2010_5_3_45-49
DESCRIPTION
2010_5_3_45-49TRANSCRIPT
-
, 2010, . 5, 3
2
ISSN 1819-1487
.. , .. , .. , .. . - -
3
.. , .. , .. . 10
.. , .. , .. .
18
. . , . . , . . . 13 -[(1-R-3-C3H4)Pd(Me2C=O)2]
+ 26
.. , .. , .. , .. , .. .
30
.. . , EXCEL 34
.. , .. , .. . N-(2--5-)--
41
.. , .. , .. . 45
.. , .. . 50
.. , .. , .. , .. . 57
.. , .. , .. , .. , .. , .. , .., .. . PdCl2CuCl2/Al2O3
62
.. , .. , .. , .. , .. , .. , .. , .. . 8--2- 2-- -
69
.. , .. , .. , .. . - . 2. - ,
75
.. , .. , .. , .. .
77
.. , .. . 2-- () 79
.. , .. , .. , .. , .. , .. , .. , .. , .. , .. . - -,
82
.. , .. , .. , .. .
88
.. , .. , .. , .. , .. , .. .
92
.. , .. , ... 97
.. -, A.. , .. , .. , .. .
102
3/2010
-
2006 .
. ..
: . ..
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: . ..
. .. . ..
. .. . ..
. .. .- . ..
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. .. . ..
.. , .. , .. , .. . , -
108
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, 2010, . 5, 3
2
CONTENTS
THEORETICAL BASED OF CHEMICAL TECHNOLOGY P.G. Rumyantsev, V.I. Zhuchkov, A.K.Frolkova, A.V.Anisimov. Using gas-liquid chromatrography to choose solvents for separation of biazeotropic benzene perfluorobenzene mixture by extractive rectification
3
L.. Serafimov, .V. Frolkova, V.V. Illarionov. Elements of the set of diagrams of binary systems
10
T.V. Chelyuskina, M.Yu. Marchenkova, A.A. Kulakova. Mathematical simulation and research of vapor-liquid equilibrium in systems ethanol/water/ethylenediamine and ethanol/water/butylamine
18
M.H. Elhussien, E.M. Evstigneeva, V.R. Flid. Linear free energy relationships in theoretical NMR 13 spectra of sin-[(1-R-3-C3H4)Pd(Me2C=O)2]
+ complexes 26
CHEMISTRY AND TECHNOLOGY OF INORGANIC MATERIALS L.Yu. Alikberova, D.V. Albov, T.A. Antonenko, I.M. Kochetova, N.S. Rukk. Thiourea complexes of neodymium(III) and gadolinium(III) iodides. synthesis and structure
30
V.V. Apanasenko. The balance scheme of trichlorosilane production process made in EXCEL
34
D.V. Bychenkov, S.A. Semenov, A.M. Reznik. Complextion of scandium upon its extraction by N-(2-hydroxy-5-nonylbenzyl)--hydroxyethylmethylamine (NBEA-2) from chloride solutions in octanol
41
A.Yu. Gervald, N.I. Prokopov, Yu.M. Shiryakina. Synthesis of superparamagnetic magnetite nanoparticles
45
O.V.Petrakova, D. V. Drobot. Anodic dissolution of rhenium in methanol/acetylacetone mixture
50
Yu.S. Suntsova, D.V. Bychenkov, S.A. Semenov, A.M. Reznik. Molecular design of phenolic type extractants
57
D.N. Titov, L.G. Bruk, I.V. Oshanina, O.N. Temkin, G.M. Kuzmicheva, Ya.V.Zubavichus, A.A. Veligzhanin, N.V. Sadovskaya. The state of palladium and copper on the surface of freshly prepared low temperature carbon monoxide oxidadation catalyst PdCl2-CuCl2/-Al2O3
62
CHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND BIOLOGICALLY ACTIVE SUBSTANCES
D.S. Esipov, E.V. Sidorenko, O.V. Esipova, T.A. Gorbacheva, T.S.Nevredimova, A.L. Krushinskiy, V.S. Kuzenkov, V.P. Reutov. Determining 8-oxo-2-deoxyguanosine/2-deoxyguanosine ratio in DNA by reverse phase HPLC combined with amperometric detection
69
D.S. Lutokhina, G.S. Veryasov, A.V. Bakhtin, Yu.M. Kiselev. Mass spectrometry of metalloporphyrins. 2. Vapor pressure of cobalt, nickel, and copper octaethylporphyrinates
75
L.A. Poruchikova, T.N. Liu, D.A. Bezrukov, A.P. Kaplun. Interaction of spherical amorphous nanoparticles of birchbark triterpenoids with bilirubin
77
N.Yu. Rubanyak, E.Yu. Bulychev. Industrial synthesis of 2-amino-ethanesulfonic acid (taurine): problems and perspectives
79
SYNTHESIS AND PROCESSING OF POLYMERIC COMPOSITES Z.B. Artykova, I.A. Gritskova, S.A. Gusev, L.Y. Basyreva, V.A. Sotchilin, M.I.Shtilman, A.V. Goryachaya, G.P. Kheynman, S.A. Kedik, N.I. Prokopov. The synthesis diagnostic test systems on the basis of polymer microspheres in the presence of polyvinylpyrrolidone modified with an amino acid
82
M.Y. Boksha, M.M. Antipova, O.M. Popova, Y.A. Naumova. Investigation of styrene-acrylonitrile copolymer and polyurethane compatibility in solutions
88
V.B. Ivanov, S.I. Voinov, A.A. Olkhov, M.V. Solin, M.A. Goldshtrakh, S.V.Vlasov. Photooxidation of blends of vinyl alcohol vinyl acetate copolymer with polyhydroxybutyrate.
92
T.V. Konovalova, V. D. Yulovskaya, O. A. Serenko. Influence of rubber nature on properties of dynamic thermoplastic elastomer 97
I.D. Simonov-Emelianov, A.Y. Zarubina, A.N. Trofimov, P.V. Surikov, L.K.Sheulova. Rheokinetics curing of epoxy oligomers produced by industry with amine hardener.
102
Review
MITHT
3/2010
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: (495) 936-82-88 e-mail: [email protected]
16.06.2010 . 60x90/8.
. Times.
. . . 4,4.
197. 500 .
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119602, , . , 38, . 1
I.Y. Skvortsov, L.B. Kandyrin, P.V. Surikov, V.N. Kuleznev. The composites based on epoxy resin modified of low concentrations of carbon nanotubes and their properties investigation.
108
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, 2010, . 5, 3
3
66.048.65
. . , , . . , , . . , , . . ,
. ..
e-mail:[email protected]
,
. Gas-liquid chromatography was used for estimating the selectivity of solvents for the separation of biazeotropic benzene perfluorobenzene mixture based on extractive rectification.The selected optimal solvents enable two theoretically feasible variants of the mixture separation.
: , , , , , .
Key words: extractive rectification, separating agent, gas-liquid chromatography, stationary liquid phase, selectivity, retention time.
1. -
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R :
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jVVpVRTN
oRoR
R . (5)
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R , - R , :
VtjpVRTN
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1 28.5 34.3 37.4 5.8 8.9 1.5 2 28.4 43.0 58.7 14.6 30.3 2.1 3 26.5 31.5 44.5 5.0 18.0 3.6 4 -4 32.0 70.0 85.0 38.0 53.0 1.4 5 27.0 45.0 147.0 18.0 120.0 6.6 6 35.3 42.4 64.3 7.1 29.0 4.1 7 33.0 39.0 64.2 6.0 31.2 5.2 8 33.4 53.6 75.8 20.2 42.4 2.1 9 Kel-F-10 28.9 198.3 125.5 169.4 96.6 0.57
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. ( 0ik t t ) , , 0.19 0.68 , (). , - .
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- . , , 9F20 (=125) 10F22 (=238-240) [10].
, .
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:
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( - ).
2. ( ) - -1, Kel-F-10. Kel-F-10 - - - - ( ).
3. , , [8] - - - - - --.
.
1. , . .
/ . . , . . // . . . 1997. . 31, 2. . 193201.
2. , . . / . . . . : , 1971. 432 .
3. , . . / . . , . . , . . // . . . 2009. . 43, 6. . 648657.
4. , . . / . . . .: , 1986. 239 .
5. , . . / . . . . : , 1985. 239 .
6. , . . : / . . . . : , 1978. 440 .
7. , . . / . . . . : , 1978. 247 .
8. - / . . [ .] // . . 2004. 5. . 911.
9. , . . : 3 . / . . , . . , . . . . 1, . 2. . . : . , 1962. 502 .
10. . 5 . . 5. . : . , 1967. 595 . 11. : . . / . . . . . :
, 1989. 503 . 12. / . . [ .]. . : , 1993. 464 .
-
, 2010, . 5, 3
10
66.048:548
.. , , .. , ,
.. ,
. .. e-mail: [email protected]
: , , -, - , - . .
All the possible elements of the set of binary systems (ideal, zeotropic, mono-, bi-, triazeotropic, homo- and heterogeneous) were explored. The overall amount of the possible types of diagrams of binary systems was calculated.
: , , , .
Key words: azeotropy, thermodynamics of heterophase balance, equilibrium, stratifying, binary systems.
- , - (, , ), ( [1]), (-, - [25] [6]).
, -, .. [7]. - - . - , , - .
, - .. , - - . , - , - . - .. [8], .. - [9], , [10] [11]. - [9]. - , - [11]. , , , - [12]. .. - [11] , - , , [1315].
,
, [9, 10, 1619], , .
[12, 20].
, -, , - . , - . , - -- , -, - - .
.1 - , [21], - - -lnP1
0/P20.
: ln1=(1-1)
2 ln2=12,
. , -
. . . , , , - . . =0, , 1=1, 2=1. . 1. (, ) , - . - - (. 1).
-
, 2010, . 5, 3
11
. 1. , .
P1
01/ P202=1,
, 1/2=P2
0 /P10. , P2
0
/P10 ,
(. 1), - , , . . - . , - , ln1= ln2=1 P2
0 P10, . = P2
0 +P10.
[22] - - NRTL - . . 2.
, ( ). - .
. 2. NRTL ,
[22].
-
, 2010, . 5, 3
12
. 3. (), () (-).
G. - G>0, ; G0 . , . 3, , G>0, G0. . 4 .3.
-, - - . [23] , , - 1
0>20,
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).
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. 10. (I-IV, IX X , V-VIII ).
. (. 9).
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: GE - ; P0
; ; ; ; ; .
: 1, 2, 3 .
: 1. , . / . : . . / . . .
. . : , 1969. 239 . 2. Gaw, W. J. Thermodynamic properties of binary systems containing hexafluorobenzene / W. J. Gaw,
F. I. Swinton // Trans. Faraday Soc. 1968. Vol. 64, 8. P. 20232024. 3. Srivastava, R. Total pressure vapor-liquid equilibrium data for binary systems / R. Srivastava, B. D.
