Adjuvants & Formulations

Adjuvants & Formulations – January-February 2020 - page 1

Bimonthly magazine for agchem specialists

Editor in Chief: Hans de Ruiter Volume 17 – Issue 1 – January/February 2020

Contents: Adjuvant development for foliar fertilisers requires insight into plant
nutrition (page 1) – News in brief (7) – Patents in brief (10) – Literature (12) –
Item of the month (14) – Agenda online (15) – Advertisers (15)

Developments

Adjuvant development for foliar fertilisers requires insight

into plant nutrition
 Adjuvants & Formulations – January-February 2020 - page 2
Adjuvants can greatly improve the
performance of foliar fertilisers. To
unlock the potential of adjuvants
with foliar fertilisers, it is necessary
to combine present adjuvant know-
ledge with the most recent findings
in the field of plant nutrition.
Adjuvants & Formulations presents
an impetus to the exploration of
adjuvants for foliar fertilisers.
When pear leaves get chlorotic, the
trees may need iron. The roots of the
pear tree grow in calcareous soil which
contains plenty of iron. However, the
availability of this micronutrient in the
soil solution is far too limited. Will foliar
application of this micronutrient help?
It depends.
NUTRITIONAL STATUS
To come straight to the point: the best
time for foliar fertilisation might be
over. Often, but not necessarily, the
nutritional status of a plant affects the
uptake of foliar-applied nutrients
negatively. Nutrient deficiency can alter
plant cuticle characteristics and disturb
stomatal performance, as is observed in
experiments with iron-deficient pear
and peach trees. A reduced uptake of
foliar-applied nutrients is also found in
boron-deficient soybean and in wheat
plants with a too low phosphorus
status. In some citrus and olive
experiments it is shown that nitrogen
starvation enhanced the uptake of this
macronutrient, but other citrus
experiments demonstrated opposite
results. As far as the nutritional status
of a crop affects leaf wettability, this is
determining the choice of adjuvants in
the fertiliser spray solution. Thus it can
matter whether foliar fertilisation is
intended to prevent nutrient deficiency
in a healthy growing crop, or as remedy
to an existing shortage as quickly as
possible. The vast majority of foliar
fertiliser experiments have been carried
out with well-supplied plants or with
nutrient-deficient plants. Application of
(differently) adjuvanted foliar fertilisers
is hardly tested in both well-supplied
and deprived plants, if at all.
A related topic is the interaction
between crop water status and the
performance of foliar fertilisers. A study
with glyphosate (a relatively small and
water-soluble molecule) demonstrated
that drought-stressed black nightshade
absorpted less active ingredient as
compared to well-watered plants.
Addition of a surfactant enhanced
glyphosate absorption in the drought-
stressed weeds (De Ruiter and Meinen;
1998). Maize populations from regions
differing in water availability are found
to differ in wettability and in stomatal
and trichome densities (Revilla et al.;
2016). Such aspects are not taken into
account in the choice of adjuvants for
foliar fertilisers. The potentially
detrimental effects of nutrient
deficiency and drought stress on the
foliar absorption of fertilisers calls for
the development of formulations that
overcome these effects - thus
formulations appropriate for both
‘preventive’ and ‘curative’ action.
THREE UPTAKE PATHWAYS
The pathway of nutrients into plant
tissues is another largely overlooked
aspect of foliar fertilisation. Decades-
long one believed that the (lipohilic)
cuticle was the main route for
hydrophilic, ionic foliar fertilisers to
enter the leaf. It was thought that the
nutrients entered the living leaf tissue
Leaf burning
Foliar-applied fertilisers can cause leaf
burning. Usually leaf burn is caused by
a locally high salt concentration, but
can also arise from nutrient phyto-
toxicity. Leaf burn can manifest itself
as isolated necrotic spots under drying
droplets with increasing salt
concentrations and - due to the flow of
the spray solution over the leaf
surface - at leaf margins and tips. Leaf
margin and tip burn can also arise as
consequence of internal redistribution
of the applied nutrient through the
transpiration stream to these regions
(Fernández et al.; 2013). Spray drops
themselves can act as burning glass,
thus causing locally leaf damage.
Whether foliar fertilisation does result
in leaf damage depends on crop (leaf)
characteristics, spray solution
characteristics and weather conditions,
such as light, temperature and relative
humidity. Relevant foliar fertiliser
characteristics are the nutrient
via so-called aqueous pores (see box
From polar pore to dynamic
aqueous continuum on page 4).
Stomata were supposed to be
impermeable to foliar-applied nutrients.
These premises influenced thinking
about the choice of adjuvants with foliar
fertilisers, because the aim was to help
nutrients pass the cuticle. The
(re)discovery that nutrients can also
enter via stomata, at least in selected
crop species, caused debate about the
importance of both pathways. The
stomatal pathway may be most sig-
nificant in crops that have a stomatous
adaxial (upper) leaf surface, more or
less erect leaves, or that are sprayed
such that the stomatous abaxial (under)
side is hit. Organomodified siloxanes do
reach the underside of leaves, specialty
chemicals company Evonik says on its
website. The German company refers to
studies by Plant Protection Chemistry
NZ Ltd and by the Swiss Federal
Research Station for Horticulture in
cooperation with Syngenta. The latter
study shows a slight improvement
(from 9.5 to 20.6%) of the deposition
of a tracer on the underside of cauli-
flower leaves when BREAK-THRU S240
Continued page 3
species, counter-ion, solubility and
concentration of the compound and
the pH of the spray solution. A high
concentration of a salt with low point
of deliquescence can also result in leaf
burning (Fernández et al.; 2013).
The salt index of a foliar fertiliser is
also presented as indicator for the risk
of leaf burn. However, the salt index
reflects the osmotic pressure
generated by a soil-applied granular
fertiliser and is often used as indicator
for the seedling safety of furrow
applied starter fertilisers.
Adjuvants are also found to affect leaf
burning, for example via their
influence on the spreading and drying
behaviour of the landed spray
droplets. However, there are no
generally applicable rules of thumb,
since researchers have found various
and often opposite results (for more
information, see Surfactant-induced
stomatal flooding on page 5).
 Adjuvants & Formulations – January-February 2020 - page 3
Continued from page 2
was added to the spray solution
(Rueegg et al.; 2006).
Studies of researchers at the University
of Bonn revealed that stomatal uptake
of a model anion and cation was
strongly correlated with the number of
penetrated stomata, although usually
less than 10% of the stomata contrib-
uted to uptake. They also observed that
the number of penetrated stomata was
highly variable and increased with the
number of repeated drying/wetting
cycles (Eichert and Burkhardt; 2001).
Australian researchers reported recently
that trichomes are particularly
important for foliar zinc absorption in
sunflower. Trichomes of tomato and
soybean are not important for foliar zinc
absorption, according to these
researchers. Others found that
trichomes have a role in phosphate
uptake in wheat. Apart from a handful
Israeli studies from the 1970s and
