Halloysite Tubes as Nanocontainers for Herbicide and Its Controlled

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Halloysite tubes as nanocontainers for herbicide and its controlled release in biodegradable poly(vinyl alcohol)/starch film Bangchao Zhong, Song Wang, Huanhuan Dong, Yuanfang Luo, Zhixin Jia, Xiangyang Zhou, Mingzhou Chen, Dong Xie, and Demin Jia J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b04220 • Publication Date (Web): 13 Nov 2017 Downloaded from http://pubs.acs.org on November 16, 2017

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Journal of Agricultural and Food Chemistry

Halloysite tubes as nanocontainers for herbicide and its controlled release in biodegradable poly(vinyl alcohol)/starch film Bangchao Zhong1, Song Wang1, Huanhuan Dong1, Yuanfang Luo1, Zhixin Jia1*, Xiangyang Zhou2*, Mingzhou Chen3, Dong Xie3, Demin Jia1 1

Key Lab of Guangdong for High Property and Functional polymer Materials, South

China University of Technology, Guangzhou 510640, China 2

Department of Chemistry and Chemical Engineering, Zhongkai University of

Agriculture and Engineering, Guangzhou 510225, China 3

Guangzhou Sugarcane Industry Research Institute, Guangdong Academy of Sciences,

Guangzhou 510316, China *Corresponding author, E-mail address: [email protected] (Zhixin Jia); [email protected] (Xiangyang Zhou)

1

ACS Paragon Plus Environment


1

Abstract: Commercial herbicide atrazine (AT) was first loaded into the lumen of

2

halloysite nanotubes (HNTs) with the amount of 9 wt%, and then the AT-loaded

3

HNTs (HNTs-AT) were further incorporated into poly(vinyl alcohol)/starch

4

composites (PVA/ST, with the weight ratio of 80/20) to construct dual drug delivery

5

system. AT loaded in nanotubes displayed much slower release from PVA/ST film in

6

water than free AT, e.g., the total release amount of AT from PVA/ST film with

7

loaded AT was only 61% after 96 hours, while this value reached 97 % in PVA/ST

8

film with free AT. The release behavior of AT from PVA/ST film with HNTs-AT was

9

first dominated by the mechanism of matrix erosion and then by the mechanism of

10

Fickian diffusion. In addition, the combining HNTs and PVA/ST blends together in

11

the controlled release of herbicide also reduced its leaching through soil layer, which

12

would be useful for diminishing the environmental pollution caused by pesticide.

13

Keywords: Controlled release; Herbicide; Biodegradable polymer; Halloysite

14

nanotubes; Leaching.

15

INTRODUCTION

16

Pesticides are effective in controlling weeds and pests, which significantly

17

improves the crop yields.1-3 However, the extensive use of pesticides in agronomic

18

practices is becoming a serious environmental concern because of the potential runoff

19

and leaching of these toxic compounds through the soil, leading to the contamination

20

in water and food.4, 5 Therefore, the improvement of pesticide safety has always been

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a highly useful and challenging topic in agriculture.6, 7 Many efforts have been

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devoted to minimizing the risk of pesticides.5, 8 Typically, Ludovic F. Dumée et al. 2


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synthesized a novel hybrid thin film composite catalytic membrane.9 In their work,

24

catalytic silver-metal nano-materials were uniformly templated and encapsulated

25

across metal organic frameworks (MOF) nano-particles and incorporated across the

26

top surface of poly(amide) thin films during interfacial polymerization for the first

27

time. Results showed that the kinetics of Ag@MOF nano-crystal catalyzed

28

degradation of 2,4-Dichlorophenoxyacetic acid was extremely fast and complete

29

degradation was achieved within a very short time. The utilization of sorbents to carry

30

pesticides is an effective approach to avoid the runoff and leaching of pesticides.

31

Many kinds of sorbent materials were synthesized to construct controlled release

32

systems for pesticides or other active materials. Shirish H. Sonawane, Bharat A.

