Induction Period Method Research Articles

Expression of Cyclooxygenase-2, Nitric Oxide Synthase 2 and Heme Oxygenase-1 mRNA Induced by Bis-Eugenol in RAW264.7 Cells and their Antioxidant Activity Determined Using the Induction Period Method

To clarify the mechanisms responsible for the anti-inflammatory/proinflammatory activities of eugenol-related compounds, we investigated the cytotoxicity and up-regulatory/down-refgulatory effects of the biphenols curcumin, bis-eugenol, magnolol and honokiol, and the monophenols eugenol and isoeugenol, on major regulators of cyclooxygenase-2 (Cox-2), nitric oxide synthase 2 (Nos2) and heme oxygenase-1 (HO-1) mRNA in RAW264.7 cells. mRNA expression was investigated using real-time reverse transcriptase-polymerase chain reaction (RT-PCR), and the theoretical parameters were calculated using the DFT/B3LYP/6-31* method. Also, the antioxidant activity of eugenol-related compounds in combination with 2-mercapto-1-methylimidazole (MMI, as a model for glutathione (GSH)) was investigated using the induction period method for polymerization of methyl methacrylate initiated by benzoyl peroxide (BPO). The cytotoxicity of eugenol-related compounds showed a linear relationship with their softness (σ) and electrophilicity (ω). At a concentration of 50 μM, biphenols except for bis-eugenol elicited the expression of mRNA for both Cox-2 and Nos2, but monophenols did not. In contrast, bis-eugenol elicited Cox-2 gene expression, but down-regulated Nos2 gene expression. bis-Eugenol alone induced the expression of HO-1 mRNA, and when combined with MMI it showed a potent antagonistic effect on BPO-induced antioxidant activity. The ability of methoxyphenols to inhibit LPS-stimulated Cox-2 gene expression declined in the order curcumin >> isoeugenol > bis-eugenol >> eugenol, and the rank of ability was related to their ω value. Most eugenol-related compounds had proinflammatory activity at high concentrations. However, they had also anti-inflammatory activity at lower concentrations. Eugenol-related compounds may exert antioxidant and anti-inflammatory activity in LPS-stimulated RAW264.7 cells possibly by inhibiting the activation of nuclear factor-kappa B (Nf-ĸB), whereas bis-eugenol requires induction of HO-1 expression. bis-Eugenol as well as curcumin, may have anti-inflammatory and anticancer therapeutic applications.

Anti-inflammatory Activity of β-Carotene, Lycopene and Tri-n-butylborane, a Scavenger of Reactive Oxygen Species.

The polyene carotenoids β-carotene and lycopene are antioxidants that not only quench singlet oxygen but also inhibit lipid peroxidation. Tri-n-butyl borane (TBB) is used as an initiator for dental resin materials and is extremely reactive with oxygen and reactive oxygen species (ROS). This reactionability of TBB may be analogous to that of carotenoids with ROS. To clarify the biological activity of such ROS scavengers, we investigated the anti-inflammatory activity of β-carotene, lycopene and TBB in terms of the expression of RNA for lipopolysaccharide (LPS)-induced cyclooxygenase-2 (Cox2), nitric oxide synthase 2 (Nos2) and tumor necrosis factor-alpha (Tnfa), and mRNA expression and up-regulation of heme oxygenase 1 (Hmox1) mRNA in RAW264.7 cells. mRNA expression was investigated using real-time reverse transcriptase-polymerase chain reaction (PCR). The antioxidant activity of carotenoids was evaluated using the induction period method in the azobisisobutyronitrile or benzoyl peroxide-methyl methacrylate system. Hmox1 mRNA, but not Cox2 and Nos2 mRNA, was up-regulated by 100 μM β-carotene and lycopene, and by 0.125% TBB. LPS-stimulated Cox2, Nos2 and Tnfa gene expression was inhibited by 50 μM β-carotene and lycopene, and by 0.5-1% TBB. Both β-carotene and lycopene had weak antioxidant activity, but β-carotene showed pro-oxidant activity at higher concentrations. The anti-inflammatory activity of β-carotene, lycopene and TBB may be related to their ROS-scavenging activity. Additionally, the activity of carotenoids and TBB may be attributed to the electrophilicity of ROS-induced carotenoid intermediates and boranes, respectively. Their anti-inflammatory activity may be attributable to enhancement of the potency of the electrophile/antioxidant response element transcription system in view of their up-regulation of Hmox1 mRNA expression.