1980s, the well-known stomatal flooding
effect of organosilicon surfactants is also
hardly investigated for foliar fertilisers
(see box Surfactant-induced tomatal
flooding on page 5). So far the
(re)discovery of stomata and trichomes
as pathways for foliar-applied nutrients
did not result in development of specific
types of adjuvants. As the stomatal
pathway depends heavily on plant
species, soil water status and the
climatic conditions, this seems
understandable.
Researchers at the Polish specialty
fertiliser company PPC ADOB showed
that surfactants differently affected the
leaf coverage of Zn-IDHA 2.0, a zinc
chelate foliar fertiliser. This study did
not relate leaf coverage to nutrient
uptake (Januszkiewicz et al.; 2019).
Particularly with foliar fertilisers, the
relation between spray deposition
pattern and uptake is poorly understood
so far.
HYGROSCOPICITY
Hygroscopicity of adjuvants is a ‘mode
of action’ that facilitates the uptake of
foliar-applied nutrients. Humectants are
hygroscopic by nature, but other
adjuvants can, depending on their
chemical structure, also be more or less
hygroscopic. At high relative humidities
(90-100%), surfactants from the Silwet
range showed more hygroscopic water
retention than the conventional
surfactants Agral 90 and Triton-X-45.
This may be correlated with the
enhancement of foliar uptake by
surfactants (Stevens and Zabkiewicz;
1990).
Adjuvants & Formulations addressed
the relevance of humectants in drying
drop deposits in a feauture published in
the November/December 2017 issue.
VARIOUS ADJUVANTS CAN YIELD
SAME RESULT
Foliar fertilisation of crops suffering
from a (latent) nutrient deficiency
creates great demand of the nutrients
concerned. The foliar fertiliser must be
both effective and mild to the crop.
Adjuvants affect the efficacy of foliar
feeders in different ways. Adjuvants
that vary significantly in ‘mode of
action’ may be equally effective with
respect to the uptake of nutrients.
Researchers at Evonik have illustrated
Bitter pit in apple is caused by
calcium deficiency. Foliar
application of calcium is one of
the measurements taken by
fruit growers to prevent this
nutritional disorder.
this with a field experiment in wheat
treated with a manganese nitrate spray
solution containing various adjuvants
from the Break-Thru range. All seven
tested adjuvants improved the uptake of
this salt, albeit in different ways. The
alkoxylated alcohol surfactant Break-
Thru Vibrant doubled the uptake of
manganese nitrate as compared to the
control (manganese nitrate only),
thereby outperforming the super-
spreading organomodified trisiloxane
Break-Thru S240 (Sievering and
Giessler-Blank; 2010).
This is reminiscent of previous studies
with calcium chloride. This calcium salt
is widely used and studied as foliar
fertiliser to reduce bitter pit incidence in
apple and a number of other calcium
deficiency related disorders in fruit and
vegetable crops. Alkyl polyglucoside,
ethoxylated fatty alcohol, organosilicon,
polysorbate, rapeseed oil and
carboxymethylcellulose are all reported
to improve the efficacy of calcium foliar
sprays (Baur and Schönherr; 1997,
Schönherr; 2001, Schmitz‐Eiberger,
Haefs and Noga; 2002, Blanco,
Fernández and Val; 2010, Val and
Fernández; 2011).
TRANSLOCATION
PPC ADOB researchers observed in an
experiment that foliar application of
Zn IDHA 2.0 with the polyglucoside
surfactant was highly effective in
improving the zinc concentration in
wheat grains (Mrozek-Niećko et al.;
2017). The researchers didn’t discuss
this observation, nor did they report
whether they have examined possible
effects of other surfactants on the zinc
content of the grains.
In many cases the translocation of
foliar-applied nutrients is of paramount
importance. Take for instance the
biofortification of staple food crops with
iron and/or zinc – an emerging field of
research that is highly relevant in
African, Asian and Latin-American
countries. Added chemicals affect the
translocation of foliar fertilisers, but this
aspect is not widely studied yet.
Incidentally, arable farmers and fruit
growers in highly developed countries
can also benefit from an improved
translocation of nutrients. But without
thorough insights into crop fertilisation,
these and other potentials of adjuvants
for foliar fertilisers are not utilised.
 Adjuvants & Formulations – January-February 2020 - page 4
From polar pore to dynamic aqueous continuum
Water droplets cannot infiltrate
stomata at ambient pressure, unless
surface tension is extremely reduced,
at least to 30 mN/m2. Plant
physiologist Jörg Schönherr and
research horticulturist Martin J. (John)
Bukovac concluded this in a widely
cited study with frozen and lyophilized
Zebrina purpusii leaves having open
stomata (Schönherr and Bukovac;
1972). They explicitly declared that
the assessment of stomatal
penetration by liquids was based on
the theory of capillary rise. The
researchers didn’t discuss to what
extent the freeze-dried stomata
behaved like functional stomata in
living leaf tissues; at the time they
probably did not suspect the possibility
of water films in stomatal pores that
may help infiltrate nutrients.
As stomata are thought to be inaccess-
ible to foliar-applied nutrients and the
more or less hydrophobic cuticle is not
conducive to these ionic, hydrophilic
substances, researchers sought an
explanation for the quantities of
Model of the formation of an aqueous connection traversing the cuticle. In this simplified
model, the cuticle consists of a matrix of cutin and waxes (CW) interspersed with hydrophilic
domains provided by polysaccharides; PF, polysaccharides fibrils for depicting cellulose and
other hydrophilic constituents of the cuticle, such as pectins and polar moieties of the cutin
matrix. The overlying layer of epicuticular waxes (EW) facing the outer side is devoid of
polysaccharides. Water clusters (WC) are formed by adsorption of water by the hydrophilic
domains. If air humidity is low water clusters mainly originate from the epidermal cells
underneath the cuticle (A). With increasing external air humidity, more water is sorbed by
the cuticle from the outer surface (A–C). At high humidity a tortuous connection between the
leaf surface and the leaf interior emerges (D). Externally applied solutes may diffuse in these
connections through the cuticle (white arrow in D). For clarity, other water clusters in the
cuticle adjacent to the depicted emerging connection are not shown. Fernández et al.; 2017
absorbed nutrients they recorded in nutrition expert Victoria Fernández and
their experiments. Jörg Schönherr her German and Spanish colleagues
suggested more than four decades ago suggested to expand the term
the existence of ‘polar pores’ in the ‘aqueous continuum’ to ‘dynamic
cutin matrix of the cuticle (Schönherr; aqueous continuum’ (Fernández et al.;
1976). In the following years Schönherr 2017) in their review of the physico-
and his colleagues spoke about chemical properties of plant cuticles
‘aqueous pores’ (Schönherr; 2000 and with respect to the foliar uptake of
Schönherr and Schreiber; 2004) or nutrients. They also presented a
‘water-filled pores’ (Schreiber; 2005). simplified model of the formation of an
Others suggested the existence of an aqueous connection traversing the
‘aqueous continuum’, which reflects the cuticle and how hydrophilic substances
network-like distribution of water within may pass the cuticle at high relative
the cuticle (Beyer et al.; 2005). Foliar air humidity.
 Adjuvants & Formulations – January-February 2020 - page 5

