J Porous Mater (2016) 23:557–562 DOI 10.1007/s10934-015-0109-4
Synthesis of nanoporous materials to dispense pheromone for trapping agricultural pests Sung Man Seo1 • Jae Myeong Lee1 • Ha Young Lee1 • Jihyun An2 Sang June Choi3 • Woo Taik Lim1
•
Published online: 14 December 2015 Ó Springer Science+Business Media New York 2015
Abstract In this study, to develop an effective pheromone dispenser, zeolite A was modified with cetyltrimethylammonium ion as a cationic surfactant. Its capacity for aggregation of the pheromone components was confirmed by total organic carbon analysis before and after field testing. Furthermore, weekly examinations of soybean fields (Daewonkong variety) and plum orchards were undertaken from April to August in 2014 to determine the number of Riptortus pedestris trapped by the aggregation pheromone dispersed from the pheromone loaded surfactant-modified zeolite A (SMZ-A) in a netted cylindrical trap. The powder-type SMZ-A exhibited superior performance when compared to other dispensers in a comparative study of attractiveness using cylinder- and powder-type surfactant-modified zeolite A (CSMZ-A and PSMZ-A), microporous titanosilicate ETS-10, and a commercial product (CP). The performance followed the trend PSMZ-A [[ CSMZ-A [ ETS-10 [ CP, suggesting that the SMZ-A material has potential as a slow-releasing pheromone dispenser. Keywords Pheromone dispenser Surfactant modified zeolite Aggregation pheromone Riptortus pedestris Attractiveness
& Woo Taik Lim
[email protected];
[email protected] 1
Department of Applied Chemistry, Andong National University, Andong 760-749, Korea
2
Department of Chemistry Education, Seoul National University, Seoul 151-748, Korea
3
Department of Environmental Engineering, Kyungpook National University, Daegu 702-701, Korea
1 Introduction Hemipteran bugs have become major pests of numerous crops in Korea and other Asian countries in the twentyfirst century [1–5] due to both climate and cropping system changes [2, 6]. The adults and nymphs of the soybean bug Riptortus pedestris, the red-banded shield bug Piezodorus hybneri, the green stink bug Nezara antennata, the Sole bug Dolycoris baccarum, and the brown marmorated stink bug Halyomorpha halys are well known for soybean damage [7], while the bean bug R. pedestris, the brown winged green bug Plautia stali, brown marmorated stink bug H. halys, and Glaucias subpunctatus are known as destructive pests of fruit trees [2]. Vetches [8], red clover [8], persimmon [2], apple [9], yuzu [2, 10], barley [11], foxtail millet [12], broomcorn [12], and particularly soybeans [2, 5, 9, 13–16] have been reported to be extensively damaged by R. pedestris. Aggregation pheromone traps, designed to store and release aggregation pheromones from adult R. pedestris to attract conspecific adults and nymphs, have been developed and used commercially to control pest populations [5, 17]. Although various innovative efforts have been made to impede the destructive tendencies of R. pedestris, rubber septum and polyethylene vial are still commonly used as pheromone dispensers for practical purposes. Aluminosilicate zeolites are hydrated crystalline materials with channels and cavities of a size, shape, and dimension which influence guest molecules [18, 19]. Charge balancing cations within zeolites allow for selectivity in sorption. They are mobile and can be easily replaced by other cations via cation exchange [18, 20, 21]. Zeolites are widely used in industrial applications as ion exchangers, sorption agents, and catalysts primarily due to excellent structural stability, large and accessible
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Fig. 1 Synthetic strategy of hydrophobic surfactant-modified zeolite via ion-exchange of CTA? into hydrophilic zeolite
pore volumes, high activities, and high regenerability [22]. Zeolites X, Y, ZSM-5, and Beta were studied as pheromone dispensers for insect attractants such as n-decanol, the female sexual pheromone from Agrotis segetum and Cydia pomonella, and trimedlure, the male synthetic attractant for Ceratitis capitata [tert-butyl 4(5)-chloro-2methylcyclohexane carboxylate] [23]. Hydrophobic materials were prepared to be lipophilic pheromone dispensers by surface modification with alkyl ammonium ions [24, 25]. Zeolite A modified with hexadecyltrimethylammonium bromide as a cationic surfactant, was utilized as a slow release phosphorus fertilizer and thoroughly characterized using powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) [24]. In this study, a pheromone dispenser using zeolite A, which has a higher cation-exchange capacity than other zeolites due to the lower Si/Al ratio, was synthesized by modification of zeolite A with cetyltrimethylammonium (CTA?) ions to maximize sorption for aggregation of the pheromone components. Furthermore, a comparative study for attractiveness of surfactant modified zeolite A (SMZA), microporous titanosilicate ETS-10, and a commercial product (CP) was performed.
