44

-

................................................................................................. 1

................................................................................................. 1

................................................................................................. 2

.......................................................................................... 2

........................................................................................................................ 4

1 . ..................................................................................................... 4

2 . .................................................................................................... 4

3 . ........................................................................................................... 5

4. 5A ........................... 6

5. ................................. 15

.................................................................................................................. 23

.............................................................................. 24

.................................................................................................. 25

- 1 -

.

.

,

.

(, , ,

) ,

, ,

.

? .

. 5A

.

1.

2. 5A (Ag+, Cu2+, Zn2+, Fe3+)

1)

2)

3)

4) - , ,

5) SEM,TEM

3. (,, )

1) LB media 2ml -

E.coli(, )

1416 (600nm) OD

2) -

disk (1)

Nutrient agar petri dish E.coli disk

(1)

3)

- 2 -

.

1996 . 12 . 31

1997 . 1 . 1 1998 . 3 . 31 1998 . 4 . 1 1998 . 4 . 30 data 1998 . 5 . 1 1998 . 5 . 20 1998 . 5 . 21 1998 . 6 . 1 1998 . 6 . 2 1998 . 6 . 7 1998 . 6 . 8 1998 . 6 . 10 1998 . 8 . 15 1998 . 8 . 23 44

. (zeolite) 1756 Baron Von Cronsted

aluminosilicate ,

. "Zeo(

) litos() zeolite(boiling stone)

. Molecular Sieve()

. .

, 40

Clinoptilolite, Mordenite, Heulandite, Chabazite, Phillipsite,

Faujasite and Analcime . Clinoptilolite

, , , ,

, , , , .

clinoptilolite ,

, ,

.

2

.

1945 union carbide Milton Linde A A

X Y

120 .

, cracking, , ,

, ,

, , ,

.

- 3 -

, .

M2/nO.Al2O3.xSiO2.yH2O (M: )

TO4 4, 5, 6, 8, 12 4, 5, 6,

8, 12 ring 24 TO4 sodalite cage

.

.

Si4+ Al3+ (isomorphous substitution)

Al

.

(cation site) .

.

Fig1. 5A A

Fig. 1 5A sodalite cage D4R

4.1 8 ring .

,

. OH

. Activity

.

metal hole

. hole M(OH)n

M-O-(M-O)n- hole

.

.

- 4 -

.

.

,

,

. (Borja, R 1994)

. (Wistreich GA 1968, 1972)

.

- .

.

1.

1)

(1)

Ag+, Cu2+, Zn2+, Fe3+

(2)

[Ag(py)2]+, [Ag(NH3)2]SO4, [Cu(NH3)4](NO3)2

2)

Spectrophotometer(ultrospec )

Atomic Absorption Spectrophotometer(SHIMADZU AA-600)

. .

(furnace)

SEM, TEM,

( )

2.

(1) 4A

Al(OH)3 + NaSiO35H2O + Ca2+ Ca2+(SiAl)O4

- 5 -

(2) 5A

4A

H2O 1015wt%

1% H2SO4 pH pH = 5

CaCl2 20wt% 70, 4

(zeolite 3)

cake 120, 8 600650, 4

5A

3.

(1) [Ag(py)2]+

AgNO3 17g 70ml , 50ml

.

.

.(

)

.

(NaClO4 H2O : 140.46) 18g( 1H2O

21g) 20ml .

10 .

30ml 6

.

( ) .

(2) [Ag(NH3)2]SO4

AgNO3 17g .

1M H2SO4 50ml Ag2SO4() .

Sand bath NO2

.

- 6 -

.

[Ag(NH3)2]SO4 .

5% .

(3) [Cu(NH3)4](NO3)2

Cu(NO3)2

.

.

[Cu(NH3)4](NO3)2 .

.

4. 5A

1) (Ag+, Cu2+, Zn2+, Fe3+)

(1) Ag+

5A 6g .

45.02 PPM AgNO3 20ml .

30, 60, 90, 180, 240, 300 70

.

10ml AA

Ag+ .

Table 3. Ag+

( : 6g, : 70, : 45.02 PPM)

() (PPM) (%) 45.02 0.0030 23.52 48.8760 18.34 59.2690 13.14 70.81180 0.715 98.41 240 0.272 99.40300 0.113 99.75

(2) Cu2+

5A 6g .

