Trends in polymers functionalized nanostructures for analysis of environmental pollutants

Journal Pre-proof Trends in Polymers Functionalized Nanostructures for Analysis of Environmental Pollutants Ganjar Fadillah, Ozi Adi Saputra, Tawfik A. Saleh

PII:

S2214-1588(20)30002-7

DOI:

https://doi.org/10.1016/j.teac.2020.e00084

Reference:

TEAC 84

To appear in:

Trends in Environmental Analytical Chemistry

Received Date:

10 January 2020

Revised Date:

7 February 2020

Accepted Date:

11 February 2020

Please cite this article as: Fadillah G, Saputra OA, Saleh TA, Trends in Polymers Functionalized Nanostructures for Analysis of Environmental Pollutants, Trends in Environmental Analytical Chemistry (2020), doi: https://doi.org/10.1016/j.teac.2020.e00084

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Trends in Polymers Functionalized Nanostructures for Analysis of Environmental Pollutants Ganjar Fadillaha, Ozi Adi Saputrab , Tawfik A. Salehc,* a

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Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Islam Indonesia, Yogyakarta 55584, Indonesia b Master Program of Chemistry, Graduate School of Universitas Sebelas Maret, Surakarta 57126, Indonesia c Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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Corresponding author E-mail address: [email protected] ; [email protected]

Polymers functionalized nanostructures have fueled the development of new generation of sensors.

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Highlights

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The review introduces the development work in the area of polymers based sensors.

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The review discusses the latest developments of these materials for various

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Abstract

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electrochemical sensing applications

Functional polymers have attached attention in recent years due to their wide applications and

unique properties such as sound sensitivity, electrical, catalytic activity, etc for analysis pollutants. The synthesis of functionalized polymers can be affected by several factors, such as the polymerization process, the composition of polymers, and functionalization. However, the scalingup process from laboratory to industrial is still limited due to its matrix process and steps. We have 1

discussed: i) types of nanostructures and polymer functionalizations, ii) the analytical performance of the functionalized polymers for the analysis of pollutants like toxic gas, pesticide residues, heavy metal, and aromatic compounds, iii) the design and simple concept of the scaling-up process, iv) a parameter affecting the scaling-up process of the synthesis and application of the functionalized polymer nanostructures for the analysis of pollutants. This review will help industry

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experts and researchers with developing the analysis.

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Keywords: functional polymers; nanostructure; analysis; pollutants; scaling up

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1. Introduction For many years, rapid population, urbanization, and industrialization issues have caused the continuous degradation of environmental quality due to the high concentration of pollutants released. Some industries such as plastics, paper printing, leather, metallurgy, petrochemical, and manufacture release a high level of contaminants like toxic gases, heavy metal ions, hydrocarbon,

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and aromatic compounds [1-3]. Therefore, the monitoring of these pollutants is still of great

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importance to control the environmental quality. The functionalized polymer nanostructures in nanotechnology have become an exciting topic in various fields, and especially for the analysis of

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pollutants. Nanostructures provide good performance over their bulk structure because of their tunable physicochemical properties such as catalytic activity, high sensitivity, electrical and

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thermal conductivities, scattering properties, etc [4]. Wu et al. (2019) concluded that the critical

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factor for developing devices for the monitoring of pollutants is the property of sensitivity due to the fact that the pollutants in nature are mostly present in low concentrations [5]. In recent years,

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nanostructures have been developed for the monitoring of pollutants because of their functional groups. Nanostructures and nanomaterials have nanoscale dimensions between 1-100 nm and can be defined depending on their composition, size, shape, and origin [6, 7]. Although the nanomaterial and nanostructure have abundant functional groups for binding analyte targets, the

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poor selectivity of nanomaterials becomes a limitation for the materials. Combination with organic molecules to produce the functional group polymers for highly binding analyte targets is the best method to produce highly selective materials [8]. Polymer functionalized nanostructures have more advantages in analytical applications due to their unique properties. The containment of specific chemical functional groups can lead to increased surface activity and reactivity, association, and phase separation [9, 10]. The 3

functionalized polymer contains the specific chemical groups which provide tailor-made and novel properties, as well as give advantages for several applications, especially for analytical measurement. Generally, the functionalized polymers include different structures and arrangements, such as functionalized polymer-based nanoparticles, functionalized polymer molecule conjugates, functionalized micelles, and self-assembled functionalized polymers [11].

