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Green synthesis of copper oxide nanoparticles using Punica granatum peels extract: Effect on green peach Aphid
Environmental Nanotechnology, Monitoring & Management 6 (2016) 95–98
Contents lists available at ScienceDirect
Environmental Nanotechnology, Monitoring & Management journal homepage: www.elsevier.com/locate/enmm
Green synthesis of copper oxide nanoparticles using Punica granatum peels extract: Effect on green peach Aphid Alaa Y. Ghidan a , Tawfiq M. Al-Antary a , Akl M. Awwad b,∗ a b
Department of Plant Protection, School of Agriculture, The University of Jordan, Amman, 11942, Jordan Department of Nanotechnolgy, Royal Scientific Society, P.O. Box 1438, Amman 11941, Jordan
a r t i c l e
i n f o
Article history: Received 19 June 2016 Received in revised form 22 August 2016 Accepted 24 August 2016 Keywords: Green synthesis Copper oxide nanoparticles Green peach Aphid
a b s t r a c t Copper oxide nanoparticles (CuONPs) were synthesized by a simple and green method using Punica granatum peels extract at room temperature. Biosynthesized copper oxide nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV–vis absorption spectroscopy, and X-ray diffraction (XRD). The particles are crystalline in nature with average size 40 nm. The morphology of the copper oxide nanoparticles could be controlled by tuning the amount of Punica granatum peels aqueous extract and copper ions. This study determined the mortality efficacy of the synthesized CuONPs against green peach Aphid. © 2016 Elsevier B.V. All rights reserved.
1. Introduction Copper oxide (CuO) is an important metal oxide semiconductor with a narrow band gap of 1.7 eV. Further it can be used in pesticides formulation, and antibacterial agents. Copper oxide nanoparticles are synthesized through different techniques and methods including precipitation (Sahooli et al., 2012), sonochemical route (Safarifard and Morsali, 2012), sol-gel (Pandiyarajan et al., 2013), hydrothermal approach (Mohamed et al., 2014; Outokesh et al., 2011), chemical bath deposition (Jiang et al., 2015), chemical reduction (Karthik and Geetha, 2013), non-vacuum and spin coating sol-gel techniques (Yahia et al., 2016) and reflux contestation (Bouazizi et al., 2015). These methods have many disadvantages due to the difficulty of scale up the process of synthesis, separation and purification of the nanoparticles, energy consumption and using hazardous chemicals. Recently, there have been related works employed the potential of green methods to synthesize copper oxide nanoparticles using plant aqueous extracts such as Gundelia tournefortii leaves and stems (Nasrollahzadeh et al., 2015), Tinospora cordifolia (Udayabhanu et al., 2015), Calotropis gigantean leaf (Sharma et al., 2015), Aloe barbadensis leaves (Gunalan et al., 2012; Kumar et al., 2015), Carica papaya leaves (Sankar et al., 2014), Gloriosa superba L (Naika et al., 2015), Citrus limon juice (Mohan et al., 2015), Tabernaemontana divaricate leaf (Sivaraj et al., 2014), carob leaf (Awwad and Ibrahim, 2015), and Malva sylvestris leaf (Awwad et al., 2015).
∗ Corresponding author. E-mail addresses: [email protected], [email protected] (A.M. Awwad). http://dx.doi.org/10.1016/j.enmm.2016.08.002 2215-1532/© 2016 Elsevier B.V. All rights reserved.
Aphids are insects able to attack several plants, secreting honey dew and transmitting viral diseases economic plants (Al-Antary and Khadir, 2013). The green peach aphid Myzus persicae Sulzer (Homoptetra: Aphidae) is worldwide distributed, polyphagous and with wide host range. In Jordan, the green peach Aphid attacks several economic plants and vegetables particularly sweets and hot peppers. The present study was designed with a novel, rapid, and costeffective route for biosynthesis of copper oxide nanoparticles (CuONPs) using Punica granatum peels extract. The synthesized copper oxide nanoparticles obtained by the green method are under investigation of their effect on green peach Aphid. 2. Experimental 2.1. Materials Copper acetate monohydrate [Cu(CH3 COO)2 ·H2 O] is analytical grade purchased from Merck, Darmstadt, Germany and used without further purification. Deionized distilled water was used in all experimental work. 2.2. Preparation of Punica granatum peels extract Fresh peels of healthy Punica granatum fruits were collected from local market, Jordan. Peels were washed several times with water to remove dust particles and then dried in shade for two weeks to remove the residual moisture. Punica granatum peels aqueous extract was prepared by placing 10 g of dried fine powder in 500 ml glass beaker along with 400 ml of sterile distilled water.
