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Novel carriers for dicarboxilic acids on the basis of α-aminophosphonates and calix[4]arenes. Ivan I.Stoikov, Igor S.Antipin, Alexander I.Konovalov. Source Phase. Membrane Phase. Receiving Phase. Membrane Transport. Substrate. Carrier. Substrate-Carrier Complex. - PowerPoint PPT Presentation
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MOLECULAR RECOGNITION 1
Novel carriers for dicarboxilic Novel carriers for dicarboxilic acids on the basis of α-acids on the basis of α-aminophosphonates and aminophosphonates and calix[4]arenescalix[4]arenes
Ivan I.Stoikov,
Igor S.Antipin,
Alexander I.Konovalov
MOLECULAR RECOGNITION 2
Source Phase Receiving PhaseMembrane Phase
Membrane Transport
Substrate Carrier Substrate-Carrier Complex
MOLECULAR RECOGNITION 3
NH HN
NH HN
HNNH
NH HN
NH
NH
NH
HN
HN
HN
OO
BrN
ON Bu
O
OBr
N
O
NBu
H
H
H
O
O
OH
O
HN
HN
HN
HN
HN
HN
O OO
OO
S S S
N
N
O
N
N
N
O
NH
H
H
H H
H
Co2+
Co2+
O O
OO
N N CH3
O
CH3
HH
O O
R
H
O O
NN
O
CH3
O
CH3
HO O
PF6-PF6-Co+ Co+
H H
N
NN R
H
R
H
RR
O O
R
Receptor for Organic Acids
MOLECULAR RECOGNITION 4
Dicarboxylic Acids α-Hydroxy Acids α-Amino Acids
H
OC
CO
O
H
O
H
OC
CO
O
H
HH
H
NC
O
CO
Hydroden Bonding & Electrostatic Interactions
H O
N PCR' OR
OR
HH
H
NC
O
CO
ORORR'
CPN
O
H
H
OC
CO
O
H
ORORR'
CPN
O
H
H
OC
CO
O
H
O
MOLECULAR RECOGNITION 5
Phosphorus Chemical Shifts and Yields of Phosphorus Chemical Shifts and Yields of ‑Aminophosphonates‑Aminophosphonates
R4O
R4OR1NH2
R2
R3
PO
HC O
OP
R4O
R4O
CR1NH
R2 R3
-H2О
N R1 R2 R3 R4 P, ppm. Yields (%)
1 CH2Ph -(CH2)5- С5Н11 29 75
2 CH2Ph -СН3 -СН3 С2Н5 32 83
3 СН(СН3)2 -СН3 -СН3 С2Н5 31 79
4 CH2Ph -(CH2)4- С5Н11 31 88
5 CH2Ph -СН3 -СН3 С5Н11 34 87
6 CH2Ph -(CH2)4- СН2СН(С2Н5)С4Н9 33 70
7 CH2Ph -(CH2)5- СН2СН(С2Н5)С4Н9 32 72
8 CH2Ph -СН3 -СН3 СН2СН(С2Н5)С4Н9 34 87
9 CH2Ph -СН3 -Н СН2СН(С2Н5)С4Н9 28 67
10 CH2Ph -Н -Н СН2СН(С2Н5)С4Н9 28 73
11 CH2Ph С4Н9 -Н СН2СН(С2Н5)С4Н9 28 62
12 CH2Ph СН3 СН3 С10Н21 30 90
13 CH2Ph -Н -Н С10Н21 30 57
14 CH2Ph -(CH2)5- c-C6H11 28 76
15 CH2Ph Н Н c-C6H11 28 78
MOLECULAR RECOGNITION 6
Cylinder with membrane
Termostated cell
Glass thermostated cell for membrane extraction: 1-external thermostated vessel with source phase; 2-internal vessel with receiving phase; 3-ring; 4-supported liquid membrane (SLM); 5-magnetic stir bars; 6-flow-through cell; D-detector.
Membrane Transport
MOLECULAR RECOGNITION 7
Initial Glycolic Acid Fluxes through a Supported Liquid Membrane Impregnated by carrier:
NH
XP OROR
O
C
C
C
C
C
H3CCCH3
H3CCCH3
HCCH3
HCH
HCC4H9
HCH
HCH
carrier X R J.106 , mol h-1 cm-2
no carrier - - 0.6
4 С5Н11 2.4
6 СН2СН(С2Н5)С4Н9 3.7
1 С5Н11 4.0
7 СН2СН(С2Н5)С4Н9 4.5
14 c-C6H11 3.6
8 СН2СН(С2Н5)С4Н9 7.2
12 С10Н21 9.6
9 СН2СН(С2Н5)С4Н9 11.0
10 СН2СН(С2Н5)С4Н9 13.5
11 СН2СН(С2Н5)С4Н9 24
15 c-C6H11 1.4
13 С10Н21 30
MOLECULAR RECOGNITION 8
H
R2
R1
C
RO P O
RO
NR3
H OO
C
R4
H
OCH
The Complex Structure of ‑Aminophosphonates with ‑Oxy Acid.
