Accepted Manuscript

Green synthesis of manganese nanoparticles: Applications and

future perspective–A review

Vahid Hoseinpour, Nasser Ghaemi

PII: S1011-1344(18)30959-X
DOI: https://doi.org/10.1016/j.jphotobiol.2018.10.022
Reference: JPB 11387
To appear in: Journal of Photochemistry & Photobiology, B: Biology
Received date: 21 August 2018
Revised date: 25 October 2018
Accepted date: 29 October 2018

Please cite this article as: Vahid Hoseinpour, Nasser Ghaemi , Green synthesis of
manganese nanoparticles: Applications and future perspective–A review. Jpb (2018),
https://doi.org/10.1016/j.jphotobiol.2018.10.022

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Green synthesis of manganese nanoparticles: applications and future perspective - A

review

Vahid Hoseinpour 1*, Nasser Ghaemi 1

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1. School of Chemistry, College of Science, University of Tehran, Tehran, Iran

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* Corresponding author: NU
* vahidhoseinpur@ut.ac.ir
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Abstract

Nanobiotechnology is a promising and appearing field of nanotechnology. In recent years, the

necessity of making biocompatible materials for different applications in various area such as

health, medicine, water treatment and purification, etc. caused more attention to this area.

Today, green synthesis of different nanoparticles (NPs) has been extensively studied.

However, less attention has been paid to manganese as a high-performance metal in various

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applications such as medicine, biomedicine, biosensors, water treatment and purification,

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electronics, electrochemistry, photoelectronics, catalysis, and etc. Manganese oxides (Mn-

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oxides) has wealthy structures such as MnO, Mn5O8, Mn2O3, MnO2, and Mn3O4, and can be

used in a variety of fields. Mn-oxide NPs potentially hold great promise for sustainable
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nanotechnology. This review focusses on the green synthesis, applications and future

perspective of Mn NPs. Different methods of green synthesis of Mn NPs, including synthesis

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using plant extract, synthesis using microorganism, and low-temperature synthesis of Mn

NPs have been investigated and presented. Structure, and size, of green synthesized Mn NPs
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via each method have been compared. Also, various applications of the green synthesized Mn
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NPs have been reviewed. Furthermore, the future perspective of green synthesis and
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applications of the green synthesized Mn NPs are expressed. Also, different applications

explained for green synthesized Mn NPs are expressed as well as potential applications for
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green synthesized Mn NPs are suggested.

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Keywords: Nanoparticles, Green Synthesis, Manganese, Nanobiotechnology,

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1. Introduction

In recent years, the study in nanotechnology has engrossed growing fondness because of its

revolutionist and promising effects on many areas [1,2]. Nanotechnology is appearing as a

new field of research dealing with preparation of nanomaterials and nanoparticles (NPs) for

their applications in diverse fields due to their highly multifunctional, modular, and efficient

properties such as food technology, healthcare, optical devices, space industry,

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pharmaceutics, cosmetics, electrochemistry, modify membrane, textile industry, water

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treatment and purification, water supply systems, biomedicines, mechanics, optics, energy

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science, catalysis, sensors, electronics, and, etc. [2–9].

Nanobiology and nanobiotechnology are terms that appear in conjunction with

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nanotechnology and biology [10]. Nanobiotechnology is a promising and appearing field of

nanotechnology and is involved with the diverse research area of expertise, such as
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chemistry, engineering, physics, material science, medicine, and biology [3,11,12].

Nanotechnology has more benefits over another common process owing to the accessibility
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of more components by biological creatures for the preparation of NPs. The rich biodiversity

of suchlike biological creatures should be studied for the preparation of bionanomaterials

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[12].
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Usually, two strategies bottom-up and top-down are used to synthesize [13,14]. In the top-
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down approach, the bulk-materials are usually broken down to nanomaterials, whereas in the

bottom-up approach, molecules or atoms are assembled to NPs [12]. The bottom-up approach

is usually used for green synthesis and chemical synthesis of NPs. [12]. Green synthesis of

NPs is an evolved method from the nanobiotechnology [15], and todays, green nanomaterials

are the main purpose of nanotechnology research [3]. Green synthesis of nanoparticles has

been emerging as a non-toxic, environmentally friendly, clean, less costly, and almost new

approach, also, it can be done at room pressure and temperature [3,16,17]. Green synthesis of

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nanoparticles can be considered as an alternative to synthesizing biocompatible NPs, which is

the latest feasible method of connecting material-science and biotechnology [12]. Hence,

green synthesis of NPs with controlled shape and size employing genetic engineering

methods, molecular cloning, plants extracts, and other biological techniques will be a

wonderful advancement in the nanobiotechnology [12].

Nanomaterials (usually≤100 nm) can show excellent chemical and physical properties from

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their bulk due to their high specific surface area [5,18]. Biogenic-metallic NPs can be

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synthesized by various organisms, such as, plants, fungi, bacteria, yeasts, algae, and

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actinomycetes which causes considerable modifications of the properties of the metals

[3,19]. Many research and review articles on the green synthesis of gold [20–25], silver
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[4,26–37], zinc [18,38–45], Iron [3], copper [46–49] and other metals have been presented

[10,12–14,19,50–56].
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Meanwhile, manganese has not been taken into consideration despite its very interesting and
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practical properties. In this paper, a review of the green synthesis, applications and future
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perspective of manganese NPs is under consideration for the first time. Chart 1 presented a

graphical abstract of green synthesis of Mn NPs.

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Chart 1 a graphical abstract of green synthesis of Mn NPs.

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2. Manganese nanoparticles

Manganese is the most abundant element of the earth, as Mn is the twelfth most common

element on the planet and the third most abundant transition element after iron and titanium

[57]. Manganese is a necessary micro-nutrient for reproduction, prevention, and growth of

fish and terrestrial animals [58].

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Among different 3d transition metal-oxides, Mn-oxides have acquired specific interest due to

their wealthy structural and compositional variants such as MnO, Mn5O8, Mn2O3, MnO2, and

Mn3O4 [59]. Mn-oxide NPs potentially hold great promise for sustainable nanotechnology

[57]. Mn-oxides can be used in molecular sieves, solar cells, batteries, catalysts, magnetic

materials, optoelectronics, drug delivery ion-sieves, as well as other fields such as imaging

contrast agents, magnetic storage devices, water treatment and purification, due to their

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privileged physical and chemical properties [60–66]. Moreover, Mn-oxides are usually less

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toxic materials than other compounds upon which NPs are generally based, such as diverse

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chalcogenides, also they have environmental compatibility, high specific capacitance, and

cost-effectiveness [57,67]. In fact, the last studies display the potential for Mn-oxides,
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including Mn-Oxide NPs, to replace technologies based upon scarce-elements such as

platinum catalytic converters for car publication [57]. Mn-Oxides NPs have structural
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flexibility composed of different physicochemical properties [68]. Diverse nanostructures of

Mn-Oxides, such as nanorods, nanobelts, nanosheets, nanowires, nanotubes, nanofibers,

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mesoporous sieves, molecular sieves and branched structures, urchins, orchids, and other
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hierarchical structures have been prepared by different techniques [68].

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MnO2 is one of the most significant materials and a number of researchers have paid special

attention to the efficacy of manganese dioxide in addition to the electromagnetic attributes of

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the materials [63]. MnO2 is one of the most stable Mn-oxides with privileged

physicochemical attributes under ambient conditions [67]. MnO2 NPs have also applications

in ion-exchange, biosensor, medicine, molecular adsorption, supercapacitors, catalysis, and

energy storage [65,67].

Mn3O4 is a mixed-valence oxide that has been a promising candidate for a wide range of

applications containing being employed as microwave absorption materials, supercapacitors,

catalysts, anode materials, sensors, and precursors for the manufacture of LiMn2O4, Which is

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used for battery preparation [57,69,70]. Also, Mn3O4 is known to be an efficient catalyst for

the oxidation of methane reduction of nitrobenzene and decomposition of waste gas NOx

[69].

Diverse methods have been expanded to the synthesis of Mn-oxide NPs such as ambient

temperature solid reactions, self-reacting microemulsion, sonochemical, precipitation,

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hydrothermal and green synthesis techniques [63,71]. Since, the attributes of NPs are shape

and size related, the synthesis method having control on size, monodispersity, and shape is a

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significant area of study [60].