18.43 PPM CuSO4 20ml .

- 7 -

30, 60, 90, 180, 240, 300 70

.

10ml AA .

Table 4. Cu2+

( : 6g, : 70, : 18.43 PPM)

() (PPM) (%) 18.43 0.0030 13.34 27.6260 10.17 44.8290 10.05 45.47180 0.059 99.67 240 0.053 99.73300 0.060 99.67

(3) Zn2+

5A 6g .

13.87M Zn(NO3)2 20ml .

30, 60, 90, 180, 240, 300 70

.

10ml AA Zn2+

.

Table 5. Zn2+

( : 6g, : 70, : 13.87 PPM)

() (PPM) (%) 13.87 0.0030 7.628 45.0060 7.515 45.8290 7.344 47.05180 7.148 48.46240 4.733 65.88 300 4.733 65.88

(4) Fe3+ ( )

5A 6g .

0.01M Fe(NO3)3 20ml .

30, 60, 90, 180, 240, 300 70

- 8 -

0

20

40

60

80

100

0 30 60 90 180 240 300

()

(%)

.

10ml AA

.

Table 6. Fe3+

() (PPM) 30 47.2960 1.882 90 0.851 180 0.488 , 240 0.402 300 0.335

(5)

Fig2. ( 6g, 70)

4

. Ag+> Cu2+> Zn2+ .

Fe3+

. Ag+> Cu2+> Zn2+>Fe3+

.

.

- 9 -

2) (Ag+, Cu2+, Zn2+, Fe3+)

(1) 5A Ag+

.

45.02 PPM AgNO3 20ml .

70 4 .

10ml 0.1M NaCl

10ml .

AA Ag+ .

Table 7. Ag+ (

: 4, : 70, : 45.02 PPM)

5A

(g)(PPM) (%)

45.02 0.00

1.2 23.65 47.47

3.2 14.99 66.70

4.4 0.921 97.96

5.6 0.441 99.02

6.8 0.331 99.27

8.0 0.241 99.47

(2) Cu2+ ()

5A

.

18.43 PPM CuSO4 20ml .

70 4 .

10ml AA .

- 10 -

Table 8. Cu2+ ( :

4, : 70, : 18.43 PPM)

5A

(g)(PPM) (%)

18.43 0.00

4.8 0.248 98.64

5.6 0.148 99.17

6.8 0.080 99.57

8.0 0.075 99.62

10.0 0.070 99.63

12.0 0.047 99.74

(3) Zn2+

.

13.87 PPM Zn(NO3)2 20ml .

70 4 .

10ml AA

Zn2+ .

Table 9. Zn2+

5A

(g)(PPM) (%)

13.87 0.00

6.0 4.733 65.88

8.0 3.969 71.38

10.0 3.204 76.90

12.0 3.093 77.70

14.0 2.699 80.54

16.0 3.009 78.30

(4) Fe3+ ()

.

0.01M Fe(NO3)3 20ml .

70 4 .

10ml AA .

- 11 -

0

20

40

60

80

100

0 3.2 4.8 6 8 12

zeolite (g)

(%)

Table 10. Fe3+

5A

(g)(PPM)

15.0 0.339

18.0 0.217

21.0 0.199

24.0 0.192

27.0 0.098

30.0 0.068

(5) (Ag+, Cu2+, Zn2+, Fe3+)

Fig 3. (Ag+, Cu2+, Zn2+, Fe3+)

( : 4, : 70)

Fig 3 Ag+> Cu2+> Zn2+

Ag+, Cu2+, Zn2+ 10g, 16g, 24g, 36g

.

3) (Ag+, Cu2+, Zn2+, Fe3+)

(1) Ag+

5A 6g .

45.02 PPM AgNO3 20ml .

30, 50, 60, 70, 80

4 .

10ml AA Ag+

- 12 -

Table 11. Ag+

() (PPM) (%) 45.02 0.0030 1.926 95.7250 0.172 98.0660 0.138 99.69 70 0.095 99.7980 0.091 99.80

(2) Cu2+ ()

5A 6g .

18.43 PPM CuSO4 20ml .

30, 50, 60, 70, 80

4 .

10ml AA .

Table 12. Cu2+

() (PPM) (%) 18.43 0.0030 0.404 92.7750 0.229 93.6760 0.178 93.94 70 0.173 93.9680 0.126 94.20

(3) Zn2+

5A 6g .

