Method of producing highly water-soluble fullerenols

FIELD: chemistry.

SUBSTANCE: first step includes obtaining low-hydroxylated insoluble fullerenols by reacting concentrated fullerene solution in o-xylene with aqueous ammonia solution in the presence of a tetrabutylammonium hydroxide phase-transfer catalyst at 35-40°C. At the second step, the obtained low-hydroxylated insoluble fullerenols are hydroxylated to transform them into a water-soluble form by mixing with 6-15% aqueous hydrogen peroxide solution and heating for 4-5 hours at 65°C. Water-soluble fullerenols are then precipitated from an alcohol-containing solution.

EFFECT: simplifying the method while preserving quality characteristics and full extraction of the end product.

2 cl, 1 dwg, 4 tbl, 3 ex

 

The invention relates to methods for producing water-soluble hydroxylated derivatives of fullerenes (fullerenols).

There are several ways to obtain water-soluble derivatives of fullerenes. The most simple and widely used methods include methods hydroxylation of fullerenes dissolved in an aromatic solvent (benzene or toluene) with concentrated alkali in the presence of a catalyst phase transfer tetrabutylammonium hydroxide (TBAH) or of polyethylene glycol PEG 400 [1]: 1. Chinese Journal of Chemistry, 2004, 22, 1008-1011; [2]: J. Braz. Chem. Soc., 2006, vol. 17, No. 6, p.1186-1190).

Advantages ways alkaline hydroxylation of fullerenes are quick and easy synthesis. For example, according to /1/ the process is carried out in air as follows. A benzene solution (C60with vigorous stirring slowly added to the NaOH and PEG 400 (20 mol. %) at room temperature in air (or in the environment of N2). When mixing there is a transformation of the initially deep violet benzene solution in colorless due to the transition hydroxyisovalerate C60in the aqueous phase using the phase transfer catalyst PEG 400 and the formation of a black suspension due to the fact that the content formed of fullerenol exceeds its solubility in a given volume of water (2 ml). The benzene is removed upari�against under reduced pressure. Then water is added with stirring to completely dissolve the black mist. To remove insoluble in water of fullerenol the mixture was filtered. The residue obtained after filtration, is discoverability water-insoluble fullerenol containing 8-9 hydroxyl groups. The brown filtrate pariveda and added to the methyl alcohol to precipitate vysokomehanizirovannogo of fullerenol (brown color). The deposition process is repeated until complete removal of PEG and NaOH. After drying under reduced pressure turned out to be a solid product vysokomehanizirovannogo of fullerenol with a solubility of ~ 20 mg/ml, containing 27 of the hydroxyl groups of brown color (yield 80.4% of mass.).

The disadvantages of the method alkaline hydroxylation is described in [3]: J. Am. Chem. Soc. 2004, 126, 12055-12064). It is shown that the alkaline products hydroxylation fullerenols are in the form of their salts with alkali cations, which involves conducting time-consuming procedures for transfer of such salts in salt-free form and continuous purification of the resulting products from the residues of catalysts and alkali. This circumstance is a significant limiting factor in the wide use of methods of alkaline hydroxylation. Besides, along with water-soluble fullerenols formed a significant proportion of n�of soluble fullerenol, that is, of fullerenol with a low degree of hydroxylation. Fullerenols with the number of hydroxyl groups ≤12 practically insoluble in water. Their formation reduces the overall yield of the target product and complicates the procedure of separation and purification.

For the application of fullerenol in medicine, biology and pharmacy required drugs with high solubility in water and in salt-free form. There are several ways for the synthesis of such fullerenols.

A method of producing water soluble fullerenols (with a high degree of hydroxylation), free from alkali cations described in [4]: Fullerenes, Nanotubes and Carbon Nanostructures, 2009, vol. 17, issue 4, p.440-456. The method is as follows. Suspension of powdered C60in a mixture of 30% aqueous H2O2and 28% aqueous NH3stirred at 60°C in air for 12 hours. In the reaction process occurs a color change of the mixture from black to dark yellow. After careful and decant the solution was divided into two parts: net solution A and the remaining solid substance B. the solution A was added ethanol to precipitate the solute. Re-treatment of the resulting solid precipitate with water and then ethanol was designed to enhance the purity of the obtained product. You have received a new water-soluble fullerene derivative of the C60(OH)16(NH 2)8(NO2)8with a solubility of >200 mg/ml in the form of a yellowish powder. Solid B were dried to remove residual NH3and dissolved in deionized water. Clean solution obtained after centrifugation and decantation, mixed with ethanol to precipitate the fullerenol. Received another water-soluble fullerene derivative of the C60(OH)18(NH2)2(NO2)6with a solubility of 30 mg/ml in the form of a yellowish powder (0,077 g).

