An Extractive Spectrophotometric Method for
the Determination of Pymetrozine in Various Ecological Samples of Bilaspur District
(C.G.)
Jyoti Goswami1*, Thakur Vikram
Singh1, Chhaya Bhatt1, Deepak Kumar Sahu1,
Kalpana Wani1, Ajay Kumar Sahu1, Prashant Mundeja1,
Manish Kumar Rai1, Joyec Rai2
1School of Studies
in Chemistry, Pt. Ravishankar Shukla University Raipur (Chhattisgarh), 492010,
India
2Chhattisgarh
Council of Science and Technology, Saddu Rd Mowa, Raipur (Chhattisgarh), 492014,
India.
*Corresponding author:
mkjkchem@gmail.com., jyoti.chemistry11@gmail.com
[Received: 13 December 2019; Revised version: 26 September 2020;
Accepted: 28 September 2020]
Abstract: Pesticides are designated
mixture of substances for extenuating and destroying any group of pests such as
insects and vegetation. Pymetrozine
[6-methyl-4-[(E)-pyridin-3-ylmethylideneamino]-2, 5-dihydro-1, 2,
4-triazin-3-one] is a pyridine azomethine compound which represents a class of
insecticide. A Spectrophotometric
method has been developed on the modified Fujiwara reaction for the
determination of pymetrozine. Pymetrozine directly reacts with chloroform the
45-500C turns out the violet color in the formation of Schiff’s Base
(Glutaconic Aldehyde). In the present reaction, the violet color obtained is
discharged with a few drops of acetic acid followed by the addition of p- nitro
aniline reagent which gives yellow color dyes. The absorption maxima of yellow-colored
dye measured at 430 nm. Beer’s law is obeyed over the range of 1 to 10 µg per
10 ml of pymetrozine. The molar absorptivity of the colored system
is 1.38×105 L mol-1 and Sandall’s sensitivity is 1.0×10-3µg
cm-2. This method is free from the interference of other interfering
and can be successfully applied for the determination of various ecological
samples.
Keyword: Fujiwara Reaction, Pymetrozine, Chloroform, Schiff’s
Base, Ecological Sample.
Introduction
Pymetrozine (C10H12N5O),
pyridine azomethine speaks to another substance class of bug sprays with a
momentous selectivity for plant-sucking creepy crawlies, for example, aphids,
whiteflies, and planthoppers, because of its foundational Action [Neuen et al.,
2013]. Pymetrozine rapidly affects the feeding behavior of insect pests. Pymetrozine
may take effect through the nervous system, with a unique mode of action that
differs from other well-known insecticides [Ausborn et al 2005; Hong et al 2011]. Pymetrozine
is probably not going to sully groundwater at the prescribed application in
Owing to its high effectiveness, low poisonousness, high selectivity, and
ecological amicability, Pymetrozine has pull in far reaching enthusiasm as a
pesticide. Pymetrozine 50 WG is the bug spray from the pyridine azomethines
bunch with a one of a kind method of activity that keeps the creepy crawly from
embeddings the stylet into the plant tissue [Cui et al., 2013; Deekshita and Ramarao 2018].
The present investigation is carried out to
evaluate the efficacy of Pymetrozine along with different insecticides against
Ecological field conditions [Boina et al., 2011; Qiong et al., 2012]. Consequently, pymetrozine buildups may prompt
potential wellbeing injury. A few investigation strategies have been produced
for deposits of Pymetrozine in various frameworks, for example, differential spectrophotometric
method molar absorptivity and sandal’s sensitivity observed [Jixin et al., 2018;
Zhang et al., 2015]. A simple, sensitive, and selective method were obeying
beers lambert law for quantification of Pymetrozine was developed to study the
dissipation behavior and final residue of Pymetrozine in various fields in the
ecosystem. However, the current knowledge of the behavior of Pymetrozine in
Ecological systems is lacking. It is important to explore the sorption-desorption
processes of Pymetrozine and factors that modulate its samples [Jansen et al 2011; Mingxing et al 2016]
LC-MS analysis of pesticides in soya grain
samples, [Pizzuti et al., 2007]. Pymetrozine main metabolites, CGA128632,
GS23199, and CGA266591 in Chinese kale using liquid chromatography with tandem
triple quadrupole mass spectrometry LC-MS [Gong et al., 2018]. The mechanisms
responsible for contaminant removal were elucidated at different pH,
temperature, contact time and initial ions concentration using sorption
kinetics and isotherms [Cui et al., 2013]. LC-MS/MS determination with
comparison by two other methods of extraction as described [Abdelselam et al., 2006], HPLC-UV
with liquid-liquid partition cleanup, Pre-treatment [Zhang et
al., 2007]. FTIR microspectroscopy is combined with principal
component-discriminant function analysis [Baker et al., 2018].
