Synthesis of Copper (II) Oxide Nanoparticles using Vitis vinifera L. Leaf Ex-tract and its Application as a Catalyst in Doebner Reaction

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Makara Journal of Science Makara Journal of Science

Volume 27

Issue 3 September Article 8

9-25-2023

Synthesis of Copper (II) Oxide Nanoparticles using Vitis vinifera L.

Leaf Ex-tract and its Application as a Catalyst in Doebner Reaction Leaf Ex-tract and its Application as a Catalyst in Doebner Reaction

Felie Virgayani Kurniawan

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 16424, Indonesia

Antonius Herry Cahyana

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 16424, Indonesia, [email protected]

Rika Tri Yunarti

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Recommended Citation Recommended Citation

Kurniawan, Felie Virgayani; Cahyana, Antonius Herry; and Yunarti, Rika Tri (2023) "Synthesis of Copper (II) Oxide Nanoparticles using Vitis vinifera L. Leaf Ex-tract and its Application as a Catalyst in Doebner Reaction," Makara Journal of Science: Vol. 27: Iss. 3, Article 8.

DOI: 10.7454/mss.v27i3.1442

Available at: https://scholarhub.ui.ac.id/science/vol27/iss3/8

This Article is brought to you for free and open access by the Universitas Indonesia at UI Scholars Hub. It has been accepted for inclusion in Makara Journal of Science by an authorized editor of UI Scholars Hub.

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**Synthesis of Copper (II) Oxide Nanoparticles using Vitis vinifera L. Leaf Extract and its Application as a Catalyst in Doebner Reaction**

Felie Virgayani Kurniawan, Antonius Herry Cahyana

^*

, and Rika Tri Yunarti

*E-mail: [email protected]

Received October 13, 2022 | Accepted June 30, 2023

Abstract

Plant extracts can be used to synthesize nanoparticle because it is efficient, economical, and friendly to the environment.

Copper oxide nanoparticles (CuO NPs) were synthesized using an aqueous fraction of Vitis vinifera L leaf extract and Cu(NO3)2 solution as a precursor. This fraction contains secondary metabolites as a reduction agent and stabilizing agents to formed CuO NPs. CuO NPs can be used as a catalyst in a chemical reaction, one of which is the Doebner reaction, which is a simple and efficient reaction of aniline, aromatic aldehydes, and pyruvic acid under reflux conditions to produce derivatives quinoline-4-carboxylic acid. CuO NPs were effectively used in the Doebner reaction and yielded a product is 79.84%. The CuO NPs characterized by Fourier Transform Infra-Red (FTIR), and X-ray Diffraction (XRD) which showed CuO NPs were formed with a size of 24.39 nm. The product synthesized was characterized by TLC (Thin Layer Chromatography), FTIR, UV-Vis Spectrophotometry, and Liquid Chromatography Mass Spectrometry (LC-MS) and confirmed 2-phenylquinoline-4-carboxylic acid was formed.

Keywords: copper (II) oxide nanoparticles, doebner reaction, plant mediated synthesis, quinoline, Vitis vinifera L.

Introduction

Nanoparticles are materials with sizes between 1 to 100 nm, which can be used in everyday life such as in the health sector, the environment, and in chemical reactions that can be used as catalysts [1]. There are several methods for synthesizing nanoparticles such as chemistry, physics, and biology. The use of plant-mediated green synthesis methods has advantages compared to chemical and physical methods, as low-cost, easy to do, can be carried out on a large scale, is environmentally friendly, and is energy-efficient [2, 3]. Plants extract can be used in the synthesis of nanoparticles because contain secondary metabolites [4]. Several studies have synthesized CuO NPs using plant extracts such as Oldenlandia corymbosa L. Leaf [4], coffee grounds [5], Gloriosa superba L [6], and Allium sativum [7], and this study synthesized CuO NPs using Vitis vinifera L extract.

