In vitro hypoglycemic potentials of ginger and its bioactive constituents.
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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
\n'}],latestNews:[{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"}]},book:{item:{type:"book",id:"215",leadTitle:null,fullTitle:"Aeronautics and Astronautics",title:"Aeronautics and Astronautics",subtitle:null,reviewType:"peer-reviewed",abstract:"In its first centennial, aerospace has matured from a pioneering activity to an indispensable enabler of our daily life activities. In the next twenty to thirty years, aerospace will face a tremendous challenge - the development of flying objects that do not depend on fossil fuels. The twenty-three chapters in this book capture some of the new technologies and methods that are currently being developed to enable sustainable air transport and space flight. 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His research interests are twofold. He studies manual control cybernetics and its use in modelling pilot perception and performance, in particular the modelling of pilot self-motion perception and neuromuscular system characteristics. Secondly, he investigates cognitive systems engineering and its application in the design of ecological human-machine systems for pilots and air traffic controllers. Max teaches several graduate courses on stochastic signal analysis and stochastic control systems, avionics, human-machine systems and air traffic management. 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\r\n\tThis book will focus on the wide specter of mucosal inflammation intending to provide the reader with a comprehensive overview of the current knowledge on the topic. More and more studies are focused on finding different aspects of mucosal inflammation since it is involved in the pathogenesis of many diseases - from gut to lungs, urogenital system, etc. To better understand the causes of its occurrence as well as the search for therapeutic strategies, many resources are invested in scientific developments in this field.
\r\n\r\n\tFacts about the role of calprotectin and other biomarkers were accumulated. Participation of neutrophils appears an attractive way to explain the involvement of different subpopulations of immunocompetent cells and cytokines in mucosal inflammation. Over the last five years, scientific developments in the field have discovered more genes involved in the pathogenesis of mucosal inflammation elucidating the interaction of innate immune mechanisms with the microorganisms in the gut and their role in maintaining intestinal homeostasis. Besides, the science aims at identifying and characterizing immune and non-immune cells involved in the emergence and maintenance of chronic inflammation.
\r\n\r\n\tThe book aims to cover the developing diagnostic methods for identifying the mucosal inflammation, towards a better analysis of the inflammation, understanding of the relationship between genetic and proteomic markers and response to therapy; and improving therapeutic options for patients who have mucosal inflammation.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"2e7bde3621cdf64518356b76e3132542",bookSignature:"Dr. Tsvetelina Velikova",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8843.jpg",keywords:"Inflammation, Neutrophils, Cytokines, Mucosal Biomarkers, Gut Tolerance, Antigen Tolerance, Mayo Score, Lesions, Acute Inflammation, Chronic Inflammation, Gut Permeability, Asthma",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 16th 2020",dateEndSecondStepPublish:"July 7th 2020",dateEndThirdStepPublish:"September 5th 2020",dateEndFourthStepPublish:"November 24th 2020",dateEndFifthStepPublish:"January 23rd 2021",remainingDaysToSecondStep:"8 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:"Dr. Velikova research focuses on autoimmune disorders, such as celiac disease, IBD, diabetes, asthma, as well as on the delicate autoimmunity mechanisms involving Th17 and Treg cells, cytokines, biomarkers, novel biologic therapies. She has been engaged in fifteen projects in the field of immunology and internal medicine. She is an editorial board member and reviewer for several medical journals and has publications in eminent journals and book chapters in the field of gastrointestinal immunology.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"180979",title:"Dr.",name:"Tsvetelina",middleName:null,surname:"Velikova",slug:"tsvetelina-velikova",fullName:"Tsvetelina Velikova",profilePictureURL:"https://mts.intechopen.com/storage/users/180979/images/system/180979.jpg",biography:"Dr. Tsvetelina Velikova received her MD and Ph.D. degrees, both with honors, from the Medical University of Sofia, Bulgaria. Subsequently, she became involved in active immunology research and teaching. Dr. Velikova also received advanced training in Clinical Immunology at University Hospital St. Ivan Rilski, Sofia, Bulgaria. \r\nShe is currently an assistant professor of Clinical immunology affiliated to the Sofia University and University Hospital Lozenetz, Bulgaria. \r\nHer research focuses on autoimmune disorders, such as celiac disease, IBD, diabetes, asthma, as well as on the delicate autoimmunity mechanisms involving Th17 and Treg cells, cytokines, biomarkers, novel biologic therapies and their implication in clinical practice.