Glycine betaine-based ionic liquids and their influence on bacteria, fungi, insects and plants

Article abstract of DOI:10.1039/d1nj00498k

A new group of bioinspired ionic liquids (ILs) based on glycine betaine and natural or synthetic anions was synthesized. The developed synthesis methods enabled the preparation of designed salts with high yields. The melting points for 17 of the 21 betaine-based salts were below 100 °C, allowing them to be classified as ionic liquids. Moreover, the solubilities of the novel salts in water and organic solvents of different polarities were examined, and their surface activity was determined. In the greenhouse experiment, all ILs were used as pesticide adjuvants, and their impact on the herbicidal activity of iodosulfuron-methyl was determined. Additionally, the effects of the obtained salts on the deterrent properties towards pests as well as on toxicity to microorganisms and plants were determined. It turned out that most of the ILs were weak feeding deterrents; however, their toxicity to the examined organisms was relatively low. The conclusion is that some of the presented salts are high-quality pesticide adjuvants that are safe for the environment and exhibit potential weak activity towards storage pests. An essential aspect of this work was also the correlation of herbicidal activity with the wettability of hydrophobic surfaces.

Full text of DOI:10.1039/d1nj00498k

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Glycine betaine-based ionic liquids and their
influence on bacteria, fungi, insects and plants†
Cite this: New J. Chem., 2021,
45, 6344
Damian Krystian Kaczmarek, *a Daniela Gwiazdowska,b Krzysztof Jus,b
´
a
a
Tomasz Klejdysz,c Marta Wojcieszak,a Katarzyna Materna
and Juliusz Pernak
A new group of bioinspired ionic liquids (ILs) based on glycine betaine and natural or synthetic anions
was synthesized. The developed synthesis methods enabled the preparation of designed salts with high
yields. The melting points for 17 of the 21 betaine-based salts were below 100 1C, allowing them to be
classified as ionic liquids. Moreover, the solubilities of the novel salts in water and organic solvents of
different polarities were examined, and their surface activity was determined. In the greenhouse
experiment, all ILs were used as pesticide adjuvants, and their impact on the herbicidal activity of
iodosulfuron-methyl was determined. Additionally, the effects of the obtained salts on the deterrent
properties towards pests as well as on toxicity to microorganisms and plants were determined. It turned
out that most of the ILs were weak feeding deterrents; however, their toxicity to the examined
organisms was relatively low. The conclusion is that some of the presented salts are high-quality
pesticide adjuvants that are safe for the environment and exhibit potential weak activity towards storage
pests. An essential aspect of this work was also the correlation of herbicidal activity with the wettability
of hydrophobic surfaces.
Received 30th January 2021,
Accepted 16th March 2021
DOI: 10.1039/d1nj00498k
rsc.li/njc
The latest studies indicate a significant increase in interest
in natural compounds in agrotechnical treatments. The main
Introduction
Since crop cultivation started on an industrial scale, various focus is on glycine betaine, which is an inexpensive compound
substances have been used to increase yields. The application used for the synthesis of many new biosubstances that have a
of many active substances simultaneously and their inappropriate reduced impact on living organisms and the environment.4
usage has resulted in negative effects on the environment. Currently, glycine betaine is applied in medicine,5,6 cosmetics,7
Inappropriate application of plant protection products increases livestock breeding8,9 or scientific research.10 Due to both the
their accumulation in the soil, leads to contamination of ground- structure and properties of glycine betaine, glycine betaine has
water, rivers and lakes, and increases the resistance of weeds and become an essential source of cations in the synthesis of
insects to herbicides, insecticides or antifeedants.1 Therefore, in biobased quaternary ammonium salts (QASs) and ionic liquids
recent years, large-scale research has been conducted to resolve (ILs).11 Furthermore, ILs containing betainium cations or their
these problems. Currently, challenges have been addressed by the derivatives enable novel products to be obtained that exhibit
use of natural compounds to obtain new products that will reduce rationally designed physicochemical properties and biological
the pollution of our planet.2,3
activity.12 Betaine-based ionic liquids belong to the third
generation of ILs,13 which are very important chemical
compounds due to their biological activity. This property has
been used to obtain potential substitutes for active substances
in pharmaceuticals (drugs or active substance carriers),14
medicines (used in cancer therapy or dentistry),15 and
agrochemicals (herbicides, fungicides, feeding deterrents, or
adjuvants).16,17 Unfortunately, in 2018 and 2020, alarming reports
have reported that glycine betaine reacting with pelargonic acid or
indole-3-butyric acid did not lead to the production of ILs but
resulted in binary mixtures.18,19 However, Pernak and coworkers
noted a different reaction character when replacing a methyl
substituent at a quaternary nitrogen atom with a dodecyl
substituent.20 This modification of the structure of glycine betaine
a Department of Chemical Technology, Poznan University of Technology, ul.
Berdychowo 4, Poznan 60-965, Poland.
E-mail: damian.rom.kaczmarek@doctorate.put.poznan.pl
b Department of Natural Science and Quality Assurance, Poznan University of
´
Economics and Business, Al. Niepodległosci 10, Poznan 61-875, Poland
c Institute of Plant Protection – National Research Institute, ul. W. W˛egorka 20
Poznan 60-318, Poland
† Electronic supplementary information (ESI) available: Experimental section;
Elemental analysis (Table S1); NMR and IR spectra of salts (Fig. S1–S63); surface
tension of the aqueous solutions of the obtained salts (Fig. S64–S66); deterrent
activity (Table S2); germination test (Tables S3 and S4); microbial toxicity assay
(Table S5–S7). See DOI: 10.1039/d1nj00498k
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resulted in a change in the reaction path and yielded suitable ILs.
