Applications of EIS in analysis and characterizations of different drug materials in variable matrices.
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More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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Nowadays, this marginality has ceased as the need for healthcare is rising. Healthcare is now at the center of attention influenced by the never-ending demand of medical technology and substantial resource scarcity that imposes substantial organizational and entrepreneurial innovations. One decisive challenge that has emerged from such a situation is the management of healthcare processes, in the broad sense: healthcare professionals are called upon to demonstrate their ability to cope with complex problems because they are characterized in an institutional, ethical, organizational, and economic sense. With its eight chapters in a single segment, this book makes it possible to realize the specific nature of the problem. Its multidimensionality and the original approach are contributed and harmonized by scholars belonging to different disciplines.",isbn:"978-953-51-3438-1",printIsbn:"978-953-51-3437-4",pdfIsbn:"978-953-51-4694-0",doi:"10.5772/65535",price:119,priceEur:129,priceUsd:155,slug:"advances-in-health-management",numberOfPages:156,isOpenForSubmission:!1,hash:"964451b7f2d30a4d8f4dbadd374df7ea",bookSignature:"Ubaldo Comite",publishedDate:"August 23rd 2017",coverURL:"https://cdn.intechopen.com/books/images_new/5808.jpg",keywords:null,numberOfDownloads:6473,numberOfWosCitations:7,numberOfCrossrefCitations:4,numberOfDimensionsCitations:8,numberOfTotalCitations:19,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"September 28th 2016",dateEndSecondStepPublish:"November 10th 2016",dateEndThirdStepPublish:"February 2nd 2017",dateEndFourthStepPublish:"March 30th 2017",dateEndFifthStepPublish:"June 1st 2017",remainingDaysToSecondStep:"4 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:"Edited by",kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"195399",title:"Prof.",name:"Ubaldo",middleName:null,surname:"Comite",slug:"ubaldo-comite",fullName:"Ubaldo Comite",profilePictureURL:"https://mts.intechopen.com/storage/users/195399/images/system/195399.jpg",biography:"Ubaldo Comite was born in Cosenza, Italy, on June 14, 1971. He has a degree in Law (1994) and Economics (1996) at the University of Messina (Italy) and earned his PhD degree in Public Administration at the University of Calabria (Italy), in 2005. Currently, he is a professor of Health Management, Budget and Business Organization at the University of Calabria. Furthermore, he is a professor of Business Administration at the University 'Giustino Fortunato” (Italy). He has authored several book chapters and over 60 peer-reviewed journals/proceeding papers. He served as an International Program Committee member for several conferences. 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Urinary tract infections (UTI) are among the most common bacterial infections in humans. Approximately 50%-60% of adult women experience a UTI during their lifetime. Furthermore, a significant number of patients can be characterized as having recurrent UTIs if they meet the criteria of ≥2 uncomplicated UTIs in 6 months or ≥3 positive cultures within the preceding 12 months. Applying this definition, it is estimated that recurrent UTIs affect 25% of women with a history of UTI.
E. coli represents the main causative pathogen in recurrent UTI and is responsible for approximately 80% of all episodes of infection. Further important pathogens include Proteus mirabilis, Staphylococcus saprophyticus, and Klebsiella pneumonia.
Symptomatic UTIs cause significant discomfort such as dysuria, polyuria, and suprapubic tenderness. If left untreated, a UTI can progress to acute pyelonephritis with the risk of permanent renal scarring and loss of renal function.
Patients with recurrent urinary tract infections undergo frequent antibiotic treatment and/or low-dose antibiotic prophylaxis. Additionally, a subset of patients is required to undergo a systematic radiological and endoscopic evaluation of the urinary tract in order to rule out any underlying structural abnormalities or urinary calculi. The immense use of antibiotics for the treatment of urinary tract infections has resulted in the development of considerable bacterial resistance and therefore, increasing difficulties in eradicating infections. Due to the development of bacterial resistance, UTIs are a substantial economic burden and a noteworthy public health issue. Therefore, new treatment strategies and preventive measures against UTIs such as immune-stimulation/modulation, vaccine development, the use of probiotics, and the instillation of attenuated bacteria into the urinary bladder are currently being researched.
This chapter will review the most recent literature and provide up-to-date information on developments in immune-based treatment strategies for patients with recurrent UTIs from a pre-clinical and clinical point of view.
To identify all relevant materials, comprehensive literature searches were performed via the data sources: MEDLINE, EMBASE, CINAHL and OVID using the key words: urinary tract infection, urine culture, UTI, vaccines, adherence, fimbriae, biofilms, probiotics. Relevant articles and references between 1970 and 2012 were reviewed and analyzed. Reference lists from relevant review articles were also searched. Only articles published as formal papers in peer-reviewed journals were selected for inclusion if they reported findings of interest. The data base searches resulted in 710 articles, of which 75 of 710 pertained directly to immune-based treatment strategies. The entirety of these articles was reviewed, forming the basis for the current review.