Smith // J. of Chem. Eng. Data. 1985. Vol. 30, 3. P. 308313. 4. / . . ,
. . , . . , . . // . . . 1992. . 66, 3. . 832835. 5. / . . , . . ,
. . , . . // . . . 1993. , 66, 1. . 171176. 6. , . . -c, -
/ . . , . . // . . 1970. . 192, 6. . 1311 7. C, . . / . . . : . . /
. . . . . : , 1968. 244 . 8. , . . -
/ . . // . . . 1958. . 32, 9. . 19801996. 9. , . . - / . . , . .
. . : , 1975. 239 . 10. , . .
: . . . . : 02.00.08 / . ., 1967. 44 .
11. , . . VII. - / . . // . . . 1970. . 44, 4. . 10211027.
12. , . . - / . . // . . . 2002. . 76, 8. . 13511365.
13. , . . / . . , . . , . . // . . 1983. . 269, 1. . 129132.
14. , . . - / . . , . . , . . // . . . 1971. . 5, 3. . 368372.
15. , . . - / . . , . . , . . // . . . 1988. . 22, 4. . 535542.
16. , . . - - / . . // . . . 1987. . 21, 1. . 7485.
17. , . . / . . , . . . . : , 1992. 452 .
18. . / . . , . . , . . , . . . . : , 1993. 412 .
19. Serafimov, L.A. Thermodynamic and Topological Analysis of Liquid-Vapor Phase Equilibrium Diagrams and Problems of Rectification of Multicomponent Mixtures. Chapter 10. Mathematical Methods in contemporary chemistry. Gordon and Breach Publishers, 1996. . 557.
20. , . . - / . . // . . . 2002. . 76, 8. . 13511365.
21. / . , . , . , . : . . / . . . . . : , 1962. 439 .
22. , . . -- NRTL / . . , . . // . . . 1997. . 71, 4. . 637641.
23. , . . / . . , . . // . . . 2003. . 37, 3. . 272277.
-
, 2010, . 5, 3
18
541.123
-- --
.. , , .. , , .. ,
. ..
e-mail: [email protected]
NRTL -- --,
. Wilson and NRTL model parameters for binary components of ethanol-water-ethylenediamine and ethanol-water-butylamine systems were estimated. Besides, the mathematical simulation of vapor-liquid equilibrium in binary and ternary systems under atmospheric pressure was realized.
: , , , , , , .
Key words: mathematical simulation, azeotrope, phase diagram, vapor-liquid equilibrium, model parameters, binary system, ternary system.
- - , -, , , , . , - , , . - () . - -. - , [1]. - , [2].
- - - [3] [4, 5]. - -, -, -
. -
: () () () () () (). - :
, - -;
- ;
- .
-- -- - [6, 7]. - ( , , .), . - . ( , -- , - , - ), , , . - -. , - , ,
-
, 2010, . 5, 3
19
- . , , . [6, 7] , - , .
, -, ( UNIFAC) NRTL - -- -- , .
, - -, , - - , - .
- ,
- (, ) (, . .) .
- () 1, 2 = f(x1), .
--- -- - .
- , . = 760 . . [8]. NRTL, - . . 1 , .
1. (1)-(2) NRTL.
( )
Wilson NRTL Wilson NRTL
, 1, .. , 1, .. , 1, .. , 1, .. 0.14 0.0060 0.13 0.0031 0.15 0.0051 0.13 0.0021
, - , - -. NRTL ,
[3]. , - (. 2) , [9] ( 0.8940 .. =78.10 78.15) - , - .
2. (1)- (2), NRTL.
Wilson NRTL Wilson NRTL
, .. 0.8900 0.9150 0.8800 0.9200
., 78.10 78.20 78.04 78.23
, . , , - - - -
. . 1
- , . , - 0.8900 .. 78.10.
-
, 2010, . 5, 3
20
75
80
85
90
95
100
105
0 0.2 0.4 0.6 0.8 1
1 , 1 ..
,
x1, .
y1,..
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
1 , ..
1,
.
.
() ()
. 1. = f (x1, y1) (), y1 = f (x1) () (1)-(2) = 760 . .
- - 20 . - [6, 10], - ( UNIFAC) - = 760 . . -
NRTL, , - - , , , - (. 3).
3. (1)-(2), NRTL.
Wilson NRTL Wilson NRTL
, .. 0.4200 0.4050 0.4200 0.4100
., 121.11 120.5 121.31 120.68
[9] : 0.444 . . =118.7. , .
. 2 = f(1, 1) y1 = f(x1) - , . -, 0.4200 .. - 121.11.
100
105
110
115
120
125
0 0.2 0.4 0.6 0.8 1
1 , 1 , ..
,
1, ..
1, ..
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
1 , ..
1,
..
() ()
. 2. = f(x1, y1) (), y1 = f(x1) () (1)-(2) = 760 . .
-
, 2010, . 5, 3
21
- 20, - ; [6, 7] 760 . . - . . -,
[6], NRTL ( ). , - ( UNIFAC), - NRTL (. 4).
4. (1)-(2) NRTL.
( )
Wilson NRTL Wilson NRTL
, 1, .. , 1, .. , 1, .. , 1, .. 0.10 0.0017 0.14 0.0022 0.07 0.0015 0.18 0.0024
, - - , NRTL. ,
. - -, - - (. 3).
75
80
85
90
95
100
105
110
115
120
0 0.2 0.4 0.6 0.8 1
1 , 1, ..
, 1,.
1,.
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
1 , ..
1,
.
.
() ()
. 3. = f (x1, y1) (), y1 = f (x1) () (1)-(2) = 760 . .
- 20, . = 760 . . [6], NRTL -
. - , - (. 5) - (. 6), - [6, 7] ( - 0.41 .. =81.8).
5. (1)-(2) NRTL.
( )
Wilson NRTL Wilson NRTL
, 1, .. , 1, .. , 1, .. , 1, .. 0.84 0.0068 1.00 0.0134 1.07 0.0141 1.09 0.0138
-
, 2010, . 5, 3
22
6. (1)- (2), NRTL.
Wilson NRTL Wilson NRTL , .. 0.4250 0.4850 0.4850 0.4850
., 83.04 83.18 83.28 83.36
. 4 -, - -
. , - 0.4250 .. 83.04.
77
78
79
80
81
82
83
84
0 0.2 0.4 0.6 0.8 1
1 , 1 , ..
,
1, ..
1, ..
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
1 , ..
1,
..
() ()
. 4. = f(x1, y1) (), y1 = f(x1) () (1)-(2) = 760 . . -
20 . - -
=760 . . [6, 7, 11]. . 7 - [6], .
7. (1)-(2) NRTL.
( )
Wilson NRTL Wilson NRTL
, 1, .. , 1, .. , 1, .. , 1, .. 0.84 0.0277 0.96 0.0349 0.88 0.0285 0.95 0.0356
, .
- . - [6, 7] ( 0.93 .. =76.7) -,
(. 8). , -- - , - .
8. (1)- (2), NRTL.
Wilson NRTL Wilson NRTL , .. 0.9650 0.9100
., 77.44 77.45
-
, 2010, . 5, 3
23
70
75
80
85
90
95
100
105
0.0 0.2 0.4 0.6 0.8 1.0 1 , 1 , ..
,
1, ..
1, ..
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0
1 , ..
1,
..
() () . 5. = f (x1, y1) (), y1 = f (x1) () (1)-(2)
= 760 . .
= f(x1, y1) y1 = f(x1) - . 5.
, -- --, -
, . , , . 9. - -- --. (. 10).
9. .
i j Aij Aji 299.71 970.53 -538.201 1753
-916.22 264.55 -677.02 1651.9 1166.4 1093.6
10. -- -- .
( ) , .. ,
1 2 3 (1) (2) (3)
0.0543 0.0332 0.0362 3.93 (1) (2) (3)
0.0170 0.0147 0.0203 0.56
, . - - - - (=const).
. 6 () 7 () - = 760 . . - -- --, . , - ,
- - ( - , - ), - ; , (- - - -, - -). - (. 6 () 7 ()), -
-
, 2010, . 5, 3
24
- - , -- -- ( 0.3200 . ., 0.4200
.=81.85). [9] : - 0.3350 . ., 0.4590 . . .=81.8. , - --.
() ()
. 6. --: () -, () .
() ()
. 7. --: () -, () .
: 1. -
- -. , , - .
2. , - -
, - - .
3. - .
(2009-2010 ), 6880.
-
, 2010, . 5, 3
25
:
; ; ; ; ; Az ; 1, 2 ; .. .
:
1. , . . / . . , . . // -17 : . . XVII . ., , , 1 3 2004. , 2004. . 9. . 56.
2. , . . / . . , . . , . . // . . . 2007. . 81, 6. . 971977.
3. , . . / . . , . . , . . . .: , 1989. 344 .
4. , . . NRTL / . . , . . , . . // . . . 2002. . 36, 4. . 388394.
5. , . . / . . , . . , . . // . . . 2003. . 37, 2. . 174183.
6. , . . - ( ) : . . : 05.343 : 26.06.72 : . 26.08.72 / . ., 1972. 224 .
7. , . . . / . . , . . , . . // . 1972. . 2, . 2. . 102106.
8. , . . : 2 . / . . , . . , . . . . 1. . . : , 1966. 1426 .
9. , . . : / . . , . . , . . . . : , 1971. 848 .
10. , . . - : / . . . . : . 2007. 32 .
11. , . . - : / . . , . . , . . . . : , 1987. 336 .
-
, 2010, . 5, 3
26
544.163.2:544.163.3:544.142.3:544.176:544.473-039.63-386:544.182.32
13
-[(1-R-3-C3H4)Pd(Me2C=O)2]+
. . , , . . , , . . ,
. .. . ..
e-mail:[email protected]
13 ( DFT) -[(1-R-3-C3H4)Pd(Me2C=O)2]
+ - +, - - R+, R- F.
Both theoretical values of NMR 13 chemical shifts and frontier orbital energies (DFT method) for syn-[(1-R-3-C3H4)Pd(Me2C=O)2]
+ follow one- and two-parameter linear regressions which involve + and - constants, as well as Swain-Lupton parameters R+, R- and F.
: DFT, , , -, 13, .
Key words: DFT, substituent constants, Hammett equation, Swain-Lupton parameters, NMR 13C, allyl complexes of palladium
: -, , , 1,4- , . [1]. - , -.
- - (, , -
) - , , - . , - (1) [(1-R-3-C3H4)PdCl2]
- [(1-R-3-C3H4)PdCl]2 13, - (.) (3) [2].
R
Pd
O O(Me)2C C(Me)2
1
2
3
+
1
R = Me (a), Ph (b), CH2OMe (c), CO2Me (d), COMe (e), CHO (f), C2H (g),CF3 (h), COCl (i)
1 1b [4]. . (3) ( ) Pd-C(3) 1a-f, DFT [4]. , + - (R+ R-) (F) ( -), (1) [3]. (3) (2), R/F .
+ = R+ + F - = R- + F (1)
((3)) = const + RR+(R-) + FF (2)
, , [4], - (3) (4), , , - R+ F.
. (C(3)) = 59.84 + 10.22 (0.748R+ - -0.252F), r = 0.9448, n = 5 (3)
. (C(3)) = 57.68 + 7.08 (0.680R- + +0.320F), r = 0.9296, n = 5 (4)
- - 1 -, , -
-
, 2010, . 5, 3
27
. , , ., - (DFT) [4], - , - 15 ..
