1 s2.0 S0734975022000015 Main

Biotechnology Advances 58 (2022) 107905
Contents lists available at ScienceDirect
Biotechnology Advances
journal homepage: www.elsevier.com/locate/biotechadv
Research review paper
Antimicrobial properties and applications of metal nanoparticles

biosynthesized by green methods
Olga Maťátková *, Jana Michailidu , Anna Miškovská , Irena Kolouchová , Jan Masák ,
Alena Čejková
University of Chemistry and Technology, Prague, Department of Biotechnology, Technická 5, Prague 6, 166 28, Czechia
A R T I C L E I N F O A B S T R A C T
Keywords: There is a growing interest in the potential and application of metal nanoparticles across many fields. A vast
Metal nanoparticles biosynthesis array of techniques for metal nanoparticle synthesis has been discovered; however, sustainability, cost-
Green methods effectiveness, and environmental concerns favor the green biological approach, using various plant and micro
Antimicrobial properties
bial sources. This review describes the diversity in green methods for nanoparticle biosynthesis, antimicrobial
Nanoparticles application
Limitations and safety
properties of metal nanoparticles and their potential applications. Metal nanoparticle biosynthesis by extracts
and solutions obtained from plants, bacteria, fungi and templates such as viruses are discussed. As biosynthesized
nanoparticles have been proven to possess antibacterial, antifungal, and even antiviral properties, these are
discussed in detail, with silver and gold nanoparticles as the most studied and with the highest potential for
medical application. The focus on prospective antimicrobial applications of nanoparticles stems from the arising
resistance of many serious pathogens to traditional disinfectants and antibiotics. Other fields for the application
of biosynthesized nanoparticles are also stated briefly, such as in agriculture as pesticides, in wastewater
treatment and bioremediation. Finally, the limitations and safety issues connected with widespread use of
nanoparticles are discussed.
1. Introduction et al., 2012), but also in their biological activity, such as antimicrobial or
antiviral (Dikshit et al., 2021; Salem and Fouda, 2021). In the nanoscale,
The field of nanotechnology concerns the engineering, production the surface to volume ratio changes considerably, which results in
and application of materials in the scale range of 1 to 100 nm. During the higher reactivity in comparison with the parent material (Sahoo et al.,
last decades, nanotechnology has become one of the most researched 2021). The material composition of NPs can include various metals (and
fields due to its broad potential and many applications in various in metal oxides and salts), non-metal elements (such as carbon nanotubes,
dustrial fields. The number of research publications in the last 20 years, graphenes, and fullerenes), organic nanomaterials (e.g. lipid based NPs)
based on Web of Science search with keywords “biosynthesis” and or hybrids and composites (polymers, ceramics, cements etc.) (Khar
“metal nanoparticles” steadily increased during the timeframe, with a issova et al., 2019).
maximum of 612 publications in 2019. This research interest in bio Nanoparticles can be formed in natural environment, via abiotic and
logical methods of metal nanoparticles (NPs) synthesis is demonstrated biotic mechanisms, including precipitation, erosion, combustion or
in Fig. 1. volcanic activities (Sharma et al., 2015). Although the natural routes of
Nanoparticles often exhibit unique physio-chemical properties, NPs synthesis are being explored, many methods were devised to create
differing significantly from their macroscale counterparts. These dif synthetic NPs, including physical, chemical and biological approaches,
ferences and subsequent application potential are reflected in their op see Fig. 2 (Maurer-Jones et al., 2013; Salem and Fouda, 2021). These
tical, mechanical, chemical, magnetic, and electrical properties (He methods can be classified as either “top-down” or “bottom-up” (Das
et al., 2008; Khan and Fulekar, 2016; Kimber et al., 2018; Valizadeh et al., 2017; Thakkar et al., 2010).
Abbreviations: DNA, deoxyribonucleic acid; MBC, minimum bactericidal concentration; MFC, minimum fungicidal concentration; MIC, minimum inhibitory
concentration; NPs, nanoparticles; OD, optical density; RNA, ribonucleic acid; ROS, reactive oxygen species.
* Corresponding author.
E-mail address: [email protected] (O. Maťátková).
https://doi.org/10.1016/j.biotechadv.2022.107905
Received 14 September 2021; Received in revised form 15 December 2021; Accepted 7 January 2022
Available online 11 January 2022
0734-9750/© 2022 Elsevier Inc. All rights reserved.
O. Mať átková et al. Biotechnology Advances 58 (2022) 107905
The top-down approach usually encompasses nanoparticle produc with the NPs source is the main focus of this review. Additionally,
tion by size reduction from bulk material and is the basis of most various applications and limitations of NPs are discussed, as well as
physical methods (such as pulsed laser ablation, spray pyrolysis, perspectives, challenges and ongoing research into as yet unanswered
evaporation-condensation, ball milling, plasma arc, vapor and gas phase questions regarding the environmental toxicity of various NPs.
and lithography (Iravani et al., 2014; Kharissova et al., 2019; Shnoudeh
et al., 2019)). The methods which produce NPs from smaller building 2. Green NPs Synthesis
blocks (such as atoms and molecules) belong to the bottom-up approach
and can be found among chemical synthesis methods (e.g. micro In NP production, green methods employ substances with a biolog
emulsion, coprecipitation, chemical reduction, electrochemical, micro ical origin as reducing agents (metal ion reduction), capping agents and
wave, sonochemical, solvothermal and thermal decomposition) and stabilizers (shape, size control and prevention of agglomeration) and as
green biological synthesis methods, which are based on elimination of ligands (coating of NPs surface, metal passivation) (Kharissova et al.,
hazardous substances via employment of biological catalysts, such as 2019). Biological reducing agents can include small molecules like H2,
plant extracts or microbial cell-based systems (see section 2). Biological but they are more commonly larger water soluble biomolecules such as
synthesis methods using whole organisms or biological molecules bring reducing polysaccharides, various enzymes, amides, ketones, aldehydes,
significant advantages over physical and chemical methods as they carboxylic acids, polyphenols, flavonoids, alkaloids and terpenoids
represent non-toxic and more sustainable approaches to NPs synthesis (Jeevanandam et al., 2016; Nasrollahzadeh and Sajadi, 2015a; Prabhu
(Das et al., 2017; Salem and Fouda, 2021). The green chemistry and Poulose, 2012). Polysaccharides, proteins and peptides are consid
approach has been defined as a “design of chemical products and pro ered suitable capping agents and stabilizers, while typical ligands
cesses to reduce or eliminate the use and generation of hazardous sub include amines, thiols, and phosphines (Kharissova et al., 2019). These
stances”, with its main aim being the modernization of traditional biological agents can include complex mixtures or individual com
chemistry processes with a focus on environmental issues, efficiency and pounds (vitamins, saccharides, polyphenols) derived from plants (whole
economy (de Souza et al., 2019; Horton, 1999; Salem and Fouda, 2021). plants, plant products, extracts) or microorganisms (whole cell, cell-free
Green synthesis methods are usually regarded as environmentally- extracts; bacteria, fungi and actinomycetes, algae etc.), in both intra
friendly, biocompatible processes, usually conducted at mild pH (4–9) cellular and extracellular settings in both living and inactivated cells
(Akl et al., 2020; Desai et al., 2020; Kredy, 2018), pressure (atmospheric (Ahmad et al., 2019; Mohamed et al., 2019; Varma, 2012), see Fig. 3.
pressure) (Vijayaraghavan and Ashokkumar, 2017; Voeikova et al., The use of templates such as biomolecules, DNA, membranes, and vi
2020), and temperature (room temperature) (Lade and Shanware, ruses has also been reported (de Souza et al., 2019; Lee et al., 2002;
2020), avoiding hazardous materials and conditions and also cost Rafique et al., 2017). NPs could be synthesized using single bio
effective (Salem and Fouda, 2021). molecules from nature origin, for example various noble metal nano
This critical review concerns biological (“green”) methods of metal particles were synthesized using glutathione (Ag, Au, Pt, Pd) or
NPs synthesis using plant material and extracts, bacteria, fungi, algae riboflavin (Au, Pt) (Baruwati et al., 2009; Nadagouda and Varma, 2006).
and even viruses and other templates and discussed their properties and The biomolecules in this instance serve as reducing and stabilizing
applications. The antibacterial, antifungal and antiviral properties are agents.
discussed in detail and the interconnection of antimicrobial properties The biological synthesis of NPs is carried out by combining a metal
Fig. 1. Web of Science analysis of research publications on the biosynthesis of metal nanoparticles in the last 20 years.
2
precursor compound (salts, acids) with a biological agent under specific applicability of original research on NPs biosynthesis into their large
conditions (Nath and Banerjee, 2013). Studies on biological synthesis of scale industrial production, which can be benefited by the use of key
NPs using various biological agents include metals and their derivative variables determination, e.g. with modelling, such as proposed by Cin
compounds, often aiming to produce Ag, Au, Zn, Ni, Pd, Pt, Se, and Cu elli et al. (2015) – see chapter 4.5.1 for further discussion.
nanoparticles (Dikshit et al., 2021). Specifically, metal compounds such The two main biological systems used for the synthesis of metal NPs
as AgNO3, HAuCl4, (CH3COO)2Zn, (NiNO3)2FeCl3, PdCl2, H2PtCl6, are summarized in the following sections – plant and microbial NPs
Na2SeO3 and Cu(NO3)2 are commonly used for the synthesis of their synthesis.
respective metal NPs (Dikshit et al., 2021). The presence of specific
suitable biomolecules results in the reduction, capping, and stabilizing 2.1. Plant-mediated NPs biosynthesis
of the parent metal compound in the form of NPs (Dikshit et al., 2021;
Kuppusamy et al., 2016). The biosynthesis of NPs using plants originates in the ability of plants
The technological implementation of the biological NPs synthesis to avoid toxic effects of excess metals by various mechanisms. Com
depends mainly on the type of bioagent. For example, the synthesis of pounds with antioxidant properties play an important role in these
metal NPs using plant extracts usually begins with collecting and protective processes, as many metals generate ROS whose activity can
washing the desired part of the plant (leaf, fruit, peel, etc.) with distilled result in serious damage to the cell (Kharissova et al., 2019). For
water, followed by drying, crushing and finally extraction into water/ example, plant antioxidant mechanisms can be facilitated by phenolic
solvent (most often ethanol or methanol) (Mohamad et al., 2014). The compounds. Accumulation of metals and their reduction and stabiliza
solid plant residues are then separated from the extract by filtration or tion inside plant tissues has been studied with respect to bioremediation
centrifugation and mixed with the metal precursor compound under applications (phytoremediation). The research into these processes led
certain conditions. The reaction time (and thus the characteristics of to the observation of metal deposits in plants in the form of NPs (Gardea-
nanoparticles) is influenced by the ratio of reactant concentrations, Torresdey et al., 2002; Makarov et al., 2014).
