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konst@km3241.spb.edu



­ , , , ,
­ , ,

2


:
: , , , , :





, , , , , -


, , , ,

3


pH


50 0 -50

... ()

-100 -150 -200

1e-3 1e-4 1e-5



RT E E0 lg a zI F E E0

I

-250 -6 -5 -4 -3 -2 -1

lg(aI)



RT lg aI K IJ a zI F

J



4



, ( )
N O O O

O O O NH O O NH

O

K+ (Rb+)
3

O O N O

Ca2+
O O

O O O O O O O O O O O O

NH4+
O P O O O Ca O O O P O

O S NH NH S

NH

Cl

-

O C O C O CF
3

NH

CO

3

2

: logkH2O

n-Octanol

5



()
Cl


O



O O
O

O

K+, Cs+, NR4+, R+, +
Cl B
_ +

Cl K



O O O

Cl

NO3, ClO4 , Br , SCN , R ,



O


N
+ _

NO2

Cl

Br

Cl

B

_

Cl

N

+

O

Cl


ETH 500

O O O

6


: J+


I X-
+

L
a
IX

(1995, , )

J+
H+

I+ L R- C



aH/a

­ (1988, , )
I

J+ I+ X-

I

+

L R-



(1966, )
I

lga

7


,









-10 -9 -8 -7 -6 -5 -4 -3 -2 -1

loga

:

Ca2+, Pb

2+



, ,

T. Sokalski, A. Ceresa, T. Zwickl, E. Pretsch J. Amer. Chem. Soc. 119 (1997) 11347.

8



1. 2. 3. 4. 5. 6. 7. 8. E. Lindner, R.E. Gyurcsanyi, R.P. Buck Electroanalysis 1999 11 10-11 695. W. E. Morf, M. Badertscher, T. Zwickl, N.F. de Rooij, E. Pretsch J. Electroanal. Chem. 2002 526 19. A. Michalska, J. Dumanska, K. Maksymiuk Anal. Chem. 2003 75 19 4964. A. Michalska Electroanalysis 2005 17 5-6 400. I. Bedlechowicz, T. Sokalski, A. Lewenstam, M. Maj-Zurawska Sens. Act. B 2005 108 6 836. I. Bedlechowicz-Sliwakowska, P. Lingenfelter, T. Sokalski, A. Lewenstam, M. Maj-Zurawska J. Anal. Bioanal. Chem. 2006 385 1477. I. Bedlechowicz-Sliwakowska, E. Bakker, E. Pretsch Pittcon 2007. L. Hofler, I. Bedlechowicz, T. Vigassy, R.E. Gyurcsanyi, E. Bakker, E. Pretsch Anal. Chem. 2009, 81, 3592.

: 1. , ,

2.

9



J. Moody, J.D.R. Thomas Ion-Selective Electrode Rev. 1979 1 3-30.


150

Ca-

100

ETH 1001 23 / KTCl 16 / ETH 500 17 / , Ag/AgCl : 0.01 CaCl : Ag/AgCl 3.5 M KCl
N O O O N
Cl

()

50

0

HEPES 0.01 M TA 0.002 M CaCl2 0.001 M KCl 0.1 M

2

-50
Cl

O O

O NO2
O O O
Cl B

-100
_ +

Cl K

-12

-11

-10

-9

-8

-7

-6
Ca

-5

-4

-3

-2

-1

log a

Cl

Cl

B

_

Cl

N

+

H4TA: pK1 = 2.01 pK2 = 2.66 pK3 = 6.18 pK4 = 10.23

Ca TA log KCaHL = 3.51; log KCaL = 10.59

Cl

G. Anderegg, Critical survey of stability constants of EDTA complexes IUPAC Chem. data series #14

Ca2+ , 10-9

10



ELGA Purelab Ultra, 18.2 c



-9

-8

-7

-6

-5

logC

- Autolab 30 FRA 2 3- , : Ca, : Ag/AgCl, 3.5 M KCl, :



Metrohm 700 Dosino Metrohm 711 Liquino Controller



CaCl2 0.001 M KCl

Ca2+, Cd

2+

: ( ) ­ , , .. , ,

11



2+ 2+ h (Ca) Ca ISEs mV

-80 -60 -40 -20 0 0

:

h i

(1)

10 , 10 , 10 M
10 M
-7

-8

-9

-10

iopt
10 M
-4

SN i S

(2)

300

20

40

60
2)

80

iopt(nA/cm2)

i(nA/cm

225 150 75 0 -10 -9

Ca Cd

-90

h

10 (mV)