\r\nDr. Velikova has been engaged in fifteen projects in the field of immunology and internal medicine. 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This requires extensive analysis of developing trends in scientific research in order to offer our readers relevant content. Creating the book catalogue is also based on keeping track of the most read, downloaded and highly cited chapters and books and relaunching similar topics. I am also responsible for consulting with our Scientific Advisors on which book topics to add to our catalogue and sending possible book proposal topics to them for evaluation. Once the catalogue is complete, I contact leading researchers in their respective fields and ask them to become possible Academic Editors for each book project. Once an editor is appointed, I prepare all necessary information required for them to begin their work, as well as guide them through the editorship process. I also assist editors in inviting suitable authors to contribute to a specific book project and each year, I identify and invite exceptional editors to join IntechOpen as Scientific Advisors. 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It is a heterogeneous group of diseases, all of which ultimately lead to an elevation of glucose in the blood (hyperglycemia) and loss of glucose in the urine as hyperglycemia increases. It is characterized by increased urine production (polyurea) excessive thirst (polydipsia) and excessive eating (polyphagia).
\nDiabetes mellitus is a chronic metabolic disorder of the endocrine system that is characterized by defects in impaired metabolism of glucose, lipid and protein as well as insulin secretion or insufficiency. Diabetes continues to be a major health care problem worldwide and its prevalence is expected to rise from the current 382–471 million individuals by 2035 [1, 2]. There are three main types of diabetes-Type 1 diabetes (T1D), which is an autoimmune disorder leading to the destruction of pancreatic beta-cells; Type 2 diabetes (T2D), which is much more common and primarily caused by impaired glucose regulation due to a combination of dysfunctional pancreatic beta cells and insulin resistance and gestational diabetes mellitus (GDM).
\nDifferent treatments, such as insulin, pharmacotherapy and diet therapies, which exert antidiabetic effects through different mechanisms, are currently used for the management of diabetes. Such mechanisms include stimulation of insulin secretion by sulfonylurea and meglitinides drugs, increase of peripheral absorption of glucose by biguanides and thiazolidinediones, delay in the absorption of carbohydrates from the intestine by alpha-glucosidase and reduction of hepatic gluconeogenesis by biguanides [3, 4, 5].
\nIn spite of the appreciable progress that has been made in the management of diabetes through the use of conventional drugs and management strategies, diabetes and its complications continue to be a major medical problem and rising burden of disease. Most synthetic oral hypoglycemic agents available for the treatment of the disease have some disadvantages, including drug resistance, serious side effects, cannot be used during pregnancy, are toxic and also costly [6, 7].
\nSpices and herbs have played important roles in civilization and history of many nations of the world. Their flavor and pungency makes them indispensable in the preparation of palatable dishes; but beyond adding flavor, spices are reputed to possess several medicinal and pharmacological properties and hence find use in the preparation of a number of medicines. Spices can be the dried leaf (e.g., bay leaf), buds (cloves), bark (cinnamon), rhizome/root (ginger), berries (grains of pepper), seeds (cumin), or even the stigma of the flower (saffron) [8].
\nThe Zingiberaceae plant family consists of many species used as culinary herbs and spices, frequently cited for their antidiabetic and hypoglycemic properties. Ginger (Zingiber officinale) belongs to this family, and has a long and wide history of usage both as a culinary spice and in traditional/alternative medicine. This study attempts to update the available scientific information on the antidiabetic and hypoglycemic potentials of ginger.
\nOnline published articles from Google Scholar, ScienceDirect, Scopus, ResearchGate, PubMed and SciELO were explored for data collection. For literature search, key words such as spices, diabetes, Zingiberaceae, ginger, in vivo, in vitro, pharmacological, medicinal, hypoglycemic and antidiabetic were used. The study reviewed all important literature from 2000 to 2018.
