a critical review on the toxicity of some widely used engineered nanoparticles

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Review

A critical review on the toxicity of some widely used engineered nanoparticlesV Srivastava, Deepak Gusain, and Yogesh Chandra Sharma

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A critical review on the toxicity of some widely used engineered nanoparticles

Varsha Srivastava, Deepak Gusain, Yogesh Chandra Sharma*

Green Chemistry and Renewable Energy Laboratories Department of Chemistry Indian Institute of Technology (Banaras Hindu University) Varanasi Varanasi 221 005, India. * Corresponding Author Tel No +91 5426701865, Fax No +91 5422368428, E Mail [email protected]

ABSTRACT

With tremendous increase in development of nanotechnology, there is a developing

enthusiasm towards the application of nanoparticles in diverse areas. Carbon nanotubes,

fullerenes, quantum dots, dendrimers, iron oxide, silica, gold and silver nanoparticles are

frequently used in different applications such as drug delivery, as ceramic materials,

semiconductors, electronics, in medicine, cosmetics, etc. Some of these nanoparticles have

shown major toxic effects on fauna, flora and human beings like inflammation, cytotoxicity,

tissue ulceration and reduction of cell viability. SWCNT and MWCNT can induce oxidative

stress and fibrosis in the lungs of rat and mice. SWCNTs can also induce oxidative stress to

the nervous system in human beings. Inflammatory injury and respiratory distress can be

observed due to TiO2 nanoparticles with small diameter. Nanoparticles can also pose

detrimental effects on plants such as decreased growth rate, genomic and proteomic changes,

etc. Toxicity of nanoparticles arises because of their specific characteristics such as greater

‘surface area to volume ratio’ compared with bulk particles of the same chemistry. The

objective of this review is to critically evaluate the current literature on the toxicity of

nanoparticles.

Key words: Carbon nanotubes; Nanotechnology; Nanomaterial; Nanotoxicity; Silver nano-

particles, TiO2 nanoparticles; ZnO nanoparticles.

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1. INTRODUCTION

In today’s world, nanoparticles (NPs) and nanotechnology have attracted attention of the

scientific community globally and have emerged as a fast developing and fascinating area of

research. In December 1959, Nobel Laureate Richard Feynman gave an infamous lecture

entitled “There’s plenty of room at the bottom” at the California Institute of Technology

during a meeting with the American Physical Society.1 At this meeting, he first mentioned the

process which could potentially manipulate individual atoms and molecules and hence

advance the field of synthetic chemistry. He was one of the first to recognize the potential of

nano-scale materials for our industrial society. In order to describe the process of moving or

manipulating atoms at the nano-scale (1-100 nm), this type of technology would later be

officially termed “nanotechnology” in 1974.2 Nanotechnology can be defined as follows3:

“Nanotechnology is the design, characterization, production and application of structures,

devices and systems by controlling shape and size at nanometer scale”.

Nanoparticles, the building blocks for nanotechnology, are engineered materials with at least

one dimension less than 100 nm. Nanoparticles may be having one (e.g., nanolayers), two

(nanowires and nanotubes) or three dimensions on the nanoscale (nanoparticles, quantum

dots, metal nanoparticles and fullerenes).4

In general, these Engineered nanoparticles (ENPs) can be categorized into carbon-based

materials such as fullerenes and carbon nanotubes: single walled carbon nanotube (SWCNT)

and multiwalled carbon nanotube (MWCNT) and inorganic nanoparticles including the ones

based on metal oxides (TiO2, ZnO and Al2O3, Fe3O4, Fe2O3, CeO2, etc.), metals (gold, silver,

aluminium, and iron), quantum dots (cadmium sulfide and cadmium selenide), dendrimers

(which are nano-sized polymers built from branched units capable of being tailored to

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perform specific chemical functions) and composites, which combine nanoparticles with

other nanoparticles or with larger, bulk-type materials.5,6

At nanoscale, materials show novel attributes and, because of their small size, they possess

‘substantial surface zone to volume’ ratio which renders engineered nanoparticles (ENPs)

more biologically reactive.7,8 Because of their high surface area, nanoparticles have a more

prominent number of active sites for interaction with diverse chemical species.9,10 In addition

to a large surface area, these particles show unique characteristics, such as catalytic potential

and high reactivity, which make them better materials than usual bulk materials. ENPs are

actually not new and have existed in the environment since the beginning of Earth’s history.

Introduction of nanoparticles into our environment may be natural or anthropogenic. The

ENPs enter the environment through natural sources such as volcanoes, forest fires, gas to

particle conversion and also through anthropogenic sources like power plants, airplane jet

metal fumes, combustion, ENPs (CNTs, quantum dots, metal nanoparticles etc.), etc.7,8 The

review intends to emphasize vividly the adverse health effects of the frequently applied

ENPs.

There are many review articles on synthesis, characterization and application of nano

particles, but there are very limited number of reviews in this important area which relates to

human life. The review will certainly compel the scientists to ponder over the indiscriminate

applications and consequences of application of ENPs. Further work is needed for recovery

safe disposal of nanoparticles. Until 2000, the research work on ENPs was mostly focused

on their synthesis, characterization and applications. However, few articles related to toxicity

of ENPs were also reported.4,7 It was after the year 2000 when studies on the toxicity of ENPs

started appearing in literature. In present review, the authors have concentrated on the articles

on the topic for 1990 to 2012 duration.

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It was reported that the same nanoparticles obtained/synthesized from different sources may

have different physicochemical properties and this may further affect ENPs’ interactions with

organisms.7 Recently nanoparticles have received significant concern due to their rapidly

expanding applications in different areas. Sol-gel method, inert gas condensation, spark

discharge generation, ion sputtering, spray pyrolysis, laser pyrolysis, photothermal synthesis,

thermal plasma synthesis, flame synthesis, low-temperature reactive synthesis, flame spray

pyrolysis, sol-gel process, mechanical alloying/milling, pulsed laser ablation, mechano-

chemical synthesis and electro-deposition are the various methods which have been used for

the synthesis of nanoparticles.9 Nanoparticles of alumina can be prepared by sol-gel method,

hydrolysis, supersonic thermal plasma expansion process, mechanical milling, combustion

synthesis, and hydrothermal method.10–15 Carbon nanotubes (CNTs) are grand development

of nanotechnology. CNTs are prepared by several methods such as thermal decomposition,

precipitation route, sol–gel route, modified sol–gel route, microwave assisted combustion

route, spray-drying, sonochemical, wet chemical method, colloidal synthesis of nanoparticles

method etc.16–27 Various other nanoparticles such as magnesium aluminate (MgAl2O4),

nanosilica, zirconia, tin oxide (SnO2), zinc oxide (ZnO), gold, titanium dioxide (TiO2), iron

oxide, ceria nanoparticles, copper nanoparticles, cadmium sulphide (CdS) etc. have also been

prepared for different application by using different methods.28-66

3. APPLICATION OF NANOPARTICLES

Due to the attractive and unique properties of nanoparticles, they have been used in a variety

of applications, including cosmetics, suntan lotions, paints, self-cleaning windows, stain-

resistant clothing, fillers, opacifiers, catalysts and semiconductors.8,67 Metal oxide

nanoparticles are extensively used in different applications like food, material, chemical and

biological sciences.68 Nanoparticles are also used in goods such as tennis, golf, and bowling

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balls; in the fabrication of high-performance tires; pharmaceutical products, and new

therapeutic treatments.

Recently, nanoparticles are also being used in filters and membranes for water purification

and other environmental solutions.Variety of nanoparticles are used in chemical-biological

arms detectors or for the fabrication of lighter but more powerful weapons.69 The most

common material according to “The Nanotechnology Consumer Products Inventory” are the

carbon nanoparticles.70 Silver is the second most common NP which is used in variety of

applications. Nanoparticles have also been proved to be a prominent alternate of conventional

adsorbent for the treatment of wastewater.71, 72

Titanium dioxide and zinc oxide NPs are frequently used in personal-care products such as

sunscreens , beauty products, toothpaste etc.73,74 In addition, silver NPs are increasingly used

as antimicrobial additives in detergents, food packaging and textiles.70 Potential global

market value for nanotechnology-related products in 2011–2015 was estimated to be up

to100 billion US dollars per annum.75 Various applications of different nanoparticles have

been summarized in Table 1 .

