Biological Activities of Polymers - American Chemical Society

5 Poly(thiosemicarbazide) Copper(II) Complexes as Potential Algicides and Molluscicides L. G. DONARUMA Polytechnic Institute of New York, Brooklyn, NY 11201

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S. KITOH The Lion Company, Ltd., Odawara-Shi, Kanagawa-Ken, Japan J. V. DEPINTO, J. K. EDZWALD, and M. J. MASLYN Clarkson College of Technology, Department of Civil and Environmental Engineering, Potsdam, NY 13676 Polymeric poly (thiosemicarbazide) copper (II) complexes have been made and are being evaluated as algicides and molluscicides. This endeavor showed considerable promise i n the laboratory and slow release data for copper (II) indicate that reusable cartridge type copper (II) systems for schistosomaisis and algae control may be feasible. A number of poly (thiosemicarbazides) have been prepared which complex copper (II) so strongly that mineral acids and even ethylenediamine tetraacetic acid do not effectively remove the copper ion from the polymers (see Scheme 1)A. However, in water, i n i t i a l studies indicated that over longer periods of time, copper (II) ions were released i n such fashion that the polymers might be useful for the slow release of copper (II) to provide algae or schistosomiasis control agents (see T&ble 1) i n natural waters. The effect of algae polluting natural waters i s a common sight which we a l l are familiar with. Schistosomiasis i s a serious, often f a t a l , disease which attacks humans where aquatic snails are the disease carrier—. Such snails l i v e i n irrigation ditches, streams, swamps, and other natural waters i n the warmer climates. The disease carrying snails can be k i l l e d by adding copper (II) to their aquatic habitat, and the classic source of the needed copper (II) i s cupric sulfate. However, in this case and for algae the salt rapidly migrates away i n moving waters or i s exchanged into the surrounding s o i l being very rapidly lost. Thus, frequent additions are required to provide effectiveness. One way tried to retard loss of copper (II) has been to m i l l copper sulfate into rubber pellets from which water slowly leaches out copper (II) to provide the needed ions to k i l l snails. However, i n natural waters these pellets float away or sink into the channel s o i l . Of course, any ion exchange resin could provide a substrate to hold copper (II) so that natural water soluble salts would ex-

0097-6156/82/0186-0055$5.00/0 © 1982 American Chemical Society Carraher and Gebelein; Biological Activities of Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

BIOLOGICAL ACTIVITIES OF POLYMERS

=C = N R N =

C=

S

H Nt/

+

\NH

2

•N-R-N-C-NN H H || H

2

Cu(II)

NN-C / H ||

S

S

S

J


I-V N—N -N-R-NC'

N—N V u-'

\

P

>-|

C

l d l , i

rtduct"

Cu(I) complex Ib-Vb

/ S

Ia-Va

S

CH

R•

III,

3

[O C0 Et 2

iv,

r

.JO} C02Ci6H 3-/» 3

V,

Scheme 1.

R •

Preparation of poly(thiosemicarbazides).

Carraher and Gebelein; Biological Activities of Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.


9 da.

21.6(28.8) 10.1(20.2) 19.4(28.8) 11.5(20.2) 2

3

8.41

2

-Log Concentration

6.80

+2

D

= 2 X 10" M; C

CuC0 (aq)

Cu

Species

T

Speciation of Copper in Synthetic Water at pH = 8 (Cu

2

T

3

6

= 2 X 10" M)

Exact value not available due to the method of computer solution. Cu (OH) C0 (s) was the only solid phase considered.

Table 2


B

w

a

1-4 m c/a o *

H

oo

On

5.

DONARUMA ET AL.

Algicides

and

Molluscicides

69

The s h i f t of dominance i n solid phase for the synthetic natural water used, occurs between total inorganic carbon concentrations 10~ and 10" M as shown i n Table 3. Therefore, for most of the experiments conducted i n the laboratory i t i s assumed that the solid phase present was malachite. A natural water could easily reduce the free copper concentration to a very low value even i n the presence of high t o t a l copper. This can easily be seen i n Tables 3 and 4. The presence of organic complexing agents and a variation of pH were also examined to see what effects these might have i n synthetic water. EDTA was once again chosen for the model organic ligand and pH was varied from 6 to 9. For lower pH values higher free copper concentrations were found as shown i n Figure 8. As EDTA concentration increased the copper that i t complexed seemed to originate from the solid phase, thus not affecting the free C u u n t i l the solid phase was completely dissolved. At this point the free copper along with some other species such as CuOH+ and Cu2^ ^5 provided the source for the EDTA. Figures similar to Figure 8 can be used to predict free copper concentration changes that might result from pH or organic ligand concentrations. On the basis of these findings and the examination of the literature i t i s quite evident the overall picture of copper speciation should be examined i n toxicity studies. Organic and inorganic complexation play a very important role i n the speciation and toxicity and can not be ignored. Before applying these resins to aquatic organism control more testing i n dynamic systems along with toxicity studies should be performed. The resins show high promise as controlled release substrates for copper(II). 4


Potential

3

2 +

OH



Table 3

+

2

10.46

-

3

7.57

-

CuC0

N.A.

