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189

J. Electroanal. Chem., 271 (1990) 189-196


Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

Electrochemical properties
of some naturally occurring quinones

S.A. Petrova, M.V. Kolodyazhny and OS. Ksenzhek


Institute of Chemical Technology, Dniepropetrovsk (U.S.S.R.)
(Received 22 November 1988; in revised form 13 July 1989)

ABSTRACT

The electrochemical properties of some hydroxy-l+naphthoquinones of plant origin, namely juglon,


lawson and plumbagin, have been investigated using thin layer voltammetry on pyrolytic graphite
electrodes. The pH-potential diagrams for all three quinones are plotted on the basis of the experimental
data. Five different forn.s of lawson and plumbagin and four forms of juglon are shown to exist in the
whole range of pH. Equilibrium constants and formal redox potentials for all conjugated forms are
obtained.

INTRODUCTION

Quinones are widespread in living organisms, performing a variety of biochem-


ical and physiological functions. Thus, they are components of biological electron-
transfer chains located in the membranes of mitochondria, bacteria and chloro-
plasts. Some quinones are used as vitamins and drugs. Quinones are also known to
play the role of toxin in plants and of chemical “weapon” in insects. The biochem-
ical functions of quinones are connected to a great extent with their ability to
undergo reversible redox conversion and therefore the investigation of their electro-
chemical properties has aroused significant interest [l-3].
The aim of the present work was to investigate the redox properties of the
following hydroxy-1,Cnaphthoquinones of plant origin: juglon, lawson and
plumbagin. The yellow pigment lawson is contained in the leaves of the tropical
bush Lawsonia inermis (henna). Juglon (an isomer of lawson) is a phytotoxin
contained in the peel of unripe walnuts. Plumbagin, derived from different types of
Indian woody plants (P/u&ago), possesses some medicinal properties.

EXPERIMENTAL

The investigation was carried out by thin-layer voltammetry. A cell with two
plane-parallel pyrolytic graphite electrodes with a total area of 2.26 cm2 was used.

0022-0728/90/%03.50 0 1990 Elsevier Sequoia S.A.


The effective thickness of the solution layer was 13 pm. The auxiliary and reference
electrodes were silver/silver chloride; potential values quoted are given versus the
SHE. Measurements were made at T = 22 If: 0.5 OC.
Preparations of 2-hydroxy-1,4~~aphth~uinone (lawson), 5-hydroxy-1,4-naph-
thoquinone (juglon) and 2-methyl~S-~ydroxy-1,4-naph~oquinone (plumbagin) were
from Sigma Chemical Co. In most experiments with lawson the concentration used
was about 1 mM, whereas in the case of the fess soluble jugion it was 0.4 mM. At
some values of pH the experiments were carried out in soiutions of various
concentration from about 0.03 mM up to the limiting ~~~entration determined by
the solubility of the quinone. The water-insoluble plumbagin was deposited on the
surface of carbon electrodes from dimethylforma~de solution in the form of a very
thin film containing a few molecular layers. The amount of quinone deposited on
the electrode was about 3 X low9 mol per cm2.
A solution of Na,SQ was used as supporting electrolyte. One of the following
buffers was added to the solution: acetic (pH < 5.8), phosphate (pH 5.8-8), “&is”
(pN 7.2-9-l), glycine (pH 8.2-12) or carbonate (pH 9.2-11). The ionic strength of
the solution was about 1.0. The redox properties of juglon were investigated in the
pH range up to 12 because in more basic media this compound is unstable. The
other quinones were examined up to pH 14.
A p~ten~ostat was used to monitor the linear potential sweep with a rate of I
mV/s. The cyclic voltammetric curves were recorded. The midpoint potentials at
various pH values were obtained from the voftammetric curves. The experimental
data were plotted as pH-potential diagrams.