MOLECULAR RECOGNITION 9
1 2
3
OctO
OctOP
ONH OctO
OctOP
ONH
OctO
OctOP
ONH
OctO
OctOP
ONH CH
CH2OH
C2H5
OCH34
OctO
OctOP
ONH CH
CH2OH
C2H5
5
DecO
DecOP
ONH
C7H15
CHCH2OH
C2H5
6
DecO
DecOP
ONH
C9H19
CHCH2OH
C2H5
7
DecO
DecOP
ONH
CH2O
CHCH2OH
C2H5CHCH2
8
Carriers: α-Aminophosphonates 1-8. Substrates d,l-Glutamic
acid, lg P=-3.69, pKa=4.33
Sodium acetate,
lgP=-4.24
Tartaric acid,lgP=-1.95, pKa=2.89
Oxalic acid,lgP=-0.53, pKa=1.25
Glycolic acid,lgP=-1.11, pKa =3.83
Malonic acid,lgP=-0.58, pKa=1.38
Succinic acid,lgP=-0.59, pKa=4.21
d,l-Mandelic acid,
lgP=0.64, pKa=3.37
H3C C
O
ONa
C
O
OH
CH(OH)CH(OH)C
HO
O
C
HO
O
C
O
OH
H2C
HO
C
O
OH
C
HO
O
C
O
OH
CH2
C
O
OH
CH2CH2C
HO
O
CH
HO
C
O
OH
C
O
OH
CH2CH2CH
H3N
C
O
O
MOLECULAR RECOGNITION 10
Дополнительно...
Янв Фев Мар Апр Май Июн Июл Авг Сен Окт Ноя
Этап 1Этап 1
Этап 2Этап 2
Этап 3Этап 3
Дек
0
1000
2000
3000
4000
5000
6000
7000
1 2 3 4 5 6 7 8
Glutamicacid
Sodiumacetate
Tartaricacid
Oxalic acid
Glycolicacid
Malonicacid
Succinicacid
Mandelicacid
The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates 1-8.
OctO
OctOP
ONH CH
CH2OH
C2H5
OCH3
OctO
OctOP
ONH
4
3
ε
MOLECULAR RECOGNITION 11
0
100
200
300
400
500
600
700
800
900
1 2 3 4 5 6 7 8
Tartaricacid
Glycolicacid
Malonicacid
Succinicacid
Mandelicacid
The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates 1-8.
OctO
OctOP
ONH
2
ε
MOLECULAR RECOGNITION 12
The histogram of enhancement coefficients in the processes of membrane extraction by α-aminophosphonates 1-8.
0
50
100
150
200
250
1 2 3 4 5 6 7 8
Tartaric acid
Glycolic acid
Mandelic acid
OctO
OctOP
ONH
DecO
DecOP
ONH
C9H19
CHCH2OH
C2H5
1
7
OctO
OctOP
ONH CH
CH2OH
C2H5
OCH3
4
OctO
OctOP
ONH
3
ε
MOLECULAR RECOGNITION 13
0
10
20
30
40
50
60
70
80
90
100
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
6
7
8
C, mol/l
j∙10 7 , mol/(h∙sm2)
0
510
15
2025
30
35
4045
50
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
6
7
8
j ·107, mol/(h·sm2)
C, mol/l
Malonic acid
Succinic acid
02
46
81012
1416
1820
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
6
7
8
j ·107, mol/(h·sm2)
C, mol/l
0
1
2
3
4
5
6
7
8
9
10
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
6
7
8
j ∙107, mol/(h∙sm2)
C, mol/l
Glycolic acid
Tartaric acid
The Influences of Concentrations of Substrate in Source Phase on Initial Fluxes of Organic Acids through a SLM (298K).
MOLECULAR RECOGNITION 14
The Influences of Concentrations of Substrate in Source Phase on Initial Fluxes of Organic Acids through a SLM (298K).
0
20
40
60
80
100
120
0 0,1 0,2 0,3 0,4 0,5
6
7
8
j ·107, mol/(h·sm2)
C, mol/l
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
0 0,1 0,2 0,3 0,4 0,5
6
7
8
C, mol/l
j ·107, mol/(h·sm2)
Mandelic acid
Oxalic acid
MOLECULAR RECOGNITION 15
h
H H
OOO O
NH HNR R
RPP
R O OO
OOO
OOO O
R
PRO
O
HN
O
NHR
PR O
OO
O
O
N
P
HH3C
OH3C
PheDOPA
TyrHis
Trp
0
1
2
3
4
5
6
7
8
9
10
jх10-6
10
11 12
10 11 12
Calix[4]arenes
OO O OH HHH
MOLECULAR RECOGNITION 16
(13) R1=-t-Bu, R2=-CH2-Ph,
(14) R1=-t-Bu, R2=--CH2-naphtyl,
(15) R1=-t-Bu, R2=-9-CH2-Flu,
(16) R1=-t-Bu, R2=-trans-CH2-СH=CH-Ph,
(17) R1=-t-Bu, R2=-4-CH2-С6Н4-NO2,
(18) R1=-t-Bu, R2=-4-CH2-С6Н4-CN,
(19) R1=-t-Bu, R2=-4-CH2-С6Н4-COOEt,
(20) R1=-t-Bu, R2=-CH2-COOEt,
(21) R1=-NO2, R2=-CH2-Ph
(22) R1=-t-Bu, R2=4-CH2-Pyr
(23) R1=-t-Bu, R2=-CH2-CH2-NH-C(O)-С6Н5
R1
OO O O
R1
H R2HR2
O O
OH
HO
HH
O O
OH
HO
A
C
B
AC
B S
O O
OH
HO
A
C
B
AC
B
SAC
B
X
XH
MOLECULAR RECOGNITION 17
ε
13 14 15 16 17 18 19 20 21 22 23
Glutamic acid
Sodium acetate
Tartaric acid
Oxalic acid
Glycolic acid
Malonic acid
Succinic acid
Mandelic acid
0
50
100
150
200
250
300Glutamic acid
Sodium acetate
Tartaric acid
Oxalic acid
Glycolic acid
Malonic acid
Succinic acid
Mandelic acid
ε
The histogram of enhancement coefficients in the processes of membrane extraction by calix[4]arenes 13-23
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