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3. Green synthesis of Mn NPs

From the perspective of the environment, green methods for synthesizing Mn NPs are
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considered, as a particular chemical it is not necessary to be stabilized and reduced, and also

it’s preparation can be done under mild conditions such as ambient temperature and pressure
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[66,72]. In the biological synthesis of Mn NPs, raw materials, vegetables and fruits, plant
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extracts, microbes, and fungi are utilized to prepare Mn and Mn-oxide nanoparticles [2,19].
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The control of the shape and size of green synthesized Mn NPs and their applications are still

two major challenges in nanobiotechnology [10]. In general, three methods of green synthesis
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using plant extracts, green synthesis using microorganism, and low-temperature synthesis
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have been used for Mn green synthesis, which is presented below.

3.1.Green synthesis using plant extracts

There are various reports of green synthesis of Mn NPs in different methods. Employing

plant extract reduction and stabilization of manganese metal into Mn NPs are the simplest,

inexpensive and environmentally friendly approaches in green chemistry [10,63]. Green

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synthesis by plant extracts has advantages, including scalability, medical applicability, and

biocompatibility [10,51]. In the synthesis of NPs employing plant extracts, the plant extract is

simply mixed with the metal salt solution at ambient temperature and the reaction is complete

in a few minutes. The metal reduction is attributed to the different compounds which are

present in the plant extract such as polysaccharides, terpenoids, flavones, and phenolics

[52,73]. So far, several plant extracts have been used in the synthesis of manganese NPs.

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Table 1 Green synthesis of Mn NPs using extracts of plants and their applications.

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Method Organism Mn NPs Size Application/Property References
structure
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lemon methanolic extract MnO2 NPs 50 nm Antibacterial and Jayandran et al.
Antifungal [63]
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Kalopanax pictus leaf MnO2 NPs 1-60 Dye degradation Moon et al. [65]
extract nm
clove, i.e., Syzygium MnO NPs 4 nm Electrochemical Kumar et al.
aromaticum aqueous [61]
extract
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Phyllanthus amarus leaf MnO2 40-50 Fluorescence studies Prasad and

extract nanorods nm Patra [66]
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Adalodakam leaf extract Mn3 O4 NPs 44 and - Prasad [59]

66 nm
Plant Ananas comosus (L.) peel Mn3 O4 NPs 10–34 Nutritional supplements Asaikkutti, A.
Extract extract nm et al. [58]
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Dittrichia graveolens (L.) MnO NPs 38 nm Dye degradation Souri et al. [64]
extract
Yucca gloriosa leaf MnO2 NPs 80 nm Dye degradation Hoseinpour et
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extract al. [74]

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Jayandran et al. (2015) reported the synthesis of manganese nanoparticles by reducing

manganese acetate with the help of lemon methanolic extract as a reducing agent and

turmeric curcumin as a stabilizing agent with an average crystallite size of particles in the

range of 50 nm (Figure 1A). At their experience, pH was kept among 3-4 and the temperature

was at 50-60 ˚C during the reaction [63].

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Figure 1 TEM and SEM images of green synthesized MN NPs using (A) lemon methanolic extract as

reducing agent and turmeric curcumin as a stabilizing agent [63], (B) aqueous leaf extract of
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Kalopanax pictus [65], (C) clove, i.e., Syzygium aromaticum aqueous extract [61], (D) Phyllanthus

amarus leaf extract [66], (E) Ananas comosus (L.) peel extract [58], (F) Bacillus sp. cells [60], and
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(G) Streptomyces sp. HBUM171191 [75]

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Moon et al. (2015) used an aqueous leaf extract of Kalopanax pictus as the reduction agent of
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potassium permanganate (KMnO4) to produce manganese dioxide (MnO2) nanoparticles that

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had an average particle size of 19.2 nm with a particle diameter ranging from 1 to 60 nm

(Figure 1B). The synthesis was occurred without stirring at ambient temperature. [65].

Kumar et al. (2017) reported the synthesis of MnO NPs with different sizes via clove, i.e.,

Syzygium aromaticum aqueous extract as reducing and stabilizing agents. The TEM image

(Figure 1C) and XRD analysis showed that MnO NPs were 2.5 and 1.8 nm in size,

respectively [61]. To obtain MnO NPs of different sizes, they synthesized MnO NPs in

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various conditions (metal concentration: 1 to 80 mM, plant extraction concentration: 0.25 to 1

ml, metal ion volume, 1 to 5 ml, plant extraction: 1 to 4 ml, temperature: 25 to 85 ˚C).

Synthesis of manganese nanorods using a leaf extract of Phyllanthus amarus was reported by

Prasad and Patra (2017) with an average size of 40–50 nm and TEM images are shown in

figure 1D. in this research, the mixture was stirred 1 h at ambient temperature and pH 6.8

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[66].

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In an experiment conducted by Prasad, Mn3O4 NPs were prepared using manganese sulphate

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monohydrate and the leaf extract of Malabar Nut (Adhatoda vasica Nees / Justicia adhatoda)

was employed as the precursor salt and reductant respectively (pH 7, temperature 90). In his
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research, crystallographic structure, optical characteristics, the mechanism of the formation,

the crystallite sizes, and thermal behavior of the NPs were studied. The XRD analysis
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confirmed the formation of Mn3O4 in tetragonal body-centered lattice system. Also, the

average size of 44 nm and an effective crystallite size of 66 nm were measured using Debye-
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Scherer equation and Hall-Williamson technique, respectively. The optical analysis in the
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UV–Vis-NIR range displayed the energy band gap of Mn3O4 equal to 2.50 eV. Furthermore,
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the thermo-gravimetric analysis study showed the absolute phase transformation from Mn3O4

to Mn5O8 at 498.3 °C and more decomposition to Mn2O3 which crystallized at 581.3 °C [59].
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In another study, Mn3O4 NPs (10–34 nm) were synthesized using Ananas comosus (L.) peel

extract at room temperature. HR-SEM images (Figure 1E) displayed Mn3O4, with an average

size of 40–50 nm and spherical in shape. The Zeta potential showed the negative surface

charge for Mn3O4 NPs [58].

Souri et al. (2018) reported the optimization of green synthesis of MnO NPs with Dittrichia

graveolens (L.) extract via RSM. The central composite design was employed to measure the

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effect of the extract, metal ratio, time, and pH on the preparation of MnO NPs (Figure 2). The

experience occurred at room temperature. The result showed that the most effective

parameter was the extract to the metal ratio. The MnO NPs average size at optimal condition

was measured about 38 nm [64].

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Figure 2. 3D plot showing the effect of (a) pH and Dittrichia graveolens (L.) extract, (b) Dittrichia

graveolens (L.) extract and time, (c) pH and time, On absorbance of green synthesized MnO NPs and
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(d) normal plot [64]

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Also, Hoseinpour et al. (2018) described the green synthesis of MnO2 NPs by Yucca gloriosa

leaf extract [74]. The reaction condition was pH 8 and room temperature. The XRD analysis

confirmed the formation of MnO2. Also, the average size of 80 nm was measured using

Debye-Scherer equation [74].

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Green synthesis of Mn NPs using different plant extracts and their structure and size are

compared in Table 1.

3.2. Green synthesis using microorganism

Microorganisms have a high potential for synthesizing NPs [19]. Ever, various

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microorganisms, containing yeast, bacteria, and funguses have been used for the preparation

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of metal NPs [19]. Microorganisms have the capability to remove and accumulate heavy

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metals owning to several reeducates enzymes, which are capable to reduce metal salts to

metal NPs with a limited size distribution and, thus, better dispersity [19]. The literature on
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manganese green synthesis using microorganisms is presented below

In one work MnO2 NPs were synthesized via Bacillus sp. cells [60]. A control experiment
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was similarly run without inoculating with the cells to check for any abiotic precipitation of

the manganese during the operational experimental conditions. The cells efficiently
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synthesized MnO2 NPs of the average size of 4.62 nm (Figure 1F). In another study, Mn

sulfate was synthesized using Streptomyces sp. HBUM171191 in 35˚C with the size ranging
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from 10 to 20 nm (Figure 1G). [75]. Also, in a work, Mn0.6Fe2.4O4 magnetic NPs were

prepared via Thermoanaerobacter sp. TOR-39 on a large scale with the average size of 80
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nm and a maximum yield of 4.5 (g/l). The incubation was kept at 65 ˚C for 3 weeks, and the

mixture was supplemented with 10 mM glucose every 4 days. pH was kept between 7.2 and

7.5. Pending the incubation, continuous purging with an N2 gas maintained anaerobic

conditions of the mixture and abducted CO2 gas in the headspace. The contents of the reactor

were stirred continuously at 40 rpm, and vigorous mixing was performed for more than 30

min every day [76].