Among various nanoparticles, CNTs have distinct position and have various applications

such as in biology and medicine, as a composite and as an adsorbent material for the removal

of pollutants from water.76-81 Tin oxide (SnO2) nanoparticles are used in transparent

conducting coatings of glass, gas sensors and solar cells.82,83 Various nanoparticles such as

Al2O3, zirconia, CeO2, SiO2, and TiO2, have attracted more attention of researchers for varied

applications.84-94 Carbon nanohorns can be used for drug delivery.95-97 ZnO, Fe3O4, metallic

copper nanoparticles, Ag, magnesium–aluminum oxide, MgAl2O4,CdS,zero-valent iron (Fe0),

gold nanoparticles (II), ZnS, fullerene (C60) are some of the other nanoparticles which have

various applications in different fields.98-112

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Table 1

Due to their unique characteristics, ENPs have been reported to offer high capacity for the

removal of various pollutants from aqueous solutions and effluents and have attracted

scientific community. The ENPs have been used for the removal of pollutant materials

covering a broad spectrum. They have also been used for the removal of inorganic as well as

organic pollutants from water/waste water. Cupric oxide nanoparticles were found to be very

efficient for the removal of both pentavalent and trivalent forms of arsenic from aqueous

solutions.113 Nanoparticles of alumina in the size range of 2-30 nm were used for the removal

of DEClP (diethylchlorophosphate).114 It is clear from the Table 2 that there are wide variety

of nanoparticles which have been used for the removal of Cr(VI), congo red and Cu(II).115-

121 The Spirulina platensis nanoparticles were obtained by a mechanical method for the

biosorption of food dyes.122 Magnetic nanoparticles were found to be very efficient for the

treatment of Floride, Au(III) and uranium ions.123-125

Superparamagnetic nanoparticles with average size distribution of 9 ± 2.5 nm have been

utilized for acridine orange dye removal.126 Nanoparticles of Fe3O4@PAA with an average

diameter of 50 nm had been successfully synthesized by hydrothermal method were used as

adsorbent for the removal of rhodamine 6G (R6G).127 Another nanoparticle viz. hexadecyl

functionalized magnetic silica nanoparticles was also proved to be a good adsorbent for the

removal of rhodamine 6G (R6G) from aqueous solutions.128 Further, adsorption capacity of

Fe3O4@C nanoparticles with average size ∼250 nm for methylene blue and cresol red was

determined to be 44.38 mg/g and 11.22 mg/g respectively.129

The removal efficiency of different nanoparticles such as cadmium sulfide nanoparticles,

akaganeite nanocrystals, ZrO2 , CdSe ,BiFeO3 ,chitosan nanoparticles, NiO nanoparticles for

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different metallic species, organic pollutant, and different kind of dyes were also investigated

by different researchers (Table 2).113-153

Table 2.

Recently application of coated nanoparticles has attracted several researchers due to their

enhanced efficiency for different applications. It was observed that surface coating of

nanoparticle gives better results in comparison to their bare form. By coating with suitable

material, specific surface characteristic can be developed which can make them a suitable

candidate for a particular application. However, in some cases coated nanoparticle have been

proved more toxic than bare nanoparticles. Some of the coated nanoparticles with their

coating materials and applications are summarized in Table 3.154-178

Table 3

Recently, application of nanoparticles for biomedical applications is increasing day by day

due to their better efficiency in comparison to their bulk materials. Few years ago, only some

nanopartcsles were frequently used for different applications like CNTs, fullerene, quantum

dots, iron oxide, silica, silver nanoparticle zero valent nanoiron etc. But presently, researchers

are developing various types of nanoparticles with enhanced properties which make them

better for biomedical applications. Bagre et al., 2013, developed alginate coated chitosan

core shell nanoparticles for oral delivery of enoxaparin.154 In another study, β-lactoglobulin-

coated gold nanoparticles have been used for investigation of the fate of ingested inorganic

nanoparticles in gastrointestine.156 Polymerized-glucose coated Fe3O4 magnetic nanoparticles

were synthesized for drug delivery.160 Salicylic acid-coated magnetic nanoparticles have

been synthesized by Zhongwu Zhou et al. in 2013 for Genomic DNA extraction170. Dibetics

is very common and for oral insulin delivery, PEG coated silica nanoparticle was synthesised

by Ana Luiza R et al., 2014175. In other studies, oleic acid-coated Fe3O4 nanoparticles and

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Polyethylene glycol (PEG) coated Fe3O4 nanoparticles were prepared for biomedical

applications.176

4. ENVIRONMENTAL TOXICITY OF NANOPARTICLES

During 1990-2000, the researchers concentrated on the development of new processes for the

synthesis of various nanoparticles and their applications in various fields, but at the same

time they have inadvertently increasing the amount of nanoparticles in the atmosphere. Later

on, around the year 2000, scientists started thinking about the safe disposal of nanoparticles.

Due to the active development and application of nanotechnology, nanoparticles have

emerged as a new class of environmental pollutants that may significantly impact the

environment and human health. Increasing application of ENPs in commercial products and

industrial applications has eventually resulted in their release into atmospheric, terrestrial,

and aquatic environments.

There are various routes of exposure of nanoparticles such as occupational exposure in

which any person comes in contact with nanoparticles during manufacturing and research,

and consumer exposure in which person comes in contact with engineered nanoparticles

during use of different personal care products having engineered nanoparticles.179-181 In the

third type, the exposure may be due to the entire ecosystem to engineered nanoparticles

through the water and soil.8

Nanotoxicology refers to the investigation of interactions of nanostructures with biological

systems, explaining the relationship between the physical and chemical properties viz.

surface chemistry, composition, size, shape and aggregation with induction of toxic

biological responses.70 According to Kirchner et al., there are three possible ways by which

nanoparticles can affect any organism. Sometime due to release of toxic metal used in

nanosynthesis; nanoparticles can attach to the surface of cell membranes and finally their

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size or shape can also pose different effect on any organism such as CNT has more toxic

effect then than carbon-black and graphite.182

Sometimes, toxicity can be due to the toxicity of precursors which have been used for their

preparation. Thus nanoparticles may differ in their toxicological effects which depend on the

variety and size of the particles, test organism species, and test methods. Though the

nanoparticles may primarily target the respiratory organs, they also could get into the

gastrointestinal tract by many ways, such as indirectly via mucociliary movement or directly

via oral intake of drugs, water and food.183

Presence of nanoparticles in ecosystem can pose threatening results. CNTs, fullerenes, silver

nanoparticles, TiO2, ZnO and nano sized iron particles are frequently used in various

applications and their presence in the environment directly affects human beings, animals,

plants and aquatic species. The increased use of metal oxide nanoparticles in various fields

such as catalysis, sensors, environmental remediation and commercial products leads the

generation of higher amount of nanoparticles into the environment.184

TiO2, Fe2O3, ZnO and CuO nanoparticles are utilized in cosmetics and antimicrobial

products, so there is a strong possibility that these nanoparticles will ultimately enter aquatic

ecosystems through waste water discharges and wash offs during recreational activities such

as swimming and water skiing. Nanoparticles have many applications in different fields and

their extensive use may pose toxic effects on flora, fauna and humans. Several in vivo and in

vitro studies have been carried out to observe the toxicity of nanoparticles. It was reported

that the results of in vitro study show good correlation with in vivo study but some times

results of in vitro study do not implement on in vivo study. To observe the correlation

between in vitro and in vivo study, Sayes et al. (2007) compared in vitro and in vivo

pulmonary toxicity profile of some carbonyl iron, crystalline silica, amorphous silica nano

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zinc oxide and fine-sized on rats.185 They observed that there was little correlation between

the measurement of in vivo and in vitro studies.

In 2013, in vitro and in vivo studies were demonstrated to investigate the effect of selenium

nanoparticle on Leishmania major.186 In another study, in vitro and in vivo studies for

determination of toxicity of metallic nanoparticles were performed and it was observed that

the nature of nanoparticle like size, shape and stability can affect toxicity level.187 But results

for in vivo and in vitro study was not in good correlation. It may have been due to tested cell

line. In vitro and in vivo genotoxicity and cytotoxcicity of silver nanoparticles was

demonstrated by Ghosh et al., in 2012 where they reported good correlation between the in

vitro and in vivo experiments.188

Kwon et al. studied the genotoxic potential of ZnO nanoparticles for this purpose they

selected four kinds of ZnO nanoparticles (20 nm and 70 nm size, +ve and –ve) and almost

similar result were obtained for in vitro and in vivo studies.189 Occupational Safety and

Health Administration (OSHA) standard has decided some standard for nanoparticles

human exposure.190 According to OSHA, maximum limit for nanodust to human exposure is

3x10-5 x10-3 µg/cm3/h and 2-300 particles /cell/h, respectively.

The main focus of this review paper is to debate the toxicity of widely used ENPs

like CNTs, fullerenes, quantum dots, TiO2, Ag, ZnO, Iron/ iron compound and some other

other nanoparticles on flora and fauna.

4.1. Toxicity of carbon nanotubes (CNTs)

Among the various types of nanoparticles, carbon nanotubes (CNTs) are the most promising

nanoparticles due to their specific mechanical, electrical and magnetic characteristics. Carbon

nanotubes are allotropic modifications of carbon that can be represented as a sheet of

graphene (single layer of graphite) rolled into a cylinder. They are chemically and thermally

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very stable.191-193 It was first discovered by Ijima in 1991.194 CNTs are cylindrical molecules

composed solely of carbon atoms. CNTs are distinct from carbon fibers, which are strands of

layered graphite sheets. They can be imagined as a seamless cylinder formed from a graphite

sheet with a hexagonal lattice structure.195

There are two main forms of manufactured CNTs, the single-walled or SWCNT, and multi-

walled or MWCNT.196-198 In terms of structure, the SWCNT is a single-layered graphene

sheet which is rolled-up as cylindrical shapes, with a diameter of approximately 1 nm and a

length of several micrometers, whereas the MWCNT contains two or more concentric layers

with various lengths and diameters.199 Both SWCNTs and MWCNTs have attracted

widespread interest for commercial and industrial applications due to their novel properties

and unique electronic properties. CNTs exhibit several unique physical and chemical

properties which allow their application in numerous technological applications. The unique

properties of CNTs in addition to the wide range of functionality afforded by chemical

modification, allow them for many applications.70-75

The CNTs have unique absorption in the near-infrared region, which enables its utility for

biological sensing.200,201 Due to nanosize, CNTs have the potential to interact with

macromolecules such as proteins and DNA.202 The near infrared optical absorption of carbon

nanotubes being used for laser heating cancer therapy and the unusual one dimension hollow

nanostructure particularly makes CNTs useful as novel drug and gene delivery tools.203,204

Because of the rich electronic properties of CNTs, they have been explored for the

development of highly sensitive and specific nanoscale biosensors.205

CNTs have also been used for manufacturing various electro analytical nanotube devices

and as electro mechanical actuators for artificial muscles.206,207 The more extensive scope of

expanding nanotechnology applications for Cnts will probably bring about the expanded

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potential for both human and environmental exposures to this nanomaterial. Therefore, it's

necessary to examine the toxicity and also the biocompatibility of CNTs.