In this work, we found that the reaction of fullerene C60with an aqueous solution of NH3(28%) with stirring at room temperature and heated at 60°C does not leak even within a few days. The interaction occurs only in the presence of an aqueous solution of hydrogen peroxide.

The disadvantage of this method is the formation of mixture of products of complex structure, having in its composition in addition to hydroxyl and other groups, such as NH2and NO2., i.e. a complex mixture of products, which ultimately leads to poor performance of the methods on the target component. In addition, the synthesis of fullerenol with high solubility in water (vysokointegrirovannyh) is characterized by difficulties associated with the careful removal of alkaline reagents, long time �more deep hydroxylation.

A method of producing a highly water-soluble derivatives of fullerene C60described in [5]: ACS Nano, 2(2), 327-333, 2008 - as a prototype.

The method is as follows. In the first stage receive discoverarchive - insoluble fullerenols, then spend the hydroxylation process is to redefine them in water-soluble form by heating with an aqueous solution of hydrogen peroxide, after which the water-soluble fullerenols precipitated from alcoholic solution.

Discoverability fullerenol, prepared by hydrolysis of cyclomethicone derived C60[6]: J. Org. Chem. 1994, 59, 3960-3968. Cyclomethicone C60(99.9% pure) is carried out in undiluted fuming sulfuric acid (oleum) at 55-60°C under nitrogen (N2to obtain politicocultural fullerene derivatives. Hydrolysis of these cyclomethicone or derivatives in the presence of water at 85-90°C, either in NaOH solution at ambient temperature gives the corresponding discoverarchive fullerenols with output reaching 80% of the original C60. In this way attached an average of 10 to 12 hydroxyl groups to the fullerene C60. Obtained in salt-free form C60(OH)12(100 mg) is added to 30% of the resultant solution of hydrogen peroxide (10 ml). The mixture was stirred for 4 days at 60°C in air while suspended platforms�Oia does not turn into a transparent yellow solution. After cooling the solution, adding the mixed solvent of 2-propanol, diethyl ether and hexane (each 50 ml) gradually gives a white residue (stage deposition and flushing vysokomehanizirovannogo of fullerenol). After centrifugation and filtration the solid residue was washed twice with diethyl ether, dried under vacuum at room temperature for 18 h. the C60(OH)36·8H2O (97 mg, 67%) as a powder pale yellow-brown color with a solubility in water of 17.5 mg/ml. Similar processing nizkoreaktsionnogo C60(OH)12(100 mg) 30% solution of hydrogen peroxide for 2 weeks at 60°C, followed by precipitation and washing gives fullerenol C60(OH)40·9H2O (103 mg, 68%) as a powder milky white color with a solubility in water of 58.9 mg/ml.

The disadvantages of this method are the need for use of hazardous reagents (oleum) and conducting additional operations hydrolysis with alkali or water to obtain nizkoreaktsionnogo of fullerenol. It requires a long time for this operation and washing of the product from the alkali.

The technical result is to simplify the method while maintaining the quality characteristics and the completeness of the discharge end vysokomehanizirovannogo of fullerenol.

<> The object of this invention is the elimination of hazardous reagents and ensuring the process of obtaining nizkoreaktsionnogo of fullerenol without hydrolysis step and complexities involved in washing products.

This problem is solved in that in the known method of producing a highly water soluble fullerenols, namely that the first stage of the process get discoverarchive insoluble fullerenols, then spend the hydroxylation process is to redefine them in water-soluble form by heating with an aqueous solution of hydrogen peroxide, after which the water-soluble fullerenols precipitated from alcoholic solution, what is new is that discoverarchive insoluble fullerenols is produced by the interaction of concentrated solution of fullerene in o-xylene with aqueous ammonia in the presence of a catalyst phase transfer tetrabutylammonium hydroxide at a temperature of 35-40°C.

The hydroxylation process discoverability of insoluble fullerenols carried out by heating and stirring with 6-15% aqueous solution of hydrogen peroxide for 4-5 hours at 65°C.