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The presence of abundant chemical groups in functional polymers can improve their reactivity, stability, and solubility. Several applications of the functionalized polymers have been reported

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for the analysis of pollutants such as metal ions [12], water purification [13, 14], organic molecules [15], aromatic hydrocarbons [16] and others. Yusoff et al. (2017) synthesized Lanthanide-ion

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imprinted polymers (La-IIPs) via Schiff base polymerization for the selective removal of rare ion

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metals such as Pr, Sm, Nd, Gd, and Eu [17]. The functionalized polymers were synthesized by a batch system at a temperature of 60 oC for 48 h in magnetic stirring to complete thermal

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polymerization and resulted in good selectivity for adsorption and separation of the Lanthanide ion metals over the presence of other rare-earth ions. Although the functionalized polymers have

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shown excellent analytical performance, there are still technical gaps between industry and academic research for the production of functionalized polymers. Scaling up the process from lab to industry is still limited because it is a very complex process and it requires a fundamental understanding of fluidal mechanics, mass transfer, thermodynamics, and heat process transfer. In

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the industrial process, there are some essential requirements for material characteristics such as a simple and economical synthesis route, excellent hydrophilicity, high selectivity, and good chemical constancy [18]. Therefore, this review aims to describe a detailed synthesis of nanostructures, types of polymer functionalization, the application of functionalized polymers to analyze some pollutants that are commonly produced from industrial processes and a systematic

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scale-up approach based on design analysis. Furthermore, in the scale-up process, it is essential to keep some parameters constant such as reaction time, temperature process, the homogeneity of product, pressure, current density, and the chemical composition to complete the polymerization process. 2.

Methods

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Nanomaterials exhibit unique properties because of their particle size and nanostructure. In various applications, nanostructured materials are an important issue to discuss. Nanostructured

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materials can be designed by at least considering the method to prepare the nanomaterial, the precursor, and the condition of the synthesis system [19, 20]. Nevertheless, two general methods

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can be classified to prepare different kinds of nanostructures (spherical nanoparticles, nano-

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hollow, nano-cubes, nano-sheet, nano-rod, nano-flower, and many more), i.e. templating and nontemplating methods.

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2.1 Templating Method

The design of nanostructured nanomaterials via the templating method can be classified into

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two routes, called soft-templating and hard-templating [21, 22]. Basically, the soft-templating assisted synthesis of nanomaterials does not require a fixed-rigid structure of the template molecules. Meanwhile, the hard-templating method demands a fixed and rigid structure of the template to create the desired nanostructures. Although the soft-templating method is more

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profitable from an economic standpoint, this method makes it difficult to control the particle size and shape the monodispersity of the nanoparticles compared to the hard-templating method [23]. In this section, some examples of using the soft-templating and hard-templating methods are discussed.

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Generally, the soft-templating method employs a self-assembly aggregate as template molecules to direct the structure of the nanomaterials, could be surfactants, biopolymers, water-oil emulsion, etc. [22] Mesoporous silica nanoparticles with a dendritic-like nanostructure were fabricated by combining two kinds of templates, cetyltrimethylammonium bromide (CTAB) and the commercially available surfactant Capstone FS-66 [24]. The MSN particle shape orientation

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turned to the dendritic-like structure after Capstone FS-66 addition, where the MSN prepared only with a CTAB surfactant has a spherical nanostructure. The size of the nanoparticles became larger

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after incorporating a high concentration of Capstone FS-66. Moreover, the porous diameter was not controlled with the addition of 0.66 g of Capstone FS-66. A hollow nanostructured mesoporous

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silica nanoparticle was successfully prepared by Xu et al. using a soft-templating approach that

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used a CTAB surfactant as a porogen assisted triethanolamine [25]. The HMS nanoparticles, as observed by TEM and SEM, have a spherical hollow interior morphological structure with an

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average diameter of about 350 nm and a SiO2 shell thickness of about 80 nm. The N2 adsorptiondesorption isotherm clarified that the HMS nanoparticle revealed a type IV isotherm confirming a

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mesoporous structure with a narrow pore distribution of around 2.3 nm and a high BET surface area about 1355 m2 g−1. The polymeric micelle template, like poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA), can be used as a soft-template to create porous-spherical nanostructured rhodium particles [26]. The micelle structure of the polymer is easily engineered

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by considering the behaviour of polymer in a water-DMF environment. This polymeric micelle template is removed by the solvent extraction method and leaves cavities on the particle nanostructures.