Surfactant-induced stomatal flooding

Organosilicon surfactants significantly

reduce the surface tension of spray
solutions. This results in the well-
known super-spreader and stomatal
flooding effects. Experiments with
glyphosate and the model compound
deoxyglucose revealed that organo-
silicon surfactants differ in stomatal
infiltration (Stevens et al.; 1991) and
that well-chosen cosurfactants can
enhance infiltration (Policello et al.;
1996).
Studies into effects of organosilicon
adjuvants on foliar fertiliser perform-
ance yield various and sometimes
contrasting results. Levy and Horesch
(1984) have investigated whether
organosilicon surfactants actually
enhance the stomatal uptake of foliar
fertilisers. Treatment of the
astomatous adaxial leaf surface of
orange didn’t result in any uptake of
ferrous sulphate (FeSO4) in the
presence of Silwet L-77. Application to
the stomatous abaxial side resulted in
a significant correction of lime-induced
chlorosis – as iron deficiency
symptoms are often described.
Correction of lime-induced chlorosis by
foliar sprays of iron compounds plus
low-surface-tension surfactants has
become a well-established practice in
various fruit crops, according to the
Israeli researchers (Levy and Horesh;
1984). This experiment has been
preceded by other trials in which
Silwet L-77 enhanced the uptake of
ferrous sulphate in citrus (Horesh and
Levy; 1981) and in common bean
(Neumann and Prinz; 1975). Ferrous
sulphate plus Silwet L-77 was found to
form a film on bean leaves, whereas
ferrous sulphate plus Tween 80
(polysorbate 80) formed drops on the
leaf surface, which was accompanied
by severe leaf burn damage.
Neumann and Prinz (1975) also
investigated the performance of Silwet
L-77 with differently charged nutrients.
They concluded that mono- and
divalent cations which were not subject
to oxidation did not affect the
spreading properties of this
organosilicon surfactant. However,
trivalent aluminium and iron rapidly
inhibited spreading ability, which they
believed may have been caused by the
formation of complexes. They didn’t
present pH values of the substances
tested. Experiments with Silwet L-77 in
growth regulators sprays showed that
the pH of the spray solution affected
the stability of this surfactant (Knoche
et al.; 1991).
On the other side, adjuvants that
change the pH of the spray solution can
affect the solubility of nutrients in the
spray solution. Silwet L-77 is found to
decrease the pH of the copper fungicide
Kocide with two percent points (from
9.9 to 7.8), which is assumed to have
increased the concentration of free
copper ions that could pass stomata in
isolated citrus leaf cuticles (Orbovíc et
al.; 2007).
Fernandez et al. (2013) refer to
observations of enhanced risk of
phytotoxicity by organosilicones due to
increased penetration rates, without
mentioning their sources of this
information. Investigation of reports
that they may have used for this
statement yields a meager
substantiation of this claim. One paper
reports an unspecified rate of leaf burn
with Break-Thru S240 plus Fe(II)-
sulphate, Fe(III)-EDTA, Fe(III)-DTPA
and Fe-(III)-citrate, but not in
combination with Fe(III)-IDHA
(Fernández et al.; 2008). However,
this organosilicon surfactant
outperformed two other surfactants (a
rapeseed oil derivative, an alkyl
polyglucoside and a mixture of ionic
and non-ionic surfactants). Another
study presented as evidence for the
risk of phytotoxicity actually shows the
opposite: a freshly prepared solution
of ferrous sulphate (Fe(II)-sulphate)
caused severe leaf damage in common
bean, whereas addition of Silwet L-77
resulted in no leaf burn at all
(Neumann and Prinz; 1975). Stevens
et al. (1991) refer to rapid scorch
caused by a contact herbicide and by
formulated glyphosate, as a result of
stomatal infiltration.

Further reading and literature cited

The effect of organosilicone surfactants in foliar nutrient sprays on increased absorption of phosphate and iron salts through
stomatal infiltration. Israel Journal of Agricultural Research 23(1974): 123-128
The reduction by surfactants of leaf burn resulting from foliar sprays and a salt‐induced inhibition of the effect. J Sci Food Agr
26(1975)7: 909-914
Response of iron-deficient citrus trees to foliar iron sprays with a low-surface-tension surfactant. Sci Hortic-Amsterdam
15(1981)3: 227-233
 Adjuvants & Formulations – January-February 2020 - page 6

