Some works on the use of pure chitosan form as corrosion inhibitor.
\r\n\tIn this book, the authors will present the highlights of basic research of biomechanical and biochemical pathways of bone homeostasis and the developing clinical methods for treatment of bone loss, either following trauma or systemic disease.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"a67783226e0c4e1343d82c3a811ba1b3",bookSignature:"Dr. Nahum Rosenberg",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8442.jpg",keywords:"Bone Homeostasis, Osteoblast, Bone Matrix, Inorganic Component, Organic Componet, Bone Resorption, Cellular Mechanotransduction, Hormonal Regulation, Autografts, Allografts, Distraction Osteogenesis",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"April 11th 2019",dateEndSecondStepPublish:"September 20th 2019",dateEndThirdStepPublish:"November 19th 2019",dateEndFourthStepPublish:"February 7th 2020",dateEndFifthStepPublish:"April 7th 2020",remainingDaysToSecondStep:"a year",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"68911",title:"Dr.",name:"Nahum",middleName:null,surname:"Rosenberg",slug:"nahum-rosenberg",fullName:"Nahum Rosenberg",profilePictureURL:"https://mts.intechopen.com/storage/users/68911/images/system/68911.png",biography:"Nahum Rosenberg MD, MOrthop (magna cum laude), FRCS\n(England), MBA is an orthopedic surgeon with an MD degree\nfrom Technion – ITT in 1990. He completed his residency in Orthopedic Surgery at the Rambam Medical Center, Haifa between\n1990-97. He received his MOrthop with honors from the Tel Aviv\nUniversity in 1996 and was a Nuffield Fellow (Orthopedic Surgery) in Oxford University in 1998-9. Dr. Nahum was a Fellow\nin Orthopedic Surgery at the University of Nottingham in 2002. He completed his\nMBA from the College of Management Academic Studies, Israel in 2018. Dr. Nahum\nis a senior orthopedic surgeon at the Rambam Health Care Campus since 2003. He\nhas been an Assistant Clinical Professor in the Faculty of Medicine, Technion -ITT,\nHaifa since 2007. He is also a Professor in the Department of Traumatology, Orthopedic Surgery and Disaster Medicine in IM Sechenov First Moscow State Medical\nUniversity 2018-19. Dr. Nahum is a member of the editorial boards in 8 scientific\njournals, as well as a member of the Shoulder Committee of ISAKOS (International Society of Arthroscopy, Knee Surgery and Orthopedic Sports Medicine). He is\nthe author of 80 peer review scientific publications, and the editor of 7 books. His\nresearch interests include: shoulder surgery, the outcome of orthopedic procedures,\nbone biology, bone regeneration, human biomechanics.",institutionString:"Israel Institute of Technology",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"Tel Aviv Sourasky Medical Center",institutionURL:null,country:{name:"Israel"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"194667",firstName:"Marijana",lastName:"Francetic",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/194667/images/4752_n.jpg",email:"marijana@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"43776",title:"Treatment of Generalized Anxiety Disorders: Unmet Needs",doi:"10.5772/53453",slug:"treatment-of-generalized-anxiety-disorders-unmet-needs",body:'Generalized anxiety disorder (GAD) is defined in the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition (DSM-IV) as the presence of persistent, excessive anxiety and worry about a number of events and activities occurring on most of the days for at least 6 months. The patient must also experience at least three of the following six symptoms: restlessness or feeling keyed up or on edge, being easily fatigued, difficulty concentrating or mind going blank, irritability, muscle tension, and sleep disturbance.
GAD has a 12-month prevalence of 1% – 2.1% and a lifetime prevalence of 2.8% – 4.1% in Europe and in the US (Grant et al., 2005), often occurs early in life with twice the number of women suffering from it compared to men (ESEMeD/MHEDEA Investigators, 2000). GAD is chronic and disabling, and is associated with high rates of psychiatric comorbidity and substantial personal, social and economic costs (Wittchen et al., 1994; Ballenger et al., 2001; Wittchen, 2002). Evidence shows GAD’s impact on social functioning, distress levels, and utilization of medical care is equivalent to those of other major psychiatric disorders (Mennin et al. 2004). In the National Comorbidity Survey, Wittchen and colleagues found that ~38% of patients with GAD may have another anxiety disorder and 48% may have major depression in addition to GAD (Wittchen et al., 1994). In addition to psychiatric comorbidities, patients with anxiety disorders have a higher risk for developing medical diseases in the areas of cardiovascular, gastrointestinal and respiratory as compared with control groups (Bowen et al., 2000).
Remission criteria defined by Ballenger include no or minimal symptoms of anxiety (Hamilton Anxiety Scale score ≤7-10), no functional impairment (Sheehan Disability Scale score ≤1 on each item) and no or minimal symptoms of depression (Hamilton Depression Scale score ≤7) for generalized anxiety disorder (Ballenger, 1999). Remission rates are considerably low in generalised anxiety disorder. Yonkers and colleagues have shown that the remission rates are only 15% and 25% among 164 patients after one and two years respectively (Yonkers et al., 1996). The probability of remission of GAD is only 38% at 5 years, and the probability of relapse after remission is 27-39% by 3 years (Yonkers et al., 2000).
GAD is often unrecognized or misdiagnosed as a physical condition due to the range of clinical presentations, including somatic symptoms, and the frequent occurrence of comorbid conditions. The main treatment approaches for GAD comprise pharmacotherapy or psychotherapy or a combination of both. The chronic and disabling nature of GAD often means that some individuals may fail to respond fully to first-line treatment (Bandelow et al., 2008; Goodwin et al., 2002; Altamura et al., 2008; Allgulander et al., 2002; Baldwin et al; 2005). Patients may therefore require a sequential trial of treatments or possibly a combination therapy (Davidson et al; 2010).