Kinetic analysis and self-accelerating decomposition temperature (SADT) of β-nitroso-α-naphthol

To study the thermal hazard of β-nitroso-α-naphthol, both dynamic and isothermal tests were performed with a differential scanning calorimeter (DSC). The dynamic tests indicated that the initial decomposition temperature of β-nitroso-α-naphthol ranged from 153°C to 173°C. The interrupt-rescanning method verified the autocatalytic characteristic of β-nitroso-α-naphthol decomposition. DSC curves obtained at five constant temperatures confirmed that the decomposition of β-nitroso-α-naphthol was an autocatalytic reaction. Activation energy E was 149±8kJmol−1 calculated by Kissinger method. E values calculated by induction period method and isothermal method were in line with that obtained by Friedman method. On the basis of the kinetic analysis, the safety parameter SADT of β-nitroso-α-naphthol in 50kg standard packaging was 81°C based on Semenov model and 67°C based on Frank-Kamenetskii model.

Radical-Scavenging Activity of Thiols, Thiobarbituric Acid Derivatives and Phenolic Antioxidants Determined Using the Induction Period Method for Radical Polymerization of Methyl Methacrylate

The radical-scavenging activities of two thiols, eight (thio)barbituric acid derivatives and six chain-breaking phenolic antioxidants were investigated using the induction period method for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2’-azobisisobutyronitrile (AIBN) and monitored by differential scanning calorimetry (DSC). The induction period (IP) for the thiols 2-mercaptoethanol (ME) and 2-mercapto-1-methylimidazole (MMI) was about half that for phenolic antioxidants. Except for the potent inhibitor 5,5-dimethyl-2-thiobarbituric acid (3), the IP for thiobarbituric acid derivatives was about one tenth of that for phenolic antioxidants. The IP for 1,3,5-trimethyl-2-thiobarbituric acid (1) and 5-allyl-1, 3-dimethyl-2-thiobarbituric acid (7) was less than that of the control, possibly due to inhibition by a small amount of atmospheric oxygen in the DSC container. The ratio of the chain inhibition to that of chain propagation (CI/CP) for the thiols and thiobarbituric acid compounds except for 1, 3 and 7 was about 10 times greater or greater than that for phenolic compounds. A kinetic chain length (KCL) about 10% greater than that of the control was observed for 1, suggesting that 1 had chain transfer reactivity in the polymerization of MMA. The average molecular weight of polymers formed from thiobarbituric acid derivatives is discussed.

Radical-Scavenging Activity of Dietary Phytophenols in Combination with co-Antioxidants Using the Induction Period Method

The radical-scavenging activity of dietary phytophenols has been investigated by many researches due to their antioxidant, anti-inflammatory and anticancer property but the radical-scavenging effect of 2-phytophenol and the phytophenol:co-antioxidants, vitamin C and thiol combination under nearly anaerobic conditions still remains unknown. The radical-scavenging activity for seventeen phytophenols and for six synthetic phenols (positive controls) was investigated using the induction period method in the polymerization of methyl methacrylates (MMA) initiated by thermal decomposition of benzoyl peroxide (BPO) by monitoring differential scanning calorimetery (DSC). The kinh for the phytophenols was likely with the range 0.5 × 103 M−1s−1−2.2 × 103 M−1s−1, whereas that for synthetic phenols, hydroquinone and galvinoxyl, was with the range 7 × 103 M−1s−1−8 × 103 M−1s−1. Also, the additive scavenging effect of the (−)-epigallocatechin (EGC):(−)-epicatechin (EC) and the (+)-catechin:epicatechin (EC) combination was observed at 1:1 molar ratio, whereas that of the EC:quercetin combination showed the cancel (prooxidative) effect. Furthermore, the EGC:ASDB (L-ascorbyl 2,6-dibutylate) or 2-ME (2-mercaptoethanol) combination showed the prooxidative effect. Such enhancement of prooxidation in the combination may increase their toxic effects due to their cooxidation. Also, the synergic, additive or cancel effects of the flavonoid:vitamins E combination on the induction period in the BPO (a PhCOO* radical) and 2,2′-azobisisobutyronitrile (AIBN, an R* radical) systems are discussed.