Plant-derived therapies have long been used in Ayurvedic and traditional Chinese medicine (Wollenweber, 1988). The interest in plant antimicrobials for treatment or prevention of UTIs has been driven both by the prevalence of antibiotic-resistant uropathogens and growing popularity of complementary and alternative medicine. Still, little evidence exists for the effectiveness of these treatments and therapeutic dose requirements. More than 5000 plant polyphenols have been identified so far. The spectrum of biological effects include anti-microbiol, anti-inflammatory and anti-carcinogenic activities (Beretz et al., 1978). Plant derived extracts contain different chemical compounds with multiple antimicrobial activities (Burt, 2004). The most studied species include cranberry, berberine, blueberry, bearberry, and certain herbs such as cinnamon. According to Ohno et al., the potential for bacteria to develop resistance to plant derived anti-microbials is relatively small (Ohno et al., 2003).
Cranberry, Vaccinium macrocapron, is the best known and most studied plant-derived therapy for UTIs (Seeram, 2008). Historically its antimicrobial effects were believed to be due increased excretion of hippuric acid and urinary acidification, although this was disproved in the 1950’s (Bodel et al., 1959). More recent studies have proved Cranberry compounds fructose and proanthocyanidin to inhibit E. Coli adhesins
Berberine sulfate is an alkaloid found in the Berberine arisata plant, as well as the roots of Oregon Grape (Mahonia aquifolium), Goldenseal (hydrastis canadensis), and Goldenthread (Coptis chinesis). It is present in the root, rhizome, and stem bark of the plants (Yarnell, 2002). Head et al. could show that berberine extracts are effective against a variety of organisms, including bacteria, viruses, fungi, and protozoans (Head, 2008). Growth inhibitory effects were described for several bacterial pathogens such as Staphylococcus aureus, Pseudomonas aeruginosa,, E. coli, Bacillus subtilis and Chlamydia (Cernakova &Kostalova, 2002, Head, 2008, Scazzocchio et al., 2001). In one study berberine was found to decrease synthesis and expression of E. Coli Pap fimbriae, thus decreasing bacterial adhesion to epithelia
Blueberry, part of the Vaccinium genus, is closely related to cranberry. Studies suggest that high molecular weight pranthocyanidins found in wild blueberry inhibit E. Coli adhesion
Bearberry, Arcystaphylos uva-ursi, is a member of the Ericaceae family, as are cranberry and blueberry. The glycoside arbutin is the main constituent of bearberry leaves and dried preparation. Arbutin is metabolized into hydroquinone, which has a urinary availability of approximately 65% of the administered arbutin dose (Schindler et al., 2002). Hydroquinone is an antimicrobial according to
Currently, bearberry is used in Germany to cure mild UTI, defined as asymptomatic or bacteriuria less than 105 colony-forming units/mL (Schindler et al., 2002). It is not, however, recommended for long-term prevention due to concern of hydroquinone carcinogenic effects (DeCaprio, 1999).
Trans-cinnamaldehyde is an extract of the bark of cinnamon (Adams et al., 2004). It has a wide margin of safety between conservative estimates of intake and no observed adverse effects (Adams et al., 2004).
These results justify further pre-clinical studies and make trans-cinnamaldehyde a potential candidate for use as an antimicrobial agent for controlling UTIs.
The existing literature lists many other herbs for the treatment of UTIs, while most of them lack a scientific basis for this purpose. They include Taraxacum officinalis leaf (dandelion), Juniperus communis (juniper), Hydrangea aborescens (hydrangea), Agrimonia eupatoria (agrimony), Elymus repens (couchgrass), Althea officinalis (marshmallow), Zea mays (corn silk), Apium graveolens (celery seed), Ulmus fulva (slippery elm), Arctium lappa (burdock), and Mentha piperita (peppermint). For others some scientific background exists. Extracts from Salvia officinalis (Garden sage or common sage) has been shown to be active against Klebsiella, Enterobacter species, UPEC, Proteus mirabilis and Morganella morganii obtained from the urine samples from patients with UTIs (Pereira et al., 2004).
Another potentially useful herb is Barosma betulina (bachu). It has been used in the treatment of UTI and urethritis for a long time. It was found to have anti-microbial effects against uropathogens
Studies could demonstrate that Lactobacilllus species in the form of probiotics reduced the risk of UTIs and vaginal infections (Bruce &Reid, 2003, Reid et al.,1985). However, despite ongoing research the mechanisms are poorly understood (Spiegel et al., 1980). In the literature were different mode of action proposed including downregulation of pro-inflammatory cytokines (IL-6, IL-8, TNF-alpha) (Anukam et al., 2009), production of hydrogen peroxide, which protects against the UPEC (Czaja et al., 2007) production of a 29-kDa biosurfactant proteins which inhibits bacterial adhesion (Osset et al., 2001, Xia et al., 2006). Some of the commensal bacteria such as Lactobacillus species and Bifidobacteria species are known to produce immunoregulatory factors that modulate the immune response and may therefore decrease UTIs (Wilson et al., 1998). From a clinical standpoint, there is a close correlation between loss of the normal genital microbiota, particularly Lactobacillus species, and an increased incidence of genital and bladder infections. Vaginal colonization with Lactobacillus spp. was found to prevent recurrent UTIs (Bruce &Reid, 1988, Reid et al., 1992). A Phase I clinical trial assessed the safety of the use of vaginal Lactobacillus suppositories to prevent recurrent (Czaja et al., 2007). Reid et al. investigated in a randomized study the role of probiotic lactobacilli in controlling re-infection in women after treatment of an acute UTI (Reid et al., 1992). 235 patients were treated with antibiotics for three days. Recurrence occurred in 41% of the patients. Individuals with recurrence were randomly assigned to Lactobacillus suppositories treatment group or placebo suppository group. Treatment was given twice weekly for two weeks, then once a month for the next two months. The recurrence rate was 21% in the Lactobacillus group compared to 47% in the placebo group. Oral use of Lactobacilli was also investigated. Reid et al. demonstrated L. rhamonosus GR-1 and L. fermentum RC-14 taken orally lead to colonization of vaginal epithelium within one week. In pediatric patients the oral intake of L. rhamnosus GG resulted in a reduction in UTI incidence rate compared to the placebo group (Dani et al., 2002). These results are promising and warrant further pre-clinical and clinical studies for the use of probiotics in controlling UTIs.