Research in the treatment of GAD has primarily focused on the efficacy of pharmacotherapy. Antidepressant and anxiolytic drugs are the two most commonly used pharmacological treatments for anxiety disorders. Newer anticonvulsant and sometimes antipsychotic drugs are also used in the treatment of some anxiety disorders including generalized anxiety disorder. More recently, there has been an increasing interest in the efficacy of psychotherapy. Of all the therapies, cognitive behavioral therapy (CBT) has established the most empirical support as an effective treatment for GAD (Gould et al. 2004).
In recent years, GAD-related disability (Wittchen, 2002) as well as impairment in quality of life and functioning has gain importance. Anxiety disorders result in considerable economic loss both decreasing working performance and increasing the number of applications for health care services (Wittchen, 2002; DuPont et al., 1996; Greenberg et al., 1999 ). GAD poses both personal and public substantial economic and social burden (Pollack et al., 2009).
According to the preliminary findings of our ongoing study on the evaluation of patient burden due to wrong diagnosis and treatment in patients with generalized anxiety disorder (GAD), the mean duration of GAD was 5.6±6.1 years, and the patients received initial treatment for their GAD 27.6±36.7 for months ago. It was noted that GAD was mostly accompanied by major depression (60.5%), followed by other anxiety disorders (31.6%). Of the patients diagnosed with GAD, 86.4% were using medication for GAD and 40.9% were admitted to an emergency service for any reason within the last 6 months. The mean number of emergency admissions was 3.1±3.7. Of the patients admitted to emergency services, 51.9% underwent analyses such as blood analysis, radiological examination, electrocardiography (ECG) and ultrasonography (USG), and 48.5% were referred to another specialist for consultation. The preliminary findings of the present study indicate that admissions of GAD patients to emergency services due to various complaints continue when these patients are not treated adequately and sufficiently, and that financial burden of this disorder increases incrementally due to laboratory analyses and imaging techniques, consultations and additional therapies performed during these admissions (Dilbaz and Karamustafalıoğlu 2012a).
This chapter presents the unmet needs in the treatment of generalised anxiety disorders and new strategies in treatment for GAD.
The primary goal of treatment of GAD is to alleviate psychic and somatic complaints, promote sleep, improve patient’s functioning and enhance patient quality of life. Besides, treating other concomitant medical conditions (psychiatric and/or medical co-morbidity) and consequently providing remission and preventing relapses are also aimed. The important requirements for the therapy drug include rapid action, broad spectrum, increasing remission rates, preventing relapses, absence of symptoms due to discontinuation of drug, minimum interaction with other drugs, and safety for elderly and children (Dilbaz et al., 2011; Davidson et al., 2010). Treatment of GAD comprises drug therapy together with behavioral therapy and psychotherapy. Characteristics and severity of symptoms, co-morbidities, presence of substance addiction and risk for suicide, results of previous therapies, costs, availability of drug and patient preference should be considered while planning GAD treatment (Davidson et al., 2010).
Many randomized, double-blind trials have demonstrated the efficacy of benzodiazepines in the acute treatment of GAD (Greenblatt et al., 1983; Rickels et al., 1987; Hollister et al., 1993). However, there is evidence that more than a third of patients will not meet remission criteria in the treatments with benzodiazepines (Shader and Greenblatt, 1983).
The risks and benefits of using benzodiazepines should be carefully considered in each patient. Benzodiazepines have rapid onset, relatively low toxicity, and anxiolytic potency but these benefits should be weighed against for potential motor impairment, dependence and withdrawal symptoms esspecially when prescribed for >4 weeks (Rynn and Brawman-Mintzer, 2004).
Particularly in older people, benzodiazepine use can be problematic due to side effects such as falls, memory impairment, incoordination, drowsiness, and confusion (Petrovic et al., 2003). They can also disrupt sleep architecture, and rebound insomnia may occur after stopping treatment (Longo and Johnson, 2000).
Selective serotonin reuptake inhibitors (SSRIs), serotonin noradrenalin reuptake inhibitors (SNRIs), tricyclic antidepressants (TCAs, particularly imipramine), and, in a single controlled trial, trazodone have demonstrated efficacy in treatment of GAD compared to placebo (Rickels et al., 1993). Several analyses have shown similar efficacy among antidepressant agents in the management of GAD (Kapczinski et al, 2003).
Of these, SSRIs and SNRIs are the recommended first-line drugs for treatment of anxiety based on strength of evidence and acceptable tolerability. Antidepressants, particularly SSRI, may be associated with an initial worsening of anxiety symptoms in some patients. A retrospective cohort study defined characteristics of patients which developed emergent anxiety following an antidepressant intiation as young age, white and women sex (Li et al.,2011). Li et al. also found that receiving bupropion, fluoxetine or sertraline had lower risk of anxiety development than citalopram, paroxetine, venlafaxine and mirtazapine (Li et al, 2009). It is recommended to start on low doses and slowly titrate up to a therapeutic dose to reduce these “activation” symptoms (Sinclair et al., 2009). Patients should be advised of the potential for initial increase/worsening of symptoms and the likely delay of clinical effect (some response often seen by 4 weeks). Patient awareness of these factors when commencing SSRI treatment assists in reducing early discontinuation of treatment. Concomitant use of benzodiazepines during early treatment with SSRI may be useful in moderating these “activation effects” of SSRI early in treatment, although the potential for dependence must be considered. SSRI need to be taken for up to 12 weeks in order to assess a patient’s response to treatment. Dosing requirements (like initiation in lower doses and reaching optimal doses by weekly increments) for antidepressants differ to that needed in the treatment of depression. All patients being treated with antidepressants (irrespective of diagnosis) should be monitored for worsening of their clinical condition and the emergence of suicidal ideation (Anxiety Disorders – Drug Treatment Guidelines, 2008)
According to Western Australian Psychotropic Drugs Committee; sertralin, escitalopram and venlafaxin have second line of evidence in treatment of generalized anxiety disorders whereas paroxetine has first line evidence (Hidalgo et al., 2007; Kapczinski et al., 2003; Anxiety Disorders – Drug Treatment Guidelines, 2008). There was a small statistically significance in favour of escitalopram compared with paroxetine based on a reduction in HAM-A scores. In addition, there was a 40% reduction in risk of non-response and lower risk (although not statistically significant) of discontinuation of treatment due to adverse events for escitalopram compared with paroxetine (Baldwin et al., 2006). There were no statistically significant differences found between paroxetine and sertraline on any outcomes (Ball et al., 2005).
