Metal ion vs. log βMY values.
\r\n\tThis field has grown exponentially over the past decade resulting in less postoperative pain, risk of complications, and recovery times. Arthroscopy has evolved from a diagnostic tool to a therapeutic tool capable of treating a wide range of injuries and disorders in most of the joints. Many injuries, particularly those that at one time would have been career-ending for athletes, can now be addressed with arthroscopy allowing a quicker return to a competitive level. While arthroscopy has resulted in an overall decrease in morbidity compared with open techniques, it is still an invasive procedure and inherently involves risks.
\r\n\r\n\tWith this book, we attempt to summarize the most common arthroscopic procedures, diagnosis, risks, and complications.
\r\n\tAll of the above aspects are addressed in this book, which describes the current applications of arthroscopy, explaining the mechanisms of injury for each condition, and describing the role of arthroscopy in diagnosis and treatment.
\r\n\t
DNA is constantly damaged by both endogenous and exogenous sources, and genotoxicity can be considered as an imbalance between DNA damage and DNA repair mechanisms. Maintenance of DNA integrity is essential for proper cellular and organismal function, and the capacity to withstand genotoxic challenge is important to avoid long-term genetic instability and population vulnerability. Unrepaired DNA damage can lead to mutations, cellular senescence, apoptosis, progression of cancer, and the process of aging [1]. Mutation is a broad term covering a whole range of changes to the informational molecule, DNA packaged into chromosomes, of an organism from gene changes to modifications of the number and/or structure of chromosomes. Mutagenicity in normal cells is one of the most serious problems due to the possibility of inducing secondary malignancies and abnormal reproductive outcomes such as Down, Klinefelter, and Turner syndromes [2]. Such changes can be assessed directly by measuring the interaction of agents with DNA or more indirectly through the assessment of DNA repair or the production of gene mutations or chromosome alterations.
\nGenotoxicity covers a broader spectrum of endpoints than mutagenicity. For example, unscheduled DNA synthesis, sister chromatid exchanges, and DNA strand breaks are the measures of genotoxicity, not mutagenicity, because they are not themselves transmissible from cell to cell or generation to generation. Mutagenicity on the other hand refers to the production of transmissible genetic alterations. Although all cells of an organism contain the same DNA, somatic cells in different organs and tissues of the adult body become specialized to perform defined functions so that only some parts of the genome are expressed. A common feature of mutations in cancer-causing genes, such as those controlling cell division and proliferation, is that this results in genes being expressed in the wrong tissue at the wrong time. The effect of a mutation will depend upon the position of the mutation within the DNA and the location and activity of the particular gene in which the mutation has been induced. Mutations in the many genes that have been implicated in the multistage events leading to cancer can be produced by a variety of mechanisms and interactions and modifications of the genetic material [2, 3].
\nWith the recent focus on environmental problems, increasing awareness of the harmful effects of industrial and agricultural pollution has created a demand for progressively more sophisticated pollutant and toxicity detection methods. In recent years, there has been a growing concern about the increasing number of environmental pollutants that may disrupt normal endocrine function in exposed humans and animals. Endocrine disrupting compounds comprise a large group of synthetic chemicals that mimic the actions of natural hormones, act as antagonist, or block their synthesis, release, or metabolism. The xenoestrogen bisphenols have received much attention due to their high production volume and widespread human exposure. Recent research in various animal models has shown the genotoxic activity of bisphenols using in vivo and in vitro assays. Nevertheless, notable differences have been reported, leading to opposite conclusions, which may well have been caused by differences in the screening test, the organisms used, and the exposure conditions assayed [4].
\nMany important agricultural products, especially those rich in carbohydrates, are attractive colonization sites for fungi. Some toxic secondary metabolites of fungal growth are identified as mycotoxins and may be found to contaminate agricultural products [5]. Mycotoxins are virtually ubiquitous at some concentration in the average human diet. Mycotoxins are able to resist decomposition or being broken down by mammalian digestion, even by ruminant livestock, allowing these compounds to persist in meat and even dairy products [6]. This gives rise to certain partially metabolized mycotoxins, such as aflatoxin M1, which are present in milk from cows or humans that consumed feed or food contaminated by aflatoxins. Even temperature treatments, such as cooking and freezing, do not inactivate some mycotoxins. This section broadly discusses the genotoxic properties of the environmental genotoxicants bisphenols and aflatoxins, which are prominent environmental contaminates, and is believed to be genotoxic agents that contributes to the high incidence of genotoxicity and carcinogenicity among populations.
\nBisphenols are a group of chemicals known as diphenylmethanes, which contain two benzene rings separated by one central carbon atom, usually with a 4-OH substituent on both benzene rings (e.g., bisphenol A, bisphenol F, bisphenol AF, and bisphenol Z). Bisphenol A is employed to make certain plastics and epoxy resins (Figure 1). In some bisphenols, the central carbon atom is replaced by a sulphone group (e.g., bisphenol S or bisphenol 1) or sulphide moiety (e.g., bisphenol 2). Some bisphenol A analogues seem to be safer alternatives to bisphenol A in industrial applications. For example, the production of bisphenol S, which is stable at high temperatures and resistant to sunlight, is increasing from year to year [7, 8]. The largest US manufacturer of thermal paper has been using bisphenol S as a replacement for bisphenol A since 2006. However, insufficient data are available to tell whether these bisphenol S-containing papers are safer than bisphenol A-containing papers. While bisphenol A is moderately susceptible to environmental breakdown, bisphenol S may be more persistent [9].
\nSome industrial applications of bisphenols.
From the viewpoint of biodegradability in the aquatic environment, bisphenol F is more biodegradable under aerobic and anaerobic conditions than bisphenol A and may replace bisphenol A to lower environmental risks [10]. Bisphenol AF also occurs as a monomer of phenol-formaldehyde resin. Bisphenol AF is a component of certain plasters and used as a rubber bridging material, while bisphenol A is a monomer that is polymerized to manufacture polycarbonate plastic products, epoxy, and polyester resins (Figure 2). Polycarbonate plastics have many applications including use in some food and drink packaging such as water and baby bottles, compact discs, impact-resistant safety equipment, and medical devices including those used in hospital settings. Epoxy resins are used to coat metal products such as food cans, bottle tops, and water supply pipes. Bisphenol A can also be found in certain thermal paper products, including some cash register and ATM receipts. Some dental sealants and composites may also contribute to bisphenol A exposure [11, 12].