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The mixture was boiled for 10 min until the color of aqueous solution changed from watery to brown-yellow. Then the mixture was cooled to room temperature and filtered with Whatman No. 1 filter paper before centrifuging at 1200 rpm for 5 min to remove biomaterials. The extract was stored at room temperature in order to be used for further experiments. 2.3. Green synthesis of copper oxide nanoparticles (CuONPs) In a typical reaction mixture, 2.8 g of copper acetate monohydrate was dissolved in 500 ml of the deionized water and stirred magnetically at room temperature for 5 min. Afterwards, P. granatum peels aqueous extract was added dropwise under stirring, as soon as, the peels extract comes in contact copper ions spontaneous change the blue color of copper ions to green color. The obtained green mixture was left under stirring at room temperature. After 10 min, the green mixture started changing to a brown suspended mixture, indicating the formation of water soluble monodispersed copper oxide nanoparticles. 2.4. Characterization techniques Scanning electron microscopy (SEM) analysis of synthesized copper oxide nanoparticles was done using a Hitachi S-4500 SEM machine. Powder X-ray diffraction was performed using a X-ray diffractometer, Shimadzu, XRD-6000 with CuK␣ radiation = 1.5405 Å over a wide range of Bragg angles (20◦ ≤ 2 ≤ 80◦ ). Fourier transform infrared spectroscopic measurements were done using Shimadzu, IR-Prestige-21 spectrophotometer. UV–vis spectrum of copper oxide nanoparticles was recorded, by taking 0.1 ml of the sample and diluting it with 2 ml deionized water, as a function of time of reaction using a Schimadzu1601 spectrophotometer in the wave length region 300–700 nm operated at a resolution of 1 nm.
Fig. 1. XRD pattern of the synthesized CuO nanoparticles using P. granatum peels extract.
with those of powder CuO obtained from the International Center of Diffraction Data card (JCPDS-45-0937) confirming the formation of a crystalline structure. No extra diffraction peaks of other phases are detected, indicating the phase purity of CuONPs. The average crystallite size of the synthesized copper oxide nanoparticles was calculated using Debye-Scherrer equation (Sankar et al., 2014; Vidhu et al., 2011): D = Lambda K/cos where D – The crystallite size of copper oxide nanoparticles, – Represents wavelength of X-ray source 0.15406 nm used in XRD,  – The full width at half maximum of the diffraction peak, K – The Scherrer constant with value from 0.9 to 1 and is the Bragg angle. The average particle size of CuONPs was calculated 40 nm by using above Debye-Scherrer, s formula.
3. Results and discussion 3.2. Fourier infrared spectroscopy (FT-IR) analysis 3.1. X-ray diffraction analysis Fig. 1 shows the X-ray diffraction (XRD) pattern of the synthesized CuONPs powder. The XRD pattern revealed the orientation and crystalline nature of copper oxide nanoparticles. The peaks position with 2 values of 35.22◦ , 38.36◦ , 48.05◦ , 52.4◦ , 56.56◦ , 60.78◦ , 65. 4◦ , and 73.89◦ are indexed as (0 0 2), (1 1 1), (2 0 2), (0 2 0), (202), (113), (311), (113), planes, which are in good agreement
Fourier transform infrared spectroscopy is used to identify and get an approximate identification of the possible biomolecules in plant extract. FT-IR spectrum of P. granatum peels extract is shown in Fig. 2. FT-IR displays a number of absorption peaks, reflecting its complex nature due to biomolecules. Strong and broad peak at 3379 cm−1 attributed to hydrogen bonded O H groups of alcohols and phenols and also to the presence of amines N H of amide. The
Fig. 2. FT-IR spectrum of Punica granatum peels extract.