Importance of penetration through stomata in the correction of chlorosis with iron salts and low‐surface‐tension surfactants. J
Plant Nutr 7(1984)1-5: 279-281
New formulation technology - Silwet organosilicone surfactants have physical and physiological properties which enhance
performance of sprays. Proceedings of the 9th Australian Weeds Conference (1990): 327-331
Contributions of stomatal infiltration and cuticular penetration to enhancements of foliar uptake by surfactants. Pestic Sci
33(1991)3: 371-382
The influence of cosurfactant and role of spreading in stomatal infiltration by organosilicone. Pesticide Formulations and
Application Systems 15(1996): 59-66
Formulation of sprays to improve the efficacy of foliar fertilisers. New Zeal J For Sci 24(1994)1: 27-34
Adjuvants affect penetration of copper through isolated cuticles of Citrus leaves and fruit. HortScience 42(2007)6: 1405-
1408 Open Access
Improved application techniques: Ways to higher efficacy of fungicides and insecticides in field grown vegetables. Outlooks
on Pest Management 17(2006)2: 80-84
Influence of water stress and surfactant on the efficacy, absorption, and translocation of glyphosate. Weed Sci 46(1998)3:
289-296
Leaf physico-chemical and physiological properties of maize (Zea mays L.) populations from different origins. Plant Physiol
Bioch 107(2016): 319-325
Penetration of stomata by liquids. Plant Physiol 49(1972)5: 813-819 Open Access
Salinity damage to Norfolk Island pines caused by surfactants. III. Evidence for stomatal penetration as the pathway of salt
entry to leaves. Aust J Plant Physiol 5(1978)3: 397-413
Stability of the organosilicone surfactant Silwet L-77 in growth regulator sprays. HortScience 26(1991)12: 1498-1500
Evidence for the uptake of large anions through stomatal pores. Bot Acta 111(1998)6: 461-466
Polar paths of diffusion across plant cuticles: new evidence for an old hypothesis. Ann Bot-London 95(2005)7: 1069-1073
Open Access
Uptake of hydrophilic solutes through plant leaves: Current state of knowledge and perspectives of foliar fertilization. Crit Rev
Plant Sci 28(2009)1-2: 36-68
Physico-chemical properties of plant cuticles and their functional and ecological significance. J Exp Bot 68(2017)19: 5293-530
Water permeability of isolated cuticular membranes: The effect of pH and cations on diffusion, hydrodynamic permeability
and size of polar pores in the cutin matrix. Planta 128(1976)2: 113-126
Calcium chloride penetrates plant cuticles via aqueous pores. Planta 212(2000)1: 112-118
Size selectivity of aqueous pores in astomatous cuticular membranes isolated from Populus canescens (Aiton) Sm. leaves.
Planta 219(2004)3:405-411
Studies on water transport through the sweet cherry fruit surface: IX. Comparing permeability in water uptake and
transpiration. Planta 220(2005)3: 474-485
Foliar iron fertilization of peach (Prunus persica (L.) Batsch): Effects of iron compounds, surfactants and other adjuvants.
Plant Soil 289(2006):239-252
Cuticular calcium penetration is directly related to the area covered by calcium within droplet spread area. Sci Hortic-
Amsterdam 120(2009)2: 201-206
Cuticular penetration of calcium salts: effects of humidity, anions, and adjuvants. J Plant Nutr Soil Sc 164(2001)2: 225-231
Enhancing biological efficacy and rainfastness of foliar applied calcium chloride solutions by addition of rapeseedoil
surfactants. J Plant Nutr Soil Sc 165(2002)5: 634-639
In‐season calcium‐spray formulations improve calcium balance and fruit quality traits of peach. J Plant Nutr Soil Sc
174(2011)3: 465-472
Improving the performance of calcium-containing spray formulations to limit the incidence of bitter pit in apple (Malus x
domestica Borkh.). Sci Hortic-Amsterdam 127(2010)1: 23-28
Rates of foliar penetration of chelated Fe(III):  Role of light, stomata, species, and leaf age. J Agric Food Chem 54(2006)18:
6809-6813
Quantification of stomatal uptake of ionic solutes using a new model system. J Exp Bot 52(2001)357: 771–781 Open Access
Penetration of an ethoxylated fatty alcohol surfactant across leaf cuticles as affected by concentration, additives, and
humidity. J Plant Dis Protect 104(1997)4: 380-393
Foliar fertilization of peach (Prunus persica (L.) Batsch) with different iron formulations: Effects on re-greening, iron con-
centration and mineral composition in treated and untreated leaf surfaces. Sci Hortic-Amsterdam 117(2008)3: 241-248
Comparison of various adjuvants by their mode of actions. Proceedings ISAA 2010 p. 515
Foliar fertilization: scientific principles and field practices. IFA publication Open Access
The influence of tensides on ZnIDHA 2.0 adhesion to the leaf surface of wheat, canola and corn. Proceedings XVIII
International Plant Nutrition Colloquium (2017): 848-849
Effect of surfactants and leaf surface morphology on the evaporation time and coverage area of ZnIDHA droplets. Plant Soil
434 (2019)1-2: 93-105
The timing of application and inclusion of a surfactant are important for absorption and translocation of foliar phosphoric acid
by wheat leaves. Front Plant Sci 10(2019): 1532
Mathematical modelling of hydrophilic ionic fertiliser diffusion in plant cuticles: Lipophilic surfactant effects. Plants 8(2019)7:
202 Open Access
 Adjuvants & Formulations – January-February 2020 - page 7
News in brief
Surfactin is a bacterial cyclic lipopeptide.It is a
very powerful surfactant commonly used as an
antibiotic; Louisajb / Wikipedia
LOW‐TOXIC AND NONIRRITANT
BIOSURFACTANT SURFACTIN
Dan Fei et al. (East China University of
Science and Technology, Shanghai,
China) isolated surfactin (lipopeptide)
from cell‐free broth of Bacillus subtilis
HSO121 and purified it by reversed‐
phase high‐performance liquid chroma-
tography. The biodegradability, acute
dermal irritation, acute oral toxicity
(LD50 and LC50), surface activity,
washing efficiency and compatibility with
hard water of the purified biosurfactant
surfactin was investigated. Acute oral
toxicity tests (LD50 > 5000 mg kg−1,
LC50 > 1000 mg kg−1) and skin irritation
tests (PII = 0) indicate that surfactin is
a low‐toxic and nonirritant ingredient for
detergent formulations. Moreover,
surfactin showed excellent surface and
interfacial properties of emulsification
and wettability, high compatibility and
stability in a wide range of temperat-
ures, pH and in hard water. The authors
also mention acceptable biodegradability
and foaming ability. They conclude that
surfactin is a promising ingredient for
detergent formations in our daily life and
for industrial applications. More online.
WETTING PROPERTIES OF
SAPONARIA OFFICINALIS SAPONINS
Edyta Rekiel et al. (Maria Curie-
Skłodowska University, Lublin, Poland)
used saponins from Saponaria officinalis
(“soapwort”) to investigate their wetting
properties on solid surfaces. They
measured the contact angles of aqueous
solutions of saponins on poly-
tetrafluoroethylene (PTFE), poly(methyl
methacrylate) (PMMA) and quartz sur-
faces. They also measured the contact
angle of water, formamide and diiodo-
methane on the polytetrafluoroethylene
(PTFE), poly(methyl methacrylate)
(PMMA) and quartz covered with the
saponins. The authors concluded that
the saponins are poor wetting agents.
More online.
INSECTICIDAL ACTIVITY OF SPRAY
DRIED MICROENCAPSULATED
ESSENTIAL OILS
Rosmarinus officinalis and Zataria
multiflora (Lamiaceae) essential oils
(EOs) contain components with
insecticidal properties that can be used
as pesticides for stored product pests.
Sayed Mohammad Ahsaei et al.
(Department of Plant Protection,
University of Tehran, Karaj, Iran)
encapsulated the oils in octenyl succinic
anhydride (OSA) - starch in order to
test their insecticidal activity against
Tribolium confusum. First an oil-in-
water emulsion was prepared and after-
wards, it was dried by spray-drying
technique. The solid formulations were
characterized by particle size
(8.29–11.35 μm), encapsulation
efficiency (5–52%) and water activity
(0.19–0.26). Fumigant toxicity results
revealed that microencapsulated oils
were more effective than non-
formulated oils against beetles in long
time. Similarly, it was demonstrated
that microencapsulation of the essential
oils increases their persistence: non-
formulated oils do not have insecticidal
activity after 15 days of storage,
whereas at the same period,
microencapsulated rosemary and
Zataria oils resulted in a mortality rate
of T. confusum of 46.6 and 35.5%,
respectively. More online.
FUNGAL‐BASED BIOHERBICIDES
FOR WEED CONTROL: A MYTH OR A
REALITY?
After their survey, M. Triolet et al.
(INRA, Université Bourgogne Franche‐
Comté, Dijon, France), mention that a
real gap exists between the number of
experimental studies and the small
number of fungal-based bioherbicides
products currently on the market. A
dozen fungal‐based bioherbicides are on
the market in the United States and
Canada, while countries, such as China
and South Africa, have one, and none is
available in Europe. The active
ingredients in these bioherbicides are
living fungi, but no fungal molecule‐
based product is thus far on the market.
Reasons for this gap include production
hurdles, formulation process, ecological
fitness, duration of herbicidal effects and
costly and time‐consuming registration
procedures. The authors also state that
the literature shows an extended
interest in bioherbicides and that many
potential microorganisms and natural
fungal molecules have been proposed.
They conclude that analysis of fungus-
weed interactions still offers
perspectives for environment‐friendly,
sustainable weed control. More online.
BIOPESTICIDES R&D: CHALLENGES
AND PROSPECTS
Building on a recent international work-
shop with biopesticides practitioners
from across the globe, Dennis Ndolo et
al. (International Centre for Genetic
Engineering and Biotechnology, UCT
Campus, Cape Town, South Africa) list
challenges to biopesticide research and
development. They mention that bio-
pesticides in comparison with conven-
tional synthetic chemical pesticides are
usually less toxic, generally affect only
the target pest and closely related
organisms, are often effective in relat-
ively small quantities and decompose
faster, resulting in lower exposure.
Consequently, over the last few years,
biopesticides have attracted global
attention as a safer pest control strategy
for incorporation into Integrated Pest
Management (IPM) programmes.
Besides, in the last decade, adoption of
IPM programmes has significantly
enhanced pest management practices
and, in some cases, reduced pesticide
use, consequently reducing the rise in
demand for synthetic chemical
pesticides. Also, the development of new
synthetic chemical pesticides has
declined considerably in the recent past,
as regulations have become tighter, with
products being withdrawn from the
market. This resulted in a more limited
choice of chemical solutions such that
biopesticides have become a more
feasible option. Many countries have
also increasingly lowered chemical
Maximum Residue Levels for agricultural
 Adjuvants & Formulations – January-February 2020 - page 8

imports, which have made it increasingly Tuta absoluta is a serious pest

necessary to explore pest control of tomato crops in Europe,
options that would ensure reduced Africa, western Asia and South
reliance on the use of synthetic chemical and Central America;
pesticides. Prospects for biopesticide Marja van der Straten,
application are detailed using a case NVWA Plant Protection Service,
study on the fall armyworm (Spodoptera Wikipedia
frugiperda) in Africa. More online.