Therefore, it is essential to carry out detailed analyses of the
products obtained with betaine derivatives.
This study focused on QASs and ILs containing glycine
betaine and its derivatives (butylbetaine and dodecylbetaine)
as cations and natural (glycolate, D-gluconate, L-pyroglutamate,
cholate, and a-ketoglutarate) or synthetic (dioctyl sulfosuccinate,
docusate; bis(2-ethylhexyl)phosphate, DEHPA) anions. The
combination of the abovementioned ions resulted in new
products that increase the effectiveness of biologically active
substances. Furthermore, they perfectly fit into the current trend
for natural origin compounds that have a negligible impact on
the environment. Moreover, the previous studies have already
indicated the significant influence of functional groups and
anion structure on the application potential of adjuvant ILs.
However, this is the first publication where the effect of alkyl
substituent length in the cation of pesticide adjuvant ILs on
improving weed control efficacy was demonstrated. We also
highlighted that additives to tank mixes, apart from improving
surface activity, can further contribute to pest control. This
innovative solution potentially eliminates the need for using
additional active ingredients.
The first stage of the study included a description of the
efficient synthesis and purification methods for new QASs and
ILs. Then, the influence of alkyl substituents in the cation and
anion structure on the surface activity, thermal stability, phase
transformations, and solubility were determined. Additional
studies were conducted to define the effect of the obtained QASs
and ILs on biological activity (use of synthesized compounds as
adjuvants for herbicides or feeding deterrents) as well as to
determine the toxicity to plants, fungi, bacteria, and warehouse
insects. The results of these studies ultimately present the best
combination of cations and anions, resulting in a new pesticide
additive that will be environmentally friendly.
Fig. 1 Structure of ILs with the anion structures.
The most economical method was to use the zwitterion form
of glycine betaine, butylbetaine, and dodecylbetaine, where no
byproducts were produced and the only residue in the process
was the solvent ethanol (Scheme 1 – Method I). After the
synthesis process, the remaining ethanol did not contain any
hazardous impurities and could be recovered in a simple
process and reused without any treatment. This operation
may reduce the generation of pollutants and represents part
of the recent trend in the development of closed-loop technology.
One of the major disadvantages of this method is the necessity of
precisely adding both substrates in an equal ratio during the
reaction to avoid the purification step when unreacted substrates
are present. By contrast, the method based on an exchange
reaction did not require precision, although an appropriate
method of purification of the product from unreacted substrates
and byproducts had to be defined (Scheme 1 – Method II).
Therefore, taking into account the above information, we
recommend using method I.
The developed and described methods of synthesis in the
experimental part in the ESI,† resulted in products with high
yields exceeding 82%, as shown in Table 1. Twenty-one salts
were obtained as a result of the reactions (see structures in
Fig. 1); only salts 1c and e were described in patents, and 1f was
described in publications.22–24 The water content in all
products was assayed by Karl Fischer measurements, and the
Results and discussion
Synthesis
The main challenge during the design of a series of QASs or ILs
with varying anion structures is to develop an efficient synthesis
method for the entire group. The optimal solution would be to
select a unified method that enables the production of all salts in
the same installation. Moreover, this solution seems to be
crucial for the urgent global economic changes observed world-
wide and the rising demand for certain products. Such a solution
would allow, among other things, the launching an additional
production line and the prevention of supply shortages.
Therefore, we have developed a method of synthesizing salts with
glycolate (a), D-gluconate (b), a-ketoglutarate (c), L-pyroglutamate
(d), cholate (e), docusate (f) and DEHPA (g) anions and betainium
(1), butylbetainium (2) and dodecylbetainium (3) cations to ensure
that both synthesis methods result in all products described
(Fig. 1). However, QASs with cholate anions cannot be obtained
by a metathesis reaction because of the difficulties in removing
the byproduct.21
Scheme 1 Methods of synthesizing ILs.
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Table 1 Salts synthesized with alkylbetainium cations
No.
–R
Anion
Yield [%]
State at 25 1C
No.
–R
Anion
Yield [%]
State at 25 1C
1a
2a
3a
–CH3
–C4H9
–C12H25
Glycolate
91
90
93
Wax
Wax
Solid
1e
2e
3e
–CH3
–C4H9
–C12H25
Cholate
97
89
95
Solid
Solid
Solid
1b
2b
3b
–CH3
–C4H9
–C12H25
D-Gluconate
97
91
92
Wax
Wax
Solid
1f
2f
3f
–CH3
–C4H9
–C12H25
Docusate
DEHPAa
99
83
92
Solid
Wax
Wax
1c
2c
3c
–CH3
–C4H9
–C12H25
a-Ketoglutarate
L-Pyroglutamate
93
70
82
Wax
Wax
Wax
1g
2g
3g
–CH3
–C4H9
–C12H25
94
92
98
Wax
Wax
Wax
1d
2d
3d
–CH3
–C4H9
–C12H25
95
90
98
Wax
Wax
Solid
a
Bis(2-ethylhexyl)phosphate anion.
