2011_leivo_gelation and gel properties of two- and three-component pyrene based low molecular weight...

8/13/2019 2011_Leivo_Gelation and Gel Properties of Two- And Three-component Pyrene Based Low Molecular Weight Organ

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th

ISBN 978-951-39-4232-8(PDF)

URN:ISBN:978-951-39-4232-8


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(nid.), 978-951-39-4232-8 (PDF)


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6 6

4

3

N,N


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C


10/138


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Gels

Organo Hydro Aero/Xero

Medium

Natural Artificial

Source

Constitution

Supramolecular Macromolecular

Physical Chemical

Crosslinking


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24 28 36

n

n

COOH

OH

CH3(CH2)11(CF2)9CF31

2

3 OH

OH OH

OH

OiPriPrO

O O

6

4

n


15/138

N

OR

OHOH

OH OHO

H

5 R = H

6 R =

O

O

OH

HOHO

OH

O

7

O

OH

O

HO

O

OCH3

O

OH

O

HO

O

OCH3

O2N

8 9

O

O10

O

HO

HO

OH


16/138

4

D

O

O

O

O

O

N

HO

O

OSi

O

OAc

OH

HHO OH

OH

O

NH

C7H15

H

11

12

13 14


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N

4

15

(CF2)6CF3NH

OHN

NH

C

C

C11H23

C11H23

O

O

HO

O

O

O

C10H20

C10H20

CO

CO

NH C10H21

NH C10H21

16 17

16


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L

18

COOH

HN

(CH2)10CH3

O

HN

NH

O

O

HH

H CH(CH3)2

O N

N

N

O

O

O

O

H

Hb

Ha

C15H31 NH

HN

OH

O CH2Ph

O CHMe2

O

20

21 22

HO

HN

NH

OH

OH

O

O

OR H

R H

19 R = CH2CH(CH3)2 (S,S)


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4

W

4

1

23 R = n-C6H1324 R = n-C14H29

O

R

NH

NH2

O

H3C(H2C)11NH

NH

NH

O O

NH

(CH2)11CH3

7

25

NH

NH

O

NH

O

HN

N

NH

HN

HN

NH

NH

(CH2)7CH3

(CH2)7CH3

NH

(CH2)7CH3

O

O O

2627


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p

n

n

28

NN

O

OO

O OC12H25

OC12H25

OC12H25

O

O

O

O

O

H25

C12

H25C12

H25C12

OC10H21

OC10H21

OH

RO

OR

OR

RO

HO

OR

RO

N

N

N

N

N

N

Ar

Ar

Ar

Ar

Ar

Ar

30Ar =

NH

HN

N

29 R = C16H33

31

p


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32

O

Cu

O

O

O

OC9H19

OC9H19

OC9H19

OC9H19C9H19O

C9H19O

C9H19O

C9H19O

N

N

N

N

Zn

HO

O

O

C16H33O

O

OC16H33C16H33O

O

Pt

N

N

O

OHN

O

R

NH

O

R 36 R = H

N

O

OC12H25

OC12H25

OC12H25

33

Fe O P C12H25

O

CH3 3

Al O P C12H25

O

CH3 3

34

35


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37

NH

NH

O

O

O

C12H25

C12H25

N

N

H2N

NH2

C16H33

NH2

38

O

OS

O

O

Cl OH

39 40

O

O

O

Na

NH

O COOH

HN

O

O

NH

O

O

NH

O

NH

O

O

HN

O

O

H2N NH210

41

42

43

N

N N

N

NH

Chol

O

Zn

HN

O

p

n


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L

1

p


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C


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Z

O

O

O

OH

O

OMe

X

n

Y

O

O

O

NO2

NO2O2N

TNF 53

X n

NHCO 16 44NHCO 10 45NHCO 6 46NHCOO 15 47NHCOO 11 48NHCOO 9 49NHCONH 15 50

Y = NH (R)-51Y = NH (S)-52

X nCOO 15 54COO 7 55CH2 14 56CH2 10 57CH2 0 58O 13 59CONH 15 60OCO 14 61

Y = -- (R)-62Y = -- (S)-63

Z = -- 64Z = NH 65


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NH

O

NH

CO2Me O

66

HN

NH

C12H25

O

N

H

C12H25O

O

67

S NH

NH

O

O

O

OH

OH

OH

OH

OH

68


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NH

R

O R

OC11H23

OC11H23

O

O

R =

NH

O

NHO

R

R

HN

O

R

R

HN

R

O R

H2N

NHO

R

R

HN

O

R

R

69

71

70

72

C


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Y

XY

X

NH

O

OC16H33

OC16H33

OC16H33

73 Y = H

74 Y = X

X =

6


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32/138

gs

gs

gs

sg

gs

gs


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!"#$%#&'(&)"#

*%+!,"+&'(#,)&)"#&%./%'(&0'%

1"+

*%+

2('&)(+ 3%+

.3$$3$

gs

g

c


34/138

ln c= HmRTg

+ constant,

Hm

ln c= Hm

R

1

Tg

1

Tm

,

m Hm

Hm Sm

ln c= HmRTg

+Sm

R .


