Bio-Composite Materials Precursor to Chitosan in the ... · Bio-Composite Materials Precursor to...

Review

Appl. Chem. Eng., Vol. 31, No. 3, June 2020, 237-257https://doi.org/10.14478/ace.2020.1034

237

1. Introduction1)

The presence of micro-pollutants in the aquatic environment can lead to serious environmental issues. These micro-pollutants are persistence and relatively toxic in nature and are found to be emerging as water contaminants. It includes a variety of anthropogenic and natural occur-ring substances. Anthropogenic substances are those which include day to day consumables viz., cosmetics, pharmaceutical products, pesticides used by cultivators and variety of industrial wastes emanating from chemical industries. These pollutants are detected in water bodies at very low level in concentrations (ng/L to µg/L) hence, it makes diffi-cult to detect and complicates the process further in regards to treating these compounds in the wastewater treatment plants (WWTPs)[1]. Since these micro-pollutants are persistence hence, it is removed/de-graded partly in the WWTPs and escaped through the WWTPs.

† Corresponding Author: Catholic Kwandong University, Department of Health and Environment, Gangneung 25601, Republic of KoreaTel: +82-33-649-7535 e-mail: [email protected]

‡ Corresponding Author: Mizoram University, Department of Chemistry, School of Physical Sciences, Aizawl-796004, IndiaTel: +91-9862323015 e-mail: [email protected]

pISSN: 1225-0112 eISSN: 2288-4505 @ 2020 The Korean Society of Industrial and Engineering Chemistry. All rights reserved.

Therefore, it resulted a continuous introduction of these pollutants into the aquatic environment[2]. Micro-pollutants which escape through WWTPs in an aquatic environment becomes a serious threat to human and other living beings because of its long- or short-term toxicity, en-docrine disrupting effects and antibiotic resistance. In this respect, since there are no intended guidelines laid down by the regulatory bod-ies for discharge of these micro-pollutants into the water bodies, there will be problems going forward related to this issue[1]. However, many of these contaminants are toxic to living beings as well and need to be continually monitored and researched to preserve human health outcomes in the future.

It is known that the pharmaceuticals/drugs which are administered to the human body could metabolize only up to 30% hence, and therefore the major pharmaceutical compounds are either unmetabolized or me-tabolized as by-products, and are excreted through urine or faeces which eventually enters into the receiving waste water treatment plants (WWTPs)[3-5]. Micro-pollutants are included with the endocrine dis-rupting chemicals (EDCs) which is known to be a serious health hazard. It is therefore, responsible of disrupting the endocrine system as well as nervous system of living organisms[1]. Apart from pharma-ceuticals, the prolonged usage of pesticides in agricultural lands for controlling crops damaging insects, fungus etc. also contributes a sig-

Bio-Composite Materials Precursor to Chitosan in the Development of Electrochemical Sensors: A Critical Overview of Its use with Micro-Pollutants and Heavy Metals Detection

Sarikokba, Diwakar Tiwari‡, Shailesh Kumar Prasad*, Dong Jin Kim**, Suk Soon Choi***, and Seung-Mok Lee****,†

Department of Chemistry, School of Physical Sciences, Mizoram University, Aizawl-796004, India*Department of Chemistry, National Institute of Technology, Jamshedpur-831043, India

**Department of Environmental Science & Biotechnology, Hallym University, Chuncheon 24252, Republic of Korea***Department of Biological and Environmental Engineering, Semyung University, Jecheon 27136, Republic of Korea****Department of Health and Environment, Catholic Kwandong University, Gangneung 25601, Republic of Korea

(Received May 12, 2020; Revised May 15, 2020; Accepted May 19, 2020)

AbstractThe role of nano bio-composites precursor to chitosan are innumerable and are known for having different applications in various branches of physical sciences. The application to the sensor development is relatively new, where only few literature works are available to address the specific and critical analysis of nanocomposites in the subject area. The bio-composites are potential and having greater affinity towards the heavy metals and several micro-pollutants hence, perhaps are having wid-er implications in the low or even trace level detection of the pollutants. The nano-composites could show good selectivity and suitability for the detection of the pollutants as they are found in the complex matrix. However, the greater challenges are associated using the bio-composites, since the biomaterials are prone to be oxidized or reduced at an applied potential and found to be a hinderance for the detection of target pollutants. In addition, the materials could proceed with a series of electrochemical reactions, which could produce different by-products in analytical applications, resulting in several complex phenomena in electrochemical processes. Therefore, this review addresses critically various aspects of an evaluation of nano bio-composite materials in the electrochemical detection of heavy metals and micro-pollutants from aqueous solutions.

Keywords: Electrochemical sensor, Bio-composite materials, Chitosan, Detection limit, Glassy carbon electrode, Heavy metals, Micro-pollutants

238 Sarikokba⋅Diwakar Tiwari⋅Shailesh Kumar Prasad⋅Dong Jin Kim⋅Suk Soon Choi⋅Seung-Mok Lee

공업화학, 제 31 권 제 3 호, 2020

nificant burden to the aquatic environment. These compounds through the washes or leaches from the farm land enters into the aquatic envi-ronment, followed by to the drinking water system and is known for causing issues to disturb the flora-fauna of the natural environment[6]. There are a variety of synthetic pesticides that are widely employed for controlling different types of pests, insects, fungi, etc. Atrazine which is an herbicide that is used to control weeds, having half-life period of 20~100 days and found to be a potent type-C carcinogen, it is noted that they are also listed in EDC even at very low concentrations. Insecticides are commonly used chemicals which are often used to control various insects. For example, diuron and paraoxon are the most common insecticides, and it was reported that the oral intake of para-oxon even at very low concentration is highly toxic for mammals as well as humans[7-9]. Additionally, Clotrimazole and Tebuconazole are commonly used fungicides and are known to be a potential health hazard. Continuous intake of these chemicals by any other means (ingestion) by living organisms is known to have a result of hampering the entire nervous system[7-11]. There are many water pollutants viz., anti-inflammatory drugs, β-blockers, antiepileptic, antimicrobial, cys-tostatic agents and 17 β-estradiol, etc. which are posing a serious threat to the aquatic environment at low concentrations (i.e., ng/L to µg/L)[12]. Although, it was reported that the presence of these chem-icals is currently at very low numbers in concentration, however, a continued intake leads to serious bio-chemical effect and could be re-sponsible for causing varied biological disorders. Most of the mi-cro-pollutants are not listed as hazardous chemicals by existing regu-latory bodies viz., EPA or WHO however, their impact is significant towards the human beings. Although there are sophisticated analytical techniques used for the efficient and accurate separation/detection of these micro-pollutants viz., high performance liquid chromatography (HPLC), liquid chromatograph mass spectrometer (LC-MS), LC/MSMS etc. are the best tools to date. However, these techniques are highly expensive, time consuming, tedious in operations and devoid with on-site detection/determination. This result notes obvious practical im-plications of these analytical methods for use with its wider applications. Therefore, several attempts are made for the development of a sensi-tive, robust miniaturize devise for the low level detection of these mi-cro-pollutants from aqueous solutions[8]. Moreover, the on-site de-tection is shown to be of use with greater applicability in a practical implication of deploying this device.

On the other hand, several metal ions are essential for living organ-isms at trace or lower levels however; the higher concentrations shown

potential for its toxicity. These heavy metal ions are increasingly in-creasing in aquatic environments, which is a serious concern for human as well as to the preservation of aquatic life[13,14]. An enhanced level of heavy metal toxic ions in an aquatic environment is mainly due to the anthropogenic activities and natural itself[15]. The heavy metal ions are inherently persistence in nature and hence, are non-bio-degradable[16]. Among these, cadmium, lead, arsenic, mercury and chromium are highly toxic even at very low concentrations of ex-posure, and for that reason poses a serious environmental and human health hazard[15,17]. Based on the toxicity and penitential health haz-ard of these heavy metal toxic ions, the regulatory bodies have laid down the maximum contamination level that can be found to be pres-ent in the drinking water system (Cf. Table 1)[18]. Therefore, based on these strict regulatory limits it has worked to compel us to detect these ions at even a much lower level.

Further, the presence of these contaminants in an aquatic environ-ment makes it complex and difficult to detect, since it is shown that different complex species of these ions are present in aqueous media. Hence, the determination of several heavy metal toxic ions from the complex matrix required highly sophisticated and sensitive analytical instruments such as with the use of atomic absorption spectroscopy (AAS)[15,19], inductively coupled plasma optical emission spectro-scopy (ICP-OES) or inductively coupled plasma mass spectroscopy (ICP-MS)[19], X-ray fluorescence spectrometry (XRF)[20], neutron ac-tivation analysis (NAA) etc.[21]. Although, these instruments are high-ly sensitive, accurate and provides the required low level detection lim-it i.e., mg/L to µg/L however, the high cost of instrumentation, off site detection and tedious operations makes limited use of this technology. Therefore, the efficient, robust, cost effective and more importantly the on-site low level detection methods are inevitable for wider practical applications going forward[22].

The role of nano bio-composite materials are having very wide ap-plications in various branches of science, including the biomedical, en-vironmental, agricultural, materials, electronics, and biological sciences, etc. Therefore, the present review aims for the nano bio-composites precursors to the natural chitosan, which is intended for its applications in the use and research of electrochemical sensors. This review high-lights intriguing properties of nanocomposite materials precursor to chitosan and their applications in the field of electrochemical sensors, as seen in the last few decades.

Broadly speaking, chitosan is a known compound for centuries and widely known to be useful when applied in biomedical applications. It

Parameters USEPA WHO ISI ICMR CPCB

Mercury (mg/L) 0.002 0.001 0.001 0.001 No relaxation

Cadmium (mg/L) 0.005 0.005 0.01 0.01 No relaxation

Arsenic (mg/L) 0.05 0.05 0.05 0.05 No relaxation

Chromium (mg/L) 0.1 - 0.05 - No relaxation

Lead (mg/L) - 0.05 0.10 0.05 No relaxation

Zinc (mg/L) - 5.0 5.0 0.10 15.0

Table 1. Permissible Limits of Several Heavy Metal Toxic Ions in Drinking Water Quality based on Several Regulatory Bodies[18]

239Bio-Composite Materials Precursor to Chitosan in the Development of Electrochemical Sensors

Appl. Chem. Eng., Vol. 31, No. 3, 2020

has received greater attention in the 19th century when Rouget dis-cussed the deacetylation of chitin to chitosan[23]. Chitosan is an im-portant and ubiquitous polysaccharide biopolymer which was obtained by the use of a partial alkaline N-deacetylation of chitin[23]. The chitin is known to be available and extracted from the shrimp and crab shells. Chitosan is also found in nature, such as in the cell walls of fungi of the class Zygomycetes and in insect cuticles[24]. Chitosan is a natural biopolymer and is considered the most abundant polymer in availability naturally found after cellulose. By the same token, it is widely obtained from the available natural products found in nature such as the exoskeleton of insects, arthropods or as a by-product of seafood processing industry[25,26]. Chitosan possesses wide medical applications because of its intriguing properties as biocompatibility, bi-odegradability, bio-renewable and non-toxic nature, low cost etc.[27]. Chitosan also has a close structure with cellulose because of their line-ar β-(1 → 4) glycosidic linkages [Figure 1(a)]. The two unit of chito-san i.e., 2-acetamido-d-glucose and 2-amino-d-glucose are combined with glycosidic linkage. Through removing an acetate moiety from chi-tin, chitosan is produced by hydration or through enzymatic hydrolysis in the presence of chitin deacetylase [Figure 1 (b)][27,28].

Generally speaking, amino and hydroxyl groups present in the chito-san compound makes it a potential use for several applications, and it is known to characteristically exhibiting polycationic character as com-pared to other natural polymers[29]. Chitosan is found to be pH sensi-tive and it can easily be dissolved in acidic media[30], because of their glycosidic linkage which results in decreasing the molecular weight of the material and its viscosity. The physical and chemical properties mainly depend on the degree of deacetylation and molecular weight of chitosan. In general, chitosan being sensitive in lower pH and has low settling properties and lower mechanical strength which hampers its varied applications[27]. A simple mixing of two polymers may enable the researcher to modify the chitosan physical properties. Similarly, the chemical modifications utilizing the functional groups of chitosan viz., carboxylic, hydroxyl and lead to the formation of hydrogen bonding and facilitating the chemical bonding to obtain the desired compound with required properties[27]. Moreover, it is emphasized that chitosan possesses an excellent film-forming ability, high permeability, good ad-hesion and nontoxicity helps in various applications including the sen-sor development research. Additionally, it is noted that the swelled chi-tosan eases the electron transfer reaction because of its hydrophilic na-ture[31,32].

This review emphasised specifically on the role of nano bio-compo-sites in the development of electrochemical sensors. The updated liter-ature critically evaluates the challenges and opportunities of utilizing nano bio-composites in the development of sensors for micro-pollutants and some of the heavy metals. The future aspects of research are in-cluded to pave the way for possible implications of nano composites in the sensor development industry.

(a)

(b)Figure 1. (a) Structure of chitosan, chitin and cellulose, (b) deacetylation of chitin to chitosan[27].

