Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду
Cationic polymer polyhexamethylene guanidine hydrochloride (PHMG-Cl) is promising biocide that combines a broad spectrum of antimicrobial activity, moderate toxicity, as well as reasonable cost. It is widely used as an effective disinfectant in cooling systems, swimming pools, and hospitals, persona...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2020
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Catalysis and petrochemistry| _version_ | 1872008974052622336 |
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| author | Kamenieva, Т.М. Tarasyuk, O.P. Derevianko, K.Yu. Aksenovska, O.A. Shybyryn, O.V. Metelytsia, L.O. Rogalsky, S.P. |
| author_facet | Kamenieva, Т.М. Tarasyuk, O.P. Derevianko, K.Yu. Aksenovska, O.A. Shybyryn, O.V. Metelytsia, L.O. Rogalsky, S.P. |
| author_institution_txt_mv | [
{
"author": "Т.М. Kamenieva",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "O.P. Tarasyuk",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "K.Yu. Derevianko",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "O.A. Aksenovska",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "O.V. Shybyryn",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "L.O. Metelytsia",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
},
{
"author": "S.P. Rogalsky",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine 50, Kharkivske schose, 02160 Kyiv, Ukraine"
}
] |
| author_sort | Kamenieva, Т.М. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2021-12-10T12:27:19Z |
| description | Cationic polymer polyhexamethylene guanidine hydrochloride (PHMG-Cl) is promising biocide that combines a broad spectrum of antimicrobial activity, moderate toxicity, as well as reasonable cost. It is widely used as an effective disinfectant in cooling systems, swimming pools, and hospitals, personal hygiene products, etc. Recently PHMG-Cl was found to have pronounced anti-inflammatory and wound healing properties and therefore may be used for the treatment of chronic wounds and thermal burns. This may indicate the antioxidant activity of polymeric biocide.
In this study, PHMG-Cl has been synthesized by melt polycondensation of guanidine hydrochloride and 1,6-hexamethylenediamine. The structure of the cationic polymer was confirmed by 1H NMR and IR spectroscopy. The viscosity-average molecular weight of PHMG-Cl was found to be 10700. The antioxidant activity of PHMG-Cl has been studied by using different methods. In the methylene blue (MB) dye test, the oxidation of MB by hydroxyl radicals generating in Fenton’s system was found to decrease in the presence of PHMG-Cl in a molar ratio to MB of 5:1 and 10:1 (by 26 % and 38 %, respectively). At the same time, complete dye oxidation was observed when guanidine hydrochloride was used instead of PHMG-Cl.
The antioxidant activity of PHMG-Cl has also been studied in the model system of radical chain oxidation of benzyl alcohol (BA). In this system, alkyl and peroxyl radicals are formed. The antioxidant activity was determined by a decrease of the initial rate of oxygen absorption during the initiated oxidation of BA. The introduction of PHMG-Cl into the oxidized system in the concentrations ranged from 1.3·10-3 - 1.6·10-2 mol/l decreased the oxidation rate of BA by 4.5–88 %. This result demonstrates that PHMG-Cl effectively inhibits radical chain oxidation of BA. However, further research is needed to elucidate the mechanism of free radical deactivation by a polymer biocide. |
| doi_str_mv | 10.15407/kataliz2020.30.073 |
| first_indexed | 2026-03-12T15:49:53Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2020, № 30 73
UDC 678.047: 544.475 © 2020
https://doi.org/10.15407/kataliz2020.30.073
Antioxidant activity of polymeric biocide polyhexamethylene
guanidine hydrochloride
T.M. Kamenieva, O.P. Tarasyuk, K.Yu. Derevianko, O.A. Aksenovska,
O.V. Shybyryn, L.O. Metelytsia, S.P. Rogalsky
V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine
50, Kharkivske schose, 02160 Kyiv, Ukraine
sergey.rogalsky@gmail.com
Cationic polymer polyhexamethylene guanidine hydrochloride (PHMG-Cl) is
promising biocide that combines a broad spectrum of antimicrobial activity, mode-
rate toxicity, as well as reasonable cost. It is widely used as an effective disinfectant
in cooling systems, swimming pools, and hospitals, personal hygiene products, etc.
Recently PHMG-Cl was found to have pronounced anti-inflammatory and wound
healing properties and therefore may be used for the treatment of chronic wounds
and thermal burns. This may indicate the antioxidant activity of polymeric biocide.
In this study, PHMG-Cl has been synthesized by melt polycondensation of guanidine
hydrochloride and 1,6-hexamethylenediamine. The structure of the cationic polymer
was confirmed by 1H NMR and IR spectroscopy. The viscosity-average molecular
weight of PHMG-Cl was found to be 10700. The antioxidant activity of PHMG-Cl
has been studied by using different methods. In the methylene blue (MB) dye test,
the oxidation of MB by hydroxyl radicals generating in Fenton’s system was found
to decrease in the presence of PHMG-Cl in a molar ratio to MB of 5:1 and 10:1 (by
26 % and 38 %, respectively). At the same time, complete dye oxidation was ob-
served when guanidine hydrochloride was used instead of PHMG-Cl.
The antioxidant activity of PHMG-Cl has also been studied in the model system
of radical chain oxidation of benzyl alcohol (BA). In this system, alkyl and peroxyl
radicals are formed. The antioxidant activity was determined by a decrease of the initial
rate of oxygen absorption during the initiated oxidation of BA. The introduction of
PHMG-Cl into the oxidized system in the concentrations ranged from 1.3·10-3 -
1.6·10-2 mol/l decreased the oxidation rate of BA by 4.5–88 %. This result demon-
strates that PHMG-Cl effectively inhibits radical chain oxidation of BA. However,
further research is needed to elucidate the mechanism of free radical deactivation by
a polymer biocide.