, - [4] (2) - - 1g-i.
1. () 1 (B3LYP/Gen).
Pd-C(1) Pd-C(2) Pd-C(3) C(1)-C(2) C(2)-C(3) Pd-* Pd-**
1g 2.201 2.165 2.160 1.419 1.406 2.209 2.201
1h 2.140 2.161 2.176 1.415 1.403 2.184 2.177
1i 2.157 2.165 2.182 1.418 1.402 2.181 2.171 *) - CHR . **) - CHR .
2. ( ) 1 (B3LYP/Gen).
C(1) C(2) C(3) Pd
1g -0.390 -0.110 -0.185 0.235 -0.346 -0.353
1h -0.352 -0.122 -0.160 0.226 -0.362 -0.357
1i -0.251 -0.100 -0.165 0.247 -0.360 -0.356 3. 13
1 (B3LYP/Gen).
(), ..
C(1) C(2) C(3)
1g 76.4 124.4 69.4
1h 79.0 121.4 77.4
1i 77.1 123.4 77.9 -
GAUSSIAN-03 [5] DFT ( B3LYP [6, 7]) Gen = LANL2DZ(Pd) + 6-311G**(H,C,O,Cl) . , - . - (. 1) (. 2) - - (GIAO). .., . 3, :
= iso(Si(CH3)4) iso, iso(Si(CH3)4)=184.5 .. Si(CH3)4, Gen.
, 13 p, (5) [8]:
ij
ijp QrEcme
p2
322
22
2
, (5)
E ,
pr
2
3 , 2p--, Qij , . p, [9]. , (13) , Pd-C [4]. . 1 2, .
, - 1g-i, 1a-f, - R Pd-C(3), Pd- Pd- (. 1). Pd- , Pd-, 0.01 , - R.
-
, 2010, . 5, 3
28
. 1. (3) 1 Pd-C(3).
. 2.
(3) 1 C(3) .
(. 2) (. 3) - [4]. . 3 - (6) (7). , + - COMe - - CH2OMe. , , , - (6) (7), .
. (C(3)) = 74.38 + 20.06 (0.788R+ - -0.212F), r = 0.9042, n = 8 (6)
. (C(3)) = 68.02 + 22.19 (0.162R- + +0.838F), r = 0.8698, n = 8
(7)
(3), (4), (6) (7) . -, (3) (6) (3) 1a-i. -, . ., (3) (6) R/F (-3.0 -3.7, ). -, - R/F -
- R [10], - - [11].
(-5.351)
(-10.277)
1
(-6.545)
(-10.961)
1i
. 3. 1, ()
0.2. (5),
() ().
-0.19 -0.18 -0.17 -0.16
68
72
76
80
84
.
(3 )
, .
.
C(3 ), ..
-
, 2010, . 5, 3
29
, (. 5). , , Me- 1,
, -, (. 3).
5. 1 - [3] (n , r ).
*) 1 .
. 4. 1 .
,
, - , - , - - .
( 08-03-00743 10-03-01035).
: 1. Handbook of organopalladium chemistry for organic synthesis : in 2 v. / red. E.-i. Negshi. NY :
Wiley, 2002. 3424 p. 2. , . . 13 [(1-R-
3-C3H4)PdCl]2 Na[(1-R-3-C3H4)PdCl2] / . . , . .
// . . . . 2008. . 57, 6. . 11711174. 3. Hansch, C. A survey of Hammett substituent constants and resonance and field parameters / C.
Hansch, A. Leo, R. W. Taft // Chem. Rev. 1991. Vol.91, 2. P.165195. 4. , . . 3-
13 - / . . , . . , . . // . . . . 2009. . 58, 3. C. 539546.
5. GAUSSIAN 03. Revision B.03. Gaussian : Pittsburg, PA. 2003. 6. Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange / A. D. Becke // J.
Chem. Phys. 1993. Vol .98, 7. P. 56485653. 7. Lee, C. Development of the Colle-Salvetti correlation-energy formula into a functional of the
electron density / C. Lee, W. Yang, R. G. Parr // Phys. Rev. B. 1988. Vol. 37, 1. P.785789. 8. Karplus, M. Theory of Carbon NMR Chemical Shifts in Conjugated Molecules / M. Karplus, J. A.
Pople // J. Chem. Phys. 1963. Vol. 38, 12. P. 28032807. 9. , . . / . . . . : , 1984. 478 . 10. Shorter, J. Correlation Analysis of Organic Reactivity. With particular reference to multiple
regression / J. Shorter. NY : Wiley, 1982. 235 p. 11. Transition metal NMR chemical shifts and polarizability effect in organometallic complexes / A. N.
Egorochkin [et al.] // Magn. Reson. Chem. 2009. Vol. 47, 9. P.782790.
r n
1. * -9.326 3.736 (0.008R+ + 0.992F) 0.9761 7 2. -9.124 4.823 (-0.061R- - 0.939F) 0.9371 7 3. -9.310 3.606F 0.9335 8
4. -5.434 1.721 (0.434R- + 0.566F) 0.9896 8 5. -5.456 0.8 - 0.9891 8 6. -5.554 2.002 (0.430R+ + 0.570F) 0.9617 8 7. -5.680 0.896 + 0.9544 8
-0.4 0.0 0.4 0.8 1.2 1.6
-6.4
-6.0
-5.6
-5.2
2 1
,
-
, 2010, . 5, 3
30
541.49+546.121+547.496.3
.. , , *.. , , .. , , .. , , .. ,
, . .. * , . ..
e-mail: [email protected]
, [Nd(H2O)9]I32CS(NH2)2 [Gd(H2O)9]I32CS(NH2)2. ,
( ), - -. , , , -. - . Data concerning the synthesis, IR-spectra, and single crystal X-ray studies for neodymium iodide and gadolinium iodide thiourea complexes of the general composition [Ln(H2O)9]I3 2CS(NH2)2 (Ln = Nd, Gd) are presented. It has been demonstrated that in the solid state the title compounds are composed from [Ln(H2O)9]
3+cations (polyhedron: monocapped tetragonal antiprism) as well as from non-coordinated thiourea molecules and iodide ions. Due to hydrogen bond formation mutually perpendicular flat molecules of thiourea are combined into goffered layers, nonaaquacations of lanthanides and iodide-ions being located in the cavities between these layers. The existence of hydrogen bonding between the mentioned species has been underlined.
: , , , , , -, .
Key words: neodymium(III) iodide, gadolinium(III) iodide, thiourea, complexes, crystal structure, IR spectra, synthesis.
- - , , CS(NH2)2, , - - - - -, - [1]. - , - , . , -: ( ). , - - , - .
, , , [27]. -, LnI3 CS(NH2)2 H2O (Ln La, Gd, Er, Tb, Nd) 0 [5 7] - -
LnI32CS(NH2)210H2O. , - [Ln(H2O)9]
3+, - . .
- - .
- , - [7] - 14 3 ( 6-09-3975-75).
, LnI39H2O CS(NH2)2 1:1.7 1:1.8. . -
-
, 2010, . 5, 3
31
- Gd - Nd. 10 15% (.) LnI3 [5, 6].
- [5]; - . - 0.2%.
- - 02 400 3800 1.
. -
CAD4 [8] (AgK MoK-, -, -). - 25 1415 ( - ) 1112 ( - ).
(. 1), 1 2 .
1. [Nd(H2O)9]I32CS(NH2)2 (I) [Gd(H2O)9]I32CS(NH2)2 (II).
, . % , . % Ln Ln CS(NH2)2
Ln CS(NH2)2
LnI3 : CS(NH2)2
Nd 17.19 18.12 17.1 18.1 1 : 2.00 Gd 18.45 17.86 18.3 17.8 1 : 2.01
, LnI32CS(NH2)210H2O (Ln La, Gd, Er, Tb, Nd). , [5, 6] .
- -
I II . 2. LnI32CS(NH2)210H2O [5 7], I II - CS , .
- .
2. (1) [Nd(H2O)9]I32CS(NH2)2 (I) [Gd(H2O)9]I32CS(NH2)2 (II).
CS(NH2)2 I II 488 465 491 (NCN) 632 (CS) 730 717 716 (CS)
1084 1035 1089 1034 1091 (CN)
1414 1378 1445 1398 1464 (CN) + (HOH)
1473 1466 1485 (CN) 1618 1611 1610 (NH2) 3175 3277 3380
3161 3368
3200 3400 (NH) + (OH)
- . 3. - - - . - WinGX [9].
SHELX97 [10]. -
- - . . - [Ln(H2O)9]I32CS(NH2)2 (Ln = Nd, Gd) - : CCDC 756954 (I), 756953 (II) (http://www.ccdc.cam.ac.uk; e-mail: data_request@ ccdc.cam.ac.uk).
-
, 2010, . 5, 3
32
3. , [Nd(H2O)9]I32CS(NH2)2 (I) [Gd(H2O)9]I32CS(NH2)2 (II).
I II C2 H26 I3 N4 Nd O9 S2 C2 H26 Gd I3 N4 O9 S2 839.33 852.21 C 2/c C 2/c a, 24.864(5) 24.801(10) b, 8.424(3) 8.3830(19) c, 14.114(4) 14.079(8) , . 124.58(3) 124.56(3) V, 3 2433.9(12) 2411(2) T, K 293(2) 293(2) Z 4 4 ., /
3 2.291 2.298 MoK AgK (K),
1 3.252 6.750 , . 1.5-20 2-26
-28 h 30; -10 k 9 -13 l 17
-30 h 9 -9 k 10 -14 l 17
, 0.2 x 0.2 x 0.2 0.3 x 0.3 x 0.3 4427 4752 2302 2361 2011 2179 98 99 GooF 1.087 1.099 R- R1/wR2[I2(I)] 0.0439/0.0375 0.0406/0.0374 max/min, /
3 1.477 / -1.306 2.383 / -1.625
. 1.
[Nd(H2O)9]I32CS(NH2)2 (I). d,:
Nd(1)O(1) = 2.497(5); Nd(1)O(2) = 2.490(4); Nd(1)O(3) = 2.482(4); Nd(1)O(4) = 2.490(4);
Nd(1)O(5) = 2.478(4); S(1) C(1) = 1.704(8); N(1)C(1) = 1.247(10); N(2)C(1) = 1.293(11) .
(.) I: N(1)C(1)N(2) = 116.4(8); N(1)C(1)S(1) =
121.8(6); N(2)C(1)S(1) = 121.8(6).
- - - ( - ), - -. , -
MERCURY CSD 1.5 [12], . 1 ([Gd(H2O)9]I32CS(NH2)2) 2 ([Nd(H2O)9]I32CS(NH2)2).
. 2.
[Gd(H2O)9]I32CS(NH2)2 (II). d,:
Gd(1)O(1) = 2.457(4); Gd(1)O(2) = 2.444(4); Gd(1)O(3) = 2.449(4); Gd(1)O(4) = 2.428(5);
Gd(1)O(5) = 2.467(5); S(1) C(1) = 1.679(9); N(1)C(1) = 1.290(11); N(2)C(1) = 1.273(11) .