value was less than 500 ppm. At 25 1C, the obtained salts analysis also showed no signs of decomposition of the analyzed
appeared in the form of wax (1–2a, 1–2b, 1–3c, 1–2d, 2–3f, 1–3g) products. Additionally, the analysis of the IR spectra allowed us to
or solid (3a, 3b, 3d, 1–3e, 1f).
further verify the structure of the obtained salts. A characteristically
The resulting IR, 1H NMR and 13C NMR spectra and significant increase in the intensity of bands at 2800–3000 cmÀ1
elementary analysis allowed us to confirm the structures of was observed, which corresponded to the length of the alkyl
the obtained salts, as described in the ESI† (Fig. S1–S63 and substituent in the cation. More importantly, however, was the
Table S1 in the ESI†). In the 1H and 13C NMR spectra, the identification of the characteristic band at 1602–1739 cmÀ1, which
expected signals from methylene groups in the cation were indicated the presence of the acid form (–COOH) and the salt form
present in the following chemical shift ranges: 3.28–3.37 ppm (–COOÀ) of the carboxylic groups. Two signals were observed for
(1H NMR) and 52.0–54.3 ppm (13C NMR). Moreover, characteristic salts 1–3a–c and e, whereas a single broad signal was observed for
signals from each anion were observed in the respective 1H NMR 1–3d, f and g. The reason for the discrepancy was the more
spectra with correct integration: 4.09 ppm (glycolate anion – a, complex structures that contributed to the overlap of signals.25
–CH2 group), 4.57 ppm (D-gluconate anion – b, –CH group), 2.61– A combination of NMR and IR spectroscopic studies was used to
2.63 ppm (a-ketoglutarate anion – c, –CH2 group), 4.25–4.27 ppm elucidate the structure and confirm that the hydrogen atom is
(L-pyroglutamate anion – d, –CH group), 2.26 ppm (cholate anion attached to the carboxyl group of alkylbetainium cations. This is
– e, –CH2 group), 4.05 ppm (docusate anion – f, –CH group), and indicated by a significant change in the chemical shifts of the
3.82–3.87 ppm (DEHPA anion – g, –CH2 group). The spectrum products relative to the initial substrates and the above-mentioned
presence of bands at the appropriate wavelength on the analysed
spectra.
Table 2 Thermal properties of salts with alkylbetainium cations
Thermal properties
Tg Tc
Tm T0.05 T0.5
Tg Tc
Tm
T0.05 T0.5
Thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) data for the salts are presented in Table 2
(the methodology is described in the ESI†). The melting point
of the four products obtained (3a, d and e) exceeded 100 1C;
therefore, they were considered QASs. Furthermore, salts 1–2e
were solid over the whole range of measurements and therefore
were classified as quaternary ammonium salts, whereas the
other salts with a melting point below 100 1C were classified as
ILs. Three salts (1e, 1g, and 2g) had no phase transitions within
the analyzed temperature range, and ten of the synthesized
salts (1–2a–b, 1–3c, 1–2d and 2e) had only a glass transition
temperature (Tg).
No. [1C] [1C] [1C] [1C] [1C] No. [1C] [1C] [1C] [1C] [1C]
1a À28 —
2a À40 —
—
—
194
182
253 1e
—
—
—
—
—
250c 374c
211d 369d
234 2e 39
3a
—
108a 117b 184
228 3e 40 107b 118b 210e 352e
1b À8
2b À14 —
3b
—
—
—
204
201
247 1f À61 36b
73b
—
265
242
314
299
295
246 2f À68 —
—
70a 96b 207
246 3f
—
À23b/ À10b/ 250
57b
—
65b
—
—
1c 14
—
—
—
—
—
—
178
169
181
218
183
249 1g
229 2g
236 3g
257
251
244
—
—
—
196
186
262
259
255
2c À18 —
—
3c À16 —
107b 118b 184
1d
3
—
2d À12 —
3d
—
108a 103b 197
Tg – glass transition temperature; Tc – temperature of crystallization; Tm
– melting point; T0.05 – decomposition temperature of 5%; T0.5
Further analysis indicated that for salts 3a, b and d, only
–
a
common phase transitions occurred (Tc = 108 1C and Tm
117 1C, Tc = 70 1C and Tm = 96 1C, and Tc = 108 1C and Tm
=
=
decomposition temperature of 50%. During the cycle of cooling.
b
c
During the cycle of heating. Two steps of decomposition: 1st –
d
186.96–299.37 1C (19.93%); 2nd – 300.01–469.91 1C (70.28%). Two
steps of decomposition: 1st – 155.40–291.77 1C (24.96%); 2nd – 291.77–
467.49 1C (69.28%). Two steps of decomposition: 1st – 141.23–
103 1C, respectively). Salts 3f and g exhibited a melting point
and crystallization temperature only in the heating cycle. In the
case of 3e, during the heating cycle, a glass transition followed
e
294.86 1C (36.14%); 2nd – 295.50–461.70 1C (61.50%).
