Colloids and Surfaces A 530 (2017) 13–19

Contents lists available at ScienceDirect

Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

High blades spreadability of chlorpyrifos microcapsules prepared with MARK

polysiloxane sodium carboxylate/sodium carboxymethylcellulose/gelatin
via complex coacervation
⁎
Run Ying Daia,c, Sheng Yong Youb, , Li Min Lua,c, Qian Liua,c, Zhong Xiu Lia, Ling Weia,c,
⁎
Xi Gen Huanga,c, Zhi Yong Yanga,
a
College of Science, Jiangxi Agricultural University, Nanchang, 330045, China
b
Institute of Applied Chemistry, Jiangxi Academy of Sciences, Nanchang, 330096, China
c
Institute of functional materials and agricultural Applied Chemistry, Jiangxi Agricultural University, Nanchang, 330045, China

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: The sustainable-release property and spreadability of microencapsulated pesticide on blades have attracted
Chlorpyrifos microcapsules special interest mainly because they are related to the utilization of pesticide. In this work, polysiloxane sodium
Sustainable-release property carboxylate (PSiSC) surfactant with double hydrophobic chains has been introduced for the first time into the
Spreadability capsule shell materials to improve the spreadability of the chlorpyrifos microcapsules on rice blades. The silicone
Polysiloxane sodium carboxylate surfactant
chlorpyrifos microcapsules have been prepared with PSiSC/gelatin (GE)/sodium carboxymethylcellulose
Complex coacervation
(NaCMC) by complex coacervation method. Optical microscopy, scanning electron microscopy, laser particle
size analyzer, fourier-transform infrared, energy dispersive X-ray spectroscopy, contact angle measurement and
UV/VIS spectrometer are used to characterize the silicone chlorpyrifos microcapsules. The PSiSC/NaCMC/GE
microcapsules that exhibit the chlorpyrifos encapsulation rate of 50.8%, surface smooth, the mean diameter

⁎
Corresponding authors.
E-mail addresses: ysygood1981@163.com (S.Y. You), zyyang200906@163.com (Z.Y. Yang).