\nSynthesis of the polymer polycarbonate from bisphenol A and phosgene.
Human exposure to bisphenols may occur in the workplace through inhalation during production, but the most common route of exposure is by oral intake. Small amounts of bisphenol A are eluted from canned beverages, foods, and baby bottles, especially when heated [12]. At higher temperatures, longer contact with, and higher pH of the contact medium, bisphenol A monomer can hydrolyse and leach into food and beverages. Recent studies also suggest that the public may be exposed to bisphenol A by handling cash register receipts. In accordance with its widespread use in many applications, bisphenol A has been detected in dietary items [13] and human biological samples [14]. Moreover, bisphenol A was detected in environmental media as well [15].
\nIn general, bisphenol A levels in humans have measured well below 50 mg/kg/day, which is the maximum acceptable dose set by the UA EPA [16]. Its ubiquitous presence and widespread distribution have provoked worldwide concerns about its possible association with human diseases such as obesity, diabetes, cardiovascular disease, reproductive disorders, and cancer [17, 18]. Despite its presence in human populations and its association with reproductive and developmental toxicity in animals, most countries have not imposed regulations on the manufacture, import, or sale of bisphenol A products. That has been due largely to conflicting scientific evidence for a direct association between low-level exposure and adverse health effects in humans. Some countries and regions, including Canada, Europe, Sweden, and the United States, on the other hand, have formally banned bisphenol A from infant and children’s products, including, variously, cans of infant formula, baby bottles, and sippy cups. Current efforts are focused on replacing bisphenol A with safer food contact materials. All of these alternative materials need to be assessed for appropriate functionality and safety using state-of-the-art methodology and scientific knowledge.
\nBisphenol A is a known endocrine disruptor compound. While initially considered to be a weak environmental estrogen, several recent publications have demonstrated that bisphenol A may be similar in potency to estradiol in stimulating some cellular responses. Furthermore, emerging evidence suggests that bisphenol A may affect multiple endocrine-related pathways [19]. In men, exposure to endocrine disruptors may be associated with decreased fertility and increased risk of testicular or prostate cancer [20]. In women, exposure may increase the risk of endometriosis, reproductive or other endocrine-related cancers, and impaired oocyte competence, ovarian function, or menstrual cycle [21]. Because females have higher levels of natural estrogens in their blood, the impact of estrogen-like compounds on females may be different from that on males. In women, high urinary bisphenol A levels were associated with reduced antral follicle counts in a cohort of 209 women undergoing infertility treatments [22], whereas no correlation was found between serum bisphenol A levels and antral follicle counts in another study on a smaller cohort of 44 patients [23]. Nevertheless, several data suggest a negative impact of bisphenol A on woman fertility. Urinary bisphenol A levels were negatively correlated with numbers and quality of oocytes retrieved in stimulated cycles for assisted reproduction [24]. Increased urinary or serum bisphenol A concentrations were also associated with decreased peak oestradiol levels [25]. Moreover, a study on 137 patients undergoing assisted reproduction suggested that high urinary bisphenol A levels might be associated with up to 50% higher chance of implantation failures, in comparison with patients with low or no evidence of bisphenol A exposure [26].
\nBecause the chemical structure of bisphenol A is similar to that of diethylstilbestrol, which is carcinogenic to mammals, the possible genotoxicity of bisphenol A has been widely tested in a variety of in vitro and in vivo studies, but the results are controversial. Several studies have shown that bisphenol A can induce chromosome aberrations and DNA adducts formation in Syrian hamster embryo cells [27] or micronuclei formation in human MCL-5 cells [28]. Aneugenic properties were also observed in Chinese hamster V79 cells after bisphenol A exposure [29]. Moreover, in estrogen receptor-positive MCF-7 cells, bisphenol A caused DNA strand breaks that were estrogen receptor-dependent [30]. A recent study has reported that the genotoxic and cytogenetic effects of bisphenol A in Chinese hamster ovary cells were manifested in the form of DNA strand breaks, micronucleus formation, and chromosome aberrations [31]. Conversely, bisphenol A is considered non-genotoxic because it was negative to a set of basic genotoxicity tests. It was not mutagenic in the Salmonella/microsome assay [32], did not induce gene mutations [27, 32] or chromosomal aberrations [33] in mammalian cells in vitro, and failed to induce chromosomal aberrations and micronucleus formation in vivo in mice [34]. Bisphenol A is considered to lead to genotoxicity through oxidative stress. Bisphenol A-3,4-quinone, which is yielded by oxidative metabolism of bisphenol A, may cause genotoxicity by reacting with DNA [35].
\nBy now, there is increasing evidence supports the notion that low bisphenol A concentrations adversely affect the epigenome of mammalian female germ cells, with functional consequences on gene expression, chromosome dynamics in meiosis, and oocyte development and quality [36]. An epigenetic impact of bisphenol A was demonstrated also on male germ cells. Male offspring of rats perinatally exposed to bisphenol A had reduced sperm counts and other changes in phenotypes not only in the first generation but also in the F3 generation [37]. Induction of sperm epimutations and male-mediated trans-generational inheritance of obesity and reproductive disturbances were also shown after bisphenol A exposure of rats [38]. When female mice were exposed during gestation and lactation to low bisphenol A doses deregulated, glucose homeostasis in the F2 generation was observed; decreased global methylation and differential methylation of a specific CpG site in the glucokinase promoter in the F1 sperm suggested that the F2 phenotype could be caused by epigenetic alterations induced in the male paternal germline by bisphenol A prenatal exposure [39].
\nWhile comprehensive information is available about the adverse health impacts of bisphenol A, toxicological properties of alternative bisphenols are yet to be investigated. Alternative bisphenols are structurally similar to bisphenol A, and therefore expected to possess similar biological activities. However, most available toxicological information is limited to endocrine disrupting potentials, and only very little is known about the genotoxicity of alternative bisphenols [7]. In turn, bisphenol F has been reported to induce DNA strand breaks, but not micronuclei, in HepG2 cells [40]. In human HepG2 cells, bisphenol F induced histone H2AX phosphorylation, an indicator of DNA double strand breaks [41]. Moreover, bisphenol F induced metaphase arrest and micronucleus formation in V79 cells [29]. In Syrian hamster embryo cells, bisphenol F did not induce gene mutation or chromosomal aberrations, but induced aneuploidy and morphological changes [42]. Bisphenol A may cause oxidative stress, and induce DNA adduct and aneuploidy in rodents [43]. Nevertheless, eight bisphenols including bisphenol A showed no positive responses based on umu-test suggesting no genotoxicity [44]. Similarly, other alternative bisphenols are expected, but to date, very little efforts have been made on this aspect.