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Green synthesis of Mn NPs using microorganisms and their structure, and size, are compared

in Table 2.

Method Organism Mn NPs Size Application/Property References

structure

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Bacillus sp. cells MnO2 NPs 4.62 - Sinha, A.
nm et al. [60]
Microorganism Streptomyces sp. Mn sulfate 10 to - Waghmare,

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HBUM171191 20 S.S. et al.
nm [75]
Thermoanaerobacter Mn0.6 Fe2.4 O4 80 Magnetic property Moon, J.-W.

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sp. TOR-39 magnetic NPs nm et al. [76]
Table 2 Green synthesis of Mn NPs using microorganisms and their applications.
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3.3.Low-temperature synthesis
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Low-temperature synthesis in aqueous solutions ever showed a user and environmentally

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friendly approach, which may be considered to be a green chemical alternative of important

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applications [77]. The flowerlike NPs of Ag-doped MnO2 were synthesized by Jana et al.

through an environment-friendly approach (Figure 3). In their research, flowerlike NPs of

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Ag-doped MnO2 were obtained by photochemical and facile wet chemical methods. UV-
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visible absorption spectroscopy study was disclosed that doping of Ag NPs in MnO2 NPs

leads to a redshift of the absorption peak and reduces the optical band gap energy compared

with MnO2. Flowerlike Ag-doped MnO2 NPs were achieved by a facile wet chemical as well

as photochemical methods .They also argued that the proposed green method is capable of

scale-up due to its simplicity and cost [77]. Also, Veeramani et al. reported one green

ambient temperature preparation of polycrystalline Mn3O4 nanowires. In this method, Mn(II)

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aqueous solution was oxidized under neutral conditions by atmospheric oxygen in the

presence of a low-cost catalyst (α-Fe2O3), and a biochemical buffer (pH 7.5). The time was

varied from 1 to 36 h [57].

Green synthesis of Mn NPs using Low-temperature method and their structure and size are

compared in Table 3.

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Figure 3 SEM images of Ag-doped MnO2 nanoflower NPs prepared via Low-temperature technique

[77]
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Method Organism Mn NPs Size Application/Property References

structure
- flowerlike NPs 1.25 Application in surface- Jana et al.
of Ag-doped µm enhanced Raman [77]
MnO2 × scattering (SERS)
Low- 500
temperature nm
- polycrystalline 7 nm - Veeramani
Mn3 O4 et al. [57]
nanowires

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Table 3 Green synthesis of Mn NPs using Low-temperature method and their applications.

4. Application of green synthesized Mn NPs

So far, several applications have been presented for green synthesized Mn, which is reviewed

below. Also, a summary of different applications of Mn NPs is given in Table 1, Table 2, and

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Table 3.

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4.1.Antibacterial and antifungal activities

The antifungal and antibacterial property of NPs has been interpreted by their capability to
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the making of highly reactive oxygen species (OH-, H2O2, and O22-) on the surface of the NPs

connected with deadly damage to the fungal and bacteria [1]. Most studies focus on the
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application of the Mn NPs in electronic properties and catalytic activities, but the

antibacterial properties of Mn NPs are seldom investigated [63]. In one study, the
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antibacterial activities of curcumin and curcumin stabilized Mn NPs against Staphylococcus

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aureus and Bacillus subtilis (gram-positive) and Escherichia coli and Staphylococcus bacillus
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(gram-negative) were appraised by disc diffusion method, and the zone of inhibition was

compared to Chloramphenicol [63]. The results are displayed in Table 4 and it was found out
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that the antibacterial activities of curcumin stabilized Mn NPs were superior to the curcumin

for all bacteria. The Mn NPs exhibited stronger antibacterial activities to Chloramphenicol

against S. aureus and almost similar activities against E. coli [63]. Also in the same work, the

antifungal activities of Curcumin and Mn NPs were studied with diffusion method against

four fungal strains Trichophyton simii, Curvularia lunata, Aspergillus niger, and Candida

albicans, and were compared with Fluconazole as a standard drug. The results are displayed

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in Table 4 and it was found out that the antifungal activities of curcumin stabilized Mn NPs

were superior to the curcumin and standard drug [63].

Table 4 Effect of curcumin and green synthesized MnO2 NPs on antifungal and antibacterial activity

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Type Species Zone of inhibition diameter (mm)
Standard Drag Curcumin MnO2 NPs
S. aureus 16 13 18

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B. subtilis 18 16 11
Bacterial E. coli 20 17 19
S. bacillu 21 15 17

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C. albicans 17 16 20
C. lunata 17 14 19
Fungal A. niger 20 15 18
T. simii 17 16 20
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[63]
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4.2. Nutritional supplements

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Manganese is a necessary micronutrient for reproduction, growth, and prevention of skeletal

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abnormalities in terrestrial animals and fish [58]. In one study, the green synthesized Mn3O4

NPs were used as dietary supplements for freshwater prawn Macrobrachium rosenbergii
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[58]. According to the results, supplementations of green synthesized MnO NPs significantly
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improved the activity of metabolic activities and antioxidant defense systems such as
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glutamic pyruvate transaminase, antioxidants enzymatic activity, and glutamic oxaloacetate

transaminase. Also, Mn3O4 NPs supplements cured the efficiency in final weight, growth, and

survival of M. rosenbergii. In conclusion, green synthesized Mn2O4 NPs were effective and

safe as diet supplements for freshwater prawn Macrobrachium rosenbergii [58]. According to

this study, it could be used as a diet supplement for other aquatic animals [58].

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4.3.Dye degradation activity

The production of electron-hole (ĕ–h+) pairs between in conduction and valence bands of NPs

with the high surface area is usually responsible for producing the active oxygen species (O2•,

O2-, HOO•, and OH-). On the other hand, the active oxygen species are responsible for the

degradation of dye into less harmful organics or minerals [78]. The massive volume of

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environmental pollutants, carcinogenic natural and nondegradable dyes, is drained by the

paper and textile industries. Todays, photocatalytic technique got the extensive attention

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owing to its efficient degradation of dyes [47,79,80]. In on work, dye degradation activity of

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MnO2 NPs was studied to degrade safranin O and congo red [65]. In their work, the MnO2

NPs were also prepared by a chemical method employing Na2S2O3 as a reducing agent at
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ambient temperature. Time analysis of the Congo red degradation displayed faster dye
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degradation for green synthesized MnO2 NPs as compared with chemically synthesized

MnO2 NPs. The dye degradation potential of green synthesized MnO2 NPs and chemically
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synthesized MnO2 NPs to degrade Safranin O was similar. The difference in the efficiency of
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green synthesized and chemically synthesized Mn NPs may be due to their size and shape

differences [65]. The green method displayed the presence of spherical NPs and chemical
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method showed whisker-shaped MnO2 NPs [65]. The comparative of chemical and green
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synthesized MnO2 NPs are summarized in Table 5.

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Table 5. Comparative study of chemical and green synthesized MnO2 NPs for dye
degradation according to Moon et al. (2015) report [65].

