Metal ion vs. log βMY values.
\r\n\tThe overall objective of the book is to propose a methodological/ technological state of play and an operational assessment on the complex issues regarding the management and optimization of the multiple components of a transportation system: users, infrastructures, technologies and services.
\r\n\r\n\tThe book welcomes topics such as smart mobility, smart transportation systems, smart vehicle, smart infrastructures, smart people: citizens and users.
",isbn:"978-1-83880-823-5",printIsbn:"978-1-83880-802-0",pdfIsbn:"978-1-83880-824-2",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"ef80dab7f0350ea7cb28f40eedea2b35",bookSignature:"Prof. Stefano De Luca, Dr. Roberta Di Pace and Dr. Chiara Fiori",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9872.jpg",keywords:"Transportation, Intelligent Information Systems, Smart Vehicles, Vehicle Management, Driving Assistance Technologies, Smart Infrastructures, Smart Transportation Systems, Sustainable Transportation Systems, Vehicle Routing, Travel Demand Modeling, Life Cycle Assessment, Environmental Impacts Modeling",numberOfDownloads:664,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:1,numberOfTotalCitations:1,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 6th 2020",dateEndSecondStepPublish:"May 27th 2020",dateEndThirdStepPublish:"July 26th 2020",dateEndFourthStepPublish:"October 14th 2020",dateEndFifthStepPublish:"December 13th 2020",remainingDaysToSecondStep:"8 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:"Scientific coordinator of the Transportation Planning and Modelling laboratory, a consultant for the Italian Ministry of Transportation, the Transport commission of Campania Region, of Salerno and Avellino Transportation Departments and member of the IEEE Intelligent Transportation Systems Society.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"271061",title:"Prof.",name:"Stefano",middleName:null,surname:"De Luca",slug:"stefano-de-luca",fullName:"Stefano De Luca",profilePictureURL:"https://mts.intechopen.com/storage/users/271061/images/system/271061.jpeg",biography:"Stefano de Luca, got a Ph.D. in transportation engineering at the University of Rome 'La Sapienza” and is an associate professor at the Department of Civil Engineering of the University of Salerno (Italy). He is a professor of Transportation Planning (BSc, Civil Eng. and Environmental Eng.) and Transportation Systems Theory (MSc, Civil Eng.). Currently, he is vice-coordinator of the Ph.D. course on 'Risk and sustainability”, scientific coordinator of the Transportation Planning and Modelling laboratory. He is a consultant for the Italian Ministry of Transportation, the Transport commission of Campania Region, of Salerno and Avellino Transportation Departments. His main research interest includes transportation planning techniques, travel demand modeling, users’ behavior modeling, signal settings design, traffic assignment models, air transportation. He is member of IEEE Intelligent Transportation Systems Society.",institutionString:"University of Salerno",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"University of Salerno",institutionURL:null,country:{name:"Italy"}}}],coeditorOne:{id:"271713",title:"Dr.",name:"Roberta",middleName:null,surname:"Di Pace",slug:"roberta-di-pace",fullName:"Roberta Di Pace",profilePictureURL:"https://mts.intechopen.com/storage/users/271713/images/system/271713.jpeg",biography:"Roberta Di Pace received both the MSc degree and the Ph.D. degree in transportation engineering from the University of Naples 'Federico II,” Naples, Italy, in 2005 and 2009, respectively. She is an assistant professor in Transportation Engineering at the Department of Civil Engineering of the University of Salerno (Italy). She is an aggregate professor of Technique and Transport Economics (BSc, Civil Eng. and Environmental Eng) and Transportation Systems Design (MSc, Civil Eng). Since 2010 she is a member of the Transportation Planning and Modelling Laboratory. Her main research fields include the development of analytical tools for advanced traveler information systems, the traffic flow modeling, the network signal setting design, the advanced traffic management systems. She is a member of IEEE Intelligent Transportation Systems Society and IEEE Women in Engineering.",institutionString:"University of Salerno",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Salerno",institutionURL:null,country:{name:"Italy"}}},coeditorTwo:{id:"321783",title:"Dr.",name:"Chiara",middleName:null,surname:"Fiori",slug:"chiara-fiori",fullName:"Chiara Fiori",profilePictureURL:"https://mts.intechopen.com/storage/users/321783/images/system/321783.jpg",biography:"Chiara Fiori is assistant professor at the Department of Civil Engineering of the University of Salerno, Italy. She earned the Ph.D. from Sapienza University of Rome, Italy in 2015. From 2016 to 2019 she was post-doc at the Department of Civil, Architectural and Environmental Engineering, University of Naples Federico II, Italy. She was Visiting Scientist at the European Commission, Joint Research Center, Directorate for Energy, Transport and Climate Change, Ispra, Italy, from 2017 to 2018. Moreover, from 2015 to 2016 she was Visiting Scientist at the Center for Sustainable Mobility of the Virginia Tech Transportation Institute, USA, and, in 2013, Visiting Scholar at the Center for Automotive Research of the Ohio State University, USA. Her research interests include: sustainable mobility; modeling and simulation for the functional and environmental efficiency improvement of container terminals; integration of microscopic energy consumption model for EVs with traffic control systems; energy consumption modeling and simulation of hybrid and electric powertrains; integration of traffic and energy consumption modeling at microscopic scale; impact assessment of emerging powertrain technologies on route choice behaviors and development of eco-routing strategies for personal and freight mobility; impact assessment of emerging powertrain technologies and charging systems on power electric infrastructure; electric freight logistics, electrification of ports and port operations; well-to-wheels analysis of conventional, hybrid and electric vehicles; impact assessment of emerging railway services (e.g. High Speed/High Capacity services); energy systems, alternative fuels, hydrogen and renewable sources.",institutionString:"University of Salerno",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Salerno",institutionURL:null,country:{name:"Italy"}}},coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"11",title:"Engineering",slug:"engineering"}],chapters:[{id:"73624",title:"BIM Approach for Smart Infrastructure Design and Maintenance Operations",slug:"bim-approach-for-smart-infrastructure-design-and-maintenance-operations",totalDownloads:115,totalCrossrefCites:0,authors:[null]},{id:"73595",title:"Advanced Vehicles: Challenges for Transportation Systems Engineering",slug:"advanced-vehicles-challenges-for-transportation-systems-engineering",totalDownloads:18,totalCrossrefCites:0,authors:[null]},{id:"73941",title:"Towards Shared Mobility Services in Ring Shape",slug:"towards-shared-mobility-services-in-ring-shape",totalDownloads:23,totalCrossrefCites:0,authors:[null]},{id:"74201",title:"Attitudes and Behaviours in Relation to New Technology in Transport and the Take-Up amongst Older Travellers",slug:"attitudes-and-behaviours-in-relation-to-new-technology-in-transport-and-the-take-up-amongst-older-tr",totalDownloads:32,totalCrossrefCites:0,authors:[null]},{id:"73973",title:"Models and Methods for Intelligent Highway Routing of Human-Driven and Connected-and-Automated Vehicles",slug:"models-and-methods-for-intelligent-highway-routing-of-human-driven-and-connected-and-automated-vehic",totalDownloads:64,totalCrossrefCites:0,authors:[null]},{id:"74412",title:"Centralised Traffic Control and Green Light Optimal Speed Advisory Procedure in Mixed Traffic Flow: An Integrated Modelling Framework",slug:"centralised-traffic-control-and-green-light-optimal-speed-advisory-procedure-in-mixed-traffic-flow-a",totalDownloads:55,totalCrossrefCites:0,authors:[null]},{id:"74333",title:"Transit Signal Priority in Smart Cities",slug:"transit-signal-priority-in-smart-cities",totalDownloads:91,totalCrossrefCites:0,authors:[null]},{id:"73356",title:"Optimal Management of Electrified and Cooperative Bus Systems",slug:"optimal-management-of-electrified-and-cooperative-bus-systems",totalDownloads:64,totalCrossrefCites:0,authors:[null]},{id:"73240",title:"Recent Progress in Activity-Based Travel Demand Modeling: Rising Data and Applicability",slug:"recent-progress-in-activity-based-travel-demand-modeling-rising-data-and-applicability",totalDownloads:138,totalCrossrefCites:0,authors:[null]},{id:"73821",title:"Driver Assistance Technologies",slug:"driver-assistance-technologies",totalDownloads:66,totalCrossrefCites:0,authors:[null]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"297737",firstName:"Mateo",lastName:"Pulko",middleName:null,title:"Mr.",imageUrl:"https://mts.intechopen.com/storage/users/297737/images/8492_n.png",email:"mateo.p@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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Photoaging is caused by excessive exposure to the ultraviolet (UV) irradiation. The skin becomes thick and rough, with coarse wrinkles, mottled pigmentation, and precancerous lesions, including actinic keratoses (AK). Actinic keratosis (AK) is a growth of dysplastic cells within the epidermis that presents clinically with a scaly localized macule or papule on chronically sun‐exposed skin [1]. Over the last few years, the relationship between AK and SCC has been a topic for much debate in the literature, as AK is believed not to be a separate entity but an SCC in situ.