temperature, pH, light, ultrasound or microwave heating, which are NPs synthetized with the use of plant material will differ in their
among the leading parameters modified to achieve optimal NPs syn properties, size and shapes depending on several factors which can be
thesis (Mittal et al., 2013; Varma, 2012). After incubation, the nano immutable (presence of compounds in specific plants acting as reducing
particles are usually centrifuged at high speed, washed thoroughly in or capping agents) and variable (extraction method, synthesis condi
water/solvent (ethanol, methanol), and collected (Singh et al., 2016), tions, such as temperature, pH, reaction time, concentration of metal
alternatively they can be applied without separating the extract. The parent compound etc.) (El-Seedi et al., 2019; Kharissova et al., 2019;
amount and morphology (shape, size distribution) of the resulting Marslin et al., 2018; Mohammadinejad et al., 2016).
nanoparticles are greatly influenced by the reaction conditions. The There is a large number of studies reporting on the synthesis of
source from which the extract is prepared has also a major influence, various metal NPs using many different plants (Das et al., 2017; Dikshit
because individual plant extracts can differ significantly in content and et al., 2021; Mittal et al., 2013; Shankar et al., 2003; Sheny et al., 2013),
combination of reducing and stabilizing biomolecules (Kumar and see Table 1. The methods of NPs biosynthesis mediated by plants use
Yadav, 2009). three main approaches; the use of whole plants, plant extracts, and in
It is important to address quality of research in the context of green dividual isolated phytochemicals (Dikshit et al., 2021).
methods as there definitely seems to be room for improvement. There
are many studies where insufficient data about the production method is 2.1.1. Whole plant mediated NPs biosynthesis
given e.g., specification of reagent ratios, reaction conditions etc. In The use of whole plants for metal NPs synthesis is based on the up
formation about sample preparation for characterization is not present take of metals from the environment by the plant and subsequent
in most studies. Moreover, results from analyses are often poorly com intracellular reduction and accumulation in the form of NPs.
mented and are not discussed sufficiently in several present studies. This process is assisted by many compounds, such as amino acids,
Finally, determination of concentration is a severe issue in studies alkaloids, flavones, proteins, polyphenols, polysaccharides, tannins,
concerning biosynthesis of metal nanoparticles, with some studies tak terpenoids, and vitamins (Ahmad et al., 2010; El-Seedi et al., 2019). This
ing scientifically unsound shortcuts, such as calculating nanoparticle method leads to a great variation in the NP properties due to the
concentration directly from the initial concentration of precursor, thus complexity of the process and lower possibility of its regulation. In a
assuming 100 % yield. Another issue not often discussed is the whole plant synthesis, the NPs can be located in various plant parts and
Fig. 2. Routes of nanoparticles synthesis – biological, chemical, and physical methods.
3
Fig. 3. Plant and microbial processes employed for green synthesis of NPs.
cell types; studies reported widespread localization (epidermis, cortex, citrus or banana peel extracts (Bankar et al., 2010; Castro et al., 2015),
and vascular tissue) with the majority of NPs being found in xylem pa aiding the profitability of the life cycle analysis of the total production
renchyma cells (Corredor et al., 2009; Marchiol et al., 2014; Sharma cost and conveniently exploiting waste materials as resources. For
et al., 2007). The localization of NPs significantly influences the example aqueous extract from grape pomace was used for successful
complexity of the subsequent process of NPs isolation and purification. biosynthesis of silver, gold, platinum and palladium NPs (Baruwati and
The use of plants for the preparation of metal NPs had been motivated by Varma, 2009).
their well-known ability to phytoremediate heavy metals from the The plant extracts can be obtained by various methods, such as hot/
environment. In order to synthesize nanoparticles using whole plants, it cold extraction, Soxhlet extraction and with the aid of different solvents
is necessary to enrich the soil or surrounding medium with a soluble (Dikshit et al., 2021). The molecular composition of the extract is key for
form of the respective metal ions (Iravani, 2011). Whole plant synthesis the viability of the process of metal reduction and NPs capping and
of silver nanoparticles was successfully achieved with the use of Mesa stabilization. However, due to the high complexity and variability of
variety alfalfa sprouts grown on silver-rich solid medium (from 40 to plant extracts, the respective roles of individual compounds are largely
320 mg/L of silver). After 9 days, the sprouts were harvested, freeze- unknown (Dikshit et al., 2021). The compounds participating in the
dried and pulverized into homogenous powder. Characterization of reduction of metal ions are known to include hydroxyl, carbonyl, amino,
the sprouts revealed successful production of silver nanoparticles and methoxide functional groups, all of which exhibit electrostatic in
ranging from 2 to 20 nm in diameter (Gardea-Torresdey et al., 2003). teractions with metal ions followed by the reduction reaction (El-Seedi
Synthesis of both silver and gold NPs by Medicago sativa and Brassica et al., 2019; Küünal et al., 2018). Important role in the process is played
juncea cultivated using aqueous substrate containing AgNO3 (from 1000 by plant secondary metabolites, alkaloids, cofactors, enzymes, flavo
to 10 000 mg/L) and KAuCl4 (1000 mg/L), respectively, was reported by noids, polyphenols, etc. (El-Seedi et al., 2019).
Bali and Harris (2010); Harris and Bali (2008). The NPs synthesis using plant extracts is carried out by combining
the plant extract with a solution containing metal ions (utilizing metal
2.1.2. Plant extract mediated NPs biosynthesis salts or acids) under controlled conditions, such as pH, temperature,
The use of plant extracts or individual plant substances utilizes a reaction time, oxygen and light exposure, etc. (Dikshit et al., 2021). The
simpler approach (in contrast to whole plant biosynthesis) with a po composition of the plant extract and its concentration (as well as the
tential for higher control and versatility, higher yield, simpler isolation metal compound concentration) mainly determine the NP morphology,
and scale-up, therefore earning most of the scientific focus in the field of while the reaction conditions (temperature, pH) are reported to modify
plant-based NPs biosynthesis (Dikshit et al., 2021; Mittal et al., 2013; the size of the NPs (Castro et al., 2011; Salayová et al., 2021; Sankar
Thakkar et al., 2010). et al., 2014). For example, spherical AuNPs (2–10 nm) were synthesized
Extracts of various plants and different parts of said plants have been using Nerium oleander leaf extract from dried, ground N. oleander leaves
used in the synthesis of metal NPs. The plant extracts can be made from which were mixed with water (0.1 g/ml) and stirred at 60 ◦ C for 5 hours.
roots, stems, bark, leaves, flowers, fruits, seeds etc. (Dikshit et al., 2021). Filtered extract was mixed with chloroauric acid to produce the NPs
Successful biosynthesis of noble metal nanoparticles (Ag, Au, Pt, Pd) was (Tahir et al., 2015).
reported using fruit extracts of blackberry, blueberry and pomegranate, Using Gnidia glauca flower extract, variable shapes (triangular,
root extracts of turmeric or beet and aqueous extracts from green tea hexagonal, spherical) of gold nanoparticles of sizes 50–150 nm were
(leaves) and coffee (Kou and Varma, 2012a; Nadagouda et al., 2014; obtained (Ghosh et al., 2012).
Nadagouda and Varma, 2008). As the management of food and agri The plant extract synthesis of metal NPs can be divided into several
culture waste products has emerged as a major concern in recent years, successive stages. The process starts with the activation step, i.e.
the NPs synthesis using derivatives of agricultural plants rich in bio reduction of metal ions to metal atoms, and is followed by the nucleation
logically active substances present an opportunity for utilization and of the reduced metal atoms into smallest NPs and further into larger
exploitation of such materials. Therefore, the plant NPs synthesis can sized NPs, accompanied by an increase in thermodynamic stability of the
utilize materials that originate as food or agriculture waste, such as dispersion. It was found that higher temperatures yield larger
4
Table 1
Plant-synthesized metal NPs and their properties.
NPs Plant species Size (nm) Applications Ref.