2. Electrochemical Detection of Micro-pollutants

2.1. Pharmaceutical drugs detectionDiclofenac (sodium[o-(2,6-dichloroanilino) phenyl] acetate) [Figure

2(a)] is a non-steroidal anti-inflammatory drug (NSAIDs). It is widely employed for the treatment of inflammatory and painful diseases viz., rheumatic, nonrheumatic and antiarthritic origin or also reduces the ef-fects of menstrual pain, dysmenorrhea etc.[33]. It was reported pre-viously that Ca 940 tons of diclofenac is consumed annually around the globe having a prescribed dose of 100 mg/day[34,35]. On the other hand, the excess intake of diclofenac by humans is shown to have


공업화학, 제 31 권 제 3 호, 2020

(a)

(b)Figure 2. (a) Diclofenac sodium, (b) CV of the bare GCE (curve a), MWCNTS/GCE electrode (curve b) and MWCNTs/CTS-Cu/GCE (curve c) in the solution containing 50 µmol/L diclofenac sodium in 0.2 mol/L PBS (pH 4.0) at 100 mV/s scan rate[41].

caused several adverse biochemical effects e.g., cytotoxicity to liver, kidney and gill cells as well the renal lesions even at a concentration of 1.0 mg/L[36-38]. It may also influence the biochemical functions of fish which leads to tissue damage in those animals[39]. Similarly, the diclofenac sodium is known to cause life-threatening cardiac problems viz., heart attack and stroke with the patients who are already having a diagnosis of diabetes and also Shy-Drager syndrome[40]. Therefore, the detection of diclofenac at low levels is an marker important for safeguarding the aquatic environment. The nano composite contained with the multi-walled carbon nanotubes (MWCNTs) composed with chitosan-copper complex (MWCNTs/CTS-Cu/GCE) was utilized for the modification glassy carbon electrode (GCE) using the drop cast method. The modified electrode was then employed for electrooxidation of di-clofenac using the cyclic voltammetric studies as shown in Figure 2(b).

Further, the detection of diclofenac sodium is conducted using the square wave voltammograms (SWV) which showed that a good line-arity was obtained with the equation Ip (mA) = 1.139 CDS (µmol/ L) + 0.128 (R2 = 0.997) with the limit of detection (LOD) = 0.021 mol/L. It is interesting to note that the real samples of human urine was in-tended for diclofenac detection at varied concentrations of diclofenac sodium using human urine, and indeed a 99.7 to 98.88% recovery was achieved upon review of these samples[41]. Similar to the diclofenac, the paracetamol (N-acetyl-paminophenol) or acetaminophen is having widespread use as analgesic and anti-pyretic drug[42,43]. It gives relief in the experience of pain of different types viz., arthralgia, neuralgia, migraine, joint pain, general pain, cancer pain, headache, toothache, backache, postoperative pain etc.[44]. An excessive dose of paracetamol

Figure 3. (a) DPVs response at f-MWCNTs/CTS-Co/GCE for differentconcentration of paracetamol between (0.01 µM~400 µM) in 0.2 M phosphate buffer solution (pH 7.0), and (b) calibration curve of peak current with PR concentration[46].

causes life threatening health hazards such as liver damage, kidney failure and severe hypersensitivity reaction[45]. Further, it is noted that the nano bio-composite of f-MWCNTs-chitosan-Co was synthesized by a self-assembly process[46]. The glassy carbon electrode which was modified by the nano bio-composite and employed for the electro-chemical oxidation/reduction of paracetamol in the well demonstrated cyclic voltammetric studies is shown in equation (1):

(1)

Further, a low level detection of paracetamol was conducted using differential pulse voltammetry (DPV) for varied concentrations of para-cetamol (Cf. Figure 3). The results showed that reasonably a good cali-bration was obtained having a calibration line Ipa (µA) = 0.636 CPR (µmol/L) + 0.273 (R2 = 0.99) with the limit of detection 0.01 µM/L, and it was further noted the sensitivity of 0.273 µA/µmol/L[46].

Generally speaking, Bisphenol A (BPA) is one of the potential endo-crine disrupters which mimics female estrogen 17-β-estradiol and it alters the normal hormonal system of animals. The biochemical effects of bisphenol A includes the morphological alterations and interferences in sex differentiation, and along with it is shown to be an agent that



Figure 4. XPS spectra of the N element in (A) CS and (B) CS-Fe3O4

nanocomposite, Fe element in (C) Fe3O4 NPs and (D) CS-Fe3O4 nanocomposite[56].

reduces fertility[47,48]. This result comes about as it causes the pro-liferation of MCF-7 human breast cancer cells[49], and exert a muta-genic action on human RSa cells[50]. In addition to this the in vitro and in vivo studies showed that bisphenol A causes an enhanced in-fertility, genital tract abnormalities and breast cancer[51,52]. In a line the US EPA (US Environmental Protection Agency) suggested a max-imum acceptable or reference dose of BPA intake of 0.05 mg/kg of body weight/day[53,54]. Therefore, the low level detection of bisphenol A is conducted utilizing the composite materials Chitosan-Fe3O4 in the modified glassy carbon electrodes. Furthermore, amperometric sensors were used for the determination of bisphenol A (BPA) by surface mod-ification of GCE using chitosan-Fe3O4 (CS-Fe3O4) nanocomposite ma-terial[56]. Likewise, the XPS data further demonstrated that Fe (2p) was changed from two characteristic bands (711.16, 723.27 eV) in Fe3O4 NPs to four characteristic bands (710.96, 714.09, 721.28, 724.82 eV) in the CS-Fe3O4 nanocomposite (Cf. Figure 4), and it was inferred that the lone pair electrons of N atom in chitosan was interacted with 3d orbital of Fe atom in Fe3O4 and hence forming a coordinate bond[55,56]. It was further observed that the surface modification of GCE by this composite material successfully enhanced its sensitivity toward the BPA detection conducted in plastic samples[56]. Moreover, the analytical method was employed for the detection of bisphenol A from the plastic samples and it was noted that reasonably a good re-covery was achieved (Cf. Table 2)[56]. Further, it was stated that the

doping of Au nanoparticles into the substrate materials were able to enhance the specific electro active surface area along with the con-ductivity of the materials hence, this eventually enhanced the peak cur-rent and was shown to be useful for identifying the trace detection of pollutants[57]. Next, the hydrothermally flower like nano molybdenum disulphide (MoS2) was obtained and the nanosheets of MoS2 was in-troduced with chitosan and gold nanoparticles to obtain the nano-composite materials (MoS2-chitisan-Au). The nanocomposite material was utilized to modify the glassy carbon electrode which was in-troduced for the trace detection of bisphenol A using the cyclic vol-tammetric studies. The electrochemical studies showed that a two elec-tron oxidation of bisphenol A takes place as shown in equation (2):

(2)

Further, utilizing the oxidation peak current the detection of bi-sphenol A was conducted as shown in Figure 5. It is evident in this case that a good linearity of peak current against the concentration was obtained having the linear line equation ip (mA) = 88.87 + 29.79 log C (mM) with correlation coefficient 0.9896 and LOD 5 nmol/L[58].

Theophylline is widely prescribed as bronchodilators and respiratory stimulator drug in order to treat the infant apnea, the asthmatic acute phase in children[59]. However, it was suggested that an accurate and careful dose needs to be adjusted for safe and effective use of this drug, which requires often determination of theophylline concentration in the blood serum[60]. Therefore, this reliable and miniaturized de-tection device is useful for an accurate detection and determination of theophylline from various biological samples. It was further reported previously that the oxidation of theophylline takes place at relatively high applied potential which restricted its detection using the electro-chemical methods[59]. However, a useful study was carried out using the MnO2 (NPs)/ionic liquid/chitosan nanocomposite modified glassy carbon electrode using the electrodeposition method. The fabricated electrode showed the oxidation of theophylline at an applied potential of Ca 1.0 V in the DPV measurements (Cf. Figure 6). In other words, it was inferred that the presence of MnO2 catalyses the oxidation of drug as shown in equations (3 & 4):

2MnOOH → 2MnO2 + 2e- + 2H+ (3)

Sample Measured (µmol/dm3)a Added (µmol/dm3) Found (µmol/dm3) RSD (%) Recovery (%)

PVC Drinking cup 1.23 1.25 2.52 3.11 101.6

PVC nursing bottle 0.14 0.50 0.68 4.12 106.2

Baby’s nipple - 0.05 0.046 3.58 92.0

PVC food package 0.54 0.50 0.98 4.27 94.2a Mean of five measurements.

Table 2. Determination of BPA in Plastic Samples[56]


공업화학, 제 31 권 제 3 호, 2020

Figure 5. (A) Cyclic voltammograms of BPA at AuNPs/MoS2/GCE in 0.1 M PBS (pH 7.0) containing different concentrations of BPA (from a to j: 0.05, 0.1, 0.2, 0.5, 0.8, 1.0, 3.0, 15.0, 25.0, 50 and 100 mmol/L); (B) the relationship of the peak current with the concentration of BPA[58].

Figure 6. DPVs recorded at bare GC (a and b) and GC/Chit/NH2-IL/ MnOx (c and d) electrodes in the absence (a and c) and presence (b and d) of 1 µmol/L TP in 0.1 M acetate buffer solution (pH 5)[61].

2MnO2 + 2H2O + → 2MnOOH +

(4)

Further, a linear least square calibration line for the studied concen-tration of theophylline 0.2~0.6 mM was found to be I (mA) = 0.804 C (µmol/L) - 0.0049 (mA) (R2 = 0.996). Similarly, the detection limit and sensitivity were found to be 50 nM and 804 nA/nM, respectively [61]. In this relation, it is known that acetaminophen (ACT) is an ex-tensively prescribed drug for relief of moderate pain, fever, lumbar

Figure 7. Cyclic voltammograms of 100 µmol/L ACT and 100 µmol/LMEF at MWCNTs-CHT/GCE in 0.1 mol/L phosphate buffer solution (pH 7) at scan rate 50 mV/s[67].

Figure 8. Electrochemical impedance studies (EIS) of a) bare GCE and b) Chit/CuTsPc/GCE in the presence of 0.1 mol/L KCl and 5 mM K3[Fe(CN)6]3-/4-[72].

pain, migraine or even non-specific indications[62] and often replaces the use of aspirin. Similarly, the Mefenamic acid (MEF) which is a nonsteroidal anti-inflammatory medicine is possessed with analgesic and antipyretic properties and is useful while employed for several diseases related to rheumatoid arthritis, osteoarthritis, nonarticular rheumatism, and sports injuries[63,64]. In what follows, the overdose of these medi-cines causes serious biochemical disorders in the human being which includes accumulation of toxic metabolites, that may cause severe and fatal hepatoxicity[65,66]. Therefore, the simultaneous determination of these two drugs i.e., acetaminophen and mefenamic acid are noted when conducted by the electroanalytical method[67]. A composite of multiwalled carbon nanotubes (MWCNTs) with chitosan was obtained and it was employed for the modification of a glassy carbon electrode. The modified electrode showed distinct oxidation peaks for the acet-aminophen and mefenamic acid, and therefore makes it possible for their simultaneous detection (Cf. Figure 7). These two drugs were sat-isfactorily detected in the real matrix samples (human serum, human urine) with the recovery of 96 to 97%[67]. Similarly, the metronida-zole, 1-(2-hydroxyethyl)-2-methyl-5-nitroimidazole is an antimicrobial drug and given for the treatment of trichomonas, Vincent's organisms, and anaerobic bacteria[68-71]. Although the drug has somewhat higher tolerable limits when used in humans (< 2 g per day) however, it has shown toxic effects at a higher intake. The detection/determination of



metronidazole was conducted using the chitosan protected tetrasulfo-nated copper phthalocyanine coated glassy carbon electrode in the elec-trochemical studies. The modified electrode was subjected for the elec-trochemical impedance spectroscopic measurements and the results are shown in Figure 8. The Rct value was estimated for the modified elec-trode and found to be 100 Ω. This result infers that the electro chemical redox behaviour of the probe to the substrate electrodes is known to be accelerated[72]. Further, the metronidazole was estimated using the modified electrode in the differential pulse voltammetry and reasonably a good calibration line was obtained y = -0.2106 (nM) - 0.0386 (R2 = 0.9976). The method hereby was greatly applied for the determination of metronidazole in urine samples[72]. In this respect, the ruthenium complexes are found with a greater attention because of its reactivity and widespread applications. Therefore, chitosan supported ruthenium complex was impregnated with the glassy carbon electrode and successfully applied for the electrochemical detection/determination of sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) from aqueous solutions[73].

