Nanoparticles: Properties, applications and toxicities

Abstract

This review is provided a detailed overview of the synthesis, properties and applications of nanoparticles (NPs) exist in different forms. NPs are tiny materials having size ranges from 1 to 100 nm. They can be classified into different classes based on their properties, shapes or sizes. The different groups include fullerenes, metal NPs, ceramic NPs, and polymeric NPs. NPs possess unique physical and chemical properties due to their high surface area and nanoscale size. Their optical properties are reported to be dependent on the size, which imparts different colors due to absorption in the visible region. Their reactivity, toughness and other properties are also dependent on their unique size, shape and structure. Due to these characteristics, they are suitable candidates for various commercial and domestic applications, which include catalysis, imaging, medical applications, energy-based research, and environmental applications. Heavy metal NPs of lead, mercury and tin are reported to be so rigid and stable that their degradation is not easily achievable, which can lead to many environmental toxicities.

Keywords

NanoparticlesFullerenesOpticalPlasmonicToxicity

Abbreviations

NPsnanoparticlesFESEMfield emission scanning electron microscopyTEMtransmittance electron microscopyXPSX-ray photon spectroscopyXRDX-ray diffractionDRSDiffuse reflectance spectroscopyFT-IRFourier transform infraredSERSsurface enhanced raman spectroscopyPLphotoluminescenceMA-SiO2methacrylate-functionalized silicaTMD-NDstransition-metal dichalcogenide nanodotsPNPpolymer nanoparticleCNTscarbon nanotubesLSPRlocalized surface plasmon resonanceCVDchemical vapor depositionPVDphysical vapor depositionMRImagnetic resonance imagingPOMpolyoxometalatesLDLlow density lipoproteinMOFsmetal organic frameworksPEGpolyethylene glycolBETBrunauer–Emmett–TellerMMTMontmorillonitePEOpolyethylene oxide (PEO)PLApolylactic acidRETresonant energy transferPECphotoelectrochemical

1. Introduction

Nanotechnology is a known field of research since last century. Since “nanotechnology” was presented by Nobel laureate Richard P. Feynman during his well famous 1959 lecture “There’s Plenty of Room at the Bottom” (Feynman, 1960), there have been made various revolutionary developments in the field of nanotechnology. Nanotechnology produced materials of various types at nanoscale level. Nanoparticles (NPs) are wide class of materials that include particulate substances, which have one dimension less than 100 nm at least (Laurent et al., 2010). Depending on the overall shape these materials can be 0D, 1D, 2D or 3D (Tiwari et al., 2012). The importance of these materials realized when researchers found that size can influence the physiochemical properties of a substance e.g. the optical properties. A 20-nm gold (Au), platinum (Pt), silver (Ag), and palladium (Pd) NPs have characteristic wine red color, yellowish gray, black and dark black colors, respectively. Fig. 1 shows an example of this illustration, in which Au NPs synthesized with different sizes. These NPs showed characteristic colors and properties with the variation of size and shape, which can be utilized in bioimaging applications (Dreaden et al., 2012). As Fig. 1 indicates, the color of the solution changes due to variation in aspect ratio, nanoshell thickness and % gold concentration. The alteration of any of the above discussed factor influences the absorption properties of the NPs and hence different absorption colors are observed.

NPs are not simple molecules itself and therefore composed of three layers i.e. (a) The surface layer, which may be functionalized with a variety of small molecules, metal ionssurfactants and polymers. (b) The shell layer, which is chemically different material from the core in all aspects, and (c) The core, which is essentially the central portion of the NP and usually refers the NP itself (Shin et al., 2016). Owing to such exceptional characteristics, these materials got immense interest of researchers in multidisciplinary fields. Fig. 2 shows scanning electron microscopy (SEM) and transmittance electron microscope (TEM) images of mesoporous and nonporous methacrylate-functionalized silica (MA-SiO2). Mesoporousity imparts additional characteristics in NPs. The NPs can be employed for drug delivery (Lee et al., 2011), chemical and biological sensing (Barrak et al., 2016), gas sensing (Mansha et al., 2016Rawal and Kaur, 2013Ullah et al., 2017), CO2 capturing (Ganesh et al., 2017Ramacharyulu et al., 2015) and other related applications (Shaalan et al., 2016).