Gold nanoparticles colorimetric detection of organophosphorus pesticide [Bala
et al., 2016], ultrasound-assisted microextraction of Carbaryl pesticides from
water sample [Bazrafshan et al., 2017], residue analysis of Pymetrozine [Gong et al., 2018], detection
of organophosphate
pesticide in rewal samples [Yola et al., 2019], physical, chemical and biological
Food analysis, food safety and human health analysis [shingh et al., 2019], argent
need for a new concept of agriculture [Stamati et al., 2016] were analyzed.
Experimental
Apparatus
A Systronic UV-Vis
spectrophotometer model – visiscan167 with coordinated silica cell was utilized
for all ghostly estimations. A Systronic pH meter model – 335 was used for pH
assessment.
Reagents
All reagents (HCl and NaOH) used were of
Anala. R. grade and Double Distilled water were utilized all through.
Standard solution of pymetrozine
Supplied by Godrej Agrovet Ltd, a stock
solution of 1mg/ml solution of pymetrozine is prepared in water. The working
standard solution is prepared by appropriate dilution of the stock solution.
Chloroform
Supplied by Thermo Fisher Scientific India
Pvt. Ltd, A 5.0 mol L-1 aqueous solution is used.
P-nitro aniline reagent
Supplied by Loba Chemie Pvt. Ltd, 0.001M
solution of p-nitro aniline with ethanol is prepared.
Procedure
An aliquot containing 1 to 12 μg of Pymetrozine
was taken1 ml in 25 ml of the calibrated test tube. The solution of the test
tube was evaporated off up to 0.5 ml on a water bath. To this 1ml of chloroform
followed by 2ml of 5 M sodium hydroxide were added and the test tube was kept
in a boiling water bath for 45-500C temperature. The violet-colored
dye obtained was cooled in ice-cold water and then de-colorized with few drops
of glacial acetic acid. Then 1ml of p-nitro-aniline reagent and 10 M HCl 0.5 ml
was added and the solution was kept for 10 minutes for full-color development.
The volume of the test tube was made up to 10 ml with distilled water and the
absorbance of the yellow-colored dye was measured at 430 nm against a reagent
blank.(Sharma et al.,2003)
Chemical Reaction (color reaction)
The reaction place three steps in the first step Pymetrozine reacts with
chloroform in an alkaline medium to obtain violet color (I), in the second step
on the addition of glacial acetic acid, the violet color disappear of formation
of Schiff;’s base of glutaconic aldehydes (II) and is converted into glutaconic
aldehydes (II), which form a yellow-colored dye (III) with p-nitro aniline
reagent in the third step (Scheme 1).
Results and Discussion
Spectral Characteristics: The
p-nitro aniline dye formed in the proposed reaction shows maximum absorption at
430 nm (Figure 2). All ghostly estimations were completed against double
refined water as the reagent clear indicated irrelevant intake at this
frequency [Eldridge et al., 2018]. The
shading structure complies with Beer's law in the range of 1 to 100 μgml-1 of
pymetrozine last arrangement at 430 nm (Figure 3 to 6). Table 1is shows the reproducibility of Method
Pymetrozine in days investigation, Table 2 is presented Optical characteristics
and Statistical Data of the Regression Equations for the Reaction, Table 3 is
presented The effect of Foreign Species, and Table 4 is presented the recovery
of pymetrozine in Various Ecological Samples [Wani et al., 2016].
