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2008, №1

pp. 5-23

Обзоры

Key words: сверхкритические флюиды, наночастицы, микрочастицы, фармпрепараты, липосомы

The preferences of drugs on the base of nano- and microparticles are reviewed in
        comparison with traditional drug forms. The application of supercritical fluids for the
        production of nano- and microforms of pharmaceutical substances including drug
        delivery systems on the base of polymers and liposomes is discussed. The methods
        based upon the use of supercritical fluids, such as RESS, GAS, ASES, SAS, SEDS were
        shown to be of the most value for the production of nano- and microforms of drugs.

2008, №1

pp. 24-33

Статьи

Formation of Micro- and Nanoparticles of Chitosan and Its Derivatives via Supercritical Assisted Atomization (SAA)

D.Yu. Zalepugin, A.I. Gamzazade, N.A. Tilkunova, V.S. Mishin, I.V. Chernyshova, A.R. Khokhlov.

Key words: сверхкритические флюиды, наночастицы, микрочастицы, хитозан

Micro- and nanoparticles of five chitosan  derivatives were obtained for the first time
using Supercritical Assisted Atomization  (SAA) method. The investigation of obtained
disperse chitosan forms using optical and  scanning electron microscopies (SEM) and
particle size distribution technique  demonstrated their uniformity. Depending on the
experimental conditions, particle size  varies in the range of 0,3÷5  mm. It was concluded
that SAA method can be efficiently used for  micronization of various chitosan
derivatives.

2008, №1

pp. 34-42

Статьи

Fabrication of Biodegradable Microparticles Comprising Bioactive Components <br> Using Supercritical Carbon Dioxide

E.N. Antonov, S.E. Bogorodski, B.M. Feldman, A.A. Markvicheva, L.D. Rumsh, V.K. Popov.

Key words: полимерные микрочастицы, инкапсуляция биоактивных компонентов, сверхкритический диоксид углерода

The results of supercritical fluid  synthesis of bioresorbable polymer microparticles
filled with bioactive plantain and  calendula extracts are presented and discussed. The
process is based on spraying of the mixture  of amorphous aliphatic polyester (D,Llactide)
plasticized by supercritical carbon dioxide  with fine-dispersed plant extract
powder into low-pressure receiver through  specific nozzle. Kinetics of extract release
from microparticles produced under  different CO<sub>2</sub> pressures is analyzed. The rate of
extract release into physiological solution  depends on both carbon dioxide pressure
and initial polymer/extract ratio.

2008, №1

pp. 43-49

Статьи

Key words: RESS, сверхкритический флюид, моделирование, микрочастицы, антрацен

RESS process can be described in the  framework of one-dimensional model, which
allows one to qualitatively analyzed the  nucleation. The effects of supercritical solvent
density and of expansion device geometry  onto the size of microparticles formed in
RESS process are examined.

2008, №1

pp. 50-58

Статьи

Synthesis of Ag Nanoparticles in the Matrix of Croos-Linked Olygouretanmetacrilate

A.O. Rybaltovskii, A.A. Aksenov, V.I. Gerasimova, V.V. Zosimov, V.K. Popov, A.B. Solovieva, P.S. Timashev, V.N. Bagratashvili.

Key words: наночастицы, сверхкритический СО<sub>2</sub>, импрегнация, олигоуретанметакрилат, оптическая спектроскопия, УФ облучение

Synthesis of Ag nanoparticles in the matrix  of cross-linked olygouretanmetacrilate
(OUM) impregnated with Ag(fod) molecules  (fod = 6,6,7,7,8,8,8-heptafluor-2,2-dimethyl-3,5-octadionate) dissolved in  supercritical carbon dioxide and ethanol was
studied using absorption spectroscopy and  scanning electron microscopy. Size
distribution and concentration of Ag  nanoparticles synthesized in polymer matrix is
controlled by polymer structure, solvent  type and by processing conditions. Treatment
with hydrogen and UV irradiation of OUM  samples impregnated with Ag(fod), causes
both significant rise of Ag nanoparticles  concentration and particles size in polymer
matrix. The new approach to fabrication of  optical structures (including microstructures)<br>
from nanoparticles in polymers is  suggested, based on combination of
polymer samples impregnation and UV  irradiation.

2008, №1

pp. 59-66

Статьи

Optical Properties of Transparent Polymers, Impregnated with Eu(Fod)<sub>3</sub> Molecules Using Supercritical Carbon Dioxide

A.Yu. Tarayeva, V.I. Gerasimova, Yu.S. Zavorotny, A.O. Rybaltovskii, V.N. Bagratashvili.