Whole plant
Au Brassica juncea 5–10 – (Bali and Harris, 2010)
Medicago sativa 10–20 – (Bali and Harris, 2010)
Plant extracts
Allophylus cobbe leaves 2–10 Antibacterial and antibiofilm (Gurunathan et al., 2014)
Annona reticulata leaves 6.48–8.13 Antibacterial, larvicidal (Parthiban et al., 2019)
Calendula officinalis leaves 30–50 – (Alanazi and Hesham, 2016)
Calendula officinalis seeds 5–10 – (Baghizadeh et al., 2015)
Camellia sinensis 34.68 ± 4.95 (DLS) Antibacterial and cytotoxicity evaluation (Rolim et al., 2019)
Eucalyptus globulus leaves 8–35 Scolicidal activity (Salih et al., 2020)
Hibiscus rosa sinensis leaves – – (Philip, 2010)
Lansium domesticum fruit peel 10–30 Antimicrobial, biocompatibility (Shankar et al., 2014)
Origanum majorana leaves 25–50 – (Zahran et al., 2018)
Ag
Panax ginseng leaves 5–15 Antimicrobial (Singh et al., 2016)
Persea americana seeds 20–40 Antimicrobial (Girón-Vázquez et al., 2019)
Phyllanthus amarus (parts of whole plant) 24 ± 8 Antibacterial (Singh et al., 2014)
Phyllanthus emblica fruit 60–80 – (Dhar et al., 2021)
Piper nigrum leaves 8–35 Scolicidal activity (Salih et al., 2020)
Tabebuia berteroi leaves 2 (average) Catalytic (Vellaichamy and Periakaruppan, 2016)
Ziziphora tenuior leaves 8–40 – (Sadeghi et al., 2015)
Ziziphus Jujuba leaves 20–30 Antibacterial, catalytic (Gavade et al., 2015)
Ziziphus Spina-Christi leaves 8–35 Scolicidal activity (Salih et al., 2020)
Camellia sinensis leaves ~10 Antibacterial (Onitsuka et al., 2019)
Elettaria cardamomum seeds 15.2 (average) Antioxidant, antibacterial, anticancer (Rajan et al., 2017)
Hibiscus rosa sinensis leaves – – (Philip, 2010)
Hygrophila spinosa (parts of whole plant) – Antioxidant and anticancer (Satpathy et al., 2020)
Lansium domesticum fruit peel 20–40 Antimicrobial, biocompatibility (Sankar et al., 2014)
Au
Nigella arvensis leaves 3–37 Antibacterial, antioxidant, cytotoxic, catalytic (Chahardoli et al., 2018)
Panax ginseng leaves 10–20 Antimicrobial (Singh et al., 2016)
Stevia rebaudiana leaves 5–20 – (Sadeghi et al., 2015)
Terminalia chebula seed 6–60 Antibacterial (Kumar et al., 2012)
Zingiber officinale root 5–15 Blood compatibility (Kumar et al., 2011)
Crotalaria candicans leaves 30 (average) Antibiofilm (Lotha et al., 2019)
Ginkgo biloba L. leaves 15–20 Catalytic (Nasrollahzadeh and Sajadi, 2015a)
Cu
Syzygium aromaticum buds 15 (average) Antimicrobial (Rajesh et al., 2018)
Ziziphus spina-christi (L.) fruit 5-20 Antibacterial, removal of crystal violet dye (Khani et al., 2018)
Citrofortunella microcarpa leaves 54–68 Photodegradation of Rhodamine B dye (Rafique et al., 2020)
CuO
Cymbopogon citratus leaves 11.4–14.5 Antibacterial and antibiofilm (Cherian et al., 2020)
Moringa oleifera leaves 3.4–7.4 Antibacterial, removal of nitrate from water (Katata-Seru et al., 2018)
Fe Moringa oleifera seeds 2.6–6.2 Antibacterial, removal of nitrate from water (Katata-Seru et al., 2018)
Trigonella foenum–graecum seeds 7–14 Antibacterial, photocatalytic dye degradation (Radini et al., 2018)
Cinnamomum camphora leaves 3.2–6.0 – (Yang et al., 2010)
Couroupita guianensis Aubl. fruit 5–15 Antibacterial and cytotoxic (Gnanasekar et al., 2018)
Pd Filicium decipiens leaves 2–22 Antibacterial (Sharmila et al., 2017)
Rosmarinus officinalis leaves 15–90 Antimicrobial and catalytic (Rabiee et al., 2020)
Sapium sebiferum leaves – Antibacterial, photocatalytic (Tahir et al., 2016)
Pd/CuO Theobroma cacao L. seeds 40 (average) Catalytic (Nasrollahzadeh et al., 2015)
Ocimum sanctum leaves 23 (average) Water electrolysis (Soundarrajan et al., 2012)
Pt Taraxacum laevigatum (parts of whole plant) 2–7 Antibacterial (Tahir et al., 2017)
Xanthium strumarium leaves 22 (average) Antimicrobial, cytotoxic (Kumar et al., 2019)
TiO2 Euphorbia heteradena Jaub root 17–45 – (Nasrollahzadeh and Sajadi, 2015a)
ZnO Spinacia oleracea leaves 40.59 (average) Effect on Vigna radiata (Lakshmi et al., 2017)
nanoparticles under Ag+ precursor abundance, however, when insuffi 2014; Si and Mandal, 2007).
cient concentration of Ag+ are present in the solution, the trend is not The resulting NPs can be used and stored within the solution
rising linearly. Conversely, under high temperatures (80-90 ◦ C), smaller including the remaining plant extract or can be further separated and
nanoparticles are produced with rising temperature (Liu et al., 2020). As purified before application (washing, centrifugation, column chroma
tempering a solution evenly using heat transfer is often a problem, tography) (Nasrollahzadeh and Sajadi, 2015a).
several studies use microwaves as a method to provide increased reac Various approaches were already successfully employed in the
tion kinetics homogeneously (Baruwati et al., 2009; Hebbalalu et al., context of plant extract synthesis. In some studies, whole plant extracts
2013; Kou and Varma, 2012b; Varma, 2012). Another parameter which were used for the production of nanoparticles. Mahitha et al. (2011)
can influence the reaction kinetics is UV light. In a study by Filip et al. reported the successful synthesis of silver nanoparticles using whole
(2019), a 6 V UV lamp (365 nm) was used for the photochemical pro plant ethanolic extract made from Bacopa monniera. Nanoparticles were
duction of silver and gold nanoparticles mediated by Cornus mas fruit prepared by mixing the extract with a 25 mM aqueous solution of silver
extract. Free radicals in the extract were formed by the UV-light and nitrate (1:30) and incubating at room temperature for one hour. This
induced the reduction of Ag+ / AuCl4- ions. Manjamadha and Muthu procedure led to the formation of mostly spherical nanoparticles with a
kumar (2016) reported that ultra-sonication can shorten reaction time. size of 5–30 nm. Similar approach for plant extract NPs synthesis was
Ultrasound reduces reaction rate and reduction time by increasing the adopted by Vijay Kumar et al. (2014), who reported successful synthesis
interactions of functional groups from the biological agent and metal of silver nanoparticles with the use whole plant extract made from
ions. Lastly, the finishing parts of the process (e.g. capping) determine Boerhaavia diffusa. Silver nanoparticles were also synthesized using
the final shape and size of the NPs (Dikshit et al., 2021; Makarov et al., whole plant extract made from Bacopa monniera (Mahitha et al., 2011)
5
and Clitoria ternatea (Malabadi et al., 2012). Moreover, biosynthesis of agents) (Zhao et al., 2018).
AuNPs using aqueous extract of Hygrophila spinosa was reported by The microbial-mediated NP synthesis can utilize both extracellular
Satpathy et al. (2020). and intracellular approaches, using whole cells or cell-free supernatants,
The most frequently reported method utilizing plant extracts seems cell lysates, or extracts (de Souza et al., 2019). In comparison with plant
to be an approach using leaf extracts. Rabiee et al. (2020) reported the mediated NPs synthesis, the microbial systems include a cultivation step
successful synthesis of palladium nanoparticles using aqueous extract of alternatively amended by a purification step aimed at obtaining the
Rosmarinus officinalis. The extract was prepared by washing R. officinalis active agents, which can be derived from various stages of microbial
leaves with distilled water, then drying at room temperature, followed metabolism – specific examples are stated in following sections.
by cutting into small pieces and grounding. The powder was mixed with
deionized water (10 g/100 ml) and boiled for 15 minutes. Finally, the 2.2.1. Bacteria mediated NPs biosynthesis
extract was filtered to remove all plant residues. Nanoparticle synthesis Bacterial production of NPs is facilitated by various extracellular and
was conducted by adding 10 ml of the extract to 20 ml of the palladium intracellular processes and compounds both during the active growth
precursor salt and stirring at room temperature for 24 hours. Palladium phase or using secondary metabolism by-products (de Souza et al., 2019;
NPs in the size range from 15 to 90 nm were obtained. Salih et al. (2020) Salem and Fouda, 2021). The cell-metal interactions are often based on
reported AgNPs synthesis with the use of leaf extracts from Piper nigrum, the ability of bacteria to suppress their toxic and adverse effects and are
Ziziphus Spina—Christi and Eucalyptus globulus. Dhar et al. (2021) re an intrinsic part of the microbial resistance mechanisms to heavy, toxic
ported AgNPs synthesis by using extract from Phyllanthus emblica. AuNPs metals (Vigneshwaran et al., 2007) e.g. by reducing and precipitating
and AgNPs were synthesized using leaf extracts of Crassocephalum rubens the toxic metal from the soluble form into insoluble non-toxic metal
(Adewale et al., 2020). AuNPs, AgNPs, and PdNPs were synthesized nanoparticles (Narayanan and Sakthivel, 2010). The biosynthesis of
using leaf extract of Rosmarinus officinalis (Rabiee et al., 2020). FeNPs metal NPs can be a part of the biomineralization process, using the cell
and PdNPs were synthetized by the leaf extract of Tabebuia berteroi as a scaffolding, or can take place during active metabolic processes,
(Vellaichamy and Periakaruppan, 2016) and Withania coagulans such as biosorption, complexation and precipitation or intracellular
together with graphene oxide to form a nanocomposite (Atarod et al., bioaccumulation (Iqtedar et al., 2019; Narayanan and Sakthivel, 2010).
2016). The cultivation of bacteria, in contrast to other microbes, is character
As mentioned above, other parts of plants used for the synthesis of ized by high growth rates and yield, and low requirements for cultiva
metal nanoparticles include stems, roots, fruits seeds and other plant tion conditions. The bacterial biosynthesis of NPs is therefore a flexible
parts, preferable from agricultural waste products. In this regard, AgNPs technique with a potential for large-scale production (Salem and Fouda,
were synthesized using fruit extract made from Phyllantus emblica 2021). Although extracellular production has obvious advantages in
(Renuka et al., 2020) and using stem extract from Phyllantus pinnatus easier down-stream processing, intracellular production has been re
(Balachandar et al., 2019). Pd/CuONPs were biosynthesized using seed ported to lead to NPs with higher monodispersity (Bao et al., 2003;
extracts from Theobroma cacao, rich in phenolic antioxidants (Nasrol Narayanan and Sakthivel, 2010). Microbial NPs synthesis is conducted
lahzadeh et al., 2015). TiO2NPs were synthetized by root extract from by combining either cell biomass or cell-free extract/supernatant ob
Euphorbia heteradena which exhibited the presence of phenolic com tained after pre-cultivation and the appropriate metal parent compound
pounds, used as both reducing and capping agents (Nasrollahzadeh and under suitable reaction conditions (time, pH, temperature and pressure)
Sajadi, 2015b). (de Souza et al., 2019).