\nSome researchers also consider actinic keratoses equivalent to squamous cell carcinoma (SCC). Yet, SCC is capable of metastasis [2, 3]. So it can be life threatening. AK is a precancerous lesion, therefore should be treated early. There are a lot of methods for AK, while not all treatments are appropriate for all patients or lesions, especially cosmetic outcome may be generally less than optimal [4, 5]. The ideal treatment for AKs should be effective, well tolerated, and have an excellent cosmetic outcome, particularly in cosmetic‐sensitive areas such as the face.
\nPhotodynamic therapy (PDT) has been under development for the treatment of various tumors by the end of the 1970s. Topical ALA‐PDT was originally used for superficial nonmelanoma skin cancers and their precursors. However, other benign diseases, such as acne vulgaris, sebaceous gland hyperplasia, and hidradenitis suppurativa, have been shown to improve with this treatment. Photodynamic therapy (PDT) is an alternative, minimally invasive treatment. Oxygen, photosensitizer, and light are the three principal elements of PDT. When illuminated by a light source with an appropriate wavelength, the photosensitizer is activated and will react with oxygen to produce singlet oxygen and reactive oxygen species (ROS) to cause the selective destruction of target tissues [6]. As a metabolic precursor of endogenous porphyrins in heme biosynthesis, the absorption of 5‐ALA induces the production and accumulation of protoporphyrin IX (Pp IX), a fluorescent substance that is as effective as a light sensitive agent (408, 506, 532, 580, and 635 nm).
\nAn ideal treatment for AK would only affect lesional skin, leaving normal surrounding skin unharmed. In the 1990s, Kennedy et al. using topic 5‐aminolaevulinic acid (5‐ALA) that has restricted the phototoxicity at the application site. Since AK lesions are capable of selectively accumulating PPIX, they are excellent targets for PDT.
\nForty‐two patients with a total of 56 AK lesions on the face were enrolled in our study. The 5‐ALA (Zhangjiang, China) was prepared at a concentration of 20% in physiological saline. A thick layer of the formulation was applied to cover the AK lesions for 5 h. Then the lesions were illuminated by laser (λ = 630 nm, light dose 100 mW/cm2) for 30 minutes All patients were reviewed in at least 2‐week intervals. The response to the PDT was evaluated 1 month after the therapy, and treatment is repeated if necessary [7].
\nInitially, AKs lesions were detected among the patients (Figure 1). The treated skin lesions were evaluated macroscopically at several time points following the treatment. Immediately after ALA‐PDT, it showed limited edema and erythema in the treated area. Conversely, the lesions were covered with necrotic tissue after 1 day. A red granulation tissue developed after 4–7 days and gradually atrophic flatten (Figure 2). Afterwards, a pink‐red contracted atrophic scar could be observed that progressively healed after 3 weeks. All the 56 lesions from 42 patients showed a complete response by histologic examination (remission rate, 85.71%) 1 month after PDT treatment. The epidermis of the photodamaged skin became thinner and more even. Clinically, there was no significant scarring or pigmentary changes after treatment (Figure 3).
\nAfter biopsy.
1 week after PDT.
1 month after PDT.
There were six patients with persistent lesions, the six patients with eight lesions received one or two additional PDT treatments; the AKs in the follow‐up biopsy resolved, and the lesions were all cleared in the end.
\nBefore treatment, histopathological analysis of the lesions showed the presence of atypical keratinocytes characteristic for AK (Figure 4). After treatment, the epidermis of the photodamaged skin became thinner and more even, and the skin structure in responsive lesions had returned to normal and the atypical cells of AK were replaced by normal keratinocytes (Figure 5). The epidermis was fully regenerated by day 30 following PDT.
\nBefore PDT.
After PDT.
The facial lesions’ mean epidermal thickness significantly decreased from 155.22 ± 70.45 to 74.35 ± 18.65 μm after treatment (P < 0.05) (Figure 6). We can observe a large number of infiltrating cells in the dermis before the treatment, and those were significantly reduced after treatment. In 5 h of 5‐ALA occlusive treatment, there were no reports of irritation, local or systemic light sensitization reaction. During the exposure to the light source all patients complained about a burning sensation, ranging from light to intense. During the treatment, variable degrees of erythema, blistering and edema occurred, all of these events were of short duration and completely reversible. During the treatment, it was possible to see progressive and evident edema and erythema on the application site. Despite the pain, none of the patients asked or interrupted the light exposition treatment.
\nEpidermal thickness.
The cosmetic outcome in all cured AKs was excellent, except for one patient; after additional sun exposure, postinflammatory hyperpigmentation developed. The method of topical application of ALA is a minimally invasive treatment. Photosensitizer\'s metabolic cycle is very quick, the period of photosenisitization is short, and can give good cosmetic effect.
\nThe investigations of the action of light on living organisms began in the nineteenth century. Since Dougherty [8] in the 1970s began clinical trials for photodynamic destruction of cutaneous and subcutaneous malignancies, PDT has been used to treat esophageal [9], laryngeal, endobronchial, gastrointestinal, genitourinary, nervous, head and neck [10], oral leucoplakia, and skin malignancies [11].