Samples UV Congo red degradation Safranin O degradation

peaks

Chemical synthesized 410 nm 20 min (68.7% 10 to 15 min (complete

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MnO2 NPs degradation) degradation)

Green synthesized MnO2 360-404 8 min (complete 10 to 15 min (complete

NPs nm degradation) degradation)

In another work, MnO NPs were used for degradation of light green and Rhodamine B dyes

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[64]. Figure 4 illustrates the UV–Visible spectra of the degradation of the light green and

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Rhodamine B. Light green and Rhodamine B degraded completely in 17 and 22 min,

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respectively [64]. Also, in another study, green synthesized MnO2 NPs were employed for

decolorization of Acid orange dye and showed promising results for the degradation of this
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organic contaminant [74].
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Figure 4 a) Light green degradation and b) Rhodamine B degradation using MnONPs with time [64]

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4.4.Electrochemical sensing

In one work, the application of the synthesized MnO NPs was examined in an

electrochemical sensing area [61]. The Green synthesized MnO NPs were employed for the

electrochemical detection of p-nitrophenol (PNP). The electrocatalytic activity of the MnO

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NPs/ butyl carbitol acetate (BCA)/gold electrode had a good low limit and sensitivity of

detection for PNP. Furthermore, the green synthesized MnO NPs can be useful for other

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chemical sensors [61].

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4.5.Fluorescence property

In one work, the solid state fluorescence emission spectra of the green synthesized Mn NPs at
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ambient temperature was studied and the emission intensity was observed at 518 nm (λex =

320 nm). [66].

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5. Future perspective
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5.1. Green synthesis

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As it was noted above, there are many methods for the green synthesis of nanoparticles [81]
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and only a few methods for the synthesis of manganese have been used. Due to the existence

of various structures for Mn-oxides (MnO, Mn5O8, Mn2O3, MnO2, and Mn3O4) [59], and also

the diversity of organisms, such as, plants, fungi, bacteria, yeasts, algae, and actinomycetes

have been used to green synthesis, further study on the green synthesis of manganese NPs can

be interesting. In addition, investigating the possibility of synthesizing metallic

nanocomposites (such as ZnO-MnO, CuO-MnO and etc.) [82–84] can help to further expand

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the applications of Mn NPs. As a suggestion, plants with high antioxidant properties can be

studied for the green synthesis of metallic nanocomposites.

5.2. Applications

So far, the green synthesized Mn NPs have been used for several different applications, as

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reviewed above. But with regard to features of the green synthesized Mn NPs, they can be

studied in various medical, biological, environmental and other applications. For example,

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several applications that have been studied for manganese synthesized by chemical methods

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are reviewed below . These applications can potentially be studied for the green synthesized

Mn NPs.
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5.2.1. Purification of DNA

Functionalized magnetic NPs are frequently noteworthy for different applications in

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biochemistry, molecular diagnostics, environment protection, etc. [85–87]. The merger of

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magnetic particles along with existing and new emerging methods can develop potential areas
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of their applications [88]. Super-paramagnetic materials have been noteworthy for analytical

chemistry and molecular diagnostics applications due to their capability to interact with
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different biomolecules and their inimitable magnetic properties [88].

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In a study, silica coated La 0.75Sr0.25MnO3 perovskite manganite nanoparticles were employed

for purification and extraction of DNAs. The surface of such particles was exposed both to

the deprotonated silanol groups (Si–O−) and silanol groups (Si–OH) under neutral pH

producing a negative zeta potential [88].

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5.2.2. Water treatment and purification

Arsenic is an abundant element in the earth's crust and is one of the water pollutants. Arsenic

is found in four oxidation states and arsenic(III) are more toxic than arsenic(V) [70]. Arsenic

can cause circulatory disorders, liver and skin cancer, and hyperpigmentation [70].

In a work, MnO–coated sand (MnCD) was provided for removing arsenic(V) and arsenic(III)

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from water [70]. The study of the kinetics of arsenic(III) removal alone and in the presence of

arsenic(V) showed that MnCDs in both of these conditions were effective and had the highest

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effect at the first hour [70]. The adsorption of arsenic is based on the following reaction

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[89,90]:

HAsO4− 2+
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H3AsO3 + MnO2 2 + Mn + H2O

In another work, MnO2-modified Clinoptilolite-Ca zeolite was prepared and its ability of
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adsorption of arsenic(V) was studied [91]. The removal of arsenic(V) efficiency of MnO2-

modified Clinoptilolite-Ca zeolite (MCZ) was compared to natural clinoptilolite-Ca zeolite

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CZ [91]. Also, the effect of feed concentration and pH was studied on arsenic (V) removal
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efficiency. According to the results, the arsenic removal efficiency of MCZ was twice as
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much as CZ. The MCZ was completely independent of pH. As a result, MCZ can remove

arsenic, even at low concentrations [91].

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GNS/GO-Mn NPs have a high potential in the field of water treatment and purification. In a
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study, Graphene-nanosheets/delta-MnO2 (GNS-MnO2) nanocomposite was provided for the

removal of nickel ions from wastewater [92]. GNS-MnO2 nanocomposite can be used for five

times with ~91 %. The capacity of the adsorption of Ni(II) for GNS/MnO2 is found to be

about 5 and 1.5 times higher than GNS and delta-MnO2, respectively [92]. Some other

GNS/GO-MnNPs employed for water treatment and purification were presented in Table 6

[5].

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In a study, silicon-doped semicrystalline MnO2 (Si-MnO2) was employed as a catalyst for the

degradation of Rhodamine B (RhB) at room temperature [71]. Si-MnO2 removed RhB from

water at room temperature in 15 min [71].

Table 6 various applications of Mn-based NPs for water treatment and purification [5]

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materials Application Efficiency
MnO2 -GNs Adsorption of Hg(II) 10.8 mg/g (30 ˚C)
delta-MnO2 -GNs Adsorption of Ni(II) 46.5–66.0 mg/g (25–45 ˚C)

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MnFe2O4–GNs Degradation of MB 34.7 mg/g (25 ˚C)
MnFe2O4–GNs Degradation of RB 22.5 mg/g (25 ˚C)
Detection limit: 0.8 μM

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MnO2-GO Detection of change in electrical current (H2 O2)

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5.2.3. Epoxidation of olefin and water oxidation

In a study, The MnO NPs showed effective catalytic activities toward the epoxidation of
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olefins and water oxidation in the attendance of hydrogen peroxide and cerium(IV)

ammonium nitrate, respectively [93]. The MnO NP displayed suitable catalytic property for
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epoxidation of aromatic olefins and slight catalytic property for epoxidation of several
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nonaromatic olefins in the attendance of bicarbonate ions and H2O2 (Figure 5) [93].
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Figure 5 Epoxidation of olefine catalyzed by Mn-oxide [93]
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5.2.4. Optical and magnetic properties
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Djerdj et al. (2007) studied the magnetic properties of MnO NPs [69]. In their work, the

super-paramagnetic behavior of MnO NPs was proved by SQUID analysis. The SQUID
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results clearly unfolded MnO NPs super-paramagnetic behavior, which is unlike prior reports
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that anticipated weak ferromagnetic property of MnO NPs [69].

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In another work, Mn incorporated ZnS Nano-rods (MnxZn1-xS NRs) were prepared. MnxZn1-
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xS NRs showed strong orange luminescence at ∼585 nm [94]. Lower Mn concentrations

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showed six-line hyperfine splitting, while higher Mn concentrations displayed broad

Lorentzian-shaped EPR spectra. Three diverse emissions in the orange, blue, and green

regions were ostensibly in the ambient temperature photoluminescence spectra .EPR analysis

confirms the attendance of magnetic dipole interaction for the MnxZn1-xS NRs with a higher

Mn concentration. MnxZn1-xS NRs with well emission attributes could be employed in

emissive devices [94].

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5.2.5. Supercapacitors and lithium-ion batteries

In a work, electrochemical behaviors of graphene-oxide supported by needlelike MnO2

nanoparticles (GO-MnO2 nanocomposites) were studied [67]. The prepared GO-MnO2

nanocomposites showed good electrochemical behaviors that are beneficial as a material for

supercapacitors electrodes. Also, GO-MnO2 nanocomposites can be used in other

applications such as catalysis reactions, absorbents, and electronica electrodes for different

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devices [67].

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In another work, hierarchical α-MnO2 Nanowires@Ni 1-xMnxOy Nanoflakes Core-Shell

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Nanostructures with high electrochemical efficiency were examined for supercapacitors [95].

The prepared nanomaterial with an Mn concentration of 75% showed excellent performance

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in supercapacitors application [95]. Also, in another study, manganese was used in a

nanocomposite composition for lithium-ion battery application [96].

