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Phytosynthesis of Cobalt Ferrite Nanoparticles by Crude Extract of Rheum Ribes.

Maryam Mohammed Hussein M. Jawad*, Raghad DHyea Abdul Jalill*, Ahmed Majeed Al‑Shammari**, Ahmed N. Abd***.

*Department of Biology/ College of Science/ AL-Mustainsiriyah, University/ Baghdad /Iraq.**

Experimental Therapy Department, Iraqi Centre for Cancer and Medical Genetic Research, Mustansiriyah. University, Baghdad /Iraq. *** Department of Physics / College of Science/ AL-

Mustainsiriyah.

Corresponding author: Dr. Raghad DHyea Abdul Jalill, Cellphone: 07700032312.

Email: [email protected], [email protected].

Abstract

The objective of this study was identifying the flavonoids in Rhizomes of Iraqi Rheum ribes and utilization these extract to phytosynthesis of cobalt ferrite nanoparticles with characterization of them. The results obtained from the HPLC analysis indicate that rhizomes of Iraqi R. ribes contain seven compounds of flavonoids which include: 1.735 μg/g aloe-emodin, 24.966 μg/g emodin, 5.533 μg/g chrysophanol, 17.542 μg/g physician, 4.242 μg/g rhein and 15.873 μg/g rutin,.

Plant extract-mediated cobalt ferrite nanoparticles were characterized by various techniques to analyze the size, shape, crystallinity. Their average size (which calculated by AFM) were:

(100.36, 68.80, 69.01) nm for (1, 2 and 3) procedures, respectively. While procedure 4 was fail to produce nanoparticles, their average size was (192.38 nm). From SEM study, it is confirmed that the particles are almost spherically shaped and uniformly arranged.

The FTIR results showed strong bands are observed in (procedure 4) around 585- 400 cm−1 confirm the presence of CoFe2O4 nanoparticles while other procedures showed tetrahedral metal stretching ν(Fe-O tetra) and octahedral metal stretching ν(Co-O) bond.

The XRD patterns of all samples indicate spinel cobalt ferrite magnetic nanoparticles having face centered cubic structure. This structure was pure in procedure 1. The average crystallite size of nanoparticles was calculated by Scherer's equation, they were: (47.41, 45.1, 50.62 and 44 nm) nm. The results of UV–visible spectral of procedures (1-4) showed that the absorption spectra of phytosynthesis NPs exhibit strong absorption at 221 nm. More than one band gaps of each sample (3.4 eV and 4.5 eV). These two energy gaps are indicating to presence of a quantum well.

These results follow quantum laws.

Keyword:

Cobalt ferrite; HPLC; Nanoparticles; Phytosynthesis, Rheum ribes.

Introduction

Rheum ribes L. is an Iraqi species belong to the family Polygonaceae, (Tanrikut et al., 2013).

It is found in eastern Turkey on dry mountain slopes, Syrian and in other related local areas. The edible part of the plant is the flowering stem, which is eaten raw salads or cooked soups in south west Asian countries, they considered it as one of the most important sources of crude drug in folk medicine (Andıç et al., 2009), (Tartık et al., 2015).

The young shoots contain vitamins A, B, C and tannins (8 %) and anthracene derivatives (0.025 %) (Andiç et al. 2009). A variety of constituents have been separated from rhizomes and

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roots, they belong to such classes as anthraquinone, stilbenes and essential oils (Wang et al., 2012; Liu et al., 2009). It also, contain a wide variety and different concentration of phenolic and Flavonoids constitutes: chrysophanol, physcion, Rhein, aloe-emodin, physcion-8-O-glucoside, aloe-emodin-8-Oglucoside, rhaponticin (Tuzlacı et al., 1991), stilbenoids and anthraquinones (Uyar et al., 2014), butylated hydroxyanisole (BHA), butylated hydroxytoluene, and tert- butylhydroquinone (Grice H.C., 1988; Wichi H.P., 1986), sennoside A (Tuzlaci and Mericli, 1992) and rhaponticin (Mericli and Tuzlaci, 1990).