There were no differences found on reduction of anxiety symptoms between escitalopram and venlafaxine while venlafaxine was associated with a greater risk of discontinuation (although this was not statistically significant) (Bose et al., 2008). Duloxetine was found to be effective in 60-120 mg/d doses in treatment of generalised anxiety disorder when compared to placebo (Rynn et al., 2008; Hartford et al., 2007). No difference was found between duloxetine and venlafaxine for reduction in anxiety and discontinuation due to adverse events (Nicolini et al; 2009).
Bystritsky and colleagues compared bupropion XL and escitalopram in 24 patients with generalised anxiety disorder in a 12-week, double-blind, randomized controlled trial and reported comparable efficacy between bupropion and escitalopram (2008).
The efficacy of 25 to 50 mg/day agomelatine in generalised anxiety disorder (GAD) was assessed in a 12-week double-blind, placebo-controlled study of 121 patients with no comorbid disorders (Stein et al., 2008). Agomelatine was found more effective than placebo at reducing anxiety (based on Hamilton rating scale for Anxiety; p=0.04). Agomelatine also improved sleep symptoms, sleep latency (p≤0.001), quality of sleep (p=0.002) and awakenings (p≤0.0001).
Valproate has been investigated for the management of GAD in a double-blind, placebo-controlled randomized trial involving 80 male patients with GAD in a double-blind placebo-controlled design (Aliyev and Aliyev, 2008). 40 patients randomized to receive 500 mg valproate three times per day and 40 patients received mathed plasebo. At week 4, valproate separated from placebo by mean total HARS score, and at 6 weeks, the mean change in HARS score reached significance. The most common side effects in the valproate group were dizziness and nausea and further investigation is recommended.
Pollack and colleagues reported two cases documenting improvements in patients with GAD, following addition of gabapentin to their treatment (Pollack et al., 1998).
There are case series documenting patients with generalised anxiety disorder treated with tiagabine successfully (Schwarts, 2002; Crane et al., 2003; Schaller et al., 2004). Schwartz et al followed up 17 patients with GAD in an 8-week, open-label trial of tiagabine (mean dose 13 mg/d) augmentation to SSRIs or benzodiazepines. 76% of patients responded [≥ 50% reduction in anxiety symptoms (HARS)] and 59% achieved remission (HARS score ≤ 7) (Schwartz et al., 2005).
Pollack et al reported on 3 large 10-week, randomized, double-blind, placebo-controlled, parallel-group studies. In the fixed-dose study, 910 patients received 4, 8, or 12 mg/d of tiagabine and in two flexible-dose studies, a total of 920 participants were enrolled. The mean doses of tiagabine were 8.9 and 9.2 mg/d. Neither study found significant differences in anxiety symptoms (HARS used) when compared to placebo and investigators concluded that these studies do not support the efficacy of tiagabine in adult patients with GAD (Pollack et al., 2008).
There have been several industry-sponsored, multicenter, outpatient, prospective, randomized, double-blind, placebo-controlled studies. Pande et al. showed a significant improvement with pregabalin compared to placebo, but no significant differences in response were observed when comparing pregabalin 50 mg tid to pregabalin 200 mg tid or lorazepam to pregabalin 200 mg tid. The most commonly associated adverse events with pregabalin were dizziness, somnolence, and headache (Pande et al., 2003). Feltner and colleagues also compared pregabalin (in different doses), lorazepam 2 mg tid, or placebo. They also found pregabalin 200 mg tid effective in treatment of GAD, however, pregabalin 50 mg tid wasn’t effective and 200 mg tid was not significantly different from lorazepam (Feltner et al., 2003). Pohl et al. found pregabalin in 100 mg bid, 200 mg bid, and 150 mg tid doses significantly effective than in reducing anxiety symptoms (Pohl et al., 2005).
In another large study of 454 participants with GAD, Rickels et al. compared pregabaline (in different doses) with alprazolam and placebo. Investigators reported that of the 5 treatment groups, the 300-mg pregabalin group was the only medication group that differed statistically in global improvement at treatment end point not only from the placebo group but also from the alprazolam group (Rickels et al., 2005). Another study found pregabaline (400-600 mg/day) effective in treatment of GAD compared to placebo and safer than venlafaxine (Montgomery et al., 2006).
Lydiard et al combined data from 6 short-term, double-blind, placebo-controlled, fixed-dose trials of pregabalin for the treatment of GAD. They concluded that pregabalin had significant efficacy in treating both HARS psychic and somatic anxiety measures. Furthermore, they indicated that a dose-response effect was evident for pregabalin that appeared to reach a plateau at a dose of 300 mg/d (Lydiard et al., 2010).