Fig. 1 presents the FTIR spectrum obtained by the claimed method sample nizkoreaktsionnogo of fullerenol on the claimed JV�soba.

Description of the proposed method.

In the present method discoverability fullerenol prepared by reacting a concentrated solution of fullerene in o-xylene with concentrated (28%) aqueous ammonia solution comprising an additive of 20% solution of tetrabutylammonium (TBAH) as a catalyst phase transfer, while mixing in an anaerobic atmosphere at a temperature of 35-40°C until colorless organic phase (specific modes indicated in the examples of the method). The end products of the process are colorless or weakly colored organic phase (o-xylene), colorless mineral phase (aqueous ammonia solution) and dispersed them in the solid fraction. The precipitate is separated through a filter paper, washed with pure o-xylene to remove unreacted fullerene, and then with water to neutral reaction and dried under vacuum at 80°C for at least 3 hours. The resulting product is insoluble in o-xylene and water. IR spectrum (KBr) of the obtained compound is shown in Fig. 1. The product yield is 100% by weight of the fullerene. The technical effect of this method is quantitative transition of fullerene in discoverarchive state by entering a solid fraction, insoluble in water and organic solvent (o-xylene). Ka� shown in [4], fullerene does not react with ammonia. However, in the present method it was found experimentally the conditions under which proceeds hydroxylation of fullerene in aqueous ammonia medium to form nizkoreaktsionnogo of fullerenol. In the methods of obtaining fullerenols by hydroxylation of fullerenes dissolved in an organic solvent, a concentrated alkali solution, as a solvent used toluene, benzene [1], [2]. They fullerenes have low solubility. In the present method is used o-xylene, in which the solubility of fullerenes in several times higher. The use of ammonia instead of oleum and facilitate the process. Since aqueous solutions of ammonia are a gas, dissolved in water, ammonia impurity is easily removed from the desired product by simple techniques such as air drying, rinse with warm water, etc. In the claimed method, the solid fraction containing discoverability fullerenol, very quickly and efficiently freed from traces of water solution of ammonia and conventional catalyst by washing with distilled water, this eliminates the difficulties associated with careful removal of alkaline reagents in methods-analogues. Getting to this stage nizkoreaktsionnogo of fullerenol avoids differs�additional hydrolysis step compared to the prototype method. In the claimed method were experimentally determined and shows that the completeness of the transition of fullerene in discoverarchive state under the action of an aqueous solution of ammonia depends on the temperature and duration of the process, the concentration of 20% aqueous solution of TBAH in the mineral phase, and the ratio of mineral and organic phases in the mixture. The completeness of the transition of the fullerene in discoverarchive status was determined by the ratio of the difference of concentrations of fullerene between the original solution in o-xylene and the ultimate solution to the concentration of the initial solution, expressed in percent. The results are presented in table. 1-4.

Table 1
The dependence of the completeness of the transition C60from the organic phase in from mineral synthesis time nizkoreaktsionnogo of fullerenol
The process temperature is 25-35°C; the Final ratio of Vorg./Vmin- 4,0; Concentration of 20% TBAG in the minefield. phase - 20,0%.
№ p/pThe time of synthesis, hThe completeness of the transition C60, %The solubility of the target product in water
124 46,0practically insoluble
212090,0partially soluble

Table 2.
The dependence of the completeness of the transition C60from the organic phase in the mineral from volumetric concentration of 20% TBAG in the mineral phase
The process temperature is 25-35°C; the Final ratio of Vorg./Vmin=2,0÷4,0; synthesis Time - 36-48 hours.
№ p/pThe concentration of 20% TBAG in the mineral. phase, vol. % The completeness of the transition C60, %The solubility of the target product in water
100there is no product
25,0Of 45.3practically insoluble
310,0Of 67.2practically insoluble
420,0 72,0practically insoluble
540,078,4practically insoluble

Table 3
The dependence of the completeness of the transition C60from the organic phase in the mineral from the process temperature
Synthesis time - 36 hours; Final ratio of Vorg./Vmin- 2,0; Concentration of 20% TBAG in the minefield. phase - 20,0%.
№ p/pThe process temperature, °CThe completeness of the transition From the60, %The solubility of the target product in water
125-30<90,0practically insoluble
230-3594,0practically insoluble
335-40100,0practically insoluble

