The main dynamic characteristics of biochemical methanol formation by the oxidation of methane using a biocatalyst were studied. The biocatalyst is based on cells of bacteria Methylosinus sporium B 2121, both suspended in a medium and immobilized in the poly(vinyl alcohol) cryogel. The change in the methane concentration and the biocatalyst amount affects the productivity of the system, the maximal concentration of methanol in the cultural liquid, and the rate of methanol accumulation. The most part of the dynamic characteristics are described by extremal curves. The experimental conditions were optimized prior to experiments. The use of the immobilized biocatalyst makes it possible to enhance the productivity of the process more than fivefold compared to that of the free cells and to achieve the highest methanol concentration in the medium: 62±2 mg L -1 .
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.
For the first time the total and relative contents of the stable ozonolysis products of fullerene C 70 solutions were identified by IR spectroscopy and elemental and chemical analy ses. At the 100% conversion of С 70 a mixture of products corresponding to the empirical formula С 70 О 14.3 Н 0.21 (epoxides : polyketones : polyesters : secondary fullerene ozonides (SFOZ) : acids = 1.07 : 6 : 6 : 0.21 : 1.02) is formed. The content of polyketones, polyesters, acids, and SFOZ increases during the whole ozonolysis time (1 h). The number of oxygen atoms in epoxides С 70 О n (n = 1-4) is lower than that in epoxides С 60 О n (n = 1-6) formed by the ozonolysis of fullerene С 60 . The kinetic curve of accumulation of epoxides С 70 О n (n = 1-4) passes through a maximum, which is observed 0.5 min after the beginning of ozonolysis. No epoxides were identified among the products 3.5 min after the ozonolysis. The photoluminescence (PL) (λ max = 645 and 685 nm) of fullerene polyketones in glassy EtO 2 /EtOH solutions frozen at 77 K was observed. This PL is much brighter, than that of polyketones formed upon the ozonolysis of fullerenes С 60 . For the first time the chemilumines cence (CL) was detected and studied upon the ozonolysis of С 70 solutions at 300 K. The CL emitters are excited states of fullerene polyketones. The CL spectrum is partially overlapped with the known CL spectrum appeared upon the ozonolysis of С 60 (λ max = 685 nm) but contains the greater number of maxima (λ max = 645 and 685 nm), which is related to a lower symmetry of the С 70 oxidation products.Key words: С 70 fullerene, ozonolisys of solutions, chemiluminescence, photoluminescence of fullerene polyketones.Studies of the mechanism and reaction products of fullerene oxidation with ozone is important from the view point of both investigation of fundamental chemical prop erties of fullerenes and development of the new, "oxida tion approach" to the synthesis of water soluble fullerene derivatives promising for medicine and pharmacology. An analysis of publications 1-8 on the study of С 70 ozo nolysis indicates that the total composition of stable products of this reaction has not been established up to presently. 1-8 For example, the most intense band in the IR spectra of the oxidation products was assigned simul taneously to the absorption of a wide range of various carbonyl containing compounds: aldehydes, ketones, acids, and lactones. 3 Fullerene С 70 usually is only men tioned in the title of an article, 1-8 whereas the experimen tal data are given only for С 60 , although the authors mention in the summary that analogous results were obtained for С 70 . Meanwhile, a comparative study of ozonolysis of these fullerenes can provide fruitful information on the influ ence of different structures of С 60 (I h ) and С 70 (D 5h ) on the reactivity of these molecules toward ozone 9,10 and on the composition of the reaction products. The purpose of this work is to determine the total composition of stable products of С 70 oxidation with ozone in solutions, to...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.