Key words: полимеры, Eu(fod)<sub>3</sub>, фотолюминесценция, сверхкритическая импрегнация, молекулы воды, температурное тушение люминесценции

The effects of temperature and humidity on optical properties of transparent polymers
impregnated with Eu(Fod)<sub>3</sub> molecules (fod = 6,6,7,7,8,8,8-heptafluor-2,2-dimethyl-
3,5-octadionate) using supercritical carbon dioxide were studied. Two bands of
Eu(Fod)<sub>3</sub> spectra both in polycrystalline phase and in polymer matrix are revealed,
related to two different forms of these molecules. To explain the observed degradation
of absorption and photoluminescence spectra of polypropylene film impregnated with
Eu(Fod)<sub>3</sub>, the model of atmospheric H<sub>2</sub>O interaction with Eu(Fod)<sub>3</sub> molecules in
polymeric matrix was suggested. The effects of reversible temperature bleaching of
Eu<sup>3+</sup> luminescence was observed and discussed in the context of fabrication of
temperature sensor.<br>

2008, №1

pp. 67-90

Обзоры

Key words: адиабатический калориметр, вода, водные растворы, кривая сосуществования фаз, критическая точка, изохорная теплоемкость, парциальный мольный объем, сверхкритическая вода, уравнение состояния, этанол

Isochoric heat capacity of binary mixture  (0.1446) H<sub>2</sub>O + (0.8554) C<sub>2</sub>H<sub>5</sub>OH have been
measured in the sub- and supercritical  conditions with a high-temperature adiabatic
and nearly constant-volume calorimeter.  Measurements of  <i>C<sub>V</sub></i> were performed as a
function of temperature along various  near-critical isochores in the range from 234.8
to 391.1 kg·m<sup>-3</sup>  at temperatures  between 439.3 and 521.5 K. In total 16 isochores — 4 vapor and 12 liquid, have been studied.  The coverage includes the one- and twophase
regions near the liquid.gas coexistence  curve at the sub- and the supercritical parameters of state. The uncertainty of  isochoric heat capacity, density, and temperature
measurements was estimated to be less than  2÷3 %, 0.05 %, and 15  mK, respectively. The
values of temperature at coexistence curve,  <i>T<sub>S</sub></i>(ρ), for each measured  densities (isochores)
were determined in calorimetric experiment  using a quasi-static thermogram
technique supplemented by the sensor of  adiabatic control. Using the measured values
of heat capacity (<i>C<sub>VS</sub></i>), temperature (<i>T<sub>S</sub></i>) and density  
(ρ<i><sub>S</sub></i>) on the coexistence curve
near the critical point (CP) the values of  the critical parameters (<i>T<sub>C</sub></i>,
ρ<i><sub>C</sub></i>) for the
mixture (0.1446 m.f.) H<sub>2</sub>O + (0.8554 m.f) C<sub>2</sub>H<sub>5</sub>OH were determined. The measured
values of <i>C<sub>V</sub></i>  and <i>T<sub>S</sub></i>, ρ<i><sub>S</sub></i> for the saturated liquid and vapor have been analyzed and
interpreted in terms of extended scaling  theory to accurately calculate the values of
the asymptotical critical amplitude (<i>A</i><sub>0</sub><sup>±</sup> and  <i>B</i><sub>0</sub>) of the power laws and in theory of
isomorphism of the critical phenomena in  binary mixtures. The values of the
characteristic parameters (<i>K</i><sub>1</sub>, <i>K</i><sub>2</sub>, τ<sub>1</sub>, τ<sub>2</sub>, &Delta&rho<sub>1</sub>, &Delta&rho<sub>2</sub>)
of the mixture were estimated by using
the critical-curve data for H<sub>2</sub>O + C<sub>2</sub>H<sub>5</sub>OH mixture. It was shown that the heat  capacity
of the mixture (o = 0.8554 m.f. C<sub>2</sub>H<sub>5</sub>OH or 96% by volume)  near the CP behave just
like of  <i>C<sub>V</sub></i>  for pure fluid. The  same behavior of <i>C<sub>V</sub></i>  for this mixture was also predicted
from the analysis of the critical line  behavior.

2008, №2

pp. 7-19

Статьи

Utilization Of Supercritical Carbon Dioxide for Improvement of Consumer Quality and Economical Production of Green Vietnamese Tea

Truong Nam Hung, A.K. Fakhreev, F.M. Gumerov, F.R. Gabitov, R.A. Usmanov, D.R. Amirkhanov, R.S. Yarullin.

Key words: зеленый вьетнамский чай, сверхкритический диоксид углерода, потребительские свойства чайного листа, декофеинизация

The effect of suggested procedures - circulation of supercritical (SC) carbon dioxide
        and periodical decompression in the system «initial raw material - SC-CO<sub>2</sub>» - of tea
        leaves treatment onto the subsequent extraction of target components by hot water.
        Some thermodynamic characteristics of SC fluid de-coffeinization process, as applied
        to green Vietnamese tea, are investigated.

2008, №2

pp. 20-32

Статьи

Mathematical Model of Oil-Bearing Crop Seeds Extraction by Supercritical Carbon Dioxide

R.N. Maksudov, A.G. Egorov, A.B. Mazo, V.A. Alyaev, I.Sh. Abdullin.

