\r\n\tIt is a relatively simple process and a standard tool in any industry. Because of the versatility of the titration techniques, nearly all aspects of society depend on various forms of titration to analyze key chemical compounds.
\r\n\tThe aims of this book is to provide the reader with an up-to-date coverage of experimental and theoretical aspects related to titration techniques used in environmental, pharmaceutical, biomedical and food sciences.
Food safety has become a global public health concern affecting both mostly developing countries and developed countries. In addition, foodborne diseases negatively impact the economy, trade, and industries of affected countries. For example, melamine has been detected in infant formula (milk powder) in China, leading to more than 290,000 infants suffering from severe health problems such as urinary tract stones [1]. Early and accurate detection of food safety is therefore very important for preventing, controlling, and mitigating the impact of potential outbreaks. Many analytic methods, including chromatography methods such as gas chromatography (GC) [2], high performance liquid chromatography (HPLC) [3], gas chromatography-mass spectrometer (GC-MS) [4], and liquid chromatography-mass spectrometer (LC-MS) [5], and immunological detection, such as enzyme linked immunosorbent assay (ELISA) [6] and lateral flow immunoassay [7], have been employed for food safety detection. Although those traditional methods are relatively sensitive and specific, they are expensive, laborious, and time-consuming and require well-trained personnel [8, 9], which make them incompatible for developing countries and areas are lacking equipped facilities and specialists. It is therefore urgent to develop rapid, accurate, sensitive, and online technologies for food safety detection.
\nModern electrochemistry provides powerful analytical techniques for sensors, with the advantages of instrumental simplicity, low cost, and miniaturization, work on-site, and the ability to measure pollutants in complex matrices with minimal sample preparation [10]. Electrochemical sensors and methods are developed as suitable tools for different applications, including bioprocess control, agriculture, and military, and, in particular, for food quality control. Voltammetric techniques, such as cyclic voltammetry (CV) [10], linear sweep voltammetry (LSV) [11], differential pulse voltammetry (DPV) [12], and square wave voltammetry (SWV) [13], have been widely used in food analysis. Among these voltammetric techniques, DPV and SWV are commonly used, as low detection limits and multiplex analysis can be achieved with the two methods. These two techniques involve potential waveforms and their respective current response are shown in Figure 1A. The waveform of DPV consists of pulses of constant amplitude superimposed on a staircase waveform. This method has the highest sensitivity in electrochemistry because the charging current can be ignored against faradaic current, and their ratio is obtained as large. Moreover, SWV consists of symmetrical square-wave pulses superimposed on a staircase waveform. During each square wave cycle, the current is sampled twice, just before the end of each forward and each backward pulse followed by subtraction of the currents. The peak current heights (values) obtained by the two methods are directly proportional to the concentrations of the analyte. Amperometry is another important electrochemical analysis method in which the potential of the working electrode is constant and the resulting current from faradic processes occurring at the electrode is monitored with a function of time. In this method, the current is integrated over relatively longer time intervals, so it gives an improved signal to noise ratio [14].
\nPotential waveforms and their respective current response for (A) differential pulse voltammetry (DPV) and (B) square wave voltammetry (SWV).
Electrochemical sensors can be used as food safety monitoring tools in the assessment of biological/ecological quality or for the chemical monitoring of both inorganic and organic pollutants. In this chapter we provide an overview of electrochemical sensor systems for food safety applications, and in the following sections, we describe the various electrochemical sensors that have been developed for food safety detection.
\nHeavy metals (HMs) are currently defined as metals with a specific gravity greater than 5 g cm−3, which are considered as a serious source for polluting the biosphere throughout the world and causing many healthy and physiological diseases due to their prolonged half-life, non-biodegradability, and potential of accumulation in different parts of the human body [15, 16]. Heavy metals like cadmium, lead, arsenic, chromium, and mercury are considered as hazardous elements even at low concentrations [17, 18, 19]. Therefore, sensitive and selective determination of toxic heavy metals with cost-effective and convenient procedures is of paramount importance.
\nDue to the speed of detection, low cost, high sensitivity, and easy adaptability for in situ measurement [20], electrochemical sensors have attracted great interest in the detection of heavy metal ions for food safety.
\nFor many years, anodic stripping voltammetry (ASV) at the mercury and its modified electrode was extensively applied to the determination of trace metal ions for the extensive cathodic potential range [21, 22]. However, the disposal of the mercury-containing device and the incorrect handling can lead to the formation of mercury vapors that are toxic and represent a significant health and environmental hazard [23]. Therefore, various mercury-free electrodes have been developed in the past few decades. For example, a nanostructured bismuth film electrode (nsBiFE) has been prepared for ASV detection of multiple heavy metals, in which the detection limits of 0.4 and 0.1 μg L−1 are obtained for Cd2+ and Pb2, respectively [24]. Similar to bismuth, antimony nanoparticles have also been proven to be highly sensitive and reliable for tracing analysis of heavy metals [25]. To take into real application, more and more electrochemical sensors based on screen-printed carbon electrode (SPCE) have been fabricated for trace heavy metal detection in food safety as it is inexpensive, portable, and easy for mass production [26, 27].