\nWith worldwide increases in population, the need for nutrient-rich food is rising. Contamination of foods by toxins, bacteria, viruses, parasites, allergens, and prions may lead to serious diseases; unhealthy foodstuffs are implicated in approximately one-third of cancer cases. Controlled storage conditions, improved packaging, and strict hygiene regulations for food production, preservation, and distribution are essential to diminish such problems. Aflatoxins are toxic metabolites produced by certain fungi in/on foods and feeds. They are probably the best-known and most intensively researched mycotoxins in the world. The occurrence of aflatoxins is influenced by certain environmental factors; hence, the extent of contamination will vary with geographic location, agricultural, and agronomic practices, and the susceptibility of commodities to fungal invasion during pre-harvest, storage, and/or processing periods. Aflatoxin B1 is a prevalent food pollutant, which is found typically in tropical countries. It imposes great costs on the world’s economy and health [45]. Thus, it is important to eliminate aflatoxin B1 from food resources and prevent production of the toxin. Due to lack of infrastructure, poor and third world countries are the major victims of aflatoxin B1. The established carcinogenesis, teratogenesis, and severe multi-organ toxicity associated with aflatoxin B1 have made it a substantial challenge for scientists [46, 47].
\nSome major sources of aflatoxins.
Aflatoxins are a type of mycotoxin produced by Aspergillus species of fungi, such as A. flavus and A. parasiticus, which grow in soil, decaying vegetation, hay, and grains [48]. Aflatoxins have received greater attention than any other mycotoxins because of their demonstrated potent carcinogenic effect in susceptible laboratory animals and their acute toxicological effects in humans. Aflatoxins are regularly found in improperly stored staple commodities such as cassava, chili peppers, corn, cottonseed, millet, peanuts, rice, sorghum, sunflower seeds, tree nuts, wheat, and a variety of spices (Figure 3). Aflatoxin B1 is highly resistant to traditional detoxification protocols, such as heat, solvents, and radiation, which have consequences for food quality and safety. However, biological procedures using microbial or enzymatic tools that possess great specificity with minimal consequences are the appropriate choices for the treatment of contaminated foodstuffs; they also offer ease of application, affordability, and environmentally friendly behavior. The use of biological procedures requires optimized conditions, such as pH and temperature, for maximum efficiency. When contaminated food is processed, aflatoxins enter the general food supply where they have been found in both pet and human foods, as well as in feed stocks for agricultural animals [49]. Moreover, animals fed contaminated food can pass aflatoxin transformation products into eggs, milk products, and meat. The four major naturally produced aflatoxins are known as aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 (Figure 4), which are based on their fluorescent color when exposed to ultraviolet light on thin-layer chromatography plates (B = blue fluorescence, G = yellow-green fluorescence), while the subscript numbers 1 and 2 indicate major and minor compounds, respectively. Aflatoxin M1 and M2 compounds are not found on cereal products themselves but are metabolites expressed in milk of mammals whose diet was contaminated by aflatoxins B1 and B2, respectively [50].
\nChemical structures of the four major naturally produced aflatoxins: aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2.
Aflatoxins have been reported to have several serious deleterious effects in humans and diverse animals with the species reacting differently to the toxicological effects. The target sites of this toxicant are also diverse and effects include hepatotoxicity, teratogenicity, immunotoxicity, hematological disorders, renal dysfunction, induction of chromosome aberrations, and mutations in somatic and germinal cells of animals and humans [51–53]. Aflatoxin B1, the most toxic, is a potent carcinogen and has been directly correlated with adverse health effects, such as liver cancer, in many animal species. Aflatoxin B1 is one of the major risk factors for the occurrence of liver injury and carcinogenesis, especially when it is combined with hepatitis B infection. Epidemiological investigations revealed that dietary contamination with aflatoxin B1 might be responsible for 5–28% of global hepatocellular carcinoma cases [54]. A great deal of evidence has demonstrated that aflatoxin B1 belongs to the indirect-acting carcinogens. Aflatoxin B1 is mainly metabolized in the liver to produce the genotoxic intermediate aflatoxin B1-exo-8,9-epoxide by the liver-specific cytochrome P450 enzymes, P4501A2, and 3A4. These epoxides can form aflatoxin B1-guanine adducts by binding covalently to DNA, thereby introducing GC-TA transversion that leads to DNA mutations and genomic instability [55]. For instance, a frequent hotspot mutation at codon 249 in the human p53 gene gives rise to a Ser to Arg substitution in the p53 protein that decreases its tumor suppressor activity [56]. Another major detoxification pathway of aflatoxin B1 in mammalian species is the glutathione conjugation of aflatoxin B1-8,9-epoxide, which is catalyzed by glutathione S-transferases [57]. Experimental studies conducted in rats have shown that rGSTA5, barely expressed in adult male liver, exhibits a greater activity toward aflatoxin B1-8,9-epoxide than other glutathione S-transferases subunits [58].
\nAflatoxin B1 is a clastogen that has been tested for genotoxicity in vivo and in vitro and giving consistently positive results. It induces chromosomal aberrations, micronuclei formation, sister chromatid exchanges, and DNA strand breaks in several published works [53, 59–61]. An important mechanism responsible for the genotoxic potential of aflatoxin B1 is the formation of DNA adducts. Biotransformation plays a crucial role in the toxicity and carcinogenicity of aflatoxin B1. The enzymatic detoxification of aflatoxin B1 was studied [62], and the pro-oxidant properties and mutagenicity of the detoxification products were compared with those of aflatoxin B1. The results indicated that the metabolized aflatoxin B1 was more toxic than the non-metabolized form of it. A previous study also demonstrated that an epoxide metabolite had an important role in aflatoxin B1-mediated genotoxicity [63]. In the Ames mutagenicity test, the T98 strain exhibits a frame-shift mutation, and T100 exhibits a base-pair substitution. Virtually, all of aflatoxin B1 toxic and carcinogenic effects are attributable to the action of its reactive metabolites that are capable of reacting with cellular macromolecules such as DNA [64]. Furthermore, DNA repair activity and modulation of repair by aflatoxin B1 seem to be also major determinants of susceptibility to aflatoxin B1-induced carcinogenesis [61].