http://dx.doi.org/10.1016/j.colsurfa.2017.06.057
Received 19 February 2017; Received in revised form 21 June 2017; Accepted 21 June 2017
Available online 01 July 2017
0927-7757/ © 2017 Elsevier B.V. All rights reserved.
R.Y. Dai et al.
around 3.5 μm and shell thickness of 285 nm, fabricated with 1.2 mmol/L PSiSC surfactant at pH 4.6. The
chlorpyrifos-loaded microcapsules are of remarkable sustainable-release property. The PSiSC/NaCMC/GE mi-
crocapsules own high spreadability on the rice blades, which promotes increasing the residual amount of
chlorpyrifos microcapsules on hydrophobic blades, thereby improving the utilization of chlorpyrifos.
1. Introduction
Chlorpyrifos (O,O-diethyl O-(3,5,6,-trichloro-2-pyridyl phosphor-
othioate)), as one of the largest amount of insecticide in the world,
widely used to control agricultural pest. However, the drawback of
chlorpyrifos is obvious, mainly because of its high toxicity, poor water
solubility, unpleasant smell, and strong photolysis that leads to a lower
residual amount on blades [1]. Significant efforts have been exerted in
this field to avoid pesticide photolysis, and provide sustainable release
into a suitable carrier [2–5]. While microencapsulation just can avoid
the target molecule to photolysis, control or trigger release, prolong
efficacy, and enhance safety and reliability [6,7]. Most pesticide mi-
crocapsules were prepared by interfacial polymerization method
[1,8,9] and solvent evaporation method [10]. For interfacial poly-
merization, the raw materials used are toxic and the particle size dis-
tribution of microcapsule is wide, which is unfavorable for being
sprayed out [10]. For solvent evaporation, micro-porous in the shell
layer would induce that the active ingredients in the microcapsule to
exhibit burst effect at the beginning of release and the release rate is
uncontrollable [4]. For complex coacervation, the raw materials used
are biodegradable and the particle size of microcapsule is uniform
[11–15]. It has bright prospects in the agriculture sector to prepare
controlled release formulation systems for pesticides.
Several pesticide microcapsules have been developed and applied in
commercial use [16,17]. Although these pesticide microcapsules are
fairly stable, many studies have focused on improving the encapsula-
tion efficiency of microcapsules [2,14], few studies have concentrated
on improving the residual amount of pesticide microcapsules on the
hydrophobic blades. Jia et al. reported a conceptual strategy for
prolonging foliar pesticide retention by using an adhesive poly-
dopamine (PDA) microcapsule to encapsulate avermectin, which can
minimize its volatilization and improve its residence time on crop
surfaces [18].
Ivanova et al. studied the spreading behavior of organosilicon sur-
factant Silwet L-77 on hydrophobic substrates. They found that the
characteristic time of spreading until a quasi-equilibrium state for
Silwet L-77 was a few seconds, which suggests the organosilicon sur-
factant has good spreading behavior [19]. The spreading ability and
hydrolysis resistance of double-tail trisiloxane surfactants are better
than that of single-tail trisiloxane surfactants [20]. Polysiloxane sodium
carboxylate (PSiSC) surfactant belongs to organosilicone anionic sur-
factant, containing carboxylic and polysiloxane groups. PSiSC with
double hydrophobic chains exhibits perfect hydrophobicity, excellent
surface activity compared to ordinary hydrocarbon surfactants and
improves the spreadability of phoxim pesticide on the leaves [21]. In
this work, by introducing PSiSC surfactant in the aqueous solution of
gelatin (GE) and sodium carboxymethylcellulose (NaCMC), the silicone
chlorpyrifos microcapsules are prepared by complex coacervation. The
chlorpyrifos encapsulation rate (ER) affected by the molar concentra-
tion of PSiSC surfactant, the chlorpyrifos release behavior and the
spreadability of PSiSC/NaCMC/GE microcapsules on hydrophobic
blades are fully investigated. Results show that the novel microcapsules
exhibit high chlorpyrifos ER, good sustainable-release property and
excellent spreadability on hydrophobic blades. It facilitates improving
the residual amount of chlorpyrifos microcapsules on the hydrophobic
blades and the utilization of chlorpyrifos.
14
Colloids and Surfaces A 530 (2017) 13–19
