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