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Fig. 3. FT-IR spectrum of synthesized CuONPs using P. granatum peels extract.
bands at 2912 cm−1 is assigned to CH2 and C H stretching mode in alkanes. The strong peak at 1728 cm−1 could be attributed to C C stretching vibrations about C O amide conjugated C O of the proteins that are responsible for reducing, capping and stabilizing process. The bands at 1612 cm−1 can be allocated to the stretching vibration of C OH bond from proteins (amide I), whereas the band at 1523 cm−1 is characteristic of amide II. The peak at 1446 cm−1 is characteristic to the C N stretching of aliphatic amines. Peaks in the region 1323 cm−1 , 1227 cm−1 and 1018 cm−1 may be attributed to the presence of the stretching vibrations of carboxylic acids and amino groups. FT-IR spectra of the synthesized CuONPs indicate a new chemistry linkage on the surface of CuONPs. This suggests that P. granatum peels extract can bind to CuONPs through hydroxyl and carbonyl of the amino acid residues in the protein of the extracts, therefore acting as reducing, stabilizing and dispersing agent for synthesized copper oxide nanoparticles and prevent agglomeration of CuO nanoparticles. The main characteristic peaks of P. granatum peels extract were observed in FT-IR spectra of CuONPs, Fig. 3. The FT-IR spectra of the CuONPs showed a strong and sharp peak at 509 cm−1 . 3.3. Scanning electron microscopy (SEM) analysis Typical SEM micrograph for as prepared CuONPs is shown in Fig. 4. The SEM micrograph clearly showed rough agglomerations of nanostructural homogeneities with spherical morphologies of CuONPs. The SEM observation showed the presence of agglomerated nanospheres with an average diameter of 10–100 nm. This slight deviation of the particle size estimation compared to that calculated from XRD analysis can be attributed to the deviation of the spherical shape of the particles that is required for the Debye–Scherrer formula and the detection limit of the XRD diffractometer. Moreover, the observed strong agglomeration of the nanoparticles prepared by this method may be interpreted in terms of the increase in the catalytic activity of the surface of the nanoparticles. 3.4. UV–vis spectroscopy analysis The addition of P. granatum peels extract to copper acetate monohydrate [Cu(CH3 COO)2 ·H2 O] solution resulted in color change of the solution from blue to green and then to brown due
Fig. 4. Scanning electron microscopy (SEM) of CuONPs synthesized using P. granatum peels extract at room temperature.
to the production of CuONPs. The color changes arise from the excitation of surface plasmon vibrations with the copper oxide nanoparticles. The SPR of CuO nanoparticles produced a peak centered near 282 nm. UV–vis absorbance of the reaction mixture was taken from 0 till 10 min, Fig. 5. It was observed that the absorbance peak was centered near 282 nm, indicating the reduction of copper acetate monohydrate into CuONPs. It was also observed that the reduction of copper acetate monohydrate ions into copper oxide nanoparticles started at the start of reaction and reduction was completed at almost 10 min at room temperature, indicating rapid biosynthesis of copper oxide nanoparticles. 3.5. Effect of CuO nanoparticles onto green peach Aphid (GPA) Preliminary results from a research project “Effect of green synthesized nanomaterials on green peach Aphid” is carried out at the University of Jordan and the Royal Scientific Society, the effect of different concentration of CuONPs on GPA are shown in Table 1. Means of mortality% of the 1st and 2nd nymphal instars caused by the five concentrations were different significantly, Table 1. Means of Mortality% of 3rd and 4th nymphal instars of the same aphid caused by the same concentrations were also different significantly. However, mortality% of both aphid categories in all concentrations was greater significantly than the control treatment.
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Table 1 Means of mortality percent [%] of green peach aphid treated by different concentrations of CuONPs. Concentration [g/mL]
Mortality% of 1st and 2nd nymphal instars ± SE
Mortality% of 3rd and 4th nymphal instars ± SE
250 1000 2000 4000 8000 Control
40 e 51d 60 c 75 b 86 a±6 5f
14 e 26 d 62 c 75 b 86 a±7 5f
* Means within the same column sharing the same letter do not differ significantly at 5% level using LSD test.
Fig. 5. UV–vis spectrum showing absorption of 10−3 M aqueous solution of copper acetate with P. granatum peels extract as a function of time.