Currently, low-dose antibiotic treatment has been the most effective prophylaxis for the prevention of recurrent UTI. However, cessation of antibiotic treatment usually results in recurrence of infection in most patients (Ha &Cho, 2008). Furthermore, with the number of antibiotic resistant strains of uropathogenic bacteria causing recurrent UTI on the rise, a substantial amount of research in alternative treatment modalities such as immuno-stimulation and attenuated vaccines is being performed. The target of such modalities consists of the Mucosa-Associated Lymphoid Tissue (MALT) lining much of the GI, respiratory, and genitourinary tract, the activation of specific receptors on dendritic cells within the genitourinary tract, and increasing the concentration bacteria-specific immunoglobulins (Ha &Cho, 2008). The objective of such therapies is to reduce the frequency and severity of UTI as well as reduce the consumption of antibiotics used to treat them.
Uro-Vaxom® (OM-89) is an extract of 18 strains of E. coli that is obtained by alkaline lysis, which destroys lipopolysaccharide (LPS) molecules produced by the gram negative bacteria and modifies other bacterial antigens, maintaining their antigenic potential (Ha &Cho, 2008). Taken orally, Uro-Vaxom® achieves immuno-stimulation by increasing the proliferation of Mucosal Associated Lymphoid Tissue (MALT) within the GI tract leading to elevated concentrations of bacteria-specific IgG, mucosal-derived IgA along with serum IgA. Furthermore, OM-89 increases the rate of dendritic cell maturation within the genitourinary tract, leading to increased numbers of circulating memory T-cells as well as an overall increase in inflammatory mediators such as TNF-alpha, IL-2, and IL-6 (Bessler et al., 2009). Treatment studies of sexually active females between the age of 20 and 50 shows that Uro-Vaxom® reduces the recurrence of UTI by 36% after 6 months of therapy compared to placebo (Bessler et al., 2009).
Solco Urovac, which is currently under phase 2 clinical trials, is a treatment modality that utilizes the vaginal mucosa via suppository to induce an immune response. The Solco Urovac vaccine consists of 6 E. coli strains along with several recombinant antigenic factors such as fimbriae proteins and 1 strain each of Proteus mirabilis, Morganella morganii, Klebsiella pneumonia, and Enterococcus faecalis (Hopkins et al., 2007). SolcoUrovac works in a similar manner to that of OM-89, however it achieves a higher overall mucosal concentration of IgA in the vagina and bladder. One characteristic of SolcoUrovac is that it must be administered on a booster schedule or else the maximum efficacy will not be achieved. The overall reduction of UTIs in female patients between the age of late teens to early 70s treated with SolcoUrovac plus multiple boosters was measured to be 46.0% (Hopkins et al., 2007).
Siderophores, such as the IroN-cell surface protein found on most strains of E. Coli, are potential targets for immune-therapy. A significant systemic-compartment IroN IgG-specific antibody response developed in serum. However, there was no IroN IgA-specific antibody response in either the systemic or the mucosal compartment. Subcutaneous immunization with denatured IroN resulted in a significant IroN immunoglobulin G (IgG)-specific response in serum but not a systemic or mucosal IroN-specific IgA response (Russo et al., 2003).
UPEC strains express a number of virulence factors used for colonization of their host. One important virulence factor is located on type 1 pili, allowing UPEC to adhere and invade host cells within the urinary tract. FimH interactions with several host factors have been documented. These include components of the glycocalyx that sparsely covers the bladder surface, carcinoembryonic antigen-related cell adhesion molecule (CEACAM) family members, soluble Tamm-Horsfall protein, the glycosylphosphatidylinositol (GPI)-anchored protein CD48, the leukocyte adhesion molecules CD11 and CD18, and uroplakin 1a (Klein et al.). Adherence to mannose residues prevents the rapid clearance of E. coli from the urinary tract by the flow of urine and enables the invasion of the host cells (Wellens et al., 2008). The binding of type one pili to bladder epithelial cells activates the innate immune system via the Toll-like receptor 4 pathway which recruits neutrophils and other inflammatory mediators to the site of insult (Wellens et al., 2008). Next, the complement system opsonizes the UPEC and counter intuitively facilitates invasion of the bacteria into the epithelial cell.