To begin with, the decarboxylation of amino acids is naturally pro-ducing the biogenic amines which are involved in several metabolic processes in the living being. However, it was reported that food con-tained with excessive amounts of biogenic amines may lead to the dis-eases viz., hypotension, headaches and diarrhoea[74-77]. In a line the decarboxylation proceeded by microbial activity of tyrosine results the formation of tyramine, or p-hydroxyphenyl ethylamine which is im-portant biogenic amine, it is shown that Tyramine is often occurred in fermented foods and beverages, meat, fish and other dairy prod-ucts[78-80]. The measurement of tyramine is challenging using the ro-bust analytical methods since the available techniques viz., HPLC, LC-MS etc. are sophisticated, expensive and more importantly time consuming. In this context, the multiwalled carbon nanotube doped with gold nanoparticle (MWCNT-AuNP) composite was employed for the molecularly imprinted polymer (MIP) using the chitosan as a bridge material to imprint the nanocomposite. The cyclic voltammetric results indicated that the imprinted film possessed an excellent selectivity for tyramine, and were shown to have displayed a good linear response with the current and concentration of tyramine in the amperometric measurements within the concentration range 1.08 × 10-7 to 1 × 10-5 mol/L showed the LOD 5.7 × 10-8 mol/L[81]. The study was further extended for use with the real matrix measurement using the spiked yogurt samples with varied concentrations of tyramine from 1.0 × 10-6 to 9 × 10-6 mol/L and showed the recovery of tyramine from 107.7.7% to 92.1%[81]. Similarly, generally speaking the warfarin[3-(α-acetonyl- benzyl)-4-hydroxycoumarin, WAR] is one of potential oral anticoagulant employed for the cardiovascular and cerebrovascular problems viz., ve-nous thromboembolism, pulmonary embolism, atrial fibrillation, valvu-lar heart disease and coronary heart diseases[82-84]. The effectiveness of the drug is based on the regulated dose hence; the therapeutic win-dow of warfarin is noted to be very narrow. Moreover, the excessive of this drug causes unwanted bleedings[85]. In this context, the deter-mination of warfarin is conducted using the CdS-quantum dots (CdS-QDs), MWCNTs and chitosan modified GCE. Hence, a well-de-

Figure 9. The effect of pH on the peak current of 5 µmol/L warfarin at the surface of QDs/CS/MWCNTs/GCE; scan rate = 100 mV/s. Inset:dependence of the peak potential (EPA) with pH solution[86].

fined oxidation peak of warfarin was occurred around applied potential of 1.0 V. Additionally, it was noted that a linear relationship was ob-tained between the peak oxidation current of warfarin against the pH of the solution (Cf. Figure 9). The obtained equation was obtained as:

EPA (mV) = -49 pH + 1110.5 (R2 = 0.9994) (4)

Therefore, the slope was found to be -49 mV/pH unit which was close to the theoretical value of -59 mV/pH unit. Further, the CdS-QDs/ CS/MWCNTs/GCE composite material shows a low detection limit (3 nmol/L) having high sensitivity and selectivity. Moreover, the real sample analysis was conducted using the urine, serum and milk sam-ples and the recovery of warfarin was satisfactorily obtained[86]. Notably, cefpirome is a new C-3’quaternary ammonium cephalosporin and known to be newer cephalosporin drug, and is shown to be highly active against both gram negative organisms including Pseudomonas aeruginosa and gram positive organisms including staphylococci. The drug is prescribed for the treatment of upper and lower urinary tract; lower respiratory tract, skin and soft tissue infections[87-89]. The de-tection of the drug was conducted using the multiwalled carbon nano-tube modified glassy carbon electrode. Therefore, the square wave vol-tammetric determination of the Cefpirome showed the regression equa-tion ip = 148.2 C - 19.12 (R2 = 0.991) with the LOD of 0.647 mg/mL. These various studies enabled that the glassy carbon electrode modified with several nanocomposites are found to be useful materials and the chitosan, which provides a bridging polymer to enhance the impregnation of nanocomposites onto the electrode surface and provides the strength and stability of thin film onto the electrode surface.

2.2. Pesticide pollutantsWidespread use of variety of pesticides in the agricultural applica-

tions has caused a serious environmental concern and greater threat to the human being. The low level detection in the aquatic environment poses innumerable health hazards. Organophosphates are widely em-ployed as pesticides but these compounds are highly toxic in nature [90], due to their ability to irreversibly modify the catalytic serine resi-due in acetyl-cholinesterases (AChE). Further, the inhibition of AChE causes the obstruction in nerve transmission by blocking breakdown of


공업화학, 제 31 권 제 3 호, 2020

Figure 10. Differential pulse voltammograms of the sensor at the different MP concentrations. Inset: calibration plot of the dependence of the measured current on MP concentrations. Supporting electrolyte: MPS (pH 5.6), scan rate: 50 mV/s[95].

the transmitter choline[91]. Therefore, the trace measurement of orga-nophosphates are important in view of several health and environmental concerns. The immobilization of AChE by using glutaraldehyde as cross-linker to multiwall carbon nanotubes (MWNTs)-chitosan (MC) composite was utilized in the modification of the glassy carbon elec-trode and utilized for the low level quantification of triazophos from aqueous solutions. MWNTs which show catalytic properties and im-proves the cathodic current in the triazpphos detection. The detection limit of triazophos was found to be 0.01 µmol/L[92]. In a line the bio-sensor made of immobilizing acetylcholinesterase (AChE) through co-valent bond to oxidize exfoliated graphite nanoplatelets (xGnPs)-chitosan cross-linked composite is employed to modify the glassy carbon electrode. The sensor was then employed for the detection of one of potential pesticide chloropyrifos (CPF). The enhanced electrochemical signal was received which was mainly due to the increased surface area and improved conductivity of the composite material and interest-ingly noted that the electrode was stable and sensitive for the longer operations[93]. The methyl parathion (O,O-dimethyl O-(4-nitrophenyl) phosphonothioate) is extensively used in agricultural crops as insecticide, acaricide and herbicides[94]. It is again organophosphorus type of pes-ticide having extensive toxic effects to the biosystem once entered into the biosystem even at low level. A novel acetylene black-chitosan com-posite immobilized glassy carbon electrode was fabricated and the elec-trochemical studies indicated the redox behaviour of parathion on the electrode surface as demonstrated in equation (5):

(5)

The differential pulse voltammetric studies indicated that a good lin-ear relationship was obtained between the parathion concentration and the reduction current (Cf. Figure 10). The regression equation was found to be ipc (mA) = 0.048 + 0.2528 C (µmol/L) (R2 = 0.993) having

Figure 11. Cyclic voltammetric behaviours of 2,4-DCP (2.0 µmol/L) in 0.1 mol/ L PBS (pH 7.0) on the bare GCE, CTAB/GCE, CDs/GCE, CS/GCE, CDs-CTAB/GCE and CS/CDs-CTAB/GCE. Accumulation time: 120 s; scan rate: 100 mV/s[100].

the LOD of 2.0 × 10-9 mol/L[95].The chlorinated herbicides such as picloram (4-amino-3,5,6-tri-

chloro-2-pyridinecarboxilic acid) is although banned but many coun-tries are still using it to control broadleaf weeds. Through the agricul-tural lands it enters into the water bodies through run off and poses serious environmental issues[96]. In order to detect the picloram, an ef-ficient, cost-effective, sensitive and selective immunosensor is developed. Indigenously a conductive chitosan/gold nanoparticles composite mem-brane was utilized in the modification of glassy carbon electrode. The picloram showed good redox behaviour on the modified electrode hence, it was detected at low level[97]. 4-dichlorophenol (2,4-DCP) is a precursor of herbicides and widely used in the industries related to the pharmaceuticals, pesticides, fungicides and insecticides[98]. The compound is highly toxic and persistent in nature and showed carcino-genic[99]. Therefore, an efficient electrochemical method was proposed using the nanocomposite of carbon dots, hexadecyltrimethyl ammo-nium bromide and chitosan for the low level detection of 2,4-DCP. The electrochemical response of the different electrodes for 2,4-DCP is shown in figure (Figure 11) using the 0.1 mol/L PBS at pH 7.0. A significant oxidation peak of 2,4-DCP was occurred at the applied po-tential of Ca 0.78 V and the oxidation peak current was significantly increased for the CDs-CTAB/GCE electrode. Further, it was suggested that the CDs-CTAB nanocomposite enables synergistic effect for effi-cient electron transfer reactions[100]. Further. the efficiency of these electrodes in terms of their detection limit with the studied concentration range for various micro-pollutants and other potential are summarized in the Table 2.

2.3. Heavy metal toxic ions determinationPresence of heavy metal toxic ions in the aquatic environment is

long known a serious environmental concern. The detection and deter-mination of these pollutants in the complex matrix poses several com-plicated issues of its measurements. Although, the advanced and so-phisticated instrumentation could enable to measure it at trace level. However, the instrumentation is highly expensive, time consuming and more importantly it requires off site determination. This eventually lacks the practical implications in such detection. Therefore, fast and



Micro-pollutants Composite materials/electrode Concentration range studied LOD Ref.

Diclofenac sodium (DS) IL/CNTPE 0.3 to 750.0 µmol/L 0.09 µmol/L [40]

Diclofenac sodium (DS) MWCNTs/Ch-Cu 0.3 µmol/L to 200 µmol/L 0.021 µmol/L [41]

Paracetamol (PR) CFE 0.02 to 100 µmol/L 0.034 µmol/L [42]

Paracetamol (PR) AuNPs/SDS-LDH 0.5 to 400 µmol/L 0.13 µmol/L [44]

Paracetamol (PR) CoHCF 3.33 × 10-6 to 1.0 × 10-3 mol/L 8.3 × 10-7 mol/L [45]

Paracetamol (PR) f-MWCNTs/Ch-Co 0.1 and 400 µmol/L 0.01 µmol/L [46]

Bisphenol A (BPA) Ch-Fe3O4 5.0 × 10-8 and 3.0 × 10-5 mol/dm3 8.0 × 10-9 mol/dm3 [56]

Dopamine (DA), ascorbic acid (AA) P2W16V2/Au-Pd 2.1 × 10-6 to 2.06 × 10-3 mol/L (DA),

1.2 × 10-6 to 1.61 × 10-3 mol/L (AA)8.3 × 10-7 mol/L (DA), 4.3 × 10-7 mol/L (AA) [57]

Bisphenol A (BPA) MoS2/Ch-AuNPs 0.05 to 100 µmol/L 5.0 × 10-9 mol/L [58]

Theophylline Nafion/MWNTs 6.0 10-7 to 4.0 10-4 mol/L 2.3 10-7 mol/L [59]

Theophylline E-MIP 10 to 50 µmol/L 3.36 µmol/L [60]

Theophylline (TP) Ch/NH2-IL/MnOx 0.1 to 120.0 µmol/L 50 nmol/L [61]

Mefenamic acid (MFA) LNW/CPE 2.0 × 10-11 to 4.0 × 10-9 mol/L 6.0 × 10-12 mol/L [66]

Acetaminophen (ACT), Mefenamic acid (MEF) MWCNTs-Ch 1 µmol/L to 145 µmol/L (ACT),

and 4 µmol/L to 200 µmol/L (MEF)0.17 mmol/L for (ACT) and

0.66 mmol/L for (MEF) [67]

Metronidazole Ch/CuTsPc 0.8 × 10-9 mol/L to 72 × 10-7 mol/L 4.1 × 10-10 mol/L [72]

Sildenafil citrate, Acetaminophen Ch-RuQT 1.25 × 10-5 to 4.99 × 10-4 mol/L 10.7 µmol/L [73]

Triazophos AChE/MWNTs-Ch - 0.01 µmol/L [81]

Cefpirome MWCNT 100 to 600 µg/mL 0.647 µg/mL [87]

warfarin CdS-QDs/Ch/MWCNTs 0.03 to 7.8 µmol/L and 7.8 to 32 µmol/L 8.5 nmol/L [86]

Phenols and pesticidesTyrosinase, peroxidase, acetylcholinesterase and

butyrylcholinesterase-

(Phenols) Catechol 0.35 and 1.7 µmol/L (pesticides), carbaryl 26

nmol/L, heptenophos 14 nmol/L and fenitrothion 0.58 µmol/L

[90]

Chloropyrifos AChE-xGnPs-Ch 0.005 to 0.039 mmol/L and 0.064 mmol/L to 0.258 mmol/L 1.58 × 10-10 mol/L [92]

Methyl parathion Acetylene black-Ch 2.0 × 10-8 to 1.0 × 10-4 mol/L 2.0 × 10-9 mol/L [95]

Picloram Ch/AuNPs 0.005 to 10 µg/mL 5 ng/mL [96]

2,4-dichlorophenol (2,4-DCP) Horseradish peroxidase (HRP) 1.0 × 10-8 to 1.3 × 10-5 mol/L 5.0 × 10-9 mol/L [98]

2,4-dichlorophenol CDs-CTAB-Ch 0.04 to 8.0 µmol/L-1 0.01 µmol/L [100]

Ochratoxin A APT/SA/Ch-f-Gr 0.01 to 1,000 × 10-6 ng/mL 1 × 10-7 ng/mL [101]

Nitric oxide CS-MPA-AuNPs 1 × 10-7 to 21.5 × 10-7 mol/L 0.45 × 10-7 mol/L [102]

Malathion CHIT-IO 0.001 ng/mL to 0.01 mg/mL 0.001 ng/mL [103]

4-nitrophenol (4-NP) AgNPs-Ch 0.07 to 2.0 µmol/L 70 nmol/L [104]

Actin Ch-ZnNPs 0.0001 to 0.1 mg/mL 21.52 ng/mL [105]

Hydrogen peroxide Ch-AgNPs 0~1.2 mmol/L 10 µmol/L [106]

Epinephrine GQD-Ch 0.36 to 380 µmol/L 0.3 µmol/L [107]

Dimethyl disulfide (DMDS) Ch/RGO 1~500 mg/L 0.9 mg/L [108]

Dopamine Gr-Ch 1.0 × 10-9 to 8.0 × 10-8 and 1.0 × 10-7 to 1.0 × 10-4 mol/L 1.0 × 10-11 mol/L [109]

Diethylstilbestrol WMMIPs/MWCNTs@Ch/CTABr/MGCE 1.5 × 10-9 to 1.5 × 10-4 mol/L 2.5 × 10-10 mol/L [110]

Hydroxy methane sulfinate CTAB-CNT-Ch 30~800 µmol/L 9.6 µmol/L [111]

Dopamine (DA) andparacetamol (PR) RGO-CB-Ch 3.2 × 10-6 to 3.2 × 10-5 mol/L (DA),

2.8 × 10-6 to 1.9 × 10-5 mol/L (PR)2.0 × 10-7 for (DA),

5.3 × 10-8 mol/L for (PR) [112]

Erythromycin Gr-AuNPs/Ch-PtNPs 7.0 × 10-8 mol/L to 9.0 × 10-5 mol/L 2.3 × 10-8 mol/L [113]

To be continued.