Vitis Vinifera L is a member of the genus Vitis of the Vitaceae family. Is one of the plants that exist in Indonesia with various benefits, such as antioxidants, antibacterial, antifungal, antihypertensive, antiacne, and others [8]. In previous studies, Vitis vinifera L leaf extract was reported to contain saponin, flavonoids, alkaloids, and tannins [9]. Secondary metabolites have an important

role in the synthesis process as reducing agents and stabilizing compounds to form good CuO NPs [4]. CuO NPs have been reported to have antimicrobial [6], antioxidant, anti-inflammatory, anti-larvicidal compounds [7], adsor- bent [10], semiconductor [11], catalyst organic [12], and others. In a chemical reaction catalyst is an important material, the catalyst can increase the reaction rate and has a high selectivity to produce product suits without side products [13].

Quinoline is a heterocyclic compound with a nitrogen atom and a benzene ring in its skeleton which has biological activities such as antimalarial, anti- inflammatory, antibacterial, antifungal, anticancer, antioxidant, antihypertensive, and analgesic [14, 15].

Quinoline can be synthesized through several reaction models, one of which is the Doebner reaction which is a simple reaction between aniline, benzaldehyde, and pyruvic acid under reflux conditions [16]. The uses of CuO NPs as a catalyst in quinoline synthesis has been used, CuO NPs reported can be used in the Friedlander reaction [17], as a catalyst in the synthesis of quinoline- 2,3-dicarboxylate [18], and used to synthesize 2- phenylquinoline [19].

In previously research p-toluenesulfonic acid used as a catalyst in the Doebner reaction to synthesize 2-

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phenylquinoline-4-carboxylic acid and getting 89% of yield [20], silica sulfuric acid catalyst reported used as catalyst to synthesis of 2-phenylquinoline-4-carboxylic acid and getting 82% yield [16]. The use of a single CuO catalyst as a catalyst has never been carried out in the Doebner reaction to synthesizes 2-phenylquinoline-4- carboxylic acid. In this study, we used CuO NPs result of synthesis as a catalyst in the Doebner reaction to synthesize 2-phenylquinoline-4-carboxylic acid.

Materials and Methods

Materials. Vitis vinifera L. leaves were collected from Pesona Depok, Depok. Cu(NO3)2 as a precursor Aniline and Benzaldehyde were purchased from Merck, and pyruvic acid from Aldrich.

Methods

Extraction of Vitis vinifera L. leaves. Vitis vinifera L leaves were washed, dried, and mashed using a blender to get the powder. A 50 g of powder was macerated using 500 mL methanol for 3 days. The solution was filtered to get a crude methanol extract. The crude extract was partitioned with hexane (1:1). The methanol fraction was concentrated and dissolved into aquabidest to get an aqueous fraction of Vitis vinifera L leaf extract (VVLE), and then tested phytochemically to determine the content of secondary metabolites in it.

Phytochemical Screening

Alkaloids (wagner test). 1 mL of all fractions was added with 1 mL of Wagner's reagent (iodine in potassium iodide solution). Reddish brown precipitate indicates the presence of alkaloids in the extract.

Flavanoids. 2 mL of all fractions were added with 20%

NaOH, and a yellow or green precipitate will form. Add concentrated HCl gradually, the color will fade. Fading of the color indicates the presence of flavonoids.

Tannins. 1-2 mL of all fractions added with water and 5% ferric chloride solution. The formation of black-blue color indicates the presence of tannins.

Saponins. 2 mL of all fractions were added with 2 mL of water and shaken for 15 minutes. The formation of foam indicates the presence of saponins.

Polyphenol. 3 mL of all fractions in alcohol is added with one drop of 5% ferric chloride solution. The formation of a blue color indicates the presence of phenol.

Terpenoid. 1 mL of all fractions was added with 0.5 mL of chloroform, added a few drops of concentrated sulfuric acid. The formation of a rreddish-brownprecipitate indicates the presence of terpenoids.

Synthesis and characterization of CuO NPs. The synthesis was using the sol-gel method. A 100 mL of 0.01M Cu(NO3)2 solution was mixed with 10 mL of VVLE and stirred for 2 hours at 60 °C. The Cu(OH)2 sol formed and heated at a temperature of 80 °C using an oven to get a gel. The gel was calcined at 400 °C for 3 hours. The black powder obtained indicated the formation of CuO NPs. The powder was characterized with XRD and FTIR to determine the bond of nanoparticle and crystallinity size.