Keywords: polyhexamethylene guanidine, polymeric biocide, antioxidant activity, methylene blue, radical chain oxida-
tion, oxygen absorption
Introduction
Polymeric biocides comprising guanidinium cations in
polymer backbone such as polyhexamethylene biguanide
hydrochloride (PHMB-Cl) and polyhexamethylene guani-
dine hydrochloride (PHMG-Cl) are being considered as
valuable and cheap alternatives to common antimicrobial
agents because of the combination of high efficacy in kill-
ing antibiotic-resistant bacteria and fungi, as well as low
toxicity to human cells [1-5]. The said cationic polymers
are widely used as effective disinfectants in cooling sys-
tems, swimming pools and hospitals, in personal hygiene
products, as well as in the food industry [2-4]. The high
activity of guanidinium-based polymeric biocides against
microorganisms is caused by the presence of multiple posi-
tive charges within a single molecule that are able to com-
pensate the negative charges present on the outer cell mem-
branes of microbes. Therefore, cationic polymers attack the
cellular envelope, and subsequently associates itself with
the head groups of the acidic phospholipids, destabilizes the
osmotic equilibrium, and destructs the cytoplasmic mem-
brane, causing leakage of a cell. The presence of hydropho-
bic aliphatic chains in the backbone ensures a better parti-
tion of polymeric biocide to the hydrophobic regions of the
phospholipids membrane, resulting in a change of mem-
brane permeability and lethal leakage of cytoplasmic mate-
rials [6-8].
From a practical point of view, PHMG-Cl has certain
advantages over PHMB-Cl. Thus, it is much cheaper than
PHMB-Cl due to simple one-step synthesis [9]. Moreover,
mailto:sergey.rogalsky@gmail.com
74 Каталіз та нафтохімія, 2020, № 30
the acute toxicity studies on rats have shown that the medi-
an lethal dose (LD50) for PHMG-Cl is 600 mg/kg [10]
whereas LD50 value for PHMB-Cl is 25.6 mg/kg [11]. Ca-
ballero Gómez and co-authors [12] tested PHMG-Cl
against a cocktail of six Staphylococcus aureus strains (in-
cluding three methicillin-resistant strains) in the planktonic
state, as well as in biofilms. Their studies revealed anti-
biofilm activity of polymeric biocide that was significantly
higher compared to common antimicrobial agents ben-
zalkonium chloride, cetrimide, hexadecylpyridinium chlo-
ride, and chlorhexidine [12].
Doroshenko and co-authors [13] studied the effect of a
nanosized silica composite with PHMG-Cl on the immuno-
logical parameters and oxidative-antioxidant homeostasis in
the blood and in the lesion of rats with an uninfected ther-
mal burn. The composite effectively reduced the level of
proinflammatory and increased the level of pro-
inflammatory cytokines, indicating the presence of anti-
inflammatory properties. Moreover, it also normalized the
oxidative-antioxidant homeostasis by normalizing the con-
tent of markers of free radical oxidation and oxidation to
accelerate the treatment of thermal burns [13]. The results
of subsequent medico-biological studies confirmed the an-
tioxidant activity of guanidine-containing polymers. For
instance, the wound-healing effect of a hydrogel based on
PHMG-Cl under conditions of thermal shock modeling has
been studied [14]. The polymeric biocide was found to ac-
tivate the growth of antioxidants and leukocytes in the
blood of animals, which indicates a pronounced reparative
effect.
Overall, the results of recent studies have shown that
PHMG-Cl is an extremely promising biocide of complex
action which combines a broad spectrum of antimicrobial
activity, pronounced anti-inflammatory and wound healing
properties and therefore may be used for the treatment of
chronic wounds and thermal burns. In chronic wounds,
there are numerous sources of reactive oxygen species in-
cluding hydrogen peroxide, superoxide anions, and hy-
droxyl radicals, which are able to cause severe damage to
cellular components [15, 16]. Patients with chronic wounds
have also been shown to have low levels of the antioxidant
molecules that are important for detoxifying. However, the
direct activity of PHMG-Cl against free radicals has not yet
been studied.
The aim of this article was to study the antioxidant ac-
tivity of polymeric biocide PHMG-Cl by using different
methods.
Materials and methods
Following chemicals were used in this research: guani-
dine hydrochloride (98 %), hexamethylenediamine (98 %),
methylene blue hydrate (95 %), iron (III) acetylacetonate
(97 %), benzyl alcohol (98 %) (Sigma-Aldrich), 2,2'-azo-
bis-isobutyronitrile (99 %) (Vesta Chemicals), hydrogen
peroxide (35 %), iron (II) sulfate heptahydrate (99 %),
(Synbias, Ukraine).
PHMG-Cl was synthesized by melt polycondensation
of guanidine hydrochloride and hexamethylenediamine
[17], according to the Scheme 1.