33

Bhanvase and their co-workers have done a remarkable job in this field. They

34

synthesized a series of novel nanocontainers, such as calcium zinc phosphate

35

pigment,10 ZnO,11 iron oxide-blended sodium zinc molybdate,12 silica,13 cerium zinc

36

molybdate14 and zinc phosphate.15 Those nanocontainers were mainly prepared by the

37

method of layer-by-layer assembly or with the aid of ultrasound. Recently, natural

38

clays have received increasing attention for their biocompatibility, thermal stability,

39

abundance, low-cost and other environmental-friendly characteristics.16-19 As a kind

40

of naturally occurring aluminosilicate minerals, halloysite nanotubes (HNTs) were

41

used as sorbent materials for the controlled release of active molecules 20-25 because of

42

their biocompatibility and tubular structure with appropriate size.26 Nonetheless, the

43

ability to retard the release of pesticides with single nanoclay delivery system was still

44

not very satisfactory.27 3



45

Agricultural mulching film has been widely used to promote the growth of crop.

46

Polyethylene (PE) is the most common material used for agricultural mulch. However,

47

PE does not decompose in soil, leading to deleterious effects on the environment.

48

Hence, developing degradable plastic mulch is a pressing environmental demand for

49

the increasing nondegradable waste and the corresponding disposal problem.28 Starch

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(ST) is a potential candidate of biodegradable mulch for being natural, renewable and

51

inexpensive, but the weak mechanical strength limits its application. While,

52

biodegradable Poly(vinylalcohol) (PVA) possesses outstanding mechanical properties

53

(strength and flexibility, etc.), but the high cost restricts its commercialization as

54

agricultural mulch.

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In this work, dual drug delivery system was constructed by first loading

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commercial herbicide atrazine (AT) into the lumen of HNTs and then adding

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AT-loaded HNTs into PVA/ST blends. The release kinetics of herbicide from this

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double delivery system was systematically investigated.

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MATERIALS AND METHODS

60

Materials

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PVA was supplied by Pritt Plastics Chemical Company, Japan. Corn ST was

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produced by Hebei Ruide Starch Company, China. HNTs were mined in Hubei, China,

63

and purified according to previous method.29 The typical dimensions were of 10–50

64

nm in outer diameter, 5–20 nm in inter diameter and 0.5–2 µm in length. AT was

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purchased from Shanghai Macklin Biochemical Co., Ltd and used without further

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purification. Methanol, glycerol and glyceryl monostearate from Sinopharm chemical 4


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reagent Co., Ltd., China, were analytically pure grade and used as received.

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Preparation of Herbicide-loaded HNTs

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The loading process of herbicide into the lumen of HNTs is shown in Figure1.

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Specifically, 3 g of HNTs were dispersed into 300 ml of AT methanol solution (0.015

71

g/ml) with the aid of a magnetic stirrer. The suspension was first placed under

72

vacuum condition (~100–200 Torr). The fizzing of the suspension indicated that air

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was being removed from the lumen of HNTs and replaced with herbicide solution.

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The suspension was kept under vacuum for 30 minutes and then was cycled back to

75

atmospheric pressure for another 30 minutes. This process was repeated five times in

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order to increase the loading efficiency of herbicide. This cycle of

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vacuum-atmospheric pressure was conducted at room temperature. Subsequently, the

78

suspension was centrifuged and washed for 10 times with water to remove the surface

79

adsorbed herbicide. The product was finally dried to constant weight with a vacuum

80

oven at 40 oC to obtain AT-loaded HNTs (HNTs-AT). The amount of the loaded AT

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in HNTs lumen was determined by the residue from thermogravimetric analysis at

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700 oC.

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Preparation of the Biodegradable Polymer Films with Herbicide

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Biodegradable polymer films were fabricated by casting method.30 The detailed

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procedure was as follows: 8 g of PVA and 2 g of ST were dissolved in distilled water

86

under stirring at 90 oC. Then, glycerol (20 % of total weight of PVA and ST), glyceryl

87

monostearate (1 wt%) and herbicide (0.2 g of AT or 2g of HNTs-AT) were added into

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the PVA/ST solution. Sequentially, stirring was employed until a homogeneous 5



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gel-like solution was formed. The gel-like solution was poured on a warmed glass

90

plate (90 oC) and dried for 24 h at 60 oC.