Table 2. The use of Nano Composites in the Determination of Various Micro-pollutants from Aqueous Solutions


공업화학, 제 31 권 제 3 호, 2020

Figure 12. Representation of Cu(II) trapping in the Ch/AuNPs matrix[123].

cost effective electrochemical methods are developed and precisely re-viewed here for wide understanding of subject and possible im-plications in practical applications. In a line Au(NPs)/Chitosan modi-fied glassy carbon electrode was employed in the detection of Cu(II). It was noted that Cu(II) is oxidized at an applied potential of Ca 0.28 V. The differential pulse voltammograms indicated that reasonably a good linearity was obtained between the concentration of Cu(II) and oxidation peak current. The results showed that the regression line was followed the equation: I(mA) = 1.665 log[Cu2+] + 13.162 (R2 = 0.9927). The Ch/Au(NPs)-modified electrode possessed with enhanced active surface area compared to the bare chitosan electrode since Au(NPs) are bound with chitosan and facilitated the surface adsorption and redox reactions on the surface (Cf. Figure 12)[123]. Similarly, the graphene/chitosan composite was utilized to modify the glassy carbon electrode at the low level determination of Cu(II). The modified elec-trode enhanced significantly the electrochemical signal which enabled the low level detection of Cu(II)[124].

Amino-functionalized graphene/chitosan composite modified glassy carbon electrode showed a greater application in the detection of Cu(II). The differential pulse voltammetric curves along with the calibration curves are shown in Figure 13. Interesting to note that two linear equa-

Figure 13. (a) DPV curves at NH2-G/Cs/GCE in 0.1 mol/L CH3COOH-CH3COONa (pH 4.6) containing Cu2+ with different concentrations, from a to o: 0.4, 1.6, 2.8, 5.2, 10, 20, 30, 40, 60, 80, 100, 120, and 140 µmol/L. Deposition time, 300 s; deposition potential, -0.7 V; amplitude, 50 mV; increment potential, 4 mV; pulse period, 0.5 s; sensitivity, 10-5 A/V; vs SCE. (b) Plot of the DPV peak current vs. the concentration of Cu2+. Insets: the linear fit of the dependence in two concentration ranges[125].

tions are obtained at varied concentration range of Cu(II): ipc = 1.0553 C + 2.9608 (ipc in µA, C in µmol/L)[Cu2+]: 0.4 to 40 µmol/L and ipc

Micro-pollutants Composite materials/electrode Concentration range studied LOD Ref.

Theophylline (TP) and caffeine (CAF) AgNPs-Ch-IL 2.50 × 10-8 to 2.10 × 10-6 mol/L (TP) and

2.50 × 10-8 to 2.49 × 10-6 mol/L (CAF)1.32 × 10-9 mol/L (TP) and

4.42 × 10-9 mol/L (CAF) [114]

Sunset yellow Graphite-Ch 2 × 10-7 to 10-4 mol/L 6.66 × 10-8 mol/L [115]

Benzylpenicillin Fe3O4@SiO2-MWNTs-Ch 5.0 × 10-8 to 1.0 × 10-3 mol/L 1.5 × 10-9 mol/L [116]

Albumin MIPs/Ch/IL-GR 1.0 × 10-10 to 1.0 × 10-4 g/L 2 × 10-11 g/L [117]

Catechol (CC) and hydroquinone (HQ) Pt-Au-OSi@Ch 0.06~90.98 µmol/L (CC) and

0.03~172.98 µmol/L (HQ)0.02 µmol/L (CC) and

0.01 µmol/L (HQ) [118]

Hydrogen peroxide GQDs-CS 1.0 × 10-6 to 2.9 × 10-3 mol/L and 2.9 to 11.78 mmol/L 0.7 µmol/L [119]

Hydrazine GO/CTS/Pt 2.0 × 10-5 to 1.0 × 10-2 mol/L 3.6 µmol/L [120]

Salmonella AgNPs-Ch 10 to 105 CFU/mL 5 CFU/mL [121]

Serum leptin F-SWCNTs/Ch 0 to 1,000 ng/mL 5 pg/mL [122]

Table 2. Continued



= 0.3745 C + 30.6545 (ipc in µA, C in µmol/L) in the range of 40 µmol/L to 140 µmol/L. Further, the detection limit of Cu2+ was found to be 0.064 µmol/L[125].

A newer composite material reduced graphene oxide-chitosan/ poly-L-lysine precursor to chitosan is synthesized and further utilized for the modification of glassy carbon electrode. It was reported that at the electrode surface heavy metals forming complexes with the immobilized chitosan (CS) and poly-L-lysine (PLL) followed by the redox reactions on the electrode surface. The studied heavy metals are oxidized at different applied potentials i.e., Cd(II), Pb(II) and Cu(II) are detected at potentials of -0.82, -0.54 and -0.11 V, respectively. This gives the advantage of their detection simultaneously in the electrochemical studies (Cf. Figure 14). Interesting to note that the regression line depends on the concentration range as shown in equations (7-12).

ip (mA) = 6.91 + 2.51 C (mg/L); (0.05 to 2.0 mg/L; R2 = 0.996)(7)

ip (mA) = 8.26 + 0.57 C (mg/L); (2.0 to 10.0 mg/L; R2 = 0.998)(8)

for Cd(II),

ip (mA) = 7.01 + 0.45 C (mg/L); (0.05 to 2.0 mg/L; R2 = 0.996)(9)

ip (mA) = 7.41 + 0.09 C (mg/L); (2.0 to 10.0 mg/L; R2 = 0.999)(10)

and for Pb(II),

ip (mA) = 7.20 + 0.51 C (mg/L); (0.05 to 2.0 mg/L; R2 = 0.996)(11)

ip (mA) = 7.62 + 0.168 C (mg/L); (0.05 to 2.0 mg/L; R2 = 0.998)(12)

The method was applied to analyse the tap water and the recovery was within the range of 96.00~103.33% for Cd(II), 93.33~97.6% for Pb(II), and 96.66~101.33 for Cu(II)[126]. Similarly, the Bi doped mes-oporous carbon xerogel (Bi-CX) mixed with chitosan to obtain the composite material BiONPs-CS. The material was coated onto the sur-face of glassy carbon electrode and attempted for the simultaneous de-

Figure 14. DPASV of heavy metal ions at RGO-CS/PLL/GCE (a) 8.0 mg/L Pb(II) and 8.0 mg/L Cu(II) with concentrations varying in the range of 0~10.0 mg/L Cd(II); (b) 8.0 mg/L Cd(II) and 8.0 mg/L Cu(II) with concentrations varying in the range of 0~10.0 mg/L Pb(II); (c) 8.0 mg/L Cd(II) and 8.0 mg/L Pb(II) with concentrations varying in the range of 0~10.0 mg/L Cu(II). Supporting electrolyte: 0.1 M acetate buffer (pH 4.5); deposition potential: -1.2 V; deposition time: 180 s; quiet time: 10 s. (d) Adsorption isotherm of RGO-CS/PLL for Cd(II), Pb(II) and Cu(II). Adsorbent dose = mg/L, contact time = 24 h, T = 298 K[126].


공업화학, 제 31 권 제 3 호, 2020

termination Cd(II) and Pb(II). The Pb(II) was detected at the applied potential of -0.40 whereas Cd(II) was detected at the potential of -1.4 V against the Ag/Ag,KClsat[127]. On the other hand, the glassy carbon electrode was suitably modified with the composite material viz., fluo-rinated multiwalled carbon nanotubes magnetite (Fe3O4). The electrode was suitably for the detection of multielements viz., Zn(II), Cd(II), Pb(II), Cu(II) and Hg(II) since they showed the oxidation peaks at the applied potential of -1.11, -0.70, -0.53, +0.01 and + 0.37 V, re-spectively in the stripping wave voltammetry at pH 5.0 acetate buffer (Cf. Figure 15). Further, the stable electrode was employed for the real matrix sample analysis in monitoring water and rice samples which showed almost 96.0% to 101.5% recovery as compared to the standard analytical methods applied i.e., ICP-MS and AFS[128]. The one pot facile synthesis carried out to obtain the reduced graphene oxide with Fe3O4 nanocomposite (rGO-Fe3O4). Further, nanocomposite modified glassy carbon electrode was intended for the low level and simulta-

neous detection of Cd2+, Pb2+ and Hg2+ using the stripping voltammetry. The stripping peak potentials were recorded for Cd2+, Pb2+ and Hg2+ at the applied potential of -0.79, -0.59, and +0.25 V, respectively. The method was employed for the analysis of lead in soil sample and re-sults were found within the permissible range[129]. Similar studies were conducted using the Fe3O4/multiwalled carbon nanotube/laser scri-bed graphene composites functionalized with chitosan modified glassy carbon electrode (Fe3O4/MWCNTs/LSG/CS/GCE). The modified elec-trode showed a sensitive sensor for the simultaneous detection of Cd(II) and Pb(II). The LOD of Cd(II) and Pb(II) was found to be 0.1 and 0.07 µg/L. Interesting to found that selectivity for several cati-ons/anions and the stability of electrode was fairly good. The 10 run of detection showed reasonable stability of electrode at least for the de-tection of Cd(II) and Pb(II) (Cf. Figure 16)[130]. Similarly, ZnO anch-ored with chitosan was useful for low level detection of Cd(II) using the modified glassy carbon electrode[131].

Figure 15. (a) SWVs of Fe3O4/FMWCNT/GCE for the simultaneous determination of Zn(II), Cd(II), Pb(II), Cu(II) and Hg(II) (from the bottom to top: 5, 10, 20, 50 nmol/L; 0.1, 0.2, 0.5, 1, 2, 5, 10, 15, 20, 30, 31.5, 32.5, 33.5 µmol/L); corresponding calibration plots of (b) Zn(II), (c) Cd(II), (d) Pb(II), (e) Cu(II) and (f) Hg(II)[128].



Figure 16. (A) Selectivity of Fe3O4/MWCNTs/LSG/CS/GCE for simultaneous detection of Cd2+ and Pb2+; (B) Ten replicated SWASV peakcurrents recorder for 60 µg/L Cd2+ and Pb2+ in 0.1 mol/L HAc-NaAc buffer containing 500 µg/L Bi3+ (Insert: Corresponding SWASV curvesof Fe3O4/MWCNTs/LSG/CS/GCE)[130].

A recent study utilized the zeolitic imidazolate framework ZIF-8 and mixed with chitosan (CS) solution which resulted a homogeneous dis-persion (ZIF-8-CS) which was then utilized to fabricate the glassy car-bon electrode. The stripping voltammetric analysis showed fairly a good response to detect the cations Hg2+, Cu2+, Pb2+ and Cd2+ simulta-neously (Cf. Figure 17)[132]. The regression lines were obtained and shown in equations (13-16):

Hg2+ (1.0~80 µmol/L): j/µA/cm2 = 18.13~13.00C (µmol/L); R2 = 0.9943 (13)

Cu2+ (1.0~100 µmol/L): j/µA/cm2 = 1.543~3.026C (µmol/L); R2 = 0.9961 (14)

Pb2+ (1.0~100 µmol/L): j/µA/cm2 = 23.83~7.426C (µmol/L); R2 = 0.9913 (15)

Cd2+ (1.0~100 µmol/L): j/µA/cm2 = 23.53~3.561C (µmol/L); R2 = 0.9701 (16)

As(III) detection was carried out using variety of materials modified glassy carbon electrode which includes silver nanoparticles built-in chi-tosan[133], Chitosan-Fe(OH)3[134], and gold nanoparticles[135]. It was reported that the redox behaviour of As takes place with 3 electron ex-change as given below (Equations 17, 18)[133]:

Figure 17. (A) Current density response of the ZIF-8-CS/GCE for the simultaneous detection of Hg2+, Cu2+, Pb2+ and Cd2+ over a concentration range from1.0 µmol/L to 100 µmol/L for each metal ion. From top to bottom, 1.0, 3.0, 5.0, 7.0, 10, 30, 60, 80, 100 µmol/L. (B) The linear plots of the stripping peak current density versus concentrations of Hg2+, Cu2+, Pb2+ and Cd2+ obtained from the data in Figure (A)[132].