A nanoparticle or ultrafine particle is a particle of matter that is between 1 and 100 nanometres (nm) in diameter. Nanoparticles have a great outstanding scientific concern as they bridge the gap between bulk materials and atomic or molecular structures (Thakkar et al., 2010).

The properties of nanoparticles often differ markedly from those of larger particles of the same substance.

Cobalt Ferrite oxide (CoFe2O4) NPs is one of the most interesting metal oxide nanoparticles (jia et al., 2012). They have unique physical properties such as: high Curie temperature, large magneto crystalline anisotropy, high magneto-strictive coefficient, mechanical hardness, good coupling efficiency, and high magnetostriction, high coactivity, low dielectric constant, moderate saturation magnetization, good physical and chemical stability, (jia et al., 2012), high magnetocrystalline anisotropy, and high intrinsic magnetocrystalline anisotropy at room temperature (Routray et al., 2018; Andersen and Christensen, 2015; Lu et al., 2015; Gore et al., 2017; Varma, et al., 2008; Tran and Webster, 2010). Additionally, the particles less than 10 nm in size, the superparamagnetic behavior is observed to increase with a decrease in particle size (Yáñez-Vilar et al., 2009). CoFe2O4 NPs have a great potential for various applications and engineering including: magnetic recording, industries, and packaging accessories, magnetic energy storage, catalysis, and waste water treatment (Issa et al., 2013; Pathak and Pramanik, 2011; Wang and Sun, 2007; Mathew and Juang, 2007; Wang et al., 2016).

Recent studies revealed their biomedical applications such as: antimicrobial activity against multidrug resistant bacterial strains (Brigger et al., 2002), anticancer activities (Park et al., 2015); (Ansari et al., 2016), drug delivery technique, (Dey et al., 2018). Cobalt ferrite nanoparticles can be prepared via chemical and physical approaches (Prabhakaran and Hemalatha, 2016; Rana et al., 2010; Tatarchuk et al., 2017). There is a need to improve an eco- friendly avenue for synthesis of nanomaterial that does not use toxic chemicals in the synthesis protocol, and to minimize or eliminate the use of environmental-risk substances, toxic chemical species and expensive surfactants (Dang et al., 2012). Accordingly, it became possible to synthesize nanoparticles by means of various biological methods, which include the use of plants extract or even their metabolism products, these procedures are generally called green synthesis or phytosynthesis (Marslin et al., 2018). Okra extract could synthesize single-phase crystalline structures of CoFe2O4 nanoparticles with size from (45-55) nm, (Kombaiah et al., 2018). In addition, Mangifera indica leaf extract succeeded in forming of smooth surface, cubic and pentagonal cobalt nanoparticles with an average size of (25-40) nm, a (Okwunodulu et al., 2019).

Several factors affect the synthesis, characterization and the nucleation and subsequent formation of stabilized nanoparticles in addition to the type of the adsorbate and the activity of the catalysts used in the synthesis process (Somorjai and Park, 2008). Some of the important factors are: pH, reaction time, and temperature (Baker et al., 2013) in addition to plant extract concentrations, bulk material concentrations. The objective of this study was identifying the flavonoids in

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Rhizomes of Iraqi Rheum ribes and utilization these extract to phytosynthesis of cobalt ferrite nanoparticles with characterization of them.

Materials and procedures

Extraction of R. ribes crude extract.

Rhizomes of Rheum ribes was purchased from the local market and authenticated by the Herbarium of Iraqi Ministry of Health according to a taxonomic procedure as Rheum ribes;

belong to the plant family Polygonaceae. After cleaning and milling, a crushed Rhizomes was kept in a dark glass bottles in refrigerator.

Methanol extraction of R. ribes crude extract

One gram of above plant powder was dissolved in 20 ml hexane to remove fat layer, then the organic layer dissolved 100 ml of 80:20 (methanol: water). The extract was subjected to ultra- sonication at 60 % duty cycles for 25 min at 25°C followed by centrifugation at 7500 rpm for 15 min. The clear supernatant of each sample was subjected to charcoal treatment to remove pigments prior to evaporation under vacuum.