Type 1 pili are the most prevalent fimbriae encoded by UPEC, consisting of the four subunits FimA, FimF, FimG, and FimH, the latter located at the tip of the pili (Wellens et al., 2008). The FimH moiety, which is the primarily subunit responsible for the initiation of bacterial adherence and invasion, is a prime target of immune-stimulation. Experiments done in mice have shown that both direct inoculation with immunogloblins against FimH, innoculation with synthetic peptides within the binding moiety for FimH, or gene knock-out of FimH could specifically block type 1 fimbriae-mediated bacterial adherence to bladder epithelial cells resulting in a dramatic loss of virulence(Thankavel et al., 1997). In experiments that utilized synthetic peptides to induce an immune response, dramatic increases in serum IgG and IgM were observed via ELISA (Thankavel et al., 1997). In addition, urine collections showed a marked increase in IgG and mucosal derived IgA along with elevated activity of mast cells within the bladder epithelium when faced with a bacterial challenge (Thankavel et al., 1997).
Catheter–associated urinary tract infections are common and often related to the existence of bacterial bio-films. Progress in this area is limited. Preventive strategies include avoiding unnecessary catheterization, limit duration of catheterization, using closed drainage system, and appropriate hygiene, including frequent catheter changes and emptying of the drainage bags (Jacobsen et al., 2008, Newman, 1998). Many mechanisms of biofilm resistance against antibiotic treatment were reported over the years. The most important type of the biofilm resistance is the development of a diffusion barrier formed by the bio-film matrix (Ishida et al., 1998). The biofilm prevents access of antimicrobial agents and even of antibodies. Despite the antibiotic treatment, the infection often persists until the device is removed (Schierholz &Beuth, 2001). Over the last 2 decades different coatings were explored to reduce the risk of bacterial bio-film formation and bacterial colonization and subsequently infection. Coating substances included various antibiotics, silvercoating and others. Infections could not be prevented, however the “abacterial window” could be prolonged. Schaeffer et al. demonstrated that in patients with acute spinal cord injury, who received long-term urinary catheters, the silver-coated catheters delayed but did not prevent the onset of bacteriuria (Schaeffer et al., 1988). The same findings were reported for antibiotic impregnation of catheters (Darouiche et al., 1999, Guay, 2001, Johnson et al., 1999). These findings are important for short-term use of urinary catheters but not for long-term use (Trautner &Darouiche, 2004). Several other substances were reported to inhibit development of bacterial bio-film formation including type A proanthocyanidins, hesperidin, apigenin,naringin and rhoifolina, and others. None of these substances made it into clinical trials so far.
One important survival mechanism of UPEC is the creation of an intracellular reservoir. Within the epithelial cell, the UPEC are able to resist antibiotic treatment by binding to Rab 27 b/CD 63 positive vesicles. Forskolin, the active component of the Coleus forskohlii, has been proven to increase the content of cyclical adenosine monophosphate (cAMP) in urothelial cells, leading uropathogenic bacteria to exit the urothelial cells. It was shown that cAMP levels regulate the exocytosis of these vesicles depending on the bladder distension. These findings could lead to new approaches for the treatment and prevention of recurrent urinary tract infections (Bishop et al., 2007, Gonzalez-Chamorro et al.).
Hormonal deficiency in postmenopausal women results in thinning of the vaginal and urethral mucosa and more importantly to disruption of the normal vaginal flora and therefore to an increased risk for UTIs (Head, 2008). Several studies could demonstrate, that replacing estrogene in this patient population can reduce the incidence of UTIs.
In a randomized study postmenopausal women received either intra-vaginally administered estradiol or placebo. At the end of the study a significant reduction in the incidence of UTIs in the treatment group compared to the placebo group was noted. Of interest is also the observation that Lactobacilli that were absent in the vaginal cultures of patients of the treatment group at the beginning of the trial reappeared in 61% (Raz &Stamm, 1993).
Darouiche et al. conducted a prospective, randomized, placebo-controlled, double-blind pilot trial to examine the efficacy of bacterial interference in preventing urinary tract infection (Darouiche et al., 2005). In this study 27 patients with spinal cord injury were included. Patients were randomly assigned either to have their bladders inoculated with either E. coli 83972 (experimental group) or sterile normal saline (control group). Patients whose bladders became colonized with E. coli 83972 were half as likely (P=.01) than non-colonized patients to develop UTI during the subsequent year.
Billips et al. demonstrated recently that deletion of the O antigen ligase gene, waaL, from the uropathogenic E. coli isolate NU14 results in a strain that stimulates enhanced urothelial cytokine secretion (Billips et al., 2009). They could show that NU14 DwaaL stimulated an enhanced interleukin-6 secretion by mouse macrophages, compared with secretion by the wild type. Of great importance is the fact that mice vaccinated via instillation into the bladder developed protective responses that prevented persistent colonization after bladder challenge with NU14, yet NU14 DwaaL failed to persistently colonize the mouse bladder. They could also show that the mice were additionally protected against challenge with a broad range of clinical UPEC isolates and developed immunity that lasted more than 8 weeks (Billips et al., 2009). These findings open a new avenue for future treatment strategies of recurrent urinary tract infection by caused by UPEC.