\nThe following sections describe various studies reporting the hypoglycemic and antidiabetic properties of ginger, phytochemical constituents responsible for these properties and its mechanisms of action.
\nThe ginger (Zingiberaceae) family consists of 53 genera and over 1200 medicinal plants, typically tropical annuals or perennials, often with large rhizomes. This plant family is well-known for its medicinal values and is distributed widely throughout the tropics, particularly in Southeast Asia.
\nGinger (Figure 1) has been used for thousands of years for the treatment of numerous ailments, such as colds, nausea, arthritis, migraines and hypertension. Several authors have reviewed the medicinal, chemical, and pharmacological properties of ginger [9, 10, 11, 12, 13]. Ginger is recognized by the U.S. Food and Drug Administration (FDA) as a food additive that is “generally recognized as safe” [14] and has a long history of use as a culinary spice and in herbal medicine to treat many ailments.
\nZingiber officinale (ginger) rhizomes. Source: www.amazon.com/Culinary-Ginger-Zingiber-Officinalecooking/dp/B01NAJQ6C6 [28].
Ginger helps to relieve various inflammatory disorders like gout, osteoarthritis and rheumatoid arthritis; as an analgesic, hypoglycemic, cardiotonic, antiemetic, antimicrobial and antifungal. Other uses include as an antidiabetic, antidyslipidemia, hypotensive, vasodilator, antiobesity and anticancer agent [15, 16, 17, 18].
\nIn addition, the spice has shown prominent protective effects on diabetic liver, kidney, eye, and neural system complications [19]. Several experimental studies have reported that administration of ginger extracts significantly decreased blood glucose level in Type 1- and Type 2-induced diabetic animals in a dose-dependent pattern [20, 21, 22, 23, 24, 25, 26, 27].
\nLamuchi-Deli et al. [29] evaluated the effects of the hydroalcoholic extract of Zingiber officinale on arginase I activity and expression in the retina of streptozotocin-induced diabetic rats. The study showed that blood glucose concentration was significantly decreased, arginase I activity and expression was significantly (P < 0.05) down regulated and 400 mg/kg of the extract reduced significant elevation in body weight in diabetic rats compared to untreated diabetic controls (P < 0.01). Serum insulin was also significantly increased in diabetic rats treated with 400 mg/kg of the extract compared to diabetic controls (P < 0.05). The study suggested that ginger could be a promising therapeutic option for treating diabetes-induced vascular disorders.
\nA recent study by de Las Heras et al. [30] which evaluated the hypolipidemic-and insulin sensitizing effects of hydroethanolic extract of ginger in the liver of high-fat diet (HFD) fed rats, revealed that ginger extract improved lipid profile and attenuated the increase of plasma levels of glucose, insulin, and leptin in HFD rats. Wei et al. [31], also reported that 6-Paradol and 6-Shogaol, the pungent compounds of ginger, promoted glucose utilization in adipocytes and myotubes, and 6-paradol reduced blood glucose in HFD-fed mice. Al-Qudah et al. [32] reported that aqueous extract of ginger was effective in lowering serum glucose, restoration of hematological indices to normal and repair damaged pancreas in alloxan-induced diabetic rats.
\nIn another study, Oludoyin and Adegoke [33] investigated the effect of ginger extracts on blood glucose in normal and streptozotocin-induced diabetic rats. The authors reported that the fasting blood glucose in diabetic rats was reduced to normal by both raw and cooked ginger extracts in a manner comparable to glibenclamide. Evaluation of the nutritional and antidiabetic activity of ginger powder, its aqueous and methanolic extract, as well as the essential oil in streptozotocin-induced diabetic rats [34] revealed reduction in levels of alanine and aspartate aminotransferase (ALT and AST), alkaline phosphatase (ALP), liver total lipid and cholesterol of diabetic rats; and increased levels of liver glycogen and triglyceride compared to positive control group. In the study, ginger oil showed the best antidiabetic activity, followed by ginger extracts. Again, another study reported that ginger extract administered at 200 mg/kg/day/kg body weight for 10 weeks to male Sprague-Dawley diabetic rats, exhibited protective activity against insulin resistance [34].