Table 4
The dependence of the completeness of the transition C60from the organic phase in the mineral of the final ratio Vorg./Vminml/ml
The process temperature is 25-35°C, synthesis Time - 36-48 hours; the Concentration of 20% TBAG in the minefield. phase - 20,0%.
№ p/pThe final ratio of Vorg./Vminml/mlThe completeness of the transition C60, %The solubility of the target product in water
11,3100,0practically insoluble
22,090,0practically insoluble
34,067,0practically insoluble
46,0Of 64.0practically insoluble

Conclusions: the greatest completeness of the transition C60in discoverarchive condition occurs when the process temperature of 35-40°C, the ratio of organic and min�General phases equal to 2÷4, the concentration of 20% aqueous solution of TBAH in the mineral phase of 20÷40% vol., synthesis time 36÷48 hours. Increasing the process temperature is above 40°C is impractical because it leads to intense evaporation of ammonia from the reaction medium and the losses nizkoreaktsionnogo of fullerenol due to the uncontrollable of its transition to water-soluble part. Therefore, the above conditions fullerene hydroxylation of the claimed method are necessary and sufficient.

Thus, obtaining an insoluble solid phase nizkoreaktsionnogo of fullerenol under the action of the fullerene aqueous ammonia solution designed to simplify and speed up the process, while maintaining the completeness of separation of the product (1.5-2 hours vs. 5-6 days in the prototype method).

Subsequent hydroxylation received nizkoreaktsionnogo of fullerenol is carried out in an aqueous solution of hydrogen peroxide. Unlike the prototype method we experimentally found that hydroxylation occurs quantitatively in a relatively short time (1.5-4 hours) at 65°C in a concentration range of hydrogen peroxide 6÷15% by weight. This improves the conditions of the process and allows you to avoid unnecessary complications (catalyzed oxidation of organic phase, churning, excessive gas emission, etc.), in�questions that arise when working with concentrated (30% of) the solutions of hydrogen peroxide. The procedure is performed as follows. The suspension obtained nizkoreaktsionnogo of fullerenol in an aqueous solution of H2O2next was mixed on a magnetic stirrer at 65°C for 4-5 hours to obtain a highly water soluble of fullerenol. After 1-1. 5 hours from the beginning of the process observed the transformation of a dark brown suspension in a transparent brown solution, which indicates the course of the process of hydroxylation. After mixing, the solution was separated from the unreacted substances by centrifugation.

Dehydrosilybin remnant, as a rule, was not observed. The liquid phase brown poured into 10-fold volume of precipitant mixture of IPA-heptane (volume ratio of 70÷90/30÷10). Fallen dust yellow-brown color was separated by centrifugation, the solid residue is washed 1-2 times pure precipitant mixture to remove residual hydrogen peroxide and dried. The resulting solid product is a light brown color was a fullerenol with a high degree of hydroxylation in salt-free form and with a high solubility in water (65,8 mg/ml), the pH of this solution is ~ 3. The number of hydroxyl groups, established by the method of thermal analysis [7. Thermochimica Acta 419 (2004), 97-104], is ~ 30. Due to the fact that we get a fuller�ol partially soluble in the precipitation mixture, you cannot achieve 100% yield of product. These IR analysis of the obtained product (a matrix of KBr), cm-1: 1081, 1387, 1626, 1721, 3415. Fullerenols C60(OH)36and C60(OH)44obtained by the method prototype, have the following characteristic bandwidth, cm-1: 1080, 1370, 1620, 1720, 3400. As follows from the above sets of characteristic bands of the infrared spectra of fullerenol obtained by the present method, are in good agreement with the infrared spectra of fullerenols of the prototype method.

Examples of embodiment of the inventive method

Example 1. 125 ml of a solution of fullerene C60(purity of 99.93%) obtained by the method [8]. Pat. Of the Russian Federation No. 2456233, substantially free of oxide impurities] in o-xylene concentration of 5.6 mg/ml was added dropwise with vigorous stirring to a mixture of 52 ml of concentrated aqueous ammonia and 13 ml of 20% TBAH in water at 40°C. the Mixture was stirred for 1.5 hours. The resulting suspension comprising insoluble in water and in o-xylene of a solid phase and a mixture of o-xylene and water were separated by filtration under vacuum through a filter paper. The solid residue is washed with distilled water until neutral. The liquid phase separated in a separating funnel. The upper organic layer was painted in a pale purple color. To�the concentration of fullerenes in organic phase was 0.5 mg/ml. The lower aqueous phase is practically colorless. The degree of transition of the C60amounted to 91.1%. The weight of the solid residue brown 1,08.