RESULTS AND DISCUSSION

The redox conversion of the quinones studied proceeds rather reversibly in the
whole range of pII. The voltammetric curves were quite reproducible in repeated
cycles. The ratio of the peak heights (,1,/,1,) was 1 & 0.1. The difference between
the peak potentials (AE, = a Ep -c I$,) did not exceed 20-25 mV. For example, in
the case of lawson the values of A&, were the following: 20 mV (pH I-95), 10 mV
(pH 6.35 and 9.7) and 8 mV (pH 12.0).
The electrochemical conversion of the quinones investigated is a~ornpa~~ by
their adsorption on the carbon electrode surface. in our experiments the electrodes
were equilibrated with the solution before the cavity of the thin-layer cell was filled
with the same solution. Thus, in the course of the experiment we obtained some
surplus of electricity above that calculated from the known values of cell volume
and concentration. The adsorbed species displayed reversible electrochemical reac-
tivity in the same range of potentials as the dissolved ones. The voltammetric curves
for all quinones had a quite symmetric shape but their width at mid-height slightly
exceeded the theoretical value for a two-electron process (45 mv). The appropriate
width of the anodic peak of lawson was 50 mV at pH 1.95 and 6.35 and 55 mV in
more basic media. The peak widths at Ed-heist for the other quinones were of the
same order. We suppose this widening of the peaks is due to the supe~osition of the
191

i?
0.3
03
,I OH
6
0.2

0.4
\ b%=-87mv
0
A-
2
-0,1

-0,z

-0,1 -\
\
\
+H+ \
\
-0,L \
\
+e- \
\
-0.E

PH
I t . I I I
-0.E

Fig. 1. pa-potential diagram for 2-hydroxy-1,4-naphthoquinone (lawson). The symbol AH stands for the
molecule of lawson shown in the figure. The dashed line (here and in the other figures) corresponds to
Hz /H * equilibrium.

redox conversion of the dissolved material and that of the adsorbed one. The
electrochemical activity of quinones in the adsorbed state was also confirmed by the
linear dependence of the peak height upon the scan rate from 1 mV/s to 25 mV/s
observed in solutions of low concentration, where the adsorbed form prevails. The
results obtained in our experiments are in contrast to those of Hubbard and
co-workers [4-71 who demonstrated that quinones adsorbed on platinum electrodes
are electrochemically inactive. This discrepancy may arise from the difference in
adsorptive properties of the electrode materials (platinum and pyrolytic graphite,
respectively).
The pH-potential diagrams of the quinones are shown in Figs. 1 to 3. As one can
see from Fig. 1, the diagram for lawson consists of four intercepts with different
slopes of the pH-potential line: - 58 mV (pH -C4.15), - 87 mV (4.15 c; pH < 8.47),
- 58 mV (8.47 < pH -C10.86) and - 29 mV (pH > 10.86). Accordingly, five differ-
ent forms of lawson may exist in aqueous solutions. Two of them are oxidized
forms, while the other three are reduced. The unchanged forms (AH and AH,) are
192

stable in the acid region. At pH > 4.15 the neutral oxidized form AH loses one
proton and an anion A- is formed. The stoichiometry of the reduction of this anion
depends upon the pH of the solution. In the pH range 4.15-8.47, anion A-
undergoes a three-proton and two-electron reduction, producing a neutral leuco-
form, AH,. At pH > 8.47 the reduced forms, namely AH; (pH x 10.86) and AH’-
(pH > 10.86) are negatively charged:

(AH*-)

The midpoint potential of lawson was found to be dependent to some extent


upon the concentration of the substance in solution. Thus, in acidic medium (pH
1.95), E, was 0.222 V at a concentration of 0.03 mM and shifted smoothly to reach
a constant value of 0.231 V at a concentration of about 1 mM. This direction of the
shift indicates a stronger adsorptivity of the oxidized form (AH). In the neutral
region (pH 6.35), where the anionic oxidized form A- is stable, the opposite
behaviour was observed. The E, value shifted from -0.081 V to -0.092 V as the
concentration was increased between the same limits as above. In this region the
adsorption coefficient for the reduced form (AH,) is larger than that for the
oxidized one. At pH 9.7, where a new reduced form appears (AH;), the limits of the
E, shift are reduced to 6 mV. In basic medium (pH 12) no shift of E, in solutions
of various concentration was observed, so the adsorptivities of the forms A- and
AH*- may be considered to be the same. The values of E O’ and pK for all possible
equilibria between the conjugated forms of lawson quoted in Tables 1 and 2 refer to
conditions where they become independent of the concentration at its higher level.
The data obtained in this study are in quite satisfactory agreement with those
determined by Fieser and Fieser at 25°C [S] (our values are in parentheses):
E”‘=0.351 V (0.344 v); E;‘= - 0.152 V (- 0.150 V); pE;,, = 3.98 (4.15); ply,,
= 8.68 (8.47); plc,, = 10.71 (10.86). The data cited in ref. 9 resemble these values
closely.