Several researchers have investigated their direct or indirect deleterious effects on the lungs,

skin and other parts of the body due to the entry of CNTs.208,209 It was demonstrated that the

toxicity of CNTs depends upon size, dosage and medium.210-217 In another study, Shen et

al.(2009), reported that neutral and negative charged MWCNTs were nontoxic to cell lines at

a concentration of up to 100 mg/L, but the positive charged ones were found to be toxic to

cells at 10 mg/L.218 Some studies on rats and mice have shown that SWCNT and MWCNT

induce oxidative stress, inflammation, granulomas and fibrosis in the lungs.219-221

Smith et al.,(2007) obtained evidence of oxidative injury in rainbow trout (Oncorhynchus

mykiss) exposed to SWCNTs.222 They concluded that CNTs acted as respiratory toxicants in

rainbow trouts. Multi-walled carbon nanotubes and carbon nanofibers have been found to be

significantly toxic to human lung tumor cells as early as 24h after exposure.223 Single-walled

nanotubes have been found to be toxic in some systems. 224

Tiana etal.,(2006) studied the toxicological effects of five carbon nanoparticles SWCNTs,

active carbon,carbon black,MWCNTsand carbon graphiteon human fibroblast cells in

vitro.225 It was observed that refined nanoparticles showed more toxic effect than its

unrefined forms. Toxic effects of both SWCNTs and MWCNTsare displayed in Table 4. 226-

266

Table 4.

CNTs were found to induce a dose and time dependent increase of intracellular reactive

oxygen species (ROS) which is ultimately responsible for cell damage.266 It was reported that

CNTs can induce growth inhibition in the case of protozoan.267 However, growth stimulation

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of a unicellular protozoan by CNT was also observed in a growth medium containing yeast

extract. This was explained by the uptake of CNT-peptone conjugates where the additional

peptone was responsible for the stimulation.268

In an alternate study, it was exhibited that coated CNTs were promptly taken up by Daphnia

magna.269 However, impact of nanoparticles were seen at the highest concentration. Acute

toxicity was only observed at the highest concentration. Japanese investigators have

hypothesized that single MWCNT together with the larger agglomerates, or by themselves,

could be responsible for inducing mesotheliomas.270 Increasing applications of CNTs in

biomedical applications may lead to potential toxic effects to human health. 271

They revealed that SWCNTs may induce oxidative stress to the nervous system. The effect of

MWCNTs on Sprague–Dawley rats were demonstrated by Muller et al (2005).272 It was

observed that both MWCNT and ground CNT were responsible for the inflammatory and

fibrotic reactions. TNF-α was found in the lung of treated animals which confirms that both

CNT and ground CNT can stimulate the production of TNF-α in the animals. Hirano et al.

(2008) studied the effect of MWCNT on the plasma membrane of macrophages.

The size of MWCNTs was 67 nm.273 It was observed that in the MWCNT-exposed

macrophages, several proteins were adsorbed onto MWCNTs. It was reported that the plasma

membrane of macrophages was disrupted and infiltrated when exposed to MWCNT fibers.

Hirano et al.(2010), studied the cytotoxicity of MWCNTs in human bronchial epithelial

cells.274 It was found that CNTs can induce pulmonary disease just like the asbestos. Cheng

et al.(2009) reported the effect of MWCNTs on zebrafish (Danio rerio).275 Bio-distribution

and long-term effects of functionalized MWCNTs in developing zebrafish was demonstrated

using an in vivo study. It was observed that the offsprings of zebrafish loaded with BSA-

MWCNTs at 1- cell stage had lower survival rates.

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Cui et al.,(2005) found that SWCNTs inhibited the proliferation of human embryo kidney

cells (HEK293) cells by inducing cell apoptosis and decreasing cellular adhesive ability.259

Ultrafine carbon particles can have impact on central nervous system because they are

capable to cross the blood–brain barrier and can have impact on the central nervous

system.276 Warheit et al.,(2004,2005) studied the pulmonary toxicity in male rats. 277,278

They reported a high mortality rate was observed due to mechanical blockage of the upper

airway. Another effect of SWCNTs was an increase in pulmonary cell proliferation and

multifocal pulmonary granulomas. Significant increase in lung weight and transient increase

in bronchoalveolar lavage were also found. Pulmonary toxicity following acute exposure to

three SWCNT preparations in male mice was explored by Lam et al.279

Inflammation and pulmonary granulomas were observed for unrefined nanotubes and

purified nanotubes (PNT). Shvedova et al.(2006) investigated the cytotoxicity of raw-CNTs

on human keratinocyte cell. This study showed that dermal exposure to raw CNTs may lead

to dermal toxicity from accelerated oxidative stress, loss of cell viability, and morphological

changes.280 A comparative study of the cytotoxicity of their nanomaterials viz. SWCNT,

MWCNT and the C60 fullerene was carried out on guinea pigs.281. It was observed that

fullerene did not show any cytotoxicity on alveolar macrophages in guinea pigs. While

SWCNT and MWCNT showed cytotoxicity on guinea pigs. It was noted that SWCNT caused

higher toxicity in comparison to MWCNT. It was observed that by increasing the dose of

SWCNTs, the cell nucleus experiences degeneration, enlargement, and rarefaction of nuclear

matrix.

Muller et al., investigated that a single intratracheal instillation of MWCNT increased the

frequency of micronucleated type II pneumocytes in rat lungs in vivo associated with a

marked pulmonary inflammation.282 Singh et al., (2009) reviewed the genotoxicity of some

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engineering nanoparticles283 and found that ENPs can cause chromosomal fragmentation,

DNA strand breakages, point mutations and alterations in gene expression profiles.

Takagi et al. (2008) reported intraperitoneal application of MWCNTs in p53+/- mouse.270

MWCNTs was found to be able to induce mesothelioma and showed carcinogenic effects on

mice. Poland et al. (2008) reported that when carbon nanotubes were introduced into the

abdominal cavity of mice, they can induce asbestos like pathogenic changes in the

mesothelial lining of the abdominal cavity.284. Radomski et al. (2005) reported that SWCNT

and MWCNT induce platelet aggregation and vascular thrombosis.285

4.2. Toxicity of fullerenes

Fullerenes are molecules with 60 atoms of carbon, commonly denoted as C60. It

(Buckminster fullerene) was first discovered by Kroto et al. (1985).286. Fullerene consist of

closed spherical shells comprised only of carbon atoms.

There are also higher mass fullerenes with different geometric structures, such as, C70, C76,

C78 and C80.287 However, the most widely explored is the C60 molecule. Fullerenes are a

class of materials which shows unique physical properties. Even after applying extreme

pressures they never lose their shape and regain their original shape on releasing the

pressure.

Due to the specific characteristics, C60 has many industrial and medical applications. For

example, the use of C60 is being investigated for use in optics and superconductors, and for

drug delivery.112,288 Fullerenes are known to be an empty structure with dimensions like

several biologically active molecules.289 Recently a number of cosmetic products such as face

creams that contain C60 nanoparticles have been introduced in the market.290 The main

exposure routes of fullerene nanoparticles are inhalation,dermal contact and ingestion.

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An in vitro and in vivo investigation of the impacts of fullerene on development of mice was

explored by Tsuchiya et al. (1996).291 Fullerene(C60) solubilized with polyvinyl pyrrolidone

inhibited cellular differentiation. Proliferation of mesencephalic cells was also observed due

to C60 fullerenes solubilized with polyvinyl pyrrolidone. C60 was distributed throughout the

embryo at 50 mg/kg and the yolk sac was reported to be impaired. In vitro mutagenic

activity in in 3 Salmonella strains exposed to C60 was reported by Sera et al. (1996).292

Iwata et al.(1998)studied the harmfulness of C60 on the hepatic catalyst and reported that the

C60 fullerene can decrease the hepatic enzyme action of glutathione in humans, mice and

rats.293In vitro exposure to the C60 fullerene induced oxidative damage in rat hepatic

microsomes.294

Mutagenic activity of three C60 fullerene derivatives on Salmonella typhimurium were

studied by Babynin et al.(2002). For this study, three fullerene derivative viz. (i)

dimethoxyphosphoryl-carbethoxy-methanofullerene, (ii) dimethoxyphosphoryl-carbmethoxy-

methanofullerene and (iii) 1-methyl-2-(3,5-di-tertbutyl-4-hydroxy-phenyl)-3,4-

fulleropyrrolidine were selected.295 It was observed that, (i) and (iii) of these derivatives

showed negative results while the second derivatives were found to be anti-mutagenic.

In an alternate study mutagenic activity of C60 fullerene containing malonic acid molecules

was demonstrated.296 Cytotoxicity (Cl50) of four different kinds of water-soluble fullerenes

was explored by Sayes et al. (2004).297 Effect of fullerene was tested on human cells and

they reported that toxicity depends on the nature of functional groups.