Pregabalin is promising in both add-on and switch therapies in treatment-resistant GAD cases. Pregabalin rapidly (within days) relieves anxiety symptoms providing substantial advantage over SSRI and SNRIs (Dilbaz and Karamustafalıoğlu, 2012a).
One case with GAD reported by Pollack, had improved with levetiracetam 250 mg/d added to citalopram treatment (Pollack, 2002).
Some first-generation antipsychotics were approved for a condition similar to GAD, and recent studies have suggested that atypical antipsychotics may also have a role in GAD. A Cochrane metaanalysis reported that nine studies investigated the effects of second-generation antipsychotics in generalised anxiety disorder. Seven of them investigated the effects of quetiapine. Participants with generalised anxiety disorder responded significantly better to quetiapine than to placebo (4 RCTs, N = 2265, OR = 2.21, 95% CI 1.10 to 4.45). However, patients on quetiapine arm were more likely to drop out due to adverse events, like gain weight or sedation. When quetiapine was compared with antidepressants in GAD, there was no significant difference in efficacy-related outcomes, but more participants in the quetiapine groups dropped out due to adverse events.
Several preliminary reports of monotherapy trials of quetiapine versus placebo have described efficacy at doses in the range of 50–150 mg/d (Chouinard et al., 2008; Khan et al., 2008; Joyce et al., 2008; Bandelow et al., 2009), but quetiapine cannot yet be recommended as a routine GAD treatment until a full description of efficacy and safety from these studies have been published. However, the use of quetiapine could be considered after other classes of drugs have proved ineffective or when certain types of symptoms are present like insomnia.
Pollack investigated olanzapine augmentation to fluoxetine at a mean dose of 8.7 mg daily and reported that olanzapine may be helpful for patients who fail to respond to SSRIs alone, considering the advers events like wight gain (Pollack et al., 2006).
Two studies demonstrate that aripiprazole has promise in augmentation at dosages starting at 10 mg daily (Menza et al., 2007; Hoge et al., 2008).
Adjunctive risperidone could be tried in patients with poor response at titrated doses up to 3 mg daily (Brawman-Mintzer et al., 2005; Simon et al., 2006).
Ziprasidone at a daily dose range of 20 to 80 mg may be helpful for patients with GAD who did not have an adequate response to other medication treatment (Snyderman et al., 2005).
Buspirone was approved for the treatment of GAD more than 20 years ago. In recent years, multiple members of the azapirone class, which comprises the partial or full 5-HTIA agonists gepirone, zalospirone, and ipsapirone, have been studied. These molecules show anxiolytic properties but have limitations in terms of tolerability. In a recent brief report, Mathew et al. tested the short-term tolerability and efficacy of PRX-00023, a nonazapirone 5-HTIA selective partial agonist, in 23 outpatients with GAD (Mathew et al., 2008). This preliminary study indicated that PRX-00023 appeared to be generally well tolerated in patients with GAD. But further investigations needed.
Although double-blind, placebo-controlled trials are lacking, several open label trials have suggested that riluzole, either as monotherapy or as augmentation of standard therapy, reduces symptoms of some psychiatric disorders including generalized anxiety disorder (Grant et al., 2007; Mathew et al., 2005).
Mathew et al.,investigated the efficacy and safety of treatment with riluzole (100 mg/day): of the 15 patients who completed the trial, 12 had a rapid improvement of anxiety symptomatology (Mathew et al., 2005). Recently, Mathew et al. (2008), in an open-label trial, used proton magnetic resonance spectroscopic imaging (1H MRSI) to examine the effects of the glutamate-release inhibitor riluzole on hippocampal N-acetylaspartate (NAA), a neuronal marker, in 14 patients with GAD. Investigators demonstrated a relationship between hippocampal NAA and symptom alleviation after the administration of riluzole in patients for 8 weeks; this result suggested that riluzole might be efficacious for GAD (and subtypes of mood disorders) in part because of reduced glutamate excitotoxicity and enhancement of hippocampal neuroplasticity. In studies of psychiatrically ill patients conducted to date, the drug has been quite well tolerated; common adverse effects include nausea and sedation. Elevation of liver function tests is common and necessitates periodic monitoring. Riluzole may hold promise for the treatment of several psychiatric conditions, possibly through its ability to modulate pathologically dysregulated glutamate levels, and merits further investigation (Pittenger et al., 2008).
One of the most successful psychosocial treatments for the treatment of GAD is cognitive-behavioral therapy (CBT). The components of this therapy may vary to include the following: education about the symptoms and causes of anxiety, cognitive restructuring, applied relaxation, increasing awareness, learning to monitor of anxious symptoms presenting as physical symptoms, and the automatic thoughts of worry created from situational and behavioral cues. Patients are taught to manage these symptoms through training in arousal reduction techniques such as pleasant imagery and diaphragmatic breathing; and imaginal and in vivo exposure to anxiety cues coupled with copings skill rehearsal (Roemer et al; 2002).
A Cochrane collaboration review concluded that current evidence demonstrates that CBT is effective for the short-term management of GAD relative to wait-list control but not active supportive therapy or supportive treatment (ie, active supportive therapies underpinned by humanistic principals). The most successful CBT treatment protocols have included motivational therapy, interpersonal psychotherapy, integrative CBT (ICBT) to treat GAD (Baer, 2003). Although CBT is the most effective of the psychological treatments available for GAD, available data indicate that a clinical response occurs in less than 50% of people receiving CBT, so unmet needs still remain (Hunot et al., 2007).
One promising form of psychotherapy emphasizes the promotion of positive emotional states and active coping behaviors, rather than focusing on how to reduce symptoms. This resilience-building treatment is referred to as “well-being therapy” and appears to be superior to CBT on some measures in treatment-resistant GAD and other forms of anxiety (Fava et al., 2005).