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Characterization

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Fourier transform infrared (FTIR) spectra were recorded by a Bruker Vector 33

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spectrometer from 400 to 4000 cm-1. Transmission electron microscopy (TEM)

94

images were taken with a JEOL2100. Scanning Electron Microscopy (SEM) was

95

employed to examine the surface morphologies of the biodegradable polymer films

96

using a Zeiss Merlin scanning electron microscope. X-ray Diffraction (XRD)

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measurements were conducted on an Bruker D8 Advance X’Pert-Pro X-ray

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diffractometer. Thermogravimetric analysis (TGA) was conducted with a TA

99

TGAQ500 at the heating rate of 20 °C/min from 30 to 700 oC under dry N2

100

atmosphere. Ultraviolet-Visible (UV-vis) spectra were monitored on an Agilent Cary

101

60 spectrophotometer and used to analyze the amount of the released drug from the

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biodegradable films. The tensile strength and elongation at break of polymer films

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were tested with a Zwich/Roell instrument following ASTM D 882012.

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To investigate the swelling degree and solubility of the biodegradable films,

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dried films were immersed in distilled water at room temperature. After equilibrium

106

was reached, free water on the surface of the films was removed and the weight of the

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samples was measured. The swelling degree was calculated by the following

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equation:31

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Swelling degree (%) =

Wt − W0 × 100 W0

(1) 6


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where Wt is the equilibrium weight of films after immersion and W0 is the initial

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weight of the dried film. The swollen films were dried again at 60 oC, and the solubility of films in water

112 113

was calculated according to the following equation:

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Solubility (%) =

115

where Wd is the weight of the dried swollen film.

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W0 − Wd × 100 Wd

(2)

The release measurements of pesticide were carried out in a flask at room

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temperature. The drug-loaded biodegradable film was immersed in 200 ml of distilled

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water. Then, 5 ml of supernatant was removed from the solution at selected time

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intervals and replaced by 5 ml of distilled water. The amount of AT in the supernatant

120

was determined by the UV-vis spectrum at 223 nm. The release data were analyzed

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by applying the Higuchi equation32 (3), Hixson-Crowell equation33 (4), Hopfenberg

122

equation34 (5), and Ritger-Peppas equation35 (6) as follows:

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M t / M ∞ = kt1 / 2

124

W0

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1/ p 1 −（1 − M t / M ∞） = kt

(5)

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ln(M t / M ∞ ) = n ln t + C

(6)

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1/ 3

− Wt

1/ 3

(3)

= kt

(4)

Where Mt and M∞ are the amount of drug released into water at time t and time ∞,

128

respectively. W0 and Wt are the initial drug amount and remaining drug amount at time

129

t, respectively. k is a constant related to the characteristics of the sorbent materials and

130

the drug, and n is a parameter that indicates the transport mechanism. p is an exponent 7



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that varies with geometry. HNTs have cylindrical-shaped tubular morphology, hence

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p=2.

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Soil burial degradation tests of PVA/ST films with different contents of ST were

134

carried out at room temperature, under moisture controlled conditions. At indicated

135

intervals, samples were recovered and fully washed with distilled water, then dried to

136

constant weight under vacuum at room temperature. The degree of degradation was

137

estimated from the weight loss normalized with respect to the initial weight of

138

polymer film.

139

The leaching potential of AT from the biodegradable films was tested with an

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experiment through a thin soil layer carried out in a Buchner funnel.31 Briefly, a thin

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layer of red soil was deposited on filter paper in a funnel. Then, the biodegradable

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film was cut into a disc with the diameter of 75 mm and placed on the top of the soil.

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The funnels were irrigated 8 times with 1 hour interval and 40 ml water was used for

144

each irrigation. The leachate was collected after each irrigation, and the AT

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concentration was determined by UV-vis spectrum.