Synthesis and characterization of quinoline-4- carboxylic acid compound. The synthesis using the Doebner reaction mechanism. Aniline (1.1 mmol), benzaldehyde (1 mmol), pyruvic acid (1 mmol), and CuO NPs 10% as a catalyst were dissolved in 5 mL ethanol and refluxed at 80 °C for 3 hours and stood by overnight at room temperature. The monitored reaction by TLC.

The mixture was poured into the ice-cold water bath, the precipitate products were filtered and collected the product. The product was characterized by TLC, FTIR, UV-Vis, and LC-MS.

Characterization. Product of synthesis via Doebner reaction was characterization by FTIR, UV-Vis, and LC- MS. Nanoparticles result of synthesis (CuO NPs) was characterization by FTIR, and XIRD. All of characterization uses instrumentation that has been calibrated with valid methods.

Results and Discussion

Phytochemical Tests. Phytochemical tests were carried out using a qualitative method. Results of the phytochemical test showed the presence of saponin, flavanoid, alkaloids, tannins, and polyphenols in an aqueous fraction. The results of the alkaloid test showed the formation of a red precipitate that is indicating the presence of alkaloids, terpenoid test not showed the reddish brown precipitatethe in sample, flavanoid test showed the fading of the color in the sample extract, polyphenol and tanins test showed the blue color of the sample extract, and the saponin test formation of foam indicates the presence of saponins [4]. Reported that alkaloids acted as a weak base to form Cu(OH)2, while saponins, polyphenols, and flavonoids as capping agents to prevent agglomeration and stabilize the CuO nanoparticles. Table 1 shows the result of phytochemical tests by qualitative.

Synthesis of CuO NPs. CuO NPs are synthesized from Cu(NO3)2 solution and secondary metabolite in an aqueous fraction of VVLE. Cu(NO3)2 solution and component metabolite secondary in VVLE reacted to produce the sol-gel Cu(OH)2, secondary metabolites such as alkaloid, saponin, polyphenol, and flavonoid acted as a weak base and capping agents to prevent agglomeration and stabilize of nanoparticles. The Cu(OH)2

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sol-gel was calcined at 400 °C for 3 hours to remove residual organic compounds After the calcination process, CuO Nps is formed, and it is identified with black powder which is characteristic of CuO nanoparticles.

The scheme for the synthesis of CuO NPs can see in Figure 2.

XRD Analysis of CuO NPs. The XRD pattern of CuO NPs is shown in Figure 4. The diffraction angle of 2θ is compared with JSPDS literature No: 01-089-5897. The peaks of 2θ of synthesized CuO NPs at 32.54°, 35.58°, 38.77°, 48.85°, 53.64°, 58.38°, 61.62°, 66.34°, 68.13°, 72.50°, and 75.18° (deg). These results identify CuO NPs that have formed with pure single-phase monocyclic

crystalline phase. These Miller indexes are (110), (-111), (111), (-202), (020), (202), (-113), (-311), (220), (311), and (004). The crystallite size of CuO NPs is 24.39 nm and was calculated by Debye-Scherrer formulae. The XRD pattern of CuO NPs can see in Figure 3.

FTIR Analysis of CuO NPs. FTIR characterization of CuO NPs (Figure 4) shows the absorption peak at wave number 543 cm^-1. The peaks indicate Cu-O bonds. This wave number indicates CuO NPs were formed [4]. FTIR spectra of CuO NPs show not appeared residual organic compounds, and of Cu2O (between 605 cm^-1 and 660 cm^-1) in the sample [7]. CuO NPs formed are pure and have a high purity phase, according to XRD results.

Table 1. Secondary Metabolite Content in Vitis Vinifera L. Leaf Extract in Various Fractions Secondary

Metabolites

Crude Methanol Extract

Hexane Fraction

Methanol Fraction

Aqueous

Fraction Reference [9]

Alkaloids (Wagner) + + + + +

Terpenoids - - - - +

Flavanoids + - + + +

Polyphenol + - + + +

Tannins + - + + +

Saponins + - + + +

Information :+ : Confirmed; -: not confirmed

Figure 1. Vitis vinifera L Leaves (fresh, a) Vitis vinifera L Leaves (dry, b), and an Aqueous Fraction of VVLE (c)

Figure 2. Scheme for Synthesis of CuO NPs

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Figure 3. XRD Pattern of CuO NPs

Figure 4. FTIR of CuO NPs

Figure 5. Scheme of Synthesis 2-Phenyl Quinoline-4-Carboxylic

Synthesis of the quinoline-4-carboxylic acid compound.