A number of approaches have integrated features of Buddhist mindfulness practices with CBT to treat a number of psychiatric disorders including GAD (Baer 2003). Mindfulness was conceptualized as being a set of skills that can be learned independently of any spiritual or cultural tradition and then applied to help manage psychiatric symptoms. These approaches have included mindfulness based stress reduction (MBSR) (Kabat-Zinn 1982, 2003), mindfulness based cognitive therapy (MBCT) (Segal et al. 2002), dialectical behavior therapy (DBT) for borderline personality disorders (Linehan 1993a, b), and acceptance and commitment therapy (ACT) mostly for anxiety and major mood disorders (Hayes et al. 1999).
There are two objectives associated with classical mindfulness (CM) skill training for treating GAD: (1) to achieve a level of sustained, detailed, non-conceptual divided attention and awareness (also known as bare attention or direct experience), and (2) develop the ability to carry out experiential based insight based on the way of experiencing as described in (1). These two objectives clearly imply that there are two major stages of mindfulness practice. The first stage is training in sustaining, detailed, nonconceptual divided attention and awareness which needs to be distinguished as significantly different from MBSR practice of mindfulness. The second stage involves the reinstatement of gradual application of discriminative processes informed by direct experience in order to enrich the process of knowing (Rapgay et al., 2011).
MBCT may be an acceptable and potentially effective treatment for reducing anxiety and mood symptoms and increasing awareness of everyday experiences in patients with GAD. Future directions include development of a randomized clinical trial of MBCT for GAD (Evans et al., 2008).
CBT in combination with a sub-therapeutic dose of diazepam produces a greater effect than the same dose of diazepam alone (Power, et al., 1989). Given that GAD has a chronic course and is often comorbid with depression it may be that the combined treatment of medication and psychotherapy may provide an important treatment option that could lead to improved outcomes beyond monotherapy (Barlow, 2002). Unfortunately, at this time there is no data to support this conclusion.
GAD is a prevalent and disabling disorder that may appear with physical and psychiatric comorbitidies. SSRIs and SNRIs defined as first line treatment options in GAD, and there is increasing interest in enhancement new strategies to deal with the disorder. Novel antidepressants agomelatine and bupropion, atypical antipsychotics and anticonvulsants are promising in the treatment of GAD but still far from expectations because the necessity of close monitoring and some adverse events. Pharmacological interventions are still the most effective interventions to manage the disorder while augmentation strategies promising. However clinicians still in need of more effective treatment options that have rapid effect and safe.
Metal corrosion is defined as a spontaneous deterioration of metallic materials caused by the adjacent environments (e.g. during the acidic cleaning process) through electrochemical and/or chemical processes. Such a phenomenon is inevitable due to its undesirable outcomes on technological and industrial applications, which leads to huge loss of natural resources, human lives and economic [1]. In this regard, researchers were compelled to perform several scientific investigations to extend the working life of these materials and to overcome the devastating impact of corrosion. Among available technical solutions, the addition of corrosion inhibitors into the aggressive environment seems to be an attractive and economic technic to effectively control corrosion [2]. Diverse organic and inorganic substances have been employed as anti-corrosion compounds for many metal-environment systems [3]. Another efficient strategy to extend the life of metallic-based materials and protect them against corrosion is the application of organic coatings [4, 5, 6, 7].
In the present chapter, we interesting in the organic inhibitor category, which its protection ability is related to its adsorption onto the metal surface via electrostatic attraction or/and chemical bond formation, leading to the formation of a protective layer resulting in corrosion mitigation [8]. It is well known that the adsorption process of these compounds occurs via their electron-donator sites like heteroatoms (N, O, S and P) and multiple bonds (π-bonds) and aromatic rings as well. Even they are efficient, recently, the exploitation of organic substances as corrosion retarders has been limited by several strict environmental rules, and such a trend aims to limit their unsafe menace to ecology and health [9].
At this time, the use of biopolymers as promising replacement of toxic corrosion inhibitors is considered a new trend and novel strategy to omit metallic corrosion. One of the key advantages of these bio-macromolecules is their increased attachment sites to the metallic substrate, rising to good film-formation and adhesion as compared to small molecule inhibitors [10]. This capability can be further boosted by the insertion of additional adsorption sites, i.e. functional groups, within the biopolymers backbone [11]. On the other hand, these biopolymers are biodegradable, biocompatible, cheap and non-toxic. Besides, they are readily available and renewable sources of materials [12]. All these characteristics have made them ideal candidates to mitigate ecologically metallic corrosion. In this regards, a large variety of natural polymers are reported to act as anti-corrosion agents to secure the metal against dissolution such as alginate, sodium chitosan, pectin, carboxymethyl and hydroxylethyl cellulose [13, 14].
Among available biopolymers, chitosan (Figure 1(a)) was especially exhibited a noticeable ability to control corrosion. It is characterized by the existence of oxygen (of alcohol and ether functional groups) and nitrogen (of amine group) atoms within its backbone chain. These sites are known to act as the effective centers of adsorption to metallic substrates. Chitosan can be obtained by the deacetylation of chitin (Figure 1(b)), a natural polysaccharide and the main structural component of crustacean exoskeletons, and is soluble in acid media as compared to chitin, which is a highly insoluble and a non-reactive biopolymer [15]. Furthermore, chitosan exhibits a polycationic character and is non–toxic and biodegradable [16, 17].
Molecular structure of (a) chitosan and (b) chitin bio-macromolecules.