2. Experimental
2.1. Materials
Polysiloxane sodium carboxylate (PSiSC) was made by ourselves
according to reference [21]. Chlorpyrifos (96.6%) was provided by
Jiangsu Jinghong Chemical Co., Ltd. Gelatin (GE, type B, alkali pro-
cessed, isoelectric point pH = 4.8) was produced by Hangzhou Qunli
Gelatin Chemical Co., Ltd. Sodium carboxymethylcellulose (NaCMC),
sodium dodecyl sulfate (SDS), anhydrous methanol, glutaraldehyde
(25 wt.%), acetic acid and tetrachloroethylene were purchased from
shanghai medical group reagent company. Hydrophobic blades, the
five-period of rice blades were provided by the testing field of Jiangxi
Agricultural University. All chemicals were used without further pur-
ification. Distilled water was used in all studies.
2.2. Preparation of the PSiSC/NaCMC/GE microcapsules
10 g of chlorpyrifos suspension served as core materials, which
comprise of chlorpyrifos as original pesticide, span 80 as emulsifier, and
tetrachloroethylene as dispersion medium. Different molar concentra-
tion of PSiSC surfactant commixed with 20 g of GE aqueous solution
(5 wt.%) and 100 g of NaCMC aqueous solution (0.2 wt.%) as shell
materials. The chlorpyrifos suspension was dispersed into the mixture
of PSiSC/NaCMC/GE aqueous solution with a homogenizer of 450 r/
min at 45 °C to form stable O/W emulsion. The pH value of system was
adjusted using acetic acid (0.4%) to form complex coacervates. The
reaction temperature was slowly cooled to 10 °C and kept the tem-
perature for 1 h. 3.5 g glutaraldehyde solution (25 wt.%) was added for
curing the capsule shell. The resulting microcapsules were washed by
distilled water until the upper solution was transparent and stored in
distilled water.
2.3. Characterization of the PSiSC/NaCMC/GE microcapsules
Fourier-transform infrared (FT-IR) spectra scanned over the range of
400–4000 cm−1 with potassium bromide pellet on a FT-IR instruments
(FT-IR-650, Tianjin Gangdong Technology Development Co., Ltd.,
China).
The elements contained in the shell of PSiSC/NaCMC/GE micro-
capsules were analyzed by Energy dispersive X-ray spectroscopy (EDX,
EMAX X-act, Horiba Co., Japan).
The morphology of PSiSC/NaCMC/GE microcapsules was char-
acterized by optical microscopy (OM, BX-51, Olympus Co., Japan) and
scanning electron microscopy (SEM, S-3400N, Hitachi Co., Japan).
Particle size distribution of PSiSC/NaCMC/GE microcapsules was
measured on laser particle size analyzer (LS 13320, Bechman Coulter
Co., USA).
Surface tension (σ) of the aqueous NaCMC solution (2 g/L) with
different surfactants was tested by ring-pulling method at 25 °C [22]
according to the formula:
ΔF (U1 − U2 ) g
σ= π(D1 + D2 )
ΔF = B
In which D1, D2 are the outside and inside diameter of ring, respec-
tively; ΔF is the difference of the ring pulled off instantly from the liquid
R.Y. Dai et al.
surface; U1, U2 are voltage of to be pulled off and being pulled off from
the liquid surface; B is the sensitivity of force sensor, its value is
29.23mhV/g generally and g is usually 9.792 m/s2.
2.4. Amount of chlorpyrifos encapsulated in PSiSC/NaCMC/GE
microcapsules
To determine the amount of chlorpyrifos encapsulated in PSiSC/
NaCMC/GE microcapsules, the percentage of initial chlorpyrifos en-
capsulation rate (ER) was tested as follows: Firstly, different mass
concentrations of chlorpyrifos dissolved in anhydrous methanol were
examined by UV/VIS spectrometer (Lambda 25, PerkinElmer,
Germany) at the optimum wavelength of 290 nm [23,24]. The standard
curve was drawn based on absorbance and the mass concentration of
chlorpyrifos, taking anhydrous methanol as a reference. Secondly, a
certain amount of PSiSC/NaCMC/GE microcapsules were dispersed in
anhydrous methanol for 120 h with magnetic stirring. The absorbance
value was determined of extracted chlorpyrifos from microcapsules
after filtration. The corresponding mass concentration of chlorpyrifos
was found on the standard curve. Finally, the percentage of chlorpyrifos
ER was calculated as the following equation [2]:
massofchlorpyrifosloadedinmicrocapsules
ER (%) = × 100
massofchlorpyrifos
2.5. Release behavior of chlorpyrifos from PSiSC/NaCMC/GE
microcapsules
The release behavior of the loaded chlorpyrifos from PSiSC/
NaCMC/GE microcapsules was studied by the accumulative release rate