Synthesis of 2-phenylquinoline-4-carboxylic acid via Doebner reaction is a reaction between aniline (1.1 mmol), benzaldehyde (1 mmol), and pyruvic acid (1 mmol) dissolved in 5 mL ethanol and synthesized CuO NP 10% mmol under reflux conditions. The final reactions were monitored by TLC. The filtrate of product and CuO NPs can be separated by simple separation. The filtrate was poured into the ice bath and the precipitate formed was dried and stored in a bottle, and monitored by TLC. The scheme of synthesis 2-phenylquinoline-4- carboxylic can see in Figure 5.

The advantages of using the Doebner reaction in the presence of CuO nanoparticles are: the reaction is easy, the catalyst is non-volatile and safe, the separation of the catalyst is simple, and good results are obtained in the synthesis of quinoline compounds. 2-phenylquinoline-4- carboxylic acid 2 is reported to have many bioactivities ability, as it is a strong antimicrobial agent [21]. The mechanism reaction of this synthesis can see in Figure 6.

Analysis of TLC of 2-phenylquinoline-4-carboxylic acid. TLC is one method that can be used to see the process of the reaction. TLC can be used to see when the

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reaction is stopped. The eluent used is (hexane: ethyl acetate, 4:1). Figure 7 (a) shows the formation of a new spot that is different from the precursors. This indicates the reaction has been completed. To ensure the formation of the product, further characterization is needed.

FTIR analysis of quinoline-4-carboxylic acid compound.

The FTIR spectrum of 2-phenylquinoline-4-carboxylic acid is shown in Figure 8. Wave numbers 3355 cm^-1 and 1360 cm^-1 indicate O-H bonds, 3030 cm^-1 indicates bonds of C-H sp², 2895 cm^-1 indicates bonds of C-H sp³, and 1705 cm^-1 indicates C=O bonds, 1601 cm^-1 indicate C=N bonds, 1497 cm^-1 indicate aromatic bond (C=C), and 1258 cm^-1 indicate C-O bonds. All bonds in the FTIR result test indicated that 2-phenylquinoline-4-carboxylic acid has formed.

UV-Vis analysis of quinoline-4-carboxylic acid compound. In the picture, we know that aniline has

wavelengths 204, 234, and 286. Pyruvic acid is 207, and 284. Benzaldehyde is 204, and 231. While the product has wavelengths of 247, 313, and 391. The wavelength of a product has shifted towards bathochromic, i.e. a shift in wavelength to a longer wavelength. In addition, there is a new wavelength at 391 nm which identifies the difference between precursors and products, so a new product has been formed.

LCMS analysis of quinoline-4-carboxylic acid compound. Product synthesis was characterized by using LCMS to detect a molecular mass. Theoretically the product 2-phenylquinoline-4-carboxylic acid has an extract mass of 250.0868. The results of the LCMS analysis of the synthetic product showed a mass extract value of 250.0866 with a retention time of 8.664 minutes.

These results indicate that 2-phenylquinoline-4-carboxylic acid has been formed.

Figure 6. Mechanism Reaction

Figure 7. TLC (a) and Product (b)

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Figure 8. FTIR Spectra of Quinoline-4-Carboxylic Acid Compound

Figure 9. UV-Vis Spectrum of Quinoline-4-Carboxylic Acid Compound

Figure 10. LC-MS of Quinoline-4-Carboxylic Acid Compound

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Conclusions

Copper (II) oxide nanoparticles (CuO NPs) were successfully synthesized using VVLE. FTIR results in CuO NPs were formed at a wave number of 543 cm^-1, and with XRD result showed a particle size of CuO NPs is 24.39 nm. CuO NPs play a role in synthesized reactions to produce a 79.84% yield of product. The result of all characterization showed that the 2-phenylquinoline was formed.

Acknowledgement

The authors gratefully acknowledge financial support from the Universitas Indonesia through the grant of Program Publikasi Terindeks International (PUTI) Q1 [Contract number: NKB-1135/UN2.RST/HKP.05.00/2022].

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