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2 Materials and methods 2.1 Preparations of surfactant modified zeolites (SMZs) White powder synthetic sodium zeolite 4A (unit cell of |Na12 (H2O)x|[Si12Al12O48], Si/Al = 1) was purchased from Aldrich Co. The SMZ-A was prepared by static (batch) ion-exchange of zeolite A with cetyltrimethylammonium bromide (CTAB, DAEJUNG, C99 %), [C19H42N]?Br- (see Fig. 1) in aqueous. The ion exchange was completed by mixing hydrated zeolite A with an aqueous solution of 0.1 M CTAB in a ratio of 1:10 and agitated for 18 h at 294 K. The product was filtered, washed with distilled water, and dried in an oven at 373 K for 1 day. To make cylinder-type materials, the SMZ-A was combined with bentonite (SAMCHUN) as a binder and distilled water in the ratio of 10:3:5. After intensive mixing, 10 g of aliquots were shaped into cylindrical shapes and dried in the shade for 1 day to avoid cracking. Finally, the shaped SMZs were dried in the oven at 353 K for 2 days. 2.2 Pheromone sorption Aggregation pheromone of R. pedestris consisted of three components: (E)-2-hexenyl-(Z)-3-hexenoate (EZ),
J Porous Mater (2016) 23:557–562 Table 1 Contents of total organic carbon (TOC) of surfactant and/or aggregation pheromone of Riptortus pedestris on surfactant-modified zeolite A at the time of field test
559
Time (weeks)
Content of TOC (ppm)
Standard SMZ-A
0.09156
0
0.20441
56.43
2
0.18420
46.32
4
0.17880
43.62
6
0.15720
32.82
8
0.15470
31.57
10
0.15240
30.42
(E)-2-hexenyl-(E)-2hexenoate (EE), and myristyl isobutyrate (MI) (Green Agro-Tech, Korea). These components were used in a ratio of 1:5:7. To prepare a pheromoneadsorbed dispenser, the dehydrated powder- or cylindershaped SMZ-A (PSMZ-A or CSMZ-A) was combined with an amount of aggregation pheromone comparable to that of the CP; 80 lL for each, dissolved in hexane (solid:pheromone:solvent = 1:0.008:10) and soaked to obtain the desired sorption loading until homogenization (3 days). After sufficient sorption, the products were filtered and kept under vacuum without contact with the atmosphere in order to prevent desorption. 2.3 Attraction test of the Riptortus pedestris To study the attraction of R. pedestris to PSMZ-A and CSMZ-A using a netted fish trap (13-cm O.D., 28-length, Green Agro-Tech, Korea), two research sites (1) soybean field with the Daewonkong variety and (2) plum field in Uiseong-gun (36°240 N, 128°720 E) were selected. Sampling was performed every week from April 12 to August 23 in 2014. After counting R. pedestris adults in bug traps including SMZ-A dispensers and the CP with the polyethylene vial, the traps were randomly allocated in selected field units and the captured individuals were removed from trap per sampling.