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by cold crystallization and a melting point was observed. The salts, including the influence of their structure, information about
appearance of this unexpected cold crystallization is the result the solvent polarity was important.28,29 The analysis also included
of salt supercooling behavior.26 Moreover, compounds with information about the dielectric constant and its impact on the
differences in one substituent in the cation, namely, hydroxyl solvent’s ability to dissolve a selected class of compounds.30,31
(–OH) or carboxyl (–COOH) group, present a large change in the
Our research clearly showed that the solubility in water and
measured parameters of phase transitions, which may be the selected organic solvents was strongly dependent on both
related to the higher hygroscopicity.21 Additionally, informa- the anions and cations. The elongation of one of the substi-
tion is available about the influence of intermolecular hydrogen tuents in the cation caused minor changes in solubility, which
bonds on the aberration of the normal phase transitions, which was linked to an increase in the size of cations and effective
may explain the occurrence of cold crystallization or two phase charge density, thus reducing the polarity of the tested ILs.32
transitions in one cycle.27
Such a result was obtained in the case of salts 1–3a–d, where
The thermogravimetric analysis results showed that all alkyl chain elongation decreased the solubility in water.
obtained salts exhibited simple thermal decomposition in However, a reversed effect was observed in ethyl acetate, which
one stage except for QASs 1–3e (Table 2). Therefore, only the is a weakly polar solvent, for ILs 1–3f, where the solubility
salts with cholate anions were characterized by two-step increased with increasing cation size (Table 3).
decomposition, regardless of the alkyl chain length. In addi-
Moreover, the solubility test pointed out a significant effect
tion, the results presented in Table 2 show that the lowest of the anion on the solubility in solvents of varied polarity. The
decomposition temperature of T0.05 was observed for salts with structures of anions did not have an influence on the solubility
butyl groups (2) and that the highest was observed for salts with in acetonitrile, acetone, 2-propanol, toluene or hexane. How-
methyl substitutions (1). The collected data showed that this ever, D-gluconate (b) and cholate (e) anions had increased
parameter appears to be poorly correlated with the length of the solubility in DMSO, and this behavior was associated with the
alkyl substituent. However, a stronger tendency may occur at presence of hydroxyl (–OH) groups in the structure of those
decomposition temperatures (T0.5), which appear to decrease anions, which contributed to a strong interaction between this
gradually with alkyl chain elongation. Natural origin anions solvent and the anion by forming hydrogen bonds and
(a–d) and the DEHPA anion (g) exhibited significantly lower generating an appropriate dipole moment.33 Furthermore, an
thermal stability than cholate anions (e) and docusate anions increased solubility in chloroform has been observed for salts 1–
(f ), as confirmed by previous reports (except for salts 1–3g).
3c, f and g. The differences observed in the solubility of those salts
correspond well with the theory that QASs are mostly immiscible
with liquids characterized by low dielectric constants. Therefore,
Solubility
An essential aspect of the analysis of all novel compounds none of the obtained compounds were soluble in hexane or
during characterization is to determine their solubility. Providing toluene. In contrast, chloroform, as the solvent with the highest
information about this parameter leads to the selection of a dielectric constant, increased the solubility of these products.30
suitable solvent for the synthesis, purification or preparation of
Note that salts with cholate (e), docusate (f) and DEHPA (g)
a useful formulation. Considering the solubility of the obtained anions did not dissolve in water owing to their hydrophobicity,
Table 3 Solubilities of the synthesized salts 1–3a–g at 25 1C
No.
Water
Methanol
DMSO
Acetonitrile
Acetone
2-propanol
Ethyl acetate
Chloroform
Toluene
Hexane
1a
2a
3a
1b
2b
3b
1c
2c
3c
1d
2d
3d
1e
2e
3e
1f
+
+
+
+
+
Æ
Æ
Æ
+
+
+
+
+
+
Æ
Æ
Æ
+
+
+
À
À
À
Æ
Æ
Æ
À
À
À
À
À
À
+
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
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À
À
À
À
À
À
À
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À
À
À
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À
À
À
À
À
À
À
À
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À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
Æ
+
À
À
À
À
À
À
Æ
Æ
Æ
À
À
À
À
À
À
+
À
À
À
À
À
À
À
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À
À
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À
Æ
+
Æ
Æ
+
+
Æ
+
+
Æ
À
À
À
À
À
Æ
À
À
À
+
Æ
À
À
À
À
À
À
2f
3f
1g
2g
3g
+
+
Æ
Æ
Æ
+
+
+
À
À
À
+: Good solubility. Æ: limited solubility. À: poor solubility.
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and supplementary studies had to be conducted to determine substituent resulted in a decrease in the surface tension from
the form of application of these salts in biological experiments. 40–47 mN mÀ1 for the methyl substituent to 28–33 mN mÀ1 for
Studies confirmed that 0.1 g of salts 1–3f–g and 3e could be the dodecyl substituent. This effect is associated with the
dissolved in 100 mL of water, while salts 1–2e were insoluble. formation of increasingly stable micelles with the elongation
Therefore, in further studies with aqueous solutions, salts 1–2e of the alkyl substituent, which leads to a longer relaxation time
were used as suspensions.
of the micelles.37 Moreover, the structure of the anions had a
significant impact on the change in surface tension. Salts with
only an amphiphilic cation in their structure had a surface
tension at 34–36 mN mÀ1 for 0.81–3.01 mmol LÀ1 (CMC), whereas
two amphiphilic ions had a surface tension at 26–33 mN mÀ1 for
0.33–0.54 mmol LÀ1 (CMC). This is a well-known phenomenon
described in the literature as a synergic effect of both ions, which
results in a decreased surface tension.
Especially important is the surface tension values for ILs
1–3f, where the influence of the anion on this parameter was so
significant that the impact of cation structure was irrelevant to
the value of this parameter; the docusate anion caused the
surface tension to remain at the constant level irrespective of
the length of the alkyl substituent (approximately 25 mN mÀ1).