Figure 2. FE-SEM micrographs of (a) nonporous MA-SiO2 NPs, (b) mesoporous MA-SiO2 NPs. TEM images of (c) nonporous MA-SiO2 NPs and (d) mesoporous MA-SiO2 NPs (Lee et al., 2011).

In this review article, we provide a general overview on the different types, synthesis methods, characterizations, properties and applications of NPs. The last section is also provided with the future aspects and recommendations.

2. Classification of NPs

NPs are broadly divided into various categories depending on their morphology, size and chemical properties. Based on physical and chemical characteristics, some of the well-known classes of NPs are given as below.

2.1. Carbon-based NPs

Fullerenes and carbon nanotubes (CNTs) represent two major classes of carbon-based NPs. Fullerenes contain nanomaterial that are made of globular hollow cage such as allotropic forms of carbon. They have created noteworthy commercial interest due to their electrical conductivity, high strength, structure, electron affinity, and versatility (Astefanei et al., 2015). These materials possess arranged pentagonal and hexagonal carbon units, while each carbon is sp2 hybridized. Fig. 3 shows some of the well-known fullerenes consisting of C60 and C70 with the diameter of 7.114 and 7.648 nm, respectively.

Figure 3. Different form of Fullerenes/buck balls (A) C60 and (B) C70.

CNTs are elongated, tubular structure, 1–2 nm in diameter (Ibrahim, 2013). These can be predicted as metallic or semiconducting reliant on their diameter telicity (Aqel et al., 2012). These are structurally resembling to graphite sheet rolling upon itself (Fig. 4). The rolled sheets can be single, double or many walls and therefore they named as single-walled (SWNTs), double-walled (DWNTs) or multi-walled carbon nanotubes (MWNTs), respectively. They are widely synthesized by deposition of carbon precursors especially the atomic carbons, vaporized from graphite by laser or by electric arc on to metal particles. Lately, they have been synthesized via chemical vapor deposition (CVD) technique (Elliott et al., 2013). Due to their unique physical, chemical and mechanical characteristics, these materials are not only used in pristine form but also in nanocomposites for many commercial applications such as fillers (Saeed and Khan, 2016Saeed and Khan, 2014), efficient gas adsorbents for environmental remediation (Ngoy et al., 2014), and as support medium for different inorganic and organic catalysts (Mabena et al., 2011).

Figure 4. Rolling of graphite layer into single-walled and multi-walled CNTs.

2.2. Metal NPs

Metal NPs are purely made of the metals precursors. Due to well-known localized surface plasmon resonance (LSPR) characteristics, these NPs possess unique optoelectrical properties. NPs of the alkali and noble metals i.e. Cu, Ag and Au have a broad absorption band in the visible zone of the electromagnetic solar spectrum. The facet, size and shape controlled synthesis of metal NPs is important in present day cutting-edge materials (Dreaden et al., 2012). Due to their advanced optical properties, metal NPs find applications in many research areas. Gold NPs coating is widely used for the sampling of SEM, to enhance the electronic stream, which helps in obtaining high quality SEM images (Fig. 1). There are many other applications, which are deeply discussed in applications section of this review.

2.3. Ceramics NPs

Ceramics NPs are inorganic nonmetallic solids, synthesized via heat and successive cooling. They can be found in amorphous, polycrystalline, dense, porous or hollow forms (Sigmund et al., 2006). Therefore, these NPs are getting great attention of researchers due to their use in applications such as catalysis, photocatalysisphotodegradation of dyes, and imaging applications. (Thomas et al., 2015).