Analysis of active ingredient in crude extract Equipment

The separation occurred on liquid chromatography Shimadzu 10AV-LC equipped with binary delivery pump model LC-10A shimadzu, the eluted peaks were monitored by UV-Vis 10 A- SPD spectrophotometer. The main listed compounds were separated under the optimum condition Column: phenomenex C-18 ,3 µm particle size (50 x 2.0 mm I.D) column, Mobile phase: linear gradient of, solvent A 0.1% phosphoric acid solvent B was (6:3:1, v/v) of acetonitrile: methanol: 0.1% phosphoric acid, linear gradient program from 0%B to 100% B for 10 minutes. Flow rate 1.0 ml/min. Detection: UV 280 nm.

Preparation of standard compounds:

Dissolve 10 mg of each of following standard compounds in 10 ml of distilled water. Five- fold dilutions were used to produce a decimal dilution series. The standard compounds were:

(Rhein, Rutin, Emodin, Aloe –emodin, Chrysophanol, Physcion).

Injection of R. ribes crude extract in HPLC

Dried samples were re-suspended in 1.0 ml HPLC grade methanol by overtaxing, the mixture was passed through 2.5 µm disposable filter, and stored at 4°C for further analysis, then 20 µl of the sample injected into HPLC system according the optimum condition.

Calculation:

Table (1): The retention time (RT) and area under curves of reference standard compounds.

No. RSt. R.T (min.) Aru. (µvolt) Con.

1 Aloe -emodin 1.085 130251 13.84

2 Emodin 2.252 126439 13.434

Concentration of sample (ug/ml) = (Area of sample of sample/ Area of standard) * concentration of standard x dilution Factor

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3 Chrysophanol 3.502 100380 10.666

4 Physcion 4.322 116612 12.39

5 Rhein 5.17 126287 13.418

6 Rutin 6.077 233077 24.765

RSt.: reference standard; R.T: retention time in minuet; Aru.: area under curves (µvolt); Con.;

concentration.

Phytosynthesis of CoFe2O4 NPs by Rhizomes of crude extract of R. ribes.

1. Preparation of CoFe2O4 bulk particles

Black powder pigment powder of bulk CoFe2O4 bulk particles procured from Chemical Book. Molecular weight was 234.62 g/mol and monoisotopic mass: 234.782728. Density 5.3 g/cm3, their average size was >5 micro meter (> 5000 nm). Purity: 99.5 %min. Distil water was used to make solution of (10 mg/ml) concentrations.

2. Phytosynthesis

These were done using two procedure:

Procedure 1 and 2: This was done by adding 1 ml of methanol crude plant extract to (1 mL, 0.1 M) of bulk CoFe2O4 particles in flask contain 15 ml distal water. Each mixture placed in magnetic stirrer hot plate at (60 and 90) Cº for (3 and 9) hours respectively.

Procedure 3 and 4: This was the same above procedure but the flask contains 25 ml distal water. The degrees were (60 and 90) Cº for (3 and 9) hours respectively.

The Revolutions per minute was 1000 rpm /second. The solutions allowed to cool at room temperature and repeated centrifugations at 15,000 rpm for 10 min. The supernatant was neglected. The precipitate formed was washed with double distilled water and then centrifuged at 1500 rpm for 10 min, (Abdul Jalill, 2018). This was repeated three times. The obtained precipitate (nanopawder) was dried at room temperature for 24 h. and characterized as described fallowing. The conditions synthesises were appeared in in table (1).

3. Characterizations

The fallowing techniques were using to measure the exact pattern of the fabricated, morphology of crystals structure average, phase purity, particle size, and distribution particle.