\nSince the discovery of these deleterious effects induced by aflatoxin B1, a large number of studies have explored the mechanisms and pathways involved in aflatoxin B1-mediated genotoxicity. However, few studies have focused on the epigenetic events involved in the induction of genotoxicity. Recently, several studies reported that cellular epigenetic aberrant changes, such as DNA methylation, histone modifications, and miRNA profiling alterations, also contributed to the hepatotoxicity and genotoxicity induced by chemical toxicants. A genome-wide miRNA-profiling analysis in an acute rat liver injury model induced by aflatoxin B1 predicted that several miRNAs and their potential targets were relevant to acute hepatotoxicity, although functional tests were not performed [65]. However, it is clear from gene expression profiling that the pathways involved in acute poisoning and chronic poisoning are not completely consistent. A recent study investigated alterations in miRNA profiles of rat liver tissues by Illumina deep sequencing and evaluated their roles in aflatoxin B1-induced hepatocellular genotoxicity and hepatotoxicity [66]. The authors demonstrated alterations in the miRNA profile in rat liver tissue, including rnomiR-34a-5p, rno-miR-200b-3p, rno-miR-429, and rno-miR-130a-3p, after aflatoxin B1 exposure. Functional tests showed that the increase in miR-34a-5p by p53 activation after aflatoxin B1 exposure led to cell cycle arrest via inhibiting cell cycle-related genes and affecting the micronuclei formation induced by aflatoxin B1, indicating that rno-miR-34a-5p played a critical role in aflatoxin B1-induced rat hepatogenotoxicity. Furthermore, the combination of circulating miR-34a-5p and the aflatoxin B1 level may be considered as a sensitive method for the detection of the genotoxic stress induced by chronic aflatoxin B1 exposure.
\nAs it is realized that absolute safety is never achieved, many countries have attempted to limit exposure to aflatoxins by imposing regulatory limits on commodities intended for use as food and feed [67]. The FDA has established specific guidelines on acceptable levels of aflatoxins in human food and animal feed by establishing action levels that allow for the removal of violate lots from commerce. The action level for human food is 20 ppb total aflatoxins, with the exception of milk, which has an action level of 0.5 ppb for aflatoxin M1. The action level for most feeds is also 20 ppb. However, it is very difficult to accurately estimate aflatoxins concentration in a large quantity of material because of the variability associated with testing procedures; hence, the true aflatoxin concentration in a lot cannot be determined with 100% certainty. However, the ability of aflatoxin-producing fungi to grow on a wide range of food commodities and the stability of aflatoxins in foods mean that control is best achieved by measures designed to prevent the contamination of crops in the field and during storage, or detection and removal of contaminated material from the food supply chain.
\nThis work was funded by the National Plane for Science, Technology, and Innovation (MAARIFAH), King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia, Award Number (12-MED2648-02).
\nStability constant of the formation of metal complexes is used to measure interaction strength of reagents. From this process, metal ion and ligand interaction formed the two types of metal complexes; one is supramolecular complexes known as host-guest complexes [1] and the other is anion-containing complexes. In the solution it provides and calculates the required information about the concentration of metal complexes.
Solubility, light, absorption conductance, partitioning behavior, conductance, and chemical reactivity are the complex characteristics which are different from their components. It is determined by various numerical and graphical methods which calculate the equilibrium constants. This is based on or related to a quantity, and this is called the complex formation function.
During the displacement process at the time of metal complex formation, some ions disappear and form a bonding between metal ions and ligands. It may be considered due to displacement of a proton from a ligand species or ions or molecules causing a drop in the pH values of the solution [2]. Irving and Rossotti developed a technique for the calculation of stability constant, and it is called potentiometric technique.
To determine the stability constant, Bjerrum has used a very simple method, and that is metal salt solubility method. For the studies of a larger different variety of polycarboxylic acid-, oxime-, phenol-containing metal complexes, Martel and Calvin used the potentiometric technique for calculating the stability constant. Those ligands [3, 4] which are uncharged are also examined, and their stability constant calculations are determined by the limitations inherent in the ligand solubility method. The limitations of the metal salt solubility method and the result of solubility methods are compared with this. M-L, MLM, and (M3) L are some types of examples of metal-ligand bonding. One thing is common, and that is these entire types metal complexes all have one ligand.
The solubility method can only usefully be applied to studies of such complexes, and it is best applied for ML; in such types of system, only ML is formed. Jacqueline Gonzalez and his co-worker propose to explore the coordination chemistry of calcium complexes. Jacqueline and et al. followed this technique for evaluate the as partial model of the manganese-calcium cluster and spectrophotometric studies of metal complexes, i.e., they were carried calcium(II)-1,4-butanediamine in acetonitrile and calcium(II)-1,2-ethylendiamine, calcium(II)-1,3-propanediamine by them.
Spectrophotometric programming of HypSpec and received data allows the determination of the formation of solubility constants. The logarithmic values, log β110 = 5.25 for calcium(II)-1,3-propanediamine, log β110 = 4.072 for calcium(II)-1,4-butanediamine, and log β110 = 4.69 for calcium(II)-1,2-ethylendiamine, are obtained for the formation constants [5]. The structure of Cimetidine and histamine H2-receptor is a chelating agent. Syed Ahmad Tirmizi has examined Ni(II) cimetidine complex spectrophotometrically and found an absorption peak maximum of 622 nm with respect to different temperatures.