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RESULTS AND DISCUSSION

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Characterization of Herbicide-loaded HNTs

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Figure 2a shows the FTIR spectra of HNTs and HNTs-AT. In the spectrum of

149

HNTs, the characteristic vibrations of the aluminol groups on the HNTs internal

150

surfaces are observed at 3696 cm-1 and 3622 cm-1. The peak of O−H bending at 1647

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cm-1 originates from the adsorbed water, while the peak at 1035 cm-1 is attributed to

152

the stretching vibration of Si−O−Si. In the spectrum of HNTs-AT, apart from the 8


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characteristic peaks of HNTs, the vibrations of organic groups from the structure of

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AT molecule are noticeable, such as the vibration of triazine at 1554 cm-1, and the

155

vibration of CH3 and CH2 at 2974 cm-1 and 2940 cm-1, respectively. To further

156

confirm the loading of AT into HNTs lumen, XRD was employed to provide more

157

information. As shown in Figure 2b, characteristic diffraction peaks of pristine HNTs

158

corresponding to 12.2°, 19.9° and 24.9° appear, which confirms that the used HNTs is

159

dehydrated halloysite with an interlayer space and nanotubular structure.36, 37 As for

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pure AT, the diffraction peaks at 12.7°, 18.1°, 19.4°, 20.2° and 22.2° are very

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intensive, reflecting the significantly high crystallinity of AT molecules.38 After

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loading AT into HNTs lumen, the main peak positions for pristine HNTs remain

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unchanged in the spectrum of HNTs-AT, proving that the crystalline structure of

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pristine HNTs is not affected in the presence of guest molecules. More importantly,

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new diffraction peaks at 12.7°, 18.1°, 19.4° and 22.2° attributing to the crystalline

166

structure of pure AT appear as well. However, the intensities of those new peaks in

167

the spectrum of HNTs-AT are much weaker than those in the spectrum of pure AT,

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which should be ascribed to the low loading amount of AT. Considering the fact that

169

scarcely any surface adsorbed AT molecules were left after sufficient washing, it can

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be concluded that herbicide molecules were successfully loaded into the lumen of

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HNTs based on the results of FTIR and XRD.

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The loaded AT in the lumen of HNTs was observed by TEM. From Figure 3a,

173

pristine HNTs show a typical nanotubular structure. However, in the case of

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HNTs-AT before the deloading of AT, the lumen of HNTs is blocked by AT (as 9



175

denoted by the arrow in Figure 3b) and is interrupted by voids. After the deloading of

176

AT, the morphology of HNTs-AT shown in Figure 3c is similar to that of the pristine

177

HNTs and the density in the nanotubes is decreased compared with HNTs-AT before

178

deloading, indicating the successful release of AT from nanotubes.

179

The TGA curves of HNTs and HNTs-AT are presented in Figure 4. HNTs-AT

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shows worse thermal stability than HNTs, because AT begins to decompose at ca. 150

181

o

182

the amount of AT loaded in the lumen of HNTs is ca. 9 wt%.

183

Effect of ST Content on the Biodegradable and Mechanical Performances of

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PVA/ST Film

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C. According to the weight loss of HNTs and HNTs-AT in the range of 150−700 oC,

Figure 5a shows the weight loss of PVA/ST films with different ST contents

186

during soil burial test. All polymer films

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elevates strongly with increasing ST, because many bacteria are capable of efficient

188

degradation of ST.39 For example, when the ST content is 40 wt%, the weight loss of

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PVA/ST film exceeds 60%, verifying that the biodegradation of PVA/ST film is

190

improved by the incorporation of ST. However, as can be found from Figure 5b, the

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mechanical performances including tensile strength and elongation at break of

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PVA/ST films sharply decline when the ST content is more than 20 wt%. In order to

193

balance the biodegradable and mechanical performances of PVA/ST film, the ST

194

content was fixed at 20 wt% to prepare herbicide-loaded biodegradable film.

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Morphologies of biodegradable films

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degrade in soil, and the degradation

Figure 6 shows the SEM images of different biodegradable films. As can be seen 10


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from Figure 6a, PVA/ST/AT film shows a rough surface with obvious rod-like

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protrusions. From the high resolution image in Figure 6b, the surface of PVA/ST/AT

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film is filled of wire-like AT crystals formed during the drying process of the polymer

200

film. However, as shown in Figure 6c, the surface of PVA/ST/HNTs-AT film is very

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flat, and no similar wire-like AT crystals exist. In addition, it is found from Figure 6d

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that HNTs-AT is uniformly semi-embedded instead of being totally exposed on the

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polymer surface, which is suggestive of a strong interfacial interaction between

204

HNTs-AT and polymer matrix. As shown in Figure 7a, the strong interfacial

205

interaction should be attributed to the hydrogen-bonding interaction between the

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surface siloxane of HNTs and polymer matrix.40 The formation of hydrogen bonding