(.) II: N(1)C(1)N(2) = 112.0(9); N(1)C(1)S(1) =
124.3(7); N(2)C(1)S(1) = 123.7(6).
, - - (2.890 3.003 ), -
-
, 2010, . 5, 3
33
; ( . 3 ). , - 4.135 . - - [2, 3] - .
. 3. I:
b.
, , . -, CS , 1.71 (. 1 2). CN : 1.246 1.294 (I), 1.272 1.290 (II)
CS(NH2)2, 1.33 . NCN CS(NH2)2, 115.6. - .
, . 3, , - -.
, -
, 0 ( 10, 9 ). , - , , . -, 0 [57], -. , 0, - - . , ( -) - , - -. , .
: 1. , . .
/ . . , . . // . . . -. 1999. . 2. . 6877.
2. ()(III) [Sm(C2H3O2)3(H2O)] SC(NH2)2 / . . [ .] // . . . 1981. . 22, 5. . 120123.
3. . [La(C2H3O2)3(H2O)2] SC(NH2)2 / . . [ .] // . . . 1980. . 21, 3. . 120126.
4. , . . / . . , . . // : . . . . . 1983. 202. . 6668.
5. 0 . / . . [ .] // . . . 1988. . 33, 3. . 777779.
6. , 0 . / . . [ .] // . . . 1992. . 37, 8. . 19111913.
7. Studies on the interaction of neodymium and terbium iodides with thiocarbamide / N. Tang, L. Yu. Alikberova, G. P. Loginova, B. D. Stepin, M. Y. Tan // Books of Abstr. XXV Intern. Conf. on Coordination Chemistry, Nanjing, China. Nanjing. 1987. P. 586.
8. Enraf-Nonius CAD-4 Software. Version 5.0. Enraf-Nonius, Delft, The Netherlands, 1989. 9. Farrugia, L. J. WinGX. X-Ray Crystallographic Programs for Windows / L. J. Farrugia // J. Appl.
Cryst. 1999. Vol. 32. P. 837. 10. Sheldrick G.M. SHELXS97 and SHELXL97. - University of Gttingen. Germany. - 1997. 11. MERCURY CSD 1.5. Cambridge Crystallographic Data Centre. http://www.ccdc.cam.ac.uk.
-
, 2010, . 5, 3
34
66.011:661.68
, EXCEL
.. ,
e-mail: [email protected]
Excel Microsoft Office , . , , .
, .., . The balance scheme of trichlorosilane production based on hydrochlorination of elemental silicon was worked out with the use of Microsoft Excel. The scheme includes the following steps: synthesis of hydrogen chloride, synthesis of trichlorosilane, separation of vapor-gas mixture and purification of trichlorosilane. If the user modifies the calculation conditions, the scheme allows to re-count automatically the material flows, specific consumption coefficients etc., and also to check the correspondence between the balance data obtained in the calculation process and required indices of production.
: , , Excel, , . Key words: trichlorosilane, balance scheme, Excel, calculation, material balance.
() - - - , - . .
- , :
Si + 3HCl = SiHCl3 + H2. (1) ,
: - ,
Si + 4HCl = SiCl4 + 2H2 (2) Si + 2HCl = SiH2Cl2, (3)
(Si2Cl6, Si3Cl8, Si2HCl5 ). - () Si2Cl6, - :
2Si + 6HCl = Si2Cl6 + 3H2. (4) ()
, - , -, .
- :
H2 + Cl2 = 2HCl. (5)
- [1], [2] : ,
(). - , HCl. , , . -, HCl, . [1]. , . - , SiHCl3 , , - , , . - , - . -, ( ). - , [3].
, (, ..), - - Excel Microsoft Office.
-
, 2010, . 5, 3
35
, . - Excel - : , .. - , . - , -
, .
Excel - [4]. , . - , Excel (. 13).
. 1. . Synthesis of HCl.
. 2. . Synthesis of SiHCl3.
-
, 2010, . 5, 3
36
. 3. .
Separation and purification.
, -, , - () - . - , , - . . 13 ( , - ..) , -, [1]. - - 12000 .
Excel - :
1) Excel ;
2) Excel - , , Excel , . , , - , , , Excel;
3) , , - , , - , - .. - -
-
, 2010, . 5, 3
37
Excel. - , - .
.
, .. , (12000 /), H3 . 3. , , - , .. SiHCl3 . (I19) , (H3) SiHCl3 (H5), SiHCl3 (H9) : = H3/(100 H5 H9)*H5 (1340.78 /). (I48): = H3/(100 H5 H9)*H9 (67.04 /). SiHCl3 , - (D15), : = I15 + I19 + I48 (13407.82 /).
( E J ) . , E15: = D15/C15*22.4 SiHCl3 / . 3/ ( C15) (22.4 . 3/). , / (C H) , .
- SiHCl3 ( I19, . 2), .. : = 'Separation and purification'!D15, Separation and purification Excel (. 3). , , .. .
( H8, . 2), (H10) (H11) , , , , [1]. (H9)
, .. = 100 H8 H10 H11 (13.70 %). SiHCl3, , (H8:H11) . , SiCl4 (I20) : = I19/H8*H9 (2135.90 /). SiH2Cl2 Si2Cl6 ( I21, I22).
- , - ( D16:D18, . 3), .. . - - ( I28, . 3) 35.86 /. , (I49) 10.91 /. - , - SiCl4 . - Si2Cl6 [3]. - SiCl4 (I27) , (I28) Si2Cl6 (H6 25.0 %), - ( ), : = I28*((100 H6)/H6) I29 I30 (97.66 /). (I23) SiCl4, (D16), (I27) 2038.24 /.
, - ( I24, . 2), 1 4, (I19:I22) HCl - SiHCl3 (H7), : = (I19/H19*3 + I20/H20*4 + I21/H21*2 + I22/H22*6)*H24/H7* (100 H7), 154.22 /. - (D31, . 2). D31 : = I24. HCl - (D25) HCl, - 1 4, : = (I19/H19*3 + I20/H20*4 + I21/H21*2 + I22/H22*6)*C25 (12697.81 /).
,
-
, 2010, . 5, 3
38
(D25, . 2 I10, . 1) - - (. 1).
, HCl ( D9, . 1) 5: 12346.80 /. [1] ( H3 - 5.0 %), HCl H2 (I11), - : =I10/H10/2*H11*(100+ H3)/100 D9/C9*H11 (17.55 /).
- , , - , H2 - ( I23, . 2) , -, H2, - 1, 2, 4. , ( D18, . 1) : = I11 + ('Synthesis of SiHCl3'!I19/'Synthesis of SiHCl3'!H19 + 'Synthesis of SiHCl3'!I20/'Synthesis of SiHCl3'!H20*2 + 'Synthesis of SiHCl3'!I22/ 'Synthesis of SiHCl3'!H22*3)*C18, Synthesis of SiHCl3 Excel, . H2 268.57 /.
, HCl (D13), H2 : = I10/H10/ 2*C13*(100 + H3)/100 D18 (99.98 /).
-, - [1]. - (H3, . 2), (H5) (H13), ( I29, I32 I31). (I25) , SiHCl3 (H12), : = (I19/H19 + I20/H20 + I21/H21 + I22/H22*2)*H25*(100 H12)/H12 I31 (131.29 /).
, (D19), : = I25 + I31 +
(I19/H19 + I20/H20 + I21/H21 + I22/H22*2)*C19 (3309.17 /). , (D20) - (D19) (H6): = D19/(100 H6)*H6 (33.43 /).
- , , .
- (. 4), - - , . Excel, - . F42 (. 4), , = B40 G40, - , - . , , , .
- , , , - - (, ..). - Excel, (. 5). , HCl, (I10, . 1), - , (C4, . 5). (/), HCl , (E4, . 5) , (I10, /, . 1) (H2, . 1) , (C10, . 5). E4 (. 5) : ='Synthesis of HCl'!I10*1000/C10/ 'Synthesis of HCl'!H2, Synthesis of HCl . - (881.79 /) F4 (. 5) (1000 / C4): = (E4 > C4; ; ). F4 ( ), , .
-
, 2010, . 5, 3
39
. 4.
.
. 5. .
-
- ( 5). , - (1000 /) (2800 /). F5 : = (E5 < B5; ; (E5 > C5; ; )).
( 6 7).
, Excel , - . . , , - Excel, - . , - , - . -
-
, 2010, . 5, 3
40
- , , . , Excel.
. - , , ,
, , .. , - , , , - .
, Excel , , . .
:
1. / . . [ .] . : , 1992. 408 .
2. / . . , . . , . . , . . // . 1991. 8. . 2931.
3. , . . / . . , . . // . 2008. 10. . 6568.
4. , . . Excel / . . // 2009. . 4, 4. . 7177.
-
, 2010, . 5, 3
41
542.61:546.633
N-(2--5-)-
- .. , , .. , ,
.. , . ..
. .. e-mail: [email protected]
3.0-4.5 N-(2--5-)- -- . ,
-, 1H--. Chemical aspects of scandium solvent extraction from its chloride solutions at pH 3.0-4.5 by N-(2-hydroxy-5-nonylbenzyl)--hydroxyethylmethylamine solutions in octanol have been studied. The extraction mechanism has been suggested. The structure of the extracted complex has been identified by 1H NMR and IR spectroscopy methods.
: , , N-(2--5-)--, , .
Key words: solvent extraction, scandium, chelate, N-(2-hydroxy-5-nonylbenzyl)--hydroxyethylmethylamine, chemical aspects of solvent extraction.
- . , , - [1]. - , - - , , , , . -, , - , . -, - , - - - [2].
[3]. , , - , - . . - - - , , -
. - [4], . , - , - , [5], . , - [68].
, - - .
N-(2--5--)-- (-2) 3.0 4.5.
- Sc2O3 (99.9%) - -. - 0.025 0.12 . - N-(2--5-)-- (-2) -, - , - - - [9]. ,
-
, 2010, . 5, 3
42
(-2=21.6
1/2) [10] , - ( ). , , - / .
- - t = 202. . V:V=1:1, 45 , , , . 30 , . . , [11]. , , (DSc) (- Cl NaCl).
- - Specord M80 400 4000 -1, 5 (42.3% TlBr, 57.6% TlI). WM250 (Bruker) 2 3% DMSO-d6 230.13 .
2 - , , . . , [12].
(. 1). - . 1
MgCl2 , - .
. 1. (CSc = 0.025 /)
MgCl2.
- S(III), , -, , lgDM . - - , , [4]. - pH. (CSc = 0.025 /, -2 = 0.25 /), 0.9 0.2, - - .
0.12 / 2 (MgCl2=2 /) lgDSc lgC-2 (C-2 ), 4.3 , Sc : 2 1. ICPMS1.
, , Sc : 2 1 : 1, 2 , , ScCl3 3.04.5 :
1 . ..