The mixture of guanidine hydrochloride (10 g, 0.1 mol)
and hexamethylenediamine (11 g, 0.095 mol) was put into
a round-bottomed flask (250 ml) equipped with a mechani-
cal stirrer. At first, it was heated to 80 °C and the melt was
stirred for 2 h. Further, the reaction was carried out for 4 h
at 120-130 °C, 4 h at 160 °C, and 3 h at 180 °C to obtain
viscous melt. The vitreous solid of PHMG-Cl was obtained
after cooling to room temperature. It was dissolved in water
(100 ml), filtered, and precipitated by the addition of a satu-
rated water solution of sodium chloride (50 ml). The poly-
mer was isolated by decantation of water solution, dried at
130 °C for 24 h, and powdered in a porcelain mortar. It has
a melting point of 136 °C.
1H NMR technique was used to characterize the struc-
ture of PHMG-Cl. The spectrum was recorded with a Vari-
an Gemini-2000 (400 MHz) NMR spectrometer in the
DMSO-d6 solution. Chemical shifts were reported down-
field in parts per million (ppm, δ) from a tetramethylsilane
reference. The vibrational properties of polymeric biocide
were studied using a Bruker Tensor-37 Fourier Transform
Infrared spectrometer (Germany). The sample was pre-
pared in KBr pellets. The spectrum was collected over the
range of 400–4000 cm−1 at a resolution of 4 cm−1 in a dry
atmosphere.
NH
2
NH
2
NH
2
NH
2
NH
2
N
H
N
H
NH
2
* *n
+
Cl
_
+
130-180 oC
+
Cl
_
(PHMG-Cl)
- NH3
Scheme 1. Synthesis of polymeric biocide PHMG-Cl
The intrinsic viscosity of PHMG-Cl was measured with
a Ubellode viscometer at 25 °С. Polymer solutions in 0.1 N
NaCl was were used to suppress the polyelectrolyte effect.
The polymer stock solution at a concentration of 5.0 g/100
Каталіз та нафтохімія, 2020, № 30 75
ml was serially diluted to concentrations of 4.0, 3.33, 2.5,
2.0, 1.66 g/100 ml. At these concentrations, the relative
viscosity was in the range 1.35–1.11. The values of the re-
duced viscosity (ηred) were calculated as a ratio of specific
viscosity to concentration (ηsp/c). The intrinsic viscosity was
determined by extrapolating these values to zero concentra-
tion.
The scavenging activity of PHMG-Cl against hydroxyl
radicals was evaluated using the qualitative methylene blue
(MB) dye test described in [18, 19]. A Fenton system was
used as the source of hydroxyl radicals which are produced
by the oxidation of ferrous ions and the reduction of hydro-
gen peroxide.
In the MB dye test, the hydroxyl radical reacts with MB
cation (which is dark blue) to produce a hydroxide ion and
a MB radical cation (which is colorless) [19]. The stock
solutions of MB (С=3·10-4 mol/l), ferric (II) sulfate (С =
3.5·10-3 mol/l), hydrogen peroxide (С = 4.5·10-2 mol/l),
guanidine hydrochloride (С=3·10-3 mol/l) and PHMG-Cl
(С=3·10-3 mol/l) were prepared. For control experiments,
the reactionary mixture was prepared by mixing of MB
stock solution (1 ml) with certain volumes of FeSO4 and
H2O2 solutions, and the total volume was adjusted to 10 ml
with deionized water. Thus, the concentration of MB in
such mixtures was 3.5·10-5 mol/l, whereas FeSO4 to MB
molar ratio was in the range from 1:1 to 10:1. The molar
ratio of H2O2 to FeSO4 was 15:1 in all cases. For testing
antioxidant activity, the molar ratio of FeSO4 to MB in the
reactionary mixture was constant (5:1 or 10:1), whereas
PHMG-Cl to MB molar ratio was in the range from 1:1 to
30:1. Guanidine hydrochloride was used as a reference
compound instead of PHMG-Cl. The pH value was adjust-
ed to the value of 3-4 by addition of diluted sulfuric acid.
UV-visible spectra were recorded over a wavelength
range from 190 to 800 nm by using a Jenway 6850 spec-
trometer (Great Britain). The calibrating graph was ob-
tained by measuring the absorbance of methylene blue
aqueous solutions in the concentration range from 1·10-6 -
1·10-5 mol/l at 664 nm [18].
The antioxidant activity of PHMG-Cl was studied in the
model reaction of radical chain oxidation of benzyl alcohol
(BA) at 50 оС and constant rate of free radicals initiation
(Wi = 2.98·10-8 mol/l·s) [20]. 2,2'-azo-bis-isobutyronitrile
was used as a free radical initiator. It was purified by recrys-
tallization from ethanol and dried in a vacuum at 30 ºC. BA
was purified from possible inhibiting impurities by one-off
passing through a column with absorbent aluminum oxide
and carbon followed by vacuum distillation (3-5 kPa) in
argon atmosphere in the presence of iron (III) acety-
lacetonate. The volume of oxygen absorbed by the reac-
tionary system was determined volumetrically. Antioxidant
activity was determined by the decrease in the initial rate of
oxygen absorption during the initiated oxidation of BA.
Under oxidative kinetic conditions the gas meter allows to
determine the rate of oxygen absorption W in the range 10-8
-10-4 mol/(l·s) at a substrate conversion of 0.1–0.3 mol/l.
The research error was 3–6 %.
Results and discussion
The molecular weight of PHMC-Cl was calculated us-
ing the Mark-Houwink equation: [η] = K·Mα, where [η] is
intrinsic viscosity, M is the viscosity-average molecular
weight, α and K are parameters, whose values depend on
the nature of the polymer and solvent. For PHMG-Cl-water
system, K = 1.83∙10–3, α = 0.38 at 25 °С [21]. The deter-
mined intrinsic viscosity was 0.062. Thus, the molecular
weight of the synthesized polymeric biocide is 10700.
