Scientific and Technical Centre NANOCLASTER
Nizhny Tagil, Russian Federation
of synthesis of fullerenols C60(OH)n
(polyhydroxylated fullerenes) cannot have prospects for industrial
use, primarily because of high cost of the fullerenol, produced by
methods (electroarc or plasma method). Cost of the fullerenol
fullerene) in the process of synthesis is increased by a factor of tens
comparison with the cost of fullerene itself, and today cost of
C60(OH)n in the world market is 2000-2500 USD/g, which makes it
economically unviable. But it has the biggest prospect in such area as
pharmacology. Besides, the fullerenol, produced by «classic» method,
always contain some potassium or sodium hydroxides.
and Technical Centre “Nanocluster” (STC “Nanocluster”) has developed an
alternative, fully chemical method of production of fullerenol C60(OH)n, based on catalytic hyperaromatization and hypercyclization
of products of glycerine dehydration with formation of carbon
with closed structure, in the result of which fullerenol C60(OH)24 is produced. Industrial cost
price of fullerenol, synthesized out of glycerine, does not exceed 2000-2500
USD/kg. The reason of this low cost price of fullerenol, synthesized
glycerine, is that the synthesis includes only glycerine,
scanty amount of catalyst – 0,02-0,05% of the
of glycerine in Russia, even produced in Germany, is about 0,90 Euro/kg
than 1 USD). The fullerenol, produced by this
does not contain hydroxides of alkaline metals.
Fullerenol C60(OH)24, produced of glycerine, under its appearance,
and chemical properties, is analogous to fullerenol Cx(OH)n,
«classic» methods: by means of hydroxylation of fullerene by sodium
or by means of alkali hydrolysis of fullerene bromide.
synthesis is based on catalytic dehydration of glycerine. The
placed in a retort connected with refrigerator, is heated over inoculum
catalyst to the temperature of 220-250 degrees Ñ (Fig 1). After 20-25
minutes, the distillation of water vapor begins. The quantity of the
catalyst is 0.02-0.05%. Such a minimum quantity of the catalyst is
reasoned by the fact that with the production of first synthesis
products, the process transits to the
mode. In such a way, the initial catalyst is only an inoculum for the
start of the dehydration process in the auto-catalytic mode. For
example, for the process of dehydration of 200 ml (252 g) of glycerine,
only 50-100 mg of catalyst is needed. Form 200 ml of glycerin, 63 g of
dehydration product can be obtained using the catalytic dehydration
method (see Fig 2).
Catalytic dehydration of Glycerine
dehydration is over
200 ml (252 g)
weight is 63 g
product of dehydration of
mechanism of fullerenols C60(OH)n out
In the product of
(see Fig 2 and Fig 3), along with fullerenols Ñ60(ÎÍ)n
(n = 2-24), compounds with not loop-closed into sphere structures are
contained, in particular, C9H12(OH)9,
(see Scheme “Synthesis mechanism of fullerenols C60(OH)n
out of Glycerine”), which are intermediate products of synthesis. A
part of those “uncompletely fullereneized” intermediate products are
loop-closed into spherical structures with the nucleus of fullerene by
the reaction of catalytic hypercyclization. The product obtained in
result of the catalytic
is a large-crystals product of black color (see Fig 4), and in the
crushed form it is a small-crystals product of brown color (see Fig
5). In appearance, the product of the glycerine dehydration stage and
the product of the cyclization stage look similar. But by their
chemical composition they are different. The cyclization stage product
does not contain compounds with not loop-closed into sphere structures,
in particular, C9H12(OH)9,
and is free
from side-components. The cyclization
stage products is nothing else but a mixture of fullerenols Ñ60(ÎÍ)12
(85-90%) and Ñ60(ÎÍ)24 (10-12%) with a little
of fullerenol Ñ60(ÎÍ)2
(1-2%) with common
The solvability of the mixture of fullerenols Ñ60(ÎÍ)n
in water is
insignificant: 2-3 mg/l, because of the predomination therein of
which is practically insoluble in water. The color of the solution of
fullerenol Ñ60(ÎÍ)n in water is bright-yellow (see Fig 6). But this
solvability is also reasoned not by the fullerenol Ñ60(ÎÍ)12,
but by the fullerenol Ñ60(ÎÍ)24
The fullerenol Ñ60(ÎÍ)24
can be extracted
from the mixture by distilled water in a Soxhlet-type apparatus. The
solvability of the fullerenol Ñ60(ÎÍ)24
in water is 40-50 mg/l. The color of the solution of the fullerenol Ñ60(ÎÍ)24
in water is yellow (see Fig 7).