\nPhotodynamic therapy (PDT) is an oxygen‐dependent process involving the use of a photosensitizing drug which accumulates in diseased tissue. The main topical agents used in dermatology are 20% 5‐aminolaevulinic acid (ALA). It produced porphyrins via the heme biosynthetic pathway. It is an endogenous chemical, which participates in heme biosynthesis in the body. As a precursor of the hemoglobin content, its production has strong photosensitive function after the activation of ALA anhydrase and a series of enzymes. Porphyrin IX (protoporphyrin IX, Pp IX) is the last step of heme biosynthesis intermediate [12]. Under normal circumstances, heme biosynthesis pathway by regulating the body negative feedback mechanism, the synthesis of ALA is regulated by the hemoglobin content in the cell, so there will not be too much ALA accumulation in the body. When given overdoses of exogenous ALA, it can increase the intracellular concentration of Pp IX to therapeutically useful concentrations. Photoactivation by visible light results in cell damage of targeted abnormal cells while preserving normal structures. This effect of PDT is connected with direct photochemical reactions mediated by singlet oxygen and other reactive species. The cooperation of photosensitizing substances with light leads to the release of cytotoxic substances. It has been described that tumor destruction of PDT is connected with indirect effects of PDT: blood vessel occlusion within vascularized tumors. These effects demonstrated [9] that PDT induces apoptosis and vascular endothelial damage [13, 14]. It has also been mediated by the release of prostaglandin E2 (PGE2) and cytokines (IL‐2, IL‐ 1, TNF).
\nIn this study, we observed pre‐ and post‐ ALA‐PDT specimens for AK and determined whether ALA‐PDT induced histologic changes reversing the destructive connective tissue events. Normally, we selected 1 month after the PDT as the point time to evaluate the histologic changes for lots of results showing this time point of the assessment might be an important consideration. The fact that 1–20% of AKs progress to squamous cell carcinoma and approximately 60% of all squamous cell carcinomas develop from AKs underscores the importance of early treatment of AKs [3]. Our findings showed approximately 85% of AKs are already cured after a single PDT exposure. As a result, the majority of patients need only one treatment, and we only performed one PDT session followed by clinical examinations at 1 and 3 months after PDT. Only those lesions that showed an incomplete response need further treatment.
The results of this study provide histologic evidence supporting the beneficial effects of ALA‐PDT for photodamaged skin. PDT appears to be a more feasible alternative to conventional therapy of skin malignancies. Our results showed that the thickness of epidermis decreased significantly after ALA‐PDT. We could see hyperkeratosis, stratum spinosum hypertrophy before the treatment. And the acanthocyte arranged in disorder. There are atypical keratinocytes in the central of the epidermis. We evaluated the histologic changes 1 month after the PDT, suggesting that the point in time of the assessment might be an important consideration. The epidermis was fully regenerated by day 30 following PDT. After treatment, the epidermis of the photodamaged skin became thinner and more even, and the skin structure in responsive lesions had returned to normal and the atypical cells of epidermis were replaced by normal keratinocyte [7]. Although the light source itself might affect the histologic changes in AKs, we still consider that ALA‐PDT is the most important reason leading to the histologic changes in the present study where the light energy is very low.
Topically applied photosensitizers are preferred for dermatological PDT because of the reduced risk for prolonged skin photosensitivity. As we all know, topical application of ALA is a minimally invasive treatment. It has a short photosenisitization period, can treat multiple lesions at the same time, and can give good cosmetic effect. Studies have shown that the depth of penetration for most tissues using 630 nm light is about 1 cm [15, 16]. This percutaneous penetration is the most important factor influencing response rates for topical ALA PDT. Photodynamic therapy is associated with epidermal necrosis and dermal inflammation, which in turn gives a series of side effects in dermatology, including pain, ecchymosis, ulceration, and blistering [17].
\nSelective photodynamic destruction of treated premalignant and malignant areas without injury of normal tissue, ability to repeat PDT without loss of normal tissue proves PDT to be a more acceptable option than surgical resection. At the same time, laser‐induced PDT almost left no obvious scar in our study. Patients treated with PDT may also benefit from minimal invasiveness, low recurrence, as well as excellent cosmetic effects in premalignant and malignant lesions of the skin.
\nThe present study is limited by the follow‐up time. In our study at 1 and 3 months after PDT, previous reports are in good agreement with the overall CR rates of 85.71 and 100% that were found, respectively. However, there are still existed residual malignant cells in the epidermis but not apparent by visual inspection. It will lead to clinical recurrence of the AKs at a later examination if the malignant cells continue to proliferate. That is the important reason why we need to observe the clearance rate after PDT for a long follow‐up time.
\nIn conclusion, the results of this study provide histologic evidence supporting the beneficial effects of PDT for AK. PDT using topical ALA was a safe and effective treatment for actinic keratoses with an excellent cosmetic outcome. It is a promising treatment that could benefit from further study. Topical PDT for AKs is now a well‐established treatment modality that showed easy handling of 5‐ALA administration with excellent efficacy and safety results.
\nBowen\'s disease (BD), or squamous cell carcinoma in situ, usually presents as a well‐defined erythematous plaque on photoexposed sites [18]. Although any body part can be involved, BD lesions are common on the head and neck and lower limbs. The diagnosis is often delayed because of the symptoms are often untypical. The early skin changes may often appear to be eczema, tinea corporis, and psoriasis. Therefore, pathological diagnosis might be necessary when clinical differentiation between these diseases is difficult [3].
\nBD is a more aggressive form of intraepidermal (in situ) squamous cell carcinoma. Risk factors for BD include fair skin, protracted sunlight damage, radiation exposure, immune compromise and human papillomavirus infection [19]. Most BD lesions are found in the elderly patients commonly at high risk for surgery.
\nSeveral equally efficacious treatment options are available for the treatment of BD including conventional surgery, Mohs’ surgery, cryosurgery, and CO2 laser. However, it is not indicated for patients with numerous or large lesions such as those located in face. Alternative treatments are needed to treat superficial malignancies on nose, ear, and other sites. CO2 laser vaporizes lesional tissues by thermal effects and causes minimal injuries, but it often fails to entirely remove lesions, especially those invisible or infiltrating into adjacent tissues, resulting in disease persistence and recurrence.
\nTopical 5‐aminolevulinic acid‐mediated photodynamic therapy (ALA‐PDT) is a minimally invasive procedure, represents a relatively new treatment modality, and, with some unique features, it is especially suitable for the local treatment of superficial epithelial disorders. It causes less damage to normal tissues than surgical treatment, radiation therapy, or chemotherapy. In addition, since PDT does not produce cumulative effect and systemic phototoxicity, it allows repetitive treatments for new, partially responding or recurrent lesions. In this study, ALA‐PDT treatment was performed following local pretreatment with CO2 laser. By the pretreatment, we could enhance photosensitizer absorption, reduce the thickness of the BD lesion, and even increase the penetration depth of the irradiation, to achieve a multiplier effect [20].
\nTwenty‐two lesions from 18 patients were randomized into two groups [21]; 11 lesions were treated with CO2 laser alone, serving as control group. The remaining 11 lesions were treated with topical ALA‐PDT (180 J/cm2 at 100 mW/cm2) + CO2 laser for 1–3 sessions.
\nBiopsies were taken from BD lesions prior to treatment. BD is histopathologically characterized by the presence of atypical keratinocytes (Figure 7). Skin biopsies from the erythematous plaque exhibited proliferation of atypical squamous cells across the entire thickness of the epidermis and the BD diagnosis was based on the finding. The initial evaluation was undertaken 1 month after treatment and biopsies were harvested for histological evaluation. The epidermis fully regenerated in the point of 30 days after ALA‐PDT + CO2 laser treatment. The epidermis of the BD lesion became thinner and more even following the treatment. Moreover, the atypical BD cells were replaced by normal keratinocytes and the skin structure in responsive lesions returned to normal (Figure 8). All patients were reviewed at ≤1‐week intervals. Patients who did not respond to the three sessions of treatment were referred to surgical treatment [21].