207

will cause the variation of chemical environment, which can be detected by the

208

variation of binding energy of the related atoms via XPS.41, 42 From Figure 7b, the

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binding energy of silicon atom in PVA/ST/HNTs-AT film, which connects to the

210

oxygen atom in the hydrogen bond directly, is shifted to lower value than that in

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HNTs (from 103.15 eV to 102.86 eV), confirming the formation of hydrogen bonding

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in PVA/ST/HNTs film.43

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Controlled Release of Herbicide from Biodegradable Polymer Films in Water

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The release profiles of AT from biodegradable films are shown in Figure 8. Both

215

PVA/ST/AT and PVA/ST/HNTs-AT film display a burst release in the first 4 hours.

216

The total release amount exceeds 30%. Then, the release of AT from

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PVA/ST/HNTs-AT film slows down when compared with that from PVA/ST/AT film.

218

For example, the total release amount of AT from PVA/ST/HNTs-AT film is only 61% 11



219

after 96 hours, while this value reaches 97 % in PVA/ST/AT film, indicating the

220

advantage of combining PVA/ST composites and HNTs in the controlled release of

221

pesticides. Actually, as shown in Figure S1, the release of AT from

222

PVA/ST/HNTs-AT film is also slower than that from the PVA/ST film with

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montmorillonite immobilized AT (MMT-AT), further demonstrating the advantage of

224

nanotubes as sorbent

material of pesticide for controlled release.

225

To better understand the release mechanism of AT, the release data were

226

checked by Higuchi, Hixson-Crowell, Hopfenberg and Ritger-Peppas models. The

227

fitting results are tabulated in Table 1. Typically, the fitting lines by Hixson-Crowell

228

and Ritger-Peppas models are also provided in Figure 9. In the case of PVA/ST/AT

229

biodegradable film, the values obtained for the correlation coefficients indicate that

230

Higuchi and Ritger-Peppas kinetic models are well fitted. According to the fitting

231

results of Ritger-Peppas model, the release process of AT from PVA/ST/AT film is

232

divided into two stages. At the first stage, the release exponent n (0.54) which is an

233

important indicator of the diffusion mechanism of a drug35 is higher than 0.45,

234

indicating that the release of AT is a non-Fickian diffusion behavior.44 This can be

235

explained by the fact that the polymer film was not fully swollen during this stage, so

236

the diffusion of AT through the polymer film was restricted. At the second stage, n

237

(0.16) is less than 0.45, indicating that the release of AT is dominated by a mechanism

238

of Fickian diffusion. This is because the polymer film was fully swollen at this stage,

239

leading to the free diffusion of AT in the polymer film.45

240

As for PVA/ST/HNTs-AT biodegradable film, the release data of AT in water 12


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only fit well with Ritger-Peppas model, and there are also two release stages.

242

However, the release of AT at the first stage is dominated by the mechanism of matrix

243

erosion (n=1.416>0.89),46 which is attributed to the loading of AT into the lumen of

244

HNTs. When the biodegradable polymer film was immersed in water, the flexibility

245

and mobility of polymer chains in the free-swelling state were largely improved.

246

Hence polymer chains easily adhered at the mouth of the nanotube as stopper, and the

247

release of AT from HNTs lumen was limited before the polymer film was totally

248

dissolved in water. After the polymer layer was fully swollen, the water could

249

permeate into the lumen of HNTs for releasing the AT molecules. When the

250

nanotubes were occupied by water, the diffusion of AT molecules into the

251

surrounding was allowed. During this stage, the release rate mainly depends on the

252

degree of polymer erosion. The n value (0.311) of the second release stage is less than

253

0.45, indicating that the release of AT from PVA/ST/HNTs-AT biodegradable film

254

follows Fickian behavior and depends on the time and initial concentration of

255

herbicide-loaded nanotubes in the release system.