Production of AgNPs by bacteria has been one of the first reported
2.2. Microbial mediated NPs biosynthesis studies on the possibilities of microbial-mediated NP biosynthesis
(Prabhu and Poulose, 2012) and although the focus has been on the
Various unicellular systems have been investigated for their poten AgNPs, there are reports on the synthesis of many other metal NPs using
tial NPs production. Reports describe successful exploitation of bacteria, a variety of microorganisms (see Table 2). Synthesis of AgNPs by cell-
yeast, actinomycetes, fungi, and algae; metal NPs under study include free extracts (e.g. from Bacillus brevis (Saravanan et al., 2018a), Strep
Ag, Au, Zn, Ti, Te, Se, Cu, Mg, their oxides, alloys, quantum dots and tomyces griseoplanus (Vijayabharathi et al., 2018)) and intracellular (e.g.
other nanocomposites (Fouda et al., 2018; Hassan et al., 2018; Lactobacillus fermentum (Sintubin et al., 2009), Pseudomonas sp. (John
Mohamed et al., 2019; Salem and Fouda, 2021). The disadvantages of et al., 2020)) has been reported. In extracellular synthesis, the first step
microbial synthesis of NPs include the need for special equipment for is usually cultivation of microorganisms in optimal growth conditions
microbial cultivation and its control and maintenance, variability of the (temperature, pH, growth medium and others) for 1-2 days. Then the
microbial product depending on cultivation conditions and, lastly, biomass is separated from the media (by centrifugation or filtration). To
biosafety issues that might arise with some microbial strains (Kharissova synthesize NPs, the obtained supernatant/filtrate is mixed with the
et al., 2019). metal precursor solution. Another option is the use of aqueous cell-free
Promising candidates for microbial mediated NPs biosynthesis can extract. In this case, the cells obtained as described above are washed
be constructed using genetic engineering. Prospective properties of the and incubated in sterile water. The biomass is then separated from the
genetically engineered organisms can include enhanced resistance to resulting suspension and formed cell-free aqueous extract is mixed with
metal toxicity, high throughput, energy efficiency and ecological pro a solution of metal ions (Kato and Suzuki, 2020; Singh et al., 2016). Wei
cedures (Iravani and Varma, 2019). Among reported studies are re et al. (2012) used aqueous extract of Bacillus amyloliquefaciens obtained
combinant E. coli coexpressing metallothioneins and phytochelatin by ultrasonication of washed pre-cultured cells and synthesized AgNPs
synthase (Choi et al., 2018) or heterologous host construction for of sizes 4–24 nm.
biosynthesis of magnetic NPs by transferring genes from Magneto Intracellular biosynthesis is done by incubation the cell suspension
spirillum gryphiswaldense to Rhodospirillum rubrum (Kolinko et al., 2014). with metal precursor for a few minutes to days. To minimize the effect of
There are studies trying to elucidate the mechanisms and compounds the culture medium components, the precultured biomass could be
involved in the microbial-mediated NPs synthesis although, as with the harvested, washed with sterile water, and then incubated with a metal
plant extracts, we can expect a high degree of specificity in each mi salt solution. The biomass of Lactobacillus casei subsp. casei was used as
crobial system, depending on the type of microorganism and the con biocatalyst for the AgNPs (25–50 nm) formation. The reaction mixture
ditions of its cultivation (temperature, pH, substrate, etc.) (Narayanan contained harvested biomass, silver nitrate, glucose (as electron donor)
and Sakthivel, 2010; Salem and Fouda, 2021). The participating com and phosphate buffer (Korbekandi et al., 2012).
pounds include cell wall polymers, quinones, enzymes (such as NADPH- Husseiny et al. (2007) synthetized AuNPs using cell-free supernatant
dependent nitrate reductase), peptides and polysaccharides (as capping from Pseudomonas aeruginosa. They mixed supernatant after culturing
6
Table 2
Microbially synthesized metal NPs and their properties.
NPs Species Source Size (nm) Applications Ref.
Bacteria
Bacillus brevis cell-free extract 41–68 Antibacterial (Saravanan et al., 2018a)
Bacillus licheniformis cell-free supernatant ~ 50 nm – (Kalishwaralal et al., 2008)
Bacillus methylotrophicus cell-free supernatant 10–30 Antimicrobial (Wang et al., 2016)
Bacillus sp. biomass 5–15 – (Pugazhenthiran et al., 2009)
Lactobacillus fermentum biomass 5–80 – (Sintubin et al., 2009)
Ag Pseudomonas sp. biomass 20–70 Antimicrobial (John et al., 2020)
Pseudomonas stutzeri biomass 200 – (Klaus et al., 1999)
Rhodococcus spp. biomass 10–12 Antimicrobial (Otari et al., 2015)
Shewanella oneidensis biomass 2–11 Antibacterial (Suresh et al., 2010)
Sinomonas mesophila cell-free supernatant 4–50 Antimicrobial (Manikprabhu et al., 2016)
Streptomyces griseoplanus cell-free extract 19–20 Antifungal (Vijayabharathi et al., 2018)
Bacillus subtilis - 20–25 Catalytic (Srinath et al., 2018)
Escherichia coli DH5α biomass 25 Direct electrochemistry of hemoglobin (Du et al., 2007)
Mycobacterium sp. cell-free supernatant 5–55 – (Camas et al., 2018)
Au Pseudomonas aeruginosa cultural supernatant 15–30 – (Husseiny et al., 2007)
Rhodopseudomonas
cell-free extract 10–20 – (He et al., 2008)
capsulata
Streptomyces sp. cell-free supernatant 90 (average) Antifungal (Gopal et al., 2013)
Kocuria flava cell-free supernatant 5–30 – (Kaur et al., 2015)
Cu
Shewanella oneidensis biomass 20–40 Catalytic (Kimber et al., 2018)
Antimicrobial, antioxidant,larvicidal and
CuO Streptomyces sp. biomass filtrate 78–80 (average) (Hassan et al., 2019)
biocontrol
Pd Shewanella oneidensis - 10–100 Catalytic (Wang et al., 2019)
Jeotgalicoccus coquinae 5.74
cell lysate supernatant Antioxidant and antimicrobial (Eramabadi et al., 2020)
ZC15 (average)
Pt
electrochemically active
Shewanella loihica 1–10 Catalytic (Ahmed et al., 2018)
biofilm
Escherichia coli biomass 2–5 – (Sweeney et al., 2004)
CdS Extracellular polymeric
Pseudomonas aeruginosa 20–40 – (Raj et al., 2016)
substances
Bacillus amyloliquefaciens biomass in culture medium 22.11–97.28 Photocatalytic degradation of dye (Khan and Fulekar, 2016)
Órdenes-Aenishanslins et al.,
TiO2 Bacillus mycoides 40–60
2014
Lactobacillus sp. biomass 8–35 – (Jha et al., 2009)
Bacillus megaterium cell-free extract 45–95 Antimicrobial (Saravanan et al., 2018b)
ZnO
Streptomyces sp. cell-free supernatant 20–50 Antimicrobial and anticancer (Balraj et al., 2017)
Fungi and yeasts
Aspergillus fumigatus cell-free filtrate 5–25 – (Bhainsa and D’Souza, 2006)
Aspergillus terreus cell-free supernatant 1–20 Antimicrobial (Li et al., 2012)
Cryptococcus laurentii cell-free supernatant 35–400 Antibacterial (Fernández et al., 2016)
Fusarium oxysporum biomass 5–13 Antibacterial and cytotoxic (Husseiny et al., 2015)
Ag
Phomopsis liquidambaris cell-free filtrate 18.7 (average) Antimicrobial and larvicidal (Seetharaman et al., 2018)
Rhizopus stolonifer mycelial extract 2.86 ± 0.3 nm – (AbdelRahim et al., 2017)
Rhodotorula glutinis cell-free supernatant 15–220 Antifungal (Fernández et al., 2016)
Trichoderma viridae cell-free filtrate 5–40 Antimicrobial (Fayaz et al., 2010)
Cladosporium
cell-free extract 60 nm Antimicrobial and antioxidant (Joshi et al., 2017)
cladosporioides
Fusarium oxysporum biomass 20–40 – (Mukherjee et al., 2002)
Pichia jadinii biomass < 100 nm – (Gericke and Pinches, 2006)
Rhizopus oryzae cell-free extract 16–43 – (Kitching et al., 2016)
Au
Saccharomyces cerevisiae biomass > 100 nm – (Lin et al., 2005)
Trichoderma harzianum biomass 26–34 Antibacterial (Tripathi et al., 2018)
Trichothecium sp. biomass – – (Ahmad et al., 2005)
Verticillium sp. biomass 12–28 – (Mukherjee et al., 2001)
Yarrowia lipolytica biomass 15 – (Agnihotri et al., 2009)
32 (Sriramulu and Sumathi,
Pd Saccharomyces cerevisiae cell-free extract Catalytic
(average) 2018)
Fusarium oxysporum biomass 10–100 – (Riddin et al., 2006)
Pt
Penicillium chrysogenum cell-free filtrate 5–40 Antibacterial and cytotoxic (Subramaniyan et al., 2018)
CdS Candida glabrata - 20 Å – (Dameron et al., 1989)
Aspergillus niger cell-free filtrate 53–69 Antimicrobial and dye degradation (Kalpana et al., 2018)
ZnO Aspergillus terreus cell-free filtrate 10–45 Antibacterial and UV- protection (Fouda et al., 2017)
Pichia kudriavzevii cell-free filtrate ~ 10–61 Antimicrobial and antioxidant (Moghaddam et al., 2017)
Algae
Polysiphonia cell-free extract 5–25 Anticancer (Moshfegh et al., 2019)
Ag
Sargassum muticum cell-free extract 43–79 Antibacterial (Madhiyazhagan et al., 2015)
Dunaliella salina cell-free extract 1–30 Anticancer (Singh et al., 2019)
Fucus vesiculosus biomass – – (Mata et al., 2009)
Chlorella vulgaris biomass 40–60 – (Luangpipat et al., 2011)
Au
Rhizoclonium fontinale biomass – – (Parial and Pal, 2015)
Sargassum wightii biomass 8–12 – (Singaravelu et al., 2007)
Spirulina platensis protein extract ~ 5 nm Antibacterial (Suganya et al., 2015)
Pd Chlorella vulgaris cell-free extract 70 Catalytic (Mishra et al., 2020)
(continued on next page)
7
Table 2 (continued )
NPs Species Source Size (nm) Applications Ref.