\nBefore PDT (×20).
After PDT (×20).
In the CO2 laser group, eight patients who underwent 1–3 sessions of laser treatment alone showed response to the therapy. Seven lesions (63.63%) achieved complete recovery, three (27.27%) showed partial response but another five lesions (45.45%) relapsed within 6 months during follow‐up. Five out of eight (62.5%) patients were satisfied with the therapeutic results of CO2 laser therapy.
\nIn the ALA‐PDT + CO2 laser group, complete response was achieved in 72.73% of the lesions after 1–3 treatment sessions. Three lesions (27.27%) showed partial response during the treatment. ALA‐PDT + CO2 laser was repeated in the cases of partial response after a single session. Out of eight lesions that initially responded completely, 1 month later one relapsed. The recurrence rate was 9.1% (1/11) and the overall clearance was 90.9% (10/11). Eight out of 10 (80%) patients were satisfied with their therapeutic outcome after ALA‐PDT + CO2 laser treatment, which is much higher than control group [21].
\nBD lesions are commonly seen on the head, neck, and lower limbs, although any site can be involved. The combination treatment of ALA‐PDT and CO2 laser could achieve a much better cosmetic outcome. Compared with CO2 laser alone, histopathological examination of the BD lesions confirmed that the response to the combination therapy was more uniform after ALA‐PDT + CO2 laser. PDT appears to be a more feasible alternative to conventional therapy for skin malignancies. BD lesions predominantly consisted of atypical keratinocytes before the treatment. We can see the large number of atypical cells in the epidermis and superficial layers of the dermis, a few lymphocytes and dilated capillaries. Following ALA‐PDT + CO2 laser treatment, the epidermis was found to have fully regenerated 30 days. Furthermore, the stratum spinosum become thinner after treatment, the atypical BD cells were replaced by normal keratinocytes and the photodamaged skin architecture in responsive lesions returned to normal.
\nOur study also showed that local ALA‐PDT after CO2 laser was highly effective for BD lesions and could be used as an ideal alternative for large and multiple BD lesions, or for other modalities of treatment (surgical or nonsurgical) are inappropriate or have failed. There was no difference in the complete remission rate between the two groups (P > 0.05). However, recurrence of BD at the treated site is common. The recurrence rate was substantially higher in the control group than in the ALA‐PDT + CO2 laser group (P < 0.05). While the overall clearance was higher in the ALA‐PDT + CO2 laser group than in the control group (P < 0.05). A complete response was seen in 72.73% of lesions after 1–3 treatment sessions. Only one lesion developed recurrence 6 month after ALA‐PDT + CO2 laser treatment. The post‐treatment recurrence rate was 45.45% (5/11) in CO2 laser alone group, and five lesions relapsed within 6 months during follow‐up. In general, we consider incomplete clearance after four or more times of PDT treatments to be a PDT failure. In terms of our experience, the vast majority of patients were cured within two or three treatment cycles. We would advise patients select alternative treatments in this failure situation. Recurrent disease can be retreated by PDT. This is another advantage of PDT and particularly applied for large or multiple areas and field change. Figure 9 showed a 55‐year‐old male hepatitis B patient who has 6‐month history of genital BD lesions. He underwent three sessions of ALA‐PDT + CO2 laser treatments, and he completely recovered from BD. He revealed no recurrence during the 6‐month follow‐up after treatment (Figure 10).
\nBefore PDT.
After PDT.
In most cases, PDT plus superficial laser vaporization was usually given as a single outpatient treatment that gave good therapeutic results. Most treatments are not suitable for BD lesions involving large and multiple lesions, but we used PDT for BD lesions in some sites such as peri‐genital areas, and succeed in the end. The efficacy of local ALA‐PDT after CO2 laser for Bowen\'s disease lesions reaches almost 80–90%. Compared with the efficacy of PDT with laser in the treatment of Bowen\'s disease demonstrated that PDT was better than laser alone [14, 22]. Compared with other treatments, PDT causes the low incidences of ulceration and absence of infections.
\nBD may be a prototype of a non‐melanoma skin cancer, and clinically PDT should be seen as a first‐line therapy, especially for elderly patients who find the need for hospital attendance limiting [23]. Many BD lesions require immediate surgical intervention in order to avoid the risk of malignant change. With local ALA and light illumination combined with CO2 laser, good results can be accomplished usually with a single outpatient treatment session without causing serious side effects except a few patients had transient pain, erythema, and scabby.
\nThe most common side effect experienced with PDT is pain, with up to 20% of patients describing pain as being “severe”. This can sometimes persist for a few hours after treatment, and it tends to be severest during the early period of irradiation. Postinflammatory hyper or hypopigmentation can also occur. Persistent erythema is often seen at 3 months but does not necessarily indicate residual disease [24, 25].
\nThis study explored the feasibility of using topical ALA‐PDT combined with CO2 laser for BD. Our preliminary results proved that the ALA‐PDT after CO2 laser is safe and effective and is associated with a low recurrence rate. The main limiting factors for PDT at the moment are pain and the inconvenience of hospital attendance. However, this study provided histological evidence that supports the beneficial effects of ALA‐PDT + CO2 laser for the treatment of BD. PDT is quite promising and could be the potential alternative, especially for large and multiple lesions; or for patients where other modalities of treatment (surgical or non‐surgical) are inappropriate or have failed.
\nPort‐wine stain (PWS) is congenital vascular malformation characterized by ectatic capillaries in the papillary layer of the dermis. PWS occurs in an estimated 0.3% of births, affecting males and females and all racial groups equally. It may be located anywhere on the body, but more often on the face. PWS are permanent, do not disappear spontaneously. They usually appear at birth and tend to become darker and thicker with age [26, 27], deepening in color from faint pink to deep red or purple or developing nodularity. It is usually isolated but may be associated with other vascular malformations or occurs as a component of a variety of congenital syndromes.
\nBecause persistent PWS lesions can cause serious psychological problems, therapy for PWS is considered a medical necessity. Many therapeutic methods have been used to treat PWS, including surgical excision, cryosurgery, dermabrasion, tattooing, and cosmetic camouflage makeup [28]. These methods are no longer used because of ineffectiveness and scarring.
\nPDT is a relatively new therapeutic modality for skin disease. The vascular effects of PDT on tumors leads to endothelial injury, vasoconstriction, thrombus formation, and blood flow stasis. These results suggest that PDT is a potential treatment for certain vascular diseases, including PWS. The advantage of PDT is its dual selectivity: precise direction of laser light to the specific target area and selective uptake of photosensitizer to target tissues. PWS have a histologic characteristic of dilated capillary vessels, the target of PDT. In vivo 23–26 and in vitro 25 studies have shown that photosensitizer accumulation occurs rapidly in vascular endothelial cells after intravenous administration.