Deposition: As3+ + 3e- → As0 (17)

Stripping: As0 → As3+ + 3e- (18)

Differential pulse anodic stripping voltammograms for As(III) are shown in Figure 18. There was a shoulder peak at –0.3 V was due to the chitosan-Fe(OH)3 complex and the As(III) showed a distinguished peak at 0.55 V. The limit of detection for As(III) was found to be 0.072 ppb[134]. Total arsenic was estimated using variety of materials precursor to natural clay bentonite in the modification of carbon paste electrode (CPE). The presence of several cation and anions were stud-ies in addition to real matrix analysis taking the river water. The LOD was obtained as 2.214, 1.502 and 1.408 µg/L respectively for the BCH, LCH and LCAH-modified CPEs, respectively (where BCH (HDTMA-loaded bentonite), LCH (HDTMA-loaded local clay) and LCAH (aluminium pillared-HDTMA-loaded local clay); HDTMA: hex-adecyl trimethyl ammonium bromide)[136]. Similarly, the silane [trichloro(octadecyl)silane (TCODS)] grafted bentonite modified carbon paste electrode was utilized for the low level detection of As(III). It was shown that single step oxidation/reduction reaction occurred for As(III) on the surface of electrode with the ΔE value 0.36 V at pH 2.0. A possible mechanism of sorption of As(III) followed by the re-dox reactions occurred on the electrode surface as shown in Figure 19.


공업화학, 제 31 권 제 3 호, 2020

Moreover, the anodic stripping voltammetric analyses showed the de-tection limit of As(III) 0.00360 ± 0.00002 µg/L[137].

A nanocomposite materials contained with the manganese oxide nanoflakes/multi-walled carbon nanotubes/chitosan utilized to modify the glassy carbon electrode. The detection of Cr(III) was conducted us-ing the modified electrode and the results are shown in Figure 20. On the other calibration line was found to be I (mA) = 0.0073 [Cr(III)] (µmol/L) + 1.5584 (mA) (R2 = 0.9906). It was further proposed that the a synergistic effect occurred for both MWCNTs and MnOx which enabled an efficient electrocatalytic activity towards Cr(III) oxidation at reduced over potential[138].

Several studies are conducted for the low level detection of lead(II) using the modified glassy carbon electrodes. The nanocomposite mate-rials viz., graphene, gold nanoparticles and chitosan[139], heparin modi-fied chitosan/graphene nanocomposite[140] and Co3O4 nanoparticles, reduced graphene oxide and chitosan[141] were employed for mod-ification of electrode. The lead was detected at the potential of -0.556 V and the DPASV response showed that a good linearity of the Pb(II)

Figure 20. CVs of Chit/MWCNTs/MnOx modified GC electrode in acetate buffer solution (pH 5) at scan rate 10 mV/s with increasing Cr(III) concentration from 40.0 to 360 µmol/dm3. Inset, plot of peak current vs. Cr(III) concentrations[138].

concentration and anodic current was obtained having the linear equa-tion: y = 0.02459X + 0.1294 (R2 = 0.9962)[141]. On the other hand,

Figure 18. Anodic stripping voltammetric response of CFC modified electrode for various concentration (2~100 ppb) of As(III) solution in 0.1 mol/L acetate buffer (Inset: calibration plot of anodic peak current as a function of concentration)[134].

Figure 19. (a) CV response of As(III) using the nanocomposite electrode as a function of pH, and (b) Scheme of As(III) sorption onto the electrode surface[137].



the mechanism of accumulation and anodic stripping of Pb(II) during SWAS measurements is demonstrated as equations (19 & 20) [140].

Accumulation: (hep/CS-rGO)es + (Pb2+)aq + 2e- →

(Pb0 … hep/CS-rGO)es (19)

Anodic stripping: (Pb0 … hep/CS-rGO)es →

(hep/CS-rGO)es + (Pb2+)aq + 2e- (20)

The detection of several heavy metals using the electrochemical methods are summarized in the Table 2. It includes the nanocomposite materials which were utilized in the modification of electrodes and

studied for the varied concentrations of pollutants. Further, the LOD calculated was included in the Table 3. These several studies indicated that the variety of hybrid materials were useful in the development of sensors for low level detection of heavy metal toxic ions in the pure form or even in the complex matrix as well. The attempts of simulta-neous detection further enhanced the applicability of electrochemical methods. The role of chitosan was numerous, providing the functional groups, binding the target materials or even possessed the conducting behaviour to ease the electron transfer reactions. However, there were several innumerable challenges ahead of utilizing the basic data for technology transfer.

Heavy metal ions Composite materials/electrode Concentration range studied LOD Ref.

Cu(II) Ch-AuNPs 1 × 10-3 to 1 × 10-8 mol/L 5 × 10-9 cmol/L [123]

Cu(II) Ch-Gr 1.0 × 10-9 to 1.5 × 10-8 mol/L 4.3 × 10-10 mol/L [124]

Cu(II) (NH2-G)Ch 0.4 to 40 µmol/L 0.064 µM/L [125]

Cd(II), Pb(II), Cu(II) RGO-Ch-PLL 0.05 to 10.0 µg/L Cd(II), 0.05 to 10.0 µg/L Pb(II),

0.05 to 10.0 µg/L Cu(II)0.01 µg/L-1 Cd(II), 0.02 µg/L Pb(II),

0.02 µg/L Cu(II) [126]

Cd(II), Pb(II) Ch-(Bi-CX) 0.2 to 2 ppb (1 to 10 pmol/L) 0.07 ppb (0.36 pmol/L) [127]

Cd(II), Pb(II), Hg(II), Zn(II),

Cu(II)F-MWCNT/Fe3O4

0.048 to 30.0 µmol/L Cd(II), 0.028 to 30.0 µmol/L Pb(II), 0.013 to 32.5 µmol/L Hg(II), 0.017 to 31.5

µmol/L Cu(II), 0.039 to 32.5 µmol/L Zn(II)

0.014 µmol/L Cd(II), 0.0084 µmol/L Pb(II), 0.0039 µmol/L Hg(II), 0.0053 µmol/L Cu(II),

0.012 µmol/L Zn(II)[128]

Cd(II), Pb(II), Hg(II) rGO-Fe3O4 0.2 to 3 µmol/L 0.008 Cd(II), 0.006 Pb(II),

0.004 Hg(II) µmol/L [129]

Cd(II), Pb(II) Fe3O4-MWCNTs-LSG-Ch 1~200 µg/L Cd(II), 1~200 µg/L Pb(II) 0.1 µg/L Cd(II), 0.07 µg/L Pb(II) [130]

Cd(II) Ch-ZnO 0.2 to 1.5 µmol/L 1.39 nmol/L [131]

Hg(II), Pb(II), Cd(II), Cu(II) ZIF-8-Ch 1.0 to 80 µmol/L Hg(II), 1.0 to 100 µmol/L Cu(II),

1.0 to 100 µmol/L Pb(II), 1.0 to 100 µmol/L Cd(II)0.029 µmol/L Hg(II), 0.11 µmol/L Cu(II), 0.062 µmol/L Pb(II), 0.14 µmol/L Cd(II) [132]

As(III) AgNPs-Ch 10 to 100 ppb 1.20 ppb [133]

As(III) Ch-Fe(OH)3 2 to 100 ppb 0.072 ppb [134]

As(III) AuNPs 0~10 µmol/L 0.014 ppb [135]

As(V) BCH, LCH and LCAH-CPEs 5.0 to 40.0 µg/L 2.214 µg/L (BCH), 1.502 µg/L (LCH) and 1.408 µg/L(LCAH) [136]

As(III) Trichloro(octadecyl)silane-bentonite 0.5 to 20.0 µg/L 0.00360 ± 0.00002 µg/L [137]

Cr(III) Ch-MWCNTs-MnOx 3 to 200 µmol/L 0.3 µmol/L [138]

Pb(II) Gr-AuNPs-Ch 0.5 to 100 µg/L 0.01 µg/L [139]

Pb(II) Hep-Ch-rGO 1.125 to 8.25 µg/L 0.03 µg/L [140]

Pb(II) Co3O4-rGO-Ch 1.0 to 200.0 nmol/L 0.35 nmol/L [141]

Pb(II), Cd(II) BiONPs-Ch 0.4 to 2.8 µmol/L Pb(II), 0.8 to 5.6 µmol/L Cd(II) 0.15 µmol/L Pb(II), 0.05 µmol/L Cd(II) [142]

As(III) Au-CRV 4 to 40 µmol/L 0.20 µmol/L [143]

As(III) AuNPs 0.001 ppm to 50 ppm 0.28 ppb [144]

As(III) PtNPs 1 µmol/L to 50 µmol/L 0.48 ± 0.02 µmol/L [145]

As(III) HCR and RecJf exonuclease 0.1 to 500 ppb 0.02 ppb [146]

As(III) NF-AuNPs 0.1 to 12.0 µg/L 0.047 µg/L [147]

Cd(II) Cd-IIP 0.5 to 40 µg/L 0.15 µg/L [148]

Cd(II) GR/IL-SPE 5.0 to 70.0 µg/L 3 µg/L [149]

Pb(II), Cd(II) Stencil-printed 1 to 200 µg/L Pb(II), 1 to 200 µg/L Cd(II) 0.3 µg/L Pb(II), 0.2 µg/L Cd(II) [150]

Cd(II) Bi/GCE 1 to 170 µg/L 0.3 µg/L [151]

Pb(II) CA-CdTe-QDs 0.22 to 4.51 ppm 30 ppb [152]

Table 3. The use of Nano Composites in the Determination of Various Heavy Metal Toxic Ions from Aqueous Solutions


공업화학, 제 31 권 제 3 호, 2020

3. Conclusion

Finally, the review as noted extensively emphasized the detection of several micro-pollutants including the pharmaceuticals, pesticides, her-bicides along with the heavy metal toxic ions using the nanocomposites precursors to the chitosan modified electrodes. It has shown that the biopolymer chitosan possesses useful properties including the bio-compatible, biodegradable, non-toxic, low cost contained with func-tional groups viz., -NH2 and -OH which enables it useful for wider ap-plications in the sensor development. It is also revealed that the bare chitosan does possess the drawbacks such as settling properties, pH sensitivity and physical/mechanical strength which restricts its use in the practical applications. However, the composite materials contained with inorganic nanomaterials enables greater applicability in the specif-ic sensor purposes. Furthermore, the presence of functional groups en-abled the composite materials to functionalize it, and to make it more selective and suitable for specific target pollutants. Moreover, the nano-composite materials enhance the sensitivity of electrode for pollutants, and the conducting behaviour of chitosan makes efficient electron transfer reactions on the surface of modified electrodes. This eventually allows to develop an efficient sensor for different organic of inorganic water pollutants.

The nanocomposite materials are useful even for simultaneous de-tection of several heavy metals and the studies are enabled for devel-oping a real matrix analysis. Various studies indicated that the labo-ratory scale results are encouraging however, the real implications needs several scientific and technological trials, which need to be con-ducted extensively for manifesting the real implications of the applica-tion in the miniaturized device development. The real technology de-velopment requires detailed trials in specific terms and the specific ma-trix also needs to be optimized. Additionally, the role of chitosan in the composite materials on the electrode surface need to be studied, since, it is possible that chitosan may take part in the electrochemical processes and may influence the detection of the target pollutant in the real matrix studies. The stability of bio-materials or bio nanocomposites employed for the working electrode preparation is having a greater concern which need to be studied for real implications.

Acknowledgement

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2019R1I1A3A01062424).

References

1. Y. Luo, W. Guo, H. H. Ngo, L. D. Nghiem, F. I. Hai, J. Zhang, S. Liang, and X. C. Wang, A review on the occurrence of micro-pollutants in the aquatic environment and their fate and removal during wastewater treatment, Sci. Total Environ., 473-474, 619-641 (2014).

2. N. Bolong, A. F. Ismail, M. R. Salim, and T. Matsuura, A review of the effects of emerging contaminants in wastewater and op-

tions for their removal, Desalination, 239, 229-246 (2009).3. A. Joss, E. Keller, A. Alder, A. Göbel, C.S. McArdell, T. Ternes,

and H. Siegrist, Removal of pharmaceuticals and fragrances in bi-ological wastewater treatment, Wat. Res., 39, 3139-3152 (2005).

4. J. Lienert, T. Buerki, and B. I. Escher, Reducing micropollutants with source control: Substance flow analysis of 212 pharmaceut-icals in faeces and urine, Wat. Sci. Technol., 56(5), 87-96 (2007).

5. K. A. Landry and T. H. Boyer, Diclofenac removal in urine using strong-base anion exchange polymer resins, Wat. Res., 47, 6432-6444 (2013).

6. J. Barek, J. Fischer, T. Navratil, K. Peckova, B. Yosypchuk, and J. Zima Nontraditional electrode materials in environmental anal-ysis of biologically active organic compounds, Electroanalysis, 19, 19-20 (2007).

7. D. M. Quinn, Acetylcholinesterase: Enzyme structure, reaction dynamics, and virtual transition states, Chem. Rev., 87, 955-979 (1987).

8. A. Roda, P. Rauch, E. Ferri, S. Girotti, S. Ghini, G. Carrea, and R. Bovara, Chemiluminescent flow sensor for the determination of Paraoxon and Aldicarb pesticides, Anal. Chim. Acta., 294, 35-42 (1994).