CuO Bifurcaria bifurcata cell-free extract 5–45 Antimicrobial (Abboud et al., 2014)
ZnO Chlamydomonas cell-free extract 55–80 Catalytic (Rao and Gautam, 2016)
reinhardtii
Chlorella cell-free extract 20 ± 2.2 Catalytic (Khalafi et al., 2019)
Chlorella vulgaris cell-free extract 20–50 Catalytic (Khalafi et al., 2019)
Viruses
bacteriophage - 20–50 Antibacterial and antibiofilm (Ahiwale et al., 2017)
Au
tobacco mosaic virus - 10–40 – (Love et al., 2015)
TiO2 20–40
M13 virus - – (Chen et al., 2015)
(nanowire) (diameter)
the microorganism with chloroauric acid (to give a 1mM solution) and to high ion concentrations are the main advantages of algae, which can
obtained spherical AuNPs in the range of 15–30 nm. In another study, be exploited in NPs synthesis. AgNPs synthesis by cell-free extracts was
Escherichia coli biomass was used to mediate the AuNPs biosynthesis (Du reported by Moshfegh et al. (2019) for Polysiphonia sp.. Extracts from
et al., 2007). The authors mixed washed biomass resuspended in sterile Parachlorella kessleri has been studied for AgNPs synthesis (Kadukova
water with an aqueous solution of chloroauric acid (to give a 1mM so et al., 2014; Velgosova et al., 2020). Velgosova et al. (2020) studied the
lution) and incubate the mixture in laboratory ambient conditions for biosynthesis of AgNPs resulting from three methods of algal extract
120 h. This led to the formation of spherical AuNPs with an average size preparation. They reported that heating of the washed pre-cultured
25 nm. algae, followed by centrifugation lead to optimal values of reaction
Other metal nanoparticles including CuNPs and CuONPs were pre rate, uniformity and stability of NPs (~20 nm).
pared using bacteria. Kaur et al. (2015) reported the successful The biomass of Chlorella vulgaris (Luangpipat et al., 2011), Rhizo
biosynthesis of CuNPs using the supernatant after cultivation of the clonium fontinale (Parial and Pal, 2015) or Sargassum wightii (Singaravelu
marine bacteria Kocuria flava. In this study, the cell-free supernatant was et al., 2007) has been used for AuNPs synthesis. Other studies were
mixed with copper nitrate and the mixture was incubated at 30 ◦ C for 24 conducted with cell-free extracts of C. vulgaris for the synthesis of PdNPs
h. The experiment resulted in the formation of spherical and quasi- (Mishra et al., 2020) or ZnONPs (Khalafi et al., 2019).
spherical CuNPs with an average size ranging between 5 and 30 nm.
Endophytic Streptomyces sp. was used for the biosynthesis of spherical 2.2.4. Template mediated NPs biosynthesis
CuONPs with average size 80 nm by mixing the aqueous biomass filtrate A novel approach to NPs synthesis is the use of biological templates
with CuSO4.5H2O and incubating the mixture at 35 ◦ C for 6 h in the dark for the nanoparticle growth. Various molecules and structures can be
(Hassan et al., 2019). used as templates, e.g. fatty acids, amino acids, nucleic acids, capsules,
S-layers, and viroid or virus particles (Narayanan and Sakthivel, 2010).
2.2.2. Fungi mediated NPs biosynthesis The use of viruses as catalysts for NPs production is based on their
Beside prokaryotic microorganisms, some species of fungi and yeast surface compounds protecting the capsid structure, which cooperate
have been studied as potential NPs producers. Although their growth specifically with metal ions (Salem and Fouda, 2021). With the use of
rates are lower than those found in bacteria, they possess some advan genetic engineering, self-assembled viral capsids were used for the
tages in NPs synthesis. Fungal mycelium presents a specific external production of quantum dot NPs. In a study by Lee et al. (2002), a M13
surface and is resilient to shear forces and other unfavorable external bacteriophage with specific recognition moiety for ZnS crystal surfaces
conditions (Fouda et al., 2017). Fungi excrete many extracellular was used to manufacture a self-supporting hybrid film material by
reductive enzymes which makes them good candidates for extracellular precipitation and suspension in ZnS precursor solution. Various metal
NPs production (Chan and Mat Don, 2012; Narayanan and Sakthivel, NPs, such as CdSNPs and PbSNPs were synthesized with the use of to
2010). Their ability to produce NPs is linked to their known metal ion bacco mosaic virus (Narayanan and Sakthivel, 2010; Shenton et al.,
tolerance and bioaccumulation abilities (Dhillon et al., 2012; Sastry 1999).
et al., 2003). Another advantage of fungi mediated synthesis of NPs is
the creation of specific shapes and sizes and high degree of mono 3. Antimicrobial properties of NPs
dispersion (Hulkoti and Taranath, 2014).
As with bacterial NPs synthesis, most published work concerns One of the major challenges of modern medicine is the search for
AgNPs and AuNPs. However, other metal NPs synthesis by fungi and new effective antimicrobial drugs, as many microbial pathogens are
yeasts has been reported (see Table 2). Cell-free filtrate of Aspergillus developing resistance to classical antibiotics. In the medical field, the
fumigatus (Bhainsa and D’Souza, 2006) and Cryptococcus laurentii potential of NPs has been studied in several applications, mostly as drug
(Fernández et al., 2016) has been used for AgNPs synthesis, as well as carriers or parts of diagnostic systems, especially in cancer treatment.
the biomass of Fusarium oxysporum (Husseiny et al., 2015). AuNPs However, their antimicrobial properties are also garnering attention
synthesis by biomass cells has been reported for a wide variety of mi (Fahimmunisha et al., 2020; Luo et al., 2014; Salem and Fouda, 2021).
croorganisms, including F. oxysporum in a study by Mukherjee et al. Various types of biosynthesized NPs were observed to possess antimi
(2002) who achieved synthesis of spherical and triangular AuNPs by crobial activity against many pathogenic microorganisms and much
extracellularly secreted reductases produced by precultured and washed effort has thus been dedicated to evaluating their potential and ascertain
Fusarium oxysporum biomass which was combined with AuCl4− ions for the mechanisms of action, which are summarized below in sections on
72 h in the dark. Other examples include Pichia jadinii (Gericke and antibacterial (section 3.1), antifungal (section 3.2) and antiviral prop
Pinches, 2006) and Trichoderma harzianum (Tripathi et al., 2018). Other erties (section 3.3) and toxicity (section 4.5.3). For more details see
metal NPs synthesized by fungi include PdNPs (cell-free extract of specialized reviews, e.g. (El-Seedi et al., 2019; Hassan et al., 2018;
Saccharomyces cerevisiae (Sriramulu and Sumathi, 2018)) or PtNPs Prabhu and Poulose, 2012; Salleh et al., 2020; Zhang et al., 2016a).
(F. oxysporum biomass, (Riddin et al., 2006)). The antimicrobial activity of biosynthesized metal NPs has already
been observed against bacteria, fungi and even viruses, which are all
2.2.3. Algae mediated NPs biosynthesis expanded on in following sections. Although there are many studies on
The low media requirements, photosynthetic abilities and resistance this topic, there is a great variability both in the NPs properties,
8
microbial reactions and defenses and also in differing experimental et al., 2020). The most reported biosynthesized NPs with antibacterial
layout of various scientific studies. properties are silver, gold, palladium, copper and copper oxide, zinc,
There are several challenges that need to be addressed in the of green and zinc oxide (Das et al., 2017; Gericke and Pinches, 2006; Narayanan
synthesis studies regarding antimicrobial testing, both from the point of and Sakthivel, 2010).
experiment design and reporting and their future medicinal application.
Majority of the studies only use well or disc diffusion methods, which 3.1.1. Silver NPs
does not constitute a comprehensive standard in microbiological The application of antibacterial properties of AgNPs has been re
studies; the use of more advanced methods e.g., examining proteomics ported in several reviews, both prepared by physico-chemical and bio
or genomics, is scarce or non-existent. A lot of studies do not disclose logical methods (Prabhu and Poulose, 2012; Rafique et al., 2017; Tran
which strains of the microorganisms tested are used for the experiments et al., 2013; Zhang et al., 2016b). The main mechanisms of action of
– this is crucial information in the context of microbiology field. Another AgNPs are the release of Ag+ ions, ROS generation, interference with
very prevalent shortcoming is non-sufficient method description, when energy metabolism and cell wall synthesis, membrane disruption and
it comes to experiment layout, reagent composition or concentration of interference with DNA, RNA and other parts of cell metabolism (Dakal
nanoparticles used. et al., 2016; Gurunathan et al., 2014; Lara et al., 2010b; Singh et al.,
The physico-chemical properties of NPs like material, size (poly 2018). These are facilitated both by the extracellular and intracellular
dispersity), shape, surface functionalization, etc. play a crucial role in presence of AgNPs, as small sized AgNPs can penetrate the cell wall and
their antimicrobial effect, therefore it is important that the studies membrane. Their transport through cell wall may be hindered by the
include a thorough characterization of NPs and connect the microbio peptidoglycan layer in Gram-positive bacteria, resulting in their lower
logical and physico-chemical properties. Smaller nanoparticles are susceptibility in some studies (Gurunathan et al., 2014). Another cor
usually reported to have higher antimicrobial activity (Nisar et al., 2019; relation has been found with the size and shape of NPs, as smaller NPs
Zhang et al., 2018). Their increased toxicity is hypothesized to results (higher surface to volume ratio) have shown quicker release of Ag+ ions
from their higher specific surface area (compared to larger NPs) and (Tang and Zheng, 2018). Similarly, it was found that spherical AgNPs
therefore a larger area available for the interaction with microbial cells exhibit higher antimicrobial activity than their triangular, platelet or
and for a quicker release of metal ions. However, there have been some nanorod counterparts because of enhanced surface binding and uptake
reports with opposing observations, i.e. that larger NPs had a better (Helmlinger et al., 2016).
antimicrobial effect. This suggests that the size is not the only factor that Bacterial species which have been reported as susceptible to bio
affects nanoparticle activity (Slavin et al., 2017a). Another factor that is synthesized AgNPs include multidrug resistant pathogens, such as Ba
known to affect the activity of a nanoparticle is shape. Cheon et al. cillus subtilis, E. coli, Enterococcus sp., Klebsiella pneumoniae, Proteus
(2019) monitored the activity of silver nanoparticles of three different mirabilis, P. aeruginosa, S. aureus, Shigella flexaneri and V. cholerae
shapes, namely, spherical, triangular plate, and disk, and found that (Ahmed et al., 2016; Nayak et al., 2016; Składanowski et al., 2017).
spherical nanoparticles had the highest activity. They found that the Synergistic effects of AgNPs with conventional antibiotics (vancomycin,
different activity of the individual shapes is connected to the amount of clindamycin, amoxicillin, erythromycin) have been shown against
silver ions released from the surface (Cheon et al., 2019). S. aureus and E. coli (Shahverdi et al., 2007; Singh et al., 2018).