From 51 g of fullerenol Ñ60(ÎÍ)n (the product
catalytic cyclization) obtained from 200 ml of glycerine, about 5 g of
can be extracted using water in the Soxhlet-type apparatus. In such a
way, from 1.0 l of glycerin, about 25 g of the fullerenol Ñ60(ÎÍ)24
can be produced.
weight is 50±1 g
product of cyclization stage
Solution of fullerenol Ñ60(ÎÍ)n
Solution of fullerenol Ñ60(ÎÍ)24
Solution of fullerenol
in ethyl alcohol
Solution of fullerenol
Ñ60(ÎÍ)24 in DMFA
Analysis of dehydroxylated fullerenol sample mass spectrum
Sample of fullerenol C60(OH)24
was exposed to high-temperature heating in hydrogen atmosphere. As a
result, there was a defucylized (dehydroxylation) of fullerenol to
fullerene-containing mixture, in which absolute, under its value, peak
(Base Peak) was the peak with «m/z» equal to 720. In case of «z»
equal to 1, this corresponds to molecular weight of fullerene C60
equal to 720 AMU. Thereby, we
assert that the center of this fullerenol is really fullerene C60.
sample, IR spectral
data was collected (see Fig 11). For
comparison, Fig 12 shows IR
spectral data from the literature
(J. Braz. Chem. Soc. vol.17 no.6 São Paulo Sept./Oct. 2006). As it can be seen from the
of those spectra, main characteristics of spectra are the same.
spectra of a fullerenols C60
|IR spectrum of fullerenol C60(OH)24
synthesized out of
glycerine, produced by STC "Nanocluster"
|Synthesis of C60(OH)18-20
in aqueous alkaline solution
Soc. vol.17 no.6 São Paulo Sept./Oct. 2006
spectra of a fullerenol C60
produced by Institute of Organic Synthesis Ural Division of RAS
spectra is the property of the STC STC NANOCLUSTER
the IR spectrum of a fullerol synthesis. The spectrum is dominated by a
broad band at 3380 cm-1due to the stretching mode of the OH groups, as
well as other peaks at 1600 cm-1 (C=C), 1390 cm-1 (C-OH) and 1055 cm-1
(C-O). All these bands have been reported before for the compound as
belonging to the fullerol molecules.21-25
In such a way, the self-cost of
synthesized from glycerine is 3 orders of magnitude lower than the
self-cost of ‘classic’ fullerenol produced from fullerene Ñ60.
More to that, fullerenol Ñ60(ÎÍ)24,
synthesized from glycerine does not contain sodium ions. The fullerenol C60(OH)24
doesn't contains any sodium.
Hydroxylation of Low
Hydroxylated Fullerenol C60(OH)12
to Mild Hydroxylated
all companies producing fullerenol Ñ60(OH)24
or selling it actually offer not fullerenol Ñ60(OH)24,
but its sodium salt Ñ60(OH)24-n(ONa)n.
That is reasoned by the fact that all technologies for production of
‘classic’ fullerenol are connected with the use of sodium (or sometimes
potassium) hydroxide, and it is very difficult to remove sodium ions
from the fullerenol. By contrast to ‘classic’ fullerenols, fullerenol Ñ60(OH)24
synthesized from glycerine is a
genuine fullerenol and does not contain sodium ions.
The ‘classic’ fullerenol, being by its nature a sodium salt Ñ60(OH)24-n(ONa)n
of fullerenol, is not soluble in spirits, in DMF (dimethylformamide),
and in DMSO (dimethylsulphoxide).
By contrast, fullerenol Ñ60(OH)24
produced from glycerine, being genuine fullerenol, is soluble in
spirits, in DMF and DMSO (see Fig
8 and Fig
Although the main direct final product of the synthesis from glycerine
is low hydroxylated fullerenol Ñ60(ÎÍ)12
(85-90%), there are methods which allow to transform low hydroxylated
hydroxylated fullerenol Ñ60(ÎÍ)24.
such methods is described in the article Water-Solubl
Single-Nano Carbon Particles: Fullerenol and Its Derivatives,
Ken Kokubo, Division of Applied Chemistry, Graduate School of
Engineering, Osaka University Japan http://cdn.intechopen.com/pdfs-wm/36889.pdf.
is a fine-crystalline product of brown color which is insignificantly
soluble in water, 40-50 mg/l, forming a pale- yellow solution (see Fig
At Scientific Research Center
own technology for production of mild hydroxylated fullerenol from low
hydroxylated fullerenol synthesized from glycerine has been developed.
However, in reality, because of the use in this technology of sodium
hydroxide NaOH, the final product is not fullerenol Ñ60(ÎÍ)24
itself, but its sodium salt Ñ60(OH)24-n(ONa)n.
