ISSN 00360236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 7, pp. 1041–1044. © Pleiades Publishing, Ltd.

, 2012.
Original Russian Text © V.G. Alekseev, A.N. Semenov, P.M. Pakhomov, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012, Vol. 57, No. 7, pp. 1115–1118.

PHYSICAL CHEMISTRY
OF SOLUTIONS

Complexation of Ag+ Ions with LCysteine

V. G. Alekseev, A. N. Semenov, and P. M. Pakhomov
Tver State University, ul. Zhelyabova 33, Tver, 170100 Russia
email: [email protected]
Received February 10, 2011

Abstract—The complexation of Ag+ ions with Lcysteine anions (Cys2–) at 25°C was studied potentiomet
rically against the background of 0.1 M KNO3. The AgCys– (logβ = 11.14 ± 0.10), AgHCys (logβ = 20.77 ±
0.06), Ag2Cys (logβ = 20.32 ± 0.17), and Ag2HCys+ (logβ = 27.28 ± 0.12) soluble complexes were found to
be formed.
DOI: 10.1134/S0036023612070029

A high antimicrobial activity of silver cations [1] The objective of our work was to study complex
and nanoparticles [2] is well known. Along with long ation processes in the Ag(I)–Cys system under the
applied aqueous AgNO3, ointments and creams con conditions typical for the formation of a silver cystein
taining silver(I) complexes with polymer and mono ate hydrogel.
mer ligands have been introduced into medical prac
tice [3, 4]. An active search for new preparations
promising on the basis of silver complexes with bioli EXPERIMENTAL
gands for medical applications is underway. In this study, we used Lcysteine (Across) and
The effect of gel formation in AgNO3 and Lcys AgNO3 (pure for analysis grade). KNO3 used to create
teine (2amino3mercatopropanic acid, H2Cys) a required ionic strength was purified before use by a
solutions is described in [5]. An interesting feature of conventional method [19]. A standard carbonatefree
the Ag(I)–Cys system is the formation of thixotropic 0.1227mol/L NaOH solution was used as a titrant.
gels even at extraordinary low concentrations of the All working solutions were prepared using bidistilled
components (0.1 wt %), although this phenomenon is water. Solutions to be titrated were placed into a tem
rarely observed in lowmolecular compound solu peraturecontrolled cell to maintain a constant tem
tions. The experimental and theoretical studies [6–8] perature of 25.0 ± 0.1°С.
performed hitherto have not yet given exhaustive Potentials were measured using I160 and I135
information on gel formation mechanisms in the ionomer millivoltmeters. A hightemperature plati
Ag(I)–Cys system. Polymer silver(I) cysteine com num electrode served as a redox electrode, an ESL
plexes constituting the molecular network of a gel are 4307 glass electrode was used as a pHselective elec
supposed to be formed. The literature data on the trode, and an EVL 1M3 saturated silver/silver chloride
character of the interaction of cysteine with Ag+ ions electrode spaced from a titrated solution by an electro
are rather diverse. As a rule, lowsoluble mercaptide lytic bridge filled with 1 M KNO3 was used as a refer
type silver cysteinate is formed, in which the hydrogen ence electrode. A silver wire piece cleaned in strong
atom of the sulfhydryl group is substituted by silver [9– HNO3 before each series of experiments served as an
11]. Solid silver cysteinate, as well as other solid mer Agselective electrode. pH and potentials were mea
captides, was shown to have a chain polymeric struc sured with an accuracy of ±0.02 and ±2 mV, respec
ture, in which sulfur atoms are bidentate [12–14]: tively. All titration curves (Figs. 1, 2) used in calcula
tions were averaged over three parallel experiments.
R R R R
S S S S RESULTS AND DISCUSION
Ag Ag Ag Ag
It is known that Ag+ ions are oxidative, and cys
Soluble silver cysteine complexes have been found teine has reductive properties. For this reason, the first
to form; they are monoligand complexes in an acidic stage of our work consisted in studying the possibility
medium [15, 16] and biligand ones in an alkaline of cysteine to be oxidized in a reation with Ag+ ions. To
medium [12, 15, 17]. There is some indirect evidence accomplish this, we titrated a 0.00103mol/L cysteine
for the formation of polynuclear complexes [9, 10]. solution with a 0.0102mol/L AgNO3 solution against
Cysteine was also shown to form stable covalent bonds the background of 0.1 M KNO3 and simultaneously
with silver nanoparticles via the sulfur atom [18]. measured the potentials of the silver and platinum

1041
1042 ALEKSEEV et al.

E, mV 12

400
10 1
2
300
8

pH
200 1
6

100 2
4

0
2
0 1 2 3 4 5
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 VNaOH, mL
ν(AgNO3)/ν(H2Cys)

Fig. 1. Potentiometric titration curves of a H2Cys solution Fig. 2. Titration curves for the Ag+–H3Cys+ system:
with an AgNO3 standard solution: (1) EAg and (2) EPt. (1) experimental and (2) calculated. cCys = 8.74 × 10–4 mol/L,
cCys = 1.03 × 10–3 mol/L, cAg = 1.02 × 10–2 mol/L, cAg = 1.11 × 10–3 mol/L, cNaOH = 0.1227 mol/L, 25°C,
25°С, I = 0.1 (KNO3). I = 0.1 (KNO3).