Moreover, it is often difficult to compare the antimicrobial properties
between individual studies due to great variability of methods, both in 3.1.2. Gold NPs
the NPs synthesis and the microbiology evaluation. Antimicrobial ac Biosynthesized AuNPs have also been widely studied, although their
tivity is usually evaluated by using well or disc agar diffusion methods, antibacterial activities are limited in comparison with AgNPs. AuNPs are
growth curve analysis, changes in viability or total cell number (see a target of studies of biocomposites, where the AuNP serves as a carrier
Table 3). Additionally, cell morphology and NPs localization or specific for an antibiotic, which showed activity against multi-drug resistant
metabolic activities are observed (Arora et al., 2008; Eid et al., 2020; bacteria including methicillin resistant S. aureus, overcoming the beta-
Salem and Fouda, 2021; Sayed and El-Sayed, 2020). lactamase based resistance of these strains (Brown et al., 2012). How
Several prospective mechanisms of NPs antimicrobial activity have ever, AuNPs alone have been reported to act at least bacteriostatically
been suggested (see Fig. 4), depending on the microbial cell type and against a variety of bacterial strains (E. coli, B. subtilis, K. pneumoniae)
particular metal NPs type. These are discussed below, however the main (Singh et al., 2018). There are two main proposed mechanisms of action
mechanisms include damage to the cell membrane and wall, interactions of AuNPs: inhibiting ATPase activity, which hinders energy metabolism,
with intracellular components, and oxidative stress generation (Anjana and preventing tRNA ribosome interaction, which stops transcription
et al., 2019; Dikshit et al., 2021; Fang et al., 2018; Salem and Fouda, (Cui et al., 2012).
2021).
In many cases, the NPs act through a combination of various mech 3.1.3. Metal oxide NPs
anisms, which can be advantageous in medical applications, as the Antibacterial activity has been found in biosynthesized ZnONPs
probability of simultaneous resistance development is limited (Slavin against a wide variety of microorganisms including carbapenem resis
et al., 2017b). The advantage of biosynthesized NPs is in the function tant Acinetobacter baumanii (Tiwari et al., 2018). This activity is con
alization, capping, and stabilizing via biological molecules, which nected to ROS generation, cell membrane damage, and interactions of
themselves might possess antimicrobial properties and also allow the both ZnONPs and Zn ions with intracellular components (Saravanan
NPs to bind to the target cell surface (Singh et al., 2018). et al., 2018b; Singh et al., 2018). Although biological synthesis of
CuONPs is a new topic, interesting mainly due to their resistance to
3.1. Antibacterial properties oxidation reactions which are likely to occur in biological media, there
have been reports on their antibacterial activity against both Gram-
Interactions of NPs with bacterial cells and their antibacterial positive and Gram-negative bacteria (DeAlba-Montero et al., 2017).
properties have been extensively studied in a variety of metal NPs and MgONPs activity is reportedly based on the generation of ROS and
strains of both Gram-positive and Gram-negative bacteria (see Table 3). direct interactions with the cell membrane (Nguyen et al., 2018);
Beside the innate antimicrobial activity of biosynthesized NPs, they however, some reports have demonstrated antibacterial activity without
have been reported to facilitate enhancement of the activity of con ROS-induction (Leung et al., 2014). Antibacterial effect of TiO2NPs that
ventional antibiotics, e.g. AgNPs were proven effective in combination has been demonstrated against various microorganisms is also con
with levofloxacin against Enterococcus faecalis, Staphylococcus aureus, nected with ROS generation, in this case induced by their photosensi
E. coli, Proteus vulgaris, Salmonella typhi, and Vibrio cholerae (Keshari tivity in the near UV spectrum (Li et al., 2012b; Singh et al., 2018).
9
Table 3
Antimicrobial properties of biosynthesized metal NPs against various microorganisms.
Target microorganism NP type, size (nm) Biological agent used for Method Ref.
synthesis
Bacteria
Acinetobacter sp. Ag, 5–20 Chlorella pyrenoidosa Well diffusion (Aziz et al., 2015)
Aeromonas hydrophila Ag, 5–20 Chlorella pyrenoidosa Well diffusion (Aziz et al., 2015)
Bacillus cereus Ag, - Ananas comosus Well diffusion (Das et al., 2019)
Enterococcus faecium Ag, - Ananas comosus Well diffusion (Das et al., 2019)
Enterococcus faecalis Ag, 5–50 Rhodococcus sp. Growth curve, well diffusion (Otari et al., 2015)
Enterobacter aerogenes ZnO, 15–30 Streptomyces sp. Well diffusion (Shanmugasundaram and
Balagurunathan, 2017)
Escherichia coli Ag, <24 Impatiens balsamina, Lantana Disc diffusion (Aritonang et al., 2019)
camara
Disc diffusion, Congo red agar, crystal violet
Ag, 20 Solanum nigrum (Jinu et al., 2017)
staining
Ag, 5–50 Rhodococcus sp. Growth curve, well diffusion (Otari et al., 2015)
Ag, 7–28 Streptomyces laurentii Well diffusion (Eid et al., 2020)
Ag, 16–70 Fusarium oxysporum Turbidimetric assay (Gopinath et al., 2015)
OD measurement, high-content screening,
Ag, 3–15 Chlorella vulgaris (da Silva Ferreira et al., 2017)
ultrastructural analysis
CuO, 2–41 Bacillus sp. Disc diffusion (Taran et al., 2017)
CuO, 20–40 Solanum lycopersicum Well diffusion, SEM (Vaidehi et al., 2018)
Pd, 15–90 Rosmarinus officinalis Well diffusion (Rabiee et al., 2020)
(Shanmugasundaram and
ZnO, 15–30 Streptomyces sp. Well diffusion
ZnO, 9–22 Fusarium solani Disc diffusion (Sayed and El-Sayed, 2020)
staining
Ag, 16–70 Fusarium oxysporum Turbidimetric assay, well diffusion (Gopinath et al., 2015)
Klebsiella pneumoniae Ag, 3–15 Chlorella vulgaris (da Silva Ferreira et al., 2017)
Ag, 2–15 Candida glabrata MIC, MBC (Jalal et al., 2018)
Listeria monocytogenes Ag, - Ananas comosus Well diffusion (Das et al., 2019)
Micrococcus lutens Pd, 15–90 Rosmarinus officinalis Well diffusion (Rabiee et al., 2020)
staining
Proteus vulgaris Ag, 5–50 Rhodococcus sp. Growth curve, well diffusion (Otari et al., 2015)
Ag, - Lantana camara Well diffusion (Patil Shriniwas, 2017)
staining
Pseudomonas
Ag, 7–28 Streptomyces laurentii Well diffusion (Eid et al., 2020)
aeruginosa
Ag, 16–70 Fusarium oxysporum Turbidimetric assay, well diffusion (Gopinath et al., 2015)
CuO, 40–110 Lactobacillus casei MIC, MBC, well diffusion (Kouhkan et al., 2020)
Pseudomonas
Ag, 10–20 Bacillus subtilis MIC, MBC (Velmurugan et al., 2014)
fluorescens
Salmonella enterica (Shanmugasundaram and
Shigella flexneri Ag, 2–15 Candida glabrata MIC, MBC (Jalal et al., 2018)
Ag, - Ananas comosus Well diffusion (Das et al., 2019)
Impatiens balsamina, Lantana
Ag, <24 Disc diffusion (Aritonang et al., 2019)
camara
Ag, - Lantana camara Well diffusion (Patil Shriniwas, 2017)
staining
Ag, 10–20 Bacillus subtilis MIC, MBC (Velmurugan et al., 2014)
Ag, 13–28 Lactobacillus plantarum Well diffusion (Garmasheva et al., 2016)
Staphylococcus aureus
Ag, 3–15 Chlorella vulgaris (da Silva Ferreira et al., 2017)
Ag, 4–50 Sinomonas mesophila Well diffusion (Manikprabhu et al., 2016)
Ag, 2–15 Candida glabrata MIC, MFC (Jalal et al., 2018)
CuO Bacillus sp. Disc diffusion (Taran et al., 2017)
CuO, 20–40 Solanum lycopersicum Well diffusion, FE-SEM (Vaidehi et al., 2018)
CuO, 40–110 Lactobacillus casei MIC, MBC, well diffusion (Kouhkan et al., 2020)
Pd, 15–90 Rosmarinus officinalis Well diffusion (Rabiee et al., 2020)
(continued on next page)
10
Table 3 (continued )
Target microorganism NP type, size (nm) Biological agent used for Method Ref.
synthesis
Staphylococcus staining
epidermidis Pd, 15–90 Rosmarinus officinalis Well diffusion (Rabiee et al., 2020)
Ag, 13–28 Lactobacillus plantarum Well diffusion (Garmasheva et al., 2016)
Fungi and yeasts
Alternaria alternata CuO, - Streptomyces zaomyceticus Well diffusion (Hassan et al., 2019)
Cu / ZnO, 10–20 /
Aspergillus awamori Fusarium solani Disc diffusion (Sayed and El-Sayed, 2020)
9–22
Cu / ZnO, 10–20 /
Aspergillus fumigatus Fusarium solani Disc diffusion (Sayed and El-Sayed, 2020)
9–22
Aspergillus niger CuO, - Streptomyces zaomyceticus Well diffusion (Hassan et al., 2019)
Ag, 13–28 Sinomonas mesophila Well diffusion (Manikprabhu et al., 2016)
Candida albicans Ag, 2–15 Candida glabrata MIC, MFC, ultrastructural analysis (Jalal et al., 2018)
Pd, 15–90 Rosmarinus officinalis Disc diffusion (Rabiee et al., 2020)
Ag, 2–15 Candida glabrata MIC, MFC, ultrastructural analysis (Jalal et al., 2018)
Candida glabrata
Candida krusei
Candida parapsilosis Ag, 5–45 Rhodotorula glutinis Disc diffusion (Cunha et al., 2018)
Cu / ZnO, 10–20 /
Fusarium solani Disc diffusion (Sayed and El-Sayed, 2020)
Fusarium oxysporum 9–22
CuO, - Streptomyces zaomyceticus Well diffusion (Hassan et al., 2019)
Pythium ultimum CuO, - Streptomyces zaomyceticus Well diffusion (Hassan et al., 2019)
(MIC – minimum inhibitory concentration, MFC – minimum fungicidal concentration, MBC – minimum bactericidal concentration, OD – optical density)
Fig. 4. Antimicrobial mechanisms of metal NPs application affecting intracellular components and cell interface.