-
, 2010, . 5, 3
43
Sc(H2O)6
3+(B) + 2Cl
(B) + HR(O) = ScCl2R2H2O(O) + 4H2O(B) + H
+(B) (1)
Sc(H2O)5()2+
(B) + Cl
(B) + HR(O)=ScCl(OH)R2H2O(O)+ 3H2O(B)+ H+
(B) (2) Sc(H2O)4()2
+(B) + HR(O) = Sc(OH)2R2H2O(O) + 2H2O(B) + H
+(B) (3)
-
( K Sc) - . - [13]. - 1 (. 2), - 1 - .
. 2. 1 3
.
, - -, - . - lgDSc lgCNaCl ( 4.6). , 1.9 0.3, .
, 2, 1H .
2 , , 1309 -1, CO(Sc) [14], 589-1 448 -1, , , ScN [15] ScCl, [16]. - - (35003200 -1 34003100 -1). -
- (1607-1) [17]. 1H - - 919, - ( = 7/2), -.
, - - ( - ) Hyper Chem Pro6. - Sc 2 - MM+. -, ZINDO/1 ( ). 2:
1. ( = 57.56 /);
2. ( = 33.19 /).
N
C9H19
CH2
O
ScCl
CH2
CH2OH
ClH2O
CH3
. 3.
, -, +3 , , - , - - . , 6. - . 3.
-
, 2010, . 5, 3
44
:
1. , . . / . . , . . . . : , 1991. 431 .
2. : 3 . : . / . . [ .] ; . . . . . . : , 1996. . 1 : . 376 .
3. , . . / . . , . . . . : , 1999. 64 .
4. , . . / . . . . : Hay, 1968. 295 .
5. , . / . , . . . : , 1983. 280 .
6. -- / . . , . . , . . , . . // . 1999. . 25, 3. . 192197.
7. , . . / . . , . . , . . // . . . 1994. . 39, 4. . 670674.
8. / . . , . . , . . , . . , . . // . 2006. . 1, 6. . 1625.
9. . 2028305 , C 08 C1/15, C 08 F236/10. (-) / . . , . . , . . , . . , . . , . . , . . , . . , . . . 4774251/05 ; 26.12.95 ; . 09.02.98.
10. , . / . . . : , 1991. 763 .
11. , . / . , . . . : , 1970. 360 .
12. , . . - / . . , . . , . . // : . . III -. ., ., , 13 14 . 2009. ., 2009. . 59.
13. , . . / . . , . . // . . . 1968. . 13, . 7. . 18051807.
14. , . . 1--3--4--5 / . . , . . , . . // . . . 1974. . 29, .10. . 19181923.
15. - / . . [ .] // . . . 1970. . 15, .5. . 12551260.
16. , . . Be, Mg, Al, Sc Y / . . , . . // . . . 1969. . 10, 5. . 820824.
17. , . . / . . . . : , 1973. 209 .
-
, 2010, . 5, 3
45
541.18:536.7
.. , , .. , ,
.. , .. ,
. .. e-mail: [email protected]
. (III) (II), , . The article is focused on the research of influence of various synthesis parameters (the rate of magnetite
formation, iron salts mole ratio, nature and concentration of precipitator and process temperature) on the magnetic properties of magnetite nanoparticles.
: , , , .
Key words: superparamagnetic nanoparticles of magnetite, immunomagnetometric assay, magnetic susceptibility.
-
. , - , , . - , , [1], [2, 3]. , , , (- ) , - . , -, [4], [5], [6], [7], [8, 9], [10], [11].
, , - [12]. - , Fe3O4 [13]. - , - . -, - , - ()
(), - , . . - - [14].
- :
3 2 3 22FeCl FeCl 8NH H O
3 4 4 2Fe O 8NH Cl 4H O
, , 1900 ., . , Fe(II) Fe(OH)2 , [13]. - - [3].
( > 20%). - - . . , .
, , . -
-
, 2010, . 5, 3
46
:
(II) (III);
; (,
).
-
: FeCl24H2O, Aldrich, 99%; FeCl3, Aldrich, 97%; , - , ; , 7, ; NaOH, , 432877, ; KOH, , 2436380, , , (Direct-Q5 Millipore, ).
- HWSLabortechnik 100 , 8310 (, ) . (200 /) Fe(II) (III), 20 . (700 /) 15 . 3000 / 10 . . - - pH -, 7.
. - LEO 912AB OMEGA , - ( ). , . - . - Delsanano C, Beckman Coulter () . 0.6 7000 , 2 4 . - , -
. - (- ) , - , - 2 . 200 . , - . - (Senova, ) - [15].
-
(II) (III) . , . 1, - - Fe(III) Fe(II), 2.75:1 ( 2:1) [3]. , (III) (II) 1 4. , (II) , .
. 1.
(III) (II)
(II): 1 FeSO47H2O; 2 FeCl2. 2 .%,
4 . %, 25 . -
. -, , ,
-
, 2010, . 5, 3
47
. , - : NH3H2 NaOH KOH LiOH. - -, -, - , , FeOOH, - -. , , - .
, - (II) (III), nFeOmFe2O3, , n=m, -. (II) (III), .
- - . 2. , , 8 c. %, - -. , - - , , , , , .
. 2.
: 1 LiOH; 2 KOH; 3 NaOH; 4 NH3H2.
2 .%, (III) (II)
2.75:1, 25 .
, . , . 3, , -, - 30 40. . , 40 2 .
. 3. :
1 5, 2 10, 3 20, 4 30, 5 40. 2 .%,
(III) (II) 2.75:1,
8 .%.
, - . , , . .
- , 100700 /. , . 4, , -. - - - . () . , , .
-
, 2010, . 5, 3
48
. 4.
, ./.: 1 100, 2 300, 3 500, 4 700.
(III) (II) 2.75:1,
8 .%, 40.
, , - ( (II) (III)) . . 4 - (dI) . , . , - , 30 , 100200 . .
, , , , .
: , . % 0.5
(III) (II) 2.75:1 , . % 8 , 40
. 5. 10 . . 6.
- - -.
. 5. ,
. 0.5 .%, (III) (II) 2.75:1,
8 .%, 40.
. 6. - . 0.5 . %,
(III) (II) 2.75:1, 8 . %, 40.
-
, 2010, . 5, 3
49
. 7.
, . 7, - - , - , - 0. , - ,
51.34 /.
(III) (II) . . (III) (II) . , , -. :
, - ;
; -
, .
( 090300888a).
: 1. Cornell, R. M. The Iron Oxides: Structure, Properties, Reactions, Occurrence and Uses / R. M.
Cornell, U. Schertmann. Weinheim : WileyVCH, 2003. 703 p. ISBN 3527302743. 2. Caruso, F. Colloids and Colloid Assemblies: Synthesis, Modification, Organization and Utilization
of Colloid Particles / F. Carus. Weinheim : WileyVCH, 2004. 761 p. ISBN 3527604170. 3. Rao, C. N. R. The Chemistry of Nanomaterials: Synthesis, Properties and Applications / C. N. R.
Rao, A. K. Cheetham, A. Mller. Weinheim : WileyVCH, 2006. 603 p. ISBN 3527306609. 4. Thermosensitive polymer coated nanomagnetic particles for separation of biomolecules / N.
Shamim, L. Hong, K. Hidajat, M.S. Uddin // Separation and Purification Technology. 2007. Vol. 53, 2. P. 164170.
5. Hafeli, U. O. Magnetically modulated therapeutic systems / U. O. Hafeli // Intern. J. of Pharmaceutics. 2004. Vol. 277, 1. P. 1924.
6. Medical application of functionalized magnetic nanoparticles / A. Ito, M. Shinkai, H. Honda, T. Kobayashi // J. of Bioscience and Bioengineering. 2005. Vol. 100, 1. P. 111.
7. Hydrolysis of sucrose by invertase immobilized onto novel magnetic polyvinylalcohol microspheres / S. Akgol, K. Yasemin, A. Denizli, M. Y. Arica, // Food Chem. 2001. Vol. 74, 3. P. 281288.
8. Gadoliniumloaded nanoparticles: new contrast agents for magnetic resonance imaging / C.H. Reynold [et al.] / J. Am. Chem. Soc. 2000. Vol. 122. P. 89408945.
9. Application of arsenazo III in the preparation and characterization of an albuminlinked, gadoliniumbased / T. N. Nagaraja [et al.] // J. of Neuroscience Methods. 2006. Vol. 157, 2. P. 238245.
10. Inductive heat property of Fe3O4/polymer composite nanoparticles in an ac magnetic field for localized hyperthermia / D.L. Zhao [et al.] // Biomedical materials. 2006. Vol. 1, 4. P.198201.
11. Improving agglutination tests by working in microfluidic channels / G. Degr, E. Brunet, A. Dodge, P. Tabeling // Lab on a chip. 2005. Vol. 5, 6. P. 691694.
12. Schmid, G. Nanoparticles: From Theory to Application / G. Schmid. Weinheim : WileyVCH, 2006. 444 p. ISBN 3527604049.
13. Jolivet, J.- P. Metal Oxide Chemistry and Synthesis: From Solution to Solid State / J. P. Jolivet. Chichester : Wiley, 2000. 338 p. ISBN 0471970565.
14. Miller, J. S. Magnetism, Nanosized Magnetic Materials (Magnetism: Molecules to Materials)/ J. S. Miller, M. Drillon. Weinheim : WileyVCH, 2002. 403 p. ISBN 3527303022.
15. Magnetic particle detection by frequency mixing for immunoassay applications / H.-J. Krause [et al.] // J. of Magnetism and Magnetic Materials. 2006. Vol. 311, 1. P.436444.
-
, 2010, . 5, 3
50
546.719
.. , , .. , . ..
. .. e-mail: [email protected]
- . .
The processes of complexing have been investigated for anodic dissolution of rhenium in a mixture of methanol and acetylacetone. A scheme of thermal decomposition of the obtained products has been suggested, and the temperature dependence of the phase composition of thermal decomposition products has been determined.
: , , , , . Key words: rhenium, alkoxo derivative, acetylacetonate, thermal decomposition, electrochemical synthesis.
, - , , , - [1].
: Re2O3(OMe)6, Re4O6-y(OMe)12+y, Re4O2(OMe)16, Re4O6(OMe)12. Re2O3(OMe)6 ReOCl4 - [2]. - - Re2O3(OMe)6 - - (5+) , - Re4O6-y(OMe)12+y. - - Re2O7 [3].
(0.8 /2) - (V) Re4O2(OMe)16, 0.07 0.10 /2 (VI) Re4O6(OMe)12 [4, 5]. - - Re4O6(OMe)12, - Re4O2(OMe)16 [6].
. - - - , - , ,
. , (acac), , , , - , - , - . (VI) Re2O5(acac)2, - - Re2O7 - ( ). - [7].
- MeOH - - ( ).
(Merck KGaA, 99.5%,
0.1%) . NaY, 300 . - : LiCl , - (P~1.3 ) 8090 1 , 180200
-
, 2010, . 5, 3
51
4060 . - . - , , , . - , : 44:1. : 6:1 .
- (. 1). 3.5 2, ( 99.99%, 48199288) 0.50.5 .