3 Results and discussion Eco-friendly nanoporous materials such as divalent cationexchanged and surfactant-modified synthetic zeolites A, X, and Y, bentonite, MCM-41 (Mobile Composition of Matter-41) [26], and ETS-10 [27] were studied for the sorption of N-decanol (the female sexual pheromone from A. segetum and C. pomonella) [23]; EZ, EE, and MI (the male adults release aggregation pheromone, R. pedestris) [28]; methyl (E,E,Z,)-2,4,6-decatiennoate (the male-produced pheromone of another pentatomid common in eastern Asia, P. stali) [29]; 2-(E)-octenyl acetate, and Octanol (both male and female produced pheromone, Leptocorisa
Content of aggregation pheromone per 10 g of SMZ-A (mg) 0
chinensis) [30, 31]. The SMZ-A, CTA ion-exchanged zeolite A, was selected as the most promising candidate to act as an effective pheromone dispenser. The CTA ion-exchanged zeolite A was thoroughly characterized by powder XRD, FT-IR, and SEM. CTA ionexchanged zeolites A, X, and Y were also characterized, and the results were consistent with the previous results [24]. The powder XRD patterns show that the crystallinity of the material is preserved after surfactant modification since no significant difference in d spacing values between the unmodified zeolite A and SMZ-A. Furthermore, a Table 2 Number of captured Riptortus pedestris adults in the soybean field Sampling date
No. of Riptortus pedestris adults (sum) CSMZ-Aa
PSMZ-Ab
ETS-10
CPc
4/12
9 (9)
45 (45)
16 (16)
38 (38)
4/19
23 (32)
27 (72)
31 (47)
17 (55)
4/26 5/3
47 (79) 36 (115)
42 (114) 44 (158)
30 (77) 32 (109)
22 (77) 10 (87)
5/10
20 (135)
32 (190)
21 (130)
18 (105)
5/17
24 (159)
41 (231)
39 (169)
27 (132)
5/24
37 (196)
31 (262)
17 (186)
13 (145)
5/31
28 (224)
47 (309)
30 (216)
23 (168)
6/7
34 (258)
52 (361)
20 (236)
29 (197)
6/14
29 (287)
47 (408)
32 (268)
17 (214)
6/21
20 (307)
43 (451)
27 (295)
32 (246)
6/28
37 (344)
62 (513)
34 (329)
33 (279)
7/5
38 (382)
32 (545)
16 (345)
21 (300)
7/12
19 (401)
25 (570)
13 (358)
8 (308)
7/19
23 (424)
46 (616)
18 (376)
16 (324)
7/26
26 (450)
31 (647)
21 (397)
6 (330)
8/2
15 (465)
28 (675)
17 (414)
7 (337)
8/9 8/16
20 (485) 13 (498)
43 (718) 41 (759)
23 (437) 19 (456)
11 (348) 10 (358)
8/23
27 (525)
36 (795)
21 (477)
14 (372)
a
Cylinder-type surfactant-modified zeolite A
b
Powder-type surfactant-modified zeolite A
c
Commercial product
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J Porous Mater (2016) 23:557–562
Sampling date
No. of Riptortus pedestris adults (sum) CSMZ-A
a
PSMZ-A
b
ETS-10
CP
c
4/12
84 (84)
127 (127)
51 (51)
48 (48)
4/19
102 (186)
78 (205)
89 (140)
27 (75)
4/26
89 (275)
113 (318)
74 (214)
57 (132)
5/3
76 (351)
57 (375)
69 (283)
41 (173)
5/10
56 (407)
40 (415)
57 (340)
23 (196)
5/17
60 (467)
74 (489)
76 (416)
43 (239)
5/24
76 (543)
52 (541)
58 (474)
49 (288)
5/31
67 (610)
89 (630)
49 (523)
38 (326)
6/7
67 (677)
96 (726)
51 (574)
45 (371)
6/14
50 (727)
48 (774)
35 (609)
19 (390)
6/21
41 (768)
62 (836)
39 (648)
26 (416)
6/28
28 (796)
54 (890)
31 (679)
26 (442)
7/5
38 (834)
49 (939)
27 (706)
21 (463)
7/12 7/19
23 (857) 25 (882)
51 (990) 42 (1032)
34 (740) 22 (762)
30 (493) 14 (507)
7/26
26 (908)
61 (1093)
15 (777)
23 (530)
8/2
29 (937)
55 (1148)
28 (805)
19 (549)
8/9
34 (971)
78 (1226)
42 (847)
16 (565)
8/16
37 (1008)
61 (1287)
30 (877)
10 (575)
8/23
17 (1025)
45 (1332)
23 (900)
21 (596)
a
Cylinder-type surfactant-modified zeolite A
b
Powder-type surfactant-modified zeolite A
c
100 80 60 40 20 0 0
5
10
15
20
Sampling date (week) Fig. 3 Number of Riptortus pedestris adults attracted by various pheromone dispensers in the plum field per week. See the caption to Fig. 2 for other details 1000
800
600
400 CSMZ-A PSMZ-A ETS-10 CP
200
0 0
5
Commercial product
CSMZ-A PSMZ-A ETS-10 CP
60
10
15
20
Sampling date (week) Fig. 4 Cumulative graph of Riptortus pedestris adults attracted by various pheromone dispensers in the soybean field. See the caption to Fig. 2 for other details
70
1400
50
1200 40 30 20 10 0 0
5
10
15
20
No. of R. clavatus adults
No. of R. clavatus adults
CSMZ-A PSMZ-A ETS-10 CP
120
No. of R. clavatus adults
Table 3 Number of captured Riptortus pedestris adults in the plum field
140
No. of R. clavatus adults
distinct cubic shape of zeolite A was observed by SEM, although the edges and corners were unclear. A successful modification of the surface of zeolite A by cationic