Moreover, the docusate anion with some other cations (including
nonamphiphilic cations) had a surface tension of 25 mN mÀ1 at
the CMC.22,38 Therefore, it can be assumed that the structure of
the anion reduced the surface tension to this low value and that
counterions only promoted the lowering of the concentration at
which this value was achieved.
Surface properties
Aqueous solutions of the obtained salts were analyzed to
determine the effect of the structure on selected surface activity
parameters: critical micelle concentration (CMC), surface
tension at the CMC point (gCMC) and contact angle at the
CMC point (CACMC) (the methodology is described in the ESI†).
The salts with a–d anions and betainium (1) or butylbetainium
(2) cations were nonamphiphilic compounds with no CMC.
Therefore, the surface tension (g) and contact angle (CA) were
determined for salts 1–2a–d at the highest concentration, where
the compounds were fully dissolved in water. The obtained
results are presented in Table 4 and Fig. S64–S66 (ESI†).
The CMC values indicated that this parameter decreased
with the elongation of the alkyl substituent in the cation34 and
with the increase in anion hydrophobicity.35,36 This correlation
is well known and has been described in the literature.
Moreover, there was a decrease in the concentration of aqueous
solutions of salts 1–2a–d with elongation of the alkyl substituent
in the cation at the maximum content. Note also that the
combination of an amphiphilic cation and amphiphilic anion
had a CMC of 0.33–0.54 mmol LÀ1, where salts with one surface-
Since salts 1–2a–d had no CMC, it was not possible to
compare them with salts 3a–d and 1–2e–g. The analysis of
surface tension at the maximum concentration was only deter-
mined to assess the potential of these compounds to reduce the
surface tension of water. Salts 1–2a–d as well as salt 1b reduce
active ion had a CMC of 0.80–7.12 mmol LÀ1
.
Similarly, a trend analogous to the CMC of IL aqueous
solutions was observed for surface tension at the CMC. The
influence of the substituent on the surface tension was noticed
for series 1–3e and g, where the elongation of the alkyl
the water surface tension by approximately 10–30 mN mÀ1
which is not satisfactory in relation to other salts.
,
Another important issue was to determine the wettability of
water solutions on the hydrophobic surface of paraffin. An
analysis of the contact angle results is essential if we are
considering compounds that will be applied in agriculture
and should remain on the plant or seed surface. Increased
wettability allows for better contact and reduces the drop
slippage from these surfaces.39–41 The analysis of the results
had to be divided into two parts as above: wettability analysis at
the CMC for salts 3a–d and 1–2e–g and at the maximum
concentration for ILs 1–2a–d. In the case of salts with a CMC,
the wettability of paraffin ranged from 36 to 851, where the best
wettability was recorded for ILs with docusate anions (1–3f).
Moreover, a well-known correlation was observed for salts 1–3e
and g, where the contact angle of the hydrophobic surface
decreased with elongation of the alkyl substituent. In contrast,
the salts whose wetting angles were measured at the maximum
concentration did not exhibit satisfactory parameters.
Table 4 Surface activity parameters of the prepared salts
CMC
gCMC
CACMC
CMC
gCMC
CACMC
No. [mmol LÀ1] [mN mÀ1] [1]
No. [mmol LÀ1] [mN mÀ1] [1]
a
b
a
b
a
b
1a
2a
—
—
—
—
—
—
1e 7.12
2e 6.75
46.64
39.65
33.00
27.31
25.91
25.58
40.12
37.86
28.39
84 Æ 1
85 Æ 1
51 Æ 2
35 Æ 1
36 Æ 3
36 Æ 2
69 Æ 1
63 Æ 2
48 Æ 1
3a 1.62
35.24
69 Æ 1 3e 0.54
c
c
c
1b
2b
—
—
—
—
—
1f 1.26
2f 0.80
d
d
d
—
3b 3.01
33.77
61 Æ 3 3f 0.33
e
e
e
1c
2c
—
—
—
—
—
1g 1.71
2g 1.59
f
f
f
—
3c 0.81
35.81
65 Æ 2 3g 0.38
g
g
g
1d
2d
—
—
—
—
h
h
h
—
—
3d 1.68
34.74
69 Æ 2
a
g = 59.94 mN mÀ1 and CA = 941 in maximum water concentration
(626.10 mmol LÀ1). g = 46.15 mN mÀ1 and CA = 691 in maximum water
Based on the surface activity data for ILs with dodecylbetainium
cations (3a–g) and a comparison with previously described salts
with identical anions and dodecyl(2-hydroxy-ethyl)dimethyl-
b
concentration (582.29 mmol LÀ1). g = 61.34 mN mÀ1 and CA = 921 in
c
maximum water concentration (408.71 mmol LÀ1). g = 35.35 mN mÀ1
d
and CA = 641 in maximum water concentration (244.70 mmol LÀ1). g =
e
31.79 mN mÀ1 and CA = 451 in maximum water concentration ammonium cations, intriguing differences were observed between
(593.60 mmol LÀ1). g = 35.71 mN mÀ1 and CA = 641 in maximum water
f
2-carboxymethyl and 2-hydroxyethyl substituents.21 The most
notable difference was observed in the case of a–d anions, where
the surface activity parameters declined and were more favorable
concentration (392.20 mmol LÀ1). g = 43.47 mN mÀ1 and CA = 971 in
g
maximum water concentration (617.20 mmol LÀ1). g = 42.54 mN mÀ1
and CA = 711 in maximum water concentration (345.50 mmol LÀ1).