-

2

N.A.

N.A.

N.A.

3.3 3.3 N.A.

N.A.

7.22

6.49

8.89

9.98

N.A.

9.25

7.09

9.49

9.14

N.A. - Not available due to the method of computer solution.

3

2

Cu (OH) (C0 ) (s)

3

N.A.

-

CuC0 (s)

3

N.A.

-

2

Cu (OH) C0 (s)

2

3.00

3.00

2

Cu(OH) (s)

Cu(C0 )

3

2

9.97

-

C^HCO*

3

8.89

8.88

4

CuS0

16.35

15.97

15.81

15.82

Cu(OH)=

11.56

11.03

10.84

11.76

10.63

10.24

10.24 10.84

8.71

7.98

7.90

8.66

CO3 = 10"

7.90

3

CO3 = 10" 8.13

4

CO3 = 10' 7.94

8.06

CO3 = 0

Cu(OH)~

2

Cu (OH>2

CuOH

Cu

+2

Species

= -3 Comparison of Speciation of Copper in Varying CO3 Concentrations at pH = 8 for 1 X 10 Cu^ (-Log Concentration)


B

g w

09

H W

i

s

S

w

^4 O


4

D

,

D

10"

4

1.5 X 10 I 2.0 X 10 ;? 5.0 X 10"

10

Is

b

-log EDTA

io-

D

2 +

11.95

8.41 8.41 8.41 8.81 11.47

Cu

pH = 8

11.93

2 +

pH = 6

= 2 X 10~ M

5.21 5.21 5.38 6.30 11.46

T

10 . 1.5 X 10"|? 2.0 X 10"? 5.0 X 10'

Cu

5

Cu

10

+ 2

11.93

8.40 8.40 8.40 8.80 11.46

CuOH

-log

13.92

7.2 7.2 7.36 8.29 13.44

CuOH

-log

+

+

18.28

11.21 11.21 11.21 12.01 17.33

2

Cu (OH)

22.25

8.81 8.81 9.14 10.99 21.30

2

Cu (OH)

The Effect of pH and EDTA on C u ,

-log EDTA

Table 4

2 +

2 +

+ 2

+

.

IO"

4

1.5 X 10 I 2.0 X 10"|? 5.0 X 10"°

D

10"

ioi

-log EDTA

4

2 +

12.74

9.92 9.92 9.92 9.92 12.30

Cu

pH = 9

11.94

6.89 6.89 6.89 7.87 11.46

Cu

2 +

pH = 7

11.73

8.90 8.90 8.90 8.90 11.29

CuOH

-log

12.93

7.87 7.87 7.87 8.86 12.45

CuOH

-log

+

+

17.87

12.22 12.22 12.22 12.22 16.99

2

Cu (OH)

20.27

10.16 10.16 10.16 12.13 19.31

2

Cu (OH)

2 +

2 +

Concentration in Synthetic Water with

* , 10 ~ 10 ;? 10"°

IO"

10 1.5 X 2.0 X 5.0 X

io;j?

-log EDTA

2

CuOH , C u ( O H )


BIOLOGICAL ACTIVITIES OF POLYMERS

72


-LOG EDTA

Figure 8.

Effect of EDTA and pH on free copper concentration in synthetic water.


5. DONARUMA ET AL.

Potential Algicides and Molluscicides

Acknowledgment ;7e are indebted to the Internatioi a l Copper Research Association for their generous support of this work. Parts of this chapter were taken from the theses submitted by Messrs. Kitch and Haslyn i n p a r t i a l fulfillment of the requirements for the Master of Science degree.

Literature Cited


1. 2. 3. 4.

Donaruma, L. G., Kitch, S., Walsworth, G., Depinto, J . V., and Edzwald, J . K., Macromolecules, 12, 435 (1979). Cheng, T. C., "Molluscicides i n Schistosomiasis Control," Academic Press, New York, NY, 1974. International Copper Research Association, private communication. Westall, J . C., Zachary, J . L., and Marel, F. M., "MINEQL," Department of Civil Engineering, Technical Note No. 13, Massachusetts Institute of Technology, July 1976.

RECEIVED January 11, 1982.


Biological Activities of Polymers - American Chemical Society

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