A fixed and rigid structure was used as the template molecules in the synthesis of nanoparticles via the hard-templating method since due to the rigid structure of the template, the

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morphology of the nanoparticles is easy to direct. In this method, removable metal oxide nanoparticles are preferred, such as MgO, iron oxide, MnO, or even coordinated-metal (like MOFs). MgO nanoparticles were used to fabricate a three-dimensional graphene nanostructure [27, 28]. The precursor, a mixture of carbon source and MgO template, was calcined at 800 °C and in the final stage, the MgO template was removed by etching method in 10% of HCl and leaving

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a porous structure as illustrated in Figure 1a. Sun et al. (2015) have successfully prepared mesoporous carbon nanocubes (MCCs) by means of the hard-templating method using MnO

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nanocubes as templating which was removed by etching in HCl solution [29]. Metal-organic frameworks (MOFs), a porous coordination polymer composed of the metal cluster and organic

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linker, are also used as a template to synthesize the carbon nanostructure. In principle, the metal

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ion of MOFs can be transformed into metal nanoparticles, metal oxide, or both by pyrolysis in an inert atmosphere at high temperatures. At this level, the organic ligand of MOFs will be carbonized

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and form a nanostructure as an origin [30, 31]. A rod-like carbon nanostructure was successfully obtained via the self-templating method [32-34]. In a typical experiment, a rod-like MOF-74 was

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firstly prepared using zinc acetate as a metal ion and 2,5-dihydroxyterephthalic acid as an organic linker. In the final stage, the zinc metal was removed by calcination and at the same time, the organic linker was carbonized to form carbon-nanorods as illustrated in Figure 1b. Further transformation of this material achieved graphene nanoribbons by the exfoliation method. Yang et

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al. also developed a MOF-derived hierarchically with a porous carbon that had a porous cubic-like morphological structure having a high surface area, in which IRMOF-1 was used as the template [35]. The same approach was previously done by Liu et al. employing MOF-5 as a self-template to fabricate a cubic-like carbon material [36, 37]. Thereby, the templated synthesis can produce nanostructures with unique properties, morphology, structure, morphology, and properties.

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Besides, this method is widely used to produce nanomaterials that are difficult to form and to obtain.

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Non-Template Method The formation of nanostructures using the non-templating approach strongly depends on

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the synthesis condition, which affects the growth of nanoparticles. Each synthesis method generates different morphological nanostructures. For example, a crystalline C8-like structure

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carbon micro- and nanocubes were successfully prepared via laser ablation in liquid [38]. The

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single carbon nanostructure was obtained from a pulsed-laser induced liquid-solid interface reaction (PLIIR). The hydrothermal method on the preparation of carbon-based nanoparticles with

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sucrose as carbon sources produced a capsule-like morphology observed by TEM with the size range between 2-7 nm [39].

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Hydrothermal is a straightforward method that is widely employed in the synthesis of nanoparticles [40, 41]. By this simple method, a two-dimensional carbon nitrite nanosheet was

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achieved and further decorated by ball-flower like Co3O4 for gas sensor applications [42]. A facile hydrothermal method also produced different morphological nanostructures of ZnO (nanoparticles, a nanoplate, and nanoflower) by adjusting the concentration of the precursor

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amount [43]. The design of nanostructures using this method is quite simple; however, some parameters should be noted, such as the concentration of the precursor, the pH, temperature, and solvents, due to all of them making a contribution to arranging the nanostructure. The synthesis of nanostructured materials using this method is not able to produce a fixed size. Generally, the nanosize produced by this method is formed due to intermolecular or intermolecular interactions

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that occur between molecules. However, this method has many advantages like the simplicity of the synthesis process and excellent repeatability. 2.3. Functionalization The functionalization of nanomaterials by the incorporation of polymers is a potential strategy to improve the performance of nanomaterials due to the polymer providing active sites for

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interaction which depend on the types of polymer, such as polar active sites (hydroxyl, amines, carboxylic groups, etc.) for accommodating interactions with mostly organic polar compounds or

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even metal ions, non-polar carbon-chain sites to interact with non-polar compound. Generally, there are two approaches to introduce the polymer onto the nanoparticle surfaces, namely the

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grafting method (covalent functionalization, such as esterification, radical polymerization, click-

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chemistry approach, and silylation) and non-covalent functionalization (such as layer-by-layer). 2.4. Bulk Polymerization and Esterification

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Bulk polymerization can be conducted by the chemical modification process on the surface of nanomaterials. The reactivity of the chemical groups of the monomer composition plays an

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important role in the characteristic of the functionalized material [44, 45, 46]. Nanomaterials that contain functional groups are easy to modify by adding polymer through the grafting method. Solyaman et al. (2014) have successfully synthesized functionalized polymer-based clay/Au/methyl methacrylate through bulk polymerization methods [47]. Bulk polymerization can