\nRecently, the General Hospital of the Peoples’ Liberation Army in China reported their decade‐long experience of PWS with PDT. Gu et al. [29, 30] reported that among 1942 PWS lesions in 1385 patients treated by either PSD‐007 or HMME from April 1991 to May 2003 showed that, after one PDT treatment session, total clearance was achieved in 128 lesions (6.6%), achieved excellent results, 746 (38.3%) good results, 923 (47.4%) fair results, 145 (7.4%) results, and seven (0.3%) with no visible change. Their data showed that PDT was an effective treatment in all patients with PWS, especially for dark‐skinned patients or patients with papules or nodules.
\nThe authors are grateful to Ying Gu academician (Department of Laser Medicine, Chinese PLA General Hospital) for constructive suggestions and the members of the department of dermatology of the Air Force General Hospital for their technical support. This work was supported by the National Natural Science Foundation of China (No. 81301386) and the China Postdoctoral Science Foundation (no. 2013M532225 and no. 2014T71009).
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.
IntechOpen implements a robust policy to minimize and deal with instances of fraud or misconduct. As part of our general commitment to transparency and openness, and in order to maintain high scientific standards, we have a well-defined editorial policy regarding Retractions and Corrections.
",metaTitle:"Retraction and Correction Policy",metaDescription:"Retraction and Correction Policy",metaKeywords:null,canonicalURL:"/page/retraction-and-correction-policy",contentRaw:'[{"type":"htmlEditorComponent","content":"IntechOpen’s Retraction and Correction Policy has been developed in accordance with the Committee on Publication Ethics (COPE) publication guidelines relating to scientific misconduct and research ethics:
\\n\\n1. RETRACTIONS
\\n\\nA Retraction of a Chapter will be issued by the Academic Editor, either following an Author’s request to do so or when there is a 3rd party report of scientific misconduct. Upon receipt of a report by a 3rd party, the Academic Editor will investigate any allegations of scientific misconduct, working in cooperation with the Author(s) and their institution(s).
\\n\\nA formal Retraction will be issued when there is clear and conclusive evidence of any of the following:
\\n\\nPublishing of a Retraction Notice will adhere to the following guidelines:
\\n\\n1.2. REMOVALS AND CANCELLATIONS
\\n\\n2. STATEMENTS OF CONCERN
\\n\\nA Statement of Concern detailing alleged misconduct will be issued by the Academic Editor or publisher following a 3rd party report of scientific misconduct when:
\\n\\nIntechOpen believes that the number of occasions on which a Statement of Concern is issued will be very few in number. In all cases when such a decision has been taken by the Academic Editor the decision will be reviewed by another editor to whom the author can make representations.
\\n\\n3. CORRECTIONS
\\n\\nA Correction will be issued by the Academic Editor when:
\\n\\n3.1. ERRATUM
\\n\\nAn Erratum will be issued by the Academic Editor when it is determined that a mistake in a Chapter originates from the production process handled by the publisher.
\\n\\nA published Erratum will adhere to the Retraction Notice publishing guidelines outlined above.
\\n\\n3.2. CORRIGENDUM
\\n\\nA Corrigendum will be issued by the Academic Editor when it is determined that a mistake in a Chapter is a result of an Author’s miscalculation or oversight. A published Corrigendum will adhere to the Retraction Notice publishing guidelines outlined above.
\\n\\n4. FINAL REMARKS
\\n\\nIntechOpen wishes to emphasize that the final decision on whether a Retraction, Statement of Concern, or a Correction will be issued rests with the Academic Editor. The publisher is obliged to act upon any reports of scientific misconduct in its publications and to make a reasonable effort to facilitate any subsequent investigation of such claims.
\\n\\nIn the case of Retraction or removal of the Work, the publisher will be under no obligation to refund the APC.
\\n\\nThe general principles set out above apply to Retractions and Corrections issued in all IntechOpen publications.
\\n\\nAny suggestions or comments on this Policy are welcome and may be sent to permissions@intechopen.com.
\\n\\nPolicy last updated: 2017-09-11
\\n"}]'},components:[{type:"htmlEditorComponent",content:'IntechOpen’s Retraction and Correction Policy has been developed in accordance with the Committee on Publication Ethics (COPE) publication guidelines relating to scientific misconduct and research ethics:
\n\n1. RETRACTIONS
\n\nA Retraction of a Chapter will be issued by the Academic Editor, either following an Author’s request to do so or when there is a 3rd party report of scientific misconduct. Upon receipt of a report by a 3rd party, the Academic Editor will investigate any allegations of scientific misconduct, working in cooperation with the Author(s) and their institution(s).
\n\nA formal Retraction will be issued when there is clear and conclusive evidence of any of the following:
\n\nPublishing of a Retraction Notice will adhere to the following guidelines:
\n\n1.2. REMOVALS AND CANCELLATIONS
\n\n2. STATEMENTS OF CONCERN
\n\nA Statement of Concern detailing alleged misconduct will be issued by the Academic Editor or publisher following a 3rd party report of scientific misconduct when:
\n\nIntechOpen believes that the number of occasions on which a Statement of Concern is issued will be very few in number. In all cases when such a decision has been taken by the Academic Editor the decision will be reviewed by another editor to whom the author can make representations.
\n\n3. CORRECTIONS
\n\nA Correction will be issued by the Academic Editor when:
\n\n3.1. ERRATUM
\n\nAn Erratum will be issued by the Academic Editor when it is determined that a mistake in a Chapter originates from the production process handled by the publisher.
\n\nA published Erratum will adhere to the Retraction Notice publishing guidelines outlined above.
\n\n3.2. CORRIGENDUM
\n\nA Corrigendum will be issued by the Academic Editor when it is determined that a mistake in a Chapter is a result of an Author’s miscalculation or oversight. A published Corrigendum will adhere to the Retraction Notice publishing guidelines outlined above.
\n\n4. FINAL REMARKS
\n\nIntechOpen wishes to emphasize that the final decision on whether a Retraction, Statement of Concern, or a Correction will be issued rests with the Academic Editor. The publisher is obliged to act upon any reports of scientific misconduct in its publications and to make a reasonable effort to facilitate any subsequent investigation of such claims.
\n\nIn the case of Retraction or removal of the Work, the publisher will be under no obligation to refund the APC.
\n\nThe general principles set out above apply to Retractions and Corrections issued in all IntechOpen publications.
\n\nAny suggestions or comments on this Policy are welcome and may be sent to permissions@intechopen.com.