Radical-Scavenging Activity and Cytotoxicity of p-Methoxyphenol and p-Cresol Dimers

Compounds with two phenolic OH groups like curcumin possess efficient antioxidant and anti-inflammatory activity. We synthesized p-cresol dimer (2,2'-dihydroxy-5,5'-dimethylbiphenol, 2a) and p-methoxyphenol dimer (2,2'-dihydroxy-5,5'-dimethoxybiphenol, 2b) by ortho-ortho coupling reactions of the parent monomers, p-cresol (1a) and p-methoxyphenol (1b), respectively. Their antioxidant activity was determined using the induction period method, and their cytotoxicity towards RAW 264.7 cells was also investigated using a cell counting kit. The stoichiometric factors n (number of free radicals trapped by one mole of antioxidant moiety) for 2a and 2b were 3 and 2.8, respectively, being greater than those for 1a and 1b. The ratio of the rate constant of inhibition to that of propagation (kinh/kp) for 2a and 2b was similar to that for 2-t-butyl-4-methoxyphenol (BHA), a conventional food antioxidant. The 50% inhibitory dose (ID50) declined in the order 1b > 1a >> 2b > 2a > BHA. The cytotoxicity for 2a and 2b was significantly greater than that for the parent monomers (p < 0.001), but smaller than that for BHA (p < 0.01). Compounds 2a and 2b may be useful as food antioxidants.

Mechanisms of cytotoxicity of 2- or 2,6-di- tert-butylphenols and 2-methoxyphenols in terms of inhibition rate constant and a theoretical parameter

To clarify the mechanism of phenol toxicity, the radical-scavenging activity of 2- or 2,6-di- tert-butyl- and 2-methoxy-substituted phenols was investigated by combining two distinct approaches: first, the induction period method for methacrylate polymerization initiated by benzoyl peroxide or 2,2′-azobisisobutyronitrile; and secondly, 1,1′-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging test. The homolytic bond dissociation enthalpy (BDE) and ionization potential (IP koopman) were calculated by the DFT/B3LYP method. The cytotoxicity was investigated using tumor cells (human submandibular gland carcinoma cells, HSG; human promyelocytic leukemia cells, HL-60) and primary cells (human gingival fibroblasts, HGF; human periodontal ligament fibroblasts, HPLF; human pulp fibroblasts, HPF) derived from oral tissues. The cytotoxicity between tumor and primary cells was similar, except for eugenol dimer showing less toxicity for primary cells. The DPPH assay was not useful for tert-butylphenols due to their steric hindrance. For both HSG and HGF cells, a linear relationship was found between 50% cytotoxic concentration (CC 50) and inhibition rate constant ( k inh), but not BDE, IP, or log P. The acceptable quantitative structure–activity relationships (QSAR) obtained for cytotoxicity vs. k inh suggested that the cytotoxicity of phenols may be dependent on radical reactions. The cytotoxicity of vanillin and 3,5-di- tert-butyl-4-hydroxy-benzaldehyde with large k inh values, weak antioxidants was markedly less than that of 2,6-di- tert-butyl-4-methylphenol, 2,4,6-tri- tert-butylphenol and curcumin with small k inh values, potent antioxidants.

A Comparative Study of the Radical-scavenging Activity of the Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid, With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method

Phenolcarboxylic acid antioxidants do not act in vivo as radical-scavengers in isolation, but rather together with GSH (glutathione), a coantioxidant, they constitute an intricate antioxidant network. Caffeic acid, p-coumaric acid, ferulic acid and chlorogenic acid with or without 2-mercaptoethanol (ME), as a substitute for GSH, was investigated by the induction period (IP) method for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN, a source of alkyl radicals, R.) and benzoyl peroxide (BPO, a source of peroxy radicals, PhCOO.) using differential scanning calorimetry (DSC). Upon PhCOO. radical scavenging, the stoichiometric factors (n, number of free radical trapped by one mole of antioxidant) for caffeic acid, ferulic acid, p-coumaric acid and chlorogenic acid were 2.4, 1.8, 1.7 and 0.9, whereas upon R. radical scavenging, the corresponding values were 1.3, 1.2, 1.0 and 0.8, respectively. Antioxidants with n values close to 2 suggest the stepwise formation of semiquinone radicals and quinones. By contrast, those with n values close to 1 suggest the formation of dimers after single-electron oxidation, possibly due to recombination of corresponding aryloxy radicals. The ratio of the rate constant of inhibition to that of propagation (kinh/kp) declined in the order chlorogenic acid > p-coumaric acid > ferulic acid > caffeic acid. The ratio of the observed IP for the phenolcarboxylic acid/2-mercapto-ethanol (ME) mixture (1:1 molar ratio) (A) to the calculated IP (the simple sum of phenol acid antioxidant and ME) (B) was investigated. Upon R. scavenging, the caffeic acid or p-coumaric acid/ME mixture was A/B>1, particularly the former was 1.2, suggesting a synergic effect. By contrast, upon PhCOO. scavenging, the corresponding mixture was A/B <1, particularly the latter was 0.7, suggesting an antagonistic effect. Upon both radicals scavenging, the A/B for the ferulic acid or chlorogenic acid/ME mixture was approximately 1. The reported beneficial antioxidant, anti-inflammatory and anticancer effects of caffeic acid and p-coumaric acid may be related to their prooxidant-antioxidant balance in the presence of GSH.