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produce high-quality polymers; however, the methods are still tricky due to their high viscosity with high-molecular-weight polymers. Graphene oxides are carbon-based material containing hydroxyl, epoxy, and the carboxylic functional group as an active site for functionalization. Weng et al. (2017) have successfully functionalized graphene oxide with poly(ε-caprolactone) through Steglich esterification [48]. The functionalization of graphene oxide (prepared by the Hammer

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method) was done by the post-synthesis method, in which poly(ε-caprolactone) prepared from ring-opening polymerization was introduced to graphene oxide for a covalent reaction mediated by the Steglich esterification. The bulk polymerization is widely used for producing the functionalized polymers because of the simplicity of the process and easy control of the size. However, the reactivity of the materials depends on the attached functional groups.

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2.5. Radical Polymerization Radical polymerization is a polymer functionalization technique to introduce a polymer on

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the surface of the material, which is promoted by the radical reaction. This reaction was employed in many functionalization pathways, one of them is a molecularly imprinted polymer. Introducing

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molecularly imprinted polymers (MIP) is a way to functionalize nanomaterial to selectively

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recognize a target compound due to the presence of tailor-made cavities on the polymer which are produced by removing the template (target molecules) [49]. Generally, in the synthesis of MIP,

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the target compound was used as a template and it was removed in the final steps. Graphene oxide, which was prepared by the Hammer method, was further modified by MIP using radical

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polymerization of methacrylic acid, ethylene dimethacrylate, and methylacryloyl-β-cyclo dextran, in which di-(2-ethylhexyl) phthalate was used as a template [50]. 2.6. Click-Chemistry

A green, simple and high atom economy approach to introduce polymers on the surface of

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materials can be achieved by “click-chemistry”. This approach was employed by Pan et al. to bind poly(N–isopropylacrylamide) onto the surface of graphene oxide [51]. The carboxylic functional group of graphene oxide was firstly transformed into alkynyl group via esterification. Meanwhile, the side chain of poly(N-isopropylacrylamide) was also transformed into an azides group. Both

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alkynyl and azides groups are reactive and easy to bind. Although this technique is relatively easy to do, however, the formation of intermediate products is relatively difficult. 2.7. Silylation technique The introduction of a substituted silyl group R3Si onto molecules or material surfaces is called silylation. This technique is usually used for derivatization or the addition of a new

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functional group for further modification. A sugar conjugated dendritic-like polyamidoamine was successfully introduced to the surface of silylated-silica nanoparticles via amidation

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polymerization [52]. The hydroxyl surface group of silica nanoparticles was derived by the silylation method using an alkoxysilane compound, aminopropyl trimethoxysilane, to form an

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amines group. The monomers, the methacrylic acid, and ethylenediamine, were self-polymerized

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to yield polyamidoamine on the silica nanoparticles surfaces. Silylation-mediated radical polymerization of poly(vinyl acetate)-co-poly(maleic anhydride) on the surface of silica

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nanoparticles was also successfully performed [24]. In this reaction, the surface of silica nanoparticles was modified by vinyltriethoxysilane to promote a vinyl group on the surface of the

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material for radical polymerization. 2.8. Layer-by-Layer Assembly

The layer-by-layer technique is a polymer functionalization method by coating a surface of the material with a layered-polymer via non-covalent bonding. Polyelectrolytes containing

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poly(sodium-4-styrene sulfonate) as a negative charge polymer and poly(allylamine hydrochloride) as a positive charge polymer were assembled on the surface of silica nanoparticles via a layer-by-layer technique [53]. Poly(sodium-4-styrene sulfonate) was first introduced to the particle surfaces and continued by the addition of poly(allylamine hydrochloride) subsequently. In this method, the number of layers is controllable; however, the layers become relatively unstable

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at a high number of layers due to weak interaction. An addition of a mixed-polymer onto nanoparticle surfaces via the layer-by-layer method also influenced the physical properties of the nanoparticles. For example, Au nanoparticles modified by poly(ethylene imine) and poly(styrene sulfonate) changed the surface charge of materials from negative to be more positive and shifted the surface plasmon resonance from 518 to 530 nm [54]. It indicates that the functionalization of

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nanomaterials by polymers via the layer-by-layer method affects the surface properties of materials. The layer-by-layer techniques are capable of producing all kinds of inorganic, organic,

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and hybrid inorganic-organic shell structures with controllable nanosizes and thickness. However, some of the problems with these methods are the large size of the prepared materials and lower

Detection of pollutants using polymeric nanostructures

3.1. Techniques involving nanostructures

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efficiency in the synthesis.