Sodium salt Ñ60(OH)24-n(ONa)n
form is a fine-crystalline product of brown color which is easily
soluble in water, 40-50 g/l, forming, depending of the concentration,
solutions of yellow to brown color (see Fig
13). The solubility in water of the sodium salt of fullerenol Ñ60(OH)24-n(ONa)n
is 1000 times greater than the solubility of the fullerenol Ñ60(ÎÍ)24
itself. But sodium salt of fullerenol is soluble neither in spirits nor
in DMF or DMSO.
quantity of sodium salt Ñ60(OH)24-n(ONa)n
which can be produced from 200 mg of
glycerine is 36-38 g
which is equivalent to 180-190 g
sodium salt Ñ60(OH)24-n(ONa)n from 1.0
l of glycerine.
of sodium salt of fullerenol Ñ60(ÎÍ)24-n(ONa)n
depending on the concentration
and its sodium salt Ñ60(OH)24-n(ONa)n
can be used in:
Antiviral medicine without cytotoxicity;
Antioxidants, comparable to fullerenes under their effectiveness;
Wound and burn healing medicine.
Modifiers of polymers, resins, glues, paint-and-lacquer and other
Modifiers of materials on base of silicate binding agents, including
Component of electrolytes for metal galvanic coatings;
Component of ultra-hard composite materials with metal matrix.
– plant cultivation and animal husbandry
Plant growth stimulants;
Antiviral and antimycotic agents;
Preparations, which increase stability of crops by complex nonspecific
Additives to fodders, which increase resistibility of agricultural
animals and birds to different diseases, and which do not accumulate in
a) as modifier of
b) as antiviral medicine of broad spectrum, without cytotoxicity.
c) as microbicids with anti-HIV activity, without cytotoxicity:
1. Dissertation (26.11.2010):
Microbicids with anti-HIV activity, Gilyazova A.V. Gamaleya
Institute of immunology, Moscow. Section 6. Research of cytotoxicity,
antiviral activity and virucidal effect of addition compounds of carbon
nanoclusters, p.18. Fullerenol corresponds to sample no.3.
2. Water Soluble Carbon Nanoclusters as Microbicides with Anti-HIV
Activity. A. Gilyazova, G. Kornilaeva, A. Ponomarev, V. Chereshnev, E.
3. Water Soluble Carbon Nanoclusters as Microbicides with Anti-HIV
Activity. A. Gilyazova, G. Kornilaeva, A. Ponomarev, V. Chereshnev, E.
Karamov. Scientific Israel, Technological Advantages http://www.sita-journal.com/files/4_v.12,%20No.3,4,2010.pdf
d) as a component of cosmetic preparations, which have antioxidant
e) as a component of electrolytes for electrochemical
deposition of nanostructured carbon film.
issued for fullerenol:
Russian patent No. 2497751
and German patent DE102012103579A1
invention can be used in production of modifiers of epoxy-filled
composites, microbicids with anti-HIV activity without cytotoxicity,
antioxidant additives to makeup preparations. Fullerenol C60 is
produced by catalytic dehydration of glycerine during heating. As a
catalyst one can use fullerene, fullerenol and other organic and
mineral compounds. It is an autocatalytic reaction, and the catalyst is
necessary only for "launching" of the synthesis. Hereafter, the
produced fullerenol catalyzes synthesis of fullerenol by itself. That’s
why the amount of catalyst for launching of the reaction is scanty,
0,02-0,05% of the glycerine mass.
|FULLERENOL C60 AND METHOD OF ITS PRODUCTION OF
1. Kozeev E.A.,
Kozeev A.A. Patent RU No. 2497751,
12.28.2011. FULLERENOL C60 AND
METHOD OF ITS PRODUCTION FROM GLYCERINE. http://www1.fips.ru/Archive/PAT/2013FULL/2013.11.10/DOC/RUNWC2/000/000/002/497/751/DOCUMENT.PDF
2. Kozeev E.A.,
Kozeev A.A. German patent DE102012103579A1,
2013.06.20. Fullerenol C60 und
Verfahren zu dessen Herstellung aus Glyzerin.
3. T.A. Nizina,
counsellor of RAACS, technical PhD, professor; A.N. Ponomarev,
candidate of technical science, professor, STC of "Applied
Nanotechnologies" Ltd., St. Petersburg; S.N. Kislyakov,
postgraduate student of Mordovsky state university; A.A. Kozeev,
scientific officer of STC of "Applied Nanotechnologies" Ltd., St.
of the research of epoxy compositions,
modified by soluble addition compounds of carbon nanoclusters.
nanocarbon coating. Electrochemical deposition of nanocarbon film on
current-carrying materials http://www.nanochemlab.ru/
5. Kozeyev A.A.
Deposizione elettrochimica di film
Nanocarbon su materiali conduttivi. Italian Science
Review. 2014; 10(19). PP. 221-223. Available at URL: http://www.ias-journal.org/archive/2014/october/Kozeyev.pdf
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