Radical-scavenging Activity of the Reaction Products of Isoeugenol with Thiol, Thiophenol, Mercaptothiazoline or Mercaptomethylimidazole Using the Induction Period Method

The reaction products in the presence of Lewis acid of isoeugenol (1) with ethanethiol, thiophenol, 2-mercaptothiazoline or 2-mercapto-1-methylimidazole (ISO-S1-ISO-S-4) were obtained. The radical-scavenging activity of these compounds was investigated using the induction period method for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO) and monitored by differential scanning calorimetry (DSC). For BPO, the stoichiometric factor (number of free radicals trapped by one mole of antioxidant moiety, n) declined in the order isoeugenol (1.8) > ISO-S-1 (1.6) > ISO-S-2 (1.2) > ISOS- 3 (0.9) > ISO-S-4 (0.3), whereas for AIBN, their n values were about 1, except for ISOS- 3 (0.6). The ratio of the rate constant of inhibition to that of propagation (k(inh)/k(p)) for BPO declined in the order ISO-S-4 (56) > ISO-S-3 (15) > ISO-S-2 (11) >ISO-S-1 (9) > isoeugenol (8). Similarly, for AIBN the k(inh)/k(p) of the reaction products (33-57) was greater than that of isoeugenol (31). The reaction products of isoeugenol with a SH group showed greater inhibition rate constants (kinh) than the parent compound isoeugenol.

Radical-scavenging Activity of Estrogen and Estrogen-like Compounds Using the Induction Period Method

The radical-scavenging activity of estrogens (estrone, 2-hydroxyestradiol),estrogen-like compounds (diethylstilbestrol, DES; bisphenol A, BPA) and the mono-phenolic compound 2,6-di-t-butyl-4-methoxyphenol (BMP) was investigated using themethod of measuring the induction period for polymerization of methyl methacrylate(MMA) initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN) andbenzoyl peroxide (BPO) at 70°C using differential scanning calorimetry (DSC). Thestoichiometric factor (n, number of free radicals trapped by one mole of antioxidantmoiety) for the AIBN system declined in the order BMP (2.0), 2-hydroxyestradiol (2.0)>DES (1.3) > BPA (1.2) > estrone (0.9), whereas that for the BPO system declined in theorder BMP (2.0) >DES (1.9), BPA (1.9) > estrone (1.3) > 2-hydroxyestradiol (0.7). Theinhibition rate constant (kinh x 10-3 M-1s-1) for the AIBN system declined in the orderestrone (2.2) > BPA (2.0) > DES (1.9) > 2-hydroxyestradiol (1.2) > BMP (1.1), whereasthat for the BPO system declined in the order 2-hydroxyestradiol (3.2) > estrone (1.4) >DES (1.2) > BPA (1.0) > BMP (0.9). The radical-scavenging activity for bioactivecompounds such as estrogens should be evaluated using these two methods (the n and kinh)to elucidate the mechanism of a particular reaction. The great difference of the n and kinhfor estrogens between the AIBN and BPO system suggested that their oxidation process iscomplex.

Kinetics for the Autoxidation of Conjugated Linoleic Acid

The oxidation rates for conjugated linoleic acid (CLA), linoleic acid (LA), and their methyl and ethyl esters were measured in aqueous and solvent systems by the induction period method. In an aqueous system, the initiation rate was almost the same for all the samples, except for ethyl conjugated linoleate (ECL). The propagation rate, oxidizability, and kinetic chain length were different for the ester and free types of CLA and LA. CLA was the most stable, its oxidizability being half that of LA. However, ECL was very susceptible to free radical oxidation. In a solvent system, the CLA derivatives had higher or almost same oxidizability as the LA derivatives, although the propagation rates of CLA and LA were lower than those of their esters.