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The synthesis of functional polymers is an exciting topic to explore, especially for pollutant analysis as summarized in Table 1. Choi et al. (2018) reported ZnO/siloxane-based polymer

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nanostructures for the gas-phase detection of dimethylmethylphosphonate (DMMP) using a quartz crystal microbalance (QCM) [55]. The presence of hydrophilic polymers such as siloxane or carboxilane could improve the binding target analyte through strong hydrogen bonding [56, 57]. The result proved that the combination of functionalized polymers with nanoparticles could

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increase the surface area of 135.1 μm2. Das et al. (2019) have successfully synthesized polysiloxane polymers using the hydrolysis of silicate groups on the QCM surface for amine vapor analysis [57]. The structure of the polymer has a significant effect on sensor sensitivity. The polymers should have a flexible and reasonable free volume with a specific size of molecules or binding interaction to produce good selectivity devices. The weak intermolecular interaction, such

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as hydrogen bonding and the Vander Walls interaction, provides significant value for a timely response and recovery time because there is no strong interaction between the functionalized polymers and the molecules’ analyte. Another research study also showed that the attached metal oxide nanoparticles on the polymer matrix could improve the sensor sensitivities due to their large surface area and conductivity [58].

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Zhang et al. (2019) have successfully developed conjugated 4,7-di(furan-2-yl) benzo thiadiazole (FBThF)/ Ag NPs-rGO-NH2 polymers for the highly sensitive determination of

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organophosphate pesticide by amperometric methods [59]. The polymers have been prepared by electropolymerization using cyclic voltammetry between 0.0 to 1.4 V vs. Ag/AgCl at a scan rate

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of 0.1 V/s for 55 cycles in TBAPF6/DCM/ACN solution containing FBThF. In the electrochemical

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polymerization process, the thickness of the polymer film can be controlled by polymerization cycles and time, so it makes the morphology of formed polymers relatively more uniform [60, 61].

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The prepared sensor showed excellent electrochemical activity for the oxidation of malathion and trichlorfon with the LOD value of 0.032 and 0.001 μg/L, respectively. The synergistic effect

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between the amine-functionalized polymers and the large surface area of Ag NPs resulted in good electrocalatalytic activity and sensitivity. The presence of -NH2 on the surface electrode could improve the binding AchE through the CO-NH bonding, which resulted in improving the catalytic properties. In addition, the formation of functionalized polymer provides a chemical heterogeneity

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structure which provides many advantages by improveing the sensitivity and reactivity of the materials.

Lee at al. (2019) synthesized the ether/thioether-functionalized network polymer (PAF1–ET)

for iron analysis with both iron (II) and iron (III) ions in wastewater [70]. The porous polymers have thermal/chemical stability, a high surface area of up to 5600 m2/g, and selectivity for complex

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and trace analysis [71, 72]. The high surface area in the porous polymers provides an accessible active site for adsorption, both the molecule and ion targets. These results showed that the prepared materials have excellent selectivity for adsorbing Fe2+ and Fe3+ in water samples and high adsorption capacity of iron ions. The porous polymers can improve the binding analyte target through the covalent coordinate bond between six oxygen atoms and the iron ions. However, the

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PAF-1-ET as a functional polymer for iron ion detection may suggest that the binding iron can occur not only in the position of oxygen but also in the position of the sulfur as shown in Figure

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2. Another hypothesis showed that the presence of sulfur in the polymer structure contributes a critical rule to create the optimal pore in PAF-1–ET. Functionalized polymers built by polymer

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combination may enhance the solubility, stability properties, and also the binding molecule targets

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through the incorporation of active groups (hydroxyl, amine, etc.). Suhail et al. (2019) reported the PANI/f-SCWT polymer nanocomposites for H2S gas sensor detection [66]. The results

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reported that the hydrophobicity of polymers could affect the electron mobility and surface properties of the electrode, which result in changes in the selectivity and sensitivity for H2S

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detection. Liu et al. (2018) revealed that the morphology is one of the most important factors for gas detection due to its provision of active sites [73]. Generally, the presence of the functionalized polymer can improve the sensitivity and selectivity measurement because the polymer structure provides a specific template. The summarized comparison of methods for the analysis of several

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pollutants using functionalized polymers is shown in Table 2. 3.2. Factors affecting the analysis efficiency Currently, functionalized polymers are an interesting material for study, especially for

pollutant analysis. Meconi et al. (2019) reported that the increased efficiency for analysis depends on the type of polymers that are combined. Different functional groups of the polymers can arrange