Recently, the application of chitosan-based compound as ecofriendly corrosion inhibitor was extended to the use of its functionalized form instead of pure one. Such tendency aims to decorate chitosan backbone with particular functional motifs, generally, through the chemical modification of the amino groups. Furthermore, the enhancement of chitosan capability for protection purposes has been also attained via its combination with other chemical materials to prepare nanoparticle composites, which are served to act as the effective coatings to mitigate corrosion. In this context, it has been reported that the combination of nano-scaled organic and inorganic fillers can successfully improve mechanical, adhesion and barrier qualities of polymer coatings [18]. Among the used additives in the matrix of chitosan-based coatings, there are zinc oxide, graphene oxide and hydroxyapatite nanoparticles.
On this basis, we aimed in the present chapter to shed more light on the merits to employ different chitosan forms as sustainable compounds for corrosion controlling of metallic materials in different aggressive environments.
Chitosan is a naturally occurring polymer that meets the requirements to be classified as a green corrosion inhibitor, which is a low-cost alternative of widely used inhibitors in industrial applications. The solubility of inhibitor into the target corrosive media is one of among key prerequisites that judges its utilization. For instance, such property has limited the use of chitin biopolymer as a corrosion inhibitor. In this regard, temperature, degree of deacetylation, solution’s pH and molecular weight are the main factors affecting the solubilization of chitosan in the aqueous media. For instance, at the higher temperatures, with higher molecular weight (>29.2 kDa) and lower deacetylation degree, low water-solubility of pure chitosan was observed [19, 20].
As an inhibiting additive, pure chitosan has been reported to act as an effective retarder of corrosion in different aggressive environments, namely saline and acidic solutions, as well as natural ones such as seawater. Up to now, pure chitosan compound is widely applied for iron and its alloys, like mild steel and carbon steel. This particular attention owing to the fact that these metallic materials are extensively used in numerous industrial applications in which their corrosion is more intense. Table 1 collects the obtained inhibition efficiency (IE) for pure chitosan for some metallic materials in different corrosive environments. From tabulated data, it is clear that pure chitosan can act as a potent ecofriendly corrosion inhibitor even in the most aggressive environments. This is attributed to the formation of a protective layer upon the metal surface, which prevents it attack by the aggressive species present in the solution.
Metallic material | Aggressive medium | IE(%) at [chitosan] | Ref. |
---|---|---|---|
mild steel | 0.1 M HCl | 93% at 1.8 mM | [21] |
carbon steel | 1.0 M HCl | 93% at 5000 ppm | [22] |
mild steel | 3.65% NaCl | 90% at 1.2 wt% | [23] |
copper | 1.0 M HCl | 87% at 0.1 mg L−1 | [24] |
copper | Synthetic seawater +20 ppm Na2S | 89% at 800 ppm | [25] |
316 austenitic | 0.1 M HCl | 71% at 11 mM | [26] |
mild steel | 0.1 M HCl | 69% at 4 μM | [27] |
Some works on the use of pure chitosan form as corrosion inhibitor.
As mentioned above, the molecular weight of chitosan biopolymer can affect its solubility, consequently, the attained prevention efficiency. In this context, lower inhibition efficiency has been obtained for mild steel in seawater employing chitosan with higher molecular weights [28]. Furthermore, the role of exposure time to the corrosive solution on the ability of pure chitosan to reduce metallic dissolution was also evaluated. In the CO2-saturated saline environment, the extension of immersion time has implied an improvement in the inhibitive action of chitosan [29]. In another study, the opposite behavior is outlined from which the reduction of the inhibition efficiency is attributed to the destruction of the dense adsorbed film on the metal surface at longer exposure times [30]. Concerning the influence of temperature on the inhibition process of pure chitosan, there is no commune agreement, which a favorable effect is observed by some researchers, whereas the opposite one is reported by other ones [26].
To improve the inhibition property of pure chitosan form for some metal/solution systems, the synergistic corrosion inhibiting effect was applied. In this enhancement strategy, additional compounds such as cations and anions species are added into the corrosive solution with chitosan. As result, remarkable enhancement of protection capabilities of chitosan is pointed out. For instance, the combination of pure chitosan (200 ppm) with 5 ppm of KI was led to a significant improvement of the inhibition efficiency for mild steel in acidic solution, which 90% prevention percentage was achieved instead of 74% in the case of chitosan alone [31]. In this regard, a similar tendency is noted for another steel variety, i.e. St37 steel, in concentrated sulfuric acid solution in which 92% inhibition efficiency is attained [32]. On the other hand, it was found that the adsorption mechanism of chitosan onto metal surface depends on the adopted circumstances. Chitosan can adsorb on the metal surface either via physisorption or chemisorption modes [22, 27].
The current trend in the use of chitosan-based compounds as corrosion inhibitors is its functionalization, afterward its application. This novel approach aims to increase the solubilization of these bio-compounds in almost corrosive media and to enhance their adsorption and adhesion abilities to the metallic surface. In this respect, further polar functional groups are attached to the chitosan molecular skeleton. The chemical modifications of chitosan biopolymer are often performed at amine group, which is an active site. As result, various chitosan-based derivatives with different structural compositions have been synthesized and then used to retard or suppressed metal corrosion in different aggressive environments. Even the simplest chitosan derivative, i.e. carboxymethyl chitosan (Figure 2(a)), an improved inhibition efficiency is attained as compared to the pure chitosan form, which is increased from 23 to 38% for steel in wastewater liquids [33].
Molecular structure of some chitosan derivatives used as corrosion inhibitors.
Depending on the molecular structure, functionalized chitosan-based inhibiting additives could be classified into several categories, namely, chitosan Schiff bases, chitosan surfactants, triazole modified chitosan, chitosan polymeric salts, PEG cross-linked chitosan, carboxymethyl hydroxypropyl chitosan, chitosan thiocarbohydrazide, acid grafted chitosan, acetyl thiourea chitosan, polymer and biomaterial grafted chitosan. Here, we limit to present the inhibition activity of the three first functionalized chitosan sets.