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6. Concluding remarks
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Nanobiotechnology is expanding as an emerging area of nanotechnology. In recent years, the

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necessity of making biocompatible materials for different applications in various area such as

health, medicine, water treatment and purification, biosensors, food industrially, etc. caused
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more attention to this area. On the other hand, the design of the green approach has become a
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necessity for the industry in the future. Therefore, further research on the green synthesis of

nanoparticles can be very promising. So far, many studies were done in the green synthesis of

metallic nanoparticles. Also, many applications have been proposed for metallic NPs such as

gold, silver, zinc, iron, etc. However, despite the great capabilities, limited research has been

done on Mn NPs.

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In this study, different green synthesis methods including green synthesis using plant extracts,

green synthesis using microorganisms, and low-temperature synthesis have been reviewed.

Structure, and size, of green synthesized Mn NPs via each method have been compared. Also,

various applications of the green synthesized Mn NPs have been reviewed. Furthermore, the

future perspective of green synthesis and applications of the green synthesized Mn NPs are

expressed. Due to the existence of various structures for Mn-oxides (MnO, Mn5O8, Mn2O3,

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MnO2, and Mn3O4), and also the diversity of plants and microorganisms that have the ability

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of green synthesizing, further study on the green synthesis of manganese NPs can be

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interesting. In addition, investigating the possibility of synthesizing metallic nanocomposites

(such as ZnO-MnO, CuO-MnO and etc.) can help to further expand the applications of Mn
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NPs. Green synthesized Mn NPs can also be used in medical, biological, environmental,

biomedical and other applications such as tissue engineering. Here are some of the
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applications of chemical synthesized Mn NPs as a suggestion.

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References

[1] V. Hoseinpour, N. Ghaemi, Novel ZnO–MnO 2 –Cu 2 O triple nanocomposite: Facial

EP

synthesis, characterization, antibacterial activity and visible light photocatalytic

performance for dyes degradation-A comparative study, Materials Research Express. 5
(2018) 85012. doi:10.1088/2053-1591/aad2c6.
C

[2] S. Ahmed, Annu, S.A. Chaudhry, S. Ikram, A review on biogenic synthesis of ZnO
AC

nanoparticles using plant extracts and microbes: A prospect towards green chemistry,
Journal of Photochemistry and Photobiology B: Biology. 166 (2017) 272–284.
doi:10.1016/j.jphotobiol.2016.12.011.
[3] P. Haddad, A.B. Seabra, N. Duran, Biogenic synthesis of nanostructured iron
compounds: applications and perspectives, IET Nanobiotechnology. 7 (2013) 90–99.
doi:10.1049/iet-nbt.2012.0047.
[4] T.C. Prathna, N. Chandrasekaran, A.M. Raichur, A. Mukherjee, Kinetic evolution
studies of silver nanoparticles in a bio-based green synthesis process, Colloids and
Surfaces A: Physicochemical and Engineering Aspects. 377 (2011) 212–216.
doi:10.1016/j.colsurfa.2010.12.047.
[5] M.R. Servos, Nanotechnology for Water Treatment and Purification, Springer

25
 ACCEPTED MANUSCRIPT

International Publishing, Cham, 2014. doi:10.1007/978-3-319-06578-6.

[6] X. Qu, P.J.J. Alvarez, Q. Li, Applications of nanotechnology in water and wastewater
treatment, Water Research. 47 (2013) 3931–3946. doi:10.1016/j.watres.2012.09.058.
[7] I. Gehrke, A. Geiser, A. Somborn-Schulz, Innovations in nanotechnology for water
treatment, Nanotechnology, Science and Applications. 8 (2015) 1–17.
doi:10.2147/NSA.S43773.
[8] G. Bülbül, A. Hayat, S. Andreescu, Portable Nanoparticle-Based Sensors for Food
Safety Assessment, Sensors. 15 (2015) 30736–30758. doi:10.3390/s151229826.
[9] V. Hoseinpour, A. Ghaee, V. Vatanpour, N. Ghaemi, Surface modification of PES

PT
membrane via aminolysis and immobilization of carboxymethylcellulose and
sulphated carboxymethylcellulose for hemodialysis, Carbohydrate Polymers. 188
(2018) 37–47. doi:10.1016/j.carbpol.2018.01.106.

RI
[10] K. Quester, M. Avalos-Borja, E. Castro-Longoria, Biosynthesis and microscopic study
of metallic nanoparticles, Micron. 54–55 (2013) 1–27.

SC
doi:10.1016/j.micron.2013.07.003.
[11] J. Nicolas, S. Mura, D. Brambilla, N. Mackiewicz, P. Couvreur, Design,
NU
functionalization strategies and biomedical applications of targeted
biodegradable/biocompatible polymer-based nanocarriers for drug delivery., Chemical
Society Reviews. 42 (2013) 1147–235. doi:10.1039/c2cs35265f.
MA

[12] K.B. Narayanan, N. Sakthivel, Green synthesis of biogenic metal nanoparticles by

terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible
agents, Advances in Colloid and Interface Science. 169 (2011) 59–79.
doi:10.1016/j.cis.2011.08.004.
D

[13] I. Hussain, N.B. Singh, A. Singh, H. Singh, S.C. Singh, Green synthesis of
TE

nanoparticles and its potential application, Biotechnology Letters. 38 (2016) 545–560.

doi:10.1007/s10529-015-2026-7.
[14] A. Schröfel, G. Kratošová, I. Šafařík, M. Šafaříková, I. Raška, L.M. Shor, Applications
EP

of biosynthesized metallic nanoparticles – A review, Acta Biomaterialia. 10 (2014)

4023–4042. doi:10.1016/j.actbio.2014.05.022.
C

[15] C.M. and G.A.E. M. Vanaja, S. Rajeshkumar, K. Paulkumar, G. Gnanajobitha, Kinetic

study on green synthesis of silver nanoparticles using Coleus aromaticus leaf extract,
AC

Advances in Applied Science Research. 3 (2013) 50–55.

[16] N. Ain Samat, R. Md Nor, Sol–gel synthesis of zinc oxide nanoparticles using Citrus
aurantifolia extracts, Ceramics International. 39 (2013) S545–S548.
doi:10.1016/j.ceramint.2012.10.132.
[17] G. Yamini, A. Shakeri, M.J. Zohuriaan-Mehr, K. Kabiri, Cyclocarbonated
lignosulfonate as a bio-resourced reactive reinforcing agent for epoxy biocomposite:
From natural waste to value-added bio-additive, Journal of CO2 Utilization. 24 (2018)
50–58. doi:10.1016/j.jcou.2017.12.007.
[18] V. Hoseinpour, M. Souri, N. Ghaemi, A. Shakeri, Optimization of green synthesis of
ZnO nanoparticles by Dittrichia graveolens ( L .) aqueous extract, Health
Biotechnology and Biopharma. 1 (2017) 39–49.

26
 ACCEPTED MANUSCRIPT

[19] P. Singh, Y.-J. Kim, D. Zhang, D.-C. Yang, Biological Synthesis of Nanoparticles
from Plants and Microorganisms, Trends in Biotechnology. 34 (2016) 588–599.
doi:10.1016/j.tibtech.2016.02.006.
[20] M.F. Zayed, W.H. Eisa, Phoenix dactylifera L. leaf extract phytosynthesized gold
nanoparticles; controlled synthesis and catalytic activity, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy. 121 (2014) 238–244.
doi:10.1016/j.saa.2013.10.092.
[21] M.F. Zayed, W.H. Eisa, A.M. Hezma, Spectroscopic and Antibacterial Studies of
Anisotropic Gold Nanoparticles Synthesized Using Malva parviflora, Journal of
Applied Spectroscopy. 83 (2017) 1046–1050. doi:10.1007/s10812-017-0406-6.

PT
[22] B. Ankamwar, Biosynthesis of Gold Nanoparticles (Green-gold) Using Leaf Extract of
Terminalia Catappa, E-Journal of Chemistry. 7 (2010) 1334–1339.

