Materials Today: Proceedings 26 (2020) 3559–3563

Contents lists available at ScienceDirect

Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

Green synthesis and characterization of manganese oxide nanoparticles

from Gardenia resinifera leaves
R. Manjula a, M. Thenmozhi a, S. Thilagavathi a, R. Srinivasan b, A. Kathirvel a,⇑
a
Department of Chemistry, K. S. Rangasamy College of Arts and Science, K. S. R. Kalvi Nagar, Tiruchengode 637215, Namakkal, Tamil Nadu, India
b
Department of Food Science and Technology, Yeungnam University, Gyeongsan-si, Gyeongsangbuk-do 38541, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Gardenia resinifera is used in several traditional medicines. The present study was aimed to the synthesis
Received 10 April 2019 and characterization of MnO2 nanoparticles from G. resinifera leaf extract. Synthesis of MnO2 nanoparti-
Received in revised form 7 June 2019 cles was achieved by mixing manganese acetate with hot aqueous extract of G. resinifera dry leaves. The
Accepted 10 July 2019
synthesized MnO2 nanoparticles were characterized using UV–Visible spectroscopy, PSA, FT-IR, XRD,
Available online 12 August 2019
SEM-EDAX, and HR-TEM analysis. The results of the above-mentioned studies indicated that the synthe-
sized MnO2 nanoparticles are 17–35 nm and spherical in shape. The results of FT-IR study shows the
Keywords:
presence of different functional groups that may exhibit various biological activities. The synthesized
Gardenia resinifera
Manganese oxide nanoparticles
MnO2 nanoparticles harbor significant antimicrobial activity.
XRD Ó 2019 Elsevier Ltd. All rights reserved.
SEM-EDAX Selection and peer-review under responsibility of the scientific committee of the International Confer-
HR-TEM ence on Emerging Materials and Modeling.
Antimicrobial activity

1. Introduction nanoparticles using an aqueous leaf extract of G. resinifera and

evaluate its antibacterial potential.
Nowadays, nanotechnology is the emerging field of medical
research. Nanoparticles are intermediate structure between micro-
materials and atomic structures which are responsible to enhance 2. Experiment
the physical properties such as surface area, volume ratio [1]. Her-
bal plants and their extracts possess several medicinal properties 2.1. Plant material
which have been used in the development of new drugs [2]. The
raw materials extracted from medicinal plants are used in the case Fresh leaves of G. resinifera was collected from Kolli hills,
of laxatives, blood thinners, antibiotics and anti-malarial medica- Namakkal district, Tamil Nadu, India. The collected plant material
tions which are in the form of tinctures, teas, poultices, powders was identified and authenticated by the Botanical Survey of India
and in some other herbal formulations [3]. Gardenia belongs to (BSI) (Ref No: BSI/SRC/5/23/2016/Tech./166), Coimbatore, Tamil
Rubiaceae family, consisting nearly 60 species which are largely Nadu, India. The authenticated plant material was examined for
distributed in Thailand, Japan, China, tropical regions of Southeast infections and insect damage, washed, dried for 15 days at room
Asia and the Pacific islands, South Africa and India [4]. Gardenia temperature and powdered.
resinifera has been used in traditional medicine to treat several ail-
ments such as liver disorders, cutaneous diseases, constipation, 2.2. Synthesis of nanoparticles
vomiting, increases appetite, relieves the pain of bronchitis, and
used as astringent. The phenolic compounds present in G. resinifera The extract was prepared hot extraction method by boiling
is a good reducing agent and exhibits good antioxidant property 100 g of dried leaf powder of G. resinifera in 400 mL of distilled
[5]. Thus, the present investigation was aimed to synthesis MnO2 water at 80 °C and the boiling was continued to obtain a dark
brown color extract solution. The filtered plant extract was made
up to 500 mL with distilled water, then 20 mL of manganese acet-
⇑ Corresponding author. ate solution was added and stirred for an hour using a magnetic
E-mail address: [email protected] (A. Kathirvel). stirrer. The reaction mixture was centrifuged at 10,000 rpm for

https://doi.org/10.1016/j.matpr.2019.07.396
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Emerging Materials and Modeling.
3560 R. Manjula et al. / Materials Today: Proceedings 26 (2020) 3559–3563

15 min and the pellet was calcinated and washed with acetone to
remove impurities.

