Fullerenes: functionalisation and prospects for the use of derivatives

Karaulova, E. N.; Bagrii, E. I.

doi:10.1070/rc1999v068n11abeh000499

Cited by 78 publications

(36 citation statements)

References 163 publications

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“…Ethylbenzene (EB), o dichlorobenzene (DCB), n dodecane (DD), and cyclo hexane (CH) (chromatographically pure) and oleic acid (OA, edible quality) were used without additional purification. Initia tors of oxidation, viz., α,α´ azobisisobutyronitrile (AIBN) and dicyclohexyl peroxydicarbonate (DCHPC) and CL activators (hereinafter A), viz., 9,10 dibromoanthracene (DBA) and europium(III) 1,10 phenanthroline tris(thenoyltrifluoroace tonate) (Eu(TTA) 3 •phen), were synthesized and purified by re crystallization as described above. 16,17 α Tocopherol (Aldrich, 97%) and 2,6 di tert butyl 4 methylphenol (ionol, pure) were used as inhibitors (InH) of oxidation.…”

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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“…According to calculations, the addition at the (636) bond is more favorable from the viewpoint of energy than at the (536) bond, for in the latter case the fullerene sphere is opened [1,7]. Thus, the (636) bond in fullerene acts as dienophile in [2 + 3]-cycloaddition reactions.…”

Section: äääääääääääämentioning

confidence: 98%

[2 + 3]-Cycloadditions to C60 fullerene. Synthesis of pyrrolidinofullerenes

Loginova

Gun’kin

2004

Russ J Gen Chem

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Pyrrolidinofullerenes were synthesized by reaction of C 60 fullerene with N-methylglycine and substituted aromatic aldehydes.A promising line in the chemistry of carbon clusters includes functionalization of fullerenes in various ways. Functionalization of C 60 fullerene is often achieved via cycloaddition reactions [1], in particular, [2 + 3] cycloaddition [235]. Especially interesting is the synthesis by [2 + 3]-cycloaddition reactions of new functional C 60 fullerene derivatives which contain pharmacophoric groups and exhibit high biological activity [1,6]. The use of fullerenes in pharmacology seems to be most reasonable from the economic view-ÄÄÄÄÄÄÄÄÄÄÄÄ point, for only a small amount of the substance is required.The present communication reports on the synthesis and chemical properties of new pyrrolidinofullerenes. We found that C 60 fullerene reacts with N-methylglycine and aromatic aldehydes in boiling toluene under argon to give pyrrolidinofullerenes I3IV (Scheme 1). The products were isolated by column chromatography on silica gel. Scheme 1. I, R 1 = H, R 2 = CH 3 O; II, R 1 = R 2 = CH 3 O; III, R 1 = H, R 2 = NO 2 ; IV, R 1 = H, R 2 = N(CH 3 ) 2 . ÄÄÄÄÄÄÄÄÄÄÄÄPresumably, the first stage of the process is condensation of aromatic aldehyde with N-methylglycine. The primary adduct successively undergoes dehydration and decarboxylation to give ylide A. Nucleophilic ÄÄÄÄÄÄÄÄÄÄÄÄ attack by the latter on fullerene at the (636) bond, followed by intramolecular ring closure, leads to a fused pyrrolidinofullerene system (Scheme 2). 76?? B R 2 CH3N3CH 2 COO ! + C CH 3 C OH C H R 1 M M ---------M M ---------

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“…The interest in polyhydroxylated fullerenes is due to their potential applications in, for example, biology and medicine (water-soluble fullerenes) and in polymer chemistry, in particular, as branching reagents in the synthesis of cross-linked polymers [1].…”

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Synthesis of New Polyhydroxylated Fullerenes

et al. 2005

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In this paper, we report on the synthesis of a new polyfunctional derivative of fullerene ë 60 containing, on average, five hydroxyalkyl groups. The synthesis was carried out by addition of an organolithium compound to fullerene ë 60 followed by transformation of ë 60 (RLi) n into poly(hydroxyalkyl)fullerene.The synthesis of hydroxyl-containing derivatives of C 60 is an area of fullerene chemistry rapidly developing since the discovery of fullerene. The interest in polyhydroxylated fullerenes is due to their potential applications in, for example, biology and medicine (water-soluble fullerenes) and in polymer chemistry, in particular, as branching reagents in the synthesis of cross-linked polymers [1].An analysis of published data on the synthesis and application of hydroxyl-containing fullerenes has shown that these derivatives can be divided into two types: type I, fullerenols, in which the hydroxyl groups are attached to the cage carbon atoms, and type II, hydroxyalkyl(aryl)fullerenes (HAFs), in which the hydroxyl groups are parts of the hydrocarbon fragments attached to the fullerene cage. Various methods for the synthesis of fullerenols have been reported [2-4]. As regards HAFs, only two representatives of this class are currently known, namely, monohydroxyalkylfullerene ë 60 (åÂ) 5 (ëç 2 ) 3 éç [5] and bis(4-hydroxyphenyl)methanofullerene ë 61 (PhOH) 2 [6].This study deals with the synthesis of previously unknown poly(hydroxyalkyl)fullerenes (PHAFs).Actually, the idea of PHAF synthesis is underlain by known reactions. It has been found [7,8] that fullerene is readily alkylated with alkyllithiums and organomagnesium compounds to give both mono-and polyalkylated fullerene derivatives even when the organometallic-tofullerene ratio is ≤ (1 : 1). It has also been found [9] that the fullerene molecule contains at least six active sites able to react with nucleophilic reagents. In particular, a fullerene molecule adds up to six polystyryllithium molecules to give (Ps) 6 C 60 Li 6 ; all six lithium atoms in the resulting compound are reactive; i.e., the adduct is able to add an equivalent number of ethylene oxide (EO) molecules [10].We prepared PHAFs via two reactions: alkylation of fullerene with excess alkyllithium and treatment of the resulting adduct with excess EO: C 60 nAlkLi Alk n C 60 Li n + A l k n C 60 CH 2 CH 2 OLi ( ) n Alk n C 60 CH 2 CH 2 OHThe alkyllithium used was sec -BuLi. For increasing the PHAF yield and attaining a full consumption of fullerene, the reaction was carried out at a sec -BuLi-tofullerene molar ratio of 16. After the addition of a benzene solution of sec -BuLi to a transparent violet solution of C 60 in toluene, the reaction mixture almost immediately became turbid and turned black. The contents of the reactor were stirred for at least 2 h, and then EO was supplied from the gas phase (the EO molar excess with respect to sec -BuLi was no less than 20%). The addition of EO to lithiumalkylfullerene was accompanied by coagulation of the reaction product to give a black precipitate. The ...

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Fullerenes: functionalisation and prospects for the use of derivatives

Cited by 78 publications

References 163 publications

Inertness of C60 fullerene toward RO2 · peroxy radicals

Inertness of C60 fullerene toward RO2 · peroxy radicals

[2 + 3]-Cycloadditions to C60 fullerene. Synthesis of pyrrolidinofullerenes

Synthesis of New Polyhydroxylated Fullerenes

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