Syed Ahmad Tirmizi have been used to taken 1:2 ratio of metal and cimetidine compound for the formation of metal complex and this satisfied by molar ratio data. The data, 1.40–2.4 × 108, was calculated using the continuous variation method and stability constant at room temperature, and by using the mole ratio method, this value at 40°C was 1.24–2.4 × 108. In the formation of lead(II) metal complexes with 1-(aminomethyl) cyclohexene, Thanavelan et al. found the formation of their binary and ternary complexes. Glycine,
Using the stability constant method, these ternary complexes were found out, and using the parameters such as Δ log K and log X, these ternary complex data were compared with binary complex. The potentiometric technique at room temperature (25°C) was used in the investigation of some binary complex formations by Abdelatty Mohamed Radalla. These binary complexes are formed with 3D transition metal ions like Cu2+, Ni2+, Co2+, and Zn2+ and gallic acid’s importance as a ligand and 0.10 mol dm−3 of NaNO3. Such types of aliphatic dicarboxylic acids are very important biologically. Many acid-base characters and the nature of using metal complexes have been investigated and discussed time to time by researchers [7].
The above acids (gallic and aliphatic dicarboxylic acid) were taken to determine the acidity constants. For the purpose of determining the stability constant, binary and ternary complexes were carried in the aqueous medium using the experimental conditions as stated above. The potentiometric pH-metric titration curves are inferred for the binary complexes and ternary complexes at different ratios, and formation of ternary metal complex formation was in a stepwise manner that provided an easy way to calculate stability constants for the formation of metal complexes.
The values of Δ log K, percentage of relative stabilization (% R. S.), and log X were evaluated and discussed. Now it provides the outline about the various complex species for the formation of different solvents, and using the concentration distribution, these complexes were evaluated and discussed. The conductivity measurements have ascertained for the mode of ternary chelating complexes.
A study by Kathrina and Pekar suggests that pH plays an important role in the formation of metal complexes. When epigallocatechin gallate and gallic acid combine with copper(II) to form metal complexes, the pH changes its speculation. We have been able to determine its pH in frozen and fluid state with the help of multifrequency EPR spectroscopy [8]. With the help of this spectroscopy, it is able to detect that each polyphenol exhibits the formation of three different mononuclear species. If the pH ranges 4–8 for di- or polymeric complex of Cu(II), then it conjectures such metal complexes. It is only at alkaline pH values.
The line width in fluid solutions by molecular motion exhibits an incomplete average of the parameters of anisotropy spin Hamilton. If the complexes are different, then their rotational correlation times for this also vary. The analysis of the LyCEP anisotropy of the fluid solution spectra is performed using the parameters determined by the simulation of the rigid boundary spectra. Its result suggests that pH increases its value by affecting its molecular mass. It is a polyphenol ligand complex with copper, showing the coordination of an increasing number of its molecules or increasing participation of polyphenol dimers used as ligands in the copper coordination region.
The study by Vishenkova and his co-worker [8] provides the investigation of electrochemical properties of triphenylmethane dyes using a voltammetric method with constant-current potential sweep. Malachite green (MG) and basic fuchsin (BF) have been chosen as representatives of the triphenylmethane dyes [9]. The electrochemical behavior of MG and BF on the surface of a mercury film electrode depending on pH, the nature of background electrolyte, and scan rate of potential sweep has been investigated.
Using a voltammetric method with a constant-current potential sweep examines the electrical properties of triphenylmethane dye. In order to find out the solution of MG and BF, certain registration conditions have been prescribed for it, which have proved to be quite useful. The reduction peak for the currents of MG and BF has demonstrated that it increases linearly with respect to their concentration as 9.0 × 10−5–7.0 × 10−3 mol/dm3 for MG and 6.0 × 10−5–8.0 × 10−3 mol/dm3 for BF and correlation coefficients of these values are 0.9987 for MG and 0.9961 for BF [10].
5.0 × 10−5 and 2.0 × 10−5 mol/dm3 are the values used as the detection limit of MG and BF, respectively. Stability constants are a very useful technique whose size is huge. Due to its usefulness, it has acquired an umbrella right in the fields of chemistry, biology, and medicine. No science subject is untouched by this. Stability constants of metal complexes are widely used in the various areas like pharmaceuticals as well as biological processes, separation techniques, analytical processes, etc. In the presented chapter, we have tried to explain this in detail by focusing our attention on the applications and solutions of stability of metal complexes in solution.
Stability or formation or binding constant is the type of equilibrium constant used for the formation of metal complexes in the solution. Acutely, stability constant is applicable to measure the strength of interactions between the ligands and metal ions that are involved in complex formation in the solution [11]. A generally these 1-4 equations are expressed as the following ways:
Thus
K1, K2, K3, … Kn are the equilibrium constants and these are also called stepwise stability constants. The formation of the metal-ligand-n complex may also be expressed as equilibrium constants by the following steps:
The parameters K and β are related together, and these are expressed in the following example:
Now the numerator and denominator are multiplied together with the use of [metal-ligand] [metal-ligand2], and after the rearranging we get the following equation:
Now we expressed it as the following:
From the above relation, it is clear that the overall stability constant βn is equal to the product of the successive (i.e., stepwise) stability constants, K1, K2, K3,…Kn. This in other words means that the value of stability constants for a given complex is actually made up of a number of stepwise stability constants. The term stability is used without qualification to mean that the complex exists under a suitable condition and that it is possible to store the complex for an appreciable amount of time. The term stability is commonly used because coordination compounds are stable in one reagent but dissociate or dissolve in the presence of another regent. It is also possible that the term stability can be referred as an action of heat or light or compound. The stability of complex [13] is expressed qualitatively in terms of thermodynamic stability and kinetic stability.
In a chemical reaction, chemical equilibrium is a state in which the concentration of reactants and products does not change over time. Often this condition occurs when the speed of forward reaction becomes the same as the speed of reverse reaction. It is worth noting that the velocities of the forward and backward reaction are not zero at this stage but are equal.
If hydrogen and iodine are kept together in molecular proportions in a closed process vessel at high temperature (500°C), the following action begins:
In this activity, hydrogen iodide is formed by combining hydrogen and iodine, and the amount of hydrogen iodide increases with time. In contrast to this action, if the pure hydrogen iodide gas is heated to 500°C in the reaction, the compound is dissolved by reverse action, which causes hydrogen iodide to dissolve into hydrogen and iodine, and the ratio of these products increases over time. This is expressed in the following reaction:
For the formation of metal chelates, the thermodynamic technique provides a very significant information. Thermodynamics is a very useful technique in distinguishing between enthalpic effects and entropic effects. The bond strengths are totally effected by enthalpic effect, and this does not make any difference in the whole solution in order/disorder. Based on thermodynamics the chelate effect below can be best explained. The change of standard Gibbs free energy for equilibrium constant is response:
Where:
R = gas constant
T = absolute temperature
At 25°C,
ΔG = (− 5.708 kJ mol−1) · log β.