Oberdorster (2004) showed that C60 fullerenes induced changes in brain of the fish even at

very low aquatic exposure level.298 Significant lipid peroxidation was found in the brains of

large mouth bass after 48 h of exposure to 0.5 mg/L of uncoated C60 fullerenes. Lovern and

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Klaper(2006) demonstrated that diameter of fullerenes is one of the important parameters

which is responsible for the toxicity.

They investigated the differential toxicity for 10–20 nm fullerenes and 20–100 nm fullerenes

and demonstrated that smaller fullerenes proved to be more toxic with a LC50 at 0.46 mg/L

while the larger fullerenes had a LC50 of 7.90 mg/ L.299 Toxic effects of fullerene C60 and

modified fullerene C60 in an in vivo/in vitro study are presented in Table 5. 300-317

A recent research on toxicity of fullerene C60 with benzo[a] pyrene in Danio rerio(zebrafish)

hepatocytes suggested that C60 can decrease cell viability.318

Table 5.

4.3. Toxicity of quantum dots

Quantum dots are spherical nanocrystals from 1 to 10 nm in diameter(Aitken).319,320 Quantum

dots have been developed within the variety of insulators, semiconductors, metals, magnetic

materials or metallic oxides. Typical structure of quantum dots has been reported by scientific

workers. 319,320

They possess unique electronic, optical, magnetic and catalytic properties.321 Semiconductor

quantum dots show specific quantal effect which is dimension-dependent. These ENPs have

attracted a special interest for their promising applications in molecular biology, medicine

and information technology.322,323

In spite of having promising applications in different fields, these ENPs show ecotoxicity.324

The ecotoxicological effects of CdTe quantum dots to freshwater mussel Elliptio complanata

have been reported showing that these ENPs are immune toxic to freshwater mussels and can

cause oxidative stress in gills causing DNA damage.325

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Wang et al., (2008) observed toxicity of two commercially used nanoparticles viz. titanium

dioxide(TiO2) and quantum dots (QDs) using the unicellular green alga Chlamydomona

sreinhardtii.326They concluded that QDs were found to be more toxic to Chlamydomonascells

in comparison to TiO2.

The cytotoxicity of Cadmium selenide (CdSe) nanocrystal solutions and of CdSe/ ZnS for

tumour cells and human fibroblasts was studied by Kirchner et al. (2005).182 It was reported

that surface chemistry also influenced cytotoxicity of any nanoparticles. Feng et al.(2012)

reported that cadmium tellurium(CdTe) QDs exhibited a dose-dependent inhibitory effect on

cell growth of Escherichia coli (E. coli).327 It was also observed that toxicity also depend on

the particle diameter. Smaller sized quantum dots were found to be more toxic for E.coli.

Derfus et al.(2004) reported the cytotoxicity of CdSe quantum dots in an in vitro study.328

The viability of hepatocytes incubated in a solution containing quantum dots decreased

according to its concentration (0.0625 < 0.25 < 1 mg/mL). They also suggested that the

quantum dots that had been exposed to UV radiations for 8 hours reduced the cellular

viability significantly. It was demonstrated that quantum dots can induce cell death by lipid

peroxidation of human neuroblastoma cells.329 CdSe quantum dots can be cytotoxic due to

the release of Cd2+ ions. 330-332 It can also be toxic on direct interaction with cells.182, 333,334

Green and Howman (2005) carried out an in vitro experiment in which they incubated coiled

double-stranded DNA in a cadmium selenide solution encapsulated in zinc sulphite

functionalized with surface biotin.335 They found that the quantum dots altered the DNA by

producing SO2 free radicals, resulting from ZnS oxidation.

In vitro cytotoxicity of CdSe/ZnS quantum dots coated with mercaptoundecanoic acid and

sheep serum albumin was demonstrated by Shiohara et al. (2004).336 In this study, they

produced three forms of quantum dots, which showed different photoluminescence. Effect

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of different concentration of CdSe/ZnS nanoparticles on human hepatocytes, primate kidney

cells and cervical cancer was demonstrated and it was reported that here was a decrease in

the viability of the 3 cell lines at concentrations of 0.1 and 0.2 mg/mL, which further

increased with the increasing concentration.

In one study, Cadmium selenide (CdSe) nanoparticles were found to be responsible for the

enhancement of vacuolar membrane permeabilization (VMP). It was observed that exposure

to nanoparticles increased in ROS accumulated cells.337 Immunocytotoxic, cytogenotoxic and

genotoxic effects of cadmium telluride QDs (CdTe QDs) on the marine mussel

Mytilusgalloprovincialis were explored by Rocha et al.,(2014). It was reported that cadmium

accumulated in mussel soft tissues and hemolymph which is the reason of immunocytotoxic,

and genotoxic effects in M. galloprovincialis .338

4.4. Toxicity of TiO2 nanoparticles

Titanium dioxide nanoparticles (TiO2 ENPs) are among the top five ENPs utilized as a part of

customer items such as paints and additives in pharmaceuticals.339

Commercial products such as sunscreens and self-cleaning window coatings consist of

anatase TiO2 ENPs.340,341 Sunlight-illuminated TiO2 catalyses DNA damage, both in vitro and

in vivo , since exposure to such nanoparticles is mainly through skin and inhalation342 .

In another investigation, it was demonstrated that exposure to nanoparticles affects the brain

Murine microglial cells. For this study, commercial anatase and rutile titania of average

crystalline size 30nm were selected and they displayed extracellular release of H2O2 and the

superoxide radical and furthermore caused hyper-polarization of mitochondrial membrane

potential.343 For example, TiO2 absorbs substantial UV radiation yielding in aqueous media

hydroxyl species. These species may cause substantial damage to DNA, resulting in

additional environmental hazards. 344,

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Hu et al., (2009) investigated the in vitro cytotoxicity of different metal oxide nanoparticles

Viz. ZnO, CuO, Al2O3, La2O3, Fe2O3, SnO2 and TiO2 to the test organisms, Escherichia

coli.345 It was observed that metal oxide (TiO2) with higher cation charge showed lower

cytotoxicity. Among all metal oxides, ZnO was found to be most toxic. Wang et al.,(2007)

reported that nano-sized TiO2 can produce free radicals and exert a strong oxidizing

ability.346

In an another study, Daphnia magna exhibited higher mortality when exposed to TiO2

nanoparticles with an average diameter of 30 nm than those exposed to 100–500 NM. 299 A

significant increase in inflammation signs was observed during the administration of 20 nm

TiO2 particles in comparison with the same mass of 250 nm particles.347,348 TiO2 exists in

three main crystallographic structures, e.g. anatase, rutile and brookite of which the first two

are usually considered the most important in the environment.349

Each of these forms presents different properties and therefore have different applications

and environmental impacts. In addition, microorganisms in the presence of light are adversely

affected by TiO2 nanoparticles due to the production of ROS.350

This experimental evidence suggests that these nanoparticles can produce oxidative stress in

aquatic organisms. Inflammatory injury and respiratory distress were observed after the

exposure to TiO2 nanoparticles in rainbow trout.351,352 Musee et al.(2010) selected freshwater

snail Physa acuta (Draparnaud) to demonstrate the effect of different nanoparticles viz. γ-

alumina,α-alumina, modified TiO2 (M-TiO2), and commercial TiO2.353

They reported that increases of γ-alumina, α-alumina concentrations caused a

vital reduction in the embryo hatchability and the embryo growth rate. It was also observed

that these nanoparticles induced developmental deformities of the embryos. In addition,

available ecotoxicological studies of TiO2 nanoparticles in aquatic organisms such as

Daphnia magna, algae, fish as well as nematodes were more prominent.299, 354-363

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Wang et al. (2011) reported the combined effect of TiO2 nanoparticles (n-TiO2) and As(V) on

Ceriodaphnia. dubia.364 Result showed that n-TiO2 presence of n-TiO2 increase the toxicity

of As(V).The Mortality increases with increasing n-TiO2. In 2006, the International Agency

for Research on Cancer (IARC) classified TiO2 as a possible carcinogen to humans and

animals also.365,366 Different phase compositions of TiO2 nanoparticles (e.g., anatase and

rutile, or a mixture of the two) affect cytotoxicity and inflammatory response in lung cells. It

was observed that anatase TiO2 nanoparticles were 100 times more toxic than an equivalent

sample of rutile TiO2 which revealed that oxidative damage in human lung epithelial cells is

strongly dependent on the crystal phase composition of nanoparticles.251

Ecotoxicity study of TiO2 nanoparticles on microalgae species, Scenedesmus sp. and

Chlorella sp.were investigated by Sadique.(2011) and they noticed a decrease in the

chlorophyll content of the treated algae species in comparison to the untreated species367.

In 2011, Lapied et al., reported the ecotoxicological effects of an aged TiO2

nanocompositeon the earthworm Lumbricus terrestris for 7 days Results showed an

enhanced apoptotic frequency which was higher in the cuticule, intestinal epithelium and

chloragogenous tissue.368 Noel et al. (2012) investigated the effect of inhaled nano-TiO2

aerosols on rat lungs and reported that the dimensions and concentrations of ENPs

agglomerates affected the biological responses.369

The effect of sub-acute exposure to nano-TiO2 on oxidative stress and histopathological

changes in juvenile Carp (Cyprinus carpio) were investigated by Linhua et al. (2009).370 This

study revealed that a higher concentration of nanoparticles of TiO2 may show abnormal

physiological and behavioral changes on carp and also may produce cytotoxic effects.