 Atomic force microscopy (AFM): The surface topography, granularity volume distribution and size of biosynthesized nanoparticles was characterized by Atomic Absorption Spectroscopy. A slim film of the sample was prepared on a glass slide, by dropping 100 μl of the sample on the slide. Permitted to dry for 10 min. Then the slides were scanned with AFM, (AA‐680, Shimadzu‐Japan), (characterized by Dr. Abdul Kareem Al-Samaraii Lab. Baghdad Iraq (Naveen, et al., 2010).

 UV–visible analysis: The UV–VIS absorption spectra of biosynthesized nanoparticles were recorded by a spectrophotometer. The (bio reduction of the CoFe2O4 NPs), was monitored by periodic sampling of aliquots (1 mL) of the aqueous component after two times dilution and measuring the UV–VIS spectrum of the solution. UV–VIS spectra of these aliquots were monitored as a function of time of reaction on a Schimadzu 1601 spectrophotometer in 200–800 nm range operated at a resolution of 1 nm (Ba-Abbad et al., 2012).

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The absorption coefficient (α) was determined from the optical spectrum using the formula, (Pannaparayil et al., 1988):

α = 2.3026 A/t

Where: (A) and (t)are the measured absorbance and thickness of the sample, respectively.

The optical bandgap energy (Eg) was evaluated from the absorption spectrum and the optical absorption coefficient (α) near the absorption edge is given by following equation, (Wang and Herron, 1991):

Where: h, ν, B, and Eg are Plank's constant, frequency of incident photons, constant, and optical band gap energy respectively. Energy gap of CoFe2O4 NPs (Eg) was estimated by plotting hν versus (αhν)1/2 according Tauc plot, (Tauc, 1974).

X-ray diffraction: X-ray diffraction (XRD) was used to confirm the crystal structure (crystal phases and to determine the crystallite size of each Phase ( of (Biosynthetic CoFe2O4

nanoparticles( . XRD analysis was performed using an X-ray diffractometer with Cu-Kα crystal radiation (λ = 1.54A°)) scanning at a rate of (5◦/min-1) for (2θ) range of (20º-70 º). The diffraction peaks of samples were identified by comparison with ((JCPDS card no. 77-0426), according to 2θ. (Raval et al., 2013). The full width at half maximum (FWHM) was used to determine the crystallite size using Scherer's equation, (Cullity, 1974):

Where: t: is the crystallite size (in nm), K: (=0.9) was the Scherer's constant,

λ

is the x-ray wavelength,

β

is (FWHM) (in radian) and

θ

the Bragg's diffraction angle (in degree).

The strain value  and the dislocation density  value can be evaluated by using the relations in the fallowing equations:

= 𝜷 𝐜𝐨𝐬 𝜽

𝟒 (Wei 𝑒𝑡 𝑎𝑙. , 2011)

= 𝟏

𝑮𝒔𝟐 (Jobst 𝑒𝑡 𝑎𝑙. , 2013)

FTIR analysis

The surface nature of samples was qualitatively assessed by using FTIR spectroscopy which show that the vibration spectrum of the infrared region, in the range between 4000-400cm-1 using KBr pellet method.

SEM analysis

CoFe2O4 biosynthetic nanoparticles were analysis by scanning electron microscope (SEM), Vega Tescan (USA), in Centre of Nanotechnology and Advanced Materials/ University of Technology/ Iraq. SEM samples were prepared according to standard procedures of Centre of Nanotechnology and Advanced Materials/ University of Technology/ Iraq.

t

,

=

,

k λ/

,

β cosθ

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Results and Discussion

The column chromatographic separations led to the purification six pure compounds (Fig. 1).

As shown in Table (1), the HPLC analysis found that Emodin was most abundant (38.25 %) (24.966 µg/ml), followed by Physcion (29.145 %) (17.542 µg/ml), Rutin (13.193 %) (15.873 µg/ml), Rhein (6.53 %) (4.242 µg/ml) and Aloe -emodin (2.58 %) (1.735 µg/ml).

(A) (B)

Figure (1): HPLC Analysis of: (A) standard flavonoids, (B) Rhizomes of R. ribes crude extract.