During the last decade, Schiff bases class compounds have been attracted exceptional attention to be applied in the field of corrosion inhibition owing to the presence of imine linkage, i.e. −CH=N–. They are reported to act as potent anti-corrosion compounds for different metallic materials, especially in acidic solutions [34]. In this respect, the synthesis of chitosan Schiff bases derivatives via condensation reaction and/or under microwave irradiations are conducted. It was found that the introduction of Schiff bases functional group into the chitosan skeleton leads to a significant enhancement in the inhibition property and film adhesion of polymer on the metal surface. Generally, the achieved prevention efficiencies using those chitosan-based derivatives were higher than 80%, which outlined that chitosan Schiff base could be an appropriate candidate to employ as effective anti-corrosion agents [35]. Recently, three chitosan Schiff bases derivatives (CSB-1, −2 and − 3, Figure 2(b)) have been synthesized under microwave irradiations and tested as corrosion inhibitors for mild steel in acidic solution. According to the obtained experimental data, these modified chitosan compounds were exhibited significant tendencies to reduce metallic corrosion even at a lower concentration, which the supreme prevention efficiencies of 91, 87 and 85% (at 50 ppm) were attained for CSB-3, −2 and − 1, respectively [36]. Another chitosan-modified Schiff base, namely, the salicylaldeyde-chitosan Schiff base (Figure 2(c)), has been reported to act as a good inhibitor (IE(%) = 95.4% at 150 ppm) for J55 steel-variety in 3.5% NaCl solution saturated with carbon dioxide at elevated temperature. The merits of developed functionalized chitosan including its eco-friendly aspect, safe, simple and cheap synthesize of used Schiff base, as well as the improvement of inhibitor solubility compared to unmodified chitosan. All these listed advantages make salicylaldeyde-chitosan Schiff base as a good anti-corrosion agent for the oil and gas industries [37].
Surfactant is a surface-active agent that characterizes by the presence of hydrophilic and hydrophobic groups per molecule. These chemical compounds are largely served as effective corrosion inhibitors in the petrochemical industry dues to their affinity to be oriented at the metal/solution interface. In 2012, over 26% was the demand for surfactants as anti-corrosion components only for the petrochemical industry, as well as this request grew by 4.1% per year [38]. To combine the attractive anti-corrosion property of surfactant set with chitosan biopolymer, several chitosan-surfactants macromolecules are synthesized and then evaluated as potential retarders of corrosion. In this regard, the introduction of hydrophobic moiety into the chitosan skeleton has been led to an increase of its hydrophobic property to become surface-active polymers, which in result an enhancement of the prevention capability of chitosan. For instance, a sequence of seven modified hydrophobically chitosan surfactants were produced and their anti-corrosion property is measured for carbon steel in acid medium. As compared to the pure chitosan, good inhibition efficiencies between 93 and 74% (at 250 ppm) are achieved for those surfactants functionalized chitosan derivatives [39]. It was found that carboxymethyl chitosan thio-derivative provides the highest protection. This finding is related to its high surface activity and the presence of more active adsorption centers within its molecular skeleton as well.
A wide range of organic heterocyclic molecules has been employed to face against metallic corrosion. In this context, azole-based compounds have shown an excellent capacity to act as good anti-corrosion compounds for several metallic materials in different corrosive environments, especially in acidic ones. The latter molecule set includes N-azole, thiazole and oxazole cyclic molecules with different architectures [40]. The chemical incorporation of azole moieties or their derivatives into the chitosan backbone has shown excellent results in terms of inhibition efficiency. Recently, a novel triazole modified chitosan (Figure 2(d)) has been reported to act as an efficient retarder of carbon steel corrosion, which a maximum inhibition efficiency of 97% is reached using just 200 ppm of developed chitosan derivative [41]. The benefic effect of this triazole-modified chitosan biomacromolecule against corrosion can be revealed from the reported scanning electron microscopy (SEM) images as depicted in Figure 3. It is clear from Figure 3(a) that the morphology of carbon steel surface is more rough and damaged in the absence of modified chitosan inhibitor. Nevertheless, in its presence (Figure 3(b)) the morphology of steel surface become smoother, which supports the protection capacity of the developed chitosan derivative. In this work, it was found that the synthesized compound could block cathodic sites at the metal surface via the physical and chemical adsorption process.
SEM images of carbon steel surface (a) without and (b) with the addition of developed triazole-modified chitosan at 200 ppm [42].
In addition to the amine group, i.e. –NH2, the functionalization of chitosan can be also carried out on both extra-functional groups including –OH group. This approach to amplify the inhibiting effect of chitosan has been attracting interest. We can list the example of poly (N-vinyl-imidazole) grafted carboxymethyl chitosan (Figure 2(e)), which is a polymer grafted chitosan. The newly synthesized chitosan derivative has exhibited interesting corrosion protection for steel metal in acid solution [43].
Chitosan composites have mainly been applied as inhibiting coatings and are used for corrosion protection purposes in different media. Some works have reported the preparation of composite coatings with chitosan to obtain protective systems to metal substrates [42, 44, 45]. To improve the anti-corrosion properties of the polymeric matrix, it is necessary to invest in improving the mechanical and adhesion properties through the incorporation of inorganic and organic fillers. It is reported that Nano-scaled fillers imply better barrier properties in the polymer coatings compared to the micron-size additives [15]. In general, a schematic for composite formation is shown in Figure 4.
Schematic presentation of chitosan-nanoparticles composites formation process.