TABLE 1
Redox equilibria in the lawson system

Transfer * Reaction EO’/V


1-3 AH+2 H+ +2 e- +t AH, 0.344
2-3 A-+3H++2e-#AH; 0.466
2-4 A-+2H++2e-+tAH; 0.218
2-5 A-+H++2e_FLAH*- - 0.101
a Numbers correspond to Fig. 1.
193

TABLE 2
Acid-base equilibria in the lawson system

Transfer a Reaction pK
1-2 AHGA-+H+ 4.15
3-4 AH,FtAH; +H + 8.47
4-5 AH; a AH2- +H+ 10.86
a Numbers correspond to Fig. 1.

Translocation of the OH group from position 2 to position 5 of the molecule of


1,4-naphthoquinone affects the topology of the pH-potential diagram appreciably.
As one may observe from Fig. 2, three regions may be distinguished on the diagram
of juglon in the pH range O-12. The slopes are as follows: - 58 mV (pH c 6.96),
- 29 mV (6.96 < pH < 8.6) and - 44 mV (pH > 8.6). The last intercept, with a slope
of - 44 mV per unit of pH, corresponds to a proton/ electron ratio of 1S : 2 in the
reduction process. Such a ratio may be explained by the formation of dimers. In
treating the overall scheme of the redox processes in solutions of juglon depicted in
the lower left-hand corner of Fig. 2 we have supposed that at least one form, namely
AH . A-, has a dimer structure. This form is stable in solutions of pH > 8.6. The
dimer AH * A- undergoes an overall three-proton and four-electron reduction to
produce two singly-charged monome~c anions:

OH

+3H++4e- = 2
0- OH
(AH.A-) (2W)

In the acid and neutral regions both the oxidized (AH) and reduced (AH,) forms
of juglon are uncharged.
According to Friedheim [8] one more leuco-compound may exist in basic
medium, namely a doubly-charged anion AH*- (pK,&, = 10.6). In our investiga-
tions this form has not been detected in solutions of pH up to 12.
In the case of juglon no well-defined dependence of the midpoint potential on
concentration was observed in the whole range of pII. This may be explained by
assuming that the adsorptivities of the oxidized and the reduced forms are rather
close. Even in solutions of pH > 8.6, in which the oxidized form is supposed to be a
dimeric one and thus a dependence of E,,, upon the concentration would be
expected, we found no such dependence in the range from 0.09 mM up to the limit
of solubility (- 0.4 mM). In more dilute solutions, accurate values of E, were not
available due to the distortion of the peak shape by the simultaneous reduction of
residual amounts of oxygen present in the solution. The independence of E, of the
concentration in solutions of pH > 8.6 seems to be accounted for by the strong
adsorption of electroactive species on the carbon surface. Thus the surface coverage
is close to unity even in solutions of the low conc~tratio~ studied. The data
194

94

HO 0
0,3
AH-A-
0.2 2

QI

-0,1

-42

Fig. 2. pH-potential diagram for 5-hydroxy-1,4-naphthoquinone (juglon). The symbol AH stands for the
molecule of juglon shown in the figure.

quoted in Tables 3 and 4 for the standard redox potentials and the pK values refer
to the concentration range from 0.09 mM up to the limit of solubility of juglon.
There are some discrepancies between the values obtained by Friedheim [8]
(T = 20” C) and our data, cited in parentheses: E O’ = 0.428 V (0.417 V); ET’ =

TABLE 3

Redox equilibria in the juglon system, concentration range 0.09-0.4 mM

Transfer a Reaction EO’/V

l-3 2AH+4H++4e-P2AHs 0.417


1-4 2AH+2H++4em*2AH; 0.213
2-4 AH.A-+3H++4emG2AH; 0.339

a Numbers correspond to Fig. 2.