256

Retarded Leaching of Herbicide in Soil

257

Figure 10 shows the leaching profiles of AT through the soil layer from different

258

biodegradable films. The amount of herbicide leached after each irrigation for

259

different polymer films is related to its release behavior in water. As can be seen, the

260

herbicide leaching from PVA/ST/HNTs-AT film for each irrigation is lower than that

261

from PVA/ST/AT film. This result proves that the loading of herbicide in the lumen

262

of HNTs is useful for reducing the leaching of herbicide in soil. After 8 cycles of 13



263

irrigation, there is still residual herbicide in the polymer films. The residual amount is

264

oppositely related to the release rate of herbicide from biodegradable polymer films.

265

The relatively high herbicide residue in PVA/ST/HNTs-AT film will be beneficial for

266

keeping the biological effect of herbicide for a long period, which can simultaneously

267

enhance the utilization efficiency of herbicide and avoid the environmental problems

268

caused by the leaching and runoff of pesticide.

269

In summary, herbicide loaded in nanotubes displayed much slower release from

270

biodegradable polymer film in water than free herbicide. Furthermore, the leaching of

271

loaded herbicide in

272

to promote the understanding of pesticide release characteristics in dual delivery

273

system comprising natural nanotubes and biodegradable polymer, as well provide new

274

opportunity for the preparation of biodegradable agriculture mulch with pesticide.

275

ACKNOWLEDGE

276

polymer film from soil was also reduced. This work is believed

This work was supported by the National Natural Science Foundation of China

277

(51703063), Provincial Produce-Learn-Research Projects of Guangdong

278

(2013B090500085), Provincial Public Interest Research and Special Capacity

279

Building of Guangdong (2014B030303004), Cooperative Innovation Project of

280

Guangzhou (201508010022), Special Fund for Applied Science and Technology

281

Research of Guangdong (2015B020235010), Fundamental Research Funds for the

282

Central Universities (2017BQ033) and China Postdoctoral Science Foundation

283

(2017M612658).

284

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Figures and tables:

Figure 1. Schematic diagram of loading halloysite nanotubes with herbicide.

Figure 2. (a) FTIR spectra of HNTs and HNTs-AT; (b) XRD spectra of pure AT, HNTs and HNTs-AT.

22


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Figure 3. TEM images of (a) pristine HNTs; (b) HNTs-AT before the deloading of AT; (c) HNTs-AT after the deloading of AT.

Figure 4. TGA curves of HNTs and HNTs-AT.

23



Figure 5. Weight loss during soil burial tests (a) and mechanical properties (b) of PVA/ST films with different contents of ST.

Figure 6. SEM images of biodegradable films: (a, b) PVA/ST/AT; (c, d) PVA/ST/HNTs-AT.

24


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Figure 7. (a) Schematic representation of hydrogen bonding interaction between HNTs-AT and polymer matrix; (b) Si 2p XPS spectra of pristine HNTs and PVA/ST/HNTs-AT film.

Figure 8. Cumulative release of AT from biodegradable polymer films in water.

25



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Table 1. Release dynamics model fitting results of biodegradable films in water. Samples

PVA/ST/AT

Fitted model

Release stage

Fitted equation

R2

Higuchi

-

Mt/M∞=0.125t1/2

0.9687

Hixson-Crowell

-

W01/3-Wt1/3=0.0507t

0.9264

Hopfenberg

-

1-(1- Mt/M∞)1/2=0.0124t

0.9210

First stage

ln(Mt/M∞)=0.538lnt+2.722

0.9927

Second stage

ln(Mt/M∞)=0.155lnt+3.905

0.9405

Higuchi

-

Mt/M∞=0.080t1/2

0.9189

Hixson-Crowell

-

W01/3-Wt1/3=0.0507t

0.8261

Hopfenberg

-

1-(1- Mt/M∞)1/2=0.006t

0.8303

First stage

ln(Mt/M∞)=1.416lnt+1.992

0.9887

Second stage

ln(Mt/M∞)=0.311lnt+2.823

0.9726

Ritger-Peppas

PVA/ST/ HNTs-AT

Ritger-Peppas

26


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Figure 9. Kinetics fitting lines of different films by Hixson-Crowell and Ritger-Peppas models: (a), (b) PVA/ST/AT; (c), (d) PVA/ST/HNTs-AT.

Figure 10. Leaching of herbicide form biodegradable polymer films through a soil layer. 27



TOC:

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Halloysite Tubes as Nanocontainers for Herbicide and Its Controlled

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