2.3. Characterization of MnO2 nanoparticles

The synthesized MnO2 nanoparticles were subjected to various

spectral studies such as particle size analyzer, FT-IR, XRD, SEM-
EDAX and HR-TEM analyses. A particle size analyzer
(NANOPHOX-0143P, Sympatec GmbH, Clausthal-Zellerfeld, Goslar,
Germany) was employed to detect the size of MnO2 nanoparticles
in the range of 0.05–10,000 nm. The FT-IR spectrum of MnO2
nanoparticles was recorded in the range of 400 to 4000 cm 1
wavelength using a FT-IR spectrometer (Cary 630, Santa Clara,
CA, USA). The X-ray diffraction patterns of MnO2 nanoparticles
were obtained from an X-ray diffractometer (MiniFlex, Rigaku,
Tokyo, Japan) which equipped with CuKa radiation source Fig. 1b. Particle size analysis of MnO2 nanoparticles.
(k = 0.154 nm). The morphology of MnO2 nanoparticles was inves-
tigated using an SEM (JSM 6390, JEOL Inc., Peabody, MA, USA) and
HR-TEM (TecnaiTM G2 F30, FEI, Hillsboro, OR, USA) techniques with
the resolution of 1 nm.

2.4. Antibacterial activity

The antibacterial potential of synthesized MnO2 nanoparticles

was examined using an agar well diffusion method [6]. The analy-
sis of variance test was carried out in a completely randomized
manner and Tukey’s multiple comparison test (p < 0.05) using SPSS
software (SPSS 16.0).

3. Result and discussion

3.1. Photoluminescence spectroscopy and particle size analysis

The green synthesized MnO2 nanoparticles showed absorption

maxima at 362 nm in the PL spectrum (Fig. 1a) which is in the
range of 350–500 nm that specified for MnO2 nanoparticles in
literature. Previous studies indicated that the absorption peak for Fig. 2. Powder X-ray diffraction of MnO2 nanoparticle.
MnO2 nanoparticles at 420 nm [7] that supports the present
findings. Particle size analysis study results (Fig.1b) revealed that
the size of synthesized MnO2 nanoparticles is in the range of
10–50 nm.

Fig. 3. The FT-IR spectrum of MnO2 nanoparticle.

3.2. Powder X-ray diffraction analysis

Fig. 2 shows the X-ray diffraction pattern of MnO2 nanoparti-

cles. The patterns are assigned to the tetragonal phase compared
with the standard data from the JCPDS card (File no: 14-644).
Fig. 1a. Photoluminescence spectra of MnO2 nanoparticles. The four main diffraction peaks corresponding to 200, 121, 211
 R. Manjula et al. / Materials Today: Proceedings 26 (2020) 3559–3563 3561

Fig. 4. SEM analysis of MnO2 nanoparticles (a–d).

Fig. 5. The TEM analysis of MnO2 nanoparticles (a–f), SEAD pattern of MnO2 nanoparticles (g and h).

3.3. Fourier transform infrared spectroscopy (FT-IR) analysis

The results of FT-IR spectrum of MnO2 (Fig. 3) show several

absorption bands at 3839, 3630, 1685, 1111, 1052, 595 and
473 cm 1. The presence of bands at 3810, 2958, 1587 and
1058 cm 1 show the presence of AOH, CAH, C@C, and C@O func-
tional groups respectively, in the synthesized MnO2 nanoparticles.
Two peaks at 607 and 492 cm 1 with low intensity indicates the
presence of the OAMnAO bond [10]. Generally, mineral structures
like MnAO which has stronger bonds and weak vibrations that
decreases the intensity of a peak in FT-IR spectra.