4. Conclusion Green synthesis of copper oxide nanoparticles CuONPs is an eco-friendly and safer to environment as compared with chemical and physical methods. We have developed a fast, eco-friendly, and convenient green method for the synthesis of CuO nanoparticles from copper acetate monohydrate using P. granatum peels aqueous extract at ambient temperature. Punica granatum peels extract was found suitable for the green synthesis of copper oxide nanoparticles within 10 min at ambient conditions. Spherical, polydispersity of CuONPs of particle sizes ranging from 10 to 100 nm with an average size of 40 nm are obtained. Color changes occur due to surface Plasmon resonance during the reaction with the ingredients present in the P. granatum peels extract resulting in the formation of CuO nanoparticles, which is confirmed by XRD, FT-IR, UV–vis spectroscopy, and SEM. FT-IR spectroscopic study confirmed that the carbonyl group of amino acid residues has a strong binding ability with copper oxide, suggesting the formation of a layer covering copper oxide nanoparticles and acting as a capping agent to prevent agglomeration and provide stability to the medium, yet further research is needed in this area to explore the possible biomolecule responsible for the bioreduction process. The activity of biologically synthesized copper oxide nanoparticles was evaluated against the mortality of green peach Aphid.
Conflict of interest The authors declare that they have no conflict of interest
Acknowledgments Authors are thankful to the University of Jordan and the Royal Scientific Society, Amman, Jordan for giving all facilities to carry out this research work. References Al-Antary, T.M., Khadir, B., 2013. Toxicity of four insecticides on longevity and fecundity of three populations of the green peach aphid for three generations. Jordan J. Agric. Sci., 52–62. Awwad, A.M., Ibrahim, Q., 2015. Optical and X-ray diffraction characterization of biosynthesis copper oxide nanoparticles using carob leaf extract. Arab J. Phys. Chem. 2, 20–24. Awwad, A.M., Albiss, B.A., Salem, N.M., 2015. Antibacterial activity of synthesized copper oxide nanoparticles using Malva sylvestris leaf extract. SMU Med. J. 2, 91–101. Bouazizi, N., Bargougui, R., Oueslati, A., Benslama, R., 2015. Effect of synthesis time on structural: optical and electrical properties of CuO nanoparticles synthesized by reflux condensation method. Adv. Mater. Lett. 6, 158–164. Gunalan, S., Sivaraj, R., Venckatesh, R., 2012. Aloe barbadensis Miller mediated green synthesis of mono-disperse copper oxide nanoparticles: optical properties. Spectrochim. Acta Part A 97, 1140–1144. Jiang, T., Wang, Y., Meng, D., Yu, M., 2015. Facile synthesis and photocatalytic performance of self-assembly CuO microspheres. Superlattices Microstruct. 85, 1–6. Karthik, A.D., Geetha, K., 2013. Synthesis of copper precursor: copper and its oxide nanoparticles by green chemical reduction method and its antimicrobial activity. J. Appl. Pharm. Sci. 3, 16–21. Kumar, P.P.N.V., Shameem, U., Koliu, P., Kalyani, R.L., Pammi, S.V.N., 2015. Green synthesis of copper oxide nanoparticles using Aloe vera leaf extract and its antibacterial activity against fish bacterial pathogens. BioNanoScience 5, 135–139. Mohamed, R.M., Harraz, F.A., Shawky, A., 2014. CuO nanobelts synthesized by a template-free hydrothermal approach with optical and magnetic characterestics. Ceram. Int. 40, 2127–2133. Mohan, S., Singh, Y., Verna, D.K., Hassan, S.H., 2015. Synthesis of CuO nanoparticles through green route using Citrus limon juice and its application as nanosorbent for Cr(VI) remediation: process optimization with RSM and ANN-GA based model. Process Safety Environ. Prot. 96, 156–166. Naika, H.R., Lingarajua, K., Manjunath, K., Kumar, D., Nagaraju, G., Suresh, D., Nagabhushana, H., 2015. Green synthesis of CuO nanoparticles using Gloriosa superba L. extract and their