510,0 mg obtained nizkoreaktsionnogo of fullerenol C60were mixed in 20 ml of a 15% H2O2for 4 hours at a temperature of 60-65°C. after About 1 hour black-brown suspension turned into a dark brown transparent solution. The hydroxylation process is accompanied by intensive gas release and foaming on the surface of the solution. The emission ends for about 4 hours. The resulting mixture was separated from unreacted substances by centrifugation. Typically, the unreacted residue is absent. The liquid phase is dark brown results in 10-fold volume (200 ml) precipitation solvent mixture of IPA: heptane (taken in a volume ratio of 70:30). Immediately slurry is formed yellowish-brown color, which is separated from the liquid phase by centrifugation. The liquid phase has a clear pale yellow color, indicating partial solubility vysokomehanizirovannogo of fullerenol in the precipitation mixture (about 0.2 mg/ml). The solid residue is washed 1-2 times pure precipitant mixture to remove traces of H2O2) and dried under vacuum at 80°C. �of alucan fullerenol light brown, corresponding to the formula C60(OH)30the solubility 65,8 mg/ml, in the amount of 567 mg (Yield 83.6 per cent). The IR analysis of the obtained product (matrix KBr), cm-1: 1081, 1387, 1626, 1721,3415.

Example 2. 330 ml o-xylene solution of fullerene C70(purity of 98, 94%) concentration 8,92 mg/ml was added dropwise with vigorous stirring to a mixture of 132 ml of concentrated aqueous ammonia and 33 ml of 20% TBAH in water at 40°C. the Mixture was stirred for 72 hours before visual discoloration o-xylene solution. After separation of the solid phase by filtration through a paper filter, rinsing it with distilled water and drying the obtained solid residue brown in the amount of 4.35 g, residual concentration of fullerenes in organic phase is 0.24 mg/ml. Completeness of the transition of fullerene C70in discoverability product to 97.3%. By the method of thermal estimates of the number of the substituents is established that the product obtained corresponds to the formula C70(OH)12-14.

2640 mg obtained nizkoreaktsionnogo of fullerenol C70mixed in 132 ml of a 15% H2O2at 65°C for 4 hours. Unreacted (dehydrosilybin) residue not detected. The resulting solution was poured into 10-fold volume of precipitant mixture of IPA:heptane. Dropped suspension orange color� was separated by centrifugation. The solid residue was dried to constant weight at 70°C. the Obtained 2500 mg solid brown color (yield ~ 60%). Loss of fullerenol C70due to the partial solubility in the precipitation mixture was 340 mg (~ 8%), the rest is due to the destructive oxidation of the product with hydrogen peroxide in the hydroxylation. The product obtained corresponds to the formula C70(OH)32solubility 67,0 mg/ml. the IR analysis of the obtained product (matrix KBr), cm-1: 1063, 1380, 1642, 1721, 3423.

Example 3. A solution of 6.8 mg of fullerene C78(chromatographic purity ~ 95%) in 10 ml of o-xylene was added dropwise to 5 ml of the mineral phase (4 ml of concentrated aqueous ammonia + 1 ml of 20% aqueous solution of TBAH) with vigorous stirring at 40°C. the Mixture was stirred for 72 hours, then separated by centrifugation. Liquid inorganic phase in the form of suspension, painted in brown color, evaporated to dryness under vacuum and dried at 70°C for 3 hours. Received 16 mg of the product brown. The completeness of the transition of fullerene C78in discoverability product was ~ 100%.

16 mg of the obtained product was stirred in 5 ml of 8% H2O2at 65°C. for 15 minutes, there was a transition of a suspension of a dark brown colour, accompanied by foaming, in a clear solution. The Sol�R added to 10-fold volume of precipitant mixture of IPA:heptane (volume ratio 25:75). Dropped out brown suspension was separated by centrifugation, the precipitate is dried. The weight of the obtained product was 20.7 mg. IR spectrum (KBr) of fullerenol C78showed the following bandwidth, cm-1: 1098,1397, 1619, 1721, 3421.

The list of references

1. Zhang J.-M, Yang W., He P., Zhu S.-Z. Efficient and Convenient Preparation of Water-Soluble Fullerenol. Chinese Journal of Chemistry, 2004, 22, 1008-1011.