1000 800 600 400 CSMZ-A PSMZ-A ETS-10 CP
200
Sampling date (week) 0
Fig. 2 Number of Riptortus pedestris adults attracted by various pheromone dispensers in the soybean field per week. Pheromone dispensers of cylinder-type surfactant-modified zeolite A (CSMZ-A), powder-type surfactant-modified zeolite A (PSMZ-A), microporous titanosilicate ETS-10 (ETS-10), and a commercial product (CP) were used
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0
5
10
15
20
Sampling date (week) Fig. 5 Cumulative graph of Riptortus pedestris adults attracted by various pheromone dispensers in the plum field. See the caption to Fig. 2 for other details
J Porous Mater (2016) 23:557–562
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Fig. 6 Two photos of the number of captured Riptortus pedestris adults in the pheromone trap using a CP and b CSMZ-A in the soybean field
surfactants is supported by the peaks at about 2916 and 2849 cm-1, which correspond to CTAB in the FT-IR spectra. The total organic carbon (TOC) analysis shows that 0.09156 mg/L of the surfactant, CTA?, was introduced on the external surface of zeolite A (see Table 1). The hydrophobic surfactants were easily substituted on the surface of the zeolite by a conventional ion-exchange method (see Fig. 1). In sorption studies of aggregation pheromone for R. pedestris, the contents of initially loaded and remaining pheromone in CSMZ-A was confirmed by TOC analysis. Initial loading level was 56.43 mg per 10 g of CSMZ-A. After application of field test, loaded pheromone was gradually reduced due to weather-related environmental conditions such as temperature, humidity, and wind (see Table 1). As approximately half the pheromone was released after 10 weeks, SMZ-A showed good potential as a pheromone dispenser. The number of captured R. pedestris adults on a soybean and plum crops are collected and summarized in Tables 2 and 3 and Figs. 2 and 3, respectively. In both crop fields, cumulative graphs of captured R. pedestris adults are presented in Figs. 4 and 5. Since the traps were installed on April 5, field colonization of R. pedestris adults was started from the second week of April. In the soybean field, the population of R. pedestris adults was higher in June than other months. Comparing R. pedestris adults among four traps designs (CSMZ-A, PSMZ-A, ETS-10, and CP) in both fields, the PSMZ-A dispenser generally had superior performance and the trend followed PSMZ-A [[ CSMZA [ ETS-10 [ CP (see Fig. 6). The R. pedestris aggregation pheromone is composed of MI, EE, and EZ at a ratio of 1:5:1 [28]. The attraction of R. pedestris to different component compositions of aggregation pheromone in the field by using sticky traps was investigated [32]. The degree of attractiveness and the dosages of EE or EZ added to MI did not correlate. Significant differences in the numbers of insects caught between traps baited with three component blends (EE ? EZ ? MI) and traps with two component blends (EE ? MI or
EZ ? MI at the ratio of 2:1) were not observed. The role of each component to attract the bean bugs was studied in the field using synthetic chemicals [33]. Blends of EE ? EZ showed no attractiveness, however, the addition of MI to EE ? EZ (tertiary blend) showed significantly higher attractiveness to the R. pedestris than the control. The EE ? MI blend and the tertiary blend were equally attractive. The impact of zeolite variables (framework Si/Al ratio, nature of compensating cations, nature and strength of acid groups, and pore dimensions) on the kinetics of emission has been studied with semiochemicals in an effort to design more effective and more adaptable dispensers [26]. A combination of various zeolites can accommodate mixtures of two or more pheromone components maintaining a proportional release similar to the emission that occurs in nature. The SMZ-A material was synthesized and successfully developed as a slow- and rapid release pheromone dispenser for R. pedestris in this work. The SMZ-A, which have high cation-exchange capacity due to the lower framework Si/Al ratio, could be potentially used as ecofriendly and slow releasing pheromone dispensers. Acknowledgments This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP: Ministry of Science, ICT and Future Planning) (Grant No. 2012M2B2B1055496).
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