of chlorpyrifos. The accumulative release rate of chlorpyrifos from the
microcapsules was calculated by measuring the mass concentration of
released chlorpyrifos dissolved in the 90% methanol/water (90:10, v/v)
mixture solution with UV/VIS spectrometer at different intervals time
at 25 °C. The test procedure was as follows: 5.0 mL of mixture was
collected at different intervals from the suspension in the constant
container firstly. Secondly, the mixture was centrifuged with 4500 rpm
for 30 min and analyzed by UV/VIS spectrometer. Finally, 5.0 mL of
mixture was poured back to the constant container. The percentage of
chlorpyrifos accumulative release rate was calculated as the following
equation:
chlorpyrifosaccumulativereleaserate(%)
massofreleasedchlorpyrifos
= × 100
massofchlorpyrifosloadedinmicrocapsules
2.6. Studies of the spreadability of PSiSC/NaCMC/GE microcapsules
To examine the spreadability of PSiSC/NaCMC/GE microcapsules
on the hydrophobic blades, the contact angle (CA) test was performed
on contact angle measurement (CAM, SL-200B, Kino Industrial Co., Ltd.
USA). The five-period of rice blades was firmly attached on a glass slide.
The samples solution was dropped on the rice blades and tested im-
mediately the CA with CAM by sessile-drop method for three times to
get the average value at 25 °C.
3. Results and discussion
3.1. Interaction between PSiSC surfactant and NaCMC in aqueous solution
Interactions between polyelectrolyte and surfactant in solution have
attracted emerging interests [25–27]. However, there are few studies on
the interaction between the polyelectrolyte and the silicone surfactant
[28]. Surface tension of sodium dodecyl sulfate (SDS)- and PSiSC- based
anionic surfactant mixed with NaCMC aqueous solution as a function of
15
Colloids and Surfaces A 530 (2017) 13–19
Fig. 1. Surface tension of anionic surfactants with NaCMC aqueous solution as a function
of surfactant concentration.
surfactant concentration are shown in Fig. 1. The surface tension of
NaCMC (2.0 g/L) aqueous solution is 70.18 mN/m, which is identical to
the value of distilled water (72.0 mN/m) at 25 °C. It indicates that
NaCMC has low surface activity and can’t be adsorbed onto the oil-
water interface [29]. The surface tension of SDS/NaCMC mixed solu-
tion decreases abruptly with the addition of SDS, which indicates that
the adsorption amount of NaCMC onto the oil-water interface in-
creased. For SDS/NaCMC mixed solution, the hydrophobic interaction
between nonpolar segments of SDS and the NaCMC may be strong
enough to overcome the intermolecular repulsive electrostatic forces
[15]. For the mixed solution of PSiSC/NaCMC, the surface tension
dropped more quickly with increasing the amount of PSiSC than SDS.
The surface tension of PSiSC/NaCMC mixed solution is 19.31 mN/m at
the critical aggregation concentration of 1.2 mmol/L, which is lower
than the surface tension of SDS/NaCMC mixed solution of 39.68 mN/m
at the critical aggregation concentration of 2.4 mmol/L. The surface
tension of NaCMC/PSiSC solution is lower than NaCMC/SDS solution
with the same surfactant concentration. Moreover, PSiSC surfactant has
double hydrophobic chains [21]. Hydrophobic interaction becomes the
main reason for the decrease of the surface tension. These indicate that
the hydrophobic interaction between PSiSC and NaCMC is stronger
than that between SDS and NaCMC. As a result, it is more likely for
PSiSC than SDS to facilitate the adsorption of NaCMC at the oil-water
interface.
3.2. Preparation of the PSiSC/NaCMC/GE microcapsules
The spreadability of pesticide microcapsules on the blades is closely
related to the surface properties of the microcapsules. Therefore, it is
important to choose appropriate preparation method and shell mate-
rials of microcapsules. Complex coacervation is viewed as an effective
technique for encapsulation of the aromatic compounds. The micro-
capsules achieved by complex coacervation depend on the electrostatic
interactions between oppositely charged polymers in solution or col-
loid. Fig. 2 shows the schematic diagram of the PSiSC/NaCMC/GE
microcapsules fabricated by complex coacervation. The PSiSC surfac-
tant with different molar concentration was added into the mixture of
NaCMC and gelatin to increase the amount of adsorption of NaCMC at
water-oil interface. The core materials containing chlorpyrifos and