10.96 PPM Zn(NO3)2 20ml .

30, 50, 60, 70, 80

4 .

10ml AA Zn2+

.

Table 13. Zn2+

- 13 -

0

20

40

60

80

100

0 30 50 60 70 80

(%)

() (PPM) (%) 18.37 0.0030 6.831 62.8150 6.729 63.3760 5.982 67.4470 4.733 74.24 80 4.320 76.78

(4) Fe3+ ()

5A 6g .

0.01M Fe(NO3)3 20ml .

30, 50, 60, 70, 80

4 .

10ml AA .

Table 14. Fe3+

() (%) 30 17.9650 1.17360 0.47670 0.27280 0.270

(5) (Ag+, Cu2+, Zn2+, Fe3+)

Fig 4. (Ag+, Cu2+, Zn2+, Fe3+)

Fig 4 Ag+, Cu2+, Zn2+ 6

070 . 70

.

- 14 -

6

4) 5A

5A

(H2O) 6080,4,()

23 1% H2SO4

pH=5, 70, 4(, )

( 23 3)

120, 8

600650, 4

-

5) SEM

5.1. SEM

Fig 5. Ag+ SEM Fig 6. Cu(NH3)42+ SEM

- 15 -

Fig7. Ag(NH3)42+ TEM Fig8. Cu(NH3)4

2+ TEM

5.

( : , , , )

1) LB media

(1) LB media

NaCl 10g

Trypton 10g 1L .

Yerst extract 5g

(2) LB media 2ml cap

.

(3) cap - 1g

, 37 1416 .

, , .

(- cap

.)

(4) Spectrophotometer 600nm OD

.

(OD 600nm )

- 16 -

88.17 85.61

63.72

50.68 47.51 45.27

2.890

20

40

60

80

100

1 2 3 4 5 6 7

Zeolite (4 , Zn )

%

1

Table 15. -

(- 1g)

- OD()

OD

1 2 3

1 AgNO3 4 0.154 0.349 0.258 0.254 88.17%

2 [Ag(NH3)2]+ 4 0.213 0.408 0.306 0.309 85.61%

3 [Ag(py)2]+ 4 0.931 0.692 0.714 0.779 63.72%

4 [Cu(NH3)4]2+ 4 0.950 1.179 1.049 1.059 50.68%

5 CuSO4 4 0.957 1.198 1.225 1.127 47.51%

6 Zn(NO3)2 1.177 1.188 1.161 1.175 45.27%

7 Fe(NO3)3 4 2.109 1.873 2.272 2.085 2.89%

8 Control 2.149 2.168 2.124 2.147

Fig 9. -

(- 1g)

: 1. AgNO3 2. [Ag(NH3)2]+ 3. [Ag(py)2]

+ 4. [Cu(NH3)4]2+

5. CuSO4 6. Zn(NO3)2 7. Fe(NO3)3

Table 15 Fig 9 Ag Cu, Zn Fe

. .

-Ag or Ag AgNO3> AgNO3 2

> AgNO3 4 , AgNO3> [Ag(NH3)2]+ -

.

Zn(NO3)2

.

- 17 -

69.25 68.14

48.554.08 50.95

20.33

00

20

40

60

80

1 2 3 4 5 6 7

zeolite (4 , Zn)

%

1

Table 16.

( 1g)

or-

OD()

OD

1 2 3

1 AgNO3 4 0.579 0.644 0.778 0.667 69.25%

2 [Ag(NH3)2]+ 4 0.618 0.741 0.714 0.691 68.14%

3 [Ag(py)2]+ 4 1.139 1.291 0.920 1.117 48.50%

4 [Cu(NH3)4]2+ 4 0.963 1.107 0.917 0.996 54.08%

5 CuSO4 4 1.125 1.102 0.966 1.064 50.95%

6 Zn(NO3)2 1.726 1.735 1.723 1.728 20.33%

7 Fe(NO3)3 4 2.103 2.421 2.266 2.263 0.00%

8 Control 2.174 2.128 2.205 2.169

Fig 10. -

: 1. AgNO3 2. [Ag(NH3)2]+ 3. [Ag(py)2]

+ 4. [Cu(NH3)4]2+

5. CuSO4 6. Zn(NO3)2 7. Fe(NO3)3

Table 16 Fig 10 AgNO3

[Ag(NH3)2]+, [Ag(py)2]

+, [Cu(NH3)4]2+ CuSO4 .