Immune-based treatment strategies for patients with recurrent UTIs are of special interest. Several promising new approaches including bladder colonization with attenuated bacteria and intravesical vaccination were published recently and discussed in this chapter. Furthermore, studies suggest that the use of inhibitors of bacterial adherence to urothelial cell and inhibitors of biofilm formation receptors hold great promise. Moreover, stimulators of cyclic AMP inside urothelial cells and the recent advancements in the development of vaccines are an interesting initiative in this field. For some of the plant –based prevention and treatment strategies only little scientific evidence for the prevention and treatment of urinary tract infection exist.
We would like to thank the library staff from Texas Tech University Health Sciences Center, Lubbock for their extraordinary support and assistance. On a special note, we would like to thank again Carrie Gassett who showed great interest and support in our project.
Electrochemical impedance spectroscopy (EIS) is a usually described as a
Later on, this has opened the doors for realms of applications of EIS. Applications encompassed electrocatalysis and energy [3, 4, 5]; characterization of materials, e.g. corrosion phenomenon surveillance [6, 7]; and depiction of quality of coatings [8], exploring mechanisms of processes such as electrodeposition and electro-dissolution [9, 10], food and drug analysis [11, 12, 13], detection of biomarkers [14, 15], and water analysis [16, 17].
It is noteworthy to mention that impedance spectroscopy (IS), depending on the material used, the device, and the system or process to be studied, has two main categories: EIS (the topic of this chapter) and dielectric IS. A major difference is that EIS applies to systems/materials involving chiefly ionic conduction, in contrast to electronic conduction in the case of dielectric IS. Therefore, it can be observed from the fields of EIS applications that EIS usually applies to systems like electrolytes (solid/liquid), polymers, and glasses [18, 19, 20, 21].
In general, EIS measurements involve the application of an alternating current (AC) voltage or current to the system under investigation, followed by measurement of the response in the form of AC current (or voltage) as a function of frequency. Measurements are usually performed using the potentiostat, and the measured response is analyzed using a frequency response analyzer (FRA) [18]. By and large, three factors make EIS exceptionally attractive in terms of applications:
Capability to explore the ES at relatively low frequencies using the minimal perturbation that in turn serves to keep the kinetic information of the system under investigation at near zero conditions (steady state). Therefore, EIS is said to be a steady-state and nondestructive technique. The majority of the electrochemical techniques, however, involve an application of large perturbation for sensing the membrane/electrolyte interface, with the purpose of obtaining mechanistic data following the driving of the reaction to a state that is far from equilibrium [3].
Feasibility of implementation of EIS into the system to be measured.
The usefulness of data obtained in characterizing the studied ES, where EIS provides on-site data on the relaxation data over a range of frequencies, from as low as 10−4 Hz and up to 106 Hz.
A combination of the three advantages led to the wide use of EIS as previously mentioned.
The current chapter throughout the following sections is investigating the applications of EIS in a variety of matrices, mainly in food, drug, and water analysis, and the recent advances in these fields as well as comparisons between EIS and other electroanalytical approaches applied for the same purposes.
Throughout the current chapter, readers will be exposed to the different analytical techniques, especially the electrochemical-based approaches, which are generally used for detection of pollutants in food, drug, and water.
Readers will be more focused on the applications of EIS in specific. A comparison between EIS and the other techniques commonly used in water and food analysis will be exhibited.
The safety, quantity, and the quality of food and water are becoming worldwide concerns. Water is the most crucial source for human development. With the advancement of human life, uncountable contaminants are intimidating the aquatic system. These intimidations include but not limited to automation/industrialization, widespread use of chemicals, increased population, and suburbanization. Subsequently, water pollution is becoming a significant health and environmental concern.
By and large, the safety of food and water is influenced by contaminants. Among these pollutants, heavy metals, elevated anions (sulfates, phosphates, fluoride, etc.), dyes, agricultural waste, pesticides, drugs, and pharmaceuticals are the most common. Heavy metals, in specific, are widely used in many industrial, domestic, and agricultural applications, and they are nondegradable, an issue that raises the concern about their potential influence on public health, water systems, and the ecosystem in general. As, Cd, Cr, Pb, and Hg have been reported to be the highest systemic toxicant elements.
According to the US EPA and the International Agency for Research on Cancer (IARC), these toxic elements are probable to be carcinogenic. Moreover, accumulation of Pb, Cd, and Hg in the human body over time can cause serious health problems [22, 23, 24, 25, 26].
Similarly, food, leather, and textile industries discharge huge amounts of polluted wastes. With the various structures of the chemicals used in these industries, numerous problems develop. Dyes, a key water pollutant and even if discharged as traces (as low as 1 ppm), would color large volumes of water. Reports show that amount of dyes as huge as 7 × 105 tons per annum are being produced annually, demonstrating the magnitude of the problem. Released dyes do not only affect the aquatic beings but also the human health. Their impact includes carcinogenicity, mutagenicity, poisoning, disturbance of the metabolism in aquatic bodies, etc. [27, 28].
On the other hand, and representing a significant category of aquatic pollutants, pharmaceutically active materials (PhAMs) are usually released into the aquatic systems from different sources, including but not limited to the effluents of the manufacturing sites and hospitals, illegal disposal, veterinary applications, and landfill leachate. Daily use by humans and the subsequent conversion of PhAMs into various metabolites with variable chemical structures is also a major source. The fate of these metabolites, and probably their parent drug compound, is usually the wastewater [29, 30, 31, 32, 33].