tertrachloroethylene emulsified by span 80 were dispersed into PSiSC/
NaCMC/GE aqueous solution with stirring rate of 450 r/min and
formed O/W emulsion. As the addition of acetic solution into the O/W
system, GE gradually performed positive charge characteristic. When
pH value was reduced to slightly below the isoelectric point of gelatin
(pH = 4.6), the complex coacervates of PSiSC, NaCMC and gelatin were
precipitated from the solution and formed complex coacervation layer
R.Y. Dai et al.
Fig. 2. The schematic diagram of the PSiSC/NaCMC/GE microcapsules via complex coacervation.
due to charge neutralization. After being cured by glutaraldehyde, the
PSiSC/NaCMC/GE coated chlorpyrifos microcapsules were produced.
As we all know, PSiSC surfactant exists double hydrophobic chains
[21], one chain may be involved in hydrophobic interaction with GE,
the other chain may be exposed to the outside of the capsules shell
layer, the structure of PSiSC/NaCMC/GE microcapsules is shown in
Fig. 2. Such structure of PSiSC/NaCMC/GE microcapsules is beneficial
to improve the spreadability of the microcapsules on the hydrophobic
blades.
3.3. Characterization of the PSiSC/NaCMC/GE microcapsules
The obtained microcapsules is characterized by FT-IR spectra in
Fig. 3. Comparing the absorption curves of GE solution, NaCMC solu-
tion and PSiSC surfactant, the wide and big peak at 3436 cm−1 is as-
signed to the stretching vibration of OeH bond from aqueous solution
and NaCMC. The absorption at 2966 cm−1 and 2854 cm−1 belong to
the asymmetric and symmetric stretching vibrations of CeH from PSiSC
and NaCMC. Peaks at 1632 cm−1 and 1411 cm−1 are the asymmetric
and symmetric stretching vibrations of carboxyl from GE, NaCMC and
PSiSC. The peak of SieCH3 at 1255 cm−1 coming from PSiSC can be
Fig. 3. FT-IR spectra of a. PSiSC/NaCMC/GE microcapsules; b. GE solution; c. NaCMC
solution; d. PSiSC surfactant.
16
Colloids and Surfaces A 530 (2017) 13–19
detected easily. Peak of 1076 cm−1 is the stretching vibration of both
Si-OeC from PSiSC and CeOeC from NaCMC. As the above analysis,
the shell layer of the obtained microcapsules is the complex coacervates
of PSiSC, NaCMC and GE, which demonstrates the PSiSC/NaCMC/GE
microcapsules have been obtained.
The surface morphology and EDX spectrum of PSiSC/NaCMC/GE
microcapsules obtained with 1.2 mmol/L PSiSC at pH 4.6 are given in
Fig. 4. Fig. 4a is the optical microscopy of PSiSC/NaCMC/GE micro-
capsules. The microcapsules with good appearance are optically
transparent. Fig. 4b shows the surface of single spherical microcapsule
is smooth. Fig. 4c shows that the microcapsules can extrude each other
and have obvious deformation without rupture due to the good elasti-
city of the capsule shell. Fig. 4d reveals the inner shell of the micro-
capsule is as smooth as the outer surface. Fig. 4e shows the cross-section
image of the microcapsule. The thickness of capsule shell is about
285 nm and the capsule shell without cracks and holes. It can be in-
ferred that the capsule shell is compact and flexible, which could im-
prove the sustainable-release property and spreadability of PSiSC/
NaCMC/GE microcapsules.
The composition of shell of PSiSC/NaCMC/GE microcapsules is
confirmed by the EDX spectrum in Fig. 4f. The elements of C, N, O, Na
and Si are detected obviously in EDX analysis. The elements of C and O
come from PSiSC, NaCMC and GE. The element of N is from GE. The
element of Na comes from NaCMC. The element of Si is from PSiSC,
which indicates PSiSC has successfully been introduced into PSiSC/
NaCMC/GE microcapsules.
Fig. 5 shows the particle size distribution of PSiSC/NaCMC/GE
microcapsules obtained with 1.2 mmol/L PSiSC at pH 4.6. It is obvious
that the particle size of PSiSC/NaCMC/GE microcapsules is uniform and
the mean diameter is around 3.5 μm.
3.4. Amount of chlorpyrifos encapsulated in PSiSC/NaCMC/GE
microcapsules
The amount of chlorpyrifos encapsulated in as-prepared micro-
capsules as a function of PSiSC surfactant concentration for 120 h with
magnetic stirring is shown in Fig. 6. Calculated from the aforementioned
equation, with PSiSC surfactant addition, the chlorpyrifos ER of PSiSC/
NaCMC/GE microcapsules is from 41.4% (w/w) to 50.8% (w/w). But the
R.Y. Dai et al. Colloids and Surfaces A 530 (2017) 13–19