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= F

A

1

=

v

h

=


38/138

/

= G,

=x

h

(t) =osin(t)

(t) =osin(t+),

o o


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(t) = G

osin(t) + G

ocos(t),

G = oo

cos

G = oo

sin

G

G =tan

LV E


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sg

gs

n

n

gs

C

1

sg

C

1


42/138


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2

4

1

13


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10m

m I 5II 8

III 10IV 11 V 14VI 16

VII 22

nX

n XVIII 2 COOH IX 10 COOH X 10 COOMe XI 10 CONHNH2

p

Y

Z

p Y ZXII 15 OH CH3XIII 10 H OHXIV 10 OH OH

XV

O

NO2

NO2

O2N

TNF

O

NO2

NO2

O2N

TeNF

O2N N2O

N2O

TNB

NO2


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Cl

O

pyrene + TiCl4 < 5 oC

O

8 8

1) 190-200 oC, 12h

2) 220 oC

KOH + NH2NH2H2O

OH

O

reflux 3-4h

SOCl2

1


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a

3 6 6

1

1

C


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1


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Ecoh V

=

EcohV

=

Hvap RTV

Ecoh

Ed Ep Eh

Ecoh=Ed+Ep+Eh

tot

d p h

2tot = 2d+

2p+

2h

v a

v =

2d+2

p

a =

2p+ 2h

tot


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1/2

tot d p h

tot d

p h

2


51/138

2

p

p h

i i i i

d

p

h


52/138

1/2

tot d p h

T T

T

T

T 1

1

T


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T tot

d

p

h

T

tot d p

h

1

1

C

T 1

tot

d p h

1/2

a


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T

h a

T h a a

1

1/2

1/2

1/2

Ra=

(d2 d1)2 + (p2 p1)2 + (h2 h1)2

a

a

a

a 1/2

Ra Ra


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a

a

a 1/2

a a a

T

T

T

T


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0 5 10 15 20 25 300

5

10

15

20

25

30

35

40

45

Ra

(II)

Dielectricconstant!

16 18 20 22 24 260

5

10

15

20

25

30

35

40

45

Ra

(TNF)

dielectric

constant!

6 8 10 12 14 16 18 20 22 24 260

5

10

15

20

25

30

35

40

45

Ra

(complex)

dielectric

constant!

0 5 10 15 20 25 3030

35

40

45

50

55

60

Ra

(II)

ET

16 18 20 22 24 2630

35

40

45

50

55

60

Ra

(TNF)

ET

6 8 10 12 14 16 18 20 22 24 2630

35

40

45

50

55

60

Ra

(complex)

ET

T


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d

p h

h

a

p

T a

h 1/2

a

h

p

T 1

p h

p h

1/2

T h a

a

1


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0 5 10 15 20 25 3015

15.5

16

16.5

17

17.5

18

18.5

19

Ra

(II)

!d

ofthe

solvent

0 5 10 15 20 25 300

2

4

6

8

10

12

14

Ra

(II)

!p

ofthe

solvent

0 5 10 15 20 25 300

5

10

15

20

25

Ra

(II)

!h

ofthe

solvent

16 18 20 22 24 2615

15.5

16

16.5

17

17.5

18

18.5

19

Ra

(TNF)

!d

ofthe

solvent

16 18 20 22 24 260

2

4

6

8

10

12

14

Ra

(TNF)

!p

ofthe

solvent

16 18 20 22 24 260

5

10

15

20

25

Ra

(TNF)

!h

ofthe

solvent


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6 8 10 12 14 16 18 20 22 24 260

5

10

15

20

25

Ra

(complex)

!h

ofthe

solvent

h

a 1/2

1/2 a

1/2

1/2 a

1/2

a

a

C

1


60/138

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61/138


62/138

1/2

1

1

C


63/138

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C

1

1

24

1

C

C

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2011_leivo_gelation and gel properties of two- and three-component pyrene based low molecular weight...

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