. 1. : 1 (P2O5); 2
; 3 ; 4 (Pt ); 5 ; 6
; 7 ; 8 . C, H
Heraeus CHNORAPID. ~0.2%. Re , [8].
( Co K) 3. -: 0.05, 24 . KBr EQUINOX 55 Bruker Germany. ()
Q1500 D (F. Paulik, J. Paulik, L. Erdey; MOM, ). 141.5 ( - 0.4 ). (1) 2 22 420.
1. - ( 75 , 5.54 , : = 44 : 1) Lice (0.,0125 /). : 1 : 2.7. 28 . : U = 40 100 B, I = 170 210 A. 3.83 . , -, -. 2 ( I) (. 2) . . (I) .
. 2. (I).
() (I): , %: Re 60.2, C 12.2, H 2.8. Re4O6(O)12, %: Re 61.4, C 11.9, H 3.0; Re4O2(O)16, %: Re 58.5, C 15.1, H 3.8.
(I): () = 1158 -1, (Re=O) = 964 1019 -1, (Re O) = 722 781 -1, (Re O(R)) = 427 596 -1.
2. -
( 37.5 , 37.5 , : = 6:1) LiCl (0.0125 /); : 1:19, -
-
, 2010, . 5, 3
52
( ). - 27 . - : U = 60 130 B, I = 130 220 A. 3.66 . - -, -, - - . - , -.
(. 1), -
(I) :
Re4O2(O)16 Re4O6(O)12 [4, 5] . Re4O2(O)16 Re4O6(O)12 : . (I) (. 1), , , ( * . 1) , Re4O6(O)12 Re4O2(OMe)16. - , , - . - - , . , Re4O6(O)12 Re4O2(OMe)16.
1. (I),
.
[2]
Re4O6(OMe)12 [2]
Re4O2(OMe)16 2 I/I0, % d, h k l I/I0, % d, h k l I/I0, % d, 11.3 39 9.092 0 1 1 12 9.118 0 1 1 12 9.165 11.9 58 8.635 0 1 -2 53 8.588 0 1 -2 90 8.630 14.1 62 7.293 -1 0 -1 28 7.284 15.3 100 6.724 1 1 0 100 6.707 1 1 0 66 6.707 20.5 22 5.031 1 1 -2 8 5.039 21.8* 11 4.734 22.5 22 4.588 0 2 2 14 4.564 23.5 34 4.396 1 -3 2 16 4.385 30.3 16 3.4251 0 1 -5 23 3.427 1 4 -1 11 3.4335 31.0* 9,6 3.3496 33.0 13 3.1518 1 4 -4 7 3.1866 34.2 11 3.0443 0 2 4 6 3.0329 0 2 4 6 3.0329 36.2 12 2.8813 2 -4 1 5 2.8711 2 -4 1 11 2.8667 37.3* 11 2.7992 37.7 56 2.7706 2 -3 -2 9 2.7757 2 -3 -2 9 2.7715 41.1* 11 2.5501 46.7* 16 2.2585 49.0 28 2.1586 0 6 -7 2.1536 1 7 -4 14 2.1536 50.4 13 2.1024 3 0 4 9 2.1151 52.3 20 2.0311 0 3 6 5 2.0251 1 -6 7 10 2.0749
-
Re4O6(O)12 . - (. 2) , -. , , , -, , - .
(I) ,
. 3. (I) 909 -1, Re=O, Re4O6(O)12 Re4O2(OMe)16. Re2O5(acac)2 907 -1 [7]. , (I), , , .
-
, 2010, . 5, 3
53
2. Re4O6(O)
Re4O2(O)16 [4]
Re4O6(O)12 [3]
Re4O6(O)12
a, 7.892(1) 7.893(8) 7.88(1)
b, 15.999(2) 15.994(2) 16.12(10)
c, 17.501(3) 17.501(1) 17.473(55)
, 113.39(1) 113.434(2) 113.33(13)
, 93.04(1) 93.048(2) 92.12(73)
, 92.76(1) 92.736(2) 93.10(85)
V, 3 2019(1) 2020.1(6) 2030(31)
. 3. (I)
. 4. (I). max = 420.
-
(I) 22 420 (. 4). G 132 400, 17%
100 160. (I) t = 277 ReO3 . . 3 - Re4O6(O)12 Re4O2(OMe)16) [6] c
-
, 2010, . 5, 3
54
, - . t = 420 - (I) ReO3, ReO2 ReO3 ( ) (. 5, . 4, 5).
,
(I) t =420 , - .
ReO3 : = 3.752 , a = 3.748 .
3.
tmax, WT,
/ t, m, % m, %
Re4O2(OMe)16 [6] 200 5 87146 24.2 26.4 ReO3 ReO3
Re4O2(OMe)16 [6]
200 2.5 93135 24.0 26.4 ReO3 ReO3
Re4O2(OMe)12 [6]
200 5 90134 20.1 22.8 ReO3 ReO3
Re4O2(OMe)12 [6]
200 2.5 95132 19.2 22.8 ReO3 ReO3
(I) 277 5 89-166 17.0 ReO3
. 5. ReO3, (I) t =277 ,
, ICDDJCPDS, No. 331096
4. ReO3, (I) t =420
ICDD-JCPDS, 331096
2 I/I0, % d, h k l d, I/I0, % 27.6 100 3.753 1 0 0 3.760 85 39.4 94 2.655 1 1 0 2.654 80 48.8 13 2.167 1 1 1 2.166 25 57.0 40 1.876 2 0 0 1.875 50 64.5 26 1.678 2 1 0 1.677 100 71.5 34 1.532 2 1 1 1.531 55
-
, 2010, . 5, 3
55
5. ReO2, (I) t =420
ICDD-JCPDS, 090274
2 I/I0, % d, h k l d, I/I0, % 1 28.4 10 3.649 1 1 0 3.659 100 2 37.0 27 2.821 1 1 1 2.864 100 3 43.1 14 2.437 2 0 0 2.405 80 4 46.3 22 2.277 0 0 2 2.299 80 5 55.2 12 1.932 1 1 2 1.947 80 6 57.9 25 1.849 2 2 0 1.830 10 7 61.6 20 1.748 1 3 0 1.752 30 8 63.3 17 1.706 2 2 1 1.701 100 9 71.2 37 1.538 3 1 0 1.542 50
10 75.5 16 1.462 3 1 1 1.462 50 11 77.3 15 1.433 2 2 2 1.432 10 12 78.3 10 1.419 1 1 3 1.415 50
-
ReO2 : = 4.815 , b = 5.651 , c = 4.594 ; a = 4.809 , b = 5.643 , c = 4.600 .
- (I) - - :
, -
- (I) 420, Re(VI) ( - ) Re(IV), , , ReO3 [5].
. , (I) , Re4O6(O)12, Re4O2(OMe)16 . , (I) ,
Re=O. , , DTG (I) . (I) - 420 Re(VI) Re(IV). , , (VI), ( 1 , t 420) (VI) [9]. ( n(3):n() = 44:1) .
( 060332444).
: 1. IIIVII / .
. , . . , . . , . . // . . 2007. . 43, 5. . 19.
2. Edwards, P. G. Improved syntheses of tetrachloro-oxorhenium(VI) and chlorotrioxorhenium(VII). Synthesis of alkoxo- and dialkylamido-rhenium compounds. The crystal and molecular structures of di--methoxo-tetramethoxo--oxo-dioxorhenium(VI) (ReRe), bis[lithium pentaisopropoxo-oxorhenate(VI)lithiumchloridetetrahydrofuran(1/1/2)], and trans-tetraphenoxobis(trimethylphosphine)rhenium(IV) / P. G. Edwards, G. Wilkinson // J. of the Chemical Society: Dalton Transactions. 1980. 12. P. 24672475.
-
, 2010, . 5, 3
56
3. Seisenbaeva, G. A. Heterometallic alkoxide complexes of variable composition a new way to ultrafine powders of metal alloys / G. A. Seisenbaeva, V. G. Kessler, A. V. Shevelkov // J. Sol-Gel Science and Technology. 2001. Vol. 19, 1. P. 285288.
4. - (V) Re4O2(OMe)16 / . . , . . , . . , . . , . . , . . // . . . 1995. T. 40, 9. C. 14771479.
5. Homo- and hetero-metallic rhenium oxomethoxide complexes with a M4(-O)2(-OMe)4 planar core a new family of metal alkoxides displaying a peculiar structural disorder. Preparation and X-ray single crystal study / G. A. Seisenbaeva, A. V. Shevelkov, J. Tegenfeldt, L. Kloo, D. V. Drobot, V. G. Kessler // J. of the Chemical Society: Dalton Transactions. 2001. 19. P. 27622768.
6. , . . -, - (, ) : . . . . . . : 05.17.02 : 25.12.02 / . ., 2002. 198 .
7. Kessler, V. G. Rhenium and Rhenium alloys / V. G. Kessler, G. A. Seisenbaeva, D. V. Drobot // Proceeding of the International Symposium, Orlando, Florida, USA, 10 - 14 Feb. 1997. Ed. B. D. Bryshkin, Publ. TMS, 1997. P. 167.
8. / . . [ .]; . .: . . . . . : , 1966. 1112 .
9. Dyuzheva, T. I. New high-pressure phases of ReO3 / T. I. Dyuzheva, N. A. Bendeliani, S. S. Kabalkina // J. of the less common metals. 1987. Vol. 133. P. 313317.
-
, 2010, . 5, 3
57
542.61
.. , , .. , , .. , ,
.., . ..
. .. e-mail:[email protected]
, , . .
A method of optimization of new extractants structure with the use of desirability function has been developed. The desirability function had been proposed before by Harrington for optimization of processes with several response functions. This method has been used for the design of phenolic type extractants.
: , , . Key words: molecular design, extrctants of phenolic type, desirability function
- , - [1]. , - -, , . [24]. , , , : - (D) , , - , , - - , - , - , , , - (). - () , , : , . -, - , , , (, ) [5, 6]. [7] , - ()
+3 - . - - , . , - - . [8, 9] - : - [8], , [9], , -, , , , .
, - , - [10, 11]. , - , , .
y ymax y ymin ( ) y d ( ) :
d=exp[-exp(-y')], (1)
y'=b0+b1y (2)
-
, 2010, . 5, 3
58
b0 b1 , y d, 0.2 < d < 0.8.
, d, d - - D, :
1 2...k kD d d d (3) -
() ( N(25-)). - .
1. (q), , , [3, 4], . q 3 (Parameterised Model 3) () HyperChem Release 8.0.4 (Hypercube Inc.).
2. (lgP), Chem3D Ultra version 7.0.0, () ChemOffice Ultra 7.0.1. lgP , , - .
3. - (H), 3 HyperChem Release 8.0.4 (Hypercube Inc.). [4], N(2 5),- () 4.5. , -, , , - (III) [5], - - . , . , , - , - - [12].
4. - [1315]. -
N(25 ) () (. 1). [3, 4] - N(25-) (1), -
- , .
OH
C9H19
CH2 NR
R
. 1. N(25)
(); R=CnH2n+1
- R . - - , - [7]. - . 1.