Fig. 4. Surface morphology and EDX spectrum of PSiSC/NaCMC/GE microcapsules prepared with 1.2 mmol/L PSiSC at pH 4.6: a. OM of multiple microcapsules; b. SEM of single
microcapsule; c. SEM of multiple microcapsules; d. SEM of inner shell; e. SEM of shell layer thickness; f. EDX spectrum of shell of microcapsules.

chlorpyrifos ER of NaCMC/GE mixtures without PSiSC surfactant is

higher than PSiSC/NaCMC/GE microcapsules with 1.2 mmol/L PSiSC
surfactant, because NaCMC/GE mixtures can’t form a shell, most of them
collapsed during the process of washing or drying and the chlorpyrifos
leaked from NaCMC/GE mixtures. Thus, the amount of 50.8% (w/w)
chlorpyrifos encapsulated in as-prepared microcapsules with 1.2 mmol/L
PSiSC surfactant shows a high loading capacity for chlorpyrifos.

3.5. Release behavior of chlorpyrifos from PSiSC/NaCMC/GE

microcapsules

Chlorpyrifos release behavior from the PSiSC/NaCMC/GE micro-

Fig. 5. Particle size distribution of PSiSC/NaCMC/GE microcapsules prepared with
1.2 mmol/L PSiSC at pH 4.6.
capsules prepared with different molar concentration of PSiSC were
investigated in 90% methanol/water mixture at 25 °C, as shown in
Fig. 7. Calculated from the aforementioned equations, the chlorpyrifos
accumulative release rate from microcapsules without PSiSC surfactant
(NaCMC/GE microcapsules) is releasing rapidly, and the value of 90.3%
achieves equilibrium after 20 h, which is due to the low adsorption
amount of NaCMC at the oil-water interface and weak interaction

Fig. 6. The chlorpyrifos ER of PSiSC/NaCMC/GE microcapsules as a function of PSiSC Fig. 7. Release curves of chlorpyrifos loaded in PSiSC/NaCMC/GE microcapsules pre-
surfactant concentration. pared with different molar concentration of PSiSC.