Key words: сверхкритическая экстракция, масличные культуры, математическое моделирование

A simplified mathematical model of ground  oil-bearing crop seeds extraction is developed. It is reduced to a hyperbolic  system of two equations related to the main process characteristics: (a) oil  concentration in the fluid in microscopic channels of the granular layer of  seed particles and (b) a fraction of initial oil reserve extracted from  particles. Corresponding task is solved analytically. The solution is shown to  have a structure of a running wave propagating at a constant velocity. The  applicability of the model to the simulation of real extraction processes is  confirmed by testing based on available experimental data.

2008, №2

pp. 33-36

Статьи

Bioflavonoid-Quercetin Extraction from Plant Raw Materials in Sub-critical Water Medium

A.V. Lekar, S.N. Borisenko, E.V. Maksimenko, R.N. Borisenko, E.V. Vetrova, N.I. Borisenko, V.I. Minkin.

Key words: субкритическая вода, кверцетин, экстракция

The method of quercetin extraction from plant raw materials in sub-critical water
medium is developed. It is more efficient than conventional extraction by polar organic
solvents (e.g. methanol) and does not require the use of environmentally non-friendly
solvents.

2008, №2

pp. 37-42

Статьи

Dihydroquercetin Extraction from Larch Wood by Sub-Critical Water

O.V. Filonova, S.N. Borisenko, E.V. Maksimenko, R.N. Borisenko, A.V. Lekar, N.I. Borisenko, V.I. Minkin.

Key words: субкритическая вода, дигидрокверцетин, экстракция

The method of dihydroquercetin extraction  from larch wood by sub-critical water is
developed. It is more efficient than  conventional extraction by polar organic solvents
(e.g. acetone) and does not require the use  of environmentally non-friendly solvents.

2008, №2

pp. 43-51

Статьи

Key words: эвкалипт прутовидный (Eucalyptus viminalis Labill.), сверхкритический флюидный СО<sub>2</sub>-экстракт, эфирное масло, химический состав, монотерпены, сесквитерпены, фенолоальдегиды, эвкалимин, хлорофиллипт

A phytochemical comparison of essential oil  and supercritical fluid CO<sub>2</sub>- extract (SCF-NI2-extract),  and analysis of residues obtained from the leaves of eucalyptus (Eucalyptus viminalis  Labill.) are performed. Compositions of essential oil and SCF-CO<sub>2</sub>-extract are similar qualitatively, but significantly differ in relative  amounts of their main components. SCF-CO<sub>2</sub>-extract  contains substantial amounts of sesquiterpens in addition to essential oil. The  residue remaining after the separation of lypophylic fraction is
found to be a source of phenoloaldehyds,  which can serve as constituents of pharmaceuticals (Eucaliminum and  Chlorophylli ptum). The properties of residues remaining after the SCF-CO<sub>2</sub>-extraction are more technically advantageous.

2008, №2

pp. 52-57

Статьи

Key words: экстракция, сверхкритический СО<sub>2</sub>, нефть, тяжелые нефтяные остатки

The method for purification of oils and  their heavy residues from asphaltenes and metals based on different  solubilities of the main constituents of oil and its undesirable components in  supercritical fluids (CO<sub>2</sub>). Effects of temperature, pressure and oil  dilution with carbon dioxide, as well as tar dilution with light hydrocarbons  and CO<sub>2</sub> onto asphaltenes and metals removal are  studied. The method provides with advanced purity of raw oil used further to  produce final products (gasoline, base oils).<br>

2008, №2

pp. 74-81

Статьи

Spectroscopy of Silver and Europium β-Diketonates Dissolved in Ethanol and Supercritical Carbon Dioxide

A.O. Rybaltovskii, A.A. Aksenov, V.I. Gerasimova, Yu.S. Zavorotny, V.K. Popov, V.V. Zosimov, V.N. Bagratashvili.

Key words: сверхкритический диоксид углерода, координационные соединения металлов, β-дикетонаты

Absorption spectra of silver and europium β-diketonates dissolved in supercritical
carbon dioxide and ethanol were studied. The  structure of ligand UV absorption bands
was measured by different solvent types and  temperature as well by intense UV irradiation
of solvent. The observed complex structure  of ligand bands is treated by the formation
of molecular dimer and, also by the  formation of hydrated form of β-diketonates. The
effect of silver nanoclasters synthesis  under the action of UV radiation on ethanol
solution of silver β-diketonate was revealed, accompanied by  the degradation of
ligand absorption band and formation of  plasmon band at 420 nm.

2008, №2

pp. 82-92

Статьи

Key words: сверхкритическая вода, наночастицы, оксид индия, диоксид циркония, льюисовская кислотность

X-Ray diffraction, Raman and  diffusion-reflectance absorption IR-spectroscopy are  used to compare  physical-chemical surface properties of In-Zr mixed nanocrystalline oxides, synthesized in  supercritical water (SCW) and via conventional co-preci pitation technique. Samples synthesized in SCW have  more stable surface properties. The basicity  of mixed In-Zr oxides  increases along with increasing In content.