RI
doi:10.1155/2010/745120.
[23] Y. Park, Y.N. Hong, A. Weyers, Y.S. Kim, R.J. Linhardt, Polysaccharides and

SC
phytochemicals: a natural reservoir for the green synthesis of gold and silver
nanoparticles, IET Nanobiotechnology. 5 (2011) 69. doi:10.1049/iet-nbt.2010.0033.
[24] A. Annamalai, V.L.P. Christina, D. Sudha, M. Kalpana, P.T.V. Lakshmi, Green
NU
synthesis, characterization and antimicrobial activity of Au NPs using Euphorbia hirta
L. leaf extract, Colloids and Surfaces B: Biointerfaces. 108 (2013) 60–65.
doi:10.1016/j.colsurfb.2013.02.012.
MA

[25] S. Ahmed, Annu, S. Ikram, S. Yudha S., Biosynthesis of gold nanoparticles: A green
approach, Journal of Photochemistry and Photobiology B: Biology. 161 (2016) 141–
153. doi:10.1016/j.jphotobiol.2016.04.034.
D

[26] L. Christensen, S. Vivekanandhan, M. Misra, A. Kumar Mohanty, Biosynthesis Of

Silver Nanoparticles Using Murraya Koenigii (Curry Leaf): An Investigation On The
TE

Effect Of Broth Concentration In Reduction Mechanism And Particle Size, Advanced

Materials Letters. 2 (2011) 429–434. doi:10.5185/amlett.2011.4256.
EP

[27] J.Y. Song, B.S. Kim, Rapid biological synthesis of silver nanoparticles using plant leaf
extracts, Bioprocess and Biosystems Engineering. 32 (2009) 79–84.
doi:10.1007/s00449-008-0224-6.
C

[28] U.K. Parashar, V. Kumar, T. Bera, P.S. Saxena, G. Nath, S.K. Srivastava, R. Giri, A.
Srivastava, Study of mechanism of enhanced antibacterial activity by green synthesis
AC

of silver nanoparticles., Nanotechnology. 22 (2011) 415104. doi:10.1088/0957-

4484/22/41/415104.
[29] M.N. Ullah, A. Umer, M.A. Aadil, F. Rehman, N. Ramzan, Plant-based synthesis of
silver nanoparticles and their characteristic properties, Bioinspired, Biomimetic and
Nanobiomaterials. 6 (2017) 20–36. doi:10.1680/jbibn.16.00033.
[30] S. Ahmed, M. Ahmad, B.L. Swami, S. Ikram, A review on plants extract mediated
synthesis of silver nanoparticles for antimicrobial applications: A green expertise,
Journal of Advanced Research. 7 (2016) 17–28. doi:10.1016/j.jare.2015.02.007.
[31] C. Dong, C. Cao, X. Zhang, Y. Zhan, X. Wang, X. Yang, K. Zhou, X. Xiao, B. Yuan,
Wolfberry fruit (Lycium barbarum) extract mediated novel route for the green
synthesis of silver nanoparticles, Optik - International Journal for Light and Electron

27
 ACCEPTED MANUSCRIPT

Optics. 130 (2017) 162–170. doi:10.1016/j.ijleo.2016.11.010.

[32] N. Kannan, S. Subbalaxmi, Green Synthesis of Silver Nanoparticles using Bacillus
subtillus IA751 and its Antimicrobial Activity, Research Journal of Nanoscience and
Nanotechnology. 1 (2011) 87–94. doi:10.3923/rjnn.2011.87.94.
[33] S. Li, Y. Shen, A. Xie, X. Yu, L. Qiu, L. Zhang, Q. Zhang, Green synthesis of silver
nanoparticles using Capsicum annuum L. extract, Green Chemistry. 9 (2007) 852.
doi:10.1039/b615357g.
[34] S.M. Pourmortazavi, M. Taghdiri, V. Makari, M. Rahimi-Nasrabadi, Procedure
optimization for green synthesis of silver nanoparticles by aqueous extract of

PT
Eucalyptus oleosa, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy. 136 (2015) 1249–1254. doi:10.1016/j.saa.2014.10.010.
[35] H. Bar, D.K. Bhui, G.P. Sahoo, P. Sarkar, S.P. De, A. Misra, Green synthesis of silver

RI
nanoparticles using latex of Jatropha curcas, Colloids and Surfaces A:
Physicochemical and Engineering Aspects. 339 (2009) 134–139.

SC
doi:10.1016/j.colsurfa.2009.02.008.
[36] V. Kumar, D.K. Singh, S. Mohan, R.K. Gundampati, S.H. Hasan, Photoinduced green
synthesis of silver nanoparticles using aqueous extract of Physalis angulata and its
NU
antibacterial and antioxidant activity, Journal of Environmental Chemical Engineering.
5 (2017) 744–756. doi:10.1016/j.jece.2016.12.055.
[37] V.K. Sharma, R.A. Yngard, Y. Lin, Silver nanoparticles: Green synthesis and their
MA

antimicrobial activities, Advances in Colloid and Interface Science. 145 (2009) 83–96.
doi:10.1016/j.cis.2008.09.002.
[38] Y. Anzabi, Biosynthesis of ZnO nanoparticles using barberry (Berberis vulgaris)
D

extract and assessment of their physico-chemical properties and antibacterial activities,

Green Processing and Synthesis. 7 (2018) 114–121. doi:10.1515/gps-2017-0014.
TE

[39] F.M. Mohammadi, N. Ghasemi, Influence of temperature and concentration on

biosynthesis and characterization of zinc oxide nanoparticles using cherry extract,
EP

Journal of Nanostructure in Chemistry. 8 (2018) 93–102. doi:10.1007/s40097-018-

0257-6.
[40] R. Jalal, E.K. Goharshadi, M. Abareshi, M. Moosavi, A. Yousefi, P. Nancarrow, ZnO
C

nanofluids: Green synthesis, characterization, and antibacterial activity, Materials

Chemistry and Physics. 121 (2010) 198–201.
AC

doi:10.1016/j.matchemphys.2010.01.020.
[41] C. Vidya., C. Manjunatha., M.. Chandraprabha., M. Rajshekar, A. Raj.M.A.L, Hazard
free green synthesis of ZnO nano-photo-catalyst using Artocarpus Heterophyllus leaf
extract for the degradation of Congo red dye in water treatment applications, Journal of
Environmental Chemical Engineering. 5 (2017) 3172–3180.
doi:10.1016/j.jece.2017.05.058.
[42] G. Sangeetha, S. Rajeshwari, R. Venckatesh, Green synthesis of zinc oxide
nanoparticles by aloe barbadensis miller leaf extract: Structure and optical properties,
Materials Research Bulletin. 46 (2011) 2560–2566.
doi:10.1016/j.materresbull.2011.07.046.
[43] S.S.M. Hassan, W.I.M. El Azab, H.R. Ali, M.S.M. Mansour, Green synthesis and

28
 ACCEPTED MANUSCRIPT

characterization of ZnO nanoparticles for photocatalytic degradation of anthracene,

Advances in Natural Sciences: Nanoscience and Nanotechnology. 6 (2015) 45012.
doi:10.1088/2043-6262/6/4/045012.
[44] S. Gunalan, R. Sivaraj, V. Rajendran, Green synthesized ZnO nanoparticles against
bacterial and fungal pathogens, Progress in Natural Science: Materials International.
22 (2012) 693–700. doi:10.1016/j.pnsc.2012.11.015.
[45] S. Azizi, M.B. Ahmad, F. Namvar, R. Mohamad, Green biosynthesis and
characterization of zinc oxide nanoparticles using brown marine macroalga Sargassum
muticum aqueous extract, Materials Letters. 116 (2014) 275–277.
doi:10.1016/j.matlet.2013.11.038.

PT
[46] S. Gunalan, R. Sivaraj, R. Venckatesh, Aloe barbadensis Miller mediated green
synthesis of mono-disperse copper oxide nanoparticles: Optical properties,

RI
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 97 (2012)
1140–1144. doi:10.1016/j.saa.2012.07.096.