9. H. Xing, X. Wang, G. Sunb, X. Gao, S. Xu, and X. Wang, Effects of atrazine and chlorpyrifos on activity and transcription of glutathione S-transferase in common carp (Cyprinus carpio L.), Environ. Toxicol. Pharmacol., 33, 233-244 (2012).

10. M. Kucka, K. Pogrmic-Majkic, S. Fa, S. S. Stojilkovic, and R. Kovacevic, Atrazine acts as an endocrine disrupter by inhibiting cAMP-specific phosphodiesterase-4, Toxicol. Appl. Pharmacol., 265, 19-26 (2012).

11. K. Y. Lin and W. Chu, Simulation and quantification of the natu-ral decay of a typical endocrine disrupting chemical Atrazine in an aquatic system, J. Hazard. Mater., 192, 1260-1266 (2011).

12. L. F. Delgado, P. Charles, K. Glucina, and C. Morlay, The re-moval of endocrine disrupting compounds, pharmaceutically acti-vated compounds and cyanobacterial toxins during drinking water preparation using activated carbon - A review, Sci. Total Environ., 435-436, 509-525 (2012).

13. M. Valko, H. Morris, and M. T. D. Cronin, Metals, toxicity and oxidative stress, Curr. Med. Chem., 12, 1161-1208 (2005).

14. Zirlianngura, D. Tiwari, J.-H. Ha, and S.-M. Lee, Efficient use of porous hybrid materials in a selective detection of lead(II) from aqueous solutions: An electrochemical study, Metals, 7, 124 (2017).

15. B. K. Bansod, T. Kumar, R. Thakur, S. Rana, and I. Singh, A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms, Biosen. Bioelectron., 94, 443-455 (2017).

16. M. B. Gumpua, S. Sethuramanb, U. M. Krishnanb, and J. B. B. Rayappana, A review on detection of heavy metal ions in water - An electrochemical approach, Sens. Actuat. B, 213, 515-533 (2015).

17. D. Bagal-Kestwal, M. S. Karve, B. Kakade, and V. K. Pillai, Invertase inhibition based electrochemical sensor for the detection of heavy metal ions in aqueous system: Application of ultra-mi-croelectrode to enhance sucrose biosensor’s sensitivity, Biosens. Bioelectron., 24, 657-664 (2008).

18. M. Kumar and A. Puri, A review of permissible limits of drinking water, Ind. J. Occupat. Environ. Med., 16, 1 (2012).

19. T. Gong, J. Liu, X. Liu, J. Liu, J. Xiang, and Y. Wu, A sensitive and selective sensing platform based on CdTe QDs in the pres-



ence of L-cysteine for detection of silver, mercury and copper ions in water and various drinks, Food Chem., 213, 306-312 (2016).

20. R. Sitko, P. Janik, B. Zawisza, E. Talik, E. Margui, and I. Queralt, Green approach for ultratrace determination of divalent metal ions and arsenic species using total-reflection X-ray fluorescence spec-trometry and mercapto-modified graphene oxide nanosheets as a novel adsorbent, Anal. Chem., 87, 3535-3542 (2015).

21. V. N. Losev, O. V. Buyko, A. K. Trofimchuk, and O. N. Zuy, Silica sequentially modified with polyhexamethylene guanidine and arsenazo I for preconcentration and ICPOES determination of metals in natural waters. Micro Chem. J., 123, 84-89 (2015).

22. Y. Yi, G. Zhu, C. Liu, Y. Huang, Y. Zhang, H. Li, J. Zhao, and S. Yao, A label-free silicon quantum dots-based photoluminescence sensor for ultrasensitive detection of pesticides, Anal. Chem., 85, 11464-11470 (2013).

23. M. C. Rouget, Des substances amylacees dans les tissus des animaux, specialement des Articules (chitine). Comp. Rend., 48, 792-795 (1859).

24. D. Raafat, K. von Bargen, A. Haas, and H.-G. Sahl, Insights into the mode of action of chitosan as an antibacterial compound, Appl. Environ. Microbiol., 74, 3764-3773 (2008).

25. G. Crini and P.-M. Badot, Application of chitosan, a natural ami-nopolysaccharide, for dye removal from aqueous solutions by ad-sorption processes using batch studies: a review of recent liter-ature, Prog. Polym. Sci., 33, 399-447 (2008).

26. Lalchhingpuii, D. Tiwari, Lalhmunsiama, and S. M. Lee, Chitosan templated synthesis of mesoporous silica and its application in the treatment of aqueous solutions contaminated with cadmium(II) and lead(II), Chem. Eng. J., 328, 434-444 (2017).

27. S. K. Shukla, A. K. Mishra, O. A. Arotiba, and B. B. Mamba, Chitosan-based nanomaterials: A state-of-the-art review, Int. J. Biol. Macromol., 59, 46-58 (2013).

28. J. K. F. Suh and H. W. T. Matthew, Application of chito-san-based polysaccharide biomaterials in cartilage tissue engineer-ing: A review, Biomaterials, 21, 2589-2598 (2000).

29. P. Agrawal, G. J. Strijkers, and K. Nicolay, Chitosan-based sys-tems for molecular imaging, Adv. Drug Delivery Rev., 62, 42-58 (2010).

30. Lalhmunsiama, Lalchhingpuii, B. P. Nautiyal, D. Tiwari, S. I. Choi, S.-H. Kong, and S.-M. Lee, Silane grafted chitosan for the efficient remediation of aquatic environment contaminated with arsenic (V), J. Colloid Interf. Sci., 467, 203-212 (2016).

31. B. Batra and C. S. Pundir, An amperometric glutamate biosensor based onimmobilization of glutamate oxidase onto carboxylated multiwalled carbonnanotubes/gold nanoparticles/chitosan compo-site film modified Au electrode, Biosens. Bioelectron., 47, 496-501 (2013).

32. S. J. Ling, R. Yuan, Y. Q. Chai, and T. T. Zhang, Study on im-munosensor basedon gold nanoparticles/chitosan and MnO2 nano-particles composite mem-brane/Prussian blue modified gold elec-trode, Bioprocess Biosyst. Eng., 32, 407-414 (2009).

33. C. Lalhriatpuia, D. Tiwari, A. Tiwari, and S. M. Lee, Immobilized nanopillars-TiO2 in the efficient removal of micro-pollutants from aqueous solutions: Physico-chemical studies, Chem. Eng. J., 281, 782-792 (2015).

34. D. Vogna, R. Marotta, A. Napolitano, R. Andreozzi, and M. d’Ischia, Advanced oxidation of the pharmaceutical drug diclofe-nac with UV/H2O2 and ozone, Wat. Res., 38, 414-422 (2004).

35. Y. Zhang, S. Y. Geissen, and C. Gal, Carbamazepine and diclofe-nac: Removal in wastewater treatment plants and occurrence in water bodies, Chemosphere, 73, 1151-1161 (2008).

36. J. M. Herrmann, Heterogeneous photocatalysis: Fundamentals and to the removal of various types of aqueous pollutants, Catal. Today, 53, 115-129 (1999).

37. C. Martínez, L. M. Canle, M. I. Fernández, J. A. Santaballa, and J. Faria, Aqueous degradation of diclofenac by heterogeneous photocatalysis using nanostructured materials, Appl. Catal. B: Environ., 107, 110-118 (2011).

38. J. L. G. Oaks, M. Virani, M. Z. Watson, R. T. Meteyer, C. U. Rideout, B. A. Shivaprasad, H. L. Ahmed, S. Chaudhry, M. J. I. Arshad, M. Mahmood, S. Ali, and A. A. A. Khan, Diclofenac resi-dues as the cause of vulture population decline in Pakistan, Nature, 427, 630-633 (2004).

39. A. C. Mehinto, E. M. Hill, and C. R. Tyler, Uptake and bio-logical effects environmentally relevant concentrations of the non-steroidal anti-inflammatory pharmaceutical diclofenac in rainbow trout (Oncorhynchus mykiss), Environ. Sci. Technol., 44, 2176-2182 (2010).

40. M. Goodarzian, M. A. Khalilzade, F. Karimi, V. K. Gupta, M. Keyvanfard, H. Bagheri, and M. Fouladger, Square wave voltam-metric determination of diclofenac in liquid phase using a novel ionic liquid multiwall carbon nanotubes paste electrode, J. Mol. Liq., 197, 114-119 (2014).

41. M. Shalauddin, S. Akhter, S. Bagheri, M. S. A. Karim, N. A. Kadri, and W. J. Basirun, Immobilized copper ions on MWCNTS-chito-san thin film: Enhanced amperometric sensor for electrochemical determination of diclofenac sodium in aqueous solution, Int. J. Hydro. Ener., 42, 1995-9960 (2017).

42. A. R. Khaskheli, J. Fischer, J. Barek, V. Vyskočil, S. Muhammad, and I. Bhanger, Differential pulse voltammetric determination of paracetamol in tablet and urine samples at a micro-crystalline nat-ural graphite-polystyrene composite film modified electrode, Elec- trochim. Acta, 101, 238-242 (2013).

43. A. E. Robinson, Martindale: The extra pharmacopoeia 27th edi-tion, J. Pharm. Pharmacol., 29, 647-648 (1977).

44. H. Yin, K. Shang, X. Meng, and S. Ai, Voltammetric sensing of paracetamol, dopamine and 4-aminophenol at a glassy carbon electrode coated with gold nanoparticles and an organophillic lay-ered double hydroxide, Microchim. Acta, 175, 39-46 (2011).

45. S. J. R. Prabakar and S. S. Narayanan, Amperometric determi-nation of paracetomol by a surface modified cobalt hexacyano- ferrate graphite wax composite electrode, Talanta, 72, 1818-1827 (2007).

46. S. Akhter, W. J. Basirun, Y. Alias, M. R. Johan, S. Bagheri, M. Shalauddin, M. Ladan, and N. S. Anuar, Enhanced amperometric detection of paracetamol by immobilized cobalt ion on functional-ized MWCNTs - chitosan thin film, Anal. Biochem., 551, 29-36 (2018).

47. C. E. Gattullo, H. B¨ahrs, C. E. W. Steinberg, and E. Loffredo, Removal of bisphenol A by the freshwater green alga Monora- phidium braunii and the role of natural organic matter, Sci. Total Environ., 416, 501-506 (2012)

48. Thanhmingliana, S. M. Lee, and D. Tiwari, Use of hybrid materi-als in the decontamination of bisphenol A from aqueous solutions, RSC Adv., 4, 43921-43930 (2014).

49. A. V. Krishnan, P. Stathis, S. F. Permuth, L. Tokes, and D.


공업화학, 제 31 권 제 3 호, 2020

Feldman, Bisphenol-A: An estrogenic substance is released from polycarbonate flasks during autoclaving, Endocrinology, 132, 2279-2286 (1993).

50. S. Takahashi, X. J. Chi, Y. Yamaguchi, H. Suzuki, S. Sugaya, and K. Kita, Potential human reproductive and development effects of bisphenol A, Mutat. Res., 490, 199-207 (2001).

51. M. M. Munoz de Toro, C. M. Markey, P. R. Wadia, E. H. Luque, B. S. Rubin, C. Sonnenschein, and A. M. Soto, Perinatal exposure to bisphenol-A alters peripubertal mammary gland de-velopment in mice, Endocrinology, 146, 4138-4147 (2005).

52. K. L. Howdeshell, A. K. Hotchkiss, K. A. Thayer, J. G. Vandenbergh, and F. S. vom Saal, Exposure to bisphenol A ad-vances puberty, Nature, 401, 763-764 (1999).

53. A WWF European Toxics Programme Report, Bisphenol A: A Known Endocrine Disruptor, Registered Charity No. 20170 (2000).

54. S. Yuksel, N. Kabay, and M. Yuksel, Removal of bisphenol A (BPA) from water by various nanofiltration (NF) and reverse os-mosis (RO) membranes, J. Hazard. Mater., 263, 307-310 (2013).

55. J. G. Deng, Y. X. Peng, C. L. He, X. P. Long, P. Li, and A. S. C. Chan, Magnetic and conducting Fe3O4-polypyrrole nano-particles with core‐shell structure, Polym. Int., 52, 1182 (2003).

56. C. Yu, L. Gou, X. Zhou, N. Bao, and H. Gu, Chitosan-Fe3O4 nanocomposite based electrochemical sensors for the determi-nation of bisphenol A, Electrochim. Acta, 56, 9056-9063 (2011).

57. C. Zhou, S. Li, W. Zhu, H. Pang, and H. Ma, A sensor of a poly-oxometalate and Au-Pd alloy for simultaneously detection of dop-amine and ascorbic acid, Electrochim. Acta, 113, 454-463 (2013).

58. K.-J. Huang, Y.-J. Liua, Y.-M. Liua, and L.-L. Wang, Molybdenum disulfide nanoflower-chitosan-Au nanoparticles composites based electrochemical sensing platform for bisphenol A determination, J. Hazard. Mater., 276, 207-215 (2014).

59. S. Yang, R. Yang, G. Li, J. Li, and L. Qu, Voltammetric determi-nation of theophylline ata Nafion/multi-wall carbon nanotubes composite film-modified glassy carbon electrode, J. Chem. Sci., 122, 919 (2010).

60. R. B. Pernites, R. R. Ponnapati, and R. C. Advincula, Surface plasmon resonance (SPR) detection of theophylline via electro-polymerized molecularly imprinted poly-thiophenes, Macromole- cules, 43, 9724-9735 (2010).