The enthalpy term creates free energy, i.e.,
For metal complexes, thermodynamic stability and kinetic stability are two interpretations of the stability constant in the solution. If reaction moves from reactants to products, it refers to a change in its energy as shown in the above equation. But for the reactivity, kinetic stability is responsible for this system, and this refers to ligand species [14].
Stable and unstable are thermodynamic terms, while labile and inert are kinetic terms. As a rule of thumb, those complexes which react completely within about 1 minute at 25°C are considered labile, and those complexes which take longer time than this to react are considered inert. [Ni(CN)4]2− is thermodynamically stable but kinetically inert because it rapidly exchanges ligands.
The metal complexes [Co(NH3)6]3+ and such types of other complexes are kinetically inert, but these are thermodynamically unstable. We may expect the complex to decompose in the presence of acid immediately because the complex is thermodynamically unstable. The rate is of the order of 1025 for the decomposition in acidic solution. Hence, it is thermodynamically unstable. However, nothing happens to the complex when it is kept in acidic solution for several days. While considering the stability of a complex, always the condition must be specified. Under what condition, the complex which is stable or unstable must be specified such as acidic and also basic condition, temperature, reactant, etc.
A complex may be stable with respect to a particular condition but with respect to another. In brief, a stable complex need not be inert and similarly, and an unstable complex need not be labile. It is the measure of extent of formation or transformation of complex under a given set of conditions at equilibrium [15].
Thermodynamic stability has an important role in determining the bond strength between metal ligands. Some complexes are stable, but as soon as they are introduced into aqueous solution, it is seen that these complexes have an effect on stability and fall apart. For an example, we take the [Co (SCN)4]2+ complex. The ion bond of this complex is very weak and breaks down quickly to form other compounds. But when [Fe(CN)6]3− is dissolved in water, it does not test Fe3+ by any sensitive reagent, which shows that this complex is more stable in aqueous solution. So it is indicated that thermodynamic stability deals with metal-ligand bond energy, stability constant, and other thermodynamic parameters.
This example also suggests that thermodynamic stability refers to the stability and instability of complexes. The measurement of the extent to which one type of species is converted to another species can be determined by thermodynamic stability until equilibrium is achieved. For example, tetracyanonickelate is a thermodynamically stable and kinetic labile complex. But the example of hexa-amine cobalt(III) cation is just the opposite:
Thermodynamics is used to express the difference between stability and inertia. For the stable complex, large positive free energies have been obtained from ΔG0 reaction. The ΔH0, standard enthalpy change for this reaction, is related to the equilibrium constant, βn, by the well thermodynamic equation:
For similar complexes of various ions of the same charge of a particular transition series and particular ligand, ΔS0 values would not differ substantially, and hence a change in ΔH0 value would be related to change in βn values. So the order of values of ΔH0 is also the order of the βn value.
Kinetic stability is referred to the rate of reaction between the metal ions and ligand proceeds at equilibrium or used for the formation of metal complexes. To take a decision for kinetic stability of any complexes, time is a factor which plays an important role for this. It deals between the rate of reaction and what is the mechanism of this metal complex reaction.
As we discuss above in thermodynamic stability, kinetic stability is referred for the complexes at which complex is inert or labile. The term “inert” was used by Tube for the thermally stable complex and for reactive complexes the term ‘labile’ used [16]. The naturally occurring chlorophyll is the example of polydentate ligand. This complex is extremely inert due to exchange of Mg2+ ion in the aqueous media.
The nature of central atom of metal complexes, dimension, its degree of oxidation, electronic structure of these complexes, and so many other properties of complexes are affected by the stability constant. Some of the following factors described are as follows.
In the coordination chemistry, metal complexes are formed by the interaction between metal ions and ligands. For these type of compounds, metal ions are the coordination center, and the ligand or complexing agents are oriented surrounding it. These metal ions mostly are the transition elements. For the determination of stability constant, some important characteristics of these metal complexes may be as given below.
Ligands are oriented around the central metal ions in the metal complexes. The sizes of these metal ions determine the number of ligand species that will be attached or ordinated (dative covalent) in the bond formation. If the sizes of these metal ions are increased, the stability of coordination compound defiantly decreased. Zn(II) metal ions are the central atoms in their complexes, and due to their lower size (0.74A°) as compared to Cd(II) size (0.97A°), metal ions are formed more stable.
Hence, Al3+ ion has the greatest nuclear charge, but its size is the smallest, and the ion N3− has the smallest nuclear charge, and its size is the largest [17]. Inert atoms like neon do not participate in the formation of the covalent or ionic compound, and these atoms are not included in isoelectronic series; hence, it is not easy to measure the radius of this type of atoms.
The properties of stability depend on the size of the metal ion used in the complexes and the total charge thereon. If the size of these metal ions is small and the total charge is high, then their complexes will be more stable. That is, their ratio will depend on the charge/radius. This can be demonstrated through the following reaction:
An ionic charge is the electric charge of an ion which is formed by the gain (negative charge) or loss (positive charge) of one or more electrons from an atom or group of atoms. If we talk about the stability of the coordination compounds, we find that the total charge of their central metal ions affects their stability, so when we change their charge, their stability in a range of constant can be determined by propagating of error [18]. If the charge of the central metal ion is high and the size is small, the stability of the compound is high:
In general, the most stable coordination bonds can cause smaller and highly charged rations to form more stable coordination compounds.
When an electron pair attracts a central ion toward itself, a strong stability complex is formed, and this is due to electron donation from ligand → metal ion. This donation process is increasing the bond stability of metal complexes exerted the polarizing effect on certain metal ions. Li+, Na+, Mg2+, Ca2+, Al3+, etc. are such type of metal cation which is not able to attract so strongly from a highly electronegative containing stable complexes, and these atoms are O, N, F, Au, Hg, Ag, Pd, Pt, and Pb. Such type of ligands that contains P, S, As, Br and I atom are formed stable complex because these accepts electron from M → π-bonding. Hg2+, Pb2+, Cd2+, and Bi3+ metal ions are also electronegative ions which form insoluble salts of metal sulfide which are insoluble in aqueous medium.