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the interaction between the functionalized polymers with molecule targets [85]. It has been shown that the different types of functional groups like those containing heteroatoms, oxygen, and nitrogen in the polymer structures strengthen the analyte-polymer interaction energy through the interaction of hydrogen bonds or dipole-quadrupole. The binding molecules’ target will increase with the increasing number of protic groups in the polymer structure such as amides, amine, or

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hydroxyl groups [86]. Similar to another report, the number of protic groups can influence the morphology of the material; those with large numbers tend to self-aggregate while those with

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fewer groups will spread homogeneously on the surface of materials [87-89].

The surface morphology of polymers is one of the most important factors for pollutant

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analysis due to its providing active sites. Kemiklioglu and Atik (2019) explained the effect of the

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polymer network, depending on the type of monomer used [90]. Also, the type of monomer commonly used in the polymerization process is a monomer that has a free electron pair and a

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double bond. Mostly, these characteristics will form conducting polymers with good sensitivity and selectivity [91, 92]. In the electrochemical sensor application, the formation of conducting

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polymers can increase the electron transfer rate through electron delocalization. Moreover, the selectivity of the sensor can be controlled by controlling the polymerization process. Also, the type of polymer is one of the most important in increasing efficiency. For example, polyaniline (PANI) has the advantages of environmental stability, hydrophilicity, environmental stability, and the

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extraction ability of polar compounds. The large benzene ring of aniline-based polymers has an effect on the interaction between the analyte target with functional polymers through π-π interaction. Because of this advantage, PANI has been developed as a functional material for pollutant analysis [93]. The reactivity of functionalized polymers not only depends on the

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abundance of the functional group but also on the amorphous materials, compatibility, solubility of analytes, orientation, and cavity location. 4. From lab to industrial scale Functionalized polymers have been primarily presented for many applications, especially for analysis pollutants as summarized in Table 1. Generally, the common thinking about the scale-up

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process is the need for further optimization and significant design facilities. The concept of improvement also applies to the other supporting materials used, such as raw materials, catalysts,

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additives, physical conditions, and others. Scaling-up a laboratory to an industrial-scale certainly requires proper calculations, especially in processing and higher flexibility toward materials.

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Piccino et al. (2016) presented some of the procedures to scale-up production from a laboratory to

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an industrial scale. [94] (1) A preparing protocol laboratory is summarized from the experimental activities, patent, and/or a publication; (2) this information will be used to design a simple diagram

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process, such as the main equipment, reactors, apparatus, and others needed for all steps in the process; (3) the flow diagram is upgraded according to this framework procedure; the (4) linkage

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of the process steps, including the in- and output data for all of the process steps; and the last (5) of the process steps are used to assess the performance of the system that has been developed. Figure 3 shows a simple diagram of the scale-up procedures. Another reference has reported that there are two steps for improving the process from the

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laboratory to the industrial process. Firstly, the step which is also known as the plant limitations, is to expand the existing commercial facilities by modifying or replacing production equipment. The second step of the scaling-up process is the improvement of the design plant with the same principle as in the laboratory process, but with a higher capacity [95]. In the laboratory, the functional polymer materials have been successfully synthesized through methods such as a batch

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polymerization reactor [96] or the electropolymerization process [97, 98]. While in the industrial process, the vertical cone ribbon blade reactor is commonly used in the batch polymerization reaction and is suitable for the high-viscosity process. The principle of this reactor was developed based on the continuous stirred tank process and it was proved that the process would be more efficient for polymerization on an industrial scale. Moreover, the process has many advantages at

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the industrial-scale because it can control several parameters such as the temperature, the volume being less than the standard stirred tank, continuously for a long time process without fouling and

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plugging, and producing a constant product [99]. According to previous work, the batch system

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reactor is commonly used in industry for producing the functional polymer, as shown in Figure 4. Bon et al. (2019) presented electrochemical polymerization using a stainless-steel reactor as both

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the cathode and the reaction vessel for producing poly (meth)acrylates and polystyrene [101]. The scale-up experiments were conducted by increasing by four times the total volume of the reaction,

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with a total conversion of more than 30%. The illustration of the process is shown in Figure 5. The crucial parameters of the scale-up process are to maintain the stability of the production. In

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both the batch reactor and the electrochemical polymerization case, it is important to keep some parameters constant such as the reaction time, temperature process, the homogeneity of the product, the pressure, current density, and the chemical composition. It is very important to keep

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this constant because it will affect the characteristics of the functionalized polymer produced [102, 103]. As a result, the scale-up process is a compromise between process risk minimization and capital cost minimization, within the cost of the process development. Besides, the process requires the use of extraordinary judgment and that models at several stages are developed from the lab to the commercial scale.