h
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for salts with dodecylbetainium cations (3). The CMC, g and CA herbicide applied, which resulted in
a
reduction of
values decreased by 14–27 mmol LÀ1, 10–13 mN mÀ1 and 12–251 cornflower fresh mass by 70–88%. Note that results similar to
(except for salts with a-ketoglutarate anion (c), where no change those for both surface-active ions were obtained by applying
was observed), respectively. This effect was due to the formation of dianionic ionic liquid, which contains two amphiphilic
stronger hydrogen bonds in molecules in which a carboxylic group cations (3c), and the tank mix with this IL reduced the fresh
was present, thus resulting in improved molecular orientation and mass by 75%. Curiously, the effect of alkyl substituent length
packing at the phase boundary.42 Moreover, the presence of a for ionic liquids with docusate anions was the lowest, which
surface-active anion in the structure contributed to the limited was associated with reducing the effect of the cation on the
effect of hydrogen bonding with substituents in the cation, surface activity. This result leads to the conclusion that the use
excluding ILs with bis(2-ethylhexyl)phosphate anions. However, it of IL adjuvants 3c and e, which consist of both anions and
will be necessary to use molecular modeling to determine these cations of natural origin, is a favorable solution for achieving
effects in further studies.
good herbicidal results without negative environmental
impacts.
Application in agriculture
Nevertheless, favorable additives for tank mixes were ILs
Adjuvant activity in pesticide formulations. The effect of the with the docusate anion (f), exhibiting excellent surface activity
pesticide adjuvants obtained on herbicide activity was determined and low toxicity with simultaneous very high biological activity.
by a greenhouse experiment on cornflower (Centaurea cyanus). However, Biopower was more efficient than the IL adjuvants in
Following the methodology described in the Experimental section terms of the accelerating effect of the active substance, and it
in the ESI,† plants were sprayed with aqueous solutions of was the only adjuvant to cause plant necrobiosis approximately
iodosulfuron-methyl sodium (ISM-Na) with adjuvant salts 1–3a–g. 3–4 days earlier.
Spray solutions without adjuvant (ref. 1) or with a commercially
available adjuvant (Biopower, ref. 2) were used as a reference.
Furthermore, a similar trend was observed when comparing
the data obtained from the literature results on the influence of
The results of the greenhouse experiments are presented in IL adjuvants on biological activity. Amphiphilic anions (e–g)
Fig. 2. We confirmed that the addition of an appropriately together with a cation with no less than twelve carbon atoms in
selected adjuvant was necessary to ensure high biological the alkyl chain were good additives to spray solutions used for
activity of ISM-Na. Moreover, the results showed that the weed control. In addition, the essential issue was that these
compound with low surface activity (1–2a, b and d, as well as results were achieved for various species of invasive plants,
1c and d) resulted in a relatively low herbicidal activity (from 22 which implies that they will be useful adjuvants for application
to 46% reduction in fresh weight compared to the control). The in the agricultural sector.21,22 Another noteworthy fact is that a
results were disappointing when comparing the 33% effectiveness recent study presented ionic liquids with ISM anions and
of ISM-Na (without adjuvant, ref. 1) and 88% reference betaine-based cations. These compounds were suggested to
(Biopower, ref. 2). IL adjuvants containing one amphiphilic be good herbicidal ionic liquids for oilseed rape. However, it
ion (3a, b and d, 2c and 1–2g) improved the biological activity of is important to consider that this plant is sensitive to ISM;
ISM-Na but were less successful than commercially available therefore, further studies need to be carried out on cornflowers
additives. The application of IL adjuvants composed of both or other more resistant weeds to verify whether these
amphiphilic ions (3e–g) ensured high effectiveness of the compounds are as efficient as our IL adjuvants.43
Fig. 2 Fresh weight reduction of cornflower treated with ISM-Na with and without adjuvants at 3 weeks after application; ref. 1 – without adjuvants; ref.
2 – Biopower.
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Antifeedant properties. The deterrent activity of the synthe- observed that excessive hydrophobicity contributed to
a
sized salts 1–3a–g was determined by the standard method decrease in deterrent activity.30 Thus, this is most probably
described in the literature.44 The control substance was azadir- contributing to the decrease in deterrent activity for salts with
achtin, which is a chemical compound of natural origin with the longest alkyl substituent.
very good biological activity. The studies were carried out on
Interestingly, anions have shown a crucial function in
beetles and larvae of common storage pests: beetles of granary deterrent activity for the salts studied, and it is related to the
weevil (Sitophilus granarius) and larvae of the khapra beetle abovementioned neutral character of some compounds
(Trogoderma granarium). The antifeedant activity results are towards storage pests. To the best of our knowledge, only
presented in Fig. 3. Detailed values with statistical analyses glycolic acid46 and bis(2-ethylhexyl)phosphate47 are used in
and the methodology are available in the ESI,† in Table S2.