2. G. C. Alves'; L. O. Ladeira; A. Righi; K. Krambrock; H. D. Calado; R. P. de Freitas Gil; M. V. B. Pinheiro. Synthesis of C60(OH)18-20in aqueous alkaline solution under O2-atmosphere. J. Braz. Chem. Soc., 2006, vol.17, No. 6, p.1186-1190.

3. L. O. Husebo, B. Sitharaman, K. Furukawa, T. Kato, and J. L. Wilson. Fullerenols Revisited as Stable Radical Anions. J. Am. Chem. Soc. 2004, 126, 12055-12064).

4. K. Matsubayshi, K. Kokubo, H. Tategaki, S. Kawarama, and T. Oshima. One-step Synthesis of Water-soluble Fullerenols bearing Nitrogen-containing Substituents. Fullerenes, Nanotubes and Carbon Nanostructures, 2009, vol. 17, issue 4, p.440-456.

5. K. Kokubo, K. Matsubayashi, H. Tategaki, H. Takada, and T. Oshima. Facile Synthesis of Highly Water-Soluble Fullerenes More Than Half-Covered by Hydroxyl Groups. ACS Nano, 2(2), 327-333, 2008 - as a prototype.

6. L. Y. Chiang, L.-Y. Wang, J. W. Swirczewski, S. Soled and S. Cameron. Efficient Synthesis of Polyhydroxylated Fullerene Derivatives via Hydrolysis of Polycyclosulfated Precursors. J. Org. Chem. 1994, 59, 3960-3968.

7. T. H. Goswami, R. Singh, S. Alam, G. N. Mathur. Thermal analysis: a unique method to estimate the number of substituents in fullerene derivatives. Thermochimica Acta 419 (2004), 97-104.

8. Yu. s. Grushko, Sedov V. P., Kolesnik S. G., us Pat. OF THE RUSSIAN FEDERATION NO. 2456233, IPC C01B 31/02.

1. A method of producing a highly water soluble fullerenols, namely that the first stage of the process get discoverarchive insoluble�e fullerenols, then spend the hydroxylation process is to redefine them in water-soluble form by heating with an aqueous solution of hydrogen peroxide, after which the water-soluble fullerenols is deposited from alcohol-containing solution, characterized in that discoverarchive insoluble fullerenols is produced by the interaction of concentrated solution of fullerene in o-xylene with aqueous ammonia in the presence of a catalyst phase transfer tetrabutylammonium hydroxide at a temperature of 35-40°C.

2. A method of producing a highly water soluble fullerenols according to claim 1, characterized in that the hydroxylation process discoverability of insoluble fullerenols carried out by heating and stirring with 6-15% aqueous solution of hydrogen peroxide for 4-5 hours at 65°C.



 

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9 cl, 1 dwg, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and nanotechnology. The method includes first preparing a solution of polyacrylonitrile (PAN) and acetyl acetonate Fe(CH3COCH=C(CH3)O)3·6H2O in dimethyl formamide at 40°C; adding cobalt acetate solution Co(CH3COO)2·4H2O to the dimethyl formamide; concentration of PAN is 5% of the weight of dimethyl formamide and concentration of iron and cobalt is 5-20% and 5-20% of the weight of PAN, respectively; holding the solution until complete dissolution of all components, followed by removal of dimethyl formamide by evaporation at temperature not higher than 70°C. The obtained solid residue is heated with high-intensity infrared radiation by holding for 15 minutes at 150°C-200°C and then for 10 minutes at final temperature of 600-800°C. Heating the solid residue at all steps is carried out at a rate of 20°C/min at pressure in the reaction chamber of 10-2-10-3 mmHg. The obtained metal-carbon nanocomposite FeCo/C contains FeCo nanoparticles with size of 5-50 nm.

EFFECT: avoiding the need to use additional reducing agents.

1 tbl, 3 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical industry. A method of separating fullerenes includes dissolving fullerenes in o-xylene, high-temperature treatment of the obtained solution at 70-90°C for 60-120 minutes to obtain a C60 concentrate and a solution which is fed for low-temperature treatment at temperature of (-15) to (-25)°C for 10-30 hours. Separation is carried out in multiple steps to obtain at each n step C60 and C70 concentrates with counterflow of the solutions and the solid phase from the high-temperature treatment. Several high-temperature treatment steps are carried out at each n step. At the first high-temperature treatment step of each n step, a solid extract of a fullerene mixture is fed and at the next steps, a solid phase from the previous high-temperature treatment step is fed. A solution from the first high-temperature treatment step is fed for low-temperature treatment to obtain a C70 concentrate and a solution which is fed to the last high-temperature treatment step. A solution from the next high-temperature treatment step is fed as a recycled solution to the previous step, and a solution from the second high-temperature treatment step is fed for mixing with the solid extract of the fullerene mixture of the next n>1 step. The C60 concentrate is the solid phase of the last high-temperature treatment step of each n step.