Sha et al. (2011) demonstrated the effect of TiO2 nanoparticles on liver cells from humans

and rats. It was found that cell viability exhibited is dose-dependent and time-dependent. 371

Mild cytotoxic response of TiO2 ENPs was determined as clear by the MTT and NR uptake

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measures after 48 h of exposure within the human epidermal cells (A431).372 Mice exposed

to TiO2 ENPs with a primary size of 2–5 nm was found to have a significant but moderate

inflammatory response in the lungs.373

Effect of size, surface and crystalline structure of titanium dioxide nanoparticles on pelagic

filter feeder Daphnia magna and the benthic amphipod Gammarus Fossarum were

demonstrated by Seitz et al.,(2014) and it was reported that nanoparticle toxicity depends on

particle characteristics.378 Effect of two forms of TiO2 viz. anatase (TA) and an anatase/rutile

mixture (TM) embryo of the fish Danio rerio were studied and it was demonstrated that TM

can induce greater mortality of the larvae in comparison to TA.379

The toxicity of various nanoparticles such as nano-TiO2, ZnO, CuO and Co3O4 on channel

catfish hepatocytes and human HepG2 cells were investigated(Wang ,Y., 2011).380 HepG2

cells were found to be more sensitive for nanoparticles than catfish primary hepatocytes. The

toxicity of nanoparticles on test species was due to ROS-induced cell death, cell damage and

mitochondrial membrane damage.

Several types of metal oxide nanoparticles affected mitochondrial functions and induced

lactate dehydrogenase (LDH) leakage at concentrations as low as 50–100 g/ L.381, 382

4.5. Toxicity of silver nanoparticles

Because of their antiseptic properties, silver nanoparticles are widely used in creams, textiles,

surgical prosthesis, cosmetics and as bacteriocides in fabrics and other consumer

products.383 Both silver nanoparticles and dissolved silver, are known to have significant

antibacterial properties. A higher antimicrobial activity is expected due to its larger specific

surface area. The silver nanoparticles inhibit the enzymes for the P, S, and N cycles of

nitrifying bacteria. They are also reported to block DNA transcription, and adenosine

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triphosphate (ATP) production. The silver nano particles react with proteins by combining

the –SH groups of enzymes, which leads to the inactivation of the proteins and interrupt

bacterial respiration.104,384

Due to their widespread applications, silver nanoparticles and their products have emerged

as a massive source of ENPs to the surroundings. Potential toxicity from dermal exposure

was shown with silver nanoparticles, that diminished human epidermal keratinocyte

viability.385 In an in vitro study of cultured human keratinocytes, Lam et al. (2004) observed

a substantial decrease in cell viability (0 to 9% cell viability after 30 minutes of incubation)

and concluded cytotoxicity of silver nanocrystals (released by Acticoat™).

Acticoat™ has been used for several years to heal wounds.386 Phytotoxicity of silver

nanoparticles on Phaseolus radiatus and Sorghum bicolor crop plants were investigated.387 It

was observed that seedling growth was adversely affected due to silver nanoparticles.

In another study, toxicity of silver nanoparticles on nematode, Caenorhabditis elegans were

investigated.388 The toxicity of bare silver nanoparticles and PVP-coated silver

nanoparticles were compared and it was observed that coatings on the silver nanoparticles

surface increase the toxicity of silver nanoparticles. Larese et al. (2009) demonstrated that

polyvinyl pirrolidon coated silver nanoparticles was able to affect the damaged skin in an in

vitro diffusion cell system.389 Transmission electron microscope (TEM) was used for

verification of human skin penetration due to nanoparticles. In another study, toxicity of

silver nanoparticles and ionic silver (Ag+) to photosynthesis in Chlamydomonas

reinhardtii.390 Silver nanoparticle also showed significant effects on rice (Oryza sativa L.)

seedlings391.

To investigate the effect of silver nanoparticles on seedllings of rice species, different

concentration of silver nanoparticles was taken and it was noted that there was significant

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reduction in root elongation, total chlorophyll and carotenoids contents. Toxicity of citrate

(cit-Ag NPs) or humic acid (HA-Ag NPs) capped silver nanoparticles (Ag NPs) and Ag were

demonstrated on. eggs, larvae, juveniles and adults of Platynereis dumerilii and it was

observed that cit-Ag NPs and HA-Ag NPs were more toxic than Ag.392

Effect of different sized silver nanoparticles on the seed germination and seedling growth in

jasmine rice (Oryza sativa L. cv. KDML 105) were investigated and it was observed that due

to silver nanoparticle s showed negative effects on seed germination and seedling growth.393

Vannini et al. reported that 10mg/L AgNPs dose affected the seedling growth and also

showed adverse effects on root tip cells.394

Genomic and proteomic changes were observed during AgNps exposure. Silver nanoparticles

also induced morphological modification in root tip cells(Vannini et al 2014)” Silver

nanoparticles were found to induce cytotoxic effects on fish Catla catla and Labeo rohita.395

It was observed that copper and silver nanoparticle(AgNPs) may reduce adult longevity in

Drosophila and decreased sperm competition.396

The effects of AgNPs in rainbow trout (Oncorhynchus mykiss) hepatocytes were explored.397

This study proposed that AgNPs could influence hormone-regulated cell signaling

pathways.On the exposure of Ag or Al2O3, nanoparticles cyotoxic effects were observed in

soil bacteria viz. Pseudomonas stutzeri and Bacillus cereus. A decrease in bacterial

transcriptional response was detected in NPs -treated soils.398

In another study it was reported that silver nanoparticles may inhibit the activities of

erythrocyte acetylcholinestrase(AChE) and Na+/K+-ATPase and also affected the plasma

biochemistry in adult zebrafish (Danio rerio).399 A comparative study was carried out for the

toxicity of bare and polyvinylpyrrolidone (PVP) coated silver nanoparticles on the

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nematode, Caenorhabditis elegans. Coated silver nanoparticles were found to be more toxic

in comparison to bare silver nanoparticles.400

4.6. Toxicity of zinc oxide nanoparticles (ZnO nanoparticles)

The remarkable properties of zinc oxide(ZnO) nanoparticles have attracted the interest of

many researchers in the past few years.98-100,401 One of the most remarkable commercial

applications of 20–100 nm ZnO nanoparticles is their use in the production of sunscreens and

cosmetics.402 At nanoscale, ZnO possesses novel electronic and optoelectronic properties and

frequently utilized in biosensors, sunscreens, and additionally in medicinal applications like

dental filling materials and wound healing.403-406

Due to widespread applications, ZnO nanoparticles are finally reaching the environment

unintentionally. Recently, research has been carried out on the potential toxicity of ZnO

nanoparticles in particular and other metal oxide nanoparticles.79,407-411 and it has been

concluded that these nanoparticles ultimately pose threat to fauna, flora and humans. Because

of the indiscriminate use of ZnO nanoparticles, it is compulsory to observe their fate in the

ecosystem and biocompatibility with biological system.

Nations et al., (2011) studied the effect of nano ZnO on Xenopus. laevis. X. laevis exposed to

high ZnO nanoparticles concentrations died or displayed slower growth.412 Presence of ZnO

nanoparticles in aquatic ecosystems could also reduce food resources such as algae. They

reported that ZnO nanoparticles released into aquatic ecosystems in high concentrations

could have detrimental effects on aquatic organisms such as amphibians. Exposure to ZnO

nanomaterial significantly increased mortality and decreased hatchability of zebrafish at

1mg/L.413

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Zebrafish also had an increased incidence of tissue ulceration beginning 72 hour post

fertilization (hpf) and reaching 100% tissue ulceration by 108 hpf. A recent study on ZnO

nanoparticles reported that it impels much more noteworthy cytotoxicity than non-metal

nanoparticles primary mouse embryo fibroblast cells.414 and prompts apoptosis in neural stem

cell.415 The revealed reports have demonstrated that ZnO nanoparticles restrains the seed

germination and root development.416 Adams et al.,(2006) studied the antibacterial properties

of nanoparticles on Bacillus subtilis and Escherichia. coli.417

Inhalation of ZnO may cause disturbance in pulmonary function(lung disorders) in pigs

while in case of inhalation in humans, it may responsible for metal fume fever in

humans.418,419 ZnO nanoparticles have been reported to be most toxic nanoparticle among the

engineered metal oxide nanoparticles.

ZnO nanoparticles have the lowest LD50 value.420 On the other hand, it was additionally

reported that ZnO was not discovered to be cytotoxic to human dermal fibroblasts.421 It has

reported that ZnO nanoparticles cause membrane damage in the E. coli, possibly due to

oxidative stress mechanisms.422 SEM images of E. coli treated with ZnO nanoparticles

showed considerable damage to some E. coli and it was due to the breakdown of the

bacterial membrane.