antibacterial activity. J. Taibah Univ. Sci. 9, 7–12. Nasrollahzadeh, M., Maham, M., Sajadi, S.M., 2015. Green synthesis of CuO nanoparticles by aqueous extract of Gundelia tournefortii and evaluation of their catalytic activity for the synthesis of N-monosubstituted ureas and reduction of 4-nitrophenol. J. Colloid Interface Sci. 455, 245–253. Outokesh, M., Hosseinpour, M., Ahmad, S.J., Mousavand, T., Sadjadi, S., Soltanian, W., 2011. Hydrothermal synthesis of CuO nanoparticles: study on effects of operational conditions on yield purity, and size of the nanoparticles. Ind. Eng. Chem. Res. 50, 3540–3554. Pandiyarajan, T., Udayabhaskar, R., Vignesh, S., James, R.A., Karthikeyan, B., 2013. Synthesis and concentration dependent antibacterial activities of CuO nanoflakes. Mater. Sci. Eng. C 33, 2020–2024. Safarifard, V., Morsali, A., 2012. Sonochemical syntheses of a nano-sized copper (II) supramolecule as a precursor for the synthesis of copper(II) oxide nanoparticles. Ultrason. Sonochem. 19, 823–829. Sahooli, M., Sabbaghi, S., Saboori, R., 2012. Synthesis and characterization of mono sized CuO nanoparticles. Mater. Lett. 81, 169–172. Sankar, R., Manikandan, P., Malarvizhi, V., Fathima, T., Shivashangari, K.S., Ravikumar, V., 2014. Green synthesis of colloidal copper oxide nanoparticles using Carica papaya and its application in photocatalytic dye degradation. Spectrochim. Acta Part A 121, 746–750. Sharma, J., Akhtar, J.K., Ameen, M.S., Srivastava, S., Singh, P.G., 2015. Green synthesis of CuO nanoparticles with leaf extract of Calotropis gigantea and its dye-sensitized solar cells applications. J. Alloys Compd. 632, 321–325. Sivaraj, R., Rahman, P.K.S.M., Rajiv, P., Salam, H.A., Venckatesh, R., 2014. Biogenic copper oxide nanoparticles synthesis using Tabernaemontana divaricate leaf extract and its antibacterial activity against urinary tract pathogen. Spectrochim. Acta Part A 133, 178–181. Udayabhanu, Nethravathi, Kumar, P.C., Suresh, M.A.P., Lingaraju, D., Rajanaika, K., Nagabhushana, H., Sharma, H., 2015. Tinospora cordifolia mediated facile green synthesis of cupric oxide nanoparticles and their photocatalytic, antioxidant and antibacterial properties. Mater. Sci. Semicond. Process. 33, 81–88. Vidhu, V.K., Aromal, A., Philip, D., 2011. Green synthesis of silver nanoparticles using macrotyloma uniflorum. Spectrochim. Acta A 83, 392–397. Yahia, I.S., Farag, A.A.M., El-Faify, S., Yakuphanoglu, F., Al-Ghamdi, A., 2016. Synthesis, optical constants, optical dispersion parameters of CuO nanorods. Optik 127, 1429–1433.
Contents lists available at ScienceDirect
Environmental Nanotechnology, Monitoring & Management journal homepage: www.elsevier.com/locate/enmm
Green synthesis of copper oxide nanoparticles using Punica granatum peels extract: Effect on green peach Aphid Alaa Y. Ghidan a , Tawfiq M. Al-Antary a , Akl M. Awwad b,∗ a b
Department of Plant Protection, School of Agriculture, The University of Jordan, Amman, 11942, Jordan Department of Nanotechnolgy, Royal Scientific Society, P.O. Box 1438, Amman 11941, Jordan
a r t i c l e
i n f o
Article history: Received 19 June 2016 Received in revised form 22 August 2016 Accepted 24 August 2016 Keywords: Green synthesis Copper oxide nanoparticles Green peach Aphid
a b s t r a c t Copper oxide nanoparticles (CuONPs) were synthesized by a simple and green method using Punica granatum peels extract at room temperature. Biosynthesized copper oxide nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV–vis absorption spectroscopy, and X-ray diffraction (XRD). The particles are crystalline in nature with average size 40 nm. The morphology of the copper oxide nanoparticles could be controlled by tuning the amount of Punica granatum peels aqueous extract and copper ions. This study determined the mortality efficacy of the synthesized CuONPs against green peach Aphid. © 2016 Elsevier B.V. All rights reserved.