\n\nPolicy last updated: 2017-09-11
\n'}]},successStories:{items:[]},authorsAndEditors:{filterParams:{sort:"featured,name"},profiles:[{id:"105746",title:"Dr.",name:"A.W.M.M.",middleName:null,surname:"Koopman-van Gemert",slug:"a.w.m.m.-koopman-van-gemert",fullName:"A.W.M.M. Koopman-van Gemert",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/105746/images/5803_n.jpg",biography:"Dr. Anna Wilhelmina Margaretha Maria Koopman-van Gemert MD, PhD, became anaesthesiologist-intensivist from the Radboud University Nijmegen (the Netherlands) in 1987. She worked for a couple of years also as a blood bank director in Nijmegen and introduced in the Netherlands the Cell Saver and blood transfusion alternatives. She performed research in perioperative autotransfusion and obtained the degree of PhD in 1993 publishing Peri-operative autotransfusion by means of a blood cell separator.\nBlood transfusion had her special interest being the president of the Haemovigilance Chamber TRIP and performing several tasks in local and national blood bank and anticoagulant-blood transfusion guidelines committees. Currently, she is working as an associate professor and up till recently was the dean at the Albert Schweitzer Hospital Dordrecht. She performed (inter)national tasks as vice-president of the Concilium Anaesthesia and related committees. \nShe performed research in several fields, with over 100 publications in (inter)national journals and numerous papers on scientific conferences. \nShe received several awards and is a member of Honour of the Dutch Society of Anaesthesia.",institutionString:null,institution:{name:"Albert Schweitzer Hospital",country:{name:"Gabon"}}},{id:"83089",title:"Prof.",name:"Aaron",middleName:null,surname:"Ojule",slug:"aaron-ojule",fullName:"Aaron Ojule",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"University of Port Harcourt",country:{name:"Nigeria"}}},{id:"295748",title:"Mr.",name:"Abayomi",middleName:null,surname:"Modupe",slug:"abayomi-modupe",fullName:"Abayomi Modupe",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/no_image.jpg",biography:null,institutionString:null,institution:{name:"Landmark University",country:{name:"Nigeria"}}},{id:"94191",title:"Prof.",name:"Abbas",middleName:null,surname:"Moustafa",slug:"abbas-moustafa",fullName:"Abbas Moustafa",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/94191/images/96_n.jpg",biography:"Prof. Moustafa got his doctoral degree in earthquake engineering and structural safety from Indian Institute of Science in 2002. He is currently an associate professor at Department of Civil Engineering, Minia University, Egypt and the chairman of Department of Civil Engineering, High Institute of Engineering and Technology, Giza, Egypt. He is also a consultant engineer and head of structural group at Hamza Associates, Giza, Egypt. Dr. Moustafa was a senior research associate at Vanderbilt University and a JSPS fellow at Kyoto and Nagasaki Universities. He has more than 40 research papers published in international journals and conferences. He acts as an editorial board member and a reviewer for several regional and international journals. His research interest includes earthquake engineering, seismic design, nonlinear dynamics, random vibration, structural reliability, structural health monitoring and uncertainty modeling.",institutionString:null,institution:{name:"Minia University",country:{name:"Egypt"}}},{id:"84562",title:"Dr.",name:"Abbyssinia",middleName:null,surname:"Mushunje",slug:"abbyssinia-mushunje",fullName:"Abbyssinia Mushunje",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"University of Fort Hare",country:{name:"South Africa"}}},{id:"202206",title:"Associate Prof.",name:"Abd Elmoniem",middleName:"Ahmed",surname:"Elzain",slug:"abd-elmoniem-elzain",fullName:"Abd Elmoniem Elzain",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Kassala University",country:{name:"Sudan"}}},{id:"98127",title:"Dr.",name:"Abdallah",middleName:null,surname:"Handoura",slug:"abdallah-handoura",fullName:"Abdallah Handoura",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"École Supérieure des Télécommunications",country:{name:"Morocco"}}},{id:"91404",title:"Prof.",name:"Abdecharif",middleName:null,surname:"Boumaza",slug:"abdecharif-boumaza",fullName:"Abdecharif Boumaza",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Abbès Laghrour University of Khenchela",country:{name:"Algeria"}}},{id:"105795",title:"Prof.",name:"Abdel Ghani",middleName:null,surname:"Aissaoui",slug:"abdel-ghani-aissaoui",fullName:"Abdel Ghani Aissaoui",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/105795/images/system/105795.jpeg",biography:"Abdel Ghani AISSAOUI is a Full Professor of electrical engineering at University of Bechar (ALGERIA). He was born in 1969 in Naama, Algeria. He received his BS degree in 1993, the MS degree in 1997, the PhD degree in 2007 from the Electrical Engineering Institute of Djilali Liabes University of Sidi Bel Abbes (ALGERIA). He is an active member of IRECOM (Interaction Réseaux Electriques - COnvertisseurs Machines) Laboratory and IEEE senior member. He is an editor member for many international journals (IJET, RSE, MER, IJECE, etc.), he serves as a reviewer in international journals (IJAC, ECPS, COMPEL, etc.). He serves as member in technical committee (TPC) and reviewer in international conferences (CHUSER 2011, SHUSER 2012, PECON 2012, SAI 2013, SCSE2013, SDM2014, SEB2014, PEMC2014, PEAM2014, SEB (2014, 2015), ICRERA (2015, 2016, 2017, 2018,-2019), etc.). His current research interest includes power electronics, control of electrical machines, artificial intelligence and Renewable energies.",institutionString:"University of Béchar",institution:{name:"University of Béchar",country:{name:"Algeria"}}},{id:"99749",title:"Dr.",name:"Abdel Hafid",middleName:null,surname:"Essadki",slug:"abdel-hafid-essadki",fullName:"Abdel Hafid Essadki",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"École Nationale Supérieure de Technologie",country:{name:"Algeria"}}},{id:"101208",title:"Prof.",name:"Abdel Karim",middleName:"Mohamad",surname:"El Hemaly",slug:"abdel-karim-el-hemaly",fullName:"Abdel Karim El Hemaly",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/101208/images/733_n.jpg",biography:"OBGYN.net Editorial Advisor Urogynecology.\nAbdel Karim M. A. El-Hemaly, MRCOG, FRCS � Egypt.\n \nAbdel Karim M. A. El-Hemaly\nProfessor OB/GYN & Urogynecology\nFaculty of medicine, Al-Azhar University \nPersonal Information: \nMarried with two children\nWife: Professor Laila A. Moussa MD.\nSons: Mohamad A. M. El-Hemaly Jr. MD. Died March 25-2007\nMostafa A. M. El-Hemaly, Computer Scientist working at Microsoft Seatle, USA. \nQualifications: \n1.\tM.B.