Huang et al. (2008) investigated the possible interactions that govern the bactericidal activity

of 60–100 nm polyvinyl alcohol (PVA)-ZnO nanoparticles against Streptococcus agalactiae

and Staphylococcus aureus.423 They observed the cellular damage when the PVA coated

ZnO nanoparticle concentrations were higher (> 0.016M) in the ethylene glycol (EG)

medium containing the cells. A significant change in the ZnO nanoparticle crystal structure

was observed after these cells established contact with PVA-coated ZnO nanoparticles,

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However, in their preliminary studies, contrary to previous studies, they reported that low

concentrations of ZnO nanoparticles did not induce any cellular damage.424

Heinlaan et al. (2008) investigated the toxicity of ZnO, Cuo and TiO2nanoparticles to bacteria

Vibrio. fischeri ,crustaceans Daphnia magna and Thamnocephalus platyurus.and studied the

toxic effects of metal oxides and solubilised metal ions.425 They showed that the metal oxide

nanoparticles do not necessarily have to enter to the cells to cause damage in the cell

membrane. In fact, the contact between the particle and the cell wall may increase the

solubilisation of metals.It has also been demonstrated that the release of metal ions from the

ZnO NPs i.e. from the solubilisation, was responsible for toxicity in lung cell lines.426

While under realistic environmental conditions, similar results on algae have been reported.79

Further, Lin and Xing (2008) explored that ZnO nanoparticles enter apoplast and protoplast

of the root endodermis and stele.427

Recently, Neuro behavioral toxicity of ZnO nanoparticles was investigated in developing

fish. Hatching delay and larval hyperactivity was observed in of embryo–larval zebrafish

when exposed to ZnO nanoparticles.428 Changes in plant growth, bioaccumulation and

antioxidative enzyme activity in Brassica juncea in the presence of ZnO nanoparticles were

studied by Rao et al.,(2014).

Nanoparticles of ZnO showed negative effects on plant. Bioaccumulation of ZnO

nanoparticles were also reported.429 Yoon et al., (2014) reported long term effect of ZnO

nanoparticles on the soybean [Glycine max (L.) Merrill]. It was reported that ZnO

nanoparticles adversely influenced the formative stages and reproduction of soybean

plants.430 Cytotoxic effects of ZnO nanoparticles on mouse dermal fibroblast cells (mDFs)

and human periodontal ligament fibroblast cells (hPDLFs) were investigated.431

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4.7. Toxicity of Iron/ iron oxide nanoparticles

Nanostructured iron oxides allow a wide range of potential applications in nanotechnology

related fields, including bio-medical imaging, magnetic target drug delivery, environmental

catalysis, magnetic storage and so forth. Nanostructured iron has broad applications in the

field of environment and biomedical and so it is necessary to study its environmental fate and

biocompatibility. Iron oxide NPs, Fe3O4 and Fe2O3 have been synthesized with a number of

methods involving different compositions and phases.4

Yan and Zhang (2011) showed the in-vitro cytotoxicity of nanoparticles utilizing Hek 293

cell culture system with diverse dosages.432

Nanoparticle of hematite were found to reduce cell viability. Due to such cytotoxicity,

decrease in the activity of antioxidative enzymes induced by oxidative stress in cells may

occur.

Some researchers studied the comparative toxicity of nano- and micro particles of some metal

oxides like Fe2O3, Fe3O4, TiO2 and CuO.433 They reported cell death, mitochondrial damage,

DNA damage and oxidative DNA lesions when the human cell line A549 was exposed to

these nano and microparticles. This study showed that CuO nanoparticles were much more

toxic when compared to the CuO microparticles. Similarly, the microparticles of TiO2 caused

more DNA damage compared to the nanoparticles. Toxicity of Au, Ag and Fe3O4

nanoparticles were studied on plants and microorganisms.434

Zero-valent iron nanoparticles have attracted more attention in the field of water and waste

water remediation due to their sorbing efficiency, but at the same time it is also becoming a

source of nanoparticles contamination in the environment.435-440 Zero valent iron

nanoparticles reduced high concentrations of solvents to nearly zero within days but at the

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same time, oxygen levels were reduced causing the groundwater anoxic and pH levels

changed significantly.71

Toxicity of four different iron oxide nanoparticles viz. polyvinyl pyrrolidone (PVP-IONP)

,ascorbate (ASC-IONP), dextran (DEX-IONP) and citrate (CIT-IONP), on Daphnia magna

were investigated.441 The benefits of different nanoparticles have been demonstrated in

several scientific fields, but reports on their capability to penetrate the skin are rare. Bregoli

et al.(2009)442 explored the poisonous quality of seven NPs viz. Sb2O3, TiO2,Fe2O3, Fe3O4,

Au, Co, and Ag on primary cultures of human hematopoietic progenitor cells with colony

forming unit(CFU) assays. Among all seven nanoparticles, Sb2O3 and cobalt (Co) NPs were

found to be more toxic than others. They also concluded that Sb2O3 NPs impair the

proliferation of erythroid progenitors.

4.8. Toxicity of CuO nanoparticles

Toxicity of aggregated zero valent copper nanoparticles on E. coli was studied by that by

applying the centroid mixture design of experiment.443 Various parameters viz. pH,

temperature, concentration of nanoparticles, aeration rate and concentration of bacteria were

taken under consideration. On the basis of linear and quadratic regression model it was

concluded that toxicity of copper nanoparticles depends on both primary and interactive

effects.

The lethal effects of CuO nanoparticles on freshwater shredder Allogamus ligonifer was

studied in 2012 by Pradhan et al (2010).444 Different concentration of CuO nano suspension

was prepared(0,50,100,250,500 and 1000mg/L) to observe its effect on the shredder. It was

observed that nanoparticle exposure led to lethal effects at high concentrations. Metal oxide

nanoparticles have been found to adversely affect mammalian cells and some aquatic

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organisms. For example, CuO nanoparticles induced death of H4 and SH-SY5Y cells in a

dose dependent manner.445

A comparative study on the toxicity of CuO NPs, core shell(CS-CuO) NPs and ionic copper

were compared in the aquatic macrophyte Lemna gibba. The study revealed that the polymer

coating changes the mechanism of toxicity due to changes in surface characteristics. CS-CuO

nanoparticles showed 50% decreased growth in plant in comparison to CuO nanoparticles.446

Jośko et al., (2014) demonstrated that nanoparticles (ZnO, Cr2O3, CuO and Ni )may also

affect the enzymatic activity of the soils.447

In another study it was observed Cu-nanoparticles may cause oxidative stress in the liver,

gills and muscles of juvenile Epinephelus coioides.448

4.9. Toxicity of cerium oxide nanoparticles (CeO2)

It was observed that due to the presence of cerium oxide nanoparticles in the root vascular

tissues and aerial parts of plants, the activity of root antioxidant enzyme were significantly

reduced. nCeO2 particles reached into the kidney been root via the gap in the

Casparian strip.449

Impact of CeO2 nanoparticles on two amphibian larvae viz. Pleurodeles waltl and Xenopus

laevis were reported by Bour et al.,(2014).They also demonstrated its effect on the

invertebrate Chironomus riparius and the Diatoms Nitzschia palea. Genotoxic effect was

noted in amphibian larvae and Pleurodeles.450 Nanoparticle can also pose toxic effect on

fungal population. The toxicity of nano-CeO2 was not ascribed to the dissolved Ce2+ ions,

but to the entrapment of algal cells into the aggregates of nanoparticles.451

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Phytotoxicity of four rare earth oxide nanoparticles were explored by Ma et al. (2009).

Phytotoxic behaviour of CeO2, La2O3, Gd2O3, and Yb2O3 nanoparticles were studied on

seven higher plant species (radish, rape, tomato, lettuce, wheat, cabbage, and cucumber).452

Their effects on root growth varied greatly between different nanoparticles and plant species.

It was observed that inhibitory effects different nanoparticles also differed in the different

growth process of plants.

4.10. Toxicity of chitosan/gold/silica nanoparticles

Loh et al., (2010) studied the effect of chitosan nanoparticles (1% w/v) into the cell nucleus

and after 4 h exposure, it was observed that the chitosan NPswere responsible for necrotic

or autophagic cell death.453 It may be due to damage of cell membrane and resultant enzyme

leakage.The acute toxicity of gold nanoparticles was explored by Cho et al., in 2009 by

carrying out an in vivo study using 13 nm-sized gold nanoparticles oxidative stress and

membrane damage coated with PEG (MW 5000)454.

It was found that the PEG-coated NPs can induce acute inflammation and apoptosis in the

liver. It was reported that the PEG-coated NPs were trapped in liver Kupffer cells and

spleen macrophages. Monodisperse polypyrrole (PPy) nanoparticles with five different

diameters (20, 40, 60, 80, and 100 nm) were fabricated via chemical oxidation

polymerization in order to evaluate size-dependent cytotoxicity .455

Fent et al. (2010) demonstrated the toxic effects of fluorescent silica nanoparticles (FSNP) on

early life stages of zebrafish.456 It was observed that the ∼60 and ∼200 nm-sized FSNP were

adsorbed on the chorion of eggs. The effect of some nanoparticles on humans is summarized

in Table 6.457-466 Now, researchers are focusing not only on the new synthesis method of

nanoparticles but also showing their concern regarding the fate of nanoparticles and their

effects on humans.

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Table 6

5. CONCLUSIONS

In the new century, with increasing demands for nanotechnology, there has been a drastic rise

in the synthesis as well as application of nanoparticles in widespread areas. This has led to

rapid development of commercial applications which involve the utilization of a wide variety

of engineered nanoparticles (ENPs). Moreover, the recent use of nanoparticles in biomedical

applications has made it even more demanding owing to their specific properties. Further, the

application of coated nanoparticles for various purposes is surprisingly showing a great

increase. Production of varieties of nanoparticles at astronomically immense scale and their

utilization for the benefits of humans will conclusively lead to its entrance in the environment

by direct or indirect processes such as disposal, accumulation, etc. The production, utilization

and disposal of manufactured nanoparticles will inevitably lead to unintentional discharges in

air, soil and aquatic systems which have put forward to the potential risk to the environment.