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5. Conclusions and Future Prospects In this paper, we have demonstrated that polymer functionalized nanostructures are a promising class of advanced materials for cost-effective, rapid, good selectivity, and effective analysis of some environmental pollutants such as heavy metals, hydrocarbon aromatics, organics molecules, and toxic gases [104-106]. Several researchers have reported that the

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activity of functionalized polymers depends on the specific surface area, numerous cavities sides [105], type of functional groups on the surface materials [107], and type of monomers

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[90, 108], etc. Although these materials have shown excellent performance for pollutant analysis, there are several band gaps between the industrial scale and the laboratory. In an

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industrial process, there are several essential requirements for material characteristics such as a

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simple and economical synthesis route, minimal energy consumption, good hydrophilicity, high selectivity, good chemical constancy, and good stability under various conditions. Bringing a

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process to the scale-up and implementation in the industry is a still challenge to find the optimum reaction conditions. Overall, several steps are important for application in industry

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when bringing the process to scale up: (1) determine the value of a raw material for a producing product, (2) determine the cost value of the production process, and (3) assess the regulation and environmental requirements of the produced products [109]. There are a few challenges that need to be met for further developing functional polymers,

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especially for the analysis of pollutants. Primarily, in the scale-up process, there is a need to study several technical factors both for the synthesis and the application process. The contribution of these factors needs to be elucidated based their influence on the characteristics of

functionalized

polymers

such

as

surface

area,

pore

size,

surface

hydrophilicity/hydrophobicity, structure, etc. Secondly, the type of monomers is a significant

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challenge that will affect material characteristics, especially for functional polymers in sensor/biosensor applications. Thirdly, many types of nanostructure on the functional polymers depend on the dispersion of other compounds into the polymer matrix. In contrast, homogenous dispersion has a significant effect on functional polymer characteristics.

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References [1] A.K. Singh, R. Chandra, Aquatic Toxicology 211 (2019) 202.

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There is no conflict of interest

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[3]

T.A. Saleh, G. Fadillah, O.A. Saputra, TrAC Trends in Analytical Chemistry, 118

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(2019) 194-206

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Figure 1. Illustration synthesis of (a) three-dimensional graphene and MnCo2O4/3D-G nanostructure by template method [27] copyright © 2018 ChemPubSoc Europe and (b) carbon-nanorods and carbon nanoribbons [32] copyright © 2016 Nature Chemistry

Figure 2. PAF-1–ET as a selective functionalized polymers material for iron (III) detection [70] copyright © The Royal Society of Chemistry 2019

25

Scale-up each diagram process

Linkage of the process steps

Performance

of

Lab. protocol

Simple diagram process

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Figure 3. The simple diagram process of scale-up procedures

Figure 4. The schematic illustration of producing the functional polymers using a batch reactor system

26

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Figure 5. The illustration of the polymerization process using a stainless-steel reactor as both cathode and reaction vessel [101] copyright © 2019 Elsevier

27

Procedures

GO/MIPs/Ag NPs

Propanolol (PRO)

Layer-by-layer assembly

Siloxane-based polymer/ZnO nanostructures

Dimethyl methylphosphonate (DMMP)

Silylation techniques

Poly(FBThF)/Ag NPs-rGO-NH2

Organophosphate pesticides (OPs)

Radical polymerization

Nanostructures ion-imprinted polymers methacrylic acid (MAA) Fe@SiO2@MIP

Tl+

Type of nanostructures Templating methods

Advantages of the functionalization of polymers The macroporous structures can improve the detection sensitivity and selectivity.

Techniques

Remarks

Ref.

Raman scattering (SERS)

The surface area significantly increases from 0.46 to 23.45 m2/g. The sensitivity enhancement factor has increased and was found at 3.95 x 107. The combined materials exhibited high sensitivity due to an increased surface area to 135.1 μm2. The prepared electrode showed excellent sensitivity with the LOD of 0.032 μg/L (malathion) and 0.001 μg/L (trichlorfon). The developed methods showed a wide linear range (0.05-18 μg/L) and LOD of 6.3 ng/L. The Fe@SiO2@MIP exhibited good selectivity and high capacity for removal of DnPP

[62]

Non-template methods

Quartz crystal microbalance (QCM)

Non-template methods

High conductivity, biocompatability, and catalytic activity

Amperometric biosensors

Bulk polymerization

Templating methods

PreconcentrationETAAS

Silylation techniques

Templating methods

Improving selectivity, high adsorption capacities, and affinity High adsorption ability and enhanced affinity to target molecules

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The presence of polymers enhances the hydrophobicity and hydrophilicity.