SC
[47] R. Sankar, P. Manikandan, V. Malarvizhi, T. Fathima, K.S. Shivashangari, V.
Ravikumar, Green synthesis of colloidal copper oxide nanoparticles using Carica
papaya and its application in photocatalytic dye degradation, Spectrochimica Acta Part
NU
A: Molecular and Biomolecular Spectroscopy. 121 (2014) 746–750.
doi:10.1016/j.saa.2013.12.020.
[48] M. Maham, S.M. Sajadi, M.M. Kharimkhani, M. Nasrollahzadeh, Biosynthesis of the
MA

CuO nanoparticles using Euphorbia Chamaesyce leaf extract and investigation of their
catalytic activity for the reduction of 4-nitrophenol, IET Nanobiotechnology. 11 (2017)
766–772. doi:10.1049/iet-nbt.2016.0254.
[49] S. Yallappa, J. Manjanna, M.A. Sindhe, N.D. Satyanarayan, S.N. Pramod, K.
D

Nagaraja, Microwave assisted rapid synthesis and biological evaluation of stable

copper nanoparticles using T. arjuna bark extract, Spectrochimica Acta Part A:
TE

Molecular and Biomolecular Spectroscopy. 110 (2013) 108–115.

doi:10.1016/j.saa.2013.03.005.
EP

[50] Z. Wang, H. Zhu, X. Wang, F. Yang, X. Yang, One-pot green synthesis of

biocompatible arginine-stabilized magnetic nanoparticles, Nanotechnology. 20 (2009)
465606. doi:10.1088/0957-4484/20/46/465606.
C

[51] D. Sharma, S. Kanchi, K. Bisetty, Biogenic synthesis of nanoparticles: A review,

AC

Arabian Journal of Chemistry. (2015). doi:10.1016/j.arabjc.2015.11.002.

[52] A.K. Mittal, Y. Chisti, U.C. Banerjee, Synthesis of metallic nanoparticles using plant
extracts, Biotechnology Advances. 31 (2013) 346–356.
doi:10.1016/j.biotechadv.2013.01.003.
[53] N.I. Hulkoti, T.C. Taranath, Biosynthesis of nanoparticles using microbes—A review,
Colloids and Surfaces B: Biointerfaces. 121 (2014) 474–483.
doi:10.1016/j.colsurfb.2014.05.027.
[54] C. Li, C. Ma, F. Wang, Z. Xi, Z. Wang, Y. Deng, N. He, Preparation and Biomedical
Applications of Core–Shell Silica/Magnetic Nanoparticle Composites, Journal of
Nanoscience and Nanotechnology. 12 (2012) 2964–2972. doi:10.1166/jnn.2012.6428.
[55] R. Ghosh Chaudhuri, S. Paria, Core/shell nanoparticles: Classes, properties, synthesis

29
 ACCEPTED MANUSCRIPT

mechanisms, characterization, and applications, Chemical Reviews. 112 (2012) 2373–

2433. doi:10.1021/cr100449n.
[56] O. V. Kharissova, H.V.R. Dias, B.I. Kharisov, B.O. Pérez, V.M.J. Pérez, The greener
synthesis of nanoparticles, Trends in Biotechnology. 31 (2013) 240–248.
doi:10.1016/j.tibtech.2013.01.003.
[57] H. Veeramani, D. Aruguete, N. Monsegue, M. Murayama, U. Dippon, A. Kappler,
M.F. Hochella, Low-Temperature Green Synthesis of Multivalent Manganese Oxide
Nanowires, ACS Sustainable Chemistry & Engineering. 1 (2013) 1070–1074.
doi:10.1021/sc400129n.

PT
[58] A. Asaikkutti, P.S. Bhavan, K. Vimala, M. Karthik, P. Cheruparambath, Dietary
supplementation of green synthesized manganese-oxide nanoparticles and its effect on
growth performance, muscle composition and digestive enzyme activities of the giant

RI
freshwater prawn Macrobrachium rosenbergii, Journal of Trace Elements in Medicine
and Biology. 35 (2016) 7–17. doi:10.1016/j.jtemb.2016.01.005.

SC
[59] A.S. Prasad, Green synthesis of nanocrystalline manganese (II, III) oxide, Materials
Science in Semiconductor Processing. 71 (2017) 342–347.
doi:10.1016/j.mssp.2017.08.020.
NU
[60] A. Sinha, V.N. Singh, B.R. Mehta, S.K. Khare, Synthesis and characterization of
monodispersed orthorhombic manganese oxide nanoparticles produced by Bacillus sp.
cells simultaneous to its bioremediation, Journal of Hazardous Materials. 192 (2011)
MA

620–627. doi:10.1016/j.jhazmat.2011.05.103.
[61] V. Kumar, K. Singh, S. Panwar, S.K. Mehta, Green synthesis of manganese oxide
nanoparticles for the electrochemical sensing of p-nitrophenol, International Nano
Letters. 7 (2017) 123–131. doi:10.1007/s40089-017-0205-3.
D

[62] H. Zhang, A. Wu, H. Fu, L. Zhang, H. Liu, S. Zheng, H. Wan, Z. Xu, Efficient
TE

removal of Pb( <scp>ii</scp> ) ions using manganese oxides: the role of crystal
structure, RSC Advances. 7 (2017) 41228–41240. doi:10.1039/C7RA05955H.
EP

[63] M. Jayandran, M. Haneefa, V. Balasubramanian, Green synthesis and characterization

of Manganese nanoparticles using natural plant extracts and its evaluation of
antimicrobial activity, Journal of Applied Pharmaceutical Science. 1 (2015) 105–110.
doi:10.7324/JAPS.2015.501218.
C

[64] M. Souri, V. Hoseinpour, A. Shakeri, N. Ghaemi, Optimisation of green synthesis of

AC

MnO nanoparticles via utilising response surface methodology, IET

Nanobiotechnology. 12 (2018) 822–827. doi:10.1049/iet-nbt.2017.0145.
[65] E. Sathiyamoorthi, S.A. Moon, B. Alkotaini, B.S. Kim, B.K. Salunke, Biological
synthesis of manganese dioxide nanoparticles by Kalopanax pictus plant extract, IET
Nanobiotechnology. 9 (2015) 220–225. doi:10.1049/iet-nbt.2014.0051.
[66] K.S. Prasad, A. Patra, Green synthesis of MnO2 nanorods using Phyllanthus amarus
plant extract and their fluorescence studies, Green Processing and Synthesis. (2017) 1–
7. doi:10.1515/gps-2016-0166.
[67] S. Chen, J. Zhu, X. Wu, Q. Han, X. Wang, Graphene Oxide−MnO 2 Nanocomposites
for Supercapacitors, ACS Nano. 4 (2010) 2822–2830. doi:10.1021/nn901311t.
[68] J.B. Fei, Y. Cui, X.H. Yan, W. Qi, Y. Yang, K.W. Wang, Q. He, J.B. Li, Controlled
30
 ACCEPTED MANUSCRIPT

Preparation of MnO2 Hierarchical Hollow Nanostructures and Their Application in

Water Treatment, Advanced Materials. 20 (2008) 452–456.
doi:10.1002/adma.200701231.
[69] I. Djerdj, D. Arčon, Z. Jagličić, M. Niederberger, Nonaqueous Synthesis of Manganese
Oxide Nanoparticles, Structural Characterization, and Magnetic Properties, The
Journal of Physical Chemistry C. 111 (2007) 3614–3623. doi:10.1021/jp067302t.
[70] S. Bajpai, M. Chaudhuri, Removal of Arsenic from Ground Water by Manganese
Dioxide–Coated Sand, Journal of Environmental Engineering. 125 (1999) 782–784.
doi:10.1061/(ASCE)0733-9372(1999)125:8(782).