61. S. M. Majd, H. Teymourian, A. Salimi, and R. Hallaj, Fabrication of electrochemical theophylline sensor based on manganese oxide nanoparticles/ionic liquid/chitosan nanocomposite modified glassy carbon electrode, Electrochim. Acta, 108, 707-716 (2013).

62. A. O. Maria, A. O. Roberto, and N. M. Adriana, Selective spec-trofluorimetric method for paracetamol determination through coumarinic compound formation, Talanta, 66, 229 (2005).

63. J. R. Vane, Inhibition of prostaglandin synthesis as a mechanism of action for aspirin-like drugs, Nat. New Biol., 231, 232-235 (1971).

64. S. Muraoka and T. Miura, Inactivation of creatine kinase during the interaction of mefenamic acid with horseradish peroxidase and hydrogen peroxide: Participation by the mefenamic acid radi-cal, Life Sci., 72, 1897-1907 (2003).

65. F. L. Martin and A. E. M. McLean, Comparison of paracetamol-induced hepatotoxicity in the rat in vivo with progression of cell injury in vitro in rat liver slices, Drug Chem. Toxicol., 21, 477-494 (1998).

66. L. Liu and J. Song, Voltammetric determination of mefenamic acid

at lanthanum hydroxide nanowires modified carbon paste electro-des, Anal. Biochem., 354, 22-27 (2006).

67. A. Babaei, M. Afrasiabi, and M. Babazadeh, A glassy carbon electrode modified with multiwalled carbon nanotube/chitosan composite as a new sensor for simultaneous determination of acetaminophen and mefenamic acid in pharmaceutical prepara-tions and biological samples, Electroanalysis, 22, 1743-1749 (2010).

68. L. A. Dunn, K. T. Andrews, J. S. McCarthy, J. M. Wright, T. S. Skinner-Adams, P. Upcroft, and J. A. Upcroft, The activity of protease inhibitors against Giardia duodenalis and metronida-zole-resistant Trichomonas vaginalis, Int. J. Antimicrob. Agents, 29, 98-102 (2007).

69. A. H. Davies, J. A. Mafadzean, and S. Squires, Treatment of Vincent’s stomatitis with metronidazole, Br. Med. J., 5391, 1149-1150 (1964).

70. N. Dione, S. Khelaifia, J. C. Lagier, and D. Raoult, The aerobic activity of metronidazole against anaerobic bacteria, Int. J. Antimicrob. Agents, 45, 537-540 (2015).

71. A. Katsandri, A. Avlamis, A. Pantazatou, G. L. Petrikkos, N. J. Legakis, and J. Papaparaskevas, In vitro activities of Tigecycline against recently isolated Gram-negative anaerobic bacteria in Greece, including metronidazole-resistant strains, Diagn. Microbiol. Infect. Dis., 55, 231-236 (2006).

72. S. Meenakshi, K. Pandian, L. S. Jayakumari, and S. Inbasekaran, Enhanced amperometric detection of metronidazole in drug for-mulations and urine samples based on chitosan protected tetra-sulfonated copper phthalocyanine thin- film modified glassy car-bon electrode, Mater. Sci. Eng. C, 59, 136-144 (2016).

73. F. G. Delolo, C. Rodrigues, M. Martins da Silva, L. R. Dinelli, F. N. Delling, J. Zukerman-Schpector, and A. A. Batista, A new electrochemical sensor containing a film of chitosan-supported ruthenium: Detection and quantification of sildenafil citrate and acetaminophen, J. Braz. Chem. Soc., 25, 550-559 (2014).

74. J. Sabate, J. Labanda, and J. Llorens Nanofiltration of biogenic amines in acidic conditions: Influence of operation variables and modeling. J. Membr. Sci., 310, 594-601 (2008).

75. F. Coloretti, C. Chiavari, E. Armaforte, S. Carri, and G. Castagnetti, Combined use of starter cultures and preservatives to control pro-duction of biogenic amines and improve sensorial profile in low-acid salami, J. Agri. Food Chem., 56(23), 11238-11244 (2008).

76. N. García-Villar, S. Hernández-Cassou, and J. Saurina, Characte- rization of wines through the biogenic amine contents using chro-matographic techniques and chemometric data analysis, J. Agri. Food Chem., 55(18), 7453-7461 (2007).

77. C. O. Mohan, C. N. Ravishankar, T. K. S. Gopal, K. A. Kumar, and K. V. Lalitha, Biogenic amines formation in seer fish (Scom- beromorus commerson) steaks packed with O2 scavenger during chilled storage, Food Res. Int., 42(3), 411-416 (2009).

78. N. F. Atta and A. M. Abdel-Mageed, Smart electrochemical sen-sor for some neurotransmitters using imprinted sol-gel films, Talanta, 80(2), 511-518 (2009).

79. B. J. McCabe-Sellers, C. G. Staggs, and M. L. Bogle, Tyramine in foods and monoamine oxidase inhibitor drugs: A crossroad where medicine, nutrition, pharmacy, and food industry converge, J. Food Composition Anal., 19(1), 58-65 (2006).

80. F. Galgano, F. Favati, M. Bonadio, V. Lorusso, and P. Romano, Role of biogenic amines as index of freshness in beef meat



packed with different biopolymeric materials, Food Res. Int., 42(8), 1147-1152 (2009).

81. D. Du, X. Huang, J. Cai, and A. Zhang, Amperometric detection of triazophos pesticide using acetylcholinesterase biosensor based on multiwall carbon nanotube-chitosan matrix, Sens. Actuat. B: Chem., 127, 531-535 (2007).

82. R. A. Harrington, R. C. Becker, and M. Ezekowitz, Antithrombotic therapy for coronary artery disease: The seventh ACCP confer-ence on antithrombotic and thrombolytic therapy, Chest, 126, 513-548 (2004).

83. D. N. Salem, P. T. O’Gara, C. Madias, and S. G. Pauker, Valvular and structural heart disease: American college of chest physicians evidence-based clinical practice guidelines (8th edition), Chest, 133, 593-629 (2008).

84. D. E. Singer, G. W. Albers, J. E. Dalen, A. S. Go, J. L. Halperin, and W. J. Manning, Antithrombotic therapy in atrial fibrillation: The seventh ACCP conference on antithrombotic and thrombo-lytic therapy, Chest, 126, 429-456 (2004).

85. S. Sun, M. Wang, L. Su, J. Li, H. Li, and D. Gu, Study on war-farin plasma concentration and its correlation with international normalized ratio, J. Pharm. Biomed. Anal., 42, 218-222 (2006).

86. M. B. Gholivand and L. Mohammadi-Behzad, An electrochemical sensor for warfarin determination based on covalent immobiliza-tion of quantum dots onto carboxylated multiwalled carbon nano-tubes and chitosan composite film modified electrode, Mater. Sci. Eng. C, 57, 77-87 (2015).

87. R. Jain and Vikas, Voltammetric determination of cefpirome at multiwalled carbon nanotube modified glassy carbon sensor based electrode in bulk form and pharmaceutical formulation, Coll.. Surf. B: Biointerfaces, 87, 423-426 (2011).

88. G. Wilson, Text Book of Organic Medicinal and Pharmaceutical Chemistry, 11th edition, Lippincott, London (2004).

89. A. Chaudhury, In vitro activity of cefpirome: A new fourth gen-eration cephalosporin, Ind. J. Med. Microbiol., 21, 52-55 (2003).

90. R. Solna, S. Sapelnikova, P. Skladal, M. Winther-Nielsen, C. Carlsson, J. Emneus, and T. Ruzgas, Multienzyme electrochemical array sensor for determination of phenols and pesticides, Talanta, 65, 349-357 (2005).

91. J. Massoulie, L. Pezzementi, S. Bon, E. Krejci, and F. M. Vallette, Molecular and cellular biology of cholinesterases, Prog. Neurobiol., 41, 31-91 (1993).

92. D. Du, X. Huang, J. Cai, and A. Zhang, Amperometric detection of triazophos pesticide using acetylcholinesterase biosensor based on multiwall carbon nanotube-chitosan matrix, Sens. Actuat. B: Chem., 127, 531-535 (2007).

93. A. C. Ion, I. Ion, A. Culetu, D. Gherase, C. A. Moldovan, R. Iosub, and A. Dinescu, Acetylcholinesterase voltammetric bio-sensors based on carbon nanostructurechitosan composite material for organophosphate pesticides, Mater. Sci. Eng. C, 30, 817-821 (2010).

94. J. J. Yang, C. Yang, H. Jiang, and C. L. Qiao, Overexpression of methyl parathion hydrolase and its application in detoxification of organophosphates, Biodegradation, 19, 831-839 (2008).

95. W. Yazhen, Q. Hongxin, H. Siqian, and X. Junhui, A novel methyl parathion electrochemical sensor based on acetylene black-chitosan composite film modified electrode, Sens. Actuat. B: Chem., 147, 587-592 (2010).

96. D. J. Lee, S. A. Senseman, A. S. Sciumbato, S. C. Jung, and L.

J Krutz The effect of titanium dioxide alumina beads on the pho-tocatalytic degradation of picloram in water, J. Agric. Food Chem., 51, 2659-2664 (2003).

97. L. Tang, G.-M. Zeng, G.-L. Shen, Y.-P. Li, Y. Zhang, and D.-L. Huang, Rapid detection of picloram in agricultural field samples using a disposable immunomembrane-based electrochemical sen-sor, Environ. Sci. Technol., 42, 1207-1212 (2008).

98. Q. Xu, X. Li, Y. Zhou, H. Wei, X. Y. Hu, Y. Wang, and Z. Yang, An enzymatic amplified system for the detection of 2,4-di-chlorophenol based on graphene membrane modified electrode, Anal. Methods, 4, 3429-3435 (2012).

99. Rawajfih and N. Nsour, Characteristics of phenol and chlorinated phenolssorption onto surfactant-modified bentonite, J. Colloid Interf. Sci., 298, 39-49 (2006).

100. L. Yu, X. Yue, R. Yang, S. Jing, and L. Qu, A sensitive and low toxicity electrochemical sensor for 2,4-dichlorophenol based on the nanocomposite of carbon dots, hexadecyltrimethyl ammonium bromide and chitosan, Sens. Actuat. B: Chem., 224, 241-247 (2016).

101. N. Kaura, A. Bhartia, S. Batraa, S. Ranaa, S. Ranab, A. Bhallab, and N. Prabhakara, An electrochemical aptasensor based on gra-phene doped chitosan nanocomposites for determination of Och- ratoxin A, Microchem. J., 144, 102-109 (2019).

102. E. Pashai, G. N. Darzi, M. Jahanshahi, F. Yazdian, and M. Rahimnejad, An electrochemical nitric oxide biosensor based on immobilizedcytochrome c on a chitosan-gold nanocomposite modi-fied goldelectrode, Int. J. Biol Macromol., 108, 250-258 (2018).

103. N. Prabhakar, H. Thakur, A. Bharti, and N. Kaur, Chitosan-iron oxide nanocomposite based electrochemical aptasensor for deter-mination of malathion, Anal. Chim. Acta., 939, 108-116 (2016).

104. A. Camila, D. Lima, P. S. da Silva, and A. Spinelli, Chitosan-sta-bilized silver nanoparticles for voltammetric detection of nitro-compounds, Sens. Actuat. B: Chem., 196, 39-45 (2014).

105. C. Sun, Y. Zou, D. Wang, Z. Geng, W. Xu, F. Liu, and J. Cao, Construction of chitosan-Zn-based electrochemical biosensing platform for rapid and accurate assay of actin, Sensors, 18, 1865 (2018).

106. H. V. Tran, C. D. Huynh, H. V. Tran, and B. Piro, Cyclic vol-tammetry, square wave voltammetry, electrochemical impedance spectroscopy and colorimetric method for hydrogen peroxide de-tection based on chitosan/silver nanocomposite, Arab. J. Chem., 11, 453-459 (2018).

107. J. Tashkhourian, S. F. Nami-Ana, and M. Shamsipur, Designing a modified electrode based on graphene quantum dotchitosan ap-plication to electrochemical detection of epinephrine, J. Mol. Liq., 266, 548-556 (2018).

108. S. Rajabzadeh, G. H. Rounaghi, M. H. Arbab-Zavar, and N. Ashraf, Development of a dimethyl disulfide electrochemical sensor based onelectrodeposited reduced graphene oxide-chitosan modified glassycarbon electrode, Electrochim. Acta, 135, 543-549 (2014).

109. B. Liu, H. T. Lian, J. F. Yin, and X. Y. Sun, Dopamine molecu-larly imprinted electrochemical sensor based on graphene-chitosan composite, Electrochim. Acta, 75, 108-114 (2012).

110. W.-R. Zhao, T.-F. Kang, L.-P. Lu, and S.-Y. Cheng Electroche- mical magnetic imprinted sensor based on MWCNTs@CS/CTABr surfactant composites for sensitive sensing of diethylstilbestrol, J. Electroanal. Chem., 818, 181-190 (2018).