1. Introduction Copper oxide (CuO) is an important metal oxide semiconductor with a narrow band gap of 1.7 eV. Further it can be used in pesticides formulation, and antibacterial agents. Copper oxide nanoparticles are synthesized through different techniques and methods including precipitation (Sahooli et al., 2012), sonochemical route (Safarifard and Morsali, 2012), sol-gel (Pandiyarajan et al., 2013), hydrothermal approach (Mohamed et al., 2014; Outokesh et al., 2011), chemical bath deposition (Jiang et al., 2015), chemical reduction (Karthik and Geetha, 2013), non-vacuum and spin coating sol-gel techniques (Yahia et al., 2016) and reflux contestation (Bouazizi et al., 2015). These methods have many disadvantages due to the difficulty of scale up the process of synthesis, separation and purification of the nanoparticles, energy consumption and using hazardous chemicals. Recently, there have been related works employed the potential of green methods to synthesize copper oxide nanoparticles using plant aqueous extracts such as Gundelia tournefortii leaves and stems (Nasrollahzadeh et al., 2015), Tinospora cordifolia (Udayabhanu et al., 2015), Calotropis gigantean leaf (Sharma et al., 2015), Aloe barbadensis leaves (Gunalan et al., 2012; Kumar et al., 2015), Carica papaya leaves (Sankar et al., 2014), Gloriosa superba L (Naika et al., 2015), Citrus limon juice (Mohan et al., 2015), Tabernaemontana divaricate leaf (Sivaraj et al., 2014), carob leaf (Awwad and Ibrahim, 2015), and Malva sylvestris leaf (Awwad et al., 2015).
∗ Corresponding author. E-mail addresses: [email protected], [email protected] (A.M. Awwad). http://dx.doi.org/10.1016/j.enmm.2016.08.002 2215-1532/© 2016 Elsevier B.V. All rights reserved.
Aphids are insects able to attack several plants, secreting honey dew and transmitting viral diseases economic plants (Al-Antary and Khadir, 2013). The green peach aphid Myzus persicae Sulzer (Homoptetra: Aphidae) is worldwide distributed, polyphagous and with wide host range. In Jordan, the green peach Aphid attacks several economic plants and vegetables particularly sweets and hot peppers. The present study was designed with a novel, rapid, and costeffective route for biosynthesis of copper oxide nanoparticles (CuONPs) using Punica granatum peels extract. The synthesized copper oxide nanoparticles obtained by the green method are under investigation of their effect on green peach Aphid. 2. Experimental 2.1. Materials Copper acetate monohydrate [Cu(CH3 COO)2 ·H2 O] is analytical grade purchased from Merck, Darmstadt, Germany and used without further purification. Deionized distilled water was used in all experimental work. 2.2. Preparation of Punica granatum peels extract Fresh peels of healthy Punica granatum fruits were collected from local market, Jordan. Peels were washed several times with water to remove dust particles and then dried in shade for two weeks to remove the residual moisture. Punica granatum peels aqueous extract was prepared by placing 10 g of dried fine powder in 500 ml glass beaker along with 400 ml of sterile distilled water.
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The mixture was boiled for 10 min until the color of aqueous solution changed from watery to brown-yellow. Then the mixture was cooled to room temperature and filtered with Whatman No. 1 filter paper before centrifuging at 1200 rpm for 5 min to remove biomaterials. The extract was stored at room temperature in order to be used for further experiments. 2.3. Green synthesis of copper oxide nanoparticles (CuONPs) In a typical reaction mixture, 2.8 g of copper acetate monohydrate was dissolved in 500 ml of the deionized water and stirred magnetically at room temperature for 5 min. Afterwards, P. granatum peels aqueous extract was added dropwise under stirring, as soon as, the peels extract comes in contact copper ions spontaneous change the blue color of copper ions to green color. The obtained green mixture was left under stirring at room temperature. After 10 min, the green mixture started changing to a brown suspended mixture, indicating the formation of water soluble monodispersed copper oxide nanoparticles. 2.4. Characterization techniques Scanning electron microscopy (SEM) analysis of synthesized copper oxide nanoparticles was done using a Hitachi S-4500 SEM machine. Powder X-ray diffraction was performed using a X-ray diffractometer, Shimadzu, XRD-6000 with CuK␣ radiation = 1.5405 Å over a wide range of Bragg angles (20◦ ≤ 2 ≤ 80◦ ). Fourier transform infrared spectroscopic measurements were done using Shimadzu, IR-Prestige-21 spectrophotometer. UV–vis spectrum of copper oxide nanoparticles was recorded, by taking 0.1 ml of the sample and diluting it with 2 ml deionized water, as a function of time of reaction using a Schimadzu1601 spectrophotometer in the wave length region 300–700 nm operated at a resolution of 1 nm.