PT
[71] T.-D. Dang, M. a. Cheney, S. Qian, S.W. Joo, B.-K. Min, A Novel Rapid One-Step
Synthesis of Manganese Oxide Nanoparticles at Room Temperature Using
Poly(dimethylsiloxane), Industrial & Engineering Chemistry Research. 52 (2013)

RI
2750–2753. doi:10.1021/ie302971g.
[72] M. Vanaja, G. Annadurai, Coleus aromaticus leaf extract mediated synthesis of silver

SC
nanoparticles and its bactericidal activity, Applied Nanoscience. 3 (2013) 217–223.
doi:10.1007/s13204-012-0121-9.
[73] M. Souri, A. Shakeri, Comparison of Microwave and Ultrasound Assisted extraction
NU
methods on total Phenol and Tannin Content and Biological Activity of Dittrichia
graveolens (L.) GREUTER and Its Optimisation by Response Surface Methodology,
Current Bioactive Compounds. 14 (2018).
MA

doi:10.2174/1573407214666180730110830.
[74] V. Hoseinpour, M. Souri, N. Ghaemi, Green synthesis, characterisation, and
photocatalytic activity of manganese dioxide nanoparticles, Micro & Nano Letters.
(2018). doi:10.1049/mnl.2018.5008.
D

[75] S.S. Waghmare, a M. Deshmukh, S.W. Kulkarni, L. a Oswaldo, Biosynthesis and

TE

Characterization of Manganese and Zinc Nanoparticles, Universal Journal of

Environmental Research and Technology. 1 (2011) 64–69.
EP

[76] J.-W. Moon, C.J. Rawn, A.J. Rondinone, L.J. Love, Y. Roh, S.M. Everett, R.J. Lauf,
T.J. Phelps, Large-scale production of magnetic nanoparticles using bacterial
fermentation, Journal of Industrial Microbiology & Biotechnology. 37 (2010) 1023–
1031. doi:10.1007/s10295-010-0749-y.
C

[77] S. Jana, S. Pande, A.K. Sinha, S. Sarkar, M. Pradhan, M. Basu, S. Saha, T. Pal, A
AC

Green Chemistry Approach for the Synthesis of Flower-like Ag-Doped MnO 2

Nanostructures Probed by Surface-Enhanced Raman Spectroscopy, The Journal of
Physical Chemistry C. 113 (2009) 1386–1392. doi:10.1021/jp809561p.
[78] Q.I. Rahman, M. Ahmad, S.K. Misra, M. Lohani, Effective photocatalytic degradation
of rhodamine B dye by ZnO nanoparticles, Materials Letters. 91 (2013) 170–174.
doi:10.1016/j.matlet.2012.09.044.
[79] S.-Y. Pung, Y.-L. Chan, S. Sreekantan, F.-Y. Yeoh, Photocatalytic activity of ZnO-
MnO 2 core shell nanocomposite in degradation of RhB dye, Pigment & Resin
Technology. 45 (2016) 408–418. doi:10.1108/PRT-08-2015-0082.
[80] J. Wang, W.-D. Zhang, W.-X. Ouyang, Y.-X. Yu, Hierarchically branched ZnO/CuO
thin film with enhanced visible light photoelectrochemical property, Materials Letters.

31
 ACCEPTED MANUSCRIPT

154 (2015) 44–46. doi:10.1016/j.matlet.2015.04.048.

[81] H. Agarwal, S. Venkat Kumar, S. Rajeshkumar, A review on green synthesis of zinc
oxide nanoparticles – An eco-friendly approach, Resource-Efficient Technologies. 3
(2017) 406–413. doi:10.1016/j.reffit.2017.03.002.
[82] C.-H. Hsu, L.-C. Chen, Y.-F. Lin, Preparation and Optoelectronic Characteristics of
ZnO/CuO-Cu2O Complex Inverse Heterostructure with GaP Buffer for Solar Cell
Applications, Materials. 6 (2013) 4479–4488. doi:10.3390/ma6104479.
[83] R.R. Thankalekshmi, S. Dixit, A.C. Rastogi, K. Samanta, R.S. Katiyar, Closed-Space
Flux Sublimation Growth and Properties of (Cu-Mn)-Doped ZnO Films in

PT
Nanoneedle-Like Morphologies, Integrated Ferroelectrics. 125 (2011) 130–140.
doi:10.1080/10584587.2011.574470.
[84] J.-W. Moon, Y. Roh, R.J. Lauf, H. Vali, L.W. Yeary, T.J. Phelps, Microbial

RI
preparation of metal-substituted magnetite nanoparticles, Journal of Microbiological
Methods. 70 (2007) 150–158. doi:10.1016/j.mimet.2007.04.012.

SC
[85] M. Nagy, P. Otremba, C. Krüger, S. Bergner-Greiner, P. Anders, B. Henske, M. Prinz,
L. Roewer, Optimization and validation of a fully automated silica-coated magnetic
beads purification technology in forensics, Forensic Science International. 152 (2005)
NU
13–22. doi:10.1016/j.forsciint.2005.02.027.
[86] R. Kishore, W. Reef Hardy, V.J. Anderson, N.A. Sanchez, M.R. Buoncristiani,
Optimization of DNA Extraction from Low-Yield and Degraded Samples Using the
MA

BioRobot EZ1 and BioRobot M48, Journal of Forensic Sciences. 51 (2006) 1055–
1061. doi:10.1111/j.1556-4029.2006.00204.x.
[87] D.D. Mamaev, D.A. Khodakov, E.I. Dementieva, I. V. Filatov, D.A. Yurasov, A.I.
D

Cherepanov, V.A. Vasiliskov, O. V. Smoldovskaya, D. V. Zimenkov, D.A.

Gryadunov, V.M. Mikhailovich, A.S. Zasedatelev, Method for automated extraction
TE

and purification of nucleic acids and its implementation in microfluidic system,

Applied Biochemistry and Microbiology. 47 (2011) 211–220.
doi:10.1134/S0003683811020128.
EP

[88] B. Rittich, A. Spanova, SPE and purification of DNA using magnetic particles, J Sep
Sci. 36 (2013) 2472–2485. doi:10.1002/jssc.201300331.
C

[89] T. Takamatsu, M. Kawashima, M. Koyama, The role of Mn2+-rich hydrous

manganese oxide in the accumulation of arsenic in lake sediments, Water Research. 19
AC

(1985) 1029–1032. doi:10.1016/0043-1354(85)90372-0.

[90] D.W. Oscarson, P.M. Huang, W.K. Liaw, U.T. Hammer, Kinetics of Oxidation of
Arsenite by Various Manganese Dioxides1, Soil Science Society of America Journal.
47 (1983) 644. doi:10.2136/sssaj1983.03615995004700040007x.
[91] L.M. Camacho, R.R. Parra, S. Deng, Arsenic removal from groundwater by MnO2-
modified natural clinoptilolite zeolite: Effects of pH and initial feed concentration,
Journal of Hazardous Materials. 189 (2011) 286–293.
doi:10.1016/j.jhazmat.2011.02.035.
[92] R.A. Root, S. Fathordoobadi, F. Alday, W. Ela, J. Chorover, Microscale Speciation of
Arsenic and Iron in Ferric-Based Sorbents Subjected to Simulated Landfill Conditions,
Environmental Science & Technology. 47 (2013) 12992–13000.

32
 ACCEPTED MANUSCRIPT

doi:10.1021/es402083h.
[93] M.M. Najafpour, F. Rahimi, M. Amini, S. Nayeri, M. Bagherzadeh, A very simple
method to synthesize nano-sized manganese oxide: an efficient catalyst for water
oxidation and epoxidation of olefins, Dalton Transactions. 41 (2012) 11026.
doi:10.1039/c2dt30553d.
[94] S. Biswas, S. Kar, S. Chaudhuri, Optical and Magnetic Properties of Manganese-
Incorporated Zinc Sulfide Nanorods Synthesized by a Solvothermal Process, The
Journal of Physical Chemistry B. 109 (2005) 17526–17530. doi:10.1021/jp053138i.
[95] H.Y. Wang, F.X. Xiao, L. Yu, B. Liu, X.W. Lou, Hierarchical α-MnO2

PT
nanowires@Ni1-xMn xOy nanoflakes core-shell nanostructures for supercapacitors,
Small. 10 (2014) 3181–3186. doi:10.1002/smll.201303836.
[96] B. Xu, C.R. Fell, M. Chi, Y.S. Meng, Identifying surface structural changes in layered

RI
Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint
experimental and theoretical study, Energy & Environmental Science. 4 (2011) 2223.

SC
doi:10.1039/c1ee01131f.
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Highlights

 Methods of green synthesis of Mn NPs was reviewed.

 Different applications of green synthesized Mn NPs were reviewed.
 Future perspective of green synthesis of Mn NPs was studied.
 Future perspective of applications of green synthesis of Mn NPs was studied.

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