2.4. Semiconductor NPs

Semiconductor materials possess properties between metals and nonmetals and therefore they found various applications in the literature due to this property (Ali et al., 2017Khan et al., 2017a). Semiconductor NPs possess wide bandgaps and therefore showed significant alteration in their properties with bandgap tuning. Therefore, they are very important materials in photocatalysis, photo optics and electronic devices (Sun, 2000). As an example, variety of semiconductor NPs are found exceptionally efficient in water splitting applications, due to their suitable bandgap and bandedge positions (Hisatomi et al., 2014).

2.5. Polymeric NPs

These are normally organic based NPs and in the literature a special term polymer nanoparticle (PNP) collective used for it. They are mostly nanospheres or nanocapsular shaped (Mansha et al., 2017). The former are matrix particles whose overall mass is generally solid and the other molecules are adsorbed at the outer boundary of the spherical surface. In the latter case the solid mass is encapsulated within the particle completely (Rao and Geckeler, 2011). The PNPs are readily functionalize and thus find bundles of applications in the literature (Abd Ellah and Abouelmagd, 2016Abouelmagd et al., 2016).

2.6. Lipid-based NPs

These NPs contain lipid moieties and effectively using in many biomedical applications. Generally, a lipid NP is characteristically spherical with diameter ranging from 10 to 1000 nm. Like polymeric NPs, lipid NPs possess a solid core made of lipid and a matrix contains soluble lipophilic molecules. Surfactants or emulsifiers stabilized the external core of these NPs (Rawat et al., 2011). Lipid nanotechnology (Mashaghi et al., 2013) is a special field, which focus the designing and synthesis of lipid NPs for various applications such as drug carriers and delivery (Puri et al., 2009) and RNA release in cancer therapy (Gujrati et al., 2014).

3. Synthesis of nanoparticles

Various methods can be employed for the synthesis of NPs, but these methods are broadly divided into two main classes i.e. (1) Bottom-up approach and (2) Top-down approach (Wang and Xia, 2004) as shown in Scheme 1 (Iravani, 2011). These approaches further divide into various subclasses based on the operation, reaction condition and adopted protocols.

Scheme 1. Typical synthetic methods for NPs for the (a) top-down and (b) bottom-up approaches.

3.1. Top-down syntheses

In this method, destructive approach is employed. Starting from larger molecule, which decomposed into smaller units and then these units are converted into suitable NPs. Examples of this method are grinding/milling, CVD, physical vapor deposition (PVD) and other decomposition techniques (Iravani, 2011). This approach is used to synthesized coconut shell (CS) NPs. The milling method was employed for this purpose and the raw CS powders were finely milled for different interval of times, with the help of ceramic balls and a well-known planetary mill. They showed the effect of milling time on the overall size of the NPs through different characterization techniques. It was determined that with the time increases the NPs crystallite size decreases, as calculated by Scherer equation. They also realized that with each hour increment the brownish color faded away due to size decrease of the NPs. The SEM results were also in an agreement with the X-ray pattern, which also indicated the particle size decreases with time (Bello et al., 2015).

One study revealed the spherical magnetite NPs synthesis from natural iron oxide (Fe2O3) ore by top-down destructive approach with a particle size varies from ∼20 to ∼50 nm in the presence of organic oleic acid (Priyadarshana et al., 2015). A simple top-down route was employed to synthesize colloidal carbon spherical particles with control size. The synthesis technique was based on the continuous chemical adsorption of polyoxometalates (POM) on the carbon interfacial surface. Adsorption made the carbon black aggregates into relatively smaller spherical particles, with high dispersion capacity and narrow size distribution as shown in Fig. 5 (Garrigue et al., 2004). It also revealed from the micrographs, that the size of the carbon particles become smaller with sonication time. A series of transition-metal dichalcogenide nanodots (TMD-NDs) were synthesized by combination of grinding and sonication top-down techniques from their bulk crystals. It was revealed that almost all the TMD-NDs with sizes <10 nm show an excellent dispersion due to narrow size distribution (Zhang et al., 2015). Lately, highly photoactive active Co3O4 NPs were prepared via top-down laser fragmentation, which is a top-down process. The powerful laser irradiations generate well-uniform NPs having good oxygen vacancies (Zhou et al., 2016). The average size of the Co3O4 was determined to be in the range of 5.8 nm ± 1.1 nm.