1. q lgP
q lgP 00, n=0 -0.030 5.11 11, n=1 -0.071 5.99 22, n=2 -0.082 7.05 33, n=3 -0.078 8.11 44, n=4 -0.075 9.16 55, n=5 -0.083 10.22 77, n=7 -0.085 12.34 1010, n=10 -0.091 15.51
. 1, ( ), . - , lgP . - , - [7].
- :
2 1 2D d d (4) d1, d2 .
- - (2). -
-
, 2010, . 5, 3
59
-. , - y1 y2, (. 2). - d (1).
2. d.
y1 (q) y2 (lgP)
-0.091 -0.03 15.51 5.11 d
0.65 0.3 0.65 0.25
b0 b1 (2) . 2. - d1, d2 - D2 . 3.
3. d1, d2 D2
.
d1 d2 D2
-0 0.30 0.25 0.27 -1 0.58 0.26 0.39 -2 0.54 0.29 0.40 -3 0.62 0.31 0.44 -4 0.53 0.33 0.42 -5 0.52 0.35 0.43 -7 0.47 0.39 0.43 -10 0.50 0.46 0.48
-0 0.30 0.25 0.27 -11 0.55 0.28 0.39 -22 0.61 0.33 0.44 -33 0.59 0.37 0.47 -44 0.57 0.41 0.48 -55 0.61 0.46 0.53 -77 0.62 0.54 0.58 -1010 0.65 0.65 0.65
. 3 , ( , - ) - -1010, . , , 1010 .
- - - - N(2 5) (. 2).
OH
C9H19
CH2 NC
10H
21
C10H21
R`
. 2. - N
(25) , R`(R), R`= , NO2, F, Cl, Br, I.
- - - , - -- 3. , , , .. [16], .
. 4 R`, .
4. , R`
H, /
q lgP
OH -948.53 -0.071 14.9 NO2 -795.408 -0.067 13.8
F -934.581 -0.076 15.8 Cl -746.607 -0.067 16.2 Br -685.712 -0.071 16.4 I -638.382 -0.075 16.6
(. 4), , , , - - , .
R`
C9H
O
CH2
19
NC
10H
21
C10H21
. 3. R`(R), R`= , NO2, F,
Cl, Br, I.
, . 3.
R` :
-
, 2010, . 5, 3
60
HR ++R. R`
: H=H(R) H(HR).
R`(R) . 5.
5. R`(R).
, / OH -1056.867 NO2 -982.012
F -1084.300 Cl -923.521 Br -828.330 I -767.716
R` . 6.
6. R`
,/ OH -108 NO2 -187
F -150 Cl -177 Br -143 I -129
. 6 , - - Cl NO2, , .
7. - .
-
PDKw ( ), /3
R [12] 0.001 -Cl [13] 0.0001 -NO2 [14] 0.06 -OH [14] 0.1
, - - , () . -
, . 4 : , -, - - () (. 7).
: y1=q ; y2=lgP - ; y3=H , /; y4 = PDKw - , /3; D .
- :
41 2 3 4D d d d d (5)
d1, d2, d3, d4 -.
- - . - - . , y1, y2, y3, y4, (. 8).
- d (1).
b0 b1 (2) . 8. . 9.
. 9 , ( , ) -- N(25 ). - ( , - ) - N2,3 5).
8. d.
y1 y2 y3, / y4, /3
-0.1 -0.059 15.6 13.8 -187 -98.3 0.06 0.0001 d 0.7 0.4 0.7 0.4 0.7 0.4 0.5 0.25
-
, 2010, . 5, 3
61
9. .
-
d1 (q) d2 (lgP) d3 (H) d4(PDKW) D3*) D4
**)
0.645 0.689 0.400 0.290 0.649 0.476 -NO2 0.466 0.400 0.700 0.500 0.508 0.505
-F 0.538 0.726 0.588 - 0.613 - -Cl 0.466 0.771 0.671 0.250 0.623 0.495 -Br 0.499 0.792 0.564 - 0.607 - -I 0.530 0.810 0.515 - 0.605 -
-OH 0.500 0.600 0.440 0.650 0.513 0.541
*) D3 33 1 2 3D d d d , **) D4 4 1 2 3 4D d d d d .
. 4. N(2,35-).
, , - - (. 4).
- , , -, , . .
: 1. , . . / . .
. // . 1982. . 24, 6. . 729739. 2. . , . . / . . , .
. , . . // XXI . .3. . . 1999. . 116154.
3. , . . N(25) (-1) / . . , . . , . . // . : , , , 29 . 4 . 2008. , 2008. . 111-115.
4. , . . N-(2--5-)-,- / . . , . . , . . // . . 2002. . 28, 11. . 851853.
5. , . . / . . , . . , . . . . : , 1987. 184 .
6. , . . / . . . .: , 2006. 510 .
7. , . . / . . , . . // . 1996. . 65, 11. . 10521079.
8. Hay, B. P. Toward the Computer-aided Design of Ion Sequestering Agents / B. P. Hay // Intern. Solvent Extraction Conf. (ISEC) : reports, Montreal, Canada, 15 19 sept. 2008. Montreal, 2008. P. 10111016.
9. Varnek, . From Databases to in Silico Design of Novel Metal Binders / A. Varnek // Intern. Solvent Extraction Conf. (ISEC) : reports, Montreal, Canada, 15 19 sept. 2008. Montreal, 2008. P. 10231028.
10. Harrington, E. C. The desirability function / E. C. Harrington // Industr. Quality Control. 1965. Vol. 21, 10. P. 494498.
11. , . . / . . , . . . . : , 1978. 319 .
12. , . . : 2 . / . . , . . . . 2. . : , 1970. 824 .
13. : 5 . / . . [ .]. . 4. . : . .., 2005. 752 ..
14. : 5 . / . . [ .]. . 1. . : . .., 1999. 524 .
15. : 5 . / . . [ .]. . 3. . : . ..,, 2004. 544 .
16. , . . / . . , . . // . . . 1995. . 69, 10. . 18911893.
-
, 2010, . 5, 3
62
541.128.13; 546.262.3-31
PdCl2CuCl2/Al2O3
.. , , .. , , *.. ,
, *.. , , **.. , , ***.. , , ***.., , ****.. ,
*
** , . ..
*** **** . ..
e-mai: [email protected]
(EXAFS/XANES), , () PdCl2CuCl2/Al2O3 . ,
Al2O3 Cu2Cl(OH)3 100300 . EXAFS, , PdCl. , , , .
The EXAFS/XANES, XRD, SEM methods were used for examination of freshly prepared low temperature carbon monoxide oxidation in air catalyst PdCl2-CuCl2/-Al2O3 active components states. The Cu2Cl(OH)3 phase with particle size 100-300 nm and tetrachloropalladat particles were identified on -Al2O3 surface. According to EXAFS data one of the palladium chloride bonds is longer then another ones. There is no direct interaction between palladium and copper, i.e. there is no common active center including palladium and copper on the -Al2O3 surface responsible on the low temperature carbon monoxide oxidation in air.
: , (II), (II), , , , - (II), XANES, EXAFS, .
Key words: catalyst, low temperature oxidation, carbon monoxide, palladium(II) chloride, copper(II) chloride, -aluminum oxide, trihydroxide-chloride copper(II), XANES, EXAFS, SEM.
(II) - : - , - . , , , (, ) (- ).
- . - - [1].
PdCl2CuCl2/Al2O3, , [2], - , . , - , - . CO2 , . [2] , Z(CO)(H2O)(O2) (Z - ). - - , - . - [3, 4], (II) -
-
, 2010, . 5, 3
63
(II) . - [5, 6], (II), (II) - . , . - [7]. - - [810]. (II) Al2O3 , 100, (II) , - (NiCl2, MnCl2), , - (II) [11]. - [9, 12, 13] ( , EXAFS/XANES) PdCl2CuCl2/ ( Al2O3). , - - Cu2Cl(OH)3 CuCl22H2O, Cu2Cl(OH)3 - . , +2 . [12] , - - . e [14] in situ PdCl2(CO), [Pd(CO)Cl]n Cu(CO)Cl, , - PdCl2CuCl2/Al2O3 , 2
- PdCl2CuCl2/Al2O3. - , - , - (EXAFS/XANES) ( ) ().
. 1 - Al2O3 ( 813685) 0.5 1 ( ,
, 219 3/)*. 1 - 2 3. 2 (CuCl2/Al2O3) 3 (PdCl2CuCl2/Al2O3) - 1 CuCl2 (CuCl22H2O, 416761) PdCl2 (PdCl2, 2625048002050672003) CuCl2, - [15]. 1.5% Pd, 3.5% Cu . CuCl2 , 2 3, .
1 3 . FujiFilm ImagingPlate; - FujiFilm BAS5000 100 . =0.46416 , 230 , 30 . - - Fit2D [16].
- ( XANES) ( EXAFS). - XANES/EXAFS 2 3, CuCl22H2O() PdCl2() , . Si(111), - , (Cu K) (Pd K). EXAFS IFEFFIT [17], FEFF [18]. - [19].
() - 7500 F JEOL ()
-
, 2010, . 5, 3
64
. .. . - . - Gentle Beam 1 2 (400 ).
1 3. , - , . 1. Al2O3 - .
. 1. 1 (, Al2O3), 2 (CuCl2/Al2O3) 3 (,
PdCl2CuCl2/Al2O3).
2 3, Al2O3 , - Cu2Cl(OH)3 . . R3m (. 1). 2 3 . - PdCl2CuCl2/ ( Al2O3) [9, 12].
- - 1 (, Al2O3), 2 (CuCl2/Al2O3) 3 (, PdCl2CuCl2/Al2O3) (. 2 4) - (. 1): , - Cu2Cl(OH)3 (. . R3m), 2
3, - 3.
. 2. 1 ( 20000).
. 3. 2 ( 25000).
. 4. 3 ( 20000).
3 (. 4)
, . Cu2Cl(OH)3 Al2O3. , - Cu2Cl(OH)3 PdCl2
-
, 2010, . 5, 3
65
3 - . , - (-, ) 2 (. 3) , , 3 (. 4) 10 - Al2O3.
XANES - , - . . 5 XANES K Pd .
. 5. XANES K Pd: PdCl2(), PdCl2 CuCl2,
3 (, PdCl2CuCl2/Al2O3).
1s5p . XANES, . 5, - . , Pd PdCl2(), PdCl2 ( CuCl2) Al2O3 . , +2 - .
. 6 XANES K Cu.
1s4p . - -
. E~8976 - 1s3d , p-d . - (II). 2 3 - -. (CuCl22H2O()) - - . CuCl2, - CuCl2, - - , - - .
. 6. XANES K Cu:
CuCl22H2O(), CuCl2, PdCl2 CuCl2, 2
(CuCl2/Al2O3), 3 (, PdCl2CuCl2/Al2O3).
2 3 EXAFS.
. 1 . 7 EXAFS Pd.
-
, 2010, . 5, 3
66
. 1. EXAFS K Pd: , N , R,
, 2, 2 -, Rf .