3.1.4. Mechanisms of activity of metal NPs Most of these mechanisms are executed through direct contact of the
The interactions of metal NPs are both varied and individual to NPs with the bacterial cell, which is enabled by electrostatic in
specific metal and microorganism; however, as described above, most teractions, van der Waals forces, and hydrophobic interactions (El-Seedi
metal NPs act in several different ways, which is one of the main attri et al., 2019; Slavin et al., 2017b). Penetration through the cell wall and
butes of their potential medical application. The most frequently pro membrane is size-dependent, as are the subsequent interactions with
posed antibacterial activity mechanisms of metal NPs are oxidative intracellular cell components, such as proteins, nucleic acids, ribosomes,
stress related to ROS production, metal ion release, and various non- lysosomes, etc. (Mukha et al., 2013). These interactions can cause
oxidative mechanisms. The non-oxidative mechanisms which were re oxidative stress, enzyme deactivation, modification of gene expression,
ported include direct interactions with cell wall and membrane, pene alteration of cell membrane permeability and electrolyte imbalance
tration into cell interior and subsequent inhibition of nucleic acid and (Wang et al., 2017). The mechanisms of NPs penetration into the cell
protein synthesis and regulation of gene expression. Metal NPs are also interior include depolarization of cell wall, which subsequently becomes
known to interact with and disrupt bacterial biofilm (Gurunathan et al., more permeable, ability to cause irregular pit formations on the cell
2014), thus hindering an important resistance mechanism which pre wall, consequently leading to cell wall degradation, receptor-mediated
sents the bacterial cells with a significant advantage. endocytosis and diffusion through the pores in the cell membrane (Lin
11
et al., 2010; Prabhu and Poulose, 2012; Slavin et al., 2017b). of novel approaches (Ahmed et al., 2016; El-Seedi et al., 2019; Salem
Oxidative stress induced by ROS production is one of the most and Fouda, 2021), their application potential in various areas is
studied antibacterial mechanisms of NPs. Different metal NPs produce described below, namely, medicine (section 4.1), agriculture (4.2), in
various ROS compounds, producing a wide range of specific antibacte dustry (4.3), water-treatment and bioremediation (4.4).
rial activities (Wang et al., 2017). Excessive ROS production leads to
oxidative stress for the bacterial cell, which is followed by loss of cell 4.1. Application of NPs in medicine
membrane integrity, interaction with DNA and enzymes and triggering
cell apoptosis (Cheloni et al., 2016; Pramanik et al., 2012). The development of novel drugs, treatments and diagnostic systems
The physico-chemical properties of NPs are crucial in the determi is an integral part of modern medicinal research. The ongoing research
nation of the possible mechanisms of their antibacterial action, among on green synthesized NPs for medical applications focuses on NPs from
the most important are their size, shape, roughness, specific surface various material, especially metals and their oxides, such as Ag, Au,
area, surface energy, charge, zeta potential, surface morphology, crystal ZnO, TiO2, CuO, MgO, and SiO2 (Dikshit et al., 2021; Ge et al., 2014;
structure and ligands (Wang et al., 2017). The activity of metal NPs is Nath and Banerjee, 2013). Their main potential lies in imaging systems,
also influenced by the conditions in which the antibacterial activity is biosensors, drug-delivery and treatment for multi drug resistant mi
studied. The medium composition, pH, osmotic pressure, temperature, crobes (Fahimmunisha et al., 2020; Salem and Fouda, 2021).
and irradiation can influence properties of NPs like solubility, aggre Further potential can be found in the synthesis of nanomaterials and
gation and surface charge or modification, which can all influence the nanocomposites utilizing beneficial properties of NPs with other me
observed antimicrobial properties reported in literature (Wang et al., dicinal materials, e.g. for immunoassays and antimicrobial combination
2017). therapy (Fayaz et al., 2010; Khani et al., 2018; Le et al., 2017). The use of
NPs in cancer treatment and diagnostics utilizes their large surface area
3.2. Antifungal properties and uses them as carriers in combination with targeted therapy. This
approach poses additional benefits such as little negative impact,
Metal NPs have been used as potential inhibitors of fungal patho effectivity and biocompatibility (Salem and Fouda, 2021).
genic microorganisms, with more focus on NPs obtained by physical and Medical materials like wound dressings with traditionally synthe
chemical methods than on their biosynthesized counterparts (Sousa sized AgNPs have been developed and used in clinical environment
et al., 2020; Tran et al., 2013). Their mechanisms of activity are stated as (Chaloupka et al., 2010) and were proven to reduce healing time in some
consistent with antibacterial properties, i.e. oxidative stress via ROS wound types, possibly due to their antimicrobial properties (Huang
production, cell wall and membrane damage due to direct contact with et al., 2007). The biosynthesized AgNPs might offer further advantages
NPs, cellular uptake of NPs and subsequent damaging interactions with regarding their higher biocompatibility. Similarly, there are silver-
cell interior and metal ion release (Aljabali et al., 2018; Sousa et al., coated implants (catheters, cardiovascular implants), which might
2020). benefit from integrating AgNPs, either as coatings or in nanocomposite
Gupta et al. (2014) reported antifungal activity of biosynthesized materials (Ge et al., 2014).
AgNPs against Candida albicans, Trichophyton mentagrophytes, and
Microsporum canis, both alone and in synergism with antibiotics. 4.2. Application of NPs in agriculture
AgClNPs proved antifungal activity against C. albicans, Aspergillus flavus,
and Aspergillus niger (Paulkumar et al., 2013). Modern agriculture benefits from the use of new technologies,
Moreover, studies have also shown the antifungal activity of green including the use of NPs. Their potential lies mainly in pest control and
AuNPs synthesized via both plant and microbial synthesis. This inhibi targeted nutrient delivery (Salem and Fouda, 2021).
tion of fungi by biosynthesized AuNPs has already been reported against The NPs can be part of nanopesticide formulations, targeted at mi
Puccinia graminis tritci, Microphyton gypseum, A. flavus, A. niger, Tricho crobial pathogens or insects. Wang et al. (2007) proposed emulsion-
phyton rubrum and C. albicans (Gopal et al., 2013). based products containing NPs that proved to be effective against a
variety of agricultural pests.
3.3. Antiviral properties The potential of biosynthesized NPs as antifungal agents for common
plant pathogens like Aspergillus sp., Fusarium sp. and Pythium sp. has
The search for new and effective antiviral agents is an essential part been demonstrated by Hassan et al. (2018). Biosynthesized SeNPs were
of modern medicine. Although the antiviral abilities of NPs synthesized proposed as possible control agents for malaria vector Anopheles ste
by physical and chemical methods are known (Lara et al., 2010a; Xiang phensi (Salem et al., 2021).
et al., 2011), even here the exact mechanism of their antiviral activity is Beside the control of pests, the efficient use of resources and coun
an ongoing research topic, with proposed mechanisms including inhi teracting water and soil fertility decline is another goal of sustainable
bition of virion formation, preferential binding preventing host cell agriculture and a possible area for NPs application. These include stra
attachment and inhibition of viral particles replication (Zhang et al., tegies for slow release of various fertilizers, e.g. by implementing
2016b). The antiviral properties of biosynthesized AgNPs were reported nanocoating (Duhan et al., 2017).
against SARS-CoV-2 (Al-Sanea et al., 2021), HIV type 1 (Kumar et al.,
2017), herpes simplex virus (type 1 and 2), and human parainfluenza 4.3. Application of NPs in industry
virus type 3 (Gaikwad et al., 2013). Ag2O/AgONPs and AuNPs showed
reduction activity of the cytopathic effect of the herpes simplex virus The application of NPs in textile industry has increased in recent
(type 1) (El-Sheekh et al., 2020). years, as they were found to provide beneficial properties to the pro
duction process and the fabrics (Salem and Fouda, 2021). Beside the
4. Application and limitations of NPs antimicrobial properties of various NPs (Ag, ZnO), they also add UV
blocking and self-cleaning attributes to the final product (Fouda et al.,
Due to their unique properties and advantages, metal NPs are finding 2018; Fouda et al., 2017). They provide excellent chemical stability and
applications in various medicinal, biotechnological and industrial areas. the large surface to volume ratio provides significant advantages over
In addition, the biosynthesized NPs offer their biocompatibility and organic counterparts when it comes to UV blocking efficiency (Shaheen
economical and ecological benefits of green synthesis and thus further et al., 2019).
broaden their possible applications. NPs are applicable in many tradi In food industry, the use of nanomaterials as additivities or coating of
tional and novel emerging technologies, both as substitutes and as part materials can provide significant benefits in food safety and packaging
12
due to their antimicrobial and antibiofilm properties. The use of pack activation of hydrogen peroxide and remediation of contaminated soils
aging or containers with incorporated NPs aims at food contamination (Varma, 2012).