Biopolymer chitosan-based nanocomposite coatings have been investigated for protection against copper corrosion [46]. Coatings are composed of chitosan matrix with 2-mercaptobenzothiazole and silica nanoparticles. Overall, the combination of the organic corrosion inhibitor and inorganic nanoparticles enhanced the protection efficiency of chitosan coatings, which is an important advance toward developing sustainable corrosion protection coatings for different metals.
Several researchers have reported the viability of chitosan composites films e.g. chitosan/ZnO nanoparticle composite for protection against corrosion for steel [47, 48] and bio-corrosion inhibition for S150 carbon steel [49]. All of these studies showed that the quality of the chitosan film was improved due to the addition of ZnO nanoparticles. Another study [50] evaluated and compared corrosion protection of carbon steel using two different systems of chitosan e.g. oleic acid-modified chitosan-graphene oxide composite coating and pure chitosan coating. In this case, it was observed that the corrosion protection of oleic acid-modified chitosan-graphene oxide composite coating improved by 100 folds when compared with pure chitosan coating. Thus, oleic acid-modified chitosan-graphene oxide composite is more effective in corrosion protection of carbon steel.
Another composite coating [51] consisting of graphene oxide-chitosan-silver on Cu-Ni Alloy with enhanced anti-corrosive and antibacterial properties show graphene oxide retards the diffusion of corrosive ions to the substrate and minimizes the electron transport between the electrolyte and metal, while chitosan prevents the galvanic coupling of graphene oxide with the metal surface [51].
The system chitosan/hydroxyapatite nanoparticle composites revealed that they could inhibit corrosion in steel, however, it was found that the combination of chitosan/hydroxyapatite nanoparticle with other species provides more effective protection against corrosion [52, 53, 54]. Different composites such as chitosan/hydroxyapatite-Mg [55], chitosan/hydroxyapatite-Si [56], chitosan/hydroxyapatite-multiwalled carbon nanotube [57], chitosan/hydroxyapatite-CaSiO3 [58], and chitosan/hydroxyapatite-cellulose acetate [59] were synthesized and tested as corrosion protective layers. The composites chitosan/hydroxyapatite-Mg, chitosan/hydroxyapatite-Si, chitosan/hydroxyapatite-CaSiO3 and chitosan/hydroxyapatite-cellulose acetate demonstrated that the insertion of the third component exhibit a representative improvement in the corrosion protection of the chitosan/hydroxyapatite nanoparticle composite, except for composite chitosan/hydroxyapatite-multiwalled carbon nanotube. Consequently, it could be expected that the presence of carbon nanotubes in any non-conductive polymer coating provides lower protection against corrosion.
As shown previously, the use of chitosan-nanoparticle composites led to improvements in the corrosion protection of different surfaces, i.e. copper and steel. Bahari et al. [46] concluded that addition of nanoparticles contributes to the reduction in swelling of chitosan coatings and crosslinked chitosan coatings are superior to the non-crosslinked ones vis-a-vis in mitigation of corrosion of copper surface. When, John et al. [47] concluded that mitigation of corrosion of mild steel by nanostructured chitosan/ZnO nanoparticle films was obtained based on chemical stability, oxidation control of coatings. Therefore, the process of corrosion control depends on the structure of the coating (polymeric matrix, crosslinking, adhesion, among other parameters).
Efficient inhibitors and organic coatings are able to extend the life of some metal surfaces. Chitosan is a component with a high potential for protection against corrosion of metals when exposed to corrosive media. In the first stage, the pure chitosan form is used to omit the corrosion of numerous metallic-based materials. Nevertheless, the lower water-solubility of this biopolymer was limited to its application and its utilization to a broad aggressive media range such as near-neutral solutions. Although, such weakness can overcome and the prevention performance of chitosan can be improved through different functionalization demarches. Furthermore, chitosan can be combined with the other materials to develop new chitosan-nanoparticles composites that can apply as coatings.
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\n\nIntechOpen nije formalno povezan niti s jednom vanjskom stranicom čije poveznice vode na www.intechopen.com, osim ako to nije izravno navedeno. Iz tog razloga IntechOpen nije odgovoran za sadržaj koji se pojavljuje na takvim stranicama. Poveznica na IntechOpenovu stranicu ne implicira povezanost sa IntechOpenom. Korištenje takvih poveznica isključiva je odgovornost korisnika.
\n\nZadržavamo pravo vlasništva nad cjelokupnom stranicom www.intechopen.com i nad svim materijalom na toj stranici. Koristeći se našim uslugama, slažete se da maknete sve poveznice na našu stranicu odmah nakon što to od vas zatražimo. Također, zadržavamo pravo da ove Odredbe i uvjete, i politiku o poveznicama izmjenimo u bilo koje vrijeme. Koristeći se poveznicama na naše stranice slažete se s ovim Odredbama i uvjetima.
\n\nAko smatrate da je bilo koja poveznica na našoj stranici sumnjiva iz bilo kojeg razloga, molimo vas da nas kontaktirate. U tom slučaju razmotrit ćemo micanje poveznice s naše stranice, iako nismo obvezni to napraviti.
\n\nBez prethodne privole i izričite pisane dozvole, ne možete stvarati okvire oko naših stranica ili koristiti druge tehnike koje na bilo koji način mogu promijeniti prezentaciju ili izgled naše stranice.
\n\nIntechOpen može ove Odredbe izmijeniti u bilo koje vrijeme i bez prethodne obavijesti. Koristeći ovu stranicu vi se slažete s trenutnim Odredbama i uvjetima koje su na snazi.
\n\nOve Odredbe i uvjeti su sastavljeni u skladu s odredbama prava Ujedinjenog Kraljevstva, a za sve sporove nadležan je sud u Londonu, Ujedinjeno Kraljevstvo.
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