The increasing understanding of the assembly of the food chain and the probability of infection of human with these resilient microorganisms, either directly or via the food chain, has explained largely the spread of these species. Therefore, the process of food production and commercialization is posing rigorous regulations nowadays. Different societies, such as the Food and Drug Administration (US FDA), European Union (EU), and World Health Organization (WHO) in collaboration with the Food and Agriculture Organization of the United Nations (FAO) creating the FAO/WHO Codex Alimentarius Commission (CAC), are setting up standards for the maximum residue levels (MRLs) permissible in raw and processed food products of animal or poultry origin. Yet, any food product that would conform to these criteria and the preceding risk assessments cannot be banned by countries of the World Trade Organization (WTO) [34, 35, 36, 37, 38].
The elevating concerns on food and water safety and the existence of these materials at relatively low concentrations have created the need to find sturdy as well as sensitive detection and removal/remediation technologies. Detection technologies included traditional techniques such as spectrophotometry, spectrofluorimetry, atomic absorption spectrometry (AAS), as well as electrochemical and the more sophisticated chromatographic approaches [27, 28, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49]. Each of these techniques has its pros and cons.
Electrochemical techniques are among the widely used techniques for detection of pollutants in food and water analyses. The following subsections will be focused on the electrochemical approaches and EIS in specific in detection of contaminants in water and food samples.
As an analytical approach, electroanalysis offers many advantages including but not limited to simplicity, sensitivity, specificity, and applicability in various matrices and cost-effectiveness. These advantages are of specific importance when it comes to detection of drugs and pharmaceuticals, especially in food and water samples as well as in quality control (QC) and quality assurance (QA) laboratories. According to the signal being measured (voltage/potential, current, conductance, impedance), electroanalytical techniques can be categorized into potentiometric, amperometric, conductometric, and impedimetric techniques. Subcategories for each technique also exist, and coupling with other technologies has been investigated.
Sensors, and in particular those based on the classical potentiometric technique, or the new polyion, galvanostatic, or voltammetric sensing mechanisms, now possess the foothold in analytical chemistry. Offering irresistible advantages, on the in vitro scale, such as operation simplicity, sturdiness, and remarkable sensitivity hitting nine orders of magnitude, selectivity, and functionality over wide range of matrices, suitability for on-line or real-time analyses, and most prominently their liability for miniaturization, make the use of sensors indispensable [50, 51, 52, 53].
Figure 1 shows an illustration of ISE (ion-selective electrode) potentiometric sensor and generation of potential across the different phase boundaries.
Schematic illustration of ISE cell assembly and the generation of EMF across different phase boundaries.
The sensing mechanism especially if the target analyte is a biomolecule depends on tailoring the surface of the sensor with a bio-receptor that can selectively bind to the target bio-analyte. Following the adsorption of the bio-analyte from the solution on the surface of the probe, a change in the electrochemical signal can be observed and measured. Such a change is correspondingly dependent on the bio-analyte concentration.
Figure 2 shows a schematic illustration of the sensing mechanism in plastic microfluidic channels. The left panel shows the generation of streaming potential, ΔE, as a result of pressure-driven flow and surface charge at the electric double layer (EDL). The right panel shows a sensogram with signal inversion upon adsorption of the analyte. The bottom graph shows the pulsed streaming potentials as a function of heparin with immobilized protamine.
Schematic illustration of the generation of streaming potential as a result of pressure-driven flow and surface charge at the electric double layer (EDL)—left upper panel. The right panel shows a sensogram with signal inversion upon adsorption of the analyte. The bottom graph shows the pulsed streaming potentials as a function of heparin with immobilized protamine on a surface of a cyclo-olefin copolymer (COC) microchannel. Data points were fitted using Langmuir isotherm. Graphs are replicated from the authors’ own work with permission from Copyrights@ American Chemical Society (ACS) [
EIS as an electrochemical technique entails measurement of the change in the charge transfer resistance (Rct) following the interactions between the analyte and the receptor and the consequent change in the interfacial electron transfer kinetics. The following sections will be dealing with the application for EIS for sensing different target analytes in different matrices [53, 54].
The effects of presence of the PhAMs either in waste and drinking water or even in wastewater treatment plants (WWTPs) are still inarticulate. However, what is well understood is that the impact extends to humans and animal’s health, the aquatic environment, and in the long run the ecosystem. This effect is greatly dependent on the released dose of the PhAMs as well as their pharmacological effects. The issue becomes of concern when we know that the metabolites might be of a higher risk than the parent drug compound. At the microbial level, microorganisms upon prolonged exposure to anti-infectives, for example, become more tolerant, and new strains, which cannot be cured using the conventional antimicrobials, are now in the scene [55, 56, 57].
EIS, being capable of detecting as low as 10−12 M of the target analyte, is widely used in drug analysis. Several drug categories were analyzed using EIS. Table 1 shows some examples of drugs analyzed using EIS, as well as the matrices and type of electrode used together with the sensing interface, sensing strategy (label-free or labelled), and limit of detection (LoD).