prevention and increased resistance to microbial colonization (Sharma
et al., 2017). 4.5. Limitations and safety of biosynthesized NPs
The optical properties of NPs, nanocomposite materials especially,
can be exploited in functional thin-film coatings, e.g. by thermal treat Beside the many benefits and advantages of NPs, there are many
ment of nanocrystalline AgNPs and formation of carbonaceous nano considerations that need to be discussed with respect to the possible
materials (Klaus et al., 1999). widespread use in future. The limitations arise both in the process of
The biosynthesis of nanoscale semiconductors has been studied with manufacture and in the guarantee of safety for humans and their fate in
potential application both in electrotechnical industry and for their the environment.
optical properties (Mandal et al., 2006). Nanoparticles composed of CdS,
ZnS, and PbS are studied for their luminescent properties in biological 4.5.1. Green synthesis
imaging as quantum dots. The conjugation of semiconductor NPs with The green methods of synthesis, although by principle more con
specific biomolecules via biosynthetic route can result in a wide variety scientious toward waste management and other environmental con
of quantum dots with different chemical compositions and sizes, and cerns, are not yet as advanced and widespread. The large-scale
therefore broaden their potential applications, such as cell labelling, manufacture of NPs by green methods needs case by case optimization,
imaging, compound tracking or in biosensors (Valizadeh et al., 2012). with respect to the desired properties of NPs (shape, size, biological
The biosynthesized semiconductor NPs such as CdS crystallites have also activity). Among the reported challenges are detailed knowledge of the
been studied for their quantum properties aiming at overcoming limits synthesis mechanisms with the roles of various compounds, uniformity
in microelectronics (Dameron et al., 1989). of the biological material and studies focused on the procedures, econ
Copper and copper oxide NPs have many applications in the con omy and waste management of the scaled-up processes (Salem and
struction of modern electronic circuits due to their conductive, elec Fouda, 2021).
tronic and optical properties and have also been reported in catalysis The assessment of the sustainability of green methods in synthesis of
applications (Gawande et al., 2016). metal NPs is a key element in their long-term applicability and evalua
A range of nanomaterials with novel properties can be obtained by tion. This can be aided by the use of modelling including set of decision
using NPs as input material for further modification and treatment. rules which can encompass key variables and target evaluations,
Using isolated NPs or even combining biosynthetic methods com including life cycle analysis, synthesis protocols, including identification
plemented by classical preparation methods and materials such as ce of key variable conditions and allowing for overall assessment and
ments, ceramics and plastics can yield novel hybrid and composite comparison between techniques and approaches. Cinelli et al. (2015)
materials, such as metal-organic frameworks or graphene-metal com developed a modelling approach for this purpose, allowing selecting
posites (Kharissova et al., 2019). criteria, evaluation and classification of AgNPs synthesis methods and
Magnetic NPs can aid in synthesis of industrial catalysts which are protocols (based on green chemistry) into performance classes, as well
easily recoverable and recyclable. Their use has been developed for as their robustness (Cinelli et al., 2017; Cinelli et al., 2015). The eval
various reductive, oxidative or condensation reactions and pose ad uation of the sustainability of the proposed NPs synthesis protocols or
vantages in high reaction times due to the nanocatalytic properties and developments of industrial-scale methods can be included in the models
ease of the separation due to the magnetic properties of the material as a set of environmentally oriented criteria which aim at aiding decision
after each reaction cycle (Varma, 2012). planning while incorporating both experimental results and reference
protocols. Multiple criteria analysis in a co-constructive development of
4.4. Application of NPs in water treatment and bioremediation a classification model for NPs synthesis assessment model has been
proposed by Kadziński et al. (2018). Life cycle analysis has revealed that
Sustainable water management and treatment is considered one of the choice of synthesis route for AgNPs production has a great impact on
the most urgent problems of modern society. Nanotechnology including the energy use and environmental impacts; however, the goals (with
nanomaterials can provide efficient systems for the removal of patho respect to size and antimicrobial efficacy) significantly influence the
gens, pollutants, toxic compounds and heavy metals (Uddandarao et al., performance-based comparison (Pourzahedi and Eckelman, 2015).
2019; Zonaro et al., 2017). The proposed systems include functionalized
nanofiber membranes or membranes with associated immobilized NPs. 4.5.2. NPs in environment
In wastewater treatment the NP-associated membrane aids in pollutant Although the biosynthesized NPs should present lesser toxicity then
removal based on combination of adsorption, filtration and degradation those synthesized by traditional methods, the impacts of NPs release into
mechanisms. Such membrane modules can be included in both classical the environment and the effects on ecosystem balance need to be thor
wastewater treatment plants or in ex situ bioreactor bioremediation oughly studied (de Souza et al., 2019). The fate of NPs in the environ
techniques (El-Aswar et al., 2022). Bimetallic NPs, prepared using green ment includes the direct effect of the original NPs and their
tea extracts and associated with membranes have been used in the transformation products, which all need to be considered (Levard et al.,
degradation of trichloroethylene (Varma, 2012).The feasibility of these 2012).
systems has been demonstrated for ZnONPs in pathogenic microbe or An important aspect of the evaluation of NPs impact of environment
metal removal from wastewater (Primo et al., 2020; Rambabu et al., is their origin. The toxicity of naturally occurring nanoparticles can
2021) or CuONPs in toxic dye removal from wastewater (Rafique et al., differ significantly from those of synthetic origin. Naturally formed NPs
2020). The catalytic properties of metal NPs can be used in customized (metals and their oxides and sulfides) can occur in aquatic, atmospheric,
waste treatment and bioremediation processes, as both AgNPs and lithospheric and biospheric environments, e.g. in wastewaters, around
AuNPs have been shown to catalyze degradation of organic dyes and hydrothermal vents or in ore deposits. They can be formed via physio-
other pollutants (Salem and Fouda, 2021; Suvith and Philip, 2014). chemical, mechanical, and biological routes under variety of environ
Bioremediation applications using reductive properties of nanoscale mental conditions including thermal, non-thermal, and photochemical
zero-valent iron (NZVI) towards pollutants have been applied as conditions which are influenced by various environmental factors (pH,
permeable reactive barriers or direct injection in situ (Mueller et al., temperature, oxygen, presence of ROS, ions and organic compounds of
2012). Plant waste (such as sorghum bran) derived iron NPs combined natural origin etc.). Their fate and toxicity is also significantly influ
with natural surfactants have been reported as posing a stable, envi enced by the external conditions during their formation and afterwards,
ronmentally friendly, easily stored material usable for catalytic as the functional groups derived from natural organic matter capping
13
agents strongly affect their possible interactions with the environment (Pourali et al., 2017; Rudramurthy et al., 2016).
and its organisms (Sharma et al., 2015). More research is needed to evaluate the potential adverse effects of
The direct influence of metal NPs depends on the type; however, it any medicinal NPs application and to establish all potential limitations
can include the interactions with biological matter, living organisms, in an application-dependent manner.
and inorganic components of the environment. The antimicrobial
properties of NPs can negatively affect autochthonous microflora of the 5. Concluding remarks
given ecological niche, including the spread of resistance (Miller et al.,
2010). Unutilized waste NPs can become widespread in nature and there Increasing industrial demands and environmental concerns have
are some studies concerning their presence in environment, including given rise to the development of green methods for the synthesis of
food and water, with unknown impacts (Tiede et al., 2008). metal nanoparticles. The potential of biologically synthesized nano
The transformation reactions of NPs in the environment involve particles potential lies in the eco-friendly and cost-effective methods and
dissolution and release of ions (especially in AgNPs), oxidative or materials utilized for their synthesis and in their biological compatibility
reductive reactions, aggregation, and adsorption (de Souza et al., 2019). due to the use of biological molecules as stabilizers and capping agents.
These processes are dependent on the NPs type, size and shape, their Plant and microbial organisms and extracts offer a wide variety of agents
capping agents, but also on the environmental conditions, like pH, suitable for green methods. This variety offers many benefits in the
temperature, ionic strength and presence of reactive compounds flexibility and uniqueness of the final nanoparticles properties but also
(Sharma and Zboril, 2017; Zhang et al., 2016b). The aggregation and presents a challenge for the scientific community to ascertain all the
adsorption processes are highly dependent on the type of capping agents underlying molecular mechanisms in the synthesis and to evaluate all
(biological compounds in biosynthesized NPs) and their possible in the characteristics and potential limitations of the final nanoparticles.
teractions with the environment, which can both facilitate and hinder The potential of nanoparticles is especially valuable in medical appli
the transformation processes (de Souza et al., 2019; Grillo et al., 2015). cations, due to the high effectiveness of metal nanoparticles against a
As these processes are both highly individual and also all act variety of serious human pathogens, including multidrug resistant mi
simultaneously and interfere with each other, more research is needed to croorganisms. Other potential areas of application include agriculture
evaluate the impact of potential widespread use of NPs. and food industry. This broad potential of nanoparticles application
brings an urgent need for a deep understanding of all aspects of nano
4.5.3. NPs toxicity and biological compatibility particles interaction with human body and with the environment and
The toxicity of NPs in the environment is highly dependent on the NP their overall impact on a local and global scale.
type, size and shape and on the transformations it undergoes. In AgNPs,
the oxidative dissolution is responsible for release of Ag+ ions which are Author contributions
highly toxic to many organisms even in low concentrations which can
possibly occur in the environment (Ašmonaitė et al., 2016; Jiravova The author contribution statement is based on the CReditT role
et al., 2016). The exposure and residence time of NPs in the environment system.
can be significantly prolonged by their adsorption onto organic or
inorganic matter, thus increasing their persistence (Grillo et al., 2015). Funding
In some cases, the adsorption can mitigate the toxicity of NPs by
complex-formation of stabilizing reactions, which alleviate the effect on This work was supported by the Technology Agency of the Czech
the environment (Kim et al., 2013). The biosynthesized NPs have been Republic [project TH04030109].
observed to possess lesser toxicity, which is generally contributed to the
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Biotechnology Advances 58 (2022) 107905

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Research review paper

Antimicrobial properties and applications of metal nanoparticles

Fig. 2. Routes of nanoparticles synthesis – biological, chemical, and physical methods.

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