Figure 1 contains 1H NMR spectrum of PHMG-Cl. The
sharp peaks at 1.31 and 1.46 ppm are the signals of
methylene protons a and b, respectively. The sharp and
splitting peak at 3.16 ppm is assigned to protons c of NCH2
group [6]. The broadening and splitting peaks at 7.52 and
7.81 ppm are assigned to the resonance of guanidine pro-
tons C-NH-C and C=NH2+ [9].
The IR spectrum of PHMG-Cl (Fig. 2) presents a major
band between 1528 and 1697 cm-1, assigned mainly to the
stretching vibrations of C=N groups, broad bands with
maxima at approximately 3160 and 3270 cm-1 correspon-
ding to the N-H stretching vibrations and the two well-
defined peaks at 2930 and 2855 cm-1 attributed directly to
the asymmetric and symmetric stretching vibrations of the
methylene groups, respectively. The band at 1470 cm-1 is
assigned to the bending vibrations of CH2 groups [9, 21].
The MB dye test qualitatively indicates the presence of
hydroxyl radicals which are formed during the Fenton’s
reaction through distinct bleaching of the MB dye in the
tested solution [18, 19]. Baseline experiments were per-
formed to determine the conditions (FeSO4/MB ratio) at
which rapid and deep degradation of the dye occurs.
Figure 3 contains UV-Vis absorption spectra of MB so-
lutions after 10 min treatment with Fenton system at diffe-
rent Fe2+ concentrations. Significant decrease of the 664 nm
peak intensity (by 75 %) was observed at FeSO4 to MB
molar ratio of 5:1 (violet line). The ten-fold excess of ferric
ions led to complete dye oxidation (blue line). Figure 4
demonstrates the inhibiting effect of PHMG-Cl on MB
degradation in Fenton system at Fe2+/MB molar ratio of
5:1. The presence of PHMG-Cl in equimolar ratio to the
dye did not prevent its complete oxidation after 20 min
(yellow line). However, at five-fold molar excess of
PHMG-Cl over MB, only 74 % of the dye was degraded
during the same time (pink line). Further increase of
PHMG-Cl/MB molar ratio to 10:1 significantly inhibited
dye degradation. Thus, 38 % of MB remained in the solu-
tion (Fig. 4, blue line). At a higher Fe2+/MB molar ratio of
10:1 in Fenton system, 25 % of MB was detected in solu-
tion after 20 min (Fig. 5, green line).
76 Каталіз та нафтохімія, 2020, № 30
Figure 1. 1H NMR spectrum of PHMG-Cl
Figure 2. IR-spectrum of PHMG-Cl
Overall, the obtained results demonstrate the capacity of
PHMG-Cl to deactivate hydroxyl radicals. However, gua-
nidine hydrochloride was reported to be inert toward these
highly reactive particles [22, 23]. On the other hand, 1-
methylguanidine, 1-ethylguanidine, and 1,1-
dimethylguanidine were found to possess direct scavenging
activity against hydroxyl radicals with the formation of car-
bon-centered radicals [22, 23]. The authors reasonably as-
sumed that the difference in the reactivity of hydroxyl radi-
cals toward guanidine derivatives might be attributed to the
ease of H-abstraction from their alkyl groups. The results of
our study confirm this assumption. Thus, even ten-fold mo-
lar excess of guanidine hydrochloride over MB did not pre-
vent complete dye discoloration in experimental conditions
(Fig. 5, black line; Fig. 6, b 2).
In the model system of initiated oxidation of BA
(PhCH2OH) two types of free radicals are formed: alkyl R˙
(PhCH˙OH) and peroxyl ROO ̇ (PhCH(OO˙)OH), accor-
ding to the Scheme 2 [20, 24].
Каталіз та нафтохімія, 2020, № 30 77
Figure 3. UV-visible spectra of MB solution with concen-
tration of 3·10-5 mol/l (dark blue line) and MB solutions
after 10 min treatment with Fenton system at different mo-
lar ratio of MB to FeSO4: red line – 1:1, green line – 1:3,
violet line – 1:5, blue line – 1:10 (t = 20 ºC)
Figure 4. UV-visible spectra of MB solution (C=3·10-5
mol/l, dark blue line) and MB solutions after 20 min treat-
ment with Fenton system (FeSO4 (С = 1.5·10-4 mol/l) +
H2O2 (С = 2.2·10-3 mol/l) in the presence of different con-
centrations of PHMG-Cl: 9·10-4 mol/l (green line), 6·10-4
mol/l (red line), 3·10-4 mol/l (blue line), 1.5·10-4 mol/l (pink
line), 3·10-5 mol/l (yellow line) (t = 20 ºC)
Figure 5. UV-visible spectra of MB solution with concen-
tration of 3·10-5 mol/l (dark blue line) and MB solutions
after 20 min treatment with Fenton system (FeSO4 (С =
3·10-4 mol/l) + H2O2 (С = 4.4·10-3 mol/l) (red line); black
line - in the presence of guanidine hydrochloride (C=3·10-4
mol/l), green line – PHMG-Cl (C=3·10-4 mol/l) (t = 20 ºC)
Figure 6. MB solutions (С=3·10-5 mol/l) before (a) and
after 20 min treatment with Fenton system (FeSO4 (С =
3·10-4 mol/l) + H2O2 (С = 4.4·10-3 mol/l) (b): 1 – control
solution, 2 – solution containing guanidine hydrochloride
(С=3·10-4 mol/l), 3 – solution containing PHMG-Cl
(С=3·10-4 mol/l) (t = 20 ºC)
Kinetic curves of oxygen absorption by BA in the pre-
sence of PHMG-Cl are shown in Fig. 7. The pure model
system BA-AIBN absorbed oxygen with the rate W =
4.21·10-6 mol/(l·s). The introduction of PHMG-Cl into the
oxidized system in the concentrations ranged from 2.3·10-2
g/100 ml to 2.92·10-1 g/100 ml decreased the oxidation rate
to 4.02·10-6 mol/l·s (by 4.51 %) and to 0.49·10-6 mol/l·s (by
88 %), respectively. With further increase of initial concen-
tration of PHMG-Cl the oxidation rate of BA tended to its
limit value W (Fig. 8). The chain length of stabilized oxi-
dation (W / Wi) is found to be 16 that means the process
proceeded in a chain mode. Overall, the obtained data indi-
cate the antioxidant activity of PHMG-Cl since it effective-
ly inhibits radical chain oxidation of BA.