Zn(NO3)2 Fe(NO3)3

.

.

- 18 -

67.67 67.54 67.54

54.9349.18 49.49

4.33

0

20

40

60

80

1 2 3 4 5 6 7

Zeolite (4 , Zn)

%

1

Table 17. -

(- 1g)

or-

OD()

OD

1 2 3

1 AgNO3 4 0.637 0.763 0.793 0.731 67.67%

2 [Ag(NH3)2]+ 4 0.797 0.715 0.690 0.734 67.54%

3 [Ag(py)2]+ 4 0.758 0.744 0.701 0.734 67.54%

4 [Cu(NH3)4]2+ 4 0.928 1.007 1.122 1.019 54.93%

5 CuSO4 4 1.215 1.082 1.150 1.149 49.18%

6 Zn(NO3)2 1.197 1.128 1.101 1.142 49.49%

7 Fe(NO3)3 4 2.134 2.323 2.031 2.163 4.33%

8 Control 2.297 2.178 2.308 2.261

Fig 11. () -

: 1. AgNO3 2. [Ag(NH3)2]+ 3. [Ag(py)2]

+ 4. [Cu(NH3)4]2+

5. CuSO4 6. Zn(NO3)2 7. Fe(NO3)3

Table 17 Fig 11

.

- 19 -

2) Agar plate

(1) -

(2) disk 2 , 1ml

. 35 .

(3) - 1g

1 disk .

(4) - disk

3 .

(5) Nutrient agar

Beef extract 3g

Peptone 5g 1L

Agar. 15g .

(6) Nutrient agar 65 petri dish

. Nutrient agar

. (petri dish

. 3.2.7 3.2.8 )

(7) (E. coli) 3.2.6 petri

dish Nutrient agar .

(8) petri dish 3.2.4 disk 45

.

(9)

.

- 20 -

Fig 12. petri dish -

disk

Table 18. -

(+ )

-

-

0.01g 0.1g

1 AgNO3 4 +++ ++++

2 AgNO3 2 ++ +++

3 AgNO3 + +++

4 [Ag(NH3)2]+ 4 ++ +++

5 [Ag(NH3)2]+ ++ +++

6 [Ag(py)2]+ 4 ++ +++

7 [Ag(py)2]+ ++ +++

8 [Cu(NH3)4]2+ 4 ++

9 [Cu(NH3)4]2+ +

10 CuSO4 4 +

11 CuSO4 +

- 21 -

Table 18

- .

Table 19. -

- ( 0.1g)

-

1 AgNO3 4 ++++

2 AgNO3 2 +++

3 AgNO3 +++

4 [Ag(NH3)2]+ 4 +++

5 [Ag(NH3)2]+ +++

6 [Ag(py)2]+ 4 +++

7 [Ag(py)2]+ +++

8 [Cu(NH3)4]2+ 4 ++

9 [Cu(NH3)4]2+ ++

10 CuSO4 4 ++

11 CuSO4 ++

12 Zn(NO3)4 ++

13 Zn(NO3)4 4 ++

14 Fe(NO3)3 4 +

15 Fe(NO3)3 +

, , ,

, , ,

- 22 -

Table 20. -

-(0.1g)

-

1 AgNO3 4 ++++

2 AgNO3 2 +++

3 AgNO3 +++

4 [Ag(NH3)2]+ 4 +++

5 [Ag(NH3)2]+ +++

6 [Ag(py)2]+ 4 +++

7 [Ag(py)2]+ +++

8 [Cu(NH3)4]2+ 4 ++

9 [Cu(NH3)4]2+ ++

10 CuSO4 4 ++

11 CuSO4 ++

12 Zn(NO3)4 ++

13 Zn(NO3)4 4 ++

14 Fe(NO3)3 4

15 Fe(NO3)3

, ,

.

3)

(1)

(2)

(3)

(4)

- 23 -

. 1. 5A

(1) (Ag+, Cu2+, Zn2+, Fe3+)

4 Ag+> Cu2+>Zn2+

>Fe3+ .

.

(2) (Ag+, Cu2+, Zn2+, Fe3+)

Ag+, Cu2+, Zn2+, Fe3+

8g, 16g, 24g, 36g.