|
Table 1. Reproducibility of Method
|
|
No. of Days
|
Absorbance at 430nm
|
|
1
|
0.573
|
|
2
|
0.576
|
|
3
|
0.580
|
|
4
|
0.577
|
|
5
|
0.575
|
|
6
|
0.573
|
|
7
|
0.576
|
|
Mean
|
0.576
|
|
Standard deviation
|
±0.002
|
|
Relative Standard Deviation
|
0.39%
|
|
The concentration
of Pymetrozine used was 7μg /10mL
|
|
Table 2. Optical characteristics and Statistical Data of the
Regression Equations for the Reaction
|
|
S. No.
|
Parameters
|
Values for the reaction
|
|
1
|
Lemda Max nm
|
430
|
|
2
|
Beer,s law limit,
µg mL-1
|
1 to 12
|
|
3
|
Detection limits,
µg mL-1
|
0.146
|
|
4
|
Quantification
limit µg mL-1
|
1.4
|
|
5
|
Molar
Absorptivity, L mol-1 cm-1
|
1.38×105
|
|
6
|
Sandell,s
sensitivity, µg cm-2
|
1.0×103
|
|
7
|
Regression
equation, y = b+a
|
0.045X + 0.252
|
|
8
|
Intercept(a)
|
0.252
|
|
9
|
Slope
|
0.045
|
|
10
|
Standard
Deviation
|
±0.002
|
|
11
|
Relation Standard
deviation (%)
|
0.39%
|
|
12
|
Correlation
coefficient(r2)
|
0.979
|
|
Table 3. Effect
of Foreign Species
|
|
Foreign Species & Ione
|
Tolerance limit* μg in 10 mL
|
|
Phanthoate
|
500
|
|
Fenpyroximate
|
250
|
|
Kitazine
|
300
|
|
Permethrine
|
500
|
|
Cu2+
|
100
|
|
Fe3+
|
300
|
|
Zn2+
|
200
|
|
Mg2+
|
300
|
|
Concentration of Pymetrozine 7 μg / 10 mL.
*The amount causing an error of ± 2% in
absorbance value.
|
|
Table 4. Recovery of pymetrozine in Various Ecological Samples
|
|
Sample
|
Originally
found*
(μg mL-1)
a
|
Added
(μg mL-1)
b
|
Total found
(μg mL-1)
c
|
d=c-a
|
Recovery
(% ± R.S.D.)
(d/b)×100
|
|
Potato***
|
2.502
|
3
|
5.4
|
2.898
|
96.6 ± 0.0244
|
|
Carrot***
|
2.256
|
3
|
5.239
|
2.983
|
99.43 ± 0.041
|
|
Tomato***
|
0.938
|
3
|
3.826
|
2.888
|
96.26 ± 0.056
|
|
Gherkin***
|
1.292
|
3
|
4.24
|
2.948
|
98.26 ± 0.042
|
|
Apple***
|
0.804
|
3
|
3.771
|
2.967
|
98.9 ± 0.042
|
|
Bean***
|
2.141
|
3
|
5.128
|
2.987
|
99.56 ± 0.041
|
|
Rice***
|
1.089
|
3
|
4.083
|
2.994
|
99.8 ± 0.041
|
|
Lemon***
|
0.898
|
3
|
3.881
|
2.983
|
99.43 ± 0.027
|
|
Water*
|
0.821
|
3
|
3.8132
|
2.992
|
99.73 ± 0.041
|
|
Soil**
|
2.242
|
3
|
5.221
|
2.979
|
99.3 ± 0.15
|
|
***Mean of three replicate analyses
*Water
sample 5 mL
**Amount
of Soil Sample 5 gm
|
|
|
|
|
|
|
|
|
|
|
Optimization of condition
The precision
of the method was checked by the replicate analysis of a working standard
solution containing 7μg of Pymetrozine in a 10 ml final solution over for 7
days. The standard deviation and relative standard deviation were found to be ±
0.002 and 0.39 % respectively. The molar absorptivity, Sandell’s sensitivity, correlation
coefficient, regression equation intercept, slope, LOQ, and LOD were found to
be Table 3.
Effect of
Chloroform: 1ml of chloroform was sufficient for complete
development. A higher or lower amount of chloroform decreased the absorbance value.
Effect of Temperature: it was
found that 2-3 minutes in a water bath a temperature range 45 to 500C was sufficient for the complete color
development further heating and increasing the temperature of the solution
decreases the absorbance value.
Effect of
Reagent: it was
found that 1 mL of p-nitro aniline was sufficient for complete color
development. On increasing the amount of p-nitro aniline the absorbance value
decreases.
Effect of
Foreign Species: effect of various pollutants and pesticides on the
determination of Pymetrozine was studied. To a sample containing 7 µg of
Pymetrozine known of foreign species and pesticide were added. The Pymetrozine
was analyzed as described above the method was found to be free from the interference
of other pesticides and pollutants are normally given Table-3[Parween et al., 2017].