In most cases the inhibition of free radicals proceeds via
hydrogen cleavage from antioxidant molecule AH [21]:
ROOH + ARO2
.
+ AH
.
Based on the literature data, one can assume that
PHMG-Cl may interact with free radicals similar to tertiary
amines, via -C-H bond rupture to -amino radical [25].
78 Каталіз та нафтохімія, 2020, № 30
The -amino intermediate is then intercepted by an appro-
priate reagent to furnish a new -C-R bond. Following the
general scheme of inhibition of free radicals by PHMG-Cl
could be suggested (Scheme 3).
Thus, the results of this study clearly demonstrated the
antioxidant activity of PHMG-Cl in the concentration range
from 3·10-4 to 3·10-2 mol/l at which it also shows antimi-
crobial activity [3-6, 8]. Moreover, PHMG-Cl has been
reported to stimulate plant growth, as well as significantly
improve copper stress resistance of plants in the concentra-
tion range from 5·10-4 - 5·10-3 mol/l [17]. It is well known
that the excess of copper salts in plant cells impairs the re-
dox homeostasis due to the generation of reactive oxygen
species - superoxide-anions, hydroxyl radicals, hydrogen
peroxide, causing lipid peroxidation in cells and thus en-
hancing non-specific permeability of membranes [26].
Therefore, the authors supposed that the antioxidant activity
of PHMG-Cl may be the main factor defining the mitiga-
tion of the toxic effect of copper ions on wheat seedlings
[17].
Figure 7. Oxygen absorption kinetic in the model sys-
tem of initiated oxidation of benzyl alcohol without
inhibitor (1) and in the presence of different concen-
trations of PHMG-Cl: 0.023 g/100 ml (2), 0.073 g/100
ml (3), 0.146 g/100 ml (4), 0.234 g/100 ml (5), 0.292
g/100 ml (6) (Wi = 2.98·10-8 mol/(l·s), 50 ºС)
Figure 8. The rate of inhibited oxidation of benzyl
alcohol versus initial concentration of PHMG-Cl (Wi =
2.98·10-8 mol/(l·s), 50 ºС)
H
OH
H
OH
H
OH
H
O
O
OH
H
O
O H
OH
H
OH
H
O
OH
OH
H
OH
H
O
OH
OH
H
O
.
HO
AIBN . + O
2 .
. + + .
.
+
Scheme 2. Initiated oxidation of benzyl alcohol
Каталіз та нафтохімія, 2020, № 30 79
*
N
H
N
H
NH
2
*n
*
N
H
N
H
NH
2
*n
H
*
N
H
N
H
NH
2
*n
H
*
N
H
N
H
NH
2
*n
H
+
.
+
. + RH
+
. R
.
+
R
Cl
_
Cl
_
R
R = hydroxyl, peroxyl
(PHMG-Cl)
Scheme 3. Possible mechanism of free radical inhibition by PHMG-Cl
Conclusions
The antioxidant activity of polymeric biocide PHMG-
Cl has been established by using different methods. In the
methylene blue (MB) dye test, the oxidation of MB by hyd-
roxyl radicals generating in Fenton system was found to
decrease in the presence of PHMG-Cl in molar ratio to MB
of 5:1 and 10:1 (by 26 % and 38 %, respectively). At the
same time, complete dye oxidation was observed when
guanidine hydrochloride was used instead of PHMG-Cl.
The last fact indicates that alkyl substituents near guani-
dinium cation are necessary for the hydroxyl radical sca-
venging activity.
The antioxidant activity of PHMG-Cl has also been
studied in the model system of radical chain oxidation of
benzyl alcohol (BA). In this system, alkyl and peroxyl radi-
cals are formed. Under experimental conditions, antioxi-
dant activity was determined by a decrease in the initial rate
of oxygen absorption during the initiated oxidation of BA.
It has been found that the introduction of PHMG-Cl into
the oxidized system in the concentrations ranged from
2.3·10-2 g/100 ml to 2.92·10-1 g/100 ml decreased the oxi-
dation rate of BA by 4.5–88 %. The process proceeds in a
chain mode. This result demonstrates that PHMG-Cl effec-
tively inhibits radical chain oxidation of BA. Based on li-
terature data for free radical scavenging activity of alkyl-
guanidine derivatives, it can be assumed that the interaction
of PHMC-Cl with radical species (R) proceeds through -
C-H bond hemolysis followed by the formation of a new -
C-R bond.