Volatile ligands may be lost at higher temperature. This is exemplified by the loss of water by hydrates and ammonia:
The transformation of certain coordination compounds from one to another is shown as follows:
A ligand is an ion or small molecule that binds to a metal atom (in chemistry) or to a biomolecule (in biochemistry) to form a complex, such as the iron-cyanide coordination complex Prussian blue or the iron-containing blood-protein hemoglobin. The ligands are arranged in spectrochemical series which are based on the order of their field strength. It is not possible to form the entire series by studying complexes with a single metal ion; the series has been developed by overlapping different sequences obtained from spectroscopic studies [19]. The order of common ligands according to their increasing ligand field strength is
The above spectrochemical series help us to for determination of strength of ligands. The left last ligand is as weaker ligand. These weaker ligand cannot forcible binding the 3d electron and resultant outer octahedral complexes formed. It is as-
Increasing the oxidation number the value of Δ increased.
Δ increases from top to bottom.
However, when we consider the metal ion, the following two useful trends are observed:
Δ increases with increasing oxidation number.
Δ increases down a group. For the determination of stability constant, the nature of the ligand plays an important role.
The following factors described the nature of ligands.
The size and charge are two factors that affect the production of metal complexes. The less charges and small sizes of ligands are more favorable for less stable bond formation with metal and ligand. But if this condition just opposite the product of metal and ligand will be a more stable compound. So, less nuclear charge and more size= less stable complex whereas if more nuclear charge and small in size= less stable complex. We take fluoride as an example because due to their smaller size than other halide and their highest electro negativity than the other halides formed more stable complexes. So, fluoride ion complexes are more stable than the other halides:
As compared to S2− ion, O22− ions formed more stable complexes.
It is suggested by Calvin and Wilson that the metal complexes will be more stable if the basic character or strength of ligands is higher. It means that the donating power of ligands to central metal ions is high [20].
It means that the donating power of ligands to central metal ions is high. In the case of complex formation of aliphatic diamines and aromatic diamines, the stable complex is formed by aliphatic diamines, while an unstable coordination complex is formed with aromatic diamines. So, from the above discussion, we find that the stability will be grater if the e-donation power is greater.
Thus it is clear that greater basic power of electron-donating species will form always a stable complex. NH3, CN−, and F− behaved as ligands and formed stable complexes; on the other hand, these are more basic in nature.
We know that if the concentration of coordination group is higher, these coordination compounds will exist in the water as solution. It is noted that greater coordinating tendency show the water molecules than the coordinating group which is originally present. SCN− (thiocynate) ions are present in higher concentration; with the Co2+ metal ion, it formed a blue-colored complex which is stable in state, but on dilution of water medium, a pink color is generated in place of blue, or blue color complex is destroyed by [Co(H2O)6]2+, and now if we added further SCN−, the pink color will not appear:
Now it is clear that H2O and SCN− are in competition for the formation of Co(II) metal-containing complex compound. In the case of tetra-amine cupric sulfate metal complex, ammonia acts as a donor atom or ligand. If the concentration of NH3 is lower in the reaction, copper hydroxide is formed but at higher concentration formed tetra-amine cupric sulfate as in the following reaction:
For a metal ion, chelating ligand is enhanced and affinity it and this is known as chelate effect and compared it with non-chelating and monodentate ligand or the multidentate ligand is acts as chelating agent. Ethylenediamine is a simple chelating agent (Figure 1).
Structure of ethylenediamine.
Due to the bidentate nature of ethylenediamine, it forms two bonds with metal ion or central atom. Water forms a complex with Ni(II) metal ion, but due to its monodentate nature, it is not a chelating ligand (Figures 2 and 3).
Structure of chelating configuration of ethylenediamine ligand.
Structure of chelate with three ethylenediamine ligands.
The dentate cheater of ligand provides bonding strength to the metal ion or central atom, and as the number of dentate increased, the tightness also increased. This phenomenon is known as chelating effect, whereas the formation of metal complexes with these chelating ligands is called chelation:
or
Some factors are of much importance for chelation as follows.
The sizes of the chelating ring are increased as well as the stability of metal complex decreased. According to Schwarzenbach, connecting bridges form the chelating rings. The elongated ring predominates when long bridges connect to the ligand to form a long ring. It is usually observed that an increased a chelate ring size leads to a decrease in complex stability.
He interpreted this statement. The entropy of complex will be change if the size of chelating ring is increased, i.e., second donor atom is allowed by the chelating ring. As the size of chelating ring increased, the stability should be increased with entropy effect. Four-membered ring compounds are unstable, whereas five-membered are more stable. So the chelating ring increased its size and the stability of the formed metal complexes.
The number of chelating rings also decides the stability of complexes. Non-chelating metal compounds are less stable than chelating compounds. These numbers increase the thermodynamic volume, and this is also known as an entropy term. In recent years ligands capable of occupying as many as six coordination positions on a single metal ion have been described. The studies on the formation constants of coordination compounds with these ligands have been reported. The numbers of ligand or chelating agents are affecting the stability of metal complexes so as these numbers go up and down, the stability will also vary with it.
For the Ni(II) complexes with ethylenediamine as chelating agent, its log K1 value is 7.9 and if chelating agents are trine and penten, then the log K1 values are 7.9 and 19.3, respectively. If the metal ion change Zn is used in place of Ni (II), then the values of log K1 for ethylenediamine, trine, and penten are 6.0, 12.1, and 16.2, respectively. The log βMY values of metal ions are given in Table 1.
Metal ion | log βMY (25°C, I = 0.1 M) |
---|---|
Ca2+ | 11.2 |
Cu2+ | 19.8 |
Fe3+ | 24.9 |
Metal ion vs. log βMY values.
Ni(NH3)62+ is an octahedral metal complex, and at 25 °C its log β6 value is 8.3, but Ni(ethylenediamine)32+ complex is also octahedral in geometry, with 18.4 as the value of log β6. The calculated stability value of Ni(ethylenediamine)32+ 1010 times is more stable because three rings are formed as chelating rings by ethylenediamine as compared to no such ring is formed. Ethylenediaminetetraacetate (EDTA) is a hexadentate ligand that usually formed stable metal complexes due to its chelating power.
