability was utilized by Rizzardo and Solomon181 to develop a technique for characterizing radical reactions and has been extensively used in the examination of initiation of radical polymerization (Section 3.5.2.4). In contrast DPPH, w hile an efficient... 

The addition of known radical scavengers such as the DPPH radical to a polymerizing system will halt polymerization if it is a radical reaction. Ionic polymerizations will be unaffected by such additions. One must be careful, however, not to use a radical scavengers that also affects ionic polymerization. Thus, benzoquinone would be a poor choice as a radical scavenger, since it can also act as an inhibitor in ionic polymerization. 

The radical reaction of hydrazine and methylhydrazine with some a,(3-unsaturated ketones 54 initiated by 2,2-dipenyl-l-picrylhydrazyl (DPPH) is described in [60]. At — 78°C the treatment is practically regioselective and yields pyrazoles 55, while regioisomeric heterocycles 56 are observed in trace amounts (Scheme 2.13). 

DPPH (l,l-diphenyl-2-picryhydrazyl) is a purple-colored stable free radical that is reduced to the yellow-colored diphenylpicrylhydrazine by free radicals. The DPPH assay measures one electron, such as hydrogen atom donating activity and hence provides a measure of free radical scavenging activity. This assay is suitable for the initial screening of multiple samples, such as plant extracts. Reaction mixtures containing test samples dissolved in DMSO and DPPH in absolute ethanol are incubated at 37°C for 30 min in a 96-well plate and absorbance measured at 515 nm. ... 

It was found that both sensitivity and double exposure effect are reduced with mixing of a small amount of radical scavenger, 1,l-diphenyl-2-picrylhydrazyl ( DPPH ), into the PMPS. This indicates that radical reactions are involved in the mechanism of double exposure sensitivity enhancement. 

One method is to use the steric hindrance of substituents. This prevents the approach of other radicals, and therefore prevents further reaction. DPPH (diphenylpicrylhydrazyl), nitroxide spin labels, or Yang s radical [36,37] are such species. However, because of the same steric hindrance, these molecules cannot stack well in the solid state, and therefore cannot interact well with their neighbors. 

Electron spin resonance (ESR) spectrometry measures the presence of unpaired electrons and is a widely accepted method for investigating antioxidant-radical reactions. A few ESR studies have been conducted to investigate the CLA reactions with 1,1-diphenyl-2-picrylhydrazyl (DPPH ) free radical in toluene (7,8). DPPH is... 

Fig. 10.6a. and 10.6b. DPPH fatty acid reactions in different PC(14 0 14fl) testing systems. ESR signals were recorded with 10 mW incident microwave and 100 kHz field modulation of 2Gat 37°C.The initial concentration of DPPH radical reactions was 0.25 mM and 5 mol% PC containing CLA and LA.The reaction mixtures were incubated at 60°C for 60 min and ESR experiments were performed at 37°C. 

In the presence of radical acceptors (DPPH, NO, benzidine, etc.), the interruption reactions are impeded and the mechanoradicals are stabilised by reaction with acceptors ... 

The product of reaction between polymer radical and DPPH is the stable radical... 

The efficiency of these inhibitors may depend on reaction conditions. For example the reaction of radicals with stable radicals (e.g. nitroxides) may be reversible at elevated temperatures (Section 7.5.3) triphenylmethyl may initiate polymerizations (Section 7.5.2). A further complication is that the products may be capable of undergoing further radical chemistry. In the case of DPPH (22) this is attributed to the fact that the product is an aromatic nitro-compound (Section 5.3.7). Certain adducts may undergo induced decomposition to form a stable radical which can then scavenge further. 

Well before the advent of modern analytical instruments, it was demonstrated by chemical techniques that shear-induced polymer degradation occurred by homoly-tic bond scission. The presence of free radicals was detected photometrically after chemical reaction with a strong UV-absorbing radical scavenger like DPPH, or by analysis of the stable products formed from subsequent reactions of the generated radicals. The apparition of time-resolved ESR spectroscopy in the 1950s permitted identification of the structure of the macroradicals and elucidation of the kinetics and mechanisms of its formation and decay [15]. 

The reduction of the stable 1,1 -diphenyl-2-picrylhydrazyl radical (DPPH) has been used to assess the efficiency of antioxidants in beverages (Larrauri et al, 1999 Porto et al, 2000), vegetable oils (Espin et al, 2000) and of pure phenolic compounds (Madsen et al, 2000), reaction [16.17] ... 

The DPPH radical terminates other radicals, probably by the reaction... 

The radical scavenging methods require the general caution that the stoichiometry of the reaction between scavenger and radical must be established. A problem with some scavengers is that their reaction with radicals may not be quantitative. The DPPH radical is an extremely efficient scavenger in many systems. It completely stops vinyl acetate and styrene polymerizations even at concentrations below 10 4M [Bartlett and Kwart, 1950]. However, the scavenging effect of DPPH is not universally quantitative for all monomers. 