Conflicts of Interest
The authors declare no conflict of interest.
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100851
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biocide. Skin Pharmacol. Physiol. 2010. 23. 7-16.
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Maupertuis A. M., Mauler S., Koffi-Nevry R., Dembèlè K.,
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chloride-based disinfectant: a novel tool to fight meticillin-
resistant Staphylococcus aureus and nosocomial infections.
J. Med. Microbiol. 2008. 57. 1523-1528.
4. Zhou Z., Wei D., Guan Y., Zheng A., Zhong J.-J. Ex-
tensive in vitro activity of guanidine hydrochloride polymer
analogs against antibiotics-resistant clinically isolated
strains. Mater. Sci. Eng. 2011. 31. 1836-1843.
5. Choi H., Kim K.-J., Lee D. J. Antifungal activity of
the cationic antimicrobial polymer-polyhexamethylene
guanidine hydrochloride and its mode of action. Fungal
Biol. 2017. 121. 53-60.
6. Qian L., Guan Y., He B., Xiao H. Modified guani-
dine polymers: Synthesis and antimicrobial mechanism
revealed by AFM. Polymer. 2008. 49. 2471-2475.
7. Zhou Z., Wei D., Guan Y., Zheng A., Zhong J.-J.
Damage of Escherichia coli membrane by bactericidal
agent polyhexamethylene guanidine hydrochloride: micro-
graphic evidences. J. Appl. Microbiol. 2010. 108. 898-907.
8. Lysytsya A.V., Mandygra Y. M., Bojko О. Р.,
Romanishyna O. O, Mandygra M. S. Differential sensitivi-
ty of microorganisms to polyhexamethyleneguanidine.
Mikrobiol Z. 2015. 77(5). 11-19. [In Ukrainian].
9. Zhang Y., Jiang J., Chen Y. Synthesis and antimicro-
bial activity of polymeric guanidine and biguanidine salts.
Polymer. 1999. 40. 6189-6198.
10. Asiedu-Gyekye I. J., Mahmood S. A., Awortwe C.,
Nyarko A. K. A preliminary safety evaluation of polyhex-
amethylene guanidine. Int. J. Toxicol. 2014. 33. 523-531.
11. Asiedu-Gyekye I. J., Mahmood S. A., Awortwe C.,
Nyarko A. K. Toxicological assessment of polyhexame-
thylene biguanide for water treatment. Interdiscip. Toxicol.
2015. 8. 193-202
12. Caballero Gómez N., Abriouel H., Grande J., Pulido
R. P., Gálvez A. Combined treatments of enterocin AS-48
with biocides to improve the inactivation of methicillin-
sensitive and methicillin-resistant Staphylococcus aureus
Каталіз та нафтохімія, 2020, № 30 81
planktonic and sessile cells. Int. J. Food Microbiol. 2013.
163. 96-00.
13. Doroshenko A., Gorchakova N., Zaychenko G. Ef-
fect of a nanodispersion silica composite with polyhexa-
methylene guanidine hydrochloride on immunological in-
dicators and indicators of oxidation and antioxidant homeo-
stasis in rats with thermal burn. ScienceRise: Pharmaceuti-
cal Science. 2019. 4. 45-52.
14. Lebedeva S. N., Ochirov O. S., Stelmakh S. A., Gri-
goryeva M. N., Zhamsaranova S. D., Mognonov D. M.
Wound healing effect of polyhexamethylene guanidine
hydrochloride hydrogel at burns. Acta Biomed. Sci. 2017. 2
(4). 93-96. [In Rus.].
15. Schafer M., Werner S. Oxidative stress in normal
and impaired wound repair. Pharmacol. Res. 2008. 58.
165-171.
16. Nouvong A., Ambrus A. M., Zhang E. R., Hultman
L., Coller H. A. Reactive oxygen species and bacterial bio-
films in diabetic wound healing. Physiol. Genomics. 2016.
48. 889-896.
17. Lyoshyna L., Tarasyuk O., Bulko O., Rogalsky S.,
Kamenieva T., Kuchuk M. Effect of polymeric biocide
polyhexamethylene guanidine hydrochloride on morpho-
physiological and biochemical parameters of wheat seed-
lings under copper stress. Agricultural Science and Prac-
tice. 2020. 7(1). 49-58.
18. Dutta K., Mukhopadhyay S., Bhattacharjee S.,
Chaudhuri B. Chemical oxidation of methylene blue using
Fenton-like reaction. J. Hazard. Mater. 2001. 84. 57-71.
19. Satoh A. Y., Trosko J. E., Masten S. J. Methylene
blue dye test for rapid qualitative detection of hydroxyl ra-
dicals formed in a Fenton's reaction aqueous solution. Envi-
ron. Sci. Technol. 2007. 41. 2881-2887.
20. Denisov E. T., Afanas′ev I. B. Oxidation and anti-
oxidants in organic chemistry and biology. CRC Press.
2005. Chapter 7. pp. 261-280.
21. Grigor’eva M. N., Stel’makh S. A., Astakhova S.
A., Tsenter I. M., Bazaron L. U., Batoev V. B., Mognonov
D. M. Synthesis of polyalkylguanidine hydrochloride co-
polymers and their antibacterial activity against conditional-
ly pathogenic microorganisms Bacillus Cereus and Esche-
richia Coli. Pharmaceutical Chemistry Journal. 2015. 49.
99-103.