Figure 5. SEM images of (a) The untreated carbon black, (b) and (c) 10 min and 1 h ultrasonication in POM solution (Garrigue et al., 2004).

3.2. Bottom-up syntheses

This approach is employed in reverse as NPs are formed from relatively simpler substances, therefore this approach is also called building up approach. Examples of this case are sedimentation and reduction techniques. It includes sol gel, green synthesis, spinning, and biochemical synthesis. (Iravani, 2011). Mogilevsky et al. synthesized TiO2 anatase NPs with graphene domains through this technique (Mogilevsky et al., 2014). They used alizarin and titanium isopropoxide precursors to synthesize the photoactive composite for photocatalytic degradation of methylene blue. Alizarin was selected as it offers strong binding capacity with TiO2 through their axial hydroxyl terminal groups. The anatase form was confirmed by XRD pattern. The SEM images taken for different samples with reaction scheme are provided in scheme 2. SEM indicates that with temperature elevation, the size of NPs also increases (Mogilevsky et al., 2014).

Scheme 2. Synthesis of TiO2 via bottom-up technique. SEM images showing the TiO2 NPs (Mogilevsky et al., 2014).

Well-uniform spherical shaped Au nanospheres with monocrystalline have been synthesized via laser irradiation top-down technique (Liu et al., 2015aLiu et al., 2015b). Liu et al. selectively transform the octahedra morphology to spherical shape by controlling the laser treatment time and other reaction parameters. Fig. 6 provides the SEM and TEM of the prepared Au nanospheres, which showed average diameter of 75 ± 2.6 nm of Au nanospheres (red column Fig. 6e) and 72 ± 3.1 in edge length of Au octahedra per particle (blue column Fig. 6f).

Figure 6. SEM for Au nanospheres (a) top view, (b) tilted view, (c) TEM image of Au nanospheres (d) SAED pattern (inset: TEM of single Au particle), (e) and (f) size distribution spectra of spherical and octahedral Au NPs (Liu et al., 2015aLiu et al., 2015b).

More recently, solvent-exchange method is used to achieve limit sized low density lipoprotein (LDL) NPs for medical cancer drug delivery purpose by Needham et al. In this method nucleation is the bottom approach followed by growth which is the up approach. The LDL NPs were obtained without using phospholipid and possessed high hydrophobicity, which is essential for drug delivery applications (Needham et al., 2016).

The monodispersed spherical bismuth (Bi) NPs were synthesized by both top-down and bottom-up approaches (Wang and Xia, 2004). These NPs have excellent colloidal properties. In the bottom-up approach bismuth acetate was boiled within ethylene glycol, while in top-down approach the bismuth was converted into molten form and then the molten drop was emulsified within the boiled diethylene glycol to produce the NPs. The size of the NPs obtained by both methods was varied from 100 nm to 500 nm (Wang and Xia, 2004). The details of this study are provided in Scheme 3. Green and biogenic bottom-up synthesis attracting many researchers due to the feasibility and less toxic nature of processes. These processes are cost-effective and environmental friendly, where synthesis of NPs is accomplished via biological systems such as using plant extracts. Bacteria, yeast, fungi, Aloe vera, tamarind and even human cells are used for the synthesis of NPs. Au NPs have been synthesis from the biomass of wheat and oat (Parveen et al., 2016) and using the microorganism and plant extracts as reducing agent (Ahmed et al., 2016). Table 1 provides the merits and demerits of various top-down and bottom-up techniques with general remarks (Biswas et al., 2012).