In vitro tests, used in evaluation of antioxidant properties make use of the ability of antioxidants to quench free radicals. Based on this mechanism, the methods are divided into two groups SET - single electron transfer, and HAT - hydrogen atom transfer. Reactions with antioxidants in assays with the DPPH radical, ABTS and the Folin-Ciocalteu reagent both operate according to the SET and HAT mechanism. Due to the kinetics of the reaction, they are included in the... 

Analysis of antioxidant properties relative to the DPPH" radical involves observation of colour disappearance in the radical solution in the presence of the solution under analysis which contains antioxidants. A solution of extract under analysis is introduced to the environment containing the DPPH radical at a specific concentration. A methanol solution of the DPPH radical is purple, while a reaction with antioxidants turns its colour into yellow. Colorimetric comparison of the absorbance of the radical solution and a solution containing an analysed sample enables one to make calculations and to express activity as the percent of inhibition (IP) or the number of moles of a radical that can be neutralised by a specific amount of the analysed substance (mmol/g). In another approach, a range of assays are conducted with different concentrations of the analysed substance to determine its amount which inactivates half of the radical in the test solution (ECso). The duration of such a test depends on the reaction rate and observations are carried out until the absorbance of the test solution does not change [4]. If the solution contains substances whose absorbance disturbs the measurement, the concentration of DPPH radical is measured directly with the use of electron paramagnetic resonance (EPR) spectroscopy. 

Initially, the use of HPLC in analysis of antioxidant properties with the DPPH" radical was restricted to chromatographic analysis of the radical content in solution. An assay was performed in which a solution of the radical was treated with the extract under analysis. The reaction ran in a reaction tube and the remainder of the radical after the reaction was analysed chroma-tographically. A comparison of the radical content in the blank sample and in the extract sample showed the amormt of radical that was quenched by antioxidants in the analysed sample [62, 63].However, themethoddidnotprovidemoreinformation than the colorimetricmethod. Much better results are obtained in a post-column on-line reaction in which substances separated on a chromatographic column react with a radical in a reaction coil. 

Popular EPR-based assays of antioxidant activity include the DPPH assay, in which the ability of compounds to quench (by H-atom transfer) the 1,1-diphenyl-2-picrylhydrazyl radical is used to rank their antioxidant activity. This method has been applied widely to the analysis of dietary antioxidants and extracts from medicinal plants.213 219 Extensive use has also been made of assays based on the competition between spin traps and test compounds for reaction with enzymatically-generated 02 and, in the presence of a metal catalyst, the OH rad-... 

As described in Chapter III, morusin (3) has been found to be anti-tumor promoter in a two-stage carcinogenesis experiment with teleocidin. Considering the similarity of the structures between morusin (3) and artonin E (7), artonin E (7) was expected to be an anti-tumor promoter. Furthermore we found a novel photo-oxidative cyclization of artonin E (7) as follow photo-reaction of artonin E (7) in CHCI3 containing 4% ethanol solution with high-pressure mercury lamp produced artobiloxanthone (8) and cycloartobiloxanthone (9), and the treatment of artonin E (7) with radical reagent (2,2-diphenyl-1-picrylhydrazyl DPPH) resulted in the same products, Fig. (15), [84]. 

The concentration of trapped radicals and the degree of occlusion (how deeply they are buried) have been studied extensively by Bamford and Jenkins (9). They determined the approximate radical concentration by swelling or dissolving polymer in solutions of diphenylpicryl hydrazyl (DPPH), a violet substance that becomes colorless on reaction with radicals. Nitrobenzene was generally used as the medium to dissolve the hydrazyl and to swell the polymer /3-propiolactone, a solvent for the polymer, was used also. 

The regioselectivity of pyrazole 55 formation is completely the reverse of that of pyrazoline 57 in the reaction of ketones 54 with hydrazines without DPPH. In addition, heterocycles 56 cannot be obtained from 57 by the action of DPPH. These facts show that the radical-initiated treatment of a, 3-unsaturated ketones with hydrazines does not occur via the initial pyrazoline 57 formation. 

Since the crocin-bleaching method is based on competition kinetics, it can also be used to detect pro-oxidant activity (POA), for example, of early MRPs the DPPH method cannot. In fact, in the presence of antioxidants, the crocin-bleaching rate [reaction (1)] is slowed down, because the antioxidant reacts with the radical first and the antioxidant radical formed [reaction (2)] reacts only slowly with the crocin [reaction (3) ]. On the contrary, the pro-oxidant competes with the radical for the crocin [reaction (4)], thus increasing the extent of crocin bleaching 446... 

---