3.4. Scanning electron microscopy analysis

The results of SEM analysis revealed that the surface morphol-

ogy and size of MnO2 nanoparticles (Fig. 4). The mean particle size
obtained from the SEM analysis was 50–100 nm and spherical in
shape. The increased size of MnO2 nanoparticles occurs by aggre-
Fig. 6. EDAX analysis of MnO2 nanoparticles.
gation and agglomeration of nanoparticles due to its larger surface
area and higher in number. The previous investigation reported
that manganese oxide nanoparticles synthesized from Ananas
comosus peel extract were spherical in shape and the size was
and 161 planes were detected. The lattice parameters of the MnO2
40–50 nm which is a good agreement with the present study.
tetragonal system are found to be a = 17.49 nm, b = 24.74 nm, and
c = 35.00 nm. The 2h values of synthesized MnO2 nanoparticles are
in the range of 29–61°. The synthesized MnO2 nanoparticles are 3.5. High-resolution transmission electron microscopy (HR-TEM)
poor crystalline in nature, thus the diffraction peaks are indexed analysis
as tetragonal phase [8]. None of the additional diffraction peaks
related to impurities were detected that indicated the good quality The HR-TEM and SAED pattern analysis reports of MnO2
of synthesized MnO2 [9]. nanoparticles shows the lattice fringes that indicate, the formation
3562 R. Manjula et al. / Materials Today: Proceedings 26 (2020) 3559–3563

Table 1
Comparison of MnO2 nanoparticle mineral compositions.

Elements The present study (in %) Jaganyi et al. [11] Moon et al. [12] Chatterjee et al. [13]
Mn 59.56 38.17 54.67 42.40
O 40.44 36.15 33.93 36.45

Table 2
Antibacterial potential of green synthesized MnO2 nanoparticles from G. resinifera.

S. No. Organisms The diameter of the zone of growth inhibition (in mm)*
10 20 30 PC#
a b c
1 Staphylococcus aureus 15.00 ± 1.15 19.67 ± 2.08 24.00 ± 1.00 23.33 ± 0.58d
2 Pseudomonas aeruginosa 10.33 ± 0.58a 15.33 ± 1.15b 28.00 ± 1.00c 27.00 ± 1.00c
3 Serratiam arcescens 15.67 ± 1.00a 25.00 ± 1.15b 29.33 ± 0.58c 24.67 ± 1.15b

The superscript letters (a–d) in a row indicate significant differences (at p < 0.05) when subject to Tukey’s multiple comparison test.
*
Data represented as mean ± SD (n = 3),
#
Ciprofloxacin (1 mg/mL).

Fig. 7. Antibacterial activity of MnO2 nanoparticles.

of a good nanocrystalline structure and the size is about 20–30 nm. 4. Conclusion
The literature revealed that the lattice fringes of MnO2 nanoparti-
cles represent an irregular shape with a grain size diameter The MnO2 nanoparticle was synthesized from G. resinifera
between 20 and 40 nm [11]. The HR-TEM results explore the aver- aqueous extract as a source of reducing agent. The synthesized
age size of synthesized MnO2 nanoparticles was 23 nm. The HR- MnO2 nanoparticles were characterized using photoluminescence,
TEM analysis of MnO2 nanoparticles is shown in Fig. 5. particle size analysis, P-XRD, FT-IR, SEM, EDAX, and HR-TEM
analysis. The overall results of all studies concluded that the
synthesized MnO2 nanoparticles are 20–30 nm in size and spheri-
3.6. Energy dispersive X-ray spectroscopy analysis cal in shape with 59% of Mn and 40% of O composition and possess
various biological active functional groups. MnO2 nanoparticles
The chemical composition of the synthesized MnO2 nanoparti- expressed significant high antibacterial potential against both
cles from G. resinifera leaves extract was analyzed by energy dis- gram-positive and gram-negative bacteria.
persive X-ray spectroscopy (Fig. 6). Two major peaks for Mn and
O were detected in EDAX spectra and the composition rate was
compared with literature given in Table 1. Acknowledgments