Target drug | Sensing interface | Electrode | Matrix | Sensing measurement method and strategy | LoD | Ref |
---|---|---|---|---|---|---|
Raloxifene | Nd2O5 NPs@GO/GCE | GCE | ND Serum and urine | EIS CV Amperometry (Label-free) | ND ND 18.43 nM | [58] |
OTC | Aptasensor (Fe3O4@mC900) | GCE | Milk samples | EIS (Label-free) | 0.027 pg mL−1 | [59] |
TET | Aptasensor 1: CPE/OA/anti-TET Aptasensor 2: MBCPE/Fe3O4NPs/OA/anti-TET | CPE MBCPE | Tablets, milk, honey, and serum | EIS (Label-free) | 10−1 3.0 × 10−13 M | [60] |
TOB | Aptasensor/ SnOx@TiO2@mC | GCE | Urine and serum | EIS (Label-free) | 0.01 nM | [61] |
Chloramphenicol | Au/N-G | GCE | Eye drops | EIS (Label-free) | 0.59 μM | [62] |
Sulphamethoxazole | MIP-decorated Fe3O4 MNPs | SPCE | Seawater | EIS (Label-free) | 0.001 nM | [63] |
17β-estradiol | Au nanoparticle-thiolated protein G-scaffold | Au | Serum | EIS (Label-free) | 26 pg mL | [64] |
BPA | AuNPs/PB/CNTs-COOH/GCE | GCE | Water | EIS (Labelled detection) | 0.045 pM | [65] |
P4 | ssDNA/Au | Au | Tap water | EIS (Labelled detection) | 0.90 ng mL | [66] |
Applications of EIS in analysis and characterizations of different drug materials in variable matrices.
The electrochemical properties of raloxifene, an important chemotherapeutic agent, were assessed using different techniques including EIS. Three electrodes were tested for this investigation: (1) bare screen-printed carbon electrode (SPCE), (2) graphene oxide (GO)/glassy carbon electrode (GCE), and (3) neodymium sesquioxide nanoparticles Nd2O5 NPs@GO/GCE. The target was to assess the interface properties of these electrodes. Results showed that the Rct of the third electrode was much smaller than the other electrodes. Other electrochemical techniques such as cyclic voltammetry (CV) were used in the same work [58].
Other examples included the determination of an important class of PhAMs, which is antibiotics, a subclass of antimicrobials. Label-free detection of oxytetracycline (OTC) in milk samples was performed using a mixture of iron oxide and mesoporous carbon (Fe3O4@mC) together with nanocomposites made of Fe(II)-based metal-organic frameworks (525-MOF) by calcination at different temperatures. The sensor showed a very high sensitivity with a LoD = 0.027 pg mL−1 and a linear range of 0.005–1.0 ng mL−1. Moreover, the fabricated aptasensor showed a high selectivity for oxytetracycline in the presence of similar drugs like tetracycline, doxycycline, and chlortetracycline [59].
Similarly, label-free detection of tetracycline (TET) was performed using two aptasensors made of carbon paste electrode (CPE) with oleic acid (OA) and a magnetic bar carbon paste electrode (MBCPE) with Fe3O4 magnetic nanoparticles and oleic acid (OA) following the modification of electrode surfaces using anti-TET. The LoD were 1.0 × 10−12 to 1.0 × 10−7 M and 3.0 × 10−13 M for the two aptasensors, respectively, and the sensors were applied to pharmaceutical formulations, serum samples, as well as food products (milk and honey) [60].
A sensor based on nanocomposites of mC with SnOx and TiO2 nanocrystals was used to determine tobramycin (TOB) in urine and serum samples selectively and in the presence of kanamycin, oxytetracycline, and doxycycline. The aptasensor showed an excellent sensitivity with a LoD of 0.01 nM [61].
Chloramphenicol was also determined in eye drop formulations using N-doped graphene nano-sheet-Au NP composite (Au/N-G). The LoD was 0.59 μM, and the sensor showed a selectivity in the presence of interferences like oxytetracycline, chlortetracycline, ascorbic acid, and metronidazole [62]. Other applications included sulphamethoxazole using molecularly imprinted polymers (MIPs) decorated with Fe3O4 magnetic nanoparticles (MNPs) on SPCE [63].
Immunosensors for 17β-estradiol composed of Au electrode nanoparticle-thiolated protein G-scaffold. This structure has facilitated the anchoring of a mouse monoclonal anti-estradiol antibody. The LoD was 26 pg mL−1. As per the authors, square wave voltammetry (SWV) was more sensitive (18 pg mL−1) and required less time and effort compared to EIS [64].
Bisphenol A (BPA), a xenoestrogen with an estrogen-mimicking effect and that is widely used as a precursor in plastics industry, has been determined using a labelled aptasensor made of gold nanoparticles (AuNPs), Prussian blue (PB), and functionalized carbon nanotubes (AuNPs/PB/CNTs-COOH).
Determination of progesterone (P4) in water and other clinical samples was performed using single-stranded ssDNA aptamers with high binding affinity to P4 [66].
In addition to food contamination with antimicrobials and other drugs, bacteria and other pathogens like mycotoxins (secondary metabolites of microfungi) or chemicals such as pesticides are also other sources of food contamination. Food contamination can occur at any stage of food production, storage, or dissemination. Sicknesses caused by foodborne pathogens include symptoms such as diarrhea, nausea, vomiting, septicemia, meningitis, and even death [50, 53, 67, 68]. Pathogens include famous strains of bacteria such as different species of Salmonella (e.g.,
Table 2 shows examples of different bacterial strains that have been determined in food products using EIS-based aptamers.