GENE SILENCING BY RNAI VIA ORAL

DELIVERY OF dsRNA BY BACTERIA
IN TUTA ABSOLUTA provided by sunlight. That’s why SEED COATING USING PLASMA
acifluorfen needs light for its herbicidal TECHNOLOGY
Flavia MM Bento et al. (University of São activity, as do other diphenyl ether
Paulo, Piracicaba, Brazil) demonstrated herbicides like aclonifen, bifenox, Scientists at the University of Bari Aldo
that bacteria can be used as a “tool” for fomesafen and oxyfluorfen. Mori have experimentally coated maize
the delivery of double stranded RNA The fluorescence labelling agent seeds with a fungicidal trilayer using
(dsRNA) in the South American tomato 7-hydroxycoumarin-4-acetic acid can plasma technology. A plasma is a
pinworm, Tuta absoluta. The rationale also provide the wavelength needed for radicals-rich gaseous mixture that can
behind is that double‐stranded RNA the excitation of protoporphyrin IX. The be used to disinfect seeds, devices and
(dsRNA) delivery needs to be adjusted researchers therefore examined the other surfaces, but also to assist the
to assure its stability until it reaches the possibility to incorporating this fluores- deposition of compounds.
target gene transcript for silencing. cent substance into acifluorfen formu- The plasma-assisted coating of maize
Gene silencing by RNAi offers the lations. They conjugated acifluorfen with seeds comprises three different layers.
potential to be used in the control of 7-hydroxycoumarin-4-acetic and then The inner layer is a plasma‐deposited
Tuta absoluta, one of the main insect conjugated this acifluorfen-coumarin hydrophilic coating covering the surface
pests of tomato (Solanum lycopersicum) compound with a carrier (amino- of the seeds. This layer is aimed to
worldwide. The authors tested the modified nanosilica). The experimental improve the adhesion of the second
delivery of dsRNA expressed in acifluorfen formulation performed well layer consisting of sprayed prothio-
Escherichia coli HT115(DE3) and under both high and low light intensity, conazole molecules. The outer layer is a
supplied to larvae in an artificial diet by the researchers observed in greenhouse plasma-deposited hydrophobic barrier.
screening target genes for silencing. experiments that were carried out at the This layer is aimed to encapsulate the
Using larval mortality, the duration of College of Plant Protection, China active ingredient, dose its release in the
the larval stage in days, pupal weight Agricultural University. They further soil and restore the natural hydrophobic
and the accumulation of the target gene mention the improved systemicity character of the seed surface. Water
transcript as parameters, the authors (measured in Brassica juncea seedlings) uptake of the seeds and germination
demonstrated the efficacy of bacterial and reduced cytotoxicity (measured in ability were not altered by the presence
dsRNA delivery for the functional effects Vicia faba root tip cells) and good safety of the trilayer, according to the Italian
on larval development. A significant to soybean as other advantages of the researchers. They mention that the
decrease in transcript accumulation and experimental formulations. More online. structure of the trilayer can be further
an increase in larval mortality could be optimized.
observed. More online. A plasma can be generated by heating a
gas, or subjecting a gas to a strong
CO-CRYSTALLISATION OF electro-magnetic field. A plasma is a
ESSENTIAL OILS gaseous mixture of ‘loose’ electrons
ACIFLUORFEN MORE EFFECTIVE plus the atoms that have released these
WITH BUILT-IN LIGHT SOURCE Co-crystallisation extends the use of electrons, the ions. The loose electrons
essential oils as ‘green’ pesticides. of the plasma react with the gases
Chinese scientists enhance the efficacy Researchers at the University of Parma present, creating all kinds of radicals:
of acifluorfen by formulating this and two other Italian research molecules with an odd number of
herbicide with a supplementary light institutions conclude this from electrons. The researchers used a
source. Acifluorfen inhibits the enzyme experiments with carvacrol, eugenol and home‐made plasma reactor fed with
protoporphyrinogen oxidase and thymol combined with phenazine or carbon dioxide and ethylene to prepare
consequently induces the accumulation hexamethylenetetramine. They showed the inner hydrophilic coating. For the
protoporphyrin IX, a precursor of that it is possible to design cocrystals outer hydrophobic coating they used
chlorophyll and a potent photosensitizer from essential oils to adapt the release only ethylene. The researchers used
substance. Protoporphyrin IX generates profile of these oils to different environ- several techniques to characterise the
cell-damaging reactive oxygen species mental conditions. The cocrystals are coatings, but do not provide a
upon irradiation with 410 nm ultraviolet prepared using solvent-free mechano- specification of the compounds that
light. This excitation wavelength is chemical protocols. More online. make up the inner hydrophilic and outer
 Adjuvants & Formulations – January-February 2020 - page 9
hydrophobic coating.
Plasma technology is a rapidly emerging
field. Plasmas are recognised for
sterilisation of medical devices. Plasmas
and plasma-activated water are used to
clean surfaces in the food industry and
investigated for seed treatment. Seed
treatment with cold plasma is found to
improve germination and to kill
pathogens on the seed surface. Since
plasma techniques use a minimum
amount of chemical reagents and no
solvents, they are often considered to
be eco‐friendly. Up to now plasma
deposition of protective seed coatings
has hardly been investigated.
Experiments with plasma-deposited
films using tetraethoxysilaneare are
probably the first and only published
investigations so far (Carvalho et al.;
2005 and Carvalho et al.; 2006). The
plasma-deposited hydrophobic films are
resistant to water vapour, but get
hydrolysed when dipped in water,
resulting in a change of microstructure
which turns them hydrophilic. The work
with maize seeds covered with a trilayer
coating containing prothioconazole is
probably the first of its kind.
The University of Bari researchers
report nothing about the energy
consumption of plasma-assisted coating
of seeds. It is known that plasma
technologies to produce nitrate fertiliser
from atmospheric nitrogen and oxygen
is considerably less energy-efficient
than the also energy-consuming
industrial-scale Haber-Bosch process
used to synthesise ammonia for
nitrogen fertiliser. More online.
ALGINATE-BASED FORMULATION
FOR REACTIVE OXYGEN AND
NITROGEN SPECIES
Plasma-activated water contains
reactive oxygen and nitrogen species
such as nitrite, hydrogen peroxide and
other, short-lived species. These
reactive species have both pesticidal
and biostimulatory effects. Spraying
crops with mild plasma water with a
short production time can effectively
control bacteria, according to
researchers from Wageningen UR
Greenhouse Horticulture in a Dutch-
language report (Quaedvlieg and
Hofland-Zijlstra; 2016). Strong plasma
water with a longer production time is
Schematic presentation of maize seed with a plasma ‐deposited hydrophilic coating (polymeric
coating A), sprayed protioconazole layer (antifungal layer) and plasma deposited hydrophobic
barrier (polymeric coating B); Chiara Lo Porta et al.
necessary for controlling powdery
mildew and other fungal diseases
caused by Fusarium and Botrytis. Crop
treatments with mild and strong plasma
water showed no damage on young
gerbera plants, lettuce and tomato
plants, the researchers reported. Up to
now spraying crops with plasma-
activated water has hardly been
investigated, let alone the use of
adjuvants with plasma water.
Spraying formulated radicals is equally
unknown. Spanish investigators have
recently provided a proof-of-concept
that it is feasible to use alginate
hydrogels as carrier for reactive oxygen
and nitrogen species. They have also
investigated the release profile of the
thus formulated compounds. Application
in cancer therapies was the background
of this study into the formulation of
compounds generated with help of cold
atmospheric plasmas. The researchers
published their findings in an open
access article in the journal Scientific
Reports (Labay et al.; 2019).
CONFUSION ABOUT SURFACTANTS
IN GLYPHOSATE-BASED
HERBICIDES DOCUMENTED
Research into the toxicity of commercial
pesticide formulations is often lacking in
clarity about the precise composition of
these crop protection products. Three
researchers provide insight into this
confusion in a recently published open
access article in the journal Food and
Chemical Toxicology. They focus their
study on surfactant co-formulants in
glyphosate-based herbicides. Often the
identity and concentration of these
formulation aids is not specified,
because this information is frequently
declared to be confidential business
information. Furthermore, many
researchers only report the trade name
of a glyphosate composition tested,
without reporting the country where the
formulation was sourced. Investigators
are often not aware of possible
differences in composition per country.
The three UK- and US-based
researchers illustrate this confusion
with differences between Roundup Ultra
products: the formulation sold in
Ireland is the MON 76473, while it is
MON 79351 in Greece, MON 52276 in
Germany and MON 77360 in the USA.
“Our review reveals a compelling need
for full transparency on the composition
of pesticides on product labels, MSDSs,
and all sources of technical information
on formulated pesticides. (…) Toxicity
profiles in the literature are generally
more consistent when the composition
of the formulations is accurately
reported and properly taken into
account”, the researchers say. They
also stress that the knowledge gap
regarding exposure, daily intake and
health consequences of co-formulants
for farm animals and humans needs to
be speedily addressed. More online.