electrodes: EAg and EPt. As the titrant was added, a sil this way, to take into account all possible protonation
ver cysteinate sediment was formed. The potentiomet equilibria in the system. The introduction of the back
ric titration curves are plotted in Fig. 1. Each curve has ground electrolyte into initial cysteine and AgNO3
two jumps. The first jump corresponds to the intro solutions led to that, when these solutions were com
duction of 1 mol of Ag+ per 1 mol of cysteine. Before bined, yielded a voluminous silver cysteinate sedi
this moment, the concentration of Ag+ ions in solution ment, which was not further dissolve either under stir
is small and determined by the solubility product of ring or upon mild heating. It is most likely that the col
the precipitating sediment, as indicated by nearly con loidal silver cysteinate particles formed in this way
stant EAg. Further, EAg is determined by the excess coagulated under the action of the background elec
amount of Ag+ ions introduced into the system. It is trolyte. The introduction of KNO3 into a silver cys
obvious that EPt is also determined by the concentra teinate solution in 40 min after its preparation (i.e.,
tion of Ag+ ions in solution. Hence, under experimen after opalescence disappears) does not decompose the
tal conditions, no oxidation of cysteine with Ag+ ions homogeneous system, thus indicating the change in
occurs. The second jumps in the titration curves fall on the composition and structure of Ag+–cysteine reac
the molar ratio Ag : Cys = 1.25–1.30, which is optimal tion products.
for the gel formation processes in silver cysteinate The titration curve of a solution containing cysteine
solutions [8]. Most likely, the appearance of the sec (8.74 × 10–4 mol/L) and AgNO3 (1.11 × 10–3 mol/L)
ond jump indicates the interaction of Ag+ ions with sil with a 0.1227mol/L NaOH solution is plotted in Fig. 2.
ver cysteinate to yield polynuclear complexes. It It is important that the introduction of the titrant does
should be noted that, in the experiments on the not upset the homogeneity of the solution, and no sil
amperometric titration of cysteine with an AgNO3 ver cysteinate is precipitated.
solution, the consumption of the titrant also exceeded To determine the composition and stability of the
its theoretical value by 25–35% [10, 20, 21]; and silver formed complexes, we performed the mathematical
cysteinate can dissolve in excess AgNO3 due to the for analysis of titration results using New DALSFEK
mation of polynuclear complexes under certain condi (KCM Soft, 2000), a specialized program for the cal
tions [9]. culation of chemical equilibria. The program and its
Complexation was studied using pH titration. A description can be found in the Internet at the website
solution for titration was prepared similarly to the http://sinisha.chart.ru. The operation of a potentio
solution used to prepare a gel [8] by mixing cysteine metric installation and the method used for calculat
and AgNO3 solutions in the molar ratio Ag+ : H2Cys = ing the constants were tested on the recommended
1.27 : 1. We observed light opalescence disappearing in model Ni(NO3)2–glycine system [22].
30–40 min to form a transparent yellow solution. To In our calculations, the following acid–base equi
this solution, we then added the volumes of 1 M KNO3 libria were taken into account:
required to create an ionic strength of 0.1 and 0.1 M H+ + OH–  H2O, (1)
HNO3 requried to provide the possibility of the pas
sage of cysteine into the H3Cys+ cationic form and, in H+ + Cys2–  HCys–, (2)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

 COMPLEXATION OF Ag+ IONS 1043

2H+ + Cys2–  H2Cys, (3) c, mol/L

0.0007 1
3H+ + Cys2–  H3Cys+, (4) 2
0.0006 3
4
Ag+ + OH–  AgOH. (5) 0.0005 5
We used the following literature constants: log 0.0004
log β (H2O) = 13.78 [23], log β(HCys) = 10.37,
0.0003
log β (H2Cys) = 18.60, log β(H3Cys) = 20.58 [24], and
0.0002
log β(AgOH) = 3.0 [25].
0.0001
The formation constants of the complexes were
found from calculations. Taking into account the pos 0
sibility of coordination of the sulfur atom of the Cys2– 2 4 6 8 10 12
anion to one or two Ag+ ions and of protonation of the pH
amine and carboxylate groups of the Cys2– anion, we
have considered the possibility of the following com Fig. 3. Concentration distribution of the Ag(I) complex
species in the Ag+–H+–Cys2– system: (1) Ag+,
plexation equilibria: (2) AgCys–, (3) Ag2Cys, (4) AgHCys, and (5) Ag2HCys+.

Ag+ + Cys2–  AgCys–, (6)

Ag S NH2 + O
Ag+ + H+ + Cys2–  AgHCys, (7) H3N
+
H2C CH Ag CH C
Ag+ + 2H+ + Cys2–  AgH2Cys+, (8) C O S CH2 O−
−
2Ag+ + Cys2–  Ag2Cys, (9) O AgCys– Ag Ag2HCys+
+
2Ag+ + H+ + Cys2–  Ag2HCys+, (10) Ag S NH3 H2N O
+
H2C CH Ag CH C
2Ag+ + 2H+ + Cys2–  Ag2H2Cys+. (11)
C O S CH2 O−
The formation of biligand complexes was not con − AgHCys Ag Ag2Cys
O
sidered because of the presence of excess Ag+ ions in
the system (molar ratio Ag : Cys = 1.27 : 1).
The criterion of adequacy of the set of equilibria ACKNOWLEDGMENTS
taken into consideration to the processes occurring in This work was supported by the Analytic Depart
a solution was the minimum squared deviation sum mental Target Program “Development of Scientific
(SS) obtained in the calculation of the theoretical Potential of Higher School for 2009–2011” (project
titration curve. The calculations show that the model no. 2.1.1/10767.
incorporating equilibria (1)–(7), (9), and (10) is most
adequate. The program scores the diprotonated
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