Applications
Determination
of Pymetrozine in water sample: 100ml of water taken and fortified with a known
amount of Pymetrozine add and kept for 6 hours, Pymetrozine was then extracted
in ethanol. Ethanol was evaporated off and Pymetrozine was determined by the
proposed as well as reported Pymetrozine completely soluble in ethanol. The
recuperations are appeared in the Table 4.
Determination
of Pymetrozine in soil sample: 5 gm of soil taken and fortified with known
amount of Pymetrozine and 10 mL double distilled water add and kept
for 6 hours, and then these
samples are filtered through Whatman No. 40 filter paper. Pymetrozine was
determined by the proposed as well as reported [Mahmood et al., 2015]. The
recuperations are appeared in the Table 4.
Determination
of Pymetrozine in vegetables, Fruits Grains, and soil: Potato,
Carrot, Tomato, Gherkin, Apple, Bean, Rice, and Lemon were weighed (5 gm),
crushed, and spiked with a known amount of Pymetrozine. After 6 hours
Pymetrozine was extracted in ethanol. Ethanol was evaporated off and
Pymetrozine was determined by the proposed as well as reported method the recoveries
are shown in Table 4. The recoveries range from 96 – 99% by the present method.
Conclusion
The proposed method is fast, straight-forward,
touchy, and the reagent depicted here is delicate, and specific for experiments
of Pymetrozine in different environmental samples, and strategy is more
particular than other detailed methods. It can effectively apply for the
assurance of Pymetrozine in water, soil, vegetable Fruits, and Grain analysis.
Check the recuperations, known measures of Pymetrozine were added to different
samples of vegetables, products of the soil tests, and afterward broke down by
the proposed strategy (Table 4).
Acknowledgment
Authors are appreciative of the head, school
of studies in science Pt. Ravishankar Shukla University, Director General,
Chhattisgarh Council of Science and innovation and, University Gant Commission
for giving research laboratory facility and award separately.
References
Abdelselam, S.,
John S., Wilkie, A., Kevin, N., (2006). Synthesis of Some
Hydrazones Derivatives Structurally Related to the Insecticide Pymetrozine.
Journal of Chemistry 49, 927-930.
Ausborn,
J., Wolf, H., Mader, W., Kayser,
H., (2005). The insecticide pymetrozine selectively
affects chordotonal mechanoreceptors,
Journal of Experimental Biology The Journal of Experimental Biology 208, 4451-4466
Baker, M.J.,
Gazi, E., Brown, M.D., Shanks,
J.H., Gardner,P., Clarke,N.W.,(2008).
FTIR-based spectroscopic analysis in the identification of clinically
aggressive prostate cancer, British Journal of Cancer ,99, 1859 – 1866
Bala,
R., Sharma R.K., Wangoo, N., (2016). Development of gold nanoparticles-based
aptasensor for the colorimetric detection of organophosphorus pesticide
phorate. Analytical and Bioanalytical Chemistry 408, 333–338.
Bazrafshan,
A.A., Ghaedi, M., Rafiee, Z., Hajatib, S., Ostovan, A., (2017). Nano-sized
molecularly imprinted polymer for selective ultrasound-assisted microextraction
of pesticide Carbaryl from water samples: Spectrophotometric determination.
Journal of Colloid and Interface Science Volume 498, 313-322
Boina D. R., Youn Y., Folimonov S. and Stelinski L L
(2011) Effects of pymetrozine, an antifeedant of Hemiptera, on Asian citrus
psyllid, Diaphorina citri, feeding behavior, survival, and transmission
of Candidatus Liberibacter asiaticu, Society of Chemical Industry Pest Management Science 67: 146–155
Cui, L,Yan J., Quan, G., Ding, C., Chen, T.,
Hussain, Q., (2013) Adsorption Behavior
of Pymetrozine by Four Kinds of Biochar from Aqueous Solution, Adsorption Science & Technology 31 No. 6
Deekshita K and Ramarao C. V. (2018) Pymetrozine: A Pyridine Azomethine
insecticide for management of rice brown planthopper in India Chemical Science Review Letters, 7(25), 335-339
Eldridge, B., F., (2008). Pesticide
Application And Safety Training For Applicators Of Public Health Pesticides,
Applicators May Be Obtained From The California Department Of Public Health, (916) 552-9730.