A special effect in molecules is when the atoms occupy space. This is called steric effect. Energy is needed to bring these atoms closer to each other. These electrons run away from near atoms. There can be many ways of generating it. We know the repulsion between valence electrons as the steric effect which increases the energy of the current system [21]. Favorable or unfavorable any response is created.
For example, if the static effect is greater than that of a product in a metal complex formation process, then the static increase would favor this reaction. But if the case is opposite, the skepticism will be toward retardation.
This effect will mainly depend on the conformational states, and the minimum steric interaction theory can also be considered. The effect of secondary steric is seen on receptor binding produced by an alternative such as:
Reduced access to a critical group.
Stick barrier.
Electronic resonance substitution bond by repulsion.
Population of a conformer changes due to active shielding effect.
The macrocyclic effect is exactly like the image of the chelate effect. It means the principle of both is the same. But the macrocyclic effect suggests cyclic deformation of the ligand. Macrocyclic ligands are more tainted than chelating agents. Rather, their compounds are more stable due to their cyclically constrained constriction. It requires some entropy in the body to react with the metal ion. For example, for a tetradentate cyclic ligand, we can use heme-B which forms a metal complex using Fe+2 ions in biological systems (Figure 4).
Structure of hemoglobin is the biological complex compound which contains Fe(II) metal ion.
The n-dentate chelating agents play an important role for the formation of more stable metal complexes as compared to n-unidentate ligands. But the n-dentate macrocyclic ligand gives more stable environment in the metal complexes as compared to open-chain ligands. This change is very favorable for entropy (ΔS) and enthalpy (ΔH) change.
There are so many parameters to determination of formation constants or stability constant in solution for all types of chelating agents. These numerous parameters or techniques are refractive index, conductance, temperature, distribution coefficients, refractive index, nuclear magnetic resonance volume changes, and optical activity.
Solubility products are helpful and used for the insoluble salt that metal ions formed and complexes which are also formed by metal ions and are more soluble. The formation constant is observed in presence of donor atoms by measuring increased solubility.
To determine the solubility constant, it involves the distribution of the ligands or any complex species; metal ions are present in two immiscible solvents like water and carbon tetrachloride, benzene, etc.
In this method metal ions or ligands are present in solution and on exchanger. A solid polymers containing with positive and negative ions are ion exchange resins. These are insoluble in nature. This technique is helpful to determine the metal ions in resin phase, liquid phase, or even in radioactive metal. This method is also helpful to determine the polarizing effect of metal ions on the stability of ligands like Cu(II) and Zn(II) with amino acid complex formation.
At the equilibrium free metal and ions are present in the solution, and using the different electrometric techniques as described determines its stability constant.
This method is based upon the titration method or follows its principle. A stranded acid-base solution used as titrate and which is titrated, it may be strong base or strong acid follows as potentiometrically. The concentration of solution using 103− M does not decomposed during the reaction process, and this method is useful for protonated and nonprotonated ligands.
This is the graphic method used to determine the stability constant in producing metal complex formation by plotting a polarograph between the absences of substances and the presence of substances. During the complex formation, the presence of metal ions produced a shift in the half-wave potential in the solution.
If a complex is relatively slow to form and also decomposes at measurable rate, it is possible, in favorable situations, to determine the equilibrium constant.
This involves the study of the equilibrium constant of slow complex formation reactions. The use of tracer technique is extremely useful for determining the concentrations of dissociation products of the coordination compound.
This method is based on the study of the effect of an equilibrium concentration of some ions on the function at a definite organ of a living organism. The equilibrium concentration of the ion studied may be determined by the action of this organ in systems with complex formation.
The solution of 25 ml is adopted by preparing at the 1.0 × 10−5 M ligand or 1.0 × 10−5 M concentration and 1.0 × 10−5 M for the metal ion:
The solutions containing the metal ions were considered both at a pH sufficiently high to give almost complete complexation and at a pH value selected in order to obtain an equilibrium system of ligand and complexes.
In order to avoid modification of the spectral behavior of the ligand due to pH variations, it has been verified that the range of pH considered in all cases does not affect absorbance values. Use the collected pH values adopted for the determinations as well as selected wavelengths. The ionic strengths calculated from the composition of solutions allowed activity coefficient corrections. Absorbance values were determined at wavelengths in the range 430–700 nm, every 2 nm.
For a successive metal complex formation, use this method. If ligand is protonate and the produced complex has maximum number of donate atoms of ligands, a selective light is absorbed by this complex, while for determination of stability constant, it is just known about the composition of formed species.
Bjerrum (1941) used the method stepwise addition of the ligands to coordination sphere for the formation of complex. So, complex metal–ligand-n forms as the following steps [22]. The equilibrium constants, K1, K2, K3, … Kn are called stepwise stability constants. The formation of the complex metal-ligandn may also be expressed by the following steps and equilibrium constants.
Where:
M = central metal cation
L = monodentate ligand
N = maximum coordination number for the metal ion M for the ligand
If a complex ion is slow to reach equilibrium, it is often possible to apply the method of isotopic dilution to determine the equilibrium concentration of one or more of the species. Most often radioactive isotopes are used.
This method was extensively used by Werner and others to study metal complexes. In the case of a series of complexes of Co(III) and Pt(IV), Werner assigned the correct formulae on the basis of their molar conductance values measured in freshly prepared dilute solutions. In some cases, the conductance of the solution increased with time due to a chemical change, e.g.,
It is concluded that the information presented is very important to determine the stability constant of the ligand metal complexes. Some methods like spectrophotometric method, Bjerrum’s method, distribution method, ion exchange method, electrometric techniques, and potentiometric method have a huge contribution in quantitative analysis by easily finding the stability constants of metal complexes in aqueous solutions.
All the authors thank the Library of University of Delhi for reference books, journals, etc. which helped us a lot in reviewing the chapter.
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Today his focus is on defining the growth and development strategy for the company.",institutionString:null,institution:{name:"TU Wien",country:{name:"Austria"}}},{id:"19816",title:"Prof.",name:"Alexander",middleName:null,surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/19816/images/1607_n.jpg",biography:"Alexander I. Kokorin: born: 1947, Moscow; DSc., PhD; Principal Research Fellow (Research Professor) of Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow.\r\nArea of research interests: physical chemistry of complex-organized molecular and nanosized systems, including polymer-metal complexes; the surface of doped oxide semiconductors. 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