Fig. 1. XRD pattern of the synthesized CuO nanoparticles using P. granatum peels extract.
with those of powder CuO obtained from the International Center of Diffraction Data card (JCPDS-45-0937) confirming the formation of a crystalline structure. No extra diffraction peaks of other phases are detected, indicating the phase purity of CuONPs. The average crystallite size of the synthesized copper oxide nanoparticles was calculated using Debye-Scherrer equation (Sankar et al., 2014; Vidhu et al., 2011): D = Lambda K/cos where D – The crystallite size of copper oxide nanoparticles, – Represents wavelength of X-ray source 0.15406 nm used in XRD,  – The full width at half maximum of the diffraction peak, K – The Scherrer constant with value from 0.9 to 1 and is the Bragg angle. The average particle size of CuONPs was calculated 40 nm by using above Debye-Scherrer, s formula.
3. Results and discussion 3.2. Fourier infrared spectroscopy (FT-IR) analysis 3.1. X-ray diffraction analysis Fig. 1 shows the X-ray diffraction (XRD) pattern of the synthesized CuONPs powder. The XRD pattern revealed the orientation and crystalline nature of copper oxide nanoparticles. The peaks position with 2 values of 35.22◦ , 38.36◦ , 48.05◦ , 52.4◦ , 56.56◦ , 60.78◦ , 65. 4◦ , and 73.89◦ are indexed as (0 0 2), (1 1 1), (2 0 2), (0 2 0), (202), (113), (311), (113), planes, which are in good agreement
Fourier transform infrared spectroscopy is used to identify and get an approximate identification of the possible biomolecules in plant extract. FT-IR spectrum of P. granatum peels extract is shown in Fig. 2. FT-IR displays a number of absorption peaks, reflecting its complex nature due to biomolecules. Strong and broad peak at 3379 cm−1 attributed to hydrogen bonded O H groups of alcohols and phenols and also to the presence of amines N H of amide. The
Fig. 2. FT-IR spectrum of Punica granatum peels extract.
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Fig. 3. FT-IR spectrum of synthesized CuONPs using P. granatum peels extract.
bands at 2912 cm−1 is assigned to CH2 and C H stretching mode in alkanes. The strong peak at 1728 cm−1 could be attributed to C C stretching vibrations about C O amide conjugated C O of the proteins that are responsible for reducing, capping and stabilizing process. The bands at 1612 cm−1 can be allocated to the stretching vibration of C OH bond from proteins (amide I), whereas the band at 1523 cm−1 is characteristic of amide II. The peak at 1446 cm−1 is characteristic to the C N stretching of aliphatic amines. Peaks in the region 1323 cm−1 , 1227 cm−1 and 1018 cm−1 may be attributed to the presence of the stretching vibrations of carboxylic acids and amino groups. FT-IR spectra of the synthesized CuONPs indicate a new chemistry linkage on the surface of CuONPs. This suggests that P. granatum peels extract can bind to CuONPs through hydroxyl and carbonyl of the amino acid residues in the protein of the extracts, therefore acting as reducing, stabilizing and dispersing agent for synthesized copper oxide nanoparticles and prevent agglomeration of CuO nanoparticles. The main characteristic peaks of P. granatum peels extract were observed in FT-IR spectra of CuONPs, Fig. 3. The FT-IR spectra of the CuONPs showed a strong and sharp peak at 509 cm−1 . 3.3. Scanning electron microscopy (SEM) analysis Typical SEM micrograph for as prepared CuONPs is shown in Fig. 4. The SEM micrograph clearly showed rough agglomerations of nanostructural homogeneities with spherical morphologies of CuONPs. The SEM observation showed the presence of agglomerated nanospheres with an average diameter of 10–100 nm. This slight deviation of the particle size estimation compared to that calculated from XRD analysis can be attributed to the deviation of the spherical shape of the particles that is required for the Debye–Scherrer formula and the detection limit of the XRD diffractometer. Moreover, the observed strong agglomeration of the nanoparticles prepared by this method may be interpreted in terms of the increase in the catalytic activity of the surface of the nanoparticles. 3.4. UV–vis spectroscopy analysis The addition of P. granatum peels extract to copper acetate monohydrate [Cu(CH3 COO)2 ·H2 O] solution resulted in color change of the solution from blue to green and then to brown due
Fig. 4. Scanning electron microscopy (SEM) of CuONPs synthesized using P. granatum peels extract at room temperature.