(3) (Ag+, Cu2+, Zn2+, Fe3+)

Ag+, Cu2+, Zn2+ 6070

.

(4) SEM TEM

SEM .

TEM .

2.

(1) LB media

AgNO3, [Ag(NH3)2]+, [Ag(py)2]

+, [Cu(NH3)4]2+, CuSO4, Zn(NO3)2,

Fe(NO3)3 - 4

.

- (4),

, -

OD .

.

Zn(NO3)2

.

OD 600nm .

Ag+ > Cu2+ > Zn2+ > Fe3+. Ag+

, Cu2+ , Fe3+

.

- 24 -

(2) Agar plate

Ag+ > Cu2+ > Zn2+ > Fe3+. Ag+

, Cu2+ , Fe3+

.

(3)

Ag+ > Cu2+ > Zn2+ > Fe3+. Ag+

, Cu2+ , Fe3+

.

- , ,

.

. Gruzina TG (1997)

ATPase

ATPase . Brynhil

-dsen L & Rosswall T (1989)

,

.

Ag

Ag coating (Stickler DJ , 1996; Ahearn

DJ , 1995). Ag

.

. 1. -

.

2.

.

3.

.

- 25 -

.

1. ,,. 1996.

. 18(5) : 587-602.

2. ,. 1995.

. 9 : 159-167.

3. ,,,. 1996.

. (KOR) 7(1) : 43-50.

4. ,. 1995. A .

(KOR) 5(7) : 897-902.

5. ,. 1993.

. (KOR) 15(6) : 743-753.

6. ,, 1993. .

(KOR) 26(6) : 285-290.

7. ,,. 1993. .

(KOR) 26(6) : 334-340.

8. ,. 1992.

(). (KOR) 15(2) : 6-37.

1992.

(). (KOR) 16(1) :

9. ,,,,. 1993.

. (KOR) 30(3) : 183-189.

10. . 1981. .

3 : 23-32.

11. . 8( ). . 1977.

12. . 1994. -Na2Si2O5

. .

13. f.a.cotton, g.wilkinson. basic inorganic chemistry. 1983.

14. geoffrey pass, haydn sutcliffe. Experimental Inorganic Chemistry chapman

and hall. 1983.

15. Westreich,G.A., Lechtman,M.D., Baker,R.F. and Bartholomew,J.W. 1972.

Distruption of chemically killed bacterial cells by a synthetic zeolite.

Appl. Microbiol. 23(1): 155-157.

16. Gruzina,T.G.,Balakina,M.N., Karamushka,V.I., Stepura,L.G. and Ul'berg,Z.R.

1997. Bacterial cell membrane ATPase in assessing heavy metal

toxicity. Mikrobiologiia 66(1):14-18.

- 26 -

17. Cohen,I., Bitan,R. and Nitzan,Y. 1991. The effect of zinc and cadmium ions

on Escherichia coli B.. Microbios. 68 (276-277): 157-168.

18. Brynhildsen,L. and Rosswall,T. 1989. Effects of cadmium, copper, magnesiu

-m and zinc on the decomposition of citrate by a Klebsiella sp.

Appl. Environ. Microbiol. 55 (6): 1375-1379.

19. Stickler,D.J., Morris,N.S. and Williams,T.J. 1996. An assessment of the

ability of a silver-releasing device to prevent bacterial contamination of

urethral catheter drainage systems. Br, J. Urol. 78(4): 579-588.

20. Ahearn,D.G., May,L.L. and Gabriel,M.M. 1995. Adherence of organisms to

silver-coated surfaces. J. Ind. Microbiol. 15(4): 372-376.

21. Deshpande,L.M. and Chopade,B.A. 1994. Plasmid mediated silver resistance

in Acinetobacter baumannii. Biometals 7(1): 49-56.

22. Gabriel,M.M., Sawant,A.D., Simmons,R.B. and Ahearn,D.G. 1995. Effects of

silver on adherence of bacteria to urinary catheters: in vitro studies.

Curr. Microbiol. 30 (1): 17-22.

23. Borja,R. and Banks,C.J. 1994. Kinetics of anaerobic digestion of soft drink

wastewater in immobilized cell bioreactor. J. Chem. Technol. Biotechnol.

60(3): 327-334.