Table (2): The retention time (RT) and area under curves of R. ribes crude extract.

No. Comp. R.T (min.) Aru. (µvolt) % Con. (µg/ml) 1 Aloe -emodin 1.092 10587 2.58 1.735

2 Emodin 2.287 152228 38.25 24.966

3 Chrysophanol 3.513 32507 10.289 5.533

4 Physcion 4.375 106965 29.145 17.542

5 Rhein 5.182 25982 6.53 4.242

6 Rutin 6.103 96783 13.193 15.873

Comp.: compound; R.T: retention time in minuet; Aru.: area under curves (µvolt); Con.:

concentration.

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Phytosynthesis of CoFe2O4 NPs by Rhizomes of crude extract of R. ribes.

Four procedures were used to synthesis CoFe2O4 nanoparticles. Methanol crude plant extract was used in procedures (1 to 4).

The results found that three of four procedures were success to produce CoFe2O4 in nano size, there are: (1, 2, 3) procedures, while procedure 4 was fail to produce nanoparticles, it could not reach lower than 100 nanometer which is the prerequisite for being nanoscale. The following paragraphs is explaining the characterizations in some details:

Atomic force microscopy

The calculated NPs sizes were measured using the software of the AFM. Their average sizes were: (100.36, 68.80, 69.01) nm for (1, 2 and 3) procedures, respectively. While procedure 4 was fail to produce nanoparticles, their average size was (192.38 nm), (Figure 1: A to D).

Their Roughness average (Ra) were: (8.37, 9.15 and 22.9) nm, Root mean square (Sq) were:

(9.91, 10.8 and 26.7) nm for (1, 2 and 3) procedures, respectively. (Figure 2: A to d) showed AFM topographic images of phytosynthesis nanoparticles.

SEM Analysis

The scanning electron microscopy was carried out to study the morphology and particle size of the prepared particles. In SEM image of (1 to 4) procedures (Figure 3: A to D), it can be seen that the particles are almost spherically shaped and uniformly arranged

FTIR spectroscopic

In procedure 1, the results of FTIR spectroscopic which appear in figure (3) showed that the samples exhibited very wide strong interye band located near 524.64 cm- and 501.49 cm-, which assigned to ν(Fe-O tetra), addition to medium intense band at 435.91, 459.6, 478.35, 447.48, 416.62 cm-1 attributed to octahedral ν(Co-O),

Procedure 2, showed that the samples exhibited absorption peaks located near 526.49. 482.2, 497.63, 459.06, 439.77, 408.91 cm-, which give an indication of presence tetrahedral metal stretching ν(Fe-O tetra) and octahedral metal stretching ν(Co-O) bond respectively. While procedure 3 showed 526.49 cm- as a very strong peak attributed to ν(Fe-O tetra), in addition to medium intense band at 459.06, 482.2, 497.63, 435.91, 408.91 cm-1 attributed to ν(Co-O octa),

In Procedure 4: the strong bands are observed around 585- 400 cm−1 confirm the presence of CoFe2O4 nanoparticles. The absorption band 536.21 cm-1 corresponds to intrinsic stretching vibration of metal cations at the tetrahedral site stretching ν(Fe-O tetra), while the band 489.92, 451.34, 443.63 and 405.05 cm-1 corresponds to metal cations at the octahedral sites ν(Co-O).

X-ray diffraction:

In Procedure 1: The X-ray diffraction patterns displays sharp and strong reflections which could be indexed on the basis of pure spinel cobalt ferrite magnetic nanoparticles having face centered cubic structure. The planes with h k l values were: (220), (311) and (400). Their average crystallite size of nanoparticles was calculated by Scherer's equation, they were 47.41nm, (Table 2).

In Procedure 2: X-ray diffraction (XRD) of CoFe2O4 reveals abundant information about the crystalline phase, lattice parameter X- ray (theoretical) density, etc. of the prepared material. The obtained XRD peaks shown in figure (3) are indexed using JCPDS card no. 22-1086. The sharp peaks concerning to the reflection planes (220), (311), (222), (400), (422), (511) and (440) in the

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XRD pattern confirm the formation of the cubic spinel structure the average crystallite size of nanoparticles was calculated by Scherer's equation, they were 45.1 nm.