22. Yildiz G., Demiryürek T., Sahin-Erdemli I., Kanzik
I. Comparison of antioxidant activities of aminoguanidine,
methylguanidine and guanidine by luminol-enhanced
chemiluminescence. Br. J. Pharmacol. 1998. 124. 905-910.
23. Morimoto S., Ito T., Fugita S., Nishimoto S. A pulse
radiolysis study on the reactions of hydroxyl radical and
sulfate radical anion with guanidine derivatives in aqueous
solution. Chem. Phys. Lett. 2008. 461. 300-304.
24. Kovtun G., Kameneva T., Hladyi S., Starchevsky
M., Pazdersky Y., Stolarov I., Vargaftik M., Moiseev I.
Oxidation, redox disproportionation and chain termination
reactions catalysed by the Pd-561 giant cluster. Adv. Synth.
Catal. 2002. 344. 957-964.
25. Luo W., Jang J.-D., Cheng J.-P. Towards rational
understanding of -C-H functionalization: energetic studies
of representative tertiary amines. iScience. 2020. 23(2).
100851
26. Chen J., Shafi M., Li S., Wang Y., Wu J., Ye Z.,
Peng D., Yan W., Liu D. Copper induced oxidative stress-
es, antioxidant responses and phytoremediation potential of
Moso bamboo (Phyllostachys pubescens). Sci. Rep. 2015.
5. 13554.
Надійшла до редакції 14.10.2020 р.
82 Каталіз та нафтохімія, 2020, № 30
Антиоксидантна активність полімерного біоциду
полігексаметиленгуанідин гідрохлориду
Т.М. Каменєва, О.П. Тарасюк, К.Ю. Дерев'янко, О.А. Аксеновська,
О.В. Шибирин, Л.О. Метелиця, С.П. Рогальський
Інститут біоорганічної хімії та нафтохімії ім. В.П. Кухаря НАН України
50, Харківське шосе, 02160 Київ, Україна
sergey.rogalsky@gmail.com
Катіонний полімер полігексаметиленгуанідин гідрохлорид (ПГМГ-Cl) є пе-
рспективним біоцидом, який має широкий спектр антимікробної активності,
помірну токсичність, а також невисоку вартість. Він застосовується як дезін-
фектант в системах охолодження, плавальних басейнах і медичних закладах,
засобах особистої гігієни і т. д. Нещодавно встановлено, що ПГМГ-Cl має ви-
ражені протизапальні та ранозагоювальні властивості і є ефективним для об-
робки хронічних ран та термічних опіків. Це може свідчити про антиоксидант-
ну активність полімерного біоциду.
В цій роботі синтезовано ПГМГ-Cl поліконденсацією гідрохлориду гуані-
дину та гексаметилендіаміну у розплаві. Будову катіонного полімеру підтвер-
джено методами 1H ЯМР спектроскопії та ІЧ-спектроскопії. Визначено серед-
нов’язкісну молекулярну масу ПГМГ-Cl, яка становить 10700.
Вивчено антиоксидантну активність ПГМГ-Cl різними методами. Встанов-
лено, що окиснення барвника метиленового синього (МС) гідроксильними ра-
дикалами, які генеруються в системі Фентона, суттєво сповільнюється за при-
сутності ПГМГ-Cl у мольному співвідношенні до МС 5:1 і 10:1 (на 26 % і 38 %
відповідно). В той же час, при використанні гідрохлориду гуанідину замість
полімерного біоциду відбувалось повне окиснення барвника. Досліджено ан-
тиоксидантну активність ПГМГ-Cl в модельній системі радикально-
ланцюгового окиснення бензилового спирту (БС) під дією генерованих алкіль-
них і пероксильних радикалів. Активність полімерного біоциду проти вільних
радикалів визначали за зменшенням початкової швидкості поглинання кисню
при ініційованому окисненні БС. Встановлено, що введення ПГМГ-Cl в окис-
нювальну систему в області концентрацій 1.310-3 - 1.610-2 моль/л зменшує
швидкість окиснення субстрату на 4.5-88 %. Отримані результати свідчать про
здатність катіонного полімеру ефективно інгібувати радикально-ланцюгове
окиснення БС. Однак для встановлення механізму дезактивації вільних ради-
калів полімерним біоцидом необхідне проведення наступних досліджень.