N R, 2, 2 Rf PdCl2 (.) PdCl
Pd...Pd PdCl Pd...Pd2
PdClPdCl
4 4 1 1 2
2.29 (2.302.31)) 3.28 (3.283.33)
3.37 (3.34) 3.72 (3.77)
4.57 (4.604.62)
0.0027 0.0146 0.0013 0.0040 0.0026
0.007
CuCl2+PdCl2 PdCl PdClPdCl
4 2
2.28 4.56
0.0022 0.0050
0.030
3 (PdCl2CuCl2/Al2O3)
PdCl1 PdCl2
3 1
2.26 2.36
0.0015 0.0015
0.019
) [20].
. 7. (), -
EXAFS Pd : PdCl2(), PdCl2
CuCl2, 3 (, PdCl2CuCl2/Al2O3).
PdCl2()
EXAFS PdCl2(), Pd6Cl12 , 2 (. 1), PdPd. Pd . , Pd...Pd - 3.3 .
PdCl2 CuCl2, , - [PdCl4]
2- (.
1). - - Pd...Cu .
( 3) - - , : EXAFS - PdCl (. 1). - 34 , , Pd...Pd Pd...Cu, PdAl, PdClAl - - .
. 8 . 2 EXAFS Cu.
. 8. , - EXAFS Cu
: CuCl22H2O(), CuCl2, PdCl2 CuCl2, 2 (CuCl2/Al2O3), 3
(, PdCl2CuCl2/Al2O3).
-
, 2010, . 5, 3
67
2. EXAFS K Cu: , N , R, , 2,
2 -, Rf .
N R, 2, 2 Rf CuCl22H2O CuO
CuCl CuCl
2 2 2
1.95 (1.94)) 2.27 (2.28) 2.86 (2.93)
0.0045 0.0035 0.0148
0.030
CuCl2 CuOeq CuOax
4 2
1.97 2.29
0.0043 0.0210
0.021
CuCl2+PdCl2 CuOeq CuOax
4 2
1.97 2.30
0.0044 0.0203
0.018
2 (CuCl2/Al2O3)
CuO1 CuO2 Cu...Cl
Cu...Cu1 Cu...Cu2
2 3 1
4 2
1.99 (1.98) 2.05 (2.11) 2.85 (2.79)
3.09 (3.06) 3.47 (3.41)
0.0026 0.0266 0.0065 0.0186 0.0093
0.016
3 (PdCl2CuCl2/Al2O3)
CuO1 CuO2 Cu...Cl
Cu...Cu1 Cu...Cu2
2 3 1 4 2
1.99 (1.98) 2.09 (2.11) 2.89 (2.79) 3.09 (3.06) 3.47 (3.41)
0.0028 0.0400 0.0072 0.0157 0.0116
0.016
) [21, 22].
EXAFS CuCl22H2O() - [21] (. 2). - 2 , . 2 Cu...Cl, - - - CuCl2O2.
CuCl2 ( ) - --, -, (II) [23, 24]), EXAFS 2 : (. 8 . 2). .
, , ( 3) (. 1), EXAFS (. 2) (. 4), Al2O3 Cu2Cl(OH)3 c . . R3m. - ( 3) - (. 1). , , . EXAFS
PdCl . , - Al2O3. EXAFS, .
XAFS , PdCl2CuCl2/Al2O3 . , - - -- CuCl22H2O() ( - ) - CuCl2 ( , ) - - CuCl -. , - ( ) - PdCl2(.) 3.
Al2O3 - Cu2Cl(OH)3 CuCl2 ( 2) PdCl2 ( 3). 75% Cl- Al2O3, , Cl- Pd (
-
, 2010, . 5, 3
68
EXAFS, K Pd ). Al2O3 CuCl2 2 3.
, (II) ,
. , [2], , CO, O2 . .
* ... .. -Al2O3.
: 1. , . . / . .
, . . , . . . .: , 1991. 40 . 2.
PdCl2*CuCl2/-Al2O3 / . . [ .] // . 2008. . 49, 5. . 2230. 3. Pat. 3790662 U.S., C01b 31/20, 17/68. Palladium compositions suitable as oxidation catalysts / W. G.
Lloyd, D. R. Rowe. 223970; filed 07.02.72; patented 05.02.74. 4. Low-temperature oxidation of CO by a heterogenized Wacker catalyst / M. N. Desai [et. al.] // J. of
catalysis. 1983. Vol. 79, 2. P. 95103. 5. (II) (II) / .
. [ .] // . 1984. . 25, 2. . 330. 6. .
/ . . [ .] // . 1985. . 25, 5. . 10291043.
7. Palladium-copper-DMF complexes involved in the oxidation alkenes / Takahiro Hosokawa [et. al.] // J. of Organometallic Chemistry. 1998. Vol. 551. P. 387389.
8. / . . [ .] // . 2007. . 2, 4. . 7277.
9. Effects of copper phase on CO oxidation over supported wacker-type catalysts / E. D. Park, J. S. Lee // J. of catalysis. 1998. Vol. 180. P. 123131.
10. Park, E. D. Effect of surface treatment of the support on CO oxidation over carbone-supported wacker-type catalysts / E. D. Park, J. S. Lee // J. of catalysis. 2000. Vol. 193. P. 515.
11. PdCl2*CuCl2/-Al2O3 / . . [ .] // : . III . ., , , 27 30 . 2009. , 2009. . 2. . 141142.
12. Supported PdCl2CuCl2 catalysts for carbon monoxide oxidation II. XAFS characterization / J. S. Lee [et. al.] // Applied catalysis B: environmental. 1996. Vol. 7. P. 199212.
13. Structure and electronic state of PdCl2CuCl2 catalysts supported on activated carbon / Yasushi Yamamoto [et. al.] // J. of catalysis. 1996. Vol. 161. P. 577586.
14. Choi, K. I. CO oxidation over Pd and Cu catalysts II. Unreduced bimetallic PdCl2CuCl2 dispersed on Al2O3 or carbon / K. I. Choi, M. A. Vannice // J. of catalysis. 1991. Vol. 127. P. 489511.
15. . 2267354 P, B 01 J 23/89, B 01 J 31/30, B 01 D 53/62. / . . [ .]. 2004126047/04 ; . 27.08.04 ; . 10.01.06, . 1.
16. Hammersley, A. P. FIT2D V9.129. Reference Manual. V3.1. ESRF Internal Report: ESRF98HA01T / A. P. Hammersley. 1998.
17. Ravel, B. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT / B. Ravel, M. Newville // J. synchrotron rad. 2005. Vol. 12. P. 537.
18. Real-space multiple-scattering calculation of XANES / A. L. Ankudinov [et. al] // Phys. rev. B. 1998. Vol. 58. P. 7565.
19. Structural Materials Science end-station at the Kurchatov Synchrotron Radiation Source: Recent instrumentation upgrades and experimental results / A. A. Chernyshov [et. al] // Nucl. instr. meth. phys. res. A. 2009. Vol. 603. P. 95.
20. Molecular structure of Pd6Cl12 on single crystals chemically grown at room temperature / D. B. Dell'Amico [et. al.] // Angew. chem. (int. ed. engl.). 1996. Vol. 35. P.13311333.
21. A redetermination of the crystal structure of cupric chloride dehydrate / S. Brownstein [et. al] // Z. kristallogr. 1989. Vol. 189. P. 1315.
22. The crystal structure of paratacamite / M.E. Fleet // Acta crystallogr. B. 1975. Vol. 31. P. 183187. 23. Ohtaki, H. Structure and Dynamics of Hydrated Ions / H. Ohtaki, T. Radnai // Chem. rev. 1993. Vol.
93. P. 11571204. 24. A computational and experimental study on the Jahn-Teller effect in the hydrated copper(II) ion.
Comparisons with hydrated nickel(II) ions in aqueous solution and solid Tutton's salts / B. Beagley [et. al.] // J. phys.: Condens. Matter. 1989. Vol. 1. P. 23952408.
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, 2010, . 5, 3
69
577.088.1
8--2- 2- -
*.. , , *.. , ,
.. , , .. , , .. , , *.. , ,
*.. , , **.. , . ..
* . .. **
e-mail: [email protected]
8--2-, , 2- - .
, , , .
The article presents an optimized method for the determination of the ratio of 8-oxo-2-deoxyguanosine (formed in DNA due to the action of active forms of oxygen) to 2-deoxyguanosine. The ratio was determined by reverse phase HPLC combined with amperometric detection. It was shown that the ratio increases upon oxidative stress caused by the action of large doses of ascorbic acid in samples of DNA isolated from the liver of experimental rats.
: 8--2-, , , - , .
Key words: 8-oxo-2-deoxyguanosine, oxidative stress, ascorbic acid, reverse phase HPLC, amperometric detection.
- , -. - 8--2- (8--7,8--2-) (8-oxo-dG), , , - , [1]. 8--dG . , 8--dG : , , - [2]. - / -, . - 8--dG .
8--dG - () () - (). - 8-oxo-dG 10-12
, , 10-9 10-12 3050 [3]. 8--dG - 5 2-- (dG), -, 8--dG .
- 8--dG dG - ( ) - , , .
-
, - . - - , - . - 8--dG - ().
-
, 2010, . 5, 3
70
, () - [4]. - - . - - -, , . , - . , - , , - - , -
. - - [57]. - - 8--dG , , .
(8--dG) - 2'- (dG) 20 , 20 - 2 FeSO4 37
, 3 (. 1) [8]. 8--dG - . - -- - (. 2, ).
N
NH
N
N
NH2
O
OOH
OH
N
NH
N
N
NH2
O
OOH
OH
OH
HN
NH
N
NH
NH2
O
OOH
OH
O
dG C8-OH-8-oxo-dG
O2
. 1. 8--dG.
[911], - 8--dG -110-18 (4.0250 ).
6% 0.1 ( 7.5); dG 8-oxo-dG 6.8 7.5 . , .
. 2. - () ESI-- () 8--dG.
8--dG - , 0.5 (0.142 )
+0.4 / 1 : 5. , 8--dG : dG 1 : 105,
-
, 2010, . 5, 3
71
8--dG - 2 ..
, dG 8-oxo-dG (. . ). - . dG (-): Q = 2.0021710-3A ( , ); - 2.996%; 0.998. 8-oxo-dG (- ): Q = 0.20075V ( V , ); - 0.994.
, - - . -, -
- , . , , . 0.75 - . - 12.4 , 8-oxo-dG (. 3); - - -, .. - -. . .
. 3. 8-oxo-dG . -110-18 (4.0250 ), 0.1 ( 7.5), 6 : 94, 0.8 /.
, +0.4 .
- - 8--dG , 8-oxo-dG/dG , , - . -, -. , - - [12]. Fe3+ , , - .
- 4.5 -
. , - (- , ), . , - , , , - - . : (6 ) (6 ). 20 /100 1 -
-
, 2010, . 5, 3
72
, . - . 8--dG - .
- , - 8-oxo-dG/dG
(. 4, . 1), .. , 8--dG . , 8--dG , -, - .
1. (20 /100 )
8--dG/dG .
S(8-
oxo-
dG),
A
8-
-dG
,
S(dG
),
dG,
(8-
-d
G/ d
G)
105
(8