In Procedure 3: the XRD pattern reveals that the nanoparticles are of single phase. Non impurity peak was observed in XRD pattern ensuring the purity of the sample. It was confined that all the peaks of CoFe2O4 NPs matches well with the JCPDS card number (22-1086) that was used to index all the peaks in XRD pattern. The planes with h k l values of (220), (311) and (400), the XRD pattern clearly endorsed to the presence of spinel structure and cubic symmetry.

The particle size was calculated and found to be equal to 50.62 nm from the full width half maximum of the strongest peak (311) at 2θ = 35.343.

In Procedure 4: the XRD pattern confirms that CoFe2O4 formed with space group Fd-3m and a spinel structure. The sharp diffraction peak indicates that the crystal phase of CoFe2O4 is relatively complete. The diffraction peaks around 30.918°, 35. 35° and 57.62° are attributed to the reflections of the (220), (311) and (511) planes of CoFe2O4, respectively (JCPDS card no.22- 1086). The average crystallite size of CoFe2O4 calculated using Scherrer‟s formula was approximately 44 nm.

UV–visible analysis

Ultraviolet –visible absorption spectroscopy is a powerful technique to explore the optical properties of nanoparticles. The results of UV–visible spectral of procedures (1-4) showed that the absorption spectra of phytosynthesis NPs exhibit strong absorption at 221 nm. More than one band gaps of each sample (3.4 eV and 4.5 eV), (Figure 4: A to B). These two energy gaps are indicating to presence of a quantum well. The quantum laws explain these results. These results are similar to the result of (Singh et al., 2017).

(A) Procedure 1 (Avg. Diameter:100.36 nm) (B) Procedure 2 (Avg. Diameter:68.80 nm)

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(C) Procedure 3 (Avg. Diameter:69.01 nm) (D) Procedure 4 (Avg. Diameter:192.38 nm)

Fig. (1): Granularity volume distribution chart of CoFe2O4 NPs synthesis by by procedure (1 to 4) of crude plant extract.

(A) Procedure 1 (Roughness average (8.37 nm) and Root mean square (9.91 nm)

(B) Procedure 2 Roughness average (9.15 nm) and Root mean square (10.8 nm)

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(C) Procedure 3 Roughness average (22.9 nm) and Root mean square (26.7 nm)

(D) Procedure 4 Roughness average (5.15 nm) and Root mean square (6.43 nm)

Fig. (1): AFM topographic images of CoFe2O4 NPs synthesis by procedure (1 to 4) of crude plant extract.

(A) Procedure 1 ()

مقر ةنيع 16

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(B) Procedure 2 () مقر ةنيع 17

(C) Procedure 3 () مقر ةنيع 18

(D) Procedure 4 () مقر ةنيع 19

Fig. (2): SEM image of CoFe2O4 Phytosynthesis NPs using procedure (1 to 4) of crude plant extract.

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(A) Procedure 1 (strong peck: 524.64, 435.91, 501.49, 459.6, 478.35, 447.48, 416.62)

(B) Procedure 2 (strong peck: 526.49. 482.2, 497.63, 459.06, 439.77, 408.91)

(C) Procedure 3 (strong peck: 532.35, 459.06, 482.2, 497.63, 435.91, 408.91).

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(D) Procedure 4 (strong peck: 536.21, 489.92, 451.34, 443.63 and 405.05)

Fig. (3): FT-IR spectra of CoFe2O4 synthesis by procedure (1 to 4) of crude plant extract.

Fig. (4): X-ray pattern of CoFe2O4 of procedure (1-4)

Table (2): summary of X-ray characterization of CoFe2O4 phytosynthesis nanoparticles synthesis by various plant extracts and Aspartic acid.