EFFECT: low material consumption and simple process.

2 cl, 2 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to apparatus for producing inorganic materials. The apparatus comprises a working chamber 1, which includes a high-temperature ionised medium 2 source and an inert gas 4 source, the housing of which has a cooling system in the form of a jacket 8 filled with a coolant, the cavity of the chamber 1 is linked with a container 3 of the starting inorganic powdered material - silicon or carbon, the working chamber 1 is fitted with a vacuum apparatus 5, and the cavity of the chamber 1 is fitted with a heat exchanger 8 for accumulating the processed starting material, connected to the source of a heat-exchange medium and mounted on one side of the working chamber 1, connected to the housing by a hinge 10.

EFFECT: obtaining materials with negligible power consumption when processing the starting component and high resistance to aggressive media.

1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used in producing nanoelectronic, optoelectronic, sensor and photovoltaic devices, as well as for storing energy. The method includes depositing an aluminium film with thickness of 1-100 nm on an insulated substrate, sputtering thereon a film of a transition metal, e.g. Fe, Co or Ni, with thickness of 0.1-10 nm, annealing in air at temperature of 200-950°C for 0.1-10 min, heating to temperature of 700-1000°C in a reactor which is evacuated to pressure of 10-4-10-10 Torr. The method further includes successively releasing a carbon-containing gas to pressure of 1-10-4 Torr and evacuating the reactor every 1-30 s while simultaneously cooling to room temperature at a rate of 1-100°C/min.

EFFECT: invention enables to obtain films of hybrid graphene and carbon nanotubes with a given configuration at predetermined places using a simple and technologically effective method.

5 cl, 5 dwg, 5 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention can be used in the chemical industry, cosmetics and medicine in making cosmetic products, therapeutic agents, antioxidants, antimicrobial agents, radioprotective substances, compounds for gene material delivery. An aqueous nanodispersion of fullerene is produced by solving C60 fullerite crystals in N-methylpyrrolidone. The prepared solution is mixed with water and a stabilising agent, which is presented by amino acid, monosaccharide, peptide, polyvinylpyrrolidone or glycerol. That is followed by the dialysis of the prepared mixture. After the dialysis, the solution can be concentrated, e.g. by vacuum vaporisation. The process is safe as uses no toxic solvents.

EFFECT: simplifying the process by eliminating the use of pre-milled fulleren crystals, ultrasonic treatment and heating.

2 cl, 26 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: carbon nanomaterials - nanotubes or graphene, particles of which contain hydroxyl and/or carboxyl groups on the surface are modified by treating with a solution containing triethanolamine titanate and fatty acid derivatives - triethanolamine stearate or triethanolamine palmitate. The molar ratio of said fatty acid derivative to titanium ranges from 1:1 to 3:1, and the weight ratio of said fatty acid derivative and titanium compounds with respect to titanium dioxide to nanotubes or graphene ranges from 0.75:1 to 2:1. The obtained suspension is treated with carbon dioxide gas until coagulation of the system and the precipitate is then washed with water.

EFFECT: obtained modified carbon nanomaterial disperses well in nonpolar media without using ultrasound.

2 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of chemical technology of obtaining composite carbon-metal materials and can be used in the production of catalysts, sorbents, polymer fillers, pharmaceutical preparations, immobile chromatographic phases. The nanocomposite material consists of atoms of carbon, nitrogen and nickel and cobalt nanoparticles encapsulated into the structure, which is formed by the said atoms. The carbon atoms form conic multi-wall carbon nanotubes, with the nitrogen atoms being localised on plane ends or in places of structural defects. The metal nanoparticles are located on ends of the nanotubes, in subsurface layers, with the formation of structural defects, as well as inside a channel. The method of the material preparation consists in the injection of a solution of chlorides, acetates or acetylacetonates of cobalt or nickel in toluene or benzene in a mixture with ethanol with the addition of trimethylamine or tetramethylethylenediamine into a nitrogen-blown high-temperature hermetic reactor at a temperature of 580-600°C.