Nanotoxicity of any nanoparticle is greatly influenced by its shape, size, variety, coating

material and composition. Sometimes, toxicity can be due to the toxicity of precursors which

have been used for its preparation. Toxicity may be increased/decreased depending upon the

environment like physical and chemical nature of contacting species, test organism species,

and test methods. It was also reviewed that same nanoparticles may pose different extent of

toxicity on plants, human beings and animals. Toxicity also depends upon the nature of

functional groups.

There may be a good correlation in the results for in vitro and in vivo studies, depending

upon the experimental conditions and the sensitivity of specimens. So there arises a need for

better understanding and assessment of the toxicity and eco-toxicity of engineered

nanoparticles to the key ecosystem organisms like algae, plants, and fungi which are

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continuously being exposed to these new materials. Increasing demands of nanoparticles

cannot be neglected, due to their vast applications and therefore, for better and safe use of

nanoparticles in future we have to be very attentive in understanding the fate, demeanor and

toxicity of nanoparticles. Development of some predictive models should be encouraged in

order to establish the safety of engineered nanoparticles. Academic Researcher and industries

should fixate on reuse/ regeneration of exhausted nanoparticles to obviate its ingression into

the environment.

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Table 1. Applications of engineered nanoparticles.8,58,72, 76-112

Nanoparticles Products/applications References

CNTs Electronic devices, field emission devices, and composite materials , numerous biological and medical applications, As adsorbent material for the removal of pollutants from water

(76-81)

SnO2

Transparent conducting coating of glass, gas sensors, solar cell, and heat mirror, gas sensors, catalyst supports

(82,83)

Al2O3 Batteries, adsorbent, grinding, catalysis; polishing abrasives (84)

CeO2 Abrasive materials of chemical–mechanical polishing (CMP) oxygen sensor , polishing materials, gas sensors, fuel additive; (85- 87)

SiO2 Pharmaceutical products, vegetable oil refining, ceramics, detergents, adhesives, electronics, chromatography , fire proof glass; fillers , catalysts

(88-91)

TiO2 Food colouring, photocatalyst; pigments, additive in pharmaceuticals and cosmetics ,paints, antibacterial and self-cleaning materials, sunscreen, cosmetics, uv-protection, catalysis, self-cleaning window coating; fillers, catalyst supports, and photocatalysts;

(84, 92-94)

Carbon nanohorns

Catalyst supports; and drug delivery (95-97)

ZnO Electrostatic dissipative coating ,semiconductor material , chemical sensors and solar cells paints, sunscreen, cosmetics, electrical and optical devices ,uv-protection, catalysis; diode lasers , chemical absorbent , pigments, optical materials,

(84,98-100)

Fe3O4 Removal of contaminants, sensors, magnetic resonance imaging , bio manipulation; magnetic storage media magnetic refrigeration magnetic resonance imaging (MRI) DNA detection and drug delivery system and cancer therapy

(8,72,101-103)

Metallic copper nanoparticles

Applications in catalysis (58)

Ag Dental resin composites ,coatings of medical equipments Paints, textiles, antibacterial agent,

(88,89, 104)

Magnesium–aluminum oxide, MgAl2O4

Sensors ,catalysis (105)

CdS Photodetectors, optoelectronics, and for solar cell applications (106)

zero-valent iron

(Fe0)

Water remediation; (107)

Gold nanoparticles(II)

Drug delivery applications (108)

ZnS Electroluminescent devices, solar cells and phosphors

(109)

Fullerene Superconductors and for drug delivery; sensors, cosmetics catalyst, (110-112)

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(C60) polymer modifications optical and electronic devices, sporting goods polymers, and biological and medical applications ,lubricants,

Table 2.Removal of pollutant species from effluents by various nanoparticles pollutants (inorganic/organic).113-153

Pollutants

(inorganic/organic)

Nanoparticles used for the removal of pollutants

Reference

s

As(III) and As(V) Cupric oxide nanoparticles (113) Diethylchloro phosphate (DEClP)

Al2O3nanoparticles (114)

Cr(VI) Carboxymethyl 2 cellulose-stabilized zero-valent iron nanoparticles; multiwalled carbon nanotubes

(115,116)

Congo red Maghemite nanoparticles; alumina nanoparticles (117,118)

Cu Multiwalled carbon nanotubes; kaolinite-supported zero-valent iron nanoparticles ;chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid

(119-121)

Food dyes Spirulina platensis nanoparticles (122) Fluoride Fe3O4@Al(OH)3magnetic nanoparticles (123) Gold(III) ions Chitosan coated magnetic nano-adsorbent (124) Uranium zero-valent iron nanoparticles (125) Acridine orange Magnetic nanoparticles (gamma -Fe2O3) (126)

Rhodamine 6G (R6G) Fe3O4@PAA nanoparticles; hexadecyl functionalized magnetic silica nanoparticles

(127,128)

Organic dyes Fe3O4@C nanoparticles (129) Methylene blue and crystal violet dyes

Cadmium sulfide nanoparticles (130)

Cd(II) Akaganeite nanocrystals ; Fe2O3 nanoparticles (131,132)

Pb(II) Silica–alumina nanoparticles (133)

Co(II) Magnetic chitoson nanoparticles ;zero-valent iron nanoparticles

(134,135)

Zn(II) Akaganeite nanocrystals (136) Cu(II) Iron phosphate nanoparticles multiwalled carbon

nanotubes (137,138)

Mo(VI) Maghemite (139) Hg(II) FeS (140) Arsenate Nanostructured ZrO2 (141) Acid Black-24 TiO2 and Fe0 (142) Methyl red Silica nanoparticles

(143)

Acid Orange 7and Acid Orange 10

Magnetic chitosan nanoparticles (144)

Rhodamine 13 BiFeO3 (145) Acid Green 27 Chitosan nanoparticles (146) Trichloroetheneand chlorobenzene

Palladium/magnetite (147)

TiO2

nanoparticles Acid Blue 92 ; Basic Blue 3 (148)

Flouride Mg-doped nano ferrihydrite (149,150)

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Fe3O4@Al(OH)3 magnetic nanoparticles Anthracene-9-carbonxylic acid

CdSe (151)

Methyl orange bentonite-supported nanoscale zero-valent iron

(152)

Cadmium and lead NiO nanoparticles (153)

Table 3.Application of coated nanoparticles154-178

Nanoparticles Coating materials Aim Refernces

Alginate coated chitosan core shell nanoparticles

Alginate Oral delivery of enoxaparin (154)

oleic acid-coated Fe3O4 nanoparticles

Oleic acid- pH-responsive Pickering emulsions (155)

β-lactoglobulin-coated gold nanoparticles

β-lactoglobulin Controlling the gastrointestinal fate of ingested inorganic nanoparticles.

(156)

Citrate-coated silver nanoparticles

Citrate Transformation of the morphology, dissolution behavior and reaction product of AgNPs in different amno acid -containing systems in human body

(157)

3-mercaptopropanoic acid-coated superparamagnetic iron oxide nanoparticles

3-mercaptopropanoic acid-

Arsenate removal (158)

Carbon-coated SnSb nanoparticles

Carbon lithium-ion battery anodes (159)

Polymerized-glucose coated Fe3O4 magnetic nanoparticles

Polymerized-glucose Delivery of aspirin (160)

Citrate-coated magnetic nanoparticles

Citrate For forward osmosis

(161)

Polypyrrole-coated magneticnanoparticles

Polypyrrole Extraction of nitrophenols (162)

Superparamagneticsodium alginate-coated Fe3O4nanoparticles

Malachite green (163)

Gold coated ferric oxide nanoparticles

Gold Detection of DNA hybridization processes

(164)

Carbon-coated titanium dioxide coreeshell nanoparticles

Carbon- Microbial fuel cells (165)

Hyaluronic acid-coated solid lipid nanoparticles

Hyaluronic acid Targeted deliveryof vorinostat to CD44 overexpressing cancer cells

(166)

Imidazole and imine coated ZnO nanoparticles

Imidazole and imine detection of Al(III) and Zn(II) (167)

Citric acid coated Fe3O4 magnetic nanoparticles

Citric acid Biomedical applications (168)

Nickel oxide coated carbon nanoparticles

Nickel oxide Temperature sensing materials

(169)

Salicylic acid-coated magnetic nanoparticles

Salicylic acid Genomic DNA extraction (170)

Phosphomolybdate-doped-poly(3,4-ethylenedioxythiophene) coatedgold nanoparticles

Phosphomolybdate-doped-poly(3,4-ethylenedioxythiophene)

Electrocatalyticreduction of bromate

(171)

Sulfate‐A‐coated magnetite Biomedical applications (172)

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nanoparticles PEG-coated silica nanoparticles Poly ethylene glycol Oral insulin delivery (173) Pyrolytic carbon-coated Si nanoparticles

Pyrolytic carbon- As anode materials for high-performance lithium-ion batteries

(174)

Polyethylene glycol (PEG) coated Fe3O4 nanoparticles

Polyethylene glycol (PEG)

Biomedical application (175)