 Adjuvants & Formulations – January-February 2020 - page 10
Patents in brief
CRYSTAL GROWTH INHIBITORS FOR
SDHI FUNGICIDES
Published 28-11-2019
Bayer seeks patent protection for
cellulose polymers and polymeric
surfactants that minimize crystal growth
in succinate dehydrogenase inhibitor
fungicides. It can be deduced from
patent publication WO2019224280 that
the company had particular the active
ingredients fluopyram and isoflucypram
in mind. Bayer examined Croda’s crystal
growth inhibitor Atlox 4913 (polymeric
surfactant), cellulose ether (hydroxy-
propyl methylcellulose, also known as
hypromellose) and polycarboxylate
(polycarboxylic acid salt) as crystal
growth inhibitors. The patent publication
has several exemplary formulations, a
number of which contain both Atlox
4913 and a cellulose ether.
POLYMERS STABILIZE dsRNA
Published 28-11-2019
Syngenta has filed a patent application
covering the use of hydrolysable
polymers that can form a complex with
polynucleotides, particularly double-
stranded RNA (dsRNA). Complexation of
dsRNA to the positively charged polymer
enhances protection of the dsRNA in soil.
The polymers-in-question release dsRNA
upon hydrolysis. The ratio of hydro-
lysable to non-hydrolysable monomers
of the polymer can be tuned to determ-
ine the rate of dsRNA release, according
to the company in patent application
WO2019224142. The stabilized dsRNA
formulation is developed for post-
transcriptional silencing of one or
various target genes in subterranean
insects such as Diabrotica rootworms,
wireworms, nematodes and grabs.
FLUXAMETAMIDE EC FORMULATIONS
Published 05-12-2019
The solvent in the new fluxametamide
emulsifiable concentrates from Nissan
Chemical Corporation is a mixture of the
polar solvent 3-methoxy-N,N-dimethyl-
propanamide and a non-polar solvent.
The company illustrates the application
of these solvent mixtures in EC
formulations containing fluxametamide
as the only active ingredient and also
compositions of this insecticide with the
insecticide pyridaben, the fungicide
amisulbrom or the herbicide quizalofop-
P-ethyl. Specifications and preparation
of these compositions are disclosed in
the Japanese-language patent
publication WO2019230621.
CYCLODEXTRIN STABILIZES LIQUID
PROTHIOCONAZOLE AND/OR
PENFLUFEN FORMULATIONS
Published 05-12-2019
Bayer has found that cyclodextrin
compounds stabilize liquid formulations
of the triazole fungicide prothioconazole,
the pyrazolecarboxamide fungicide
penflufen and mixtures of both active
ingredients. The formation of
prothioconazole-desthio in the stabilized
prothioconazole formulation is
significantly reduced, so that active
ingredient concentrations keep staying
within mandated limits. Bayer presents
this patent pending application of
cyclodextrins in patent publication
WO2019232201.
Previously the company informed that
organic vinyl compounds significantly
reduced the risk of prothioconazole-
desthio formation in prothioconazole-
containing liquid formulations (see
patent publications EP3415007 and
WO2018228885). Before that, Bayer
filed patent applications covering the
use of an ω-unsaturated fatty acid as
solvent to reduce prothioconazole-
Crystal growth inhibitors
and other formulation
stabilizing agents are
subject of recently filed
patent applications.
desthio formation (EP3178320 and
WO2017097882). Drawbacks of these
fatty acids let Bayer search for
alternative solutions.
EFFERVESCENT FORMULATION FOR
PPO INHIBITOR HERBICIDE
Published 05-12-2019
Sumitomo Chemical Australia has de-
veloped an effervescent tablet formula-
tion of the PPO inhibitor herbicide
flumioxazin. This formulation is de-
veloped with aquatic weed control in
water bodies like ponds in mind. The
herbicide composition is formulated to
disperse the herbicide in a first stage
below the water surface and in a second
stage at or substantially at the surface
of the body of water, according to the
company in patent application
WO2019227166. As example the
company presents an experiment with a
Ø 65 mm, 30 mm thick tablet weighing
134 gram.
CROP PROTECTION WITH
NANOBUBBLE WATER AS CARRIER
Published 05-12-2019
Nanobubbles in the carrier water help
insecticides penetrate scale insects. In
the absence of a better explanation, the
Japanese company Aquasolution
Corporation says to speculate that an
insecticide applied with nanobubble
water easily penetrates into the insect
body coating (such as shells or waxes)
and that the insecticide can reach the
insect body. The company has filed a
 Adjuvants & Formulations – January-February 2020 - page 11
patent application covering an
insecticide in an aqueous carrier that
contains such gaseous nanobubbles.
Various gases can be used for this
purpose, but oxygen is preferred, as
oxygen nanobubbles stay relatively long
in the carrier water. The invention is
described in the Japanese-language
patent application WO2019230755.
Recently, Aquasolution Corporation has
also filed patent applications covering
nanobubble water to eradicate whitefly
in cucumber, tomato (WO2019230753),
cabbage moth in cabbage or ginger
(WO2019230779) and to control spider
mites (WO2019230780). The Japanese
company suggests that nanobubble
water is also of use to eradicate
bacterial spot in various crops
(WO2019230762), to suppress clubroot
(WO2019230776) and powdery mildew
(WO2019230789) and to enhance the
efficacy of fungicides applied to prevent
fruit mold (WO2019230764). Other
applications covered by patent applica-
tions are extension of the harvesting
period of vegetables (WO2019230777)
and prevention of yield loss due to
drought in ginger (WO2019230786). The
company suggests that nanobubble
water is also of use to control tomato
fruit shape (WO2019230766), to
prevent magnesium deficiency
(WO2019230754) and to increase the
amount of nitrate, phosphoric acid and
potassium present in soil
(WO2019230778). A related patent
application covers the use of nanobubble
water to enhance fertiliser absorption
(WO2019230788). Two patent
applications are related to devices for
the generation and application of the
patent pending water (WO2019230787
and WO2019230775). These 16 patents
applications form the entire IP portfolio
of Aquasolution Corporation and are
published simultaneously on 5.
December 2019.
UREASE AND NITRIFICATION IN-
HIBITOR COMBINED IN EMULSION
Published 05 and 12-12-2019
DMPSA is a new nitrification inhibitor
developed by Eurochem Agro GmbH.
The German fertiliser manufacturer is
looking for ways to combine this
nitrification inhibitor with a urease
inhibitor to protect urea against rapid
hydrolysis and subsequent nitrification.
Eurochem’s approach is an emulsion of a
urease inhibitor (NBPT and/or NPPT)
dissolved in an organic solvent and
DMPSA dissolved in water, which can be
used to treat urea-containing fertilisers.
Details of the patent pending
urease/nitrification inhibitor solution are
presented in patent applications
DE102018208770 and WO2019233905.
SURFACTANT COMPOSITION BASED
ON GLYCINE BETAINE AMIDE SALT
Published 17 to 26-12-2019
The French start-up company
SurfactGreen (established end 2016)
seeks patent protection for surfactants
based on glycine betaine amide salts.
These surfactant compositions have a
lower surface tension than their
predecessors disclosed in patent
publication WO2013188508. Surfactant
compositions according to the invention
have a surface tension value of less than
24 mN/m, or even less than 22 mN/m
and generally greater than or equal to
20 mN/m, the company says.
SurfactGreen presents two variants of
the new surfactant compositions, along
with a comparative composition con-
taining less glycine betaine laurylamide
and more laurylammonium salt, which
therefore has a higher surface tension at
the critical micelle concentration
(25 mN/m). Synthesis protocols and
four exemplary formulations based on
the surfactant compositions (household
detergent, cleaning, water treatment
and pyrethrum/pheromone formulation)
are presented in a series of patent
applications (BR102019012423,
CA3045341, EP3584303, FR3082522,
JP2019218544 and US20190380333).
SurfactGreen says to develop, produce
and sell new surfactants that are 100 %
bio-based. The company builds on
research from the Ecole Nationale
Supérieure de Chimie de Rennes. In
close cooperation with this school of
chemistry, SurfactGreen develops
‘green’ surfactant synthesis processes.
CRYSTAL POLYMORPH OF NEW
URACIL HERBICIDE
Published 19-12-2019
BASF SE filed a patent application
covering a new crystal polymorph of a
uracil herbicide that is originally
patented by Sumitomo Chemical
Company. According to the company,
this PPO inhibitor herbicide does not
display the disadvantages of the
amorphous form of this compound
(WO2019238427). The uracil herbicide
– up to now without common name –
has the CAS registration number
344419-99-4.
Previously BASF SE filed patent
applications covering crystal polymorphs
of a related uracil herbicide with CAS
registration number 353292-31-6
(WO2018178039). This herbicide also
has no common name yet and is known
as S-3100 or SYN-523; this active
ingredient has been licensed to
Syngenta in 2005.
OTHER INTERESTING APPLICATIONS
Surface-active clopyralid formulation
with improved frost resistance
Years ago formulators at AXK AGRO
have developed a surface-active
trialkylamine modification of the
pyridine herbicide clopyralid
(RU2384064). In the Russian-language
patent application RU2708339 they
present improvements to the original
formulation. The new clopyralid
formulation is less frost-sensitive and
contains 2-ethylhexyl ester of clopyralid
as the organic solvent.
Water-dispersible flometoquin
formulation
The Japanese companies Nippon Kayaku
Co., Ltd and Meiji Seika Pharma Co., Ltd
have developed a water-dispersible
formulation of the insecticide
flometoquin. This composition has
excellent storage-stability and excellent
physical properties for preparations, the
companies say in the Japanese-
language patent application
WO2019235602.
 Adjuvants & Formulations – January-February 2020 - page 12