\nAl-Noory et al. [35] showed that fresh ginger extracts led to decrease in the levels of total cholesterol (TC) and low density lipoprotein (LDL) in the serum of alloxan-induced diabetic rats, compared with the control groups; and previous extracts caused reduction in LDL to levels comparable to normal group and equal to the effect of atorvastatin given at a dosage of 10 mg/day. Similarly, oral administration of aqueous ginger extract to streptozotocin (STZ)-induced diabetic rats for a period of 30 days was reported to give a dose-dependent antihyperglycemic effect, 68% decrease in plasma glucose level at a daily dose of 500 mg/kg body weight, indicating that ginger is a potential phytomedicine for the treatment of diabetes [36]. Iranloye et al. [37] also showed that ginger effectively reduced fasting blood glucose, malondialdehyde levels and enhanced insulin sensitivity in alloxan-induced and insulin-resistant diabetic rats compared to control rats.
\nTreatment of streptozotocin-induced Type I diabetic rats with Z. officinale juice (4 mL kg−1, p.o. daily for 6 weeks) was reported to produce a significant increase in insulin levels, decrease in fasting glucose levels, as well as significant decrease in the area under the curve of glucose in an oral glucose tolerance test [38]. According to Nammi et al. [23], treatment with an ethanolic extract of ginger at doses of 100, 200, and 400 mg/kg for 6 weeks, significantly reduced the marked increase in body weight, serum glucose, insulin, total cholesterol, LDL cholesterol, triglycerides, free fatty acid and phospholipids induced by high-fat diet.
\nThe study conducted by Al-Amin et al. [39] on the antidiabetic and hypolipidemic properties of ginger (Zingiber officinale) in streptozotocin-induced diabetic rats revealed that raw ginger at a dose of 500 mg/kg, was significantly effective in lowering serum glucose, cholesterol and triacylglycerol as well as reduction in urine protein (reversal of diabetic proteinuria) levels, of diabetic rats. Ethanolic extracts of Zingiber officinale (200 mg/kg) given orally for 20 days was reported to produce significant antihyperglycemic effect (P < 0.01) in diabetic rats, while also lowering serum total cholesterol and triglycerides, coupled with increased HDL-cholesterol levels when compared with pathogenic diabetic rats [40].
\nHypoglycemic effect of ginger (4 and 8 g/kg), administered intraperitoneally to rats after 30 min of diabetes induction, with the effect being more pronounced after 2 h has been reported. In another study, Otunola and Afolayan [41], showed that aqueous extract of a spice mixture containing ginger at 500 mg/kg body weight extract significantly (p < 0.05) lowered the elevated fasting blood glucose, lipid and hematological indices of alloxan-induced diabetic rats at equipotent level with glibenclamide.
\nSeveral in vitro hypoglycemic potentials of ginger and its bioactive constituents especially 6-shogaol have been reported (Table 1).
\nIn vitro study | \nResult/outcome | \nReferences | \n
---|---|---|
[6]-Gingerol on 3 T3-L1 cells | \nEnhanced differentiation of 3T3-L1 preadipocytes and insulin-sensitive glucose uptake | \nSekiya et al. [42] | \n
[6]-Shogaol or [6]-gingerol on 3 T3-L1 cells | \nSignificant inhibition of TNF-α-mediated adiponectin expression in 3T3-L1 adipocytes. [6]-Shogaol acted as a peroxisome proliferator-activated receptor (PPAR)γ agonist, while [6]-gingerol acted by suppressing TNF-α-induced JNKs signaling | \nIsa et al. [43] | \n
Ethyl acetate extract of ginger on L6 myotube cell surface | \nStimulated glucose uptake and GLUT4 expression in L6 myotube cell surface, reduced lipid content in 3T3 adipocyte, and inhibited protein glycation. Inhibited α-amylase (IC50 = 980.2 μg/mL) and α-glucosidase (IC50 = 180.1 μg/mL) | \nRani et al., [44] | \n
Aqueous extract of ginger at 5, 10, 20, 40 g/L incubated with (PBS), glucose + BSA for 5 weeks | \nDose-dependent, antidiabetic activity through inhibition of glucose diffusion and reduced glycation | \nSattar et al., [45] | \n
In vitro hypoglycemic potentials of ginger and its bioactive constituents.