-Bch Cairo Univ. June 1963. \n2.\tDiploma Ob./Gyn. Cairo Univ. April 1966. \n3.\tDiploma Surgery Cairo Univ. Oct. 1966. \n4.\tMRCOG London Feb. 1975. \n5.\tF.R.C.S. Glasgow June 1976. \n6.\tPopulation Study Johns Hopkins 1981. \n7.\tGyn. Oncology Johns Hopkins 1983. \n8.\tAdvanced Laparoscopic Surgery, with Prof. Paulson, Alexandria, Virginia USA 1993. \nSocieties & Associations: \n1.\t Member of the Royal College of Ob./Gyn. London. \n2.\tFellow of the Royal College of Surgeons Glasgow UK. \n3.\tMember of the advisory board on urogyn. FIGO. \n4.\tMember of the New York Academy of Sciences. \n5.\tMember of the American Association for the Advancement of Science. \n6.\tFeatured in �Who is Who in the World� from the 16th edition to the 20th edition. \n7.\tFeatured in �Who is Who in Science and Engineering� in the 7th edition. \n8.\tMember of the Egyptian Fertility & Sterility Society. \n9.\tMember of the Egyptian Society of Ob./Gyn. \n10.\tMember of the Egyptian Society of Urogyn. \n\nScientific Publications & Communications:\n1- Abdel Karim M. El Hemaly*, Ibrahim M. Kandil, Asim Kurjak, Ahmad G. Serour, Laila A. S. Mousa, Amr M. Zaied, Khalid Z. El Sheikha. \nImaging the Internal Urethral Sphincter and the Vagina in Normal Women and Women Suffering from Stress Urinary Incontinence and Vaginal Prolapse. Gynaecologia Et Perinatologia, Vol18, No 4; 169-286 October-December 2009.\n2- Abdel Karim M. El Hemaly*, Laila A. S. Mousa Ibrahim M. Kandil, Fatma S. El Sokkary, Ahmad G. Serour, Hossam Hussein.\nFecal Incontinence, A Novel Concept: The Role of the internal Anal sphincter (IAS) in defecation and fecal incontinence. Gynaecologia Et Perinatologia, Vol19, No 2; 79-85 April -June 2010.\n3- Abdel Karim M. El Hemaly*, Laila A. S. Mousa Ibrahim M. Kandil, Fatma S. El Sokkary, Ahmad G. Serour, Hossam Hussein.\nSurgical Treatment of Stress Urinary Incontinence, Fecal Incontinence and Vaginal Prolapse By A Novel Operation \n"Urethro-Ano-Vaginoplasty"\n Gynaecologia Et Perinatologia, Vol19, No 3; 129-188 July-September 2010.\n4- Abdel Karim M. El Hemaly*, Ibrahim M. Kandil, Laila A. S. Mousa and Mohamad A.K.M.El Hemaly.\nUrethro-vaginoplasty, an innovated operation for the treatment of: Stress Urinary Incontinence (SUI), Detursor Overactivity (DO), Mixed Urinary Incontinence and Anterior Vaginal Wall Descent. \nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/ urethro-vaginoplasty_01\n\n5- Abdel Karim M. El Hemaly, Ibrahim M Kandil, Mohamed M. Radwan.\n Urethro-raphy a new technique for surgical management of Stress Urinary Incontinence.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/\nnew-tech-urethro\n\n6- Abdel Karim M. El Hemaly, Ibrahim M Kandil, Mohamad A. Rizk, Nabil Abdel Maksoud H., Mohamad M. Radwan, Khalid Z. El Shieka, Mohamad A. K. M. El Hemaly, and Ahmad T. El Saban.\nUrethro-raphy The New Operation for the treatment of stress urinary incontinence, SUI, detrusor instability, DI, and mixed-type of urinary incontinence; short and long term results. \nhttp://www.obgyn.net/urogyn/urogyn.asp?page=urogyn/articles/\nurethroraphy-09280\n\n7-Abdel Karim M. El Hemaly, Ibrahim M Kandil, and Bahaa E. El Mohamady. Menopause, and Voiding troubles. \nhttp://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly03/el-hemaly03-ss\n\n8-El Hemaly AKMA, Mousa L.A. Micturition and Urinary\tContinence. Int J Gynecol Obstet 1996; 42: 291-2. \n\n9-Abdel Karim M. El Hemaly.\n Urinary incontinence in gynecology, a review article.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/abs-urinary_incotinence_gyn_ehemaly \n\n10-El Hemaly AKMA. Nocturnal Enuresis: Pathogenesis and Treatment. \nInt Urogynecol J Pelvic Floor Dysfunct 1998;9: 129-31.\n \n11-El Hemaly AKMA, Mousa L.A.E. Stress Urinary Incontinence, a New Concept. Eur J Obstet Gynecol Reprod Biol 1996; 68: 129-35. \n\n12- El Hemaly AKMA, Kandil I. M. Stress Urinary Incontinence SUI facts and fiction. Is SUI a puzzle?! http://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly/el-hemaly-ss\n\n13-Abdel Karim El Hemaly, Nabil Abdel Maksoud, Laila A. Mousa, Ibrahim M. Kandil, Asem Anwar, M.A.K El Hemaly and Bahaa E. El Mohamady. \nEvidence based Facts on the Pathogenesis and Management of SUI. http://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly02/el-hemaly02-ss\n\n14- Abdel Karim M. El Hemaly*, Ibrahim M. Kandil, Mohamad A. Rizk and Mohamad A.K.M.El Hemaly.\n Urethro-plasty, a Novel Operation based on a New Concept, for the Treatment of Stress Urinary Incontinence, S.U.I., Detrusor Instability, D.I., and Mixed-type of Urinary Incontinence.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/urethro-plasty_01\n\n15-Ibrahim M. Kandil, Abdel Karim M. El Hemaly, Mohamad M. Radwan: Ultrasonic Assessment of the Internal Urethral Sphincter in Stress Urinary Incontinence. The Internet Journal of Gynecology and Obstetrics. 2003. Volume 2 Number 1. \n\n\n16-Abdel Karim M. El Hemaly. Nocturnal Enureses: A Novel Concept on its pathogenesis and Treatment.\nhttp://www.obgyn.net/urogynecolgy/?page=articles/nocturnal_enuresis\n\n17- Abdel Karim M. El Hemaly. Nocturnal Enureses: An Update on the pathogenesis and Treatment.\nhttp://www.obgyn.net/urogynecology/?page=/ENHLIDH/PUBD/FEATURES/\nPresentations/ Nocturnal_Enuresis/nocturnal_enuresis\n\n18-Maternal Mortality in Egypt, a cry for help and attention. The Second International Conference of the African Society of Organization & Gestosis, 1998, 3rd Annual International Conference of Ob/Gyn Department � Sohag Faculty of Medicine University. Feb. 11-13. Luxor, Egypt. \n19-Postmenopausal Osteprosis. The 2nd annual conference of Health Insurance Organization on Family Planning and its role in primary health care. Zagaziz, Egypt, February 26-27, 1997, Center of Complementary Services for Maternity and childhood care. \n20-Laparoscopic Assisted vaginal hysterectomy. 