111. Z. Wu, F. Guo, L. Huanga, and L. Wanga, Electrochemical non-enzymatic sensor based on cetyltrimethylammonium bromide and


공업화학, 제 31 권 제 3 호, 2020

chitosan functionalized carbon nanotube modified glassy carbon electrode for the determination of hydroxymethanesulfinate in the presence of sulfite in foods, Food Chem., 259, 213-218 (2018).

112. M. Baccarina, F. A. Santosb, F. C. Vicentinic, V. Zucolottob, B. C. Janegitzd, and O. Fatibello-Filhoa, Electrochemical sensor based on reduced graphene oxide/carbon black/chitosan composite for the simultaneous determination of dopamine and paracetamol con-centrations in urine samples, J. Electroanal. Chem., 799, 436-443 (2017).

113. W. Lian, S. Liu, J. Yu, X. Xing, J. Li, M. Cui, and J. Huang, Electrochemical sensor based on gold nanoparticles fabricated molecularly imprinted polymer film at chitosan-platinum nano-particles/graphene-gold nanoparticles double nanocomposites modi-fied electrode for detection of erythromycin, Biosens. Bioelectron., 38, 163-169 (2012).

114. G. Yang, F. Zhao, and B. Zeng, Facile fabrication of a novel ani-sotropic gold nanoparticle-chitosan-ionic liquid/graphene modified electrode for the determination of theophylline and caffeine, Talanta, 127, 116-122 (2014).

115. L. Magerusan, F. Pogacean, M. Coros, C. Socaci, S. Pruneanu, C. Leostean, and I. O. Pana, Green methodology for the prepara-tion of chitosan/graphene nanomaterial through electrochemical exfoliation and its applicability in Sunset Yellow detection, Elec- trochim. Acta, 283, 578-589 (2018).

116. Y. Hu, J. Li, Z. Zhang, H. Zhang, L. Luo, and S. Yao, Imprinted sol-gel electrochemical sensor for the determination of benzylpe-nicillin based on Fe3O4@SiO2/multi-walled carbon nanotubes-chi- tosans nanocomposite film modified carbon electrode, Anal. Chimica Acta., 698, 61-68 (2011).

117. J. Xia, X. Cao, Z. Wang, M. Yang, F. Zhang, B. Lu, F. Li, L. Xia, Y. Li, and Y. Xia, Molecularly imprinted electrochemical bi-osensor based onchitosan/ionic liquid-graphene composites modi-fied electrodefor determination of bovine serum albumin, Sens. Actuat. B: Chem., 225, 305-311(2016).

118. D. Yuan, S. Chen, F. Hu, C. Wang, and R. Yuan, Non-enzymatic amperometric sensor of catechol and hydroquinone using Pt-Au-or- ganosilica@chitosan composites modified electrode, Sens. Actuat. B: Chem., 168, 193-199 (2012).

119. F. mollarasouli, K. Asadpour-Zeynali, S. Campuzano, P. Yáñez-Sedeño, and J. M. Pingarrón, Non-enzymatic hydrogen peroxide sensor based on graphene quantum dots-chitosan/methyl-ene blue hybrid nanostructures, Electrochim. Acta, 246, 303-314 (2017).

120. D. Rao, Q. Sheng, and J. Zheng, Preparation of flower-like Pt nanoparticles decorated chitosan-grafted graphene oxide and its electrocatalysis of hydrazine, Sens. Actuat. B: Chem., 236, 192-200 (2016).

121. C. Xiang, R. Li, B. Adhikari, Z. She, Y. Li, and H.-B. Kraatz, Sensitive electrochemical detection of Salmonella with chito-san-gold nanoparticles composite film, Talanta, 140, 122-127 (2015).

122. Q. Zhang, Y. Qing, X. Huang, C. Li, and J. Xue, Synthesis of single-walled carbon nanotubes-chitosan nanocomposites for the development of an electrochemical biosensor for serum leptin de-tection, Mater. Lett., 211, 348-351(2018).

123. H. Ciftci, U. Tamer, A. U. Metin, E. Alver, and N. Kizir, Elec- trochemical copper (II) sensor based on chitosan covered gold Nanoparticles, J Appl. Electrochem., 44, 563-572 (2014).

124. Y. Si, J. Liu, A. Wang, S. Niu, and J. Wan, A chitosan-graphene electrochemical sensor for the determination of copper(II), Instru- ment. Sci. Technol., 43(3), 357-368 (2015).

125. Z. Mo, H. Liu, R. Hu, H. Gou, Z. Li, and R. Guo, Amino-func-tionalized graphene/chitosan composite as an enhanced sensing platform for highly selective detection of Cu(II), Ionics, 24(5), 1505-1513 (2017).

126. Z. Guo, D.-D. Li, X.-K. Luo, Y.-H. Li, Q.-N. Zhao, M.-M. Li, Y.-T. Zhao, T.-S. Sun, and C. Ma, Simultaneous determination of trace Cd(II), Pb(II) and Cu(II) by differential pulse anodic strip-ping voltammetry using a reduced graphene oxide-chitosan/ poly-L-lysine nanocomposite modified glassy carbon electrode, J. Colloid Interf. Sci., 490, 11-22 (2017).

127. C. I. Fort, L. C. Cotet, A. Vulpoi, G. L. Turdean, V. Danciu, L. Baia, and I.C. Popescu, Bismuth doped carbon xerogel nano-composite incorporated in chitosan matrix for ultrasensitive vol-tammetric detection of Pb(II)and Cd(II), Sens. Actuat. B: Chem., 220, 712-719 (2015).

128. W. Wu, M. Jia, Z. Wang, W. Zhang, Q. Zhang, G. Liu, Z. Zhang, and P. Li, Simultaneous voltammetric determination of cadmium (II), lead(II), mercury(II), zinc(II), and copper(II) using a glassy carbon electrode modified with magnetite (Fe3O4) nanoparticles and fluorinated multiwalled carbon nanotubes, Microchim. Acta., 186, 97 (2019).

129. S. Xiong, B. Yang, D. Cai, G. Qiu, and Z. Wu, Individual and simultaneous stripping voltammetric and mutual interference anal-ysis of Cd(II), Pb(II)and Hg(II) with reduced graphene oxide-Fe3O4 nanocomposites, Electrochim. Acta, 185, 52-61 (2015).

130. Z. Xu, X. Fan, Q. Ma, B. Tang, Z. Lu, J. Zhang, G. Mo, J. Ye, and J. Ye, A sensitive electrochemical sensor for simultaneous voltammetric sensing of cadmium and lead based on Fe3O4/multiwalled carbon nanotube/laser scribed graphene composites func-tionalized with chitosan modified electrode, Mater. Chem. Phys., 238, 121877 (2019).

131. G. Padmalaya, B. S. Sreeja, P. S. Kumar, and M. Arivanandhan, Chitosan zinc anchored oxide nanocompositeas modified electro-chemical sensor for the detection of Cd(II) ions, Desal. Wat. Treat., 97, 295-303 (2017).

132. Y. Chu, F. Gao, F. Gao, and Q. Wang, Enhanced stripping vol-tammetric response of Hg(II), Cu(II), Pb(II) and Cd(II) by ZIF-8 and its electrochemical analytical application, J. Electroanal. Chem., 835, 293-300 (2019).

133. S. Prakash, T. Chakrabarty, A. K. Singh, and V. K. Shahi, Silver nanoparticles built-in chitosan modified glassy carbon electrode for anodic stripping analysis of As(III) and its removal from wa-ter, Electrochim. Acta, 72, 157-164 (2012).

134. S. Saha and P.Sarkar, Differential pulse anodic stripping voltam-metry for detection of As (III) by Chitosan-Fe(OH)3 modified glassy carbon electrode: A new approach towards speciation of arsenic, Talanta, 158, 235-245 (2016).

135. X. Dai, O. Nekrassova, M. E. Hyde, and R. G. Compton, Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes, Anal. Chem., 76, 5924-5929 (2004).

136. D. Tiwari, Zirlianngura, and S. M. Lee, Fabrication of efficient and selective total arsenic sensor using the hybrid materials modi-fied carbon paste electrodes, J. Electroanal. Chem., 784, 109-114 (2017).

137. J. Lalmalsawmi, Zirlianngura, D. Tiwari, and S.-M. Lee, Low cost,



highly sensitive and selective electrochemical detection of arsenic (III) using silane grafted based nanocomposite, Environ. Eng. Res., 25(4), 579-587 (2020).

138. A. Salimi, B. Pourbahram, S. Mansouri-Majd, and R. Hallaj, Manganese oxide nanoflakes/multi-walled carbon nanotubes/chitosan nanocomposite modified glassy carbon electrode as a novel electrochemical sensor for chromium (III) detection, Electrochim. Acta, 156, 207-215 (2015).

139. Z. Lu, S. Yang, Q. Yang, S. Luo, C. Liu, and Y. Tang, A glassy carbon electrode modified with graphene, gold nanoparticles and chitosan for ultrasensitive determination of lead(II), Microchim. Acta, 180, 555-562 (2013).

140. T. Priya, N. Dhanalakshmi, and N. Thinakaran, Elctrochemical behaviour of Pb(II) on a heparin modified chitosan/graphene nanocomposite film coated glassy carbon electrode and its sensi-tive detection, Int. J. Biol. Macromol., 104, 672-680 (2017).

141. Y. Zuo, J. Xu, F. Jiang, X. Duan, L. Lu, H. Xing, T. Yang, Y. Zhang, G. Ye, and Y. Yu, Voltammetric sensing of Pb(II) using a glassy carbon electrode modified with composites consisting of Co3O4 nanoparticles, reduced graphene oxide and chitosan, J. Electroanal. Chem., 801, 146-152 (2017).

142. C. Hao, Y. Shen, J. Shen, K. Xu, X. Wang, Y. Zhao, and C. Ge, A glassy carbon electrode modified with bismuth oxide nanoparticles and chitosan as a sensor for Pb(II) and Cd(II), Microchim. Acta, 183, 1823-1830 (2016).

143. M. Rajkumar, S. Thiagarajan, and S.-M. Chen, Electrochemical detection of arsenic in various water samples, Int. J. Electrochem. Sci., 6, 3164-3177 (2011).

144. A. O. Idris, J. P. Mafa, N. Mabuba, and O. A. Arotiba, Nanogold modified glassy carbon electrode for the electrochemical detection of arsenic in water, Russ. J. Electrochem., 53(2),170-177 (2017).

145. X. Dai and R. G. Compton, Detection of As(III) via oxidation to As(V) using platinum nanoparticle modified glassy carbon elec-trodes: Arsenic detection without interference from copper, Analyst, 131, 516-521 (2006).

146. H. Gu, Y. Yang, F. Chen, T. Liu, J. Jin, Y. Pan, and P. Miao, Electrochemical detection of arsenic contamination based on hy-bridization chain reaction and RecJf exonuclease-mediated ampli-fication, Chem. Eng. J., 353, 305-310 (2018).

147. J.-F. Huang and H.-H. Chen, Gold-nanoparticle-embedded nafion composite modified on glassy carbon electrode for highly se-lective detection of arsenic(III), Talanta, 116, 852-859 (2013).

148. M. Ghanei-Motlagh and M. A. Tahera, Novel imprinted poly-

meric nanoparticles prepared by sol- gel technique for electro-chemical detection of toxic cadmium(II) ions, Chem. Eng. J., 327, 135-141 (2017).

149. G. Zhao, Y. Si, H. Wang, and G. Liu, A portable electrochemical detection system based on graphene/ionic liquid modified screen-printed electrode for the detection of cadmium in soil by square wave anodic stripping voltammetry, Int. J. Electrochem. Sci., 11, 54-64 (2016).

150. D. Martín-Yerga, I. Alvarez-Martos, M. C. Blanco-Lopez, C. S. Henry, and M. T. Fernandez-Abedul, Point-of-need simultaneous electrochemical detection of lead and cadmium using low-cost stencil-printed transparency electrodes, Anal. Chimica Acta., 981, 24-33 (2017).

151. G. Zhao, H. Wang, G. Liu, and Z. Wang, Box-Behnken response surface design for the optimization of electrochemical detection of cadmium by square wave anodic stripping voltammetry on bis-muth film/glassy carbon electrode, Sens. Actuat. B: Chem., 235, 67-73 (2016).

152. X. Wang and X. Guo, Ultrasensitive Pb2+ detection based on flu-orescence resonance energy transfer (FRET) between quantum dots and gold nanoparticles, Analyst, 134, 1348-1354 (2009).

AuthorsSarikokba; M.Sc., Research Scholar, Department of Chemistry, School

of Physical Sciences, Mizoram University, Aizawl-796004, India; [email protected]

Diwakar Tiwari; Ph.D., Professor, Department of Chemistry, School of Physical Sciences, Mizoram University, Aizawl-796004, India; [email protected]

Shailesh Kumar Prasad; Ph.D., Associate Professor, Department of Chemistry, National Institute of Technology, Jamshedpur-831014, India; [email protected]

Dong Jin Kim; Ph.D., Professor, Department of Environmental Science& Biotechnology, Hallym University, Chuncheon 24252, Republic of Korea; [email protected]

Suk Soon Choi; Ph.D., Professor, Department of Biological and Environmental Engineering, Semyung University, Jecheon 27136, Republic of Korea; [email protected]

Seung-Mok Lee; Ph.D., Professor, Department of Health and Environment, Catholic Kwandong University, Gangneung 25601, Republic of Korea; [email protected]

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