The capacity of ginger for hypoglycemic, antidiabetic, insulogenic, better glucose tolerance, increased serum insulin levels, reduction in elevated lipid levels, and prevention of weight loss associated with diabetes in human diabetic patients have also been reported (Table 2).
\nHuman trials/dosage | \nResults | \nReferences | \n
---|---|---|
Type 2 diabetic men (40–60 years) given 3 g/day of dry ginger powder in divided doses for 30 days. Number-8 T2D, 8 placebo | \nSignificant reduction of blood glucose, triglyceride, total cholesterol, LDL and VLDL cholesterol | \nAndallu et al. [48] | \n
Randomized double-blind placebo-controlled trial, patients with Type 2 diabetes, given 2 g/day of ginger extract supplementation. Number-28 T2D, 30 Placebo | \nSignificantly lowered levels of insulin, LDL-C, TG, HOMA index and increased the QUICKI index; no significant changes in FPG, TC, HDL-C and HbA1c; improved insulin sensitivity | \nMahluji et al. [49] | \n
Randomized controlled trial of Type 2 diabetic men between 30 and 70 years given 1.6 g/day of ginger or wheat flour capsule. Number-33 T2D, 30 Placebo | \nDecreased fasting blood glucose, glycosylated hemoglobin, fasting insulin, homeostasis model assessment-insulin resistance index, total cholesterol and triglyceride. No change in BMI, LDL-C, LDL-C and HDL-C | \nArablou et al. [50] | \n
Randomized controlled trial of Type 2 diabetic patients (30–70 years) given either 3 g/day ginger or cellulose microcrystalline capsules for 8 weeks. Number-40 T2D, 41Placebo | \nSignificant reduction in fasting blood glucose and glycosylated hemoglobin; no change in BMI, fasting insulin and homeostasis model assessment-insulin resistance index | \nMozaffari-Khosravi et al. [51] | \n
Randomized, double-blind, placebo-controlled, clinical trial where Type 2 diabetic patients received 2 g/day of ginger powder supplement or lactose as placebo for 12 weeks. Number-22 T2D, 19 placebo | \nSignificant reduction of fasting blood sugar, hemoglobin A1c, apolipoprotein B, apolipoprotein B/apolipoprotein A-I and malondialdehyde in ginger group compared to baseline and control group, while increasing apolipoprotein A-I in Type 2 diabetic patients | \nKhandouzi et al. [52] | \n
Randomized controlled trial of Type 2 diabetic patients (20–60 y) T2DM given 3 g ginger or lactose capsule/day for 3 months. Number-22 T2D, 23 Placebo | \nReduced fasting blood glucose, glycosylated hemoglobin, fasting insulin, homeostasis model assessment-insulin resistance index | \nShidfar et al. [53] | \n
Double-blind placebo-controlled trials of Type 2 diabetic patients were randomly allocated to 2000 mg/day of ginger or placebo for 10 weeks. Number-25 T2D, 25 placebo | \nReduced serum levels of fasting blood glucose, hemoglobin A1C compared to placebo group, reduced ratio of LDL-C/HDL-C; but no significant change in serum concentrations of triglycerides, total cholesterol, LDL-C, and HDL-C | \nArzatii et al. [54] | \n
Clinical (human) trials of the antidiabetic potentials of ginger.