The authors would like to acknowledge the Indian Institute of

3.7. Antibacterial activity Technology, Bombay and Government College of Engineering,
Bargur for technical support in spectral studies.
Green synthesized MnO2 nanoparticles showed significant
broad-spectrum antibacterial activity against all tested bacterial
References
pathogens. MnO2 nanoparticles exhibited a dose-dependent
antimicrobial effect ranges from 10 mm to 29 mm (Table 2 and [1] E. Weir, A. Lawlor, A. Whelan, F. Regan, The use of nanoparticles in anti-
Fig. 7). The data obtained from the antibacterial activity of MnO2 microbial materials and their characterization, Analyst 133 (2008) 835–845.
[2] G. Samuelson, Drugs of natural origin. A text book of pharmacognosy, J. Nat.
nanoparticles (at 30 mg/mL) indicate that Serratiam arcescens was
Prod. 68 (2005) 631.
most sensitive microorganism with a maximum zone of inhibition [3] M.J. Balick, P.A. Cox, Plants, people and culture: the science of ethno botany,
(29 mm), followed by Pseudomonas aeruginosa (28 mm). Several Sci. Am. Lib. 78 (1997) 431–441.
studies [14–16] has been reported that the MnO2 nanoparticles [4] E.L. Gibson, J. Wardle, C.J. Watts, Fruit and vegetable consumption, nutritional
knowledge and beliefs in mothers and children, Appetite 31 (1998) 205–228.
synthesized from plant extract exhibited significant antimicrobial [5] J. Dai, R.J. Mumper, Plant phenolics: extraction, analysis and their antioxidant
activity which support the present investigation results. and anticancer properties, Molecules 15 (2010) 7313–7352.
 R. Manjula et al. / Materials Today: Proceedings 26 (2020) 3559–3563 3563

[6] R. Srinivasan, D. Natarajan, M.S. Shivakumar, Antimicrobial and GC-MS [12] A. Sun Moon, K. Bipinchandra Salunke, B. Alkotaini, S. Ezhaveni, B. Soo Kim,
analysis of Memecylon edule leaf extracts, Int. J. Curr. Pharm. Rev. Res. 5 Biological synthesis of manganese dioxide nanoparticles by Kalopanax pictus
(2014) 1–13. plant extract, IET Nanobiotechnol. (2015) 1–6.
[7] M. Suriyavadhana, K. Ramalingam, Nanoparticles synthesis and antibacterial [13] S. Chatterjee, J. Anita, A. Subramanian, S. Subramanian, Synthesis and
study on Anisomeles malabarica using manganese oxide, Int. J. Chem. Tech. Res. characterization of manganese dioxide using Brassica oleracea (cabbage), J.
8 (2015) 466–473. Ind. Pollut. Control. 33 (2017) 1627–1632.
[8] A. Salman, M. Mohsheemul Hasan, Exploring globally used anti-urolithiatic [14] M. Jayandran, M.M. Haneefa, V. Balasubramanian, Green synthesis and
plants of M-R families: including Myrtaceae, Phyllanthaceae, Piperaceae, characterization of manganese nanoparticles using natural plant extracts
Polygonaceae, Rubiaceae and Rutaceae, J. Pharmacogn. Phytochem. 6 (2017) and its evaluation of antimicrobial activity, J. Appl. Pharm. Sci. 5 (2015) 105–
325–335. 110.
[9] Y. Zhang, Y. Yang, X. Wang, G. Li, D. Deng, L. Jiang, C. Shu, C. Wang, Facile [15] M.M. Haneefa, M. Jayandran, V. Balasubramanian, Green synthesis
synthesis of porous Mn2O3 nanoplates and their electrochemical behavior as characterization and antimicrobial activity evaluation of manganese oxide
anode materials for lithium ion batteries, Chem. Eur. J. 20 (2014) 6126–6130. nanoparticles and comparative studies with salicylalchitosan functionalized
[10] J. Estelrich, M.J. Sanchez-Martin, M.A. Busquets, Nanoparticles in magnetic nanoform, Asian J. Pharm. 11 (2017) 65–74.
resonance imaging: From simple to dual contrast agents, Int. J. Nanomed. 10 [16] M.M. Haneefa, M. Jayandran, V. Balasubramanian, Evaluation of antimicrobial
(2015) 1727–1741. activity of green-synthesized manganese oxide nanoparticles and comparative
[11] D. Jaganyi, M. Altaf, I. Wekesa, Synthesis and characterization of whisker- studies with curcuminaniline functionalized nanoform, Asian J. Pharm. Clin.
shaped MnO2 nanostructure at room temperature, Appl. Nanosci. 3 (2013) Res. 10 (2017) 347–352.
329–333.