Literature

GENERAL
Fungal‐based bioherbicides for weed control: a myth or a reality? Weed Res 60(2019)1: 60-77
Research and development of biopesticides: challenges and prospects. Outlooks on Pest Management 30(2020)6: 267-276
Template-assisted spray-drying method for the fabrication of porous particles with tunable structures. Adv Powder Technol
30(2019)12: 2908-2924

HERBICIDES
Atrazine nanoencapsulation improves pre‐emergence herbicidal activity against Bidens pilosa without enhancing long‐term
residual effect on Glycine max. Pest Manag Sci 76(2020)1: 141-149
Tank-mix adjuvants to reduce the adverse effect of muddy rain on the activity of paraquat against winter wild oat. Crop Prot
128 (2020): 105013
Ionic liquid forms of mesotrione with enhanced stability and reduced leaching risk. ACS Sustain Chem Eng 7(2019)19:
16620-16628
Synergistic effects of adjuvant A-134 on the herbicidal effects of glyphosate. J Pestic Sci 44(2019)4: 249-254 Open Access
Chitosan/glyphosate formulation as a potential, environmental friendly herbicide with prolonged activity. J Environ Sci Heal B
54(2019)8: 681-692
Study on stability of mesosulfuron-methyl dispersible oil suspension. Agrochemicals 58(2019)11: 799-801, 815
Influence of hydrophilic and hydrophobic properties of polycarboxylate dispesants on the pesticide dispersion. Agrochemicals
58(2019)11: 802-804, 809
Study on the promoter of nicosulfuron+atrazine 24% OD with soybean oil as medium. Modern Agrochemicals 18(2019)5: 18-21
Study on formula of metamifop and penoxsulam 15 % oil-based suspension concentrates. Pesticide Science and
Administration 40(2019)8: 37-41
Study on the formula of pyrazosulfuron-ethyl and penoxsulam 10% oil dispersion. Pesticide Science and Administration
40(2019)9: 32-36

FUNGICIDES
Optimization of preparation process of triadimefon microcapsules by using response surface analysis. Agrochemicals
58(2019)10: 722-726, 732
Preparation and control effect of thifluzamide+azoxystrobin 4% spreading oil. Modern Agrochemicals 18(2019)5: 7-10
Preparation of prothioconazole·trifloxystrobin 75% water dispersible granule. World Pesticides 41(2019)5: 44-47, 57

INSECTICIDES
Control of two-spotted spider mites with neem-based products on a leafy vegetable. Crop Prot 128(2020): 105006
Insecticidal activity of spray dried microencapsulated essential oils of Rosmarinus officinalis and Zataria multiflora against
Tribolium confusum. Crop Prot 128(2020): 104996
Enzyme cum pH dual-responsive controlled release of avermectin from functional polydopamine microcapsules. Colloid
Surface B 186(2020): 110699
Synthesis of pH-responsive isolated soy protein/carboxymethyl chitosan microspheres for sustained pesticide release. J Appl
Polym Sci 137(2020)6: 48358
Inverse correlation between lethality and thermodynamic stability of contact insecticide polymorphs. Cryst Growth Des
19(2019)3: 1839-1844
Development of high-loading abamectin CS formulation. Modern Agrochemicals 18(2019)5: 15-17
Study and preparation of avermectin 1.8% effervescent emulsion granule. World Pesticides 41(2019)5: 48-52

BIOPESTICIDES
A star polycation acts as a drug nanocarrier to improve the toxicity and persistence of botanical pesticides. ACS Sustain
Chem Eng 7(2019)20: 17406-17413
Designing a palette of cocrystals based on essential oil constituents for agricultural applications. ACS Sustain Chem Eng
7(2019)21: 17929-17940
Development and stability enhancement of neem oil based microemulsion formulation using botanical synergist. J Mol Liq
296(2019): 112012
Development of Bacillus amyloliquefaciens FS6 WP. Agrochemicals 58(2019)10: 716-721
Formulation and bioactivity of allicin+eugenol 20% EW. Modern Agrochemicals 18(2019)5: 11-14

FERTILISERS
Green synthesis of iron nanoparticles using red peanut skin extract: Synthesis mechanism, characterization and effect of
conditions on chromium removal. J Colloid Interf Sci 558(2020): 106-114
Efficacy of a new N-(n-butyl) thiophosphoric triamide formulation in reducing ammonia volatilization from urea-based
fertilizers. Can J Soil Sci 99(2019)4: 395-405
 Adjuvants & Formulations – January-February 2020 - page 13

RNAI
Gene silencing by RNAi via oral delivery of dsRNA by bacteria in the South American tomato pinworm, Tuta absoluta. Pest
Manag Sci 76 (2020)1: 287-295

PLANT GROWTH REGULATORS

Synthesis and controlled release properties of β-naphthoxyacetic acid intercalated Mg–Al layered double hydroxides
nanohybrids. Arab J Chem 12(2019)8: 2563-2571

