Water-soluble polyketones and esters as the main stable products of ozonolysis of fullerene C<sub>60</sub>solutions

Булгаков, Р. Г.; Nevyadovskii, E. Yu.; Belyaeva, A. S.; Golikova, M. T.; Ushakova, Z. I.; Ponomareva, Yu. G.; Джемилев, У. М.; Разумовский, С. Д.; Valyamova, F. G.

doi:10.1023/b:rucb.0000024844.56560.31

Cited by 24 publications

(27 citation statements)

References 17 publications

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“…The technique and procedures of CL mea surement and HPLC have been described earlier. 19,20 The con tribution of the internal filter effect caused by CL absorption with fullerene was estimated from a decrease in the emission intensity of a reference radioluminescent light source. The CL absorption did not exceed 20% at [С 60 ] max = 1.8•10 -3 mol L -1 and 0.5-5% at [С 60 ] = 4.8•10 -5 -4.5•10 -4 mol L -1 .…”

Section: Methodsmentioning

confidence: 99%

Inertness of C60 fullerene toward RO2 · peroxy radicals

et al. 2005

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The reactivity of fullerene C 60 toward peroxy radicals RO 2 • was tested by the chemilumi nescence method. A comparison of the influence of C 60 and known inhibitors on the kinetics of liquid phase chemiluminescence (CL) during oxidation of a series of hydrocarbons (ethyl benzene, cyclohexane, n dodecane, and oleic acid) shows that the fullerene does not react with the RO 2 • radicals. A sharp decrease in the CL intensity observed upon C 60 addition is caused by the quenching of CL emitters with fullerene but not by inhibition of hydrocarbon oxidation.Fullerene С 60 is named the "radical sponge" due to its ability to efficiently add free radicals of different chemical nature to form fullerenyl radicals 1-3 :Then the fullerenyl radicals dimerize and/or add an additional amount of radicals. 2 Radicals Х • are usually prepared by photolysis or thermolysis of compounds be longing to different classes. At the same time, published data on the reactivity of fullerene С 60 toward peroxy radi cals RO 2 • are scarce and contradictory. For instance, the reviews on the reactions of С 60 with free radicals 2 and other reagents 1,4 contain no data on the interaction of С 60 with the RO 2 • radicals. Fullerene С 60 was found to inhibit the thermooxidative destruction (TOD) at 200-300 °С of poly(methyl methacrylate) (PMMA), 5-7 polystyrene, 5 and copolymers of methyl methacrylate (MMA) with methacrylamides. 8 The antioxidant activity of С 60 during TOD of these polymers was presumably attributed 7 to the reactionR i is macroradical.The work 9 and site of the Pushchino Scientific Center of the Russian Academy of Sciences* reported the inhibi tion effect on the peroxide oxidation of lipids by fullerene С 60 bound in a complex with polyvinylpyrrolidone. In this case, reactivity of С 60 toward free radicals was mea sured by procedures of nitroblue tetrasolium reduction and chemiluminescence (CL) arising in peroxide oxida tion of lipids. The results of using the first method indi cate that the fullerene had no antioxidative properties. However, a decrease in the overall CL intensity in the presence of fullerene С 60 suggested 9 its inhibition ability.The above facts and an important role of the RO 2 • radicals in oxidative chemical and biochemical pro cesses 10,11 and inhibition effect of fullerene С 60 on living activities of different viruses and pathogenic bacteria 4,12,13 show that the study of antioxidative properties of С 60 , namely, the reactivity toward radicals RO 2 • , is an urgent problem.In this work, the reactivity of fullerene С 60 toward peroxy radicals was studied by the CL method. The effi ciency of the CL method in studying activity of inhibitors has previously been shown 14,15 for the oxidation of differ ent classes of hydrocarbons. ExperimentalCommercial fullerite, whose purity (С 60 99.8%) was moni tored by HPLC and elemental analysis, was used. Ethylbenzene (EB), o dichlorobenzene (DCB), n dodecane (DD), and cyclo hexane (CH) (chromatographically pure) and oleic acid (OA, edible quality) were used without addi...

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Section: Methodsmentioning

confidence: 99%

Inertness of C60 fullerene toward RO2 · peroxy radicals

et al. 2005

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“…2), as well as the content of fullerene polyketones and polyethers. 9 Chemiluminescence upon hydrolysis of SFOs. We have found 19 the CL arisen upon the hydrolysis of liquid and the solid ozonolysis products of C 60 solutions.…”

Section: Resultsmentioning

confidence: 99%

“…De pending on the ozonolysis exposure (OE), we obtained either homogeneous solutions (OE ≤ 0.5 min) or a suspension of brown precipitates (OE ≥ 2 min) containing, in addition to active oxy gen, fullerene expoxides, polyketones, and polyethers, whose analysis have been described in detail earlier. 9 The "fullerenic" active oxygen in these products was analyzed using a modified iodometric spectrophotometric procedure 13-15 used for analysis of active oxygen in hydrocarbons. For this purpose, the liquid or solid products were treated with a solution of KI in an AcOH (10 mL) + H 2 O (1 mL) mixture and stored for 10 min in the dark under argon.…”