EFFECT: invention makes it possible to simplify the process, reduce energy consumption and increase the production safety.

2 cl, 9 dwg

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to pharmaceutical industry, namely to selenium nanocomposites of natural hepatotrophic galactose-containing polysaccharide matrixes, representing water-soluble orange-red powders containing zerovalent selenium (Se0) nanoparticles sized 1-100 nm in the quantitative content of 0.5 - 60 wt %, possessing antioxidant activity for treating and preventing redox-related pathologies, particularly for treating toxic liver damage, to a method for producing and to an antioxidant agent containing the above nanocomposites.

EFFECT: invention provides the targeted agent delivery to liver cells, as well as higher agent accessibility and lower toxic action of selenium.

7 cl, 11 ex, 4 tbl

FIELD: physics.

SUBSTANCE: method includes forming a near-field mask on the surface of a dielectric substrate and irradiating the obtained structure with a femtosecond laser pulse. The laser radiation is first passed through a nonlinear optical crystal with a coefficient of transformation into a second harmonic equal to 5-7%. The dielectric substrate coated with the near-field mask is irradiated with the obtained bichromatic femtosecond pulse with energy density in the range of 25-40 mJ/cm2, which is less than the laser radiation energy density normally used in similar nanopatterning.

EFFECT: high resolution and low laser radiation energy consumption.

6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for hydroconversion of heavy oil fractions - feed stock, the method including a zero step and subsequent N steps. The zero step includes feeding, into a reactor, material, a catalyst precursor - aqueous solution of a Mo (VI) salt or salts of Mo and Ni, and hydrogen at pressure of 4-9 MPa under normal conditions; reacting the material and hydrogen at 420-450°C in the presence of a precursor of a suspended nanosize molybdenum or molybdenum-nickel catalyst formed in the reactor; atmospheric or atmospheric-vacuum distillation of the hydrogenation product; removing the low-boiling fraction with a boiling point not higher than 500°C as a product and returning the high-boiling fraction or part thereof into the reactor. The next steps include feeding, into the reactor, material, a catalyst precursor, the returned part of the high-boiling fraction and hydrogen; reaction thereof; said atmospheric distillation of the hydrogenation product; removing the low-boiling fraction as a product; returning part of the high-boiling fraction into the reactor; burning at 1000-1300°C or gasification of the remaining part of the high-boiling fraction, after which trapped ash-slag residues are subjected to further oxidising burning at 800-900°C and the obtained ash product, which is carbon-free, is used to regenerate the catalyst precursor and produce an industrial concentrate of vanadium and nickel. The number of steps N is determined using formulae: bd(nn+nm+1)=a+i=1nmbi+benm, N=nn+nm+1, where nn is the number of steps with recirculation, after which equilibrium output of the low-boiling fractions is achieved; nm is the number of steps with recirculation after achieving equilibrium output of the low-boiling fractions, which enables to achieve a given output of low-boiling fractions from the feed stock; bd is the given output of low-boiling fractions, wt %; a is the output of low-boiling fractions at the zero step, wt %; bi is the output of low-boiling fractions at the i-th step before achieving equilibrium, wt %; be is the output of low-boiling fractions after achieving equilibrium, wt %, be>bd.

EFFECT: high output of low-boiling fractions, low molybdenum consumption, high degree of extraction of molybdenum, vanadium and nickel from the solution, enabling calculation of the required reactor volume, obtaining an industrial concentrate of vanadium and nickel, low hydrogen consumption.

3 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in obtaining coatings, reducing coefficient of secondary electronic emission, growing diamond films and glasses, elements, absorbing solar radiation. Colloidal solution of nano-sized carbon is obtained by supply of organic liquid - ethanol, into chamber with electrodes, injection of inert gas into inter-electrode space, formation of high-temperature plasma channel in gas bubbles, containing vapours of organic liquid. High-temperature plasma channel has the following parameters: temperature of heavy particles 4000-5000K, temperature of electrons 1.0-1.5 eV, concentration of charged particles (2-3)·1017 cm3, diameter of plasma channel hundreds of microns. After that, fast cooling within several microseconds is performed.

EFFECT: simplicity, possibility to obtain nanoparticles of different types.

3 cl, 1 dwg

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