17
R.Y. Dai et al.
Fig. 8. Release curves of chlorpyrifos loaded in PSiSC/NaCMC/GE microcapsules pre-
pared with 1.2 mmol/L PSiSC at different pH solution.
between NaCMC and GE and indicates there is no sustainable-release
performance for the prepared microcapsules without PSiSC surfactant.
As the PSiSC surfactant addition, the chlorpyrifos accumulative release
rate from PSiSC/NaCMC/GE microcapsules becomes releasing slowly
because the addition of PSiSC surfactant is beneficial to form compact
capsule shell layer. The chlorpyrifos accumulative release rate from
PSiSC/NaCMC/GE microcapsules with 1.2 mmol/L PSiSC surfactant is
just only 26.1% within 240 h, which is lower than that from PSiSC/
NaCMC/GE microcapsules with 0.3 mmol/L, 0.6 mmol/L and
2.4 mmol/L PSiSC surfactant. The PSiSC/NaCMC/GE microcapsules
with 1.2 mmol/L PSiSC surfactant exhibits sustainable releasing and
possess the best release property, which is corresponding to the result of
Fig. 1.
Fig. 8 shows the release behavior of chlorpyrifos from the PSiSC/
NaCMC/GE microcapsules with 1.2 mmol/L PSiSC in 90% methanol/
water mixture at different pH value solutions at 25 °C. At pH 5.0, the
chlorpyrifos accumulative release rate is about 17.5% after 120 h,
which is slightly less than 23.5% at pH 7.0. As the pH increasing to 9.0,
the chlorpyrifos accumulative release rate ascends to approximately
49%. It is due to the hydrolytic stability of chlorpyrifos decreased with
18
Colloids and Surfaces A 530 (2017) 13–19
increasing pH [30]. Moreover, at pH 9.0, GE as one of shell material
performed negative characteristic, which causes the capsule shell layer
(PSiSC/NaCMC/GE) to degrade easily. While in weak acid (pH 5.0) or
neutral solution (pH 7.0), the capsule shell layer (PSiSC/NaCMC/GE) is
more stable than in alkaline solution. Thus, the chlorpyrifos accumu-
lative release rate from PSiSC/NaCMC/GE microcapsules increases with
increasing pH.
3.6. Studies of spreadability of PSiSC/NaCMC/GE microcapsules
To prove that the PSiSC/NaCMC/GE microcapsules have good
spreadability behavior on the hydrophobic blades, the contact angle
was measured. The contact angle images and the contact angle results
of 10 μL solution dropped on the rice blades are presented in Fig. 9.
Fig. 9a shows the distilled water droplet is raised on the rice blades and
the average CA of distilled water droplet is 121.13°, which suggests that
rice blades is hydrophobic blades. PSiSC surfactant spreads on the rice
blades and the average CA of PSiSC surfactant droplet is 0.57°, shown in
Fig. 9b, which demonstrates that the PSiSC surfactant can be moist well
on hydrophobic blades. It may depend on Si-CH3 is the affinity group on
the blades according to the similarity principle. Fig. 9c presents the
SDS/NaCMC/GE microcapsules solution isn’t wet on rice blades. The
average CA of SDS/NaCMC/GE microcapsules droplet is 134.55°, be-
cause the shell materials have hydrophilicity and can’t spread on hy-
drophobic blades. The PSiSC/NaCMC/GE microcapsules solution is at-
tached on rice blades, as shown in Fig. 9d. The average CA of PSiSC/
NaCMC/GE microcapsules droplet of 70.27°is fast lower than 134.55°,
which suggests the wetting property of PSiSC/NaCMC/GE micro-
capsules is better than SDS/NaCMC/GE microcapsules on rice blades.
Compared the average CA of PSiSC/NaCMC/GE microcapsules to SDS/
NaCMC/GE microcapsules, the spreadability of PSiSC/NaCMC/GE mi-
crocapsules on hydrophobic blades have been improved because some
hydrophobic chains of PSiSC surfactants exposed to the outside of the
capsules shell layer, which promotes increasing the residual amount of
chlorpyrifos loaded in PSiSC/NaCMC/GE microcapsules on blades.
Therefore, the better blades spreadability of PSiSC/NaCMC/GE micro-
capsules is, the larger residual amount of chlorpyrifos microcapsules on
blades is, the higher utilization of chlorpyrifos is.
Fig. 9. 10 μL sample solution dropped on the rice
blades: a. distilled water, Average CA = 121.13°; b.
PSiSC surfactant, Average CA = 0.57°; c. SDS/
NaCMC/GE microcapsules, Average CA = 134.55°;
d. PSiSC/NaCMC/GE microcapsules, Average
CA = 70.29°.
R.Y. Dai et al.
4. Conclusions
The PSiSC/NaCMC/GE microcapsules have been fabricated with
1.2 mmol/L PSiSC surfactant at pH 4.6 via complex coacervation. The
as-prepared microcapsules exhibit the chlorpyrifos encapsulation rate
of 50.8%, surface smooth, the mean diameter around 3.5 μm and shell
thickness of 285 nm. The chlorpyrifos-loaded microcapsules are of re-
markable sustainable-release property. The chlorpyrifos accumulative
release rate from PSiSC/NaCMC/GE microcapsules increases with in-
creasing pH, it is about 17.5% and 23.5% at pH 5.0 and pH 7.0 solution,
respectively. The PSiSC surfactant with double hydrophobic chains
added into the capsule shell layer, the average CA of PSiSC/NaCMC/GE
microcapsules of 70.27° is fast lower than SDS/NaCMC/GE micro-
capsules of 134.55° dropped on rice blades, which indicates the as-
prepared microcapsules own good spreadability on rice blades. It pro-
motes increasing the residual amount of chlorpyrifos microcapsules on
blades, thereby improving the utilization of chlorpyrifos.
Acknowledgements
This research was financially supported by the National Natural
Science Foundation of China(Grant NO. 21304039); the Science &
Technology Program of Jiangxi Province (Grant NO. 2013BAB213014);
and the Department of Education Science & Technology Program of
Jiangxi Province (Grant NO. GJJ150405).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.colsurfa.2017.06.057.
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