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di-n-pentyl phthalate (DnPP)

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Target analytes

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Name of materials

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Table 1. Comparison of various nanostructured polymers for analysis of pollutants

28

SPE-HPLC

[55]

[59]

[63]

[64]

Radical polymerization

Non-template methods

PANI/fSWCNT polymers nanocomposites

H2S

Radical polymerization

Non-tempalte methods

GO-COOH/PEI

NH3

Bulk polymerization

Magnetic poly(β-cyclodextrinionic liquid) nanocomposites

polycyclic aromatic hydrocarbons

Thiol/thioetherfunctionalized porous organic polymers

Aromatic pollutants

of

Pb2+

Large surface area, high binding analyte targets, high conductivity, and high afinity to Pb2+

-p

ro

Cysteinefunctionalized GO/polypyrrole

Differential pulse anodic stripping voltammetry (DPASV)

The electrical resistance methods

Non-template methods

Increasing solubility of graphene sheets in solvent and provide active site

Cyclic voltammetry

Layer-by-layer self assembly

Non-tempalte methods

Enhanced interaction through π-π and hydrophobic interactions

GC-FID

Bulk polymerization

Non-tempalte methods

Enhanced surface area and chemical stability

PreconcnetrationHPLC

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High charge transfer, electron mobility, high active surface area, and conductivity

29

with a linear range 0.5-250 μg/L and LoD of 0.3 μg/L. The sGO/PPy sensor proved that the prepared sensor has good sensitivity with the LOD of 0.07 ppb, linear ranges of 28280 ppb. The sensing showed an excellent sensitivity at a low temperature of 50 o C. The sensor exhibited good sensitivity of 2.26 x 10-5 A μmol-1 with the LOD of 9.5 x 10-7 M. The LOD value was found at 0.010.18 μg/kg with the linear range between 0.1-500 μg/kg. The materials showed fast binding and selectivity for analysis of aromatic pollutants such as toluene and m-xylene.

[65]

[66]

[67]

[68]

[69]

of

Table 2. Comparation methods for analysis of pollutants Methods

LOD

Linear Range

Type of polymers

Ref.

Organophosphate pesticides (OPs)

HS-SPME/GC

0.017 ng/g

0.2-100 ng/g

[74]

DPV

1 fM

1 fM – 1 M

Raman spectroscopy/colorimetric Electrical resistance

0.01 mg/L

The graphene oxide incorporated poly acrylamide-ethylene glycol dimethacrylate (GOpoly AM-EDGMA) The conducting polymer, Poly(3,4ethylenedioxythiophene) (PEDOT), and multiwalled carbon nanotubes (MWCNTs) The molecularly imprinted polymers (MIPs) with methacrylic acid (MAA) as a template In situ polumerization of tin oxide/reduced graphene oxide/ polyaniline (SnO2/rGO/PANI) Polymeric ionic liquids with adsorption capacity of 1.75 mmol/g Palladium coordination polymers nanosheets Silsesquioxane-based triphenylamine functionalized porous polymer Molecularly imprinted polymers with 2thiophenecarboxaldehyde pseudo-template The poly(p-phenylenediamine) as ion imprinted polymers Polymerization of methyl methacrylate (monomer) for producing iop imprinted polymers Two-dimensional (2D) of polyaniline

Cu2+

-p NA

NA

NA

Photothermal Fluorescence titrations

30 nM NA

NA NA

GC-MS

0.029 g/L

0.5 – 40 g/L

DPV

2.7 nM

0.9 – 15 nM

GTA-AAS

0.3 g/mL

1 – 10 g/mL

Colorimetric

45 nM

0 – 25 M

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Aromatics compounds

0.05 ppm

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GC/IRGA

0.1 – 10 mg/L

re

H2S

ro

Pollutants

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NA (Not Available) HS-SPME/GC (Headspace Solid Phase Microextraction/Gas Chromatography) DPV (Differential Pulse Voltammetry) GC/IRGA (Gas Chromatography/Infrared Gas Analyzer) GC-MS (Gas Chromatography-Mass Spectrometry) GTA-AAS (Graphite Tube Analyzer-Atomic Absorption Spectrophotometry)

30

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