\nAddition of inedible substances and abuse of food additives are the prominent problems affecting food safety [28]. Typical illegal additives include melamine, clenbuterol, and Sudan I. These illegal actions may pose great threat to human health. For the detection of these chemicals, various nanomaterial-based biosensors have been developed. Various approaches aiming at analyzing specific chemical contaminants and illegal additives have been developed [29, 30, 31]. Li et al. developed a gold nanoparticles (AuNPs)-decorated reduced graphene oxide (RGO) modified electrode for detection of Sudan I in food samples including chili powder and ketchup sauce, demonstrating satisfactory sensitivity, selectivity, and recovery [11]. A sensitive and selective electrochemical sensor based on MIL-53@XC-72 nanohybrid modified glassy carbon electrode (GCE) was also fabricated to determine melamine with a linear range from 0.04 to 10 μM and detection limit of 0.005 μM (S/N = 3) [32]. In addition, the sensor displayed excellent reproducibility, high stability, selectivity, and good recoveries for the determination of melamine in liquid milk. The synergistic effect of nitrogen-doped graphene (NGR) and nitrogen-doped carbon nanotubes (NCNTs) has also been investigated and applied to prepare an electrochemical sensor for simultaneous and sensitive determination of caffeine and vanillin [33]. Electrochemical sensors have also been developed for many other food additives, such as sunset yellow [34, 35].
\nPesticides, including fungicides, herbicides, and insecticides, are widely used in most food production to control pests that would otherwise destroy or reduce food production [36]. In the area of agriculture, the usage of insecticides, herbicides, molluscicides, and fungicides has an increasing importance. However, many pesticides are toxic and can cause many health problems when consumed by animals and humans, such as bone marrow disorders, carcinogenicity, infertility, cytogenic effects, neurological diseases, and immunological and respiratory problems. Hence, pesticide residue detection is very important for food safety [37].
\nTo date, many methods have been applied to determine pesticide residues in food samples. Electrochemical methods provide the elucidation of processes and mechanisms of redox reaction of pesticides and their residues [38]. They are sensitive, reliable, and fast. They can be easily miniaturized and integrated with other analytical methods [39, 40]. A magneto-actuated enzyme-free electrochemical sensor based on magnetic molecularly imprinted polymer was developed, and it showed outstanding analytical performance for the detection of methyl parathion in fish, with a limit of detection of as low as 1.22 × 10−6 mg L−1 and recovery values ranging from 89.4 to 94.7% [41]. Da Silva and coworkers [42] developed an acetylcholinesterase (AChE) biosensor for rapid detection of carbaryl in tomato samples by using electrode modified with reduced graphene oxide (rGO). The electrochemical response increased as the concentration of acetylthiocholine chloride increased, while the response decreased in the presence of AChE inhibitor OPs with a linear response to the inhibition of the thiocholine oxidation process for carbaryl concentrations from 10 to 50 nmol L−1 and 0.2 to 1.0 mol L−1. Compared with AChE, organophosphorus hydrolase (OPH) enzymes catalyze the hydrolysis of organophosphorus pesticides (OPs) with a high turnover rate, can potentially be reused, and are, therefore, suitable for continuous monitoring of OPs [43, 44].
\nVeterinary drugs mainly include antimicrobial drugs, antiparasitic drugs, and growth promoters, which are extensively used for treatment and prevention of diseases in animals, promotion of animal growth, and feed efficiency [45]. But the possible presence of veterinary drugs in animal-derived foods is one of the key issues for food safety, which arouses great public concern. So it is very important to develop quick and accurate methods to detect veterinary drug residues in animal-derived food, and their quantity must be less than the maximum residue limits (MRL) defined in many countries on the basis of food safety [46].
\nElectrochemical sensors have drawn considerable attention in many fields such as food safety, disease diagnosis, and environmental monitoring [47, 48]. Lin et al. [49] developed a hybrid CNT-modified electrode for simultaneous determination of toxic ractopamine and salbutamol in pork samples. Conzuelo et al. developed a novel strategy to construct disposable amperometric affinity biosensors by recombinant bacterial penicillin-binding protein (PBP) tagged by an N-terminal hexahistidine tail that was immobilized onto Co2+-tetradentate nitrilotriacetic acid (NTA)-modified screen-printed carbon electrodes (SPCEs) for the specific detection and quantification of β-lactam antibiotic residues in milk, which was accomplished by means of a direct competitive assay using a tracer with horseradish peroxidase (HRP) for the enzymatic labeling [50]. The sensor showed limits of detection with the low part-per-billion level for the antibiotics tested in untreated milk samples and a good selectivity against other antibiotic residues frequently detected in milk and dairy products. In addition, Wang et al. proposed a simple, rapid, and highly sensitive homogeneous electrochemical strategy for the detection of ampicillin based on target-initiated T7 exonuclease-assisted signal amplification. This biosensor showed a low detection limit of 4.0 pM toward ampicillin with an excellent selectivity, which has been successfully applied to assay antibiotic in milk. Importantly, the sensor system could avoid the tedious and time-consuming steps of electrode modification, making the experimental processes much simpler and more convenient, which has great potential for the simple, easy, and convenient detection of antibiotic residues in food safety field [51].