10th International Annual Congress Modern Trends in Reproductive Techniques 23-24 March 1995. Alexandria, Egypt. \n21-Immunological Studies in Pre-eclamptic Toxaemia. Proceedings of 10th Annual Ain Shams Medical Congress. Cairo, Egypt, March 6-10, 1987. \n22-Socio-demographic factorse affecting acceptability of the long-acting contraceptive injections in a rural Egyptian community. Journal of Biosocial Science 29:305, 1987. \n23-Plasma fibronectin levels hypertension during pregnancy. The Journal of the Egypt. Soc. of Ob./Gyn. 13:1, 17-21, Jan. 1987. \n24-Effect of smoking on pregnancy. Journal of Egypt. Soc. of Ob./Gyn. 12:3, 111-121, Sept 1986. \n25-Socio-demographic aspects of nausea and vomiting in early pregnancy. Journal of the Egypt. Soc. of Ob./Gyn. 12:3, 35-42, Sept. 1986. \n26-Effect of intrapartum oxygen inhalation on maternofetal blood gases and pH. Journal of the Egypt. Soc. of Ob./Gyn. 12:3, 57-64, Sept. 1986. \n27-The effect of severe pre-eclampsia on serum transaminases. The Egypt. J. Med. Sci. 7(2): 479-485, 1986. \n28-A study of placental immunoreceptors in pre-eclampsia. The Egypt. J. Med. Sci. 7(2): 211-216, 1986. \n29-Serum human placental lactogen (hpl) in normal, toxaemic and diabetic pregnant women, during pregnancy and its relation to the outcome of pregnancy. Journal of the Egypt. Soc. of Ob./Gyn. 12:2, 11-23, May 1986. \n30-Pregnancy specific B1 Glycoprotein and free estriol in the serum of normal, toxaemic and diabetic pregnant women during pregnancy and after delivery. Journal of the Egypt. Soc. of Ob./Gyn. 12:1, 63-70, Jan. 1986. Also was accepted and presented at Xith World Congress of Gynecology and Obstetrics, Berlin (West), September 15-20, 1985. \n31-Pregnancy and labor in women over the age of forty years. Accepted and presented at Al-Azhar International Medical Conference, Cairo 28-31 Dec. 1985. \n32-Effect of Copper T intra-uterine device on cervico-vaginal flora. Int. J. Gynaecol. Obstet. 23:2, 153-156, April 1985. \n33-Factors affecting the occurrence of post-Caesarean section febrile morbidity. Population Sciences, 6, 139-149, 1985. \n34-Pre-eclamptic toxaemia and its relation to H.L.A. system. Population Sciences, 6, 131-139, 1985. \n35-The menstrual pattern and occurrence of pregnancy one year after discontinuation of Depo-medroxy progesterone acetate as a postpartum contraceptive. Population Sciences, 6, 105-111, 1985. \n36-The menstrual pattern and side effects of Depo-medroxy progesterone acetate as postpartum contraceptive. Population Sciences, 6, 97-105, 1985. \n37-Actinomyces in the vaginas of women with and without intrauterine contraceptive devices. Population Sciences, 6, 77-85, 1985. \n38-Comparative efficacy of ibuprofen and etamsylate in the treatment of I.U.D. menorrhagia. Population Sciences, 6, 63-77, 1985. \n39-Changes in cervical mucus copper and zinc in women using I.U.D.�s. Population Sciences, 6, 35-41, 1985. \n40-Histochemical study of the endometrium of infertile women. Egypt. J. Histol. 8(1) 63-66, 1985. \n41-Genital flora in pre- and post-menopausal women. Egypt. J. Med. Sci. 4(2), 165-172, 1983. \n42-Evaluation of the vaginal rugae and thickness in 8 different groups. Journal of the Egypt. Soc. of Ob./Gyn. 9:2, 101-114, May 1983. \n43-The effect of menopausal status and conjugated oestrogen therapy on serum cholesterol, triglycerides and electrophoretic lipoprotein patterns. Al-Azhar Medical Journal, 12:2, 113-119, April 1983. \n44-Laparoscopic ventrosuspension: A New Technique. Int. J. Gynaecol. Obstet., 20, 129-31, 1982. \n45-The laparoscope: A useful diagnostic tool in general surgery. Al-Azhar Medical Journal, 11:4, 397-401, Oct. 1982. \n46-The value of the laparoscope in the diagnosis of polycystic ovary. Al-Azhar Medical Journal, 11:2, 153-159, April 1982. \n47-An anaesthetic approach to the management of eclampsia. Ain Shams Medical Journal, accepted for publication 1981. \n48-Laparoscopy on patients with previous lower abdominal surgery. Fertility management edited by E. Osman and M. Wahba 1981. \n49-Heart diseases with pregnancy. Population Sciences, 11, 121-130, 1981. \n50-A study of the biosocial factors affecting perinatal mortality in an Egyptian maternity hospital. Population Sciences, 6, 71-90, 1981. \n51-Pregnancy Wastage. Journal of the Egypt. Soc. of Ob./Gyn. 11:3, 57-67, Sept. 1980. \n52-Analysis of maternal deaths in Egyptian maternity hospitals. Population Sciences, 1, 59-65, 1979. \nArticles published on OBGYN.net: \n1- Abdel Karim M. El Hemaly*, Ibrahim M. Kandil, Laila A. S. Mousa and Mohamad A.K.M.El Hemaly.\nUrethro-vaginoplasty, an innovated operation for the treatment of: Stress Urinary Incontinence (SUI), Detursor Overactivity (DO), Mixed Urinary Incontinence and Anterior Vaginal Wall Descent. \nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/ urethro-vaginoplasty_01\n\n2- Abdel Karim M. El Hemaly, Ibrahim M Kandil, Mohamed M. Radwan.\n Urethro-raphy a new technique for surgical management of Stress Urinary Incontinence.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/\nnew-tech-urethro\n\n3- Abdel Karim M. El Hemaly, Ibrahim M Kandil, Mohamad A. Rizk, Nabil Abdel Maksoud H., Mohamad M. Radwan, Khalid Z. El Shieka, Mohamad A. K. M. El Hemaly, and Ahmad T. El Saban.\nUrethro-raphy The New Operation for the treatment of stress urinary incontinence, SUI, detrusor instability, DI, and mixed-type of urinary incontinence; short and long term results. \nhttp://www.obgyn.net/urogyn/urogyn.asp?page=urogyn/articles/\nurethroraphy-09280\n\n4-Abdel Karim M. El Hemaly, Ibrahim M Kandil, and Bahaa E. El Mohamady. Menopause, and Voiding troubles. \nhttp://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly03/el-hemaly03-ss\n\n5-El Hemaly AKMA, Mousa L.A. Micturition and Urinary\tContinence. Int J Gynecol Obstet 1996; 42: 291-2. \n\n6-Abdel Karim M. El Hemaly.\n Urinary incontinence in gynecology, a review article.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/abs-urinary_incotinence_gyn_ehemaly \n\n7-El Hemaly AKMA. Nocturnal Enuresis: Pathogenesis and Treatment. \nInt Urogynecol J Pelvic Floor Dysfunct 1998;9: 129-31.\n \n8-El Hemaly AKMA, Mousa L.A.E. Stress Urinary Incontinence, a New Concept. Eur J Obstet Gynecol Reprod Biol 1996; 68: 129-35. \n\n9- El Hemaly AKMA, Kandil I. M. Stress Urinary Incontinence SUI facts and fiction. Is SUI a puzzle?! http://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly/el-hemaly-ss\n\n10-Abdel Karim El Hemaly, Nabil Abdel Maksoud, Laila A. Mousa, Ibrahim M. Kandil, Asem Anwar, M.A.K El Hemaly and Bahaa E. El Mohamady. \nEvidence based Facts on the Pathogenesis and Management of SUI. http://www.obgyn.net/displayppt.asp?page=/English/pubs/features/presentations/El-Hemaly02/el-hemaly02-ss\n\n11- Abdel Karim M. El Hemaly*, Ibrahim M. Kandil, Mohamad A. Rizk and Mohamad A.K.M.El Hemaly.\n Urethro-plasty, a Novel Operation based on a New Concept, for the Treatment of Stress Urinary Incontinence, S.U.I., Detrusor Instability, D.I., and Mixed-type of Urinary Incontinence.\nhttp://www.obgyn.net/urogyn/urogyn.asp?page=/urogyn/articles/urethro-plasty_01\n\n12-Ibrahim M. Kandil, Abdel Karim M. El Hemaly, Mohamad M. Radwan: Ultrasonic Assessment of the Internal Urethral Sphincter in Stress Urinary Incontinence. The Internet Journal of Gynecology and Obstetrics. 2003. Volume 2 Number 1. \n\n13-Abdel Karim M. El Hemaly. Nocturnal Enureses: A Novel Concept on its pathogenesis and Treatment.\nhttp://www.obgyn.net/urogynecolgy/?page=articles/nocturnal_enuresis\n\n14- Abdel Karim M. El Hemaly. 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