GC-MS profiling of diethyl extracts as reported by Koch et al. [46] showed the presence of monoterpenes such as (α-pinene, camphene, myrcene, and α-phellandrene), oxygenated monoterpenes (geranial, citronellal, neral, linalool, borneol, and α-terpineol), and sesquiterpenes (α-and β-farnesene, ar-curcumene, zingiberene, zingiberenol, copaene, or cadinene). The most abundant substances in the extracts were α-zingiberene (37.9%), β-sesquiphellandrene (11.4%), (E,E)-α-farnesene (9.6%), geranial (8.2%), ar-curcumene (6.3%), and γ-terpinene (5.1%).
\nSimilarly, Sharma et al. [47] reported that the essential oil of fresh ginger rhizome was characterized by high percentage of sesquiterpenes (66.66%), monoterpenes (17.28%) and aliphatic compounds (13.58%). The predominant sesquiterpene was zingiberene (46.71%) followed by valencene (7.61%), β-funebrene (3.09%) and selina-4(14),7(11)-diene (1.03%).
\nVarious mechanisms have been proposed for the antidiabetic and hypoglycemic activities of medicinal plants. These include peripheral utilization of glucose, increased synthesis of hepatic glycogen by enhancement of glycogen regulatory enzyme expression in the liver, inhibition of carbohydrate metabolizing enzymes, stimulation of pancreatic insulin release, insulomimetic actions and inhibition of hepatic glucose production [55, 56].
\nAccording to Dearlove et al. [57], spices such as cinnamon, cloves, oregano, and allspice possess bioactive compounds that have (1) antiglycation properties which inhibit the formation of AGEs; (2) antioxidant activities that neutralize the effects of ROS; and (3) anti-inflammatory potentials. Some studies associate the antidiabetic action of ginger to its bioactive principles such as gingerol and shogaol which have the capacity to enhance glucose uptake in rat’s skeletal muscle cells, and promote increased expression and translocation of GLUT-4 glucose transporter to the plasma membrane of the cells thus clearing excess glucose from the serum [34].
\nAnother mechanism proposed was the inhibition of key enzymes of carbohydrate metabolism-α-glucosidase and α-amylase by phenolic compounds (gingerols and shogaols) present in ginger [23, 45]; while other authors showed that ginger increases muscle and liver glycogen stores by enhancing peripheral utilization of glucose, thus limiting gluconeogenesis in the liver and kidney in a manner similar to insulin [37].
\nSon et al. [58], posits that-gingerol exerts its antidiabetic effects through multiple mechanisms that include—(1) increased glucose uptake in the absence of insulin, (2) induction of 5′ adenosine monophosphate-activated protein kinase phosphorylation, (3) promotion of glucose transporter 4 (GLUT4) translocation to plasma membrane, (4) suppression of advanced glycation end product-induced rise of ROS levels in pancreatic β-cells, (5) reduction of fasting blood glucose levels and improved glucose intolerance, (6) regulation of hepatic gene expression of enzymes involved in glucose metabolism toward decreased gluconeogenesis and glycogenolysis, while increasing glycogenesis, thereby reducing blood glucose concentrations.
\nThis study presented an update on the antidiabetic potentials of ginger from the Zingiberaceae family. Although several in vivo and in vitro reports were available, there were relatively few clinical (human) trials. The doses and outcomes also varied; as well as the mechanism of action through which antidiabetic effects were mediated. Although these reports are indicative of the anti-diabetic or hypoglycemic potentials of ginger, the doses and outcomes also varied; most importantly, the mechanisms of action through which anti-diabetic effects are mediated were highlighted. Ginger, according to these studies, exerts its anti-diabetic effects through restorative effects on pancreatic β-cells, increasing insulin sensitivity, insulin-like action and peripheral utilization of glucose. Other mechanisms include increased synthesis of hepatic glycogen through the enhancement of glycogen regulatory enzyme expression in the liver, inhibition of carbohydrate metabolizing enzymes, stimulation of pancreatic insulin release, and inhibition of hepatic glucose production. However, further studies, especially in humans are therefore needed and the oral safety of the various extracts under prolonged usage must be confirmed, more so, since ginger is one of the spices generally regarded as safe.
\nThe authors acknowledge the support of Govan Mbeki Research and Development Centre, University of Fort Hare.
\nThe authors declare no conflict of interest.
Stability 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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