-9

Cd

2+

ISEs
10
-7

-60

lg a

-8

-7

-6

-30

10 10
-2

-4

0 0 75 150 225 300

iopt lg a lg a

DL ( Classic )



(3)

i(nA/cm2)

12


:
E

EA E
i

DL ( Classic ) DL ( Classic )

i

A opt X opt

(1) (2)

EX E
A opt Xopt

i

E

DL

E

E
X

B A

X A

B

i

lg a X lg a

lg a A lg a

DL ( Classic ) DL ( Classic


X X

(3)

E

E

AN

lg(a)
a
A

E A E X lg a A lg a EB EX lg aB lg a

aX a

B

a

DL



(4) (5)

M.A. Peshkova, T. Sokalski, K.N. Mikhelson, A. Lewenstam, Anal. Chem. 80 (2008) 9181.

Cation Ca2+ Cd2+

Target value (log(a)) -7.6 -9.1

Measured value (log(a)) -7.6 ± 0.07 -9.0 ± 0.13

M.A. Peshkova, K. N. Mikhelson, Electrochimica Acta 110 (2013) 829.
G. Lisak, T. Sokalski, J. Bobacka, L. Harju, K. Mikhelson, A. Lewenstam, Anal. Chim. Acta 707 (2011) 1. G. Lisak, F. Ciepiela, J. Bobacka, T. Sokalski, L. Harju, A. Lewenstam, Electroanalysis 25 (2013) 123

-7.6 -8.3 -9.1

-7.7 ± 0.08 -8.4 ± 0.13 -9.1 ± 0.08

13


­
0.25 0.20

Potential (V)

N O O S
60

0.15 0.10 0.05 0.00 -50

Cd2+

Polarization (mV)

S N

50 40 30 20 10 0
C CdCl2 (M) 0.01 0.1 0.5 1

0

50

100

150

200

250

300

350

400

Time (s)

Cd2+-, ETH 5435, KClTPB, ,
250 200 150

Anodic

-50

0

50

100

150

200

250

300

350

400

Current density (nA/cm2)

EMF (mV)

100 50 0 -50 -100 -10 -8

Cd2+ Cl- 0.01 M CdCl2
ZeroCurrent Polarized

Cathodic
-6

S=28.6, r2=0.99985
-4 -2 0

1 M CdCl2

log(aCd)

14




I

,aq

Lo rg CH

,o r g

K exch IL

,o r g

C

o rg

H

,aq

= [C]/CT ­ ,

CH+ ­ C ­

=

-1



- - (1 - ) · 1 - - (- - 1 - )

1 ln ln a H ln K IL K
250



1 exch



ln C I a

I



200

S=58.7±1.4 mV/log(aNa) (E1)

EMF (mV)

150

aq

org



RT kTBA aTBACTBB ln Const 2 F kTBB aTBB CTBA

100

E1 E2 E3

50

U. Mattinen, J. Bobacka, A. Lewenstam, Electroanalysis 21 (2009) 1955. S. Anastasova-Ivanova, U. Mattinen, A. Radu, J. Bobacka, A. Lewenstam, J. Migdalski, M. Danielewski, D. Diamond, Sens. & Actuat. B 146 (2010) 199.

S=0.8±0.5 mV/log(aNa) (E2) S=2.6±1.1 mV/log(aNa) (E3)

0 -3.0 -2.5 -2.0 -1.5 -1.0

log(aNa)

15


(pH)
red: C(NaCl) = 200 mmol black: C(NaCl) = 1 mmol
1.4 1.2

optode response



1.0 0.8 0.6 0.4 0.2 0.0 4 6 8

""

Na+ VI

pH

III , NaHFPB TBATBB

pH, Na+
Sensors & Actuators B Chemical

16



· ,
EMF (mV)

250 200 150 100 50 0 -50 -100 -10 -8 -6 -4 -2 0

ZeroCurrent Polarized

S=28.6, r2=0.99985

log(aCd)

·

,

50 0

Simulated curves of the ISE response for tot tot KIL=1e8 CL =0.01 M CR =0.005 M Cin=0.01 M

Membrane potential (mV)

-50 -100 -150 -200 -250 -300 -350 -10 -8 -6 -4 -2 0

kIX=1e-8 S=57.8 (0.99999 -6 -2) kIX=1e-7 S=57.2 (0.99996 -5.5 -2.5) kIX=1e-6 S=56.2 (0.99993 -5 -3)

log(aI)

·



pH

17


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