Target | Sensing interface | Electrode | Matrix | Sensing method | LoD | Ref |
---|---|---|---|---|---|---|
GNPs@SPCE | SPCE | Poultry products | EIS | 600 | [69] | |
GNPs@SPCE | SPCE | Animal-based products | EIS | 600 | [70] | |
GO+AuNPs@GCE | GCE | Pork meat | EIS | 3.0 | [71] | |
OTA | Diazonium modified-SPCE | SPCEs | Cocoa beans | EIS | 0.15 ng mL−1 | [72] |
OTA | Thiolated DNA aptamer | Au | Food products | EIS | 0.12 | [73] |
AFB1 | Cys-PAMAM-modified electrode | Au | Peanuts and corn snacks | EIS | 0.40 ± 0.03 nM | [74] |
Acetamiprid | Ag-NG/GCE | GCE | Cucumber and tomatoes | EIS | 0.033 pM | [75] |
Applications of EIS in analysis of food and food products.
Colony-forming unit (CFU) mL−1.
A highly specific DNA—aptamer to
Another
The mycotoxin ochratoxin (OTA) has been determined in a variety of samples, e.g., in cocoa beans, using EIS aptasensor developed using a diazonium-coupling reaction mechanism for the immobilization of anti-OTA-aptamer on screen-printed carbon electrode (SPCE) [72]. EIS was also applied for the determination of OTA using a thiolated DNA aptamer immobilized by chemisorption to the surface of Au electrode [73]. Other mycotoxins, e.g., Aflatoxin B1 (AFB1) were detected using layer coating of cystamine (Cys), poly (amido-amine) dendrimers of generation 4.0 (PAMAM G4) and DNA aptamers (on Au electrode) specific to AFB1 [74].
Pesticides, e.g., acetamiprid, were determined in samples of vegetables (tomatoes and cucumber) using AgNP-modified nitrogen-doped graphene (AgNPs/NG). The designed aptasensor was sensitive, selective, and economical and did not require intricate labelling procedures [75].
Discharge of heavy metals (HMs) into the water bodies via industrial activities and other sources, e.g., mining, acid rain, agricultural waste, etc., denotes a worldwide challenge. As previously mentioned in this chapter, HMs and other emergent contaminants possess a significant influence on the environment and human health. The intensifying flux of HMs into aquatic environments and the properties of HMs (toxicity, degradation rates, accumulation, uptake, bioavailability, etc.) necessitate the presence of firm rules and action plans for monitoring, detoxification methodologies, and treatment technologies to keep their concentrations within the permitted levels [23, 24, 25, 26, 76].
Table 3 shows examples for the applications of EIS in determination of water contaminants such as HMs, pesticides, drugs, and pharmaceuticals.
Target | Sensing interface | Matrix | LoD | Ref |
---|---|---|---|---|
Hg2+, Cd2+ | Municipal wastewater | 10−20 M and 10−20 M | [77] | |
Pb2+, Cd2+ | PET-SPE | Water | 1 nM for both metals | [78] |
Hg2+ | Cu2O@NCs | River water samples | 0.15 nM | [79] |
Parathion-methyl | Municipal wastewater | 10−20 M | [77] | |
Paraoxon-methyl | Municipal wastewater | 10−18 M | [77] | |
Triazine | Municipal wastewater | 10−20 M | [77] | |
Acetamiprid | Ag-NG/GCE | Wastewater | 0.033 pM | [75] |
Sulphamethoxazole | MIP-decorated Fe3O4 MNPs@SPCE | Seawater | 0.001 nM | [63] |
BPA | AuNPs/PB/CNTs-COOH/GCE | Water | 0.045 pM | [65] |
P4 | ssDNA/Au | Tap water | 0.90 ng mL−1 | [66] |
Applications of EIS in analysis of water.
EIS has been applied for quantitative determination of HMs in water samples. In one of the investigations, a bi-enzymatic biosensor was constructed by immobilizing
In another approach, a three-electrode sensor was printed on a polyethylene terephthalate film (PET) and was applied for impedimetric determination of Pb2+ and Cd2+ in water samples at nanomolar level [78]. An electrochemical DNA biosensor based on microspheres of cuprous oxide (Cu2O) and nano-chitosan (NC) was used for Hg2+ detection in river water samples with a LoD of 0.15 nM [79].
Other contaminants like pesticides and herbicides as well as drugs and pharmaceuticals were also determined using EIS [63, 65, 66, 75, 77] (Table 3).
The literature is rich in articles and reviews that investigate the applications of electrochemical impedance spectroscopy in detections of various contaminants such as heavy metals, drugs, and pharmaceuticals, as well as pesticides. The advantages that impedance spectroscopy introduces as an electrochemical technique are innumerable. High sensitivity, specificity, selectivity, no time or effort consumption, and being label-free are the major advantages reported in the majority of the surveyed literature. As the mentioned contaminants usually exist as traces in complicated matrices, impedance spectroscopy with the mentioned advantages was usually the electrochemical technique of choice for the detection of these contaminants in water, food, and drug matrices.
The authors declare no conflict of interest.
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