to the production of CuONPs. The color changes arise from the excitation of surface plasmon vibrations with the copper oxide nanoparticles. The SPR of CuO nanoparticles produced a peak centered near 282 nm. UV–vis absorbance of the reaction mixture was taken from 0 till 10 min, Fig. 5. It was observed that the absorbance peak was centered near 282 nm, indicating the reduction of copper acetate monohydrate into CuONPs. It was also observed that the reduction of copper acetate monohydrate ions into copper oxide nanoparticles started at the start of reaction and reduction was completed at almost 10 min at room temperature, indicating rapid biosynthesis of copper oxide nanoparticles. 3.5. Effect of CuO nanoparticles onto green peach Aphid (GPA) Preliminary results from a research project “Effect of green synthesized nanomaterials on green peach Aphid” is carried out at the University of Jordan and the Royal Scientific Society, the effect of different concentration of CuONPs on GPA are shown in Table 1. Means of mortality% of the 1st and 2nd nymphal instars caused by the five concentrations were different significantly, Table 1. Means of Mortality% of 3rd and 4th nymphal instars of the same aphid caused by the same concentrations were also different significantly. However, mortality% of both aphid categories in all concentrations was greater significantly than the control treatment.
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Table 1 Means of mortality percent [%] of green peach aphid treated by different concentrations of CuONPs. Concentration [g/mL]
Mortality% of 1st and 2nd nymphal instars ± SE
Mortality% of 3rd and 4th nymphal instars ± SE
250 1000 2000 4000 8000 Control
40 e 51d 60 c 75 b 86 a±6 5f
14 e 26 d 62 c 75 b 86 a±7 5f
* Means within the same column sharing the same letter do not differ significantly at 5% level using LSD test.
Fig. 5. UV–vis spectrum showing absorption of 10−3 M aqueous solution of copper acetate with P. granatum peels extract as a function of time.
4. Conclusion Green synthesis of copper oxide nanoparticles CuONPs is an eco-friendly and safer to environment as compared with chemical and physical methods. We have developed a fast, eco-friendly, and convenient green method for the synthesis of CuO nanoparticles from copper acetate monohydrate using P. granatum peels aqueous extract at ambient temperature. Punica granatum peels extract was found suitable for the green synthesis of copper oxide nanoparticles within 10 min at ambient conditions. Spherical, polydispersity of CuONPs of particle sizes ranging from 10 to 100 nm with an average size of 40 nm are obtained. Color changes occur due to surface Plasmon resonance during the reaction with the ingredients present in the P. granatum peels extract resulting in the formation of CuO nanoparticles, which is confirmed by XRD, FT-IR, UV–vis spectroscopy, and SEM. FT-IR spectroscopic study confirmed that the carbonyl group of amino acid residues has a strong binding ability with copper oxide, suggesting the formation of a layer covering copper oxide nanoparticles and acting as a capping agent to prevent agglomeration and provide stability to the medium, yet further research is needed in this area to explore the possible biomolecule responsible for the bioreduction process. The activity of biologically synthesized copper oxide nanoparticles was evaluated against the mortality of green peach Aphid.
Conflict of interest The authors declare that they have no conflict of interest
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