\nMycotoxins are fungal secondary metabolites that have toxic effects on humans and animals. Generally, mycotoxins can be easily found in agriculture crops, dairy products, including milk and cheese, and alcohols [52]. Mycotoxins enter human or animal bodies through consumption of contaminated animals or industrial food products. Crops and food products that are highly susceptible to mycotoxin contamination include alcoholic beverages, wheat, corn, barley, sugarcane, cottonseed, peanuts, rice, sugar beets, sorghum, and hard cheese [53].
\nMany review articles have focused on mycotoxin detection using different transduction methods [54, 55]. However, only a few review articles have reported on the use of nanomaterials for the electrochemical (EC) sensing of mycotoxins [56]. The present review summarizes the recent developments of nanomaterial-based EC biosensors for mycotoxin detection. It describes the importance of mycotoxin detection and the current progress and necessity of POC analysis of food toxins [56]. Finally, it illustrates the role in mycotoxin detection of EC sensors based on carbon and graphene metal nanoparticles (NPs) combined with different recognition elements, such as aptamers, antibodies, and molecularly imprinted polymers (MIPs) [57, 58]. These sensors exhibited additional analytical merits such as a shortened analysis time with simplified analytical procedures and portability. As such, EC sensors are now acknowledged as promising options for the trace-level identification of mycotoxins in food processing and manufacturing industries.
\nMicrobial pathogens include bacteria, viruses, and protozoa, and failure to detect them can have severe impacts on public health and safety. In the food or water services industries, legislation developed by the appropriate associated regulatory bodies to monitor and control the presence of these microorganisms is vital. Rapid and cost-efficient detection methods, with high-throughput capacity, are essential to implement effective monitoring systems to protect human health [59]. In 2012, the Environmental Protection Agency (EPA) released new Recreational Water Quality Criteria recommendations for protecting human health in waters designated for primary contact recreation [60]. Guner et al. developed an electrochemical sensor for the detection of E. coli using a pencil graphite electrode that was modified with multiwalled CNT (MWCNT), chitosan, polypyrrole (PPy), and AuNPs. Anti-E. coli monoclonal antibody was immobilized on the hybrid bionanocomposite, and the detection range was from 3 × 101 to 3 × 107 CFU/mL of E. coli [61]. Gao et al. describe a novel electrochemical biosensor based on mouse monoclonal antibody immobilized on self-assembled monolayers (SAM)-modified gold (Au) electrodes for the detection of Listeria monocytogenes (LM) and the detection range is from 102 to 106 CFU/mL. More importantly, this biosensor could apply to detect LM in milk without sample pretreatment, which is a straightforward and reliable method for analysis of LM with a simple operation and sensitivity at a low cost [62]. SPCEs were modified with iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-salmonella antibodies to develop an electrochemical biosensor for Salmonella detection. The biosensor was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals and its calibration curve was established between 1 × 101 and 1 × 106 cells/mL with the detection limit of 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1 h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples [63].
\nFood safety is undoubtedly one of the major global concerns. In this chapter, we summarize some representative electrochemical sensors toward food contaminants such as heavy metals, illegal additives, pesticide residues, veterinary drug residues, biological toxins, and foodborne pathogen. These electrochemical sensors for food safety detection continue to show many advantages including rapid response, field applicability, high sensitivity, high selectivity, and online analysis. Moreover, electrochemical sensors are much cheaper and easier to be miniaturized, which may play a key role on quality control in food processing, improving product quality and safety. However, the stability of the electrochemical sensors is still a challenging problem. Recently, we have developed an electrochemical instrument and a number of electrochemical sensors for the detection of heavy metal ions with excellent sensitivity and reproducibility. The instrument and sensors are being commercialized with satisfactory user feedback.
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\\n\\nAll payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
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\\n\\nLast updated: 2020-11-27
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n1. DEFINITIONS
\n\nCorresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
\n\nCo-Author: All other Authors of the Chapter besides the Corresponding Author.
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\n\n2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
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\n\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n5. TERMINATION
\n\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\n\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\n\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\n7. MISCELLANEOUS
\n\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
\n\n\n\n
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