Scheme 3. (A) Bottom-up approach: A molecular precursor is disintegrated to simpler metal atoms that grow into colloids. (B) Top-down approach: Large drops of a metal broken into smaller drops (Wang and Xia, 2004).

Table 1. Top-down and bottom-up synthetic techniques with merits, demerits and general remarks (Biswas et al., 2012).

Top–down methodMeritsDemeritsGeneral remarks
Optical lithographyLong-standing, established micro/nanofabrication tool especially for chip production, sufficient level of resolution at high throughputsTradeoff between resist process sensitivity and resolution, involves state-of-the-art expensive clean room based complex operationsThe 193 nm lithography infrastructure already reached a certain level of maturity and sophistication, and the approach could be extended to extreme ultraviolet (EUV) sources to shrink the dimension. Also, future developments need to address the growing cost of a mask set
E-beam lithographyPopular in research environments, an extremely accurate method and effective nanofabrication tool for <20 nm nanostructure fabrication with desired shapeExpensive, low throughput and a slow process (serial writing process), difficult for <5 nm nanofabricationE-beam lithography beats the diffraction limit of light, capable of making periodic nanostructure features. In the future, multiple electron beam approaches to lithography would be required to increase the throughput and degree of parallelism
Soft and nanoimprint lithographyPattern transfer based simple, effective nanofabrication tool for fabricating ultra-small features (<10 nm)Difficult for large-scale production of densely packed nanostructures, also dependent on other lithography techniques to generate the template, and usually not cost-effectiveSelf-assembled nanostructures could be a viable solution to the problem of complex and costly template generation, and for templates of periodic patterns of <10 nm
Block co-polymer lithographyA high-throughput, low-cost method, suitable for large-scale densely packed nanostructures, diverse shapes of nanostructures, including spheres, cylinders, lamellae possible to fabricate including parallel assemblyDifficult to make self-assembled nanopatterns with variable periodicity required for many functional applications, usually high defect densities in block copolymer self-assembled patternsUse of triblock copolymers is promising to generate more exotic nanopattern geometries. Also, functionalization of parts of the block copolymer could be done to achieve hierarchy of nanopatterning in a single step nanofabrication process
Scanning probe lithographyHigh resolution chemical, molecular and mechanical nanopatterning capabilities, accurately controlled nanopatterns in resists for transfer to silicon, ability to manipulate big molecules and individual atomsLimited for high throughput applications and manufacturing, an expensive process, particularly in the case of ultra-high-vacuum based scanning probe lithographyScanning probe lithography can be leveraged for advanced bionanofabrication that involves fabrication of highly periodic biomolecular nanostructures
Bottom–up methodMeritsDemeritsGeneral remarks
Atomic layer depositionAllows digital thickness control to the atomic level precision by depositing one atomic layer at a time, pin-hole free nanostructured films over large areas, good reproducibility and adhesion due to the formation of chemical bonds at the first atomic layerUsually a slow process, also an expensive method due to the involvement of vacuum components, difficult to deposit certain metals, multicomponent oxides, certain technologically important semiconductors (Si, Ge, etc.) in a cost-effective wayAlthough a slow process, it is not detrimental for the fabrication of future generation ultra-thin ICs. The stringent requirements for the metal barriers (pure; dense; conductive; conformal; thin) that are employed in modern Cu-based chips can be fulfilled by atomic layer deposition
Sol gel nanofabricationA low-cost chemical synthesis process based method, fabrication of a wide variety of nanomaterials including multicomponent materials (glass, ceramic, film, fiber, composite materials)Not easily scalable, usually difficult to control synthesis and the subsequent drying stepsA versatile nanofabrication method that can be made scalable with further advances in the synthesis steps
Molecular self-assemblyAllows self-assembly of deep molecular nanopatterns of width less than 20 nm and with the large pattern stretches, generates atomically precise nanosystemsDifficult to design and fabricate nanosystems unlike mechanically directed assemblyMolecular self-assembly of multiple materials may be an useful approach in developing multifunctional nanosystems and devices
Physical and chemical vapor-phase depositionVersatile nanofabrication tools for fabrication of nanomaterials including complex multicomponent nanosystems (e.g. nanocomposites), controlled simultaneous deposition of several materials including metal, ceramics, semiconductors, insulators and polymers, high purity nanofilms, a scalable process, possibility to deposit porous nanofilmsNot cost-effective because of the expensive vacuum components, high-temperature process and toxic and corrosive gases particularly in the case of chemical vapor depositionIt provides unique opportunity of nanofabrication of highly complex nanostructures made of distinctly different materials with different properties that are not possible to accomplish using most of the other nanofabrication techniques. New advances in chemical vapor deposition such as ‘initiated chemical vapor deposition’ (i-CVD) provide unprecedented opportunities of depositing polymers without reduction in the molecular weights
DNA-scaffoldingAllows high-precision assembling of nanoscale components into programmable arrangements with much smaller dimensions (less than 10 nm in half-pitch)Many issues need to explore, such as novel unit and integration processes, compatibility with CMOS fabrication, line edge roughness, throughput and costVery early stage. Ultimate success depends on the willingness of the semiconductor industry in terms of need, infrastructural capital investment, yield and manufacturing cost