Ключові слова: полігексаметиленгуанідин, полімерний біоцид, антиоксидантна активність, метиленовий синій,
радикально-ланцюгове окиснення, поглинання кисню
mailto:sergey.rogalsky@gmail.com
|
| id | oai:katalizorgua:article-27 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:49:53Z |
| publishDate | 2020 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/51/113a1960fbfee40412ea417d3fc44851.pdf |
| spelling | oai:katalizorgua:article-272021-12-10T12:27:19Z Antioxidant activity of polymeric biocide polyhexamethylene guanidine hydrochloride Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду Kamenieva, Т.М. Tarasyuk, O.P. Derevianko, K.Yu. Aksenovska, O.A. Shybyryn, O.V. Metelytsia, L.O. Rogalsky, S.P. polyhexamethylene guanidine, polymeric biocide, antioxidant activity, methylene blue, radical chain oxidation, oxygen absorption полігексаметиленгуанідин, полімерний біоцид, антиоксидантна активність, метиленовий синій, радикально-ланцюгове окиснення, поглинання кисню Cationic polymer polyhexamethylene guanidine hydrochloride (PHMG-Cl) is promising biocide that combines a broad spectrum of antimicrobial activity, moderate toxicity, as well as reasonable cost. It is widely used as an effective disinfectant in cooling systems, swimming pools, and hospitals, personal hygiene products, etc. Recently PHMG-Cl was found to have pronounced anti-inflammatory and wound healing properties and therefore may be used for the treatment of chronic wounds and thermal burns. This may indicate the antioxidant activity of polymeric biocide. In this study, PHMG-Cl has been synthesized by melt polycondensation of guanidine hydrochloride and 1,6-hexamethylenediamine. The structure of the cationic polymer was confirmed by 1H NMR and IR spectroscopy. The viscosity-average molecular weight of PHMG-Cl was found to be 10700. The antioxidant activity of PHMG-Cl has been studied by using different methods. In the methylene blue (MB) dye test, the oxidation of MB by hydroxyl radicals generating in Fenton’s system was found to decrease in the presence of PHMG-Cl in a molar ratio to MB of 5:1 and 10:1 (by 26 % and 38 %, respectively). At the same time, complete dye oxidation was observed when guanidine hydrochloride was used instead of PHMG-Cl. The antioxidant activity of PHMG-Cl has also been studied in the model system of radical chain oxidation of benzyl alcohol (BA). In this system, alkyl and peroxyl radicals are formed. The antioxidant activity was determined by a decrease of the initial rate of oxygen absorption during the initiated oxidation of BA. The introduction of PHMG-Cl into the oxidized system in the concentrations ranged from 1.3·10-3 - 1.6·10-2 mol/l decreased the oxidation rate of BA by 4.5–88 %. This result demonstrates that PHMG-Cl effectively inhibits radical chain oxidation of BA. However, further research is needed to elucidate the mechanism of free radical deactivation by a polymer biocide. Катіонний полімер полігексаметиленгуанідин гідрохлорид (ПГМГ-Cl) є перспективним біоцидом, який має широкий спектр антимікробної активності, помірну токсичність, а також невисоку вартість. Він застосовується як дезінфектант в системах охолодження, плавальних басейнах і медичних закладах, засобах особистої гігієни і т. д. Нещодавно встановлено, що ПГМГ-Cl має виражені протизапальні та ранозагоювальні властивості і є ефективним для обробки хронічних ран та термічних опіків. Це може свідчити про антиоксидантну активність полімерного біоциду.В цій роботі синтезовано ПГМГ-Cl поліконденсацією гідрохлориду гуанідину та гексаметилендіаміну у розплаві. Будову катіонного полімеру підтверджено методами 1H ЯМР спектроскопії та ІЧ-спектроскопії. Визначено середнов’язкісну молекулярну масу ПГМГ-Cl, яка становить 10700.Вивчено антиоксидантну активність ПГМГ-Cl різними методами. Встановлено, що окиснення барвника метиленового синього (МС) гідроксильними радикалами, які генеруються в системі Фентона, суттєво сповільнюється за присутності ПГМГ-Cl у мольному співвідношенні до МС 5:1 і 10:1 (на 26 % і 38 % відповідно). В той же час, при використанні гідрохлориду гуанідину замість полімерного біоциду відбувалось повне окиснення барвника. Досліджено антиоксидантну активність ПГМГ-Cl в модельній системі радикальноланцюгового окиснення бензилового спирту (БС) під дією генерованих алкільних і пероксильних радикалів. Активність полімерного біоциду проти вільних радикалів визначали за зменшенням початкової швидкості поглинання кисню при ініційованому окисненні БС. Встановлено, що введення ПГМГ-Cl в окиснювальну систему в області концентрацій 1.3.10-3 - 1.6.10-2 моль/л зменшує швидкість окиснення субстрату на 4.5-88 %. Отримані результати свідчать про здатність катіонного полімеру ефективно інгібувати радикально-ланцюговеокиснення БС. Однак для встановлення механізму дезактивації вільних радикалів полімерним біоцидом необхідне проведення наступних досліджень. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2020-11-24 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/27 10.15407/kataliz2020.30.073 Catalysis and petrochemistry; No. 30 (2020): Catalysis and petrochemistry; 73-82 Каталіз та нафтохімія; № 30 (2020): Каталіз та нафтохімія; 73-82 2707-5796 2412-4176 10.15407/kataliz2020.30 en https://kataliz.org.ua/index.php/journal/article/view/27/18 |
| spellingShingle | полігексаметиленгуанідин полімерний біоцид антиоксидантна активність метиленовий синій радикально-ланцюгове окиснення поглинання кисню Kamenieva, Т.М. Tarasyuk, O.P. Derevianko, K.Yu. Aksenovska, O.A. Shybyryn, O.V. Metelytsia, L.O. Rogalsky, S.P. Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title | Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title_alt | Antioxidant activity of polymeric biocide polyhexamethylene guanidine hydrochloride |
| title_full | Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title_fullStr | Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title_full_unstemmed | Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title_short | Антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| title_sort | антиоксидантна активність полімерного біоциду полігексаметиленгуанідин гідрохлориду |
| topic | полігексаметиленгуанідин полімерний біоцид антиоксидантна активність метиленовий синій радикально-ланцюгове окиснення поглинання кисню |
| topic_facet | polyhexamethylene guanidine polymeric biocide antioxidant activity methylene blue radical chain oxidation oxygen absorption полігексаметиленгуанідин полімерний біоцид антиоксидантна активність метиленовий синій радикально-ланцюгове окиснення поглинання кисню |
| url | https://kataliz.org.ua/index.php/journal/article/view/27 |
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