Kinetics for the Autoxidation of Triacylglycerols Containing Eicosapentaenoic Acid

The oxidative rate of three kinds of synthetic triacylglycerols (TAGs) consisting of eicosapentaenoic acid (EPA) and palmitic acid was measured by the induction period method to understand the mechanism for the autoxidation of TAGs containing highly unsaturated fatty acids (HUFAs) such as marine oils. The propagation rate, oxidizability, and kinetic chain length increased with the number of moles of EPA in a single TAG molecule, although the initiation rate was almost the same for all the TAG samples. These results demonstrate that the oxidative rate of EPA in TAGs was affected by the TAG structure and that EPA highly concentrated in a TAG molecule was very susceptible to free-radical oxidation.

An evaluation of antioxidants for vegetable oils at elevated temperatures

AbstractThe antioxidant efficacy of various oxidation inhibitors in low erucic acid rapeseed oil has been studied in a screening test at 130°C by an induction period method. Hindered monophenols, sulphides, phosphites, aromatic amines and zinc dithiophosphates yielded no or only marginal stabilising effects. Remarkably increased oxidation stabilities were observed with certain hindered bisphenols, polyhydroxybenzenes, zinc and bismuth dithiocarbamates. In high oleic sunflower oil with a lesser portion of multiple unsaturation, these additives induced relatively longer induction periods. Mixtures of zinc dithiocarbamates and 4,4′‐methylenebis‐(2, 6‐di‐tert‐butylphenol) or octylated di‐phenylamine, as well as compositions of all three compounds, exhibited synergistic effects. Under the conditions employed these additives were distinctly superior to commercially recommended formulations. A mechanistic concept of the antioxidant action of zinc dithiocarbamate is briefly discussed.

Influence of aldehydes in make‐up oils on antioxidation properties

AbstractThe addition of more antioxidant to aged oils is not always effective in preventing autoxidation. To investigate this phenomenon, a solution of antioxidant and model oxide in hexadecane was examined by means of the induction period method. Aldehydes were found to be the most active species for reducing the antioxidation properties of zinc dialkyldithiophosphate (ZDTP), 2,6‐di(tert. butyl)‐4‐methylphenol (DBPC), and N‐phenyl‐1‐naphtylamine (PNA). Carboxylic acids, ethers, alcohols, and ketones to some extent reduced the induction period with these antioxidants. Esters showed almost no influence on reducing their antioxidant properties.Reaction of ZDTP with aldehyde was studied by means of 31P‐NMR analysis. It was found that (a) aldehydes accelerate conversion of ZDTP, and thereby reduce its antioxidant performance. (b) Conversion of ZDTP in the presence of aldehydes under oxygen at 130° in hexadecane and no reaction was observed under nitrogen at the same temperature. Active intermediates derived by the autoxidation of aldehyde were suspected. (c) Reaction of peroxycarboxylic acid with ZDTP took place smoothly at 0°C under nitrogen to give bis(dialkylthiorophosphoro)disulphide and the corresponding carboxylic acid. Reaction of hydroperoxide with ZDTP took place at room temperature to give oxo‐hexa(dialkylphosphorothiorothionato)‐tetrazinc.Two mechanisms for decomposition of ZDTP promoted by aldehydes, namely hydroperoxide and peroxycarboxylic acid mechanisms, are proposed. Reaction of peroxycarboxylic acid with DBPC or PNA barely took place at room temperature: for these antioxidants, the peroxycarboxylic acid mechanism would be excluded. Radical species derived by the autoxidation of aldehydes were considered as active intermediates.It is considered that classification of the types of oxides that exist in used oils in the key to optimising the effect of re‐added antioxidants.

The kinetics of the autoxidation of polyunsaturated fatty acids.

The kinetics of the autoxidation of a series of polyunsaturated fatty acids (PUFA) with increasing degrees of unsaturation and the mono-, di- and triglycerides of linoleate have been studied in homogeneous chlorobenzene solution at 37 C under 760 torr of oxygen. The autoxidations were initiated by thermal decomposition of azo initiators and followed by measuring the rate of oxygen uptake. The rate of chain initiation was determined by the induction period method using alpha-tocopherol as the chain-breaking antioxidant. The measured oxidizabilities of the PUFA are linearly dependent on the number of doubly allylic positions present in the molecule. Thus, the oxidizability of linoleate is 2.03 X 10(-2) M-1/2 sec-1/2, and the value for docosahexaenoate is five times greater, 10.15 X 10(-2) M-1/2 sec-1/2. The rate of autoxidation for all PUFA studied and for the mono- and diglyceride is proportional to the substrate concentration and to the square root of the rate of chain initiation, implying that the autoxidation of these compounds follows the usual kinetic rate law. The autoxidation of the triglyceride is more complex and does not appear to follow the same rate law at all substrate concentrations. This deviation from the usual kinetic rate expression may be due to lipid aggregation at low concentrations of the triglyceride.