TABLE 4

Acid-base equilibria in the juglon system, concentration range 0.09-0.4 mM

Transfer a Reaction PK
l-2 2AH*AH*A-+H+ 8.60
2AH,$2AH; +2H + 6.96
3-4

a Numbers correspond to Fig. 2.


195

TABLE 5
Redox equilibria in the plumbagin system a

Transfer b Reaction E“‘/V

1-3 2AH+4H++4eeP2AH, 0.343


1-4 2AH+2H++4em$2AH; 0.142
2-4 AH.A- +3 H+ +4 e- ZZ 2 AH; 0.274
2-5 AH.A- + 2 H+ +4 e- 8 AH; .AH2- 0.097

a Data refer to equal amounts of the oxidized and reduced forms on the electrode surface.
b Numbers correspond to Fig. 3.

TABLE 6

Acid-base equilibria in the plumbagin system

Transfer a Reaction PK
1-2 2AH@AH.A-+H+ 9.01
3-4 2AHse2AH; +2H + 6.83
4-5 2 AH; F? AH; .AH*- +H+ 12.10

a Numbers correspond to Fig. 3

!? CH,
93

0.2

2AH AH-A-
O,i
\ 4 2
\
0 _ 1, 2AH, .29mV
'1 3
\
\
-0, I \
\ +H+ -44mV

-0,2 k
-0,s

-0.4

0 2 4 6 8 lo 12 14
Fig. 3. pH-potential diagram for 2-methyl-5-hydroxy-1,4naphthoquinone (plumbagin). The symbol AH
stands for the molecule of plumbagin shown in the figure.
196

0.033V (0.008 V);pK,, = 8.0(8.6) and pK,,, = 6.6(6.96). However, the data of
Zuman [lo] on pK,, (8.7) and p&i (7.0) are in close agreement with our values.
Plumbagin is practically insoluble in aqueous media. Thus there is no point in
referring the measured E, values to the concentration in solution. In our experi-
ments only a very thin film of quinone of about 1 to 2 monolayers, tightly bound to
the surface, was involved in the electrochemical conversion. All the remaining
quinone deposited on the electrode surface was electrochemically inactive. Because
of the insolubility of plumbagin all the values of E " as well as pK cited in Tables 5
and 6~refer to conditions of equal surface concentration of the appropriate con-
jugated forms.
The pH-potential diagram of plumbagin is given in Fig. 3. Regions of stability of
five different forms of this compound may be seen. Two of them are oxidized forms,
while the three others are reduced. In solutions of pH > 9 the oxidized form exists
as a dimer. Its reduction in weak basic medium (pH < 12.1) proceeds with the
formation of the anion AH;, whereas at higher pH values a dimeric form,
AH; . AH2-, is produced in the overall reaction:

(AH.A-) ( AH;.AH*-)

The results obtained show that all the compounds investigated have a complex
redox behaviour in aqueous solutions. It is interesting to note that non-substituted
1,4naphthoquinone undergoes a simple two-proton, two-electron reduction in the
whole range of pH (E o'= 0.470 V) [3]. Introduction of electron-donor substitutes
such as methyl and hydroxy groups not only decreases the value of the standard
redox potential of l,Cnaphthoquinone, but also affects the structure of the
pH-potential diagram appreciably.

REFERENCES

G. Dryhurst, Electrochemistry of Biological Molecules, Academic Press, New York, 1977.


G. Dryhurst, K.M. Kadish, F. Scheller and R. Renneberg, Biological Electrochemistry, Vol. 1,
Academic Press, New York, London, 1982.
O.S. Ksenzbek and S.A. Petrova, Electrochemical Properties of Reversible Biological Redox Systems,
Nauka, Moscow, 1986 (in Russian).
M.P. Soriaga, P.H. Wilson and A.T. Hubbard, J. Electroanal. Chem., 142 (1982) 317.
M.P. Soriaga and A.T. Hubbard, J. Am. Chem. Sot., 104 (1982) 3937.
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