SEED TREATMENT
Electrospun polymer nanofibers as seed coatings for crop protection. ACS Sustainable Chem Eng 7(2019)24: 19848-19856
Production and efficacy of neem nanoemulsion in the control of Aspergillus flavus and Penicillium citrinum in soybean seeds.
Eur J Plant Pathol 155(2019)4: 1105-1116
Plasma-assisted deposition of fungicide containing coatings for encapsulation and protection of maize seeds. Plasma Process
Polym 16(2019)6: 1900022

FORMULATION
Design of a biodegradable carrier for the application of controller bacteria on air–water interfaces. Pest Manag Sci 76(2020)1:
296-303.
Kaolin-based particle film sprays reduce the incidence of pests, diseases and storage disorders and improve postharvest
quality of ‘Delicious’ apples. Crop Prot 127(2020): 104950 Open Access
Production of more sustainable emulsions formulated with eco-friendly materials. J Clean Prod 243(2020): 118661
Production of reactive species in alginate hydrogels for cold atmospheric plasma-based therapies. Sci Rep-UK 9(2019): 16160

GRANULATION
Development and application of water dispersible dranule based on wet grinding process. World Pesticides 41(2019)5: 40-43

RELEASE OF ACTIVE INGREDIENTS

Enhanced phototherapy activity by employing a nanosilica-coumarin–acifluorfen conjugate as the supplementary light source
generator. ACS Sustain Chem Eng 7(2019)21: 17706-17713
Fabrication of a sustained release delivery system for pesticides using interpenetrating
polyacrylamide/alginate/montmorillonite nanocomposite hydrogels. Appl Clay Sci 183(2019): 105347
Enzyme and pH dual-responsive avermectin nano-microcapsules for improving its efficacy. Environ Sci Pollut R 26(2019)24:
25107-25116
Advances in controlled release pesticide formulations: Prospects to safer integrated pest management and sustainable
agriculture. J Hazard Mater 385(2019): 121525

NANOTECHNOLOGY
Shape-dependent antifungal activity of ZnO particles against phytopathogenic fungi. Applied Nanosci 10(2020)2: 435-443
Nanoemulsion of eucalyptus oil: An alternative to synthetic pesticides against two major storage insects (Sitophilus oryzae
(L.) and Tribolium castaneum (Herbst)) of rice. Ind Crop Prod 143(2020): 111849

CHEMISTRY
Investigation of mixing behavior of both a conventional surfactant and different inorganic salts with a cationic gemini
surfactant in aqueous Solution. J Surfactants Deterg 22(2019)6: 1319-1330
Two-dimensional nanostructure colloids in novel nano drug delivery systems. Colloid Surface A 585(2020): 124077 Open Access
Micellar thermodynamic behavior of branch-modified xanthan gum and aggregating structures in aqueous and saline
solutions. Colloid Surface A 587(2020): 124317 Open Access
Phase behavior and microstructure of symmetric nonionic microemulsions with long-chain n-alkanes and waxes. Ind Eng
Chem Res 58(2019)7: 2583-2595

WETTING
Analysis of potential impaction and phytotoxicity of surfactant-plant surface interaction in pesticide application. Crop Prot
127(2020): 104961 Open Access
Wetting properties of Saponaria officinalis saponins. Colloid Surface A 584(2020): 123980 Open Access
Drying kinetics and viscoelastic properties of concentrated thin films as a model system for spray drying. Colloid Surface A
585(2020): 124075 Open Access
Measurement of foliar spray retention on creeping bentgrass. Weed Technol 33(2019)6: 827-832

SOLVENTS
Emerging frontiers of deep eutectic solvents in drug discovery and drug delivery systems. Journal of Controlled Release
316(2019): 168-195
Continued page 14
 Adjuvants & Formulations – January-February 2020 - page 14

Item of the month

Tank-mix adjuvants to reduce the adverse effect of muddy rain on

the activity of paraquat
Akbar Aliverdi and Goudarz Ahmadvand (Bu-Ali Sina
University, Hamedan, Iran) investigated the adverse effect
of soil settling on a weed through a simulated muddy rain on
the activity of a bipyridylium herbicide. They also compared
the efficacy of three adjuvants to decrease this adverse
effect. In a greenhouse experiment, a 0.04-mm muddy rain
containing 0, 1, 2, 4 and 8 kg soil ha−1 was rained on winter
wild oat before the doses of 0, 75, 150, 300, 600, and
1200 g paraquat ha−1 were sprayed on. In a companion
experiment, a 0.04-mm muddy rain containing 0 and 8 kg
soil ha−1 were rained on winter wild oat before the afore-
mentioned doses of paraquat were sprayed with or without
acriflavine chloride, chlormequat chloride, and mepiquat
chloride at 0.2% (w/v). Based on the dose giving 90%
dehydration of the plant, the muddy rain containing 1, 2, 4
and 8 kg soil ha−1 decreased the activity of paraquat against
winter wild oat in run 1 by 1.2-, 1.6-, 2.5- and 7.0-fold and
in run 2 by 1.4-, 3.0- and 6.4-fold in comparison with
control, respectively. All adjuvants were effective in
significantly decreasing the adverse effect of muddy rain on
the activity of paraquat against winter wild oat. In this
regard, chlormequat chloride was the most effective,
following by acriflavine chloride and mepiquat chloride.
More online.
Note editor: It seems that the authors, the reviewers of
this article and the editors of Crop Protection did not realise
that the so-called adjuvants (e.g. chlormequat chloride) are
active ingredients effecting the physiology of the weed,
thus no adjuvants.

Continued from page 13

SURFACTANTS
Review on silicone surfactants: Silicone-based gemini surfactants, physicochemical properties and applications. Tenside
Surfact Det 56(2019)4: 268-278

BIOSURFACTANTS
Low‐toxic and nonirritant biosurfactant surfactin and its performances in detergent formulations. J Surfactants Deterg
23(2020)1: 109-118
Biosurfactants, natural alternatives to synthetic surfactants: Physicochemical properties and applications. Adv Colloid Interfac
175(2020): 102061

BIOEMULSIFIERS
Production, characterization, and applications of bioemulsifiers (BE) and biosurfactants (BS) produced by Acinetobacter spp.:
A review. J Basic Microb 59(2019)3: 277-287
Sustainable microbial biosurfactants and bioemulsifiers for commercial exploitation. Process Biochem 85(2019): 143-155

PHOTOPROTECTION
Effects of nanoparticles of metal oxides on the survival of the entomopathogenic nematode: Steinernema carpocapsae. J
Nanosci Nanotechno 20(2020)3: 1434-1439
Influence of metal oxides nanoparticles on pathogenicity of Steinernema carpocapsae nematodes against lepidopteran
Galleria mellonella. J Nanosci Nanotechno 20(2020)3: 1470-1477

FOLIAR UPTAKE
Involvement of integument‐rich CYP4G19 in hydrocarbon biosynthesis and cuticular penetration resistance in Blattella
germanica (L.). Pest Manag Sci 76(2020)1: 215-226
X-ray spectroscopy fostering the understanding of foliar uptake and transport of Mn by soybean (Glycine max L. Merril):
kinetics, chemical speciation, and effects of glyphosate. J Ag Food Chem 67(2019)47: 13010-13020

APPLICATION TECHNOLOGY
Binarizing water sensitive papers – how to assess the coverage area properly?. Crop Prot 127(2020): 104949 Open Access
Evaluation of leaf deposit quality between electrostatic and conventional multi-row sprayers in a trellised vineyard. Crop Prot
127(2020): 104964 Open Access
The smart spray analytical system: Developing understanding of output air-assist and spray patterns from orchard sprayers.
Crop Prot 127(2020): 104977 Open Access
Field efficacy trials on the control of weeds in rice by UAV spread. Pesticide Science and Administration 40(2019)9: 45-51
 Adjuvants & Formulations – January-February 2020 - page 15

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