4. Characterization of NPs

Different characterization techniques have been practiced for the analysis of various physicochemical properties of NPs. These include techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared (IR), SEM, TEM, Brunauer–Emmett–Teller (BET), and particle size analysis.

4.1. Morphological characterizations

The morphological features of NPs always attain great interest since morphology always influences most of the properties of the NPs. There are different characterization techniques for morphological studies, but microscopic techniques such as polarized optical microscopy (POM), SEM and TEM are the most important of these.

SEM technique is based on electron scanning principle, and it provides all available information about the NPs at nanoscale level. Wide literature is available, where people used this technique to study not only the morphology of their nanomaterials, but also the dispersion of NPs in the bulk or matrix. The dispersion of SWNTs in the polymer matrix poly(butylene) terephthalate (PBT) and nylon-6 revealed through this technique (Saeed and Khan, 2014Saeed and Khan, 2016). The same group also provides POM study of their materials, which showed star-like spherulites of the formed materials, whose size was decreased with the incremental filling of SWNTs. The morphological features of ZnO modified metal organic frameworks (MOFs) were studied through SEM technique, which indicates the ZnO NPs dispersion and morphologies of MOFs at different reaction conditions (Fig. 7) (Mirzadeh and Akhbari, 2016).

Figure 7. SEM images of ZnO modified MOFs at different temperatures (Mirzadeh and Akhbari, 2016).

Similarly, TEM is based on electron transmittance principle, so it can provide information of the bulk material from very low to higher magnification. The different morphologies of gold NPs are studied via this technique. Fig. 8 provides some TEM micrographs showing various morphologies of gold NPs, prepared via different methods (Khlebtsov and Dykman, 2011Khlebtsov and Dykman, 2010aKhlebtsov and Dykman, 2010b). TEM also provides essential information about two or more layer materials, such as the quadrupolar hollow shell structure of Co3O4 NPs observed through TEM. These NPs founded to be exceptionally active as anode in Li-ion batteries (Fig. 9). Porous multishell structure induces shorter Li+ diffusion path length with adequate annulled space to buffer the volume expansion, good cycling performance, greater rate capacity, and specific capacity as well (Wang et al., 2013).

Figure 8. TEM images of different form of gold NPs, synthesized by different techniques (Khlebtsov and Dykman, 2011Khlebtsov and Dykman, 2010aKhlebtsov and Dykman, 2010b).

Figure 9. SEM (a–c, h), TEM (d–f), XRD patterns (g) and HRTEM (i) images of double, triple and quadruple Co3O4 hollow shells (Wang et al., 2013).

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