Radiation polymerisation of cyclohexyl methacrylate—I

Radiation polymerisation of cyclohexyl methacrylate has been carried out at various doses, dose rates and temperatures. The radical yield determined by induction period method using benzoquinone as a scavenger is 6.25. The dose rate exponent is found to be 0.517 indicating a bimolecular termination. The ( K p/K t 1 2 ) value is 0.268, which is an order of magnitude higher than for methyl methacrylate under identical conditions of dose rate and temperature. Energy of activation calculated on the basis of kinetic data is found to be 2.06 kcal/mol, which is also quite low. These results indicate the probability of the existence of an anionic initiation in addition to free radical initiation. Chain transfer constant to tonomer ( K tr / K p )is found to be 1.9 × 10 −4.

ガソリン酸化安定度（誘導期間）試験法の精度

Induction Period Method, designated by ASTM D525, has been known as one of methods to evaluate the oxidation stability of gasoline. The gasoline in a bomb is oxidized under elevated pressure of oxgen, and in the absorption process of oxgen the time required for the gasoline to reach a finite rate of pressure drop is defined as the induction period.This method may be utilized to predict the storage stability, that is, the potency to form gum in storage of gasoline.In this paper, the effect of factors, light irradiation, detergents, and bath temperature, on the induction period, and the limit of the precision of this method have been investigated. The conclusions drawn from these experiments are as follows.1) The effect of light irradiation: The history of light irradiation by the fluorescent lamp reduces the induction period of the sample. It is expected that the induction period will be reduced by 10% provided the gasoline in a colorless container is kept for 48 hours on a testing bench. Therefore, the sample should be storaged in a colored container or in a cool and dark place.2) The effect of detergent: The alkaline detergent shows insufficient detergency, and the use of the detergent gradually reduces the induction period as experiments are repeated.3) The effect of bath temperature: A consideration should be paid on the position of heater to be mounted and the flow rate of water to be supplied in the design of the water bath to heat the bomb.4) Precision: The limit of the precision of this method, which is easily attainable, is about 0.3% as coefficient of variation (1006/x).

Analytical applications of the o-dianisidine-persulfate reaction: Kinetic determination of silver and cobalt

A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead.

The autoxidation of unsaturated lipids in micelles. Synergism of inhibitors vitamins C and E

The kinetics of thermally (30 °C) initiated autoxidations of unsaturated lipids, linoleic acid, and methyl linoleate are studied in 0.50 M sodium dodecyl sulfate (SDS) micelles. The rate of chain initiation, R1, was controlled by using known amounts of the thermal initiator, di-tert-butylhyponitrite (DBHN). The initiator efficiency, e, determined by the induction period method with x-tocopherol, was 0.30 for linoleic acid and varied (0.30 to 0.36) for methyl linoleate autoxiation as the concentration of the ester increased. The rate of autoxidation of linoleic acid follows the classical rate law since it is proportional to the substrate concentration and to the square root of chain initiation. The oxidizability of linoleic acid measured in micelles is 4.09 × 10−2 M−1/2 s−1/2. The oxidizability of methyl linoleate varied from 2.37 × 10−2 to 6.92 × 10−2 M−1/2 s−1/2 as the amount of solubilized ester increased. The latter results are indicative of pooling of the ester in the micellar phase. Additions of aqueous solutions of ascorbic acid to α-tocopherol-inhibited micellar autoxidations result in very significant extensions of the efficient inhibition period compared to that obtained with α-tocopherol alone. The mechanism of this synergism is briefly discussed.

Kinetics of radiation polymerization of phenyl acrylate

Phenyl acrylate was polymerised by γ-rays from Co-60 source and the kinetics of polymerisation were studied at various temperatures. The rate of polymerization was found proportional to I 0.99 where I is the radiation intensity. The activation energy of polymerization reaction was found to be 8.5 kcal. The G-radical yield obtained by induction period method was 17.2. The rate of polymerization was high and the molecular weight was of the order of 2000. The low molecular weight has been explained as due to termination of the chain by degradative and nondegradative chain transfer.