Sample Planes 2 theta FWHM D STRAIN DIS (hkℓ) (DEG) (DEG) (nm) XE-4 X1014 Procedure

1

220 30.6 2.329 3.947 351.15 641.88 311 35.163 0.556 17.417 79.58 32.97

400 43.2 0.09 120.862 11.47 0.68

Average 47.41

Procedure 2

220 30.15 1.465 6.245 221.95 256.45 311 35.79 1.255 7.781 178.12 165.17

400 43.4 0.09 121.265 11.43 0.68

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Average 45.1

Procedure 3

220 30.908 0.669 13.789 100.52 52.6 311 35.343 0.571 17.015 81.46 34.54

400 43.3 0.09 121.063 11.45 0.68

Average 50.62

Procedure 4

220 30.918 0.487 18.933 73.2 27.9 311 35.35 0.652 14.895 93.06 45.08 511 57.62 0.152 98.183 14.12 1.04

Average 44

(hkℓ) planes: crystallographic plane; FWHM: Full width at half maximum; D: dimension of Crystal in nm;  x10-4: strain value;  x 1014: dislocation density; NPs: nanoparticles; BPs:

particles.

(A) (B)

Fig. (5): (A) absorptions spectrum and (B) (ahv)2 versus photon energy of phytosynthesis CoFe2O4 NPs using procedures 1-4 of crude plant extract, note that procedure 6 include Aspartic acid with crude extract.

Current results approved that R. ribes contain six compounds: Emodin (38.25 %), Physcion (29.145 %), Rutin (13.193 %), Rhein (6.53 %) and Aloe -emodin (2.58 %). Several studies were close related to this result, Keser and his team in (2020) and (Abdul Jalill, et al., 2015) found most of these compounds in stems and rhizomes respectively. Other constituents that have been also isolated from Rheum species are: anthocyanins, flavonoids, dianthrones, stilbenes, anthraglycosides, chromone glycosides, polyphenols, organic acids, essential oil and vitamins (Keser et al., 2020).

Current results approved that methanol crude extract success to produce CoFe2O4 in nano size in three different procedures. This ability may be due to Phenolic compounds which possess hydroxyl and ketone groups that are capable of binding to metals and showing chelation (Nasrollahzadeh et al., 2019). One of these Phenols was Rutin (as proven in HPLC analysis in the current study). This compound are capable to reduction of zinc salt to ZnO NPs (Bharathi and Bhuvaneshwari, 2019) it act as ligation agents and the aromatic hydroxyl groups of Rutin

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react readily with tin ions, which lead to the formation of a stable complex of SnO2 nanoparticles (Suresh et al., 2020; Senthilkumar and sami, 2014).

Preparation of NPs using these approaches is environmentally friendly and provides NPs with better defined sizes, morphologies, and stability (Nasrollahzadeh et al., 2019). Several studies were close to present plant, which approve their ability of R. ribes to produce silver nanoparticles (26 nm) (Zhang and Liu, 2004). In addition, Rheum turkestanicum (RT) has been utilized as the stabilizing agent to form fine zinc oxide nanoparticles with a size of 17-20 nm (Nemati et al., 2019). The fruits of another species of Rheum (Ribes khorassanicum) served as the reducing and capping agents in biosynthesis of AgNPs (Yazdi et al., 2018; Adibi et al., 2007).

Conclusions and Recommendations

Rhizomes of Iraqi Rheum ribes extract contain seven compounds of flavonoids. Four procedures were used to synthesis CoFe2O4 nanoparticles using methanol crude extract of Rhizomes of Iraqi R. ribes. The results conclude that three of those four procedures were success to produce CoFe2O4 in nano size, there were: (1, 2, 3) procedures, while procedure 4 was fail to produce nanoparticles. Studying the role of some active constituents of Rheum sp. in phytosynthesis of cobalt ferrite nanoparticles will be benefit.

Acknowledgments

The authors would like to thank Al-Mustansiriyah University (www. uomustansiriyah.edu.iq) Baghdad Iraq for its support in the present work.

References

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