Section: Methodsmentioning

confidence: 99%

“…Procedures of HPCL and IR spectroscopy have been described earlier. 9 Hydrogen peroxide in the SFO hydrolyzate was carried out 17 was qualitatively determined from the appearance of the red violet color in the ethereal layer formed upon the addition to the hydrolyzate of an aqueous solution of H 2 SO 4 (0.9 mol L -1 ), diethyl ether, a 5% aqueous solution of K 2 Cr 2 O 4 , and diphenyl carbazide. An installation for CL and procedures for measuring the kinetics and CL spectra have been described earlier.…”

Section: Methodsmentioning

confidence: 99%

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Formation of secondary fullerene ozonides in the ozonolysis of C60 solutions and chemiluminescence upon their hydrolysis

et al. 2006

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The formation of secondary fullerene ozonides (SFOs) in the ozonolysis of C 60 solutions in CCl 4 has reliably been determined for the first time; SFOs are accumulated during the whole ozonolysis time as a suspension in CCl 4 . Hydrolysis of the SFOs results in chemiluminescence (CL) (I max = 2.65•10 8 photon s -1 mL -1 ), whose spectra contain maxima at 558, 608, and 685 nm. The most probable CL emitters are excited fullerene polyketones. Hydrogen peroxide was identified as a stable hydrolysis product of the SFOs by the color reaction with diphenylcarbazide and CL arisen upon the addition of an aqueous solution of FeSO 4 •9H 2 O to the hydrolyzate of the SFO. Chemiluminescence upon hydrolysis is a selective test for SFOs and allows one to find them in a complex mixture of the ozonolysis products of C 60 . The rate constant and activation energy of SFO hydrolysis were determined from the kinetic measure ments of CL. For SFO hydrolysis several probable reactions were proposed, including the formation of the CL emitters, and their heat effects were estimated using the PM3/RHF and AM1/RHF semiempirical methods for one and two cage model structures of SFOs.

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“…Thus, CL can be attributed to thermal cleavage of the O-O groups bound to the ozonolysis transformed framework of C 60 . 7 The CL spectrum is the same as the known 2 CL spectrum recorded during the ozonolysis of C 60 solutions (see Fig. 1); i.e., in the thermolysis of 1, the emitter of CL is also the >C=O* group bound to the framework of C 60 .…”

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Chemiluminescence during thermolysis of fullerene C60 derivatives containing reactive oxygen

et al. 2004

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Chemiluminescence (CL) of fullerenes was first de tected in the ozonolysis of C 60 solutions 1,2 and later in the oxidation of sodium fullerides with a Ce IV complex. 3 In this work, a new type of the CL of fullerenes was observed during the thermolysis of complex C 60 oxides (1) formed by the ozonolysis of C 60 solutions and containing reac tive oxygen (RO) 4 and epoxide, 5 carbonyl, 6,7 and ester groups. 7 Earlier, 8,9 chemiluminescence in the thermoly sis of organic peroxides was reported. Chemiluminescence was measured by a known method. 2 The starting oxide 1 was prepared as a brown precipitate according to a known procedure 7 by the ozonolysis of C 60 solutions in CCl 4 (1.4 mmol of O 3 h -1 , [C 60 ] 0 = 1.6•10 -4 mol L -1 , V = 20 mL). Heating of the suspension of 1 in CCl 4 (20 mL) results in CL with a kinetic peak at the fifth minute (I max = 2.5•10 9 photon s -1 mL -1 ) (Fig. 1). From the excitation of CL to its complete disappearance, the content of RO in the sample (determined by iodometric titration 2 ) decreases from 1.6•10 -4 mol to zero, while the contents of epoxide, carbonyl, and ester groups (deter mined according to a procedure 7 ) do not change notice ably. The energy of activation calculated from the linear plot of logI vs. 1/T is 17.3±1.4 kcal mol -1 . Thus, CL can be attributed to thermal cleavage of the O-O groups bound to the ozonolysis transformed framework of C 60 . 7 The CL spectrum is the same as the known 2 CL spectrum recorded during the ozonolysis of C 60 solutions (see Fig. 1); i.e., in the thermolysis of 1, the emitter of CL is also the >C=O* group bound to the framework of C 60 . The CL excitation scheme can be represented only in the most general form {O-O}[C 60 ] → {*O=C}[C 60 ] → {O=C}[C 60 ] + hν (λ max = 680 nm) ([C 60 ] is the ozonolysis transformed framework of C 60 also including the epoxide, carbonyl, and ester groups), because the nature of RO in oxide 1 has not yet been specified: ozonide, peroxide, or bisperoxide forms are possible. 4

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Water-soluble polyketones and esters as the main stable products of ozonolysis of fullerene C₆₀solutions

Cited by 24 publications

References 17 publications

Inertness of C60 fullerene toward RO2 · peroxy radicals

Inertness of C60 fullerene toward RO2 · peroxy radicals

Formation of secondary fullerene ozonides in the ozonolysis of C60 solutions and chemiluminescence upon their hydrolysis

Chemiluminescence during thermolysis of fullerene C60 derivatives containing reactive oxygen

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Water-soluble polyketones and esters as the main stable products of ozonolysis of fullerene C60solutions

Cited by 24 publications

References 17 publications

Inertness of C60 fullerene toward RO2 · peroxy radicals

Inertness of C60 fullerene toward RO2 · peroxy radicals

Formation of secondary fullerene ozonides in the ozonolysis of C60 solutions and chemiluminescence upon their hydrolysis

Chemiluminescence during thermolysis of fullerene C60 derivatives containing reactive oxygen

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Water-soluble polyketones and esters as the main stable products of ozonolysis of fullerene C₆₀solutions