Sulfonated-mercaptopropanoic acid coated Fe3O4 nanoparticles

Sulfonated-mercaptopropanoic acid

Magnetic catalyst for Biginelli reaction

(176)

Oleic acid-coatedFe3O4 nanoparticles

Oleic acid- Biomedical application (177)

Chitosan coated magnetic nanoparticles

Chitosan As a support for bio ligands binding

(178)

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Table 4. In vitro/in vivo studies of Single walled carbon nanotubes(SWCNTs) and multiwalled carbon nanotubes (MWCNTs). 226-266

SWCNT /MWCNT Effects Test species Reference

MWCNT Nitrative DNA damage human lung epithelial cells (226)

SWCNT Acute toxicity on central and peripheral nervous system of chicken

chicken embryonic spinal cord (SPC) or dorsal root ganglia (DRG)

(227)

Multi-walled carbon nanotubes

In vitro cyto toxicity C6 rat glioma cells (228)

Water dispersible oxidized multiwalled carbon nanotubes

Cytotoxicity effects marine alga, Dunaliella

tertiolecta (229)

Carbon nanotube IImmunotoxcity

rainbow trout, Oncorhynchus mykiss

(230)

SWCNT Subcutaneous implantation

Mice (231)

Multi wall carbon nanotubes

Induce oxidative stress and cytotoxicity

human embryonic kidney (HEK293) cells

(232)

Carbon nanotubes Respiratory toxicity Human lungs (233)

Single-wall carbon nanotubes

Inflammation on Human macrophages Cells

human (234)

Water soluble multi-walled Carbon nanotubes

Splenic toxicity mice (235)

MWCNT Intratracheal instillation

Guinea pigs

(236)

Carbon nanotubes With impurities

In vivo immunological toxicity

mice (237)


Reactive oxygen species (ROS) increased and cell viability decreased

suspension rice cells (238)

Carbon nanotubes Genotoxicity Bacteria in vitro and in vivo assays

(239)

Single-walled carbon nanotubes dispersed in aqueous media Via non-covalent functionalization

Cytotoxicity, and epigenetic toxicity of nanotube suspensions

prokaryotic and eukaryotic cell systems

(240)

Double-walled nanotubes-contaminated food

Lethal and sub-lethal toxicity

Eisenia veneta earthworms (241)

Multi-walled carbon nanotube

Soil microbial activity decreased??

microorganisms (242)

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SWCNT Intratracheal instillation

Mice (243)

Suspended multi-walled carbon nanotube

inhibited fecundity and growth in daphnia

Daphnids. (244)

Carbon nanotubes Dermal and eye irritation and skin sensitization

Male Kbl:NZW rabbits and male Slc:Hartley guinea pigs

(245)

Carbon nanotubes In vitro cytotoxicity on lung epithelial cells

human lungs (246)

Multi-walled carbon nanotubes (MWCNT)

DNA damage in plant and mammalian cells

Allium cepa, human lymphocytes, mouse bone marrow cells and pBR322 plasmid DNA

(247)

Functionalized multi-walled carbon nanotubes

Cytotoxic and inflammatory responses

rodent macrophage cells (248)

MWCNT Intratracheal instillation

Rats, inflammatoryand fibrotic responses

(249)


release of the proinflammatory cytokine interleukin 8 from HEKs

Human epidermal keratinocytes (HEK)

(250)

Single-walled Carbon nanotubes

Single-walled carbon in vitro

cultured human dermal fibroblasts (HDF).

(251)

Single walled carbon nanotubes

Depletion in A549 lung cells

human alveolar carcinoma epithelial cell line A549 (ATCC, CCL-185)

252)

SWCNT SWCNT caused a dosedependentincrease in ROS

FE1Muta Mouse lung epithelial cell line

(253)

Single-walled Carbon nanotubes

Idecreasing glutathione (GSH) level, increasing malondialdehyde (MDA), inflammatory cell infiltration

mice (254)

SWCNT Inflammatory response of immortalised and primary human lung epithelial cells (a549 and nhbe)

human lung epithelium (255)

Genotoxicity carbon Nanotubes

increase in DNA damage , genotoxicity in human bronchial epithelial

Human bronchial epithelial cell line exhibiting an epithelial Phenotype

(256)


Cytotoxicity on human Wbroblasts

human Wbroblasts (257)

Carboxylic acid functionalized single wall carbon nanotubes

Cytotoxic effect on on the Caco-2 cells

The Caco-2 cell line from a human caucasian colon adenocarcinoma

(258)

SWCNT inhibit HEK293 cell HEK293 cells (human (259)

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proliferation and decrease cell adhesive ability

embryo kidney cells)


Human cells of the oral cavity

Human gingival fibroblast (HGF)

(260)

Single-walled carbon nanotubes

Cytotoxicity of single-walled carbon nanotubes on human hepatoma Hepg2 cells

Human hepatoma HepG2 cell

(261)

Multiwalled Carbon Nanotubes

In Vitro evaluation of cytotoxicity and oxidative Stress

Murine RAW 264.7 macrophages and human A549 lungcells

(262)

Multi-wall carbon nanotubes

Cytotoxic and genotoxic effects

Human umbilical vein endothelial cells

(263)

Single and multi walled carbon nanotubes

Cyto and genotoxicity on macrophages

mouse macrophages (264)


Alteration of protein expression in a target epithelial cell

human keratinocytes (265)


Inhibition of Lactate dehydrogenase activity

LDH activity (266)

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Table 5 Toxicity of Fullerenes300-317

Fullerene/modified Fullerene

Test species Effects References

Fullerene C60 Embryonic zebrafish; Induce oxidative stress (300) C60 fullerene Mytilus hemocytes Immune system (301) Fullerene C60 and fullerol C60(OH)18–22

Gills of fish Cyprinus carpio (Cyprinidae)

Increase in lipid peroxidation, decrease in GCL activity, and the depletion of GSH stock

(302)

C60 fullerene particles

Rat lung after inhalation Pulmonary toxicity (303)

Fullerene (C60) aquatic organisms(Daphnia

magna and Hyalella

azteca)

Delay in molting and significantly reduced offspring production

(304)

Carbon fullerene In vivo toxicity; embryonic zebrafish

Increased in malformations, pericardial edema, and mortality

(305)

Hydroxylated fullerene nanoparticles

Soil nematode caenorhabditis elegans

Decreased survival rate, shortened lifespan, apoptotic cell death

(306)

Fullerene water suspensions

Japanese medaka(Oryzias

latipes) embryos Mortality and glutathione (GSH) induction of embryos

(307)

Fullerene, C60 Aquatic species, Daphnia and Fathead minnow

Increased LPO in fish (308)

Fullerene C60 nanoparticles

lung cells of rats Genotoxicity (309)

Fullerene nanoparticles

Escherichia coli K12 Inhibits microbial respiratory activity

(310)

Functionalized fullerene

Human cells Decrease in ATP and glutathione

(311)

Fullerene C60 nanoparticles

Ames Salmonella typhimurium TA98, TA100, TA1535, and TA1537 strains and Escherichia coli strain; cultured Chinese hamster CHL/IU cells

Genotoxicity (312)

Hydroxylated fullerenes

Human epidermal keratinocytes (HEK)

Cytotoxicity, Decrease in viability,

(313)

Fullerene (C60) Polychaeta Laeonereis acuta (Nereididae)

Antioxidant and oxidative damage

(314)

Fullerene (C60) Rat liver Oxidative damage,lipid (315)

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peroxidation Fullerene (C60) nanoparticles

Mammalian cells Clastogenicity and phototoxicity

(316)

Arsenium and an organic nanomaterial (fullerene, C60)

Zebrafish hepatocytes;In vitro study

Lipid damage (317)

Table 6. Recent studies on toxicity of nanoparticles to humans. 457-467

Nanoparticles Test Organs /Species Toxic Effects References ZnO nanoparticles Human pulmonary

adenocarcinoma cell line LTEP-a-2

Cytotoxicity on human pulmonary adenocarcinoma cell line LTEP-a-2

(457)

TiO2 nanoparticles Human peripheral blood Mononuclear cells

Suppressed IDO activity and IFN-c production

(458)

Silver nanoparticles Human colon carcinoma cells

Oxidative stress and cytotoxicity (459)

Nickel oxide nanoparticles

Human pulmonary epithelial celllines: BEAS-2B and A549

Inflammation and genotoxic effect in lung epithelial cells

(460)

Fullerenol Nanoparticles

Cultured human lung fibroblasts

Cytotoxicity and Genotoxicity

(461)

ZnO nanoparticles Human polymorpho nuclear neutrophil(pmns)

Delay in human neutrophil apoptosis

(462)

Silver nanoparticles Human umbilical vein endothelial cells (huvecs)

Endothelial cell injury and dysfunction (463)

Bare titanium dioxide, zinc oxide, magnesium oxide, silver, gold nanoparticles and their Triglyceride-coated form

Suspensions of Balb/c skin cells

Cytotoxicity

(464)

Metal oxide NPs (ZnO, CeO2, TiO2 and Al2O3)

Human peripheral blood Lymphocytes (pbls).

Induced changes in the expression levels of adhesion molecules and The c-x-c chemokine receptor type 4 (cxcr4) in these cells, T-cell proliferation upon cell exposure to TiO2 and Al2O3 nps

(465)

Titanium dioxide nanoparticles

Human gastric epithelial cells

Oxidative stress, DNAdamage

(466)

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a critical review on the toxicity of some widely used engineered nanoparticles

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