Gong,J., Zheng K., Yang, G., Zhao, S., Zhang,
K., Hu., D., (2018). Determination, residue analysis, risk assessment and
processing factor of pymetrozine and its metabolites in Chinese kale under
field conditions, Food Additives & Contaminants: Part A https://doi.org/10.1080/19440049.2018.1562237
Hong,
J., Lee C., Lim J., (2011).
Comparison of Analytical Methods and Residue Patterns of Pymetrozine in
Aster scaber, Bull Environ Contam Toxicol
87:649
Jansen, J.P., Defrance, T., Warnier, A.M.,
(2011). Side effects of flonicamide and pymetrozine on five aphid natural
enemy, species Bio Control 56:759–770
Jixin, Yu., Genbo,
Xu., Wei, Li., Shiyu, J., Ting, Yu.,
Jiashou, Li., Zhongjie, Li., Tanglin, Z., (2018). Pymetrozine: A Pyridine Azomethine
insecticide for management of rice Intetnational
Journal of Environmental Research. Public Health 15, 984;
Mahmood, S., Imad, I.R.S.,
Shazadi, K., Gul Z.A., Khalid, Hakeem,
R., (2015). Effects Of Pesticides
On Environment, Springer
International Publishing Switzerland (Eds.), Plant, Soil And Microbes, DOI
10.1007/978-3-319-27455-3_13,253-269.
Mingxing, G.A.O., Yingying, LI., Hong, Y.,
Yucheng, G.U., (2016). Sorption and desorption of pymetrozine on six Chinese
soils, Frontiers. Environmentsal.
Science.and Engineering 10(1): 1–10
Nauen, R., Vonta,s J.,
Kaussmanna, M., Wolfel, K., (2013) Pymetrozine is hydroxylated by CYP6CM1, a
cytochrome P450 conferring neonicotinoid resistance in Bemisia tabaci1'Society of Chemical, Industry
Pest Management Science 69:
457–461* and T. Sherwood I
Parween,T., Jain, S., (2017). Interface
Between Pesticide Chemistry And Plant Physiology, Ecophysiology Of Pesticide,
Elsevier, ISBN 978-0-12-817614-6,
Qiong, R., Hua, Xu.Y., Chen, L.U.O.,
Hong, Z., Jones, C.M., Greg, J., Devine,
G.J., Gorman, K., Denholm, I., (2012).
Characterisation of Neonicotinoid and Pymetrozine Resistance in Strains of Bemisia tabaci from China, Journal of Integrative Agriculture 11(2): 321-326
Singh, P. K., Singh, R. P.,
Singh, P., Singh, R. L. (2019). Food Hazards: Physical, Chemical, And
Biological. Food Safety And Human Health, 15–65. DOI:10.1016/B978-0-12-816333-7.00002-3.
Stamati, P., N., Maipas, S., Kotampasi, C.,
Stamatis, P., Hens, L., (2016). Chemical Pesticides and Human Health: The
Urgent Need for a New Concept in Agriculture, Front Public Health. 4, 148. doi: 10.3389/fpubh.2016.00148.
Tsujimoto, K.,
Sanad, S., Masaya, M., (2016). A new method for monitoring the
susceptibility of the brown planthopper, Nilaparvata lugens (Hemiptera:
Delphacidae), to pymetrozine by combining topical application and measurement
of offspring number, Journal
of Entomology Zooogy studies 51, 155–160
Wani
K., Nirmal M., Patel, V., Khatoon, R., Rai, MK., Rai, J(2016) Determination of
Carbendazim in Environmental sample with Iron (III) and 1, 10 phenanthroline as
Reagents. Asian journal of Chemistryvalume 29,
161-165
Yola, M.L., (2019). Electrochemical activity
enhancement of monodisperse boron nitride quantum dots on graphene oxide: Its
application for simultaneous detection of organophosphate pesticides in real
samples. Journal of Molecular Liquids.
277, 50-57
Zhang, Y.Li., Zhang, Li., Peng, Xu.,
Jianzhong, Li., Wang, H., (2015). Dissipation and residue of pymetrozine in
rice field ecosystem, Environatal
Monitoring Assessment 187: 78
Zhou Q
Du F., Shi Y., Liu W, Liu D and Chen G (2018) Isolation and characterization of a pymetrozine grading strain
Pseudomonas sp. BYT-1 journal
of chemical research 42, 434–438