pure form or are derivatives of compounds applied to eliminate
The biological activity results with the tested storage pests or repel storage pests. Hence, perhaps the other anions did not
indicated that ILs consisting of glycolate (a) or bis(2-ethylhexyl) contribute to improving deterrent activity. Therefore, it can be
phosphate (g) anions, regardless of the length of the alkyl concluded that the obtained salts used as an adjuvant for
substituent in the cation, showed very good or good deterrent herbicides may also support plant protection against pests
activity. In contrast, the lowest repellent activity was observed feeding, but it must be noted that this may not be sufficient
for all other anions with betainium cations (1), exhibiting weak protection. By contrast, only ILs with bis(2-ethylhexyl)-
or hardly any effect on the feeding of both tested storage pests. phosphate (g) anions can be used as potential substitutes for
Most likely, the reason for this phenomenon is the lack of antifeedants. Nevertheless, the fact that no insects died during
betaine deterrent activity. Betaine is commonly detected in the experiment was significant, which may indicate the lack of
both plants and animals (in the largest amounts in sugar beets) toxicity of the tested compounds to these organisms.
that can be attacked by various insect species. Therefore,
betaine and its derivatives may be an inert factor for insects greenhouse experiments. Our previous studies have shown that
that does not impact their receptors.45
surface activity analyses for tank mixes represent an essential
Surface activity properties of the tank mixes used in the
On the other hand, it is worth pointing out that the reported assay for pesticide adjuvants. These measurements allow us
values for salts 2–3b–f indicated average activity (from 71 to to determine the correlation between herbicidal activity and
114). In addition to the good or very good activity of ILs 1–3a contact angle, namely, the linear relationship between these
and g (128–198), salts 2b–f were statistically good feeding parameters.
deterrents (115–124). The low biological activity of the salts
Since we used 0.1% aqueous solutions of adjuvants in the
with betaine cation was explained above, however, the lower greenhouse experiments, only concentrations of the salts 1–2f
deterrent activity of the salts with dodecylbetainium cation (3) and g and 3a–f were above the CMC, whereas the other tank
compared to the products with butylbetainium cation (2) mixes of examined ILs were below the CMC or the highest
requires explanation. Generally, with increasing hydrophobicity possible concentration. The addition of a proper adjuvant into
and elongation of the alkyl chain, biological activity towards ISM-Na solutions resulted in a significant decrease in both the
storage pests increases. Only a study by Niemczak et al. surface tension and contact angle compared to those tank
Fig. 3 Deterrent activity of salts (1–3a–g) towards the adult granary weevil and larvae of the khapra beetle compared to that of azadirachtin (Ref.).
Deterrence criteria based on total coefficient T – left side of the graph.
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Table 5 Surface activity of the tank mixes
Influence on the environment
Phytotoxicity. The effect of the obtained salts on germination,
as well as the length and weight of shoots or the root length of
white mustard at a concentration of 0.1%, were tested using the
commercially available Phytotoxikit test (the methodology is
described in the ESI†).50 The results are presented in Fig. 5 and
6 and Tables S3 and S4 in the ESI.† The obtained salts and
commercial adjuvant (Biopower, Ref.) stimulated plant
germination compared to the control (Fig. 5). Furthermore, it
was observed that the maximum germination was obtained on
day 3 for all the obtained salts and Biopower and on day 5 in the
control experiment. However, the positive germination effect
was not correlated with later root and shoot growth.
The analysis of the data presented in Fig. 6A and B resulted
in a significant structural effect of the obtained ILs on the
propagation of the mass or length increase of shoots and roots.
The obtained data indicated the crucial influence of cation
structure on plants, where three different plant behaviors were
noted depending on the length of the alkyl substituent at the
quaternary nitrogen atom. One behavior was the growth of all
three parameters with the elongation of alkyl chains in the
cation for salts 1–3a–c. Similar results have already been
observed previously and were explained by the increase in
hydrophobicity of the products, which resulted in a reduced
amount of chemical substances absorbed by plants and thus
reduced phytotoxicity.51 By contrast, salts 1–3d, e and g
exhibited an inverse relationship, where all measured para-
meters decreased with increasing alkyl substituent length.
This behavior is associated with the increasing water solubility
for salts 1–3d, e and g, which leads to improved migration of
substances in soil to the roots.52 The third category included ILs
that, with the elongation of the alkyl chain, reduced length of
roots and shoots but increased the mass of shoots relative to the
control. This particular case occurred in ILs 1–3f, where the plants
had significantly thicker shoots and roots than the other tested
salts, which increased the weight and may indicate an effect on
the growth mechanism of plants and an impact similar to
chlormequat chloride.53
g
CA
[1]
g
CA
[1]
No.
[mN mÀ1
]
No.
[mN mÀ1
]
1a
2a
3a
1b
2b
3b
1c
2c
3c
1d
2d
76.62
76.59
35.64
75.42
75.28
35.96
76.99
63.72
35.84
76.23
74.80
109 Æ 1
108 Æ 1
69 Æ 2
101 Æ 2
99 Æ 1
70 Æ 1
104 Æ 2
92 Æ 1
55 Æ 1
110 Æ 2
108 Æ 1
1e
2e
3e
1f
2f
3f
1g
2g
46.64
39.65
33.00
27.31
25.91
25.58
40.12
37.86
28.39
75.35
34.99
84 Æ 1
85 Æ 1
51 Æ 2
35 Æ 1
36 Æ 3
36 Æ 2
69 Æ 1
63 Æ 2
48 Æ 1
113 Æ 1
55 Æ 2
3g
Herbicidea
Herbicide +
Biopowerb
3d
36.42
67 Æ 3
a
b
Iodosulfuron-methyl sodium. Commercial agricultural adjuvant.
mixes without an adjuvant (Table 5). Moreover, the spray
solutions containing salts 1–3f and 3g had g values that were
approximately 6–10 mN mÀ1 lower than those of the ISM-Na +
Biopower system. However, in the case of CA, only salts 3e, 1–3f
and 3g had lower CAs, by 4, 19–20 and 71, respectively.
Unfortunately, compared to Biopower, the other synthesized
ILs did not improve the surface activity parameters. Moreover,
tank mixes with ILs 1–2a–d and ISM-Na had surface parameters
at the level of ISM-Na without adjuvant addition. The data
confirmed previous reports, where the surface activity of the
tank mixes was influenced by the adjuvant structure.21,22,48
Based on our previous studies on additives to herbicides, we
decided to correlate the biological activity and surface properties
of the spraying solutions.21,22,49 The relationship between CA
and fresh weight reduction is shown in Fig. 4. The analysis
indicated that the correlation of these parameters was at the
same level (R2 = 0.86) as in previous reports (R2 = 0.95 and 0.86).
Moreover, it is worth mentioning that the previous studies
were based on various types of weeds and different active
substances, which implied that the herbicidal activity can be
determined by simply and quickly examining the wettability of
the tank mixes.
Considering the effect of anions on the phytotoxicity of the
examined salts, the emphasis should be on ILs 1a–g, where the
cation effect was limited owing to the use of glycine betaine,
which has no negative effect on plant development. Moreover,
glycine betaine is managed by plants and contributes to a
positive effect during plant growth.54 In addition, glycine
betaine reduced the effect of cations and their molecular
weight in prepared 0.1% water solutions.
Therefore, if we consider the data presented in Fig. 6, it can
be observed that salts with cholate (e) and docusate (f) anions
did not statistically inhibit root growth relative to salts with
bis(2-ethylhexyl)phosphate (g) anions, which were the most
phytotoxic. This result was astonishing because bis(2-ethylhexyl)
phosphate has a very similar structure to docusate anions. However,
minor differences in their structure affected their properties a larÀge1
extent.55,56 Moreover, bis(2-ethylhexyl)phosphate (1250 mg kg
(rat)57) is more toxic to animals than docusate (3690 mg kgÀ1
(rat)58), which may also lead to increased toxicity towards plants.
Fig. 4 Relationship between the contact angle of the tank mix solution
and its herbicidal activity.
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Fig. 5 Germination capacity of synthesized salts, Ref. – Biopower, and Control – water.
Fig. 6 Effects of synthesized salts 1–3a–g on propagation of root length (A) as well as shoot length and mass (B) of cornflower seedlings, Ref. –
Biopower.
In contrast, glycolate (a), D-gluconate (b), a-ketoglutarate (c), and L-
It cannot be overlooked that appropriate modification of the
pyroglutamate (d) anions did not contribute to abnormal growth of cation by elongating the alkyl substituent and reducing the
shoots and roots relative to the control. The nonphytotoxicity of concentration of the relevant anions in the formulations
these anions at the concentrations used was associated with the enhances the propagation or inhibits the development of
biocompatibility of anion sources and their use in the plant life plants. Therefore, it can be unambiguously concluded that
cycle.59–61
the proper design of new compounds is essential, which results
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Fig. 7 MBCs and MFCs determined for the obtained ILs.
in obtaining appropriate phytotoxicity for plants, thus yeasts at concentrations o125 ppm. The results were unexpected,
improving their condition. especially considering that ionic liquids described in the literature
Toxicity to bacteria and fungi. The results of toxicity tests of with dodecyl(2-hydroxyethyl)dimethylammonium cations
ILs against various groups of microorganisms are shown in Fig. 7 exhibited their MBC/MFC at concentrations 4125 ppm.21 Further
and Tables S5–S7 in the ESI† (the methodology is described in the research is needed to assess the significance of the impact of
ESI†). The obtained data proved that the susceptibility of micro- changes in the cation structure to explain the mechanism of
organisms to the obtained salts increased with the elongation of absorption and interaction of these salts with bacteria and yeasts.
alkyl substituents in the cation.62 Moreover, Gram-positive bacteria
Moreover, a comparison of the results obtained with those
were more susceptible to ILs than Gram-negative bacteria, which of didecyldimethylammonium chloride (DDA) and benzalko-
was associated with the difference in their cell wall structure. nium chloride (BA) showed that the obtained salts had
Gram-negative bacteria contain the outer membrane in the cell potential impacts on microorganisms, although these effects
wall structure as the component responsible for resistance to were negligible compared to the aforementioned salts.
antimicrobial substances. The difference leads to the slower Therefore, due to the limited toxicity to the microbes, the ILs
transport of substances into the inside of the bacteria and obtained should also be poorly toxic or nontoxic to bacteria and
simultaneously causes higher resistance to new compounds for fungi in the soil, which implies that soil microorganisms
Gram-negative bacteria.63
should biodegrade these substances.
Moreover, a–d, and g anions were nontoxic to microorgan-
isms, and only the elongation of the substituent in the cation to
12 carbon atoms reduced the resistance of the bacteria and
yeasts. Such a phenomenon is well known and described in the
scientific literature.62
Conclusions
This study described and characterized a series of novel ionic
It is worth noting that the docusate anion connected with liquids containing natural or synthetic anions and betaine-
alkylbetaine resulted in toxicity to Gram-positive